Sept., 191j
T H E JOL7RS..1L O F I S D I ‘ S T R I A L A S D E S G I S E E R I - V G C H E M I S T R Y
737
ORIGINAL PAPERS THE IMPROVEMENT OF HIGH BOILING PETROLEUM OILS, AND THE MANUFACTURE OF GASOLINE AS A BY-PRODUCT THEREFROM, BY THE ACTION OF ALUMINUM CHLORIDE‘ By A. AI. N C A F E E
The con\-ersion of high boiling petroleum oils into lower boiling oils of greater commercial value is an old problem, and many solutions of it have been proposed. Formerly, when kerosene was worth more t h a n gasoline, naturally the effort rT-as t o increase the yield of kerosene from crude oil; nowadays. gasoline is worth more t h a n kerosene, and naturally the effort is t o increase the yield of gasoline. But in principle, gasoline making and kerosene making f r o m high boiling petroleum oils are the same, and most of t h e proposed methods make both products. K i t h 1-ery little variation, most of them will make gas equally well. A careful examination of these methods will show, in nearly all cases, the same principle, namely, what is called cracking-heating t o a sufficient temperature t o cause the high boiling oils t o become unstable and break down into loLver boiling oils. If t h e heat be intense enough and the time be long enough the product mill be gas; less heat and a shorter time will make gasoline, and a still less heat and shorter time n.ill make kerosene. The inventors ha\-e rung the permutations on this simple idea; they heat under pressure and they heat under vacuum; they heat in the presence of gases; they heat in t h e presence of catalysts; t h e y heat in tubes and they heat in boilers, etc., etc. I t is safe t o s a y t h a t in 99 per cent of the methods which have been proposed for converting high boiling oils into lolwr boiling oils. “cracking” by heat is involved. Sometimes it is disguised in ornate language: sometimes i t lurks behind intricate apparatus, but it is always there. The difficulty, however, with all these c,racking methods is a difficulty in principle. I n breaking down t h e complex, high boiling hydrocarbons into several simpler ones, there is not enough hydrogen t o saturate these newly formed bodies, and unsaturated hydrocarbons must necessarily result unless hydrogen be added or carbon subtracted. Hydrogen is too expensive and difficuit t o add and: though a part of t h e carbon is readily enough subtracted and deposited, this subtraction and deposition n e v u goes f a r enough-although the still man might not be readily convinced of this. These cracked products are in large part unsaturated, and they are not desirable commercially. They are foul smelling; they are yellow in color and become rapidly more yellow on standing; they deposit large amounts of carbon on ignition in a gas engine; they burn with a smoky flame; t h e y contain resinous bodies which cause gumming in use or on standing, etc., etc. They can, of course, be refined somewhat with sulfuric acid, b u t there
’
Read before the Seventh Semi-Annual Meeting of the hmerican Institute of Chemical Engineers, San Francisco, -4ugust 2 5 , 1915.
must be too much of the acid used and too much of the oil is lost t o permit in practice any thorough treatment iTith acid. dside from the poor quality of the liquid products obtained, the operation of the cracking process is attended with great difficulty \There uniform results are desired. There are many 7-ariables on xvhich the obtaining of such results depends-temperature, time, pressure and catalytic action of the walls of the containing vessel. A change in either of these \-ariables makes a change in the products obtained. L-sing the same apparatus, the same pressure, and consuming the same time! a difference of a comparatively f e w degrees of temperature in cracking operations makes marked differences in the yield and quality of liquid products. I n most of the cracking processes, pressure is employed: 60 t o I O O lbs. is usual and some have proposed much higher pressures. I t is here t h a t the greatest difficulty becomes manifest-the great danger t o the operators and t o t h e plant. There is always a deposition of hard (and flinty hard) coke on t h e inner walls of the heating element. Some who have had considerable experience in cracking oils have said t h a t the coke is forced into combination with the iron, making i t brittle and thus utterly unable t o withstand the high temperature and pressure employed. At a n y rate, the deposition of the carbon occurs where the element is hottest, causing a local overheating a t t h a t point. Under such conditions t h e tensile strength of the steel becomes an unknown quantity; as likely as not i t yields t o the stress without a n y warning. Oil vapors of a temperature around 6 j o o F. ignite spontaneously when they evolve from a still into the surrounding atmosphere. I n cracking processes the temperature is ; j o t o S j o o F. and even higher; hence, the manifest danger of cracking petroleum oils . under such pressures. Tl‘hen I took up the gasoline problem, some two and one-half years ago, I dismissed from consideration the idea of cracking oils. Up t o this time, or since t h e Friedel a’nd Crafts British patent, S o . 4j69, of I S j i , there had been some degree of mild interest shown as regards the effect which aluminum chloride might have on petroleum oils. but no positive results had followed from this interest. I t appeared t o me t h a t this reaction might have far more significance t h a n was then apparent. I trust this paper may in a measure exemplify its significance. I have found t h a t n.ith proper control of t h e i-apors leaving the distilling system and entering the final condenser, and with sufficient time given the aluminum chloride, high boiling oils can be completely broken down into lower boiling oils, and no matter how unsaturated the high boiling hydrocarbons may be, the low boiling oils produced therefrom are sweet smelling, Iv-ater white and saturated. The reaction giyes little gas and only about t h e right amount of carbon t o allow production of saturated products.
.
738
T H E JOCRNAL OF INDUSTRIAL. A N D ENGINEERING CHEMISTRY
T h e carbon is deposited not in t h e form of a hard baked-on carbon, b u t as a granular, coky mass, easily removed from t h e still. But there are other products t h a n gasoline t h a t can be made from petroleum u-hich are commercially worth while, although in our efforts t o incre,ase t h e supply of gasoline we have apparently forgotten this fact. If t h e market value of t h e various products which can be obtained from crude petroleum be plotted, it will be found t h a t there is a peak at t h e low boiling end and another a t the high boiling end. Gasoline is worth more t h a n kerosene a n d kerosene is worth more t h a n gas oil, while t h e products following gas oil, paraffin a n d lubricating oils, are worth as much or more t h a n t h e gasoline. The problem before me, therefore, knowing t h e reactive power of aluminum chloride. was t o apply it t o crude petroleum so t h a t good heavy oils could be obtained while a t t h e same time converting t h e less valuable portions of t h e crude into gasoline. The solution of this problem is found in my patent. I n t h e practical operation of this ,process, crude petroleum of any kind is first distilled until t h e naturally occurring gasoline a n d kerosene, if there be a n y present, is distilled off. As you are probably aware, in many of our crude oils, and especially some of those from Texas, California a n d . LIesico, there is substantially no gasoline present and very little kerosene. But in a n y event, t h e crude is first heated t o free it of any moisture which it may contain. since t h e oil must be perfectly dry before adding t h e alumin u m chloride. T h e next step is t o add anhydrous aluminum chlor i d e t o t h e remaining residual oil, and t h e n bring t h e mixture t o boiling in t h e still. Boiling is usually around j o o o F. and generally remains between joo a n d 5 5 0 ' F. during t h e entire distillation, extending over a period of 2 4 t o 48 hours. There is no need of employing extra pressure or vacuum or special a p p a r a t u s ; a n y still with a stirrer in it suffices. Granted sufficient time for t h e aluminum chloride t o get in its work, t h e success or failure of this process depends upon t h e proper control of t h e temperat u r e a t which t h e oil vapors are allowed t o leave t h e distilling system t o enter t h e final condenser. Between t h e still a n d t h e final condenser are placed two air-cooled condensers connected i n series, which separate t h e low boiling oils from t h e high boiling oils, returning t h e latter, together with any volatilized aluminum chloride, t o t h e still. For a 1,000 barrel still t h e air condensers which we are now using are drums of oval cross-section, 3 f t . X 6 f t . X 6 f t . high. I n addition t o ,the air condensers, a 3 f t . dome is a t tached t o the t o p of t h e still which serves t o return most of t h e volatilized aluminum chloride a n d its compounds. T h e operation is so controlled t h a t t h e vapor is kept a t t h e desired temperature as indicated by a thermometer placed i n t h e vapor line a t t h e point of exit of vapor into t h e final or water-cooled condenser. The temperature a t this point should not exceed 3joo F., otherwise, not only will heavy oils distil over, b u t t h e aluminum chloride (or its
Vol. 7 , No. 9
compounds with hydrocarbons) will enter t h e condenser a n d clog it u p . Under t h e first named condition, t h e distillate obtained will be a mixture of gasoline, solvent oil a n d kerosene which are afterwards separated by fractional distillation. These products are all water white, sweet smelling, saturated, a n d need n o refining with sulfuric acid. I n practice, no t r e a t m e n t is given them, except a washing with alkali, followed with water, t o remove hydrogen. sulfide. With proper back-trapping of high boiling oils into t h e still from the air-cooled condensers a n d a temperature of 300' F. in t h e vapor line, t h e distillate obtained will be gasoline alone. which is ready for t h e market when washed with a n alkaline solution. I have spoken of t h e time which should be given t h e aluminum chloride for t h e accomplishment of t h e desired results. I t is a mistake t o assume t h a t with a given amount of aluminum chloride a n d boiling it u p with oil. t h e desired results will be obtained. T h a t is far from t h e t r u t h . I do not wish t o impose upon your patience b y dismissing consideration of t h e mechanism of this reaction b y simply saying i t is catalytic. I a m fairly well satisfied t h a t it is one of association or combination in t h e liquid phase a n d dissociation in t h e vapor phase. I t is well known t h a t aluminum chloride exists in t h e solid a n d liquid states as AU2C16,and in t h e vapor state as AlCls. I t is also well known with what avidity aluminum chloride in t h e solid or liquid s t a t e will combine with other salts t o form double salts. The most common of these double salts is t h a t of aluminum and sodium chloride which, a t one time, as you know, was t h e source of metallic aluminum (Castner process). Aluminum chloride probably combines with these high boiling, complex hydrocarbons in much t h e same way as it combines with sodium chloride a n d when t h e boiling temperature is reached these double compounds become unstable a n d dissociate into lower boiling hydrocarbons, which, under the temperature control imposed in t h e vapor line, leave t h e distilling system as fast as produced; -412C16 is again formed a n d is -capable of combining further with other high boiling hydrocarbons remaining in t h e still, a n d free carbon is formed simultaneously. This view 'of t h e reaction here involved is confirmed, I believe, b y t h e operating conditions mentioned heretofore as necessary for obtaining t h e desired results. While t h e operation, using crude ail as t h e starting material, can be carried on t o produce larger or smaller quantities of gasoline, in practice it is carried on SO as t o convert t h e gas oil fraction into low boiling hydrocarbons a n d leave most of t h e high boiling hydrocarbons, t h a t is, t h e paraffins and lubricating oils. Accordingly, t h e operation is interrupted after a portion of t h e crude has been converted into low boiling products, a n d t h e high boiling oil remaining in t h e still is pumped off while hot; on cooling it is worked u p into t h e usual paraffin a n d lubricating products. The aluminum chloride remains i n t h e still enmeshed i n a mass of coke, and t h e methods of its recovery are found in my patents, referred t o below. As illustrative of t h e action of aluminum chloride
Sept., 1 9 1 j
T H E JOl-RN.4L' OF I N D C S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
on high boiling petroleum oils, results obtained on typical crudes are given in Tables I t o 111. TESTS OK THREE C R U D E OILS
For the sake of convenience, the distillate obtained b y distilling the crude before t h e addition of aluminum chloride is termed "primary distillate," the oil remaining in the still being termed "primary residual oil:" t h e distillate obtained b y distilling t h e primary residual oil with aluminum chloride is termed "see-
739
,
is obtained from this type of Texas crude (sp. gr. 20.8 Be.). By the aluminum chloride process (see Table I ) I ; . jj per cent is obtained and those who are familiar with the tests on petroleum products will see t h a t this gasoline is as good as the natural gasoline made from any crude petroleum. The gas naphtha, which might very well be mixed with the gasoline, has been increased from 0 . I t o 1 3 . 0 3 per cent. It will be observed t h a t these low boiling oils have been made a t the expense of the gas oil
TABLE I-TESTS ON TEXAS CRUDEOIL (SP.GR. 2 0 . 8 O B8.) Distilled until Free from Moisture and until the Naturallv Occurring Gasoline and Kerosene Had Been Distilled Over TESTSON SECONDARY DISTILLATE X'IELD FROM CRUDE OIL Per cent Sp.gr.51.l0BP. Distillation over 100° F crude oil Per cent.. . . . 10 20 30 40 50 60 70 80 90 95 Primary distillate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.14 U p to.. . . . . . 174' 228' 265' 294' 324' 357' 388" 428' 4 i 5 ° 5 0 ( ~ F. 0 Primary residual oil. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91.26 1.0s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.60 FRACTIONAL DISTILLATION PROPERTIES OF FRACTIOXS Total . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100.00 Per cent Per cent GasoGas line naphtha F~hcTross charge crude l i . 4 5 Color \v \v. S.W. 36.18 TESTSO N PRIMARY DISTILLATE SIneet . 26.62 12.85 Odor Sweet Bromine S o . 5 . 4 6 Sp. gr. 36' Be. 1.28 Bromine No. 4 2 . 2.65 3.2 Distillation over 260' F . 9.53 4.59 D r y test 0 . K. 0. K. 10, 52 4 3 Heat test . 2 1 . 8 0 Per cent . . . 10 20 30 40 50 60 70 80 90 95 Loss. , , , . . , 1.55 0 056c2 Sulfur . 3.22 0.054% C-p t o . , . , , . . 320c 314O 368O 386' 400' 442' 468' 490" 5 0 5 ° 5 2 0 0 F . __ 64.5 Gravity 50.2 T O T A L. . .. . . 100.00 48,24 Sp. gr. Per cent Bromine FRACiIuXAL Per cent Drsiir.1- .ITION crude OBe. Color sulfur So. Distillation of Gasoline Fraction-Above I17 F ( '.aioline , . . . . . . . . 0.303 58.0 11.. \V, 0.065 4.8 (;a. n a p h t h a . , . 0.180 -51 .n s, IT, 0,103 3 1 Per cent.. 10 20 30 40 50 60 70 80 90 08 (drypoint) \V \V.kerobene . . . . . . . . 1.260 41.6 \V.\V. 0.071 Up t o . . . . 160' 170' 179' 190' 208' 222' 239' 261' 293' 339'F. . . Sp. g r . , . . 8 2 . 1 7 9 . 0 75.3 70.9 6 6 . 0 6 1 . 8 5 7 . i 6 4 . 2 5 0 . 4 , . , . S. IV.kerosene.. . . . . . . 1.530 40.9 \I-. \T. 0.133 . . (;ai o i l . . . . . . . . . . . . . . 3 . 7 9 1 31.2 . . . 0..186 Distillation of Gas Kaphtha Fraction-Above 215O F 1.0.5 .... .. 0.076 Per cent.. 10 20 30 40 50 60 70 80 90 9 8 ( d r y p o i n t ) ' r U T 4 1 , . . . . . . . . . . . . . . 7.140 Up t o . . , 240' 246' 253' 260° 270' 280' 293' 306' 332' 350O F. S p . gr.. , , 5 7 . 0 5 5 . 0 54.1 5 2 . 8 5 1 . 3 5 0 . 2 4 9 . 1 47.5 4 5 . 4 , , , .
__
TESTSOS PRIMARYRESIDY.4L OIL Sp. gr. 19 8' Be. Viscosity 302 Distillation over 480' F. P e r c e n t . .. . . . . . . . . . 10 20 30 40 c p to... 530' 566' 600O 656O
50 680'F.
hrlrture of Primary Residual Oil and 7 . 5 Per Cent by %e' ight of Anhydrous Aluminum Chloride Brought t o Boiling Temperature of distillate Distillation test Still Vapor Per cent Sp. gr. Ozer Per cent below D r y Time OF. line charge OBe. F. 350' 450'F. point I :00p . x . . . . . . 454 268 Showed up . . . . . . . . 1 30 P . H . . .. . . 479 2.86 5 5 . 9 110 290 68 80 490 5 5 . 2 110 2.86 69 1 : 4 5 P M , ,. , . 488 300 84 490 2.86 5 4 . 4 110 2.17 P x ...... 495 302 66 80 490 2 . 4 5 P . X . . . . . . 504 290 2.86 5 4 . I 110 66 81 490 ,?:I5 P . M. . . . . . 508 2.86 5 3 . 5 110 65 80 490 290 2.86 5 3 . 7 110 4:15 P . M . . . . , , 518 65 310 80 490 4 . 4 5 ~. . .~. . . 523 2.86 340 5 3 . 7 110 65 83 490 6 : O O P.M. . . . . . 525 340 2.86 5 3 . 5 105 60 82 490 530 344 2.86 5 3 . 3 100 58 490 530 340 2.86 5 3 . 5 100 58 490 542 340 2.86 5 3 . 2 100 60 83 490 547 320 2.86 52.6 100 60 83 490 1:Od A.JI . . . . . . 547 300 2.86 5 2 . 4 100 60 83 490 2.86 5 2 . 8 100 6 : 3 0 A . Y . . . . . . 552 290 58 83 495 2.86 5 0 . 6 100 551 305 58 8.3 500 49.7 100 ! : O ~ P . M. . . . . . 557 302 8.57 55 85 510 From back trap, 1.39 Operation stopped a t end of 24 hrs. YIELD
RESIDUALOIL WITH .41Ch Per cent charge Per cent crude 48.24 Secondary distillate.. . . . . . , . . . . . . 52.86 Secondary residual oil.. . . . . . . . . . . 31.14 28.42 Loss (gas and coke). . . . . . . . . . . . . . 1 6 . 0 0 14.60 FROM D I S T I L L . ~ T I O NP R I M A R Y
TOTAL.. ....................
-
__
100.00
91.26
ondary distillate " and t h e oil remaining in the still, "secondary residual oil." Fahrenheit temperature and Baume gravity are used throughout. The distillation tests lvere made on 100-cc. samples contained in standard Engler flasks connected t o a 2 2 in. Liebig condenser. A11 flash points noted are in open cup tester. Viscosities noted are on t h e Saybolt Universal 1-iscosimeter a t 100' F. IT. W. and S. U '. are abbreviations for water white and standard white, respectively . T E X A S C R U D E OIL-In ordinary practice no gasoline
TESTSO N S E C O X D A R Y RESIDUAL OIL ( F R E E D O F A1Cla) Color Flash test Fire test Viscosity Red-green bloom.. . . . . . . 185' F. 2 5 0 O F. 105 Secondary Residual Oil Reduced with Steam TESTSO N Per cent Per cent crude LUBRICATING OIL Yield charge 2.84 Color Red-green bloom Gas oil. . . . . . . . . . . . 10.00 Luhricating o i l . . , . . , 9 0 . 0 0 25.58 Sp. gr. 21 Flash test 290 TOTAL . . . . . . . . . . . 100.00 28.42 Viscosity 122
__
.:
__
SUMMARY
Products from AlCh Process (Per Cent Crude Oil) GasoGas Kero- Gas LubricaDISTILLATC line naphtha sene oil ting oil 'roTAL 0.18 2.79 Primary . . . . . . . . . . . . . . . . 0 30 Secondary . . . . . . . . . . . . . . 17.45 12.85 5 . 8 i l i : i 5 2 5 : 5 8 f 82.17 LOSS DLTETO: Distilling primary distillate.. . . . . . . . . . . . . . . . . . . . . . . . . 1,60 14.60 Distilling with AIC13.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Redistillation of primary distillate,, . . . . . . . . . . . . . . . . . . . 0,OS} 17.83 1.55 Redistillation of secondary distillate.. . . . . . . . . . . . . . . . . .
TOTAL ......................................
100.00
COMPARISON OF .41Cli PROCESS WITH USUALPROCESS Per cent of crude oil by Ale13 process Usual process 0.00 Gasoline. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17.75 0.10 Gas n a p h t h a . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . 1 3 . 0 3 Kerosenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 . 6 6 4.30 52.00 Gas oil.. . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . 17.15 Lubricating oils.. . . . . . . . . . . . . . . . . . . . . . . . . . 2 5 . 5 8 25.50 Asphaltic residual oil. . , , . , , , . . . . . . . . . . . . . . . . . 12.00 ~
S U M OF
1,oss..
,
PRODUCTS.. , ,
., ., , , , , , , , , ,
.............. 82,li . . . . . . . . . . . . . . 17.83
.
~
TOTAL.. ....
. . . . . . . . . . . . . . 100.00
__
93.90 6.10
___
100.00
fraction and the asphaltic residual oil, the latter being broken down completely. Gas oil is t h e least valuable constituent of the crude. The asphaltic residual oil is used for fuel or is made into asphalt. The yield of lubricating oil by the aluminum chloride process is about t h e same as t h a t in the usual process, b u t t h e quality of the former is greatly improved by virtue of the saturating effect of the aluminum chloride and the elimination of asphaltic and resinous constituents from the oi1.I 1
Samples of the products were furnished for examination
740
T H E JOCR+3TALO F I N D U S T R I A L A N D ENGINEERIA-G C H E X I S T R Y
It will not be necessary t o go into so much detail with the remaining crudes of which I desire t o speak, b u t I have wanted t o give you these figures on Texas crude t o show how regularly t h e reaction proceeds over a long period of time, what the physical characteristics of the products are, and the yield as compared with the usual process. C A D D O (LA.) C R U D E on-This crude (sp. gr. 41 O Be.) belongs t o the same type as Pennsylvania crude, the type known as paraffin-base crudes. Their products are clean smelling and require b u t little acid in refining. But even this type of crude is considerably improved by t h e aluminum chloride process (see Table 11), while a t the same time the yield of gasoline is greatly' increased. The paraffin residual oil from Caddo crude is black and tarry on account of the presence of asphaltic constituents, b u t these are not usually present in large enough amounts t o prevent the manufacture of good paraffin and paraffin lubricating oil. The distillation with aluminum chloride destroys the asphaltic constituents, giving a n amber colored residual oil which may be easily worked into a product known commercially as vaseline, or into paraffin and paraffin lubricating oils. At t h e same time the yield of gasoline from the crude is increased from 18 t o 42.32 per cent. O K L A H O M A C R U D E OIL-The residual oil from this crude (sp. gr. 3 4 ' Be.) b y the usual process is a black, tarry mass, containing a large amount of asphaltic constituents and also paraffin. The amount of asphaltic constituents is so great, as a rule, t h a t it is difficult t o make paraffin and paraffin lubricating oils of the same grade as t h a t obtained from Pennsylvania or Caddo residuums. By the aluminum chloride process (see Table 111) this residual oil is cleaned of its asphaltic constituents, and paraffin wax and paraffin 1ub.ricating oils of excellent quality are made therefrom. At the same time, the yield of gasoline from the crude is greatly increased, a t the expense of the less valuable fractions of t h e crude. Although the crude petroleums from. t h e various oil-producing districts in this country differ greatly in quality and in chemical composition, yet they are generally divided into three types : asphaltic-base crude, paraffin-base crude, and paraffin-asphaltic-base crude. The oils I have spoken of in this paper are representative of each of these types: Texas, asphaltic-base crude; Caddo, paraffin-base crude; and Oklahoma, paraffin-asphaltic-base crude. T o give figures on other crudes would be merely a repetition of t h e results obtained on one of these. I shall therefore not take the time t o give further examples. I might add t h a t among the samples here are products made by the aluminum chloride process from 14 gravity California crude and 2 0 gravity hlexican crude. RECOYERY O F A L U Y I X C Y CHLORIDE
But all the good results of this process would be of no commercial value if the aluminum chloride could not be reclaimed. This chemical, when made on t h e ton scale, is not so expensive as it is when made on the pound scale, but nevertheless its cost
1101. 7, No. g
TABLE 11-TESTS O N CADDO(LA.) CRUDEOIL (SP. GR. 41' BB.) Distilled t o Free It from Moisture and hTatural Gasoline YIELDPROM Primary residual oil 71.43
Primary distillate 26.19
CRUDE OIL
Total Per cent 100,00
Lobs 2.38
TESTSON P R I M A R Y DISTILLATE S p . gr. 58.2'BC. Distillation over 16O0 F . 20 30 40 50 60 io 80 90 95 (drypoint) Per cent.. 10 Up t o . . . . 215' 232' 247' 260' 276' 296' 31.5' 343' 402' S50° 500°F. FRACTIONAL DISTILLATION Per cent charge Gasoline. . . . . . . . . . . . . . . . . . . . . . . 82.00
......................
Kerosene.
Loss. . . . . . . . . . . . . . . . . . . . . . . . .
15.00 3.00
Per cent crude 21.48 3.93 0.78
100.00
26.19
__
TOTAL
__
Mixture of primary residual oil and 5 per cent by weight of aluminum chloride was brought t o boiling and distilled during period oi 48 hrs. Temperature of the vapor line a t the point of exit into final condenser was held around 350' F. YIELD
.%lCla DISTILLATION OF P R I M A R Y DISTILLATE Per cent charge Per cent crude 41.67 Secondary distillate.. . . . . . . . . . . . . . . 58.33 18.71 Secondary residual oil.. . . . . . . . . . . . . 2 6 . 2 0 Loss (Gas and coke). . . . . . . . . . . . . . . 15.47 11.05 FROM
___
~
TOTAL. . . . . . . . . . . . . . . . . . . . . .
100.00
71.43
TESTSO N SECONDARY DISTILLATE Sp. gr. 54.0° Be. Distillation over 102' F. Per cent.. 10 20 30 40 50 60 io
80
90
212O 260' 293O 3 1 5 O 340° 36S0 388O 414'
450'
FRACTIONAL DISTILLATION Per cent Per cent crude Gasoline.. . . . . . 50.00 20.84 Solvent oil.. . . . . 40.00 16.67 6.00 2.50 Gas oil . . . . . . . . . Loss . . . . . . . . . . . 4.00 1.66
FRACTIOXScharge
_ _ _ _
9.5 98 (dry point) 480' 500'F.
PROPERTIES OF FRACTIOXS GasoSolvent line oil Color W.W. W.W. Odor Sweet Sweet Bromine No. 2 3 Dry test 0. K. 0. K .
.
TOTAL.. . . . 100.00
41.67 Heat test 2 2 s p . gr. 58.0 48.1 Distillation of Gasoline Fraction-Above 120' F. Per cent, 10 20 30 40 50 60 70 80 90 95 (dry point) 362'F. Up t o . , , . 198O 221O 240" 258' 272' 288' 301' 322' 348' Distillation of Solvent Oil Fraction-Above 340' F. Per cent.. 10 20 30 40 50 60 70 80 9Q 95 98 point) (dry point) (dry Up to..
,,
354> 360' 364O 369O 374' 381' 390' 4000 416' 430' 440' F. TESTSO N SECOKDARY RESIDUAL OIL
'
Color Red-green bloom
Sp. gr. Flash test Fire test Pour test 3 6 . 5 BC. 260' F. 300' F. 90' F. Secondary Residual Oil Distilled Yield Per cent charge Per cent crude 5.61 Gas oil, . . . . . . . . . . . . . . . . . . . . . . . . 30.00 13.10 Paraffin residual oil . . . . . . . . . . . . . 7 0 . O O
TOTAL ........................
-
--
100.00
18.il'
Tests on Paraffin Residual Oil Fire test 420' F. . i~ test F.
COLOR Amber
F:a!i
Pour test 105O F.
SUllK4RY
Products from .41C13 Process (Per Cent Crude Oil) Gaso- Solvent K,ero- Gas Paraffin DISTILLATE line oil sene oil residual oil Primary.. . . . . . . . 2 1.48 3.93 8.11 13.10 Secondary . . . . . . . 20.84 16.67 L O S S DUE TO: Aluminum chloride distillation . . . . . . . . . . . . . . . . . . . 12.7 1 3.16 Working distillates into standard products.. . . . . . . .
TOT.4L
....................................
1
TOTAL 84'13
--
100.00
COMPARISON OF A1C13 PROCESSWITH USUALPROCESS AlCL process Usual process Pcr cent of crude oil 18.00 Gasoline. ...................... 42.32 Solvent oil ..................... 16.67 12.00 35,OO Kerosene.. ..................... 3.93 Gas oil.. ....................... 8.11 21 .00 Paraffin residual oil . . . . . . . . . . . . . . 13.10 11.00 S E M OF P R O D U C T S . ,
Loss
......
....................
TOTAL
84.13 15.87
9i.00
__
3.00 -
100.00
100.00
T K E JOrRZS,-1L O F I N D I ' S T R I A L A N D E h T G I N E E R I N G C H E M I S T R Y
Sept., r q j ~
is high, a n d from a dollars and cents point of view, i t is necessary t o recover it. This is done b y the processes set forth in my patents. A4ftera time, 4 8 hours or longer, aluminum chloride used in distilling oils, even the driest of oils, loses its catalytic activity and becomes converted into a coky mass. ,Analysis of t h e coky mass shows chlorine a n d TABLE 111-TESTS op; OKLAHOMA CRUDEOIL (SP.G R . 34' BB.) Distilled t o Free It from Moisture and S a t u r a l Gasoline YIELDF R O M CRUDEOIL Primary Total residual oil Loss Per cent 78.31 0.86 100.00 TESTSON PRIMARY DISTILLATE Color TV.W. Sp. gr. 5 4 . I o Bi.. Distillation over 152' F. Per cent,, 10 20 30 40 50 60 70 80 90 95 (drypoint) , 210' 226' 2423 2.52' 271' 290' 313' 3 4 5 O 408' 455'F. Up:to FRACTIOSSL DISTILLATIOK Per cent charge Per cent crude 14.58 Gasoline. . . . . . . . . . . . . . . . . . . 7 0 . 0 0 4.1, Kerosene.. . . . . . . . . . . . . . . . . . . . 2 0 . 0 0 1.56 C:as oil.. . . . . . . . . . . . . . . . . . . . . . . . 7.50 0.52 LOSS.. . . . . . . . . . . . . . . . . . . . . . . . 2.50 Primary distillate 20.83
-
~
ToT.\L... . . . . . . . . . . . . . . . . .100.00 TESTSo s PXIYXRY RESIDL-AL OIL Color Black
20.83
Sp. gr. Flash test Fire test Pour test 29.8' Be. 170° F 2 0 5 O F. 20 Distillation over 330' F. 10 20 30 40 43 per cent 436' 484' 543O 590° Bel0rn600~F
Per cent. , , , c p to.. ....
hlistrire of primary residual oil and 5 per cent by weight of aluminum chloride TT-as distilled during period of 48 hrs. Temperature of the vapor line a t the point of exit into final condenser rras held around 350' F. T I E L D F R O M AIC% DISTILL.ATIoh. O F PRIMARY DISTILLATE Per cent crude Per cent charge Secondary distillate . . . . . . . . . . . . . . 6 4 . 6 1 50,60 Sccoiidary residual o i l . . . . . . . . . . . . . . 1 7 . 9 7 14.07 Loss. . . . . . . . . . . . . . . . . . . . . . . . . . . 1 7 . 42 13.64
Per cent.. C p to.
10
__
I 0 0 . no TESTSns SECOKDARY DISTILLATE Sp. gr. 4 8 . 3 O nB. Distillation over 140' F. 20 30 40 50 60 70 80 90
TOT11... . . . . . . . . . . . . . . . . . . . .
. ? ? S o 27OC 294O 3 2 6 O 3 5 8 O 3 8 ? O DISTILLATIOX Per cent Per cent charge crude . . . . 40.00 20.24 . . , , 50.on 25.30 . . . . i.50 3 . so . . . 250 1 .?6
FR.¶CTIONAL
Fnacriuss Gasoline. . . . Kerosene . . . G a s oil . . . . Loss,
~
ToT.qi,. . . . . . . . . 1011 00
4 1 3 O 454'
__
78.31
98
95
(dry point) 5 0 3 O 54;' 570OF.
TESTSo x GASOLINE 1V.m'. Color Odor Sweet 1.5 Bromine S o D r y test 0. K. Heat test 2 0 027 Per cent S Sp. gr. 61.5
50.60
L)istillaLion of Gasoline Fraction-Over 130' F Per c e n t . 10 20 30 40 50 60 i o 80 90 Residue U p to. . . . 160' 1 8 6 O 200' 213' 222O 238' 252' 270' 299' 8 . 3 p e r c e n t SD.n r . . 8 3 . 8 7 6 . 2 7 0 . 1 6 6 . 6 6 2 . 8 60.4 5 8 . 5 56.1 3 3 . 3 4 8 . 2 TESTSO K SECOKDARY RESIDCALOIL Color Sp.gr Pour test Flash test Red-green blooni 2 8 . 2 " Be. 90'F. 230'F. Secondary Residual Oil Distilled Yield Per cent charge Per cent crude X-au s t o c k . . . . . . . . . . . . . . . . . . . . 60.00 8.44 Cylinder o i l . . . . . . . . . . . . . . . . . . . . . . 40.00 5.63 TOTAL ..
-
. . . . . . . . . . . . . . . . . . . . 100.00
-
14.07
.
SUMMARY Products f r o m AICla Process (Per Cent Crude Oil) Gaso- KeroGas Residual DISTILLATE line sene oil oil TOTAL Primary. . . . . . . . . . . . . . . . 14.58 4.17 Secondary. . . . . . . . . . . . 2 0 . 2 4 25.30 5 : 3 6 1 4 : O i ; 83.72 LOSS DUE ' I O ' Aluminum chloride distillation. . . . . . . . . . . . . . . . . . . . Working distillate into standard products, . . . . . . . . .
-
TnT.AL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100.00 COMPARISOX OF .%1Ch P R O C E S S WITH USUALP R O C g S S Per cent of crude oil .41C13 process Usual process Gasoline. . . . . . . . . . . . . . . . . . . . . . . . 34.82 12.50 Kerosene.. . . . . . . . . . . . . . . . . . . . . . . 29.4: 41.00 Gas oil.. . . . . . . . . . . . . . . . . . . . . . . . . . 5.36 35 .OO Residual o i l . , . . . . . . . . . . . . . . . . . . . . . 14.Oi 9.00 SUM OF
LOSS..
PRODUCTS., .........
.....................
TOTAL..
...............
83.72 16.28
-_ 97.50
__
2.50 --
100.00
100.00
i4I
aluminum present in t h e right proportions t o form aluminum chloride, but the latter is. so t o speak, masked. I t does not display its ordinary reaction with petroleum hydrocarbons. The granular coky residue, after i t comes from t h e oil-converting process, carries varying amounts of oils with it. If allowed t o cool down in t h e presence of the body of oil, it may carry 40 t o j o per cent of its weight of oil. If the oil body has been separated while hot from t h e coky residue, t h e amount of oil will be reduced to 4 or j per cent. After removing the oil, or the bulk of i t , from the coky residue, the aluminum chloride can be extracted from t h e latter with water or steam t o obtain a concentrated solution of hydrated aluminurn chloride. Aluminum chloride in the hydrated state does not have the catalytic property of the anhydrous material, but the hydrated salt can be used as the raw material for making t h e anhydrous salt. T o do this, advantage is taken of the property of hydrated alumin u m chloride, breaking up when moderately heated t o form aluminum oxide and hydrochloric acid gas. The alumina, when mixed with carbon and treated with hydrochloric acid vapors a t a high temperature. reacts t o form the anhydrous chloride, hydrogen and oxides of carbon. I n utilizing this property, one portion of t h e hydrated chloride is heated t o produce hydrochloric acid 1-apors and alumina, and these vapors on drying enter a further charge of alumina and carbon heated t o redness. The hydrochloric acid vapors given off a t a moderate temperature are thus utilized in further operations a t high teniperatures. I n another method of recovery, and the preferred one, the coky residue is heated t o red heat in an atmosphere of chlorine which disengages t h e aluminum chloride from the carbon. Xluminum chloride volatilizes normally a t a temperature around 365' F., b u t t h e coky residue may be heated t o redness without much evolution of these vapors. If the heating is done in an atmosphere of chlorine, the aluminum chloride is unlocked; i. e . , it vaporizes away from t h e carbon and is condensed in suitable receivers. Of course, the last and ultimate test of any process is whether it will work, and work successfully, n-ithout undue petting. T h a t the aluminum chloride process is now an assured commercial success, is, of course, due t o its own merits. B u t I cannot forego this opportunity t o speak of t h e generous aid from the Gulf Refining Co.! which has made success possible, and . the valuable advice and help from its officers. Although this account by no means covers the full scope of the aluminum chloride reaction with petroleum oils, yet t o speak further would lead me outside of my subject. It is with deep satisfaction t h a t I have been privileged t o read this paper before t h e American Institute of Chemical Engineers, in the capacity of a recent initiate among you. and I trust I may have the pleasure of reading further papers before you in due course of time. THEGULF REFINING C O M P A K Y BAYONNE. NEW
JERSEY
