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November 1949


(23) Thomas, C. L., and Ahlberg, J. E. (tcJ Universal Oil Products
Co.), U. S. Patent 2,229,353 (Jan. 21, 1941): 2,285,314 (June
2, 1942); 2,329,307 (Sept. 14, 1943).
(24) Thomas, C. L., and Bloch, H. 8. (to Universal Oil Products C o . ) ,
U. S. Patent 2,242,553 (May 20, 1941).
(25) Ibid.,2,333,903 (Nov. 9, 1943).
(26) Ibid., 1,416,965-6 (Mar. 4, 1947).
(27) Thomas, C. L., and Danforth, J. D. (to Universal Oil Products
Go.), U. 8. Patent 2,287,917 (June 30, 1942).
(28) Thomas, C. L., Hoekstra, J., and Pinkston, J. T.,J . Am. Chem.
Soc., 66,1694 (1944).


(29) Voge, H. H., Good, G. N., and Greensfelder, B. S., IND.ENQ
38, 1033 (1946).
(30) Whitmore, F. C., Chem. Eng. News, 26, 668 (1948).
(31) Whitmore, F. C., J . Am. Chem. Sec., 54, 3274 (1932).
(32) Whitmore, F. C., and StahIy, E. E., Ibid.,55, 4153 (1933).
RECEIVEDNovomber 15, 1948. This paper is taken from
which was part of a technioal information exchange ordered
ieum Administrator for War in Recommendation 41. The
formed at the Riverside, Ill., laboratories of Universal

a 1945 report
by the Petrowork was perOil Products

Catalytic and Thermal Cracking
of Pure Hvdrocarbons

Shell Development Company, E m e r y d l e , Calif.
T h e primary cracking of pure hydrocarbons both with
and without catalysts has been studied in terms of the
distribution by carbon number of the cracked fragments
to allow arriving a t a mechanism of molecular disintegration. The secondary reactions of the cracked fragments have been followed by analyses of the product fractions to allow a further definition of the nature of the
cracking system. On the basis of this work, cracking systems are assigned to two fundamental classes; each class
is described by a set of characteristic reactions covering
both the primary cracking and the secendary reactions.
Correspondingly, two types of reaction mechanisms are
proposed, one a free radical (thermal type) mechanism
based on the Rice-Kossialroff theory of cracking, the
other a carbonium ion (acid-activated type) mechanism

derived from the work of Whitmore and others on the
properties of carbonium ion systems. Cracking catalysts
are available for either type of reaction mechanism;
those which accelerate free radical type reactions are nonacidic, and those which accelerate carbonium ion type
reactions are acidic. Commercial acid-treated clay and
synthetic silica-alumina cracking catalysts belong to the
latter class. Activated carbon, a highly active, nonacidic
catalyst, gives a unique product distribution which is
explained as a quenched free radical type of cracking.
Activated pure alumina has weakly acidic properties and
produces moderate catalysis of both types of reaction
mechanism, the primary cracking corresponding to a free
radical mechanism and the secondary reactions of product
olefins following a carbonium ion mechanism.


mental unity is thus established for a number of important hydrocarbon catalytic reaction systems.
Thermal cracking and cracking over nonacidic catalysts have
also been studied. Mechanisms are also proposed for these
systems for comparison with those of the industrial or conventional catalytic cracking process,
Despite the wide variety of products obtained in the cracking
of different hydrocarbons either thermally or by any catalytic
process, i t has become increasingly evident that certain characteristic severances of carbon-carbon bonds and secondary reactions of olefins are always obtained thermally and over certain nonacidic catalysts, whereas another set of reactions prevails
consistently in the presence of acidic oxide cracking catalysts.
The principal contrasting reactions are shown here with respect
to specific hydrocarbons or hydrocarbon types which have been
tested. Comparisons between classes refer to hydrocarbons
with the same number of carbon atoms (Table A).
Both the hydrocarbon class and the isomeric form of a given
hydrocarbon control the primary products obtained. Because
of uniformity and simplicity of structure, normal paraffins (and
olefins) were given preferred study. The use of a relatively
large aliphatic hydrocarbon assists identification of important
secondary reactions because of its extensive fragmentation.

RIOR work on the catalytic cracking of pure hydrocarbons
has led t o a general characterization of the rates of cracking
and product distributions of the principal classes of petroleum
hydrocarbons (10-13). I n addition, a number of secondary
reactions of olefins have been investigated and the effects of
structural isomerism on the rates of cracking of several types
of hydrocarbons were examined (9,54). Consistent mechanisms
of reaction are now proposed, based on the primary hypothesis
that any hydrocarbon reacting over this type of catalyst is transformed into a carbonium ion (33,which then cracks or undergoes
secondary reactions according to definite rules. This hypothesis
is directly coupled with the requirement that the acidic oxide
type of cracking catalyst must make available reactive positive
hydrogen ions (protons) capable of producing carbonium ions
on contact with the hydrocarbon feed. A similar type of approach was proposed independently by Thomas (52).
The properties of carbonium ions, which are postulated to
represent the reactive form of the hydrocarbon in conventional
catalytic cracking, also determine the mechanism of reaction and
the type of product in many other acid-catalyzed hydrocarbon
reactions, such a8 the isomerization, polymerization, parafKn
alkylation, and hydrogen transfer reactions of olefins, the isomerization of paraffins, and the alkylation of aromatics. Funda-

Tertiary hydrogen is still more easily removed. matica formed a t 500 C. Radical isomerization presumably occurs through a coiled configuration of a single radical. Of great importance is the absence of secondary reactions. or i t may first isomerize. To summarize. This will be called the "RKtheory" and is summarized from another paper (33) as follows to explain the cracking of a normal paraffin: 1. Considerable weight may be placed on the results (23)of cracking a paraffin wax (averaging n-Cz6Hsa) as further evidence for the rules cited here. Small radical. repeat process to give ethylene and propyl-1 radical. CETENE. and coke-redefined (34) t o include carbon and hydrogen-all summed on a no-loss basis (9). By successive recracking. for example. . These radicals then react with feed stock molecules t o produce new fIee radicals and are themselves converted t o methane or ethane. I n the absence of radical isomn4. long normal paraffins crack thermally to give ( a ) the complete sequence of normal alpha olefins (899). much Ci to CIS n-a-olefins. The primary radical derived from this step may immediately repeat process t o give ethylene and methyl radical. T h e apparatus and procedure used in this work have heen described (9. aliphatics mostly branched Cracked next to ring Double bond shifts rapidly: extensive skelet a l isomerization Hydrogen transfer is a n important reaction and is selective for tertiary olefins Crack a t much higher rate than corresponding. as repeated in simplified form from another paper (33). The R-K theory also concerns the manner of formation of a iadical fiom the original paraffin. and (e) fairly large amounts of methane and ethane as end products of radical d e composition. those from other hydrocarbons were separated into distillxte fractions comprising significant boiling ranges. TERMINOLOGY AND PROCEDURE. The final radical in either step 3 or 4 may be ethyl instead of methyl.4 times as fast as primary hydrogen. paraffins Crack a t about same rate a s paraffins with equivalent etructural groups Crack a t lower r a t e than paraffins Crack at higher rate than paraffins Small amounts of aromatics formed a t 500° C. few branched sliphatiis Cracked within side chain Double bond shifts slowly. Large amounts of aro. T o start the chain and to compensate for the loss of chain carriers by side reactions. 41. which corresponds to a relative rate of removal of 1 to 3. a representative normal paraffin in the gas-oil boiling range. much study was devoted to the cracking of n-hexadecane (cetane).. Cetyl radical cracks beta to free valence t o give. CRACKING OF CETANE. H H + - TABLE A Hydrocarbon n-Hexadecane (cetane) Alkyl aromatics Normal olefins Olefins Iiaphthenos ' Thermal Cracking Major product is CP with much C i a n d Ca. UECAXE. in this 3. A schematic representation of cetane cracking IS as follows: The most successful present explanation of thermal cracking of hydrocarbons is the Rice free radical theory (2b-27) as modified b y Kossiakoff and Rice (19). and of particular interest were the liquid fractions. The definitions and terminology used here correspond to those in a previous paper (10). some of the radicals in step 3 may isomerize erization. since no skeletal isomerization appears to take place. 13. Thus. which also reacts as in step 1t o continue the chain reaction. H H I1 H H H H €I H H H €I H H H H This radical may immediately crack or may undergo CHa HC -C-C-C-C-C-C-C-C-C-C-C-C-C-C-CH radical isomerization prior to cracking. Ce to Cia. ( b ) large amounts of ethylene and propylene by successive beta cracking of the resultant primary or isomerized radicals. No. such as CH8. it may be assumed t h a t a few highly activated molecules decompose spontaneously or a t the wall. combines with an I1 atom in cetane to give sion and reaction with a small free hydrocarbon radical or a free a cetyl radical and methane: hydrogen atom. AND ISODOThe authors' work on the thermal cracking of cetane a t 500 C.2 primary hydrogen atom is more securely bonded and is removed less readily than asecondary hydrogen atom. little skeletal isomerization Hydrogen transfer is a minor reaction and is nonselective for tertiary olefins Crack a t about same rate a s corresponding pariaffins Crack a t lower r a t e t h e n paraffins Catalytic Cracking Major product is Ca to Cs. only primary radicals are derived from the cracking to secondary forms.INDUSTRIAL AND ENGINEERING CHEMISTRY 2514 Therefore. Liquid products from aliphatic feed stocks were fractionated by carbon number (9). from prior cycle or from initial The normal paraffin molecule loses a hydrogen atom by collihydrocarbon rupture. radical. extent of cracking. which then recrack a t the beta bond t o give ethylene and another primary reacts as in step 1 t o continue the chain reaction. and a numerical value of 2000 calories is assigned as the difference in activation eneigies. Cracking at the beta posiHC-C-C-C=C and C-C-C-C-C-C-C-C-C--C-CH H H H H H H H H H H H H H H H tion gives directly an alpha olefin and a primary radical (lacking one hydrogen atom on a primary carbon atom). The products corresponded with those expected from the R-K theory. few n-a-olefins above C4. and 1 atmosphere gave the products shown in Table I. in which the hydrogen donor and acceptor carbon atoms must closely approach each other. but this does not enter into the cracking of normal paraffins. The agreement with the product distribution worked out by the rules of the R-K theory (33) is considered good. columns 1 and 2 (with quartz chips as inert filler in the rpactor). O . heptyl-1 radical. which were about 90% olefinic by bromine number. repeat process to give ethylene and amyl-l radical. 11 the amount of ethylene. Alternatively. repeat process t o give ethylene and respect t o the carbon skeleton. 15) with certain modifications for thermal craclcing experiments (33).PARAFFIN WAX. This last restriction affects the calculations for cetane vcry littlc ( 3 3 ) . primary radicals thus give only H H H H ethylene as the olefinic product. and percentage decomposed are used interchangeably t o include gas. analytical methods have been amplified t o include deteimination of paraffin isomers by infrared and aromatics by ultraviolet spectrometry. cracking is propagated ass a chain reaction. say. Radical isom€I H H . THERMAL CRACKING Vol. H H H H H H H H H H H H erization is a change of the position of a hydrogen 2. liquid boiling below the original. Cracking of pentene-1 and undecyl-1 radical: either the original or isomerized radical then takes place a t a carbon-carbon bond located in the beta position t o the carbon H H H H H H H H H H H H H H H H atom lacking one hydrogen atom. especially of olefins. but i t still reniains the major product. the radicals ultimately are reduced t o methyl or ethyl fragments. usually to yield a more stable radical. Radical isomerization rrduces HC-C-C--C--R H . reactions of normal paraffins. conversion.66 a t 500" C. thereby becoming a free radical itself. (9) Alkyl aromatics (with propyl or larger substituents) Aliphatics ~~ ~~ ~~ ~~ ~~ which gives propylene on cracking beta to the free valence. Undecyl-1 radical cracks beta to free valence t o give ethylstep there is no change of position of any hydrogen atom with ene and nonyl-1 radical. n atom.

. _12_ CIS 4 4 1 4 0' .s. n-dodecane (Table V of 10). had no cracking activity and had no available acidity. Puve silica has been shown to be nonacidic.0 Conversion.. ..h. moles cracked Calcd. It was demonstrated t h a t pure porous silica.4. The activated carbon used in t h e present experiments has no indicated proton availability and shows an alkaline reaction in water. such as acid-treated Californian bentonitic montmorillonite. a property common to conventional cracking catalysts. 2515 AND OBSERVED PRODUCTS IN THE TABLE I..a . % ' 31. Calcd.. Extensive work has been carried out under the direction of Tamele in t h e colloid chemistry department of these laboratories on the relation of acidity to the cracking activity of porous solids ( 3 1 ) . Obsvd. protons are incorporated into the structure when such materials are prepared in an acid environment. the preferred being the ratio of molal flow rates required for equal extents of cracking. 0. small amounts of alumina properly added to pure silica endowed the latter with considerable activity. . This work has been of essential importance to the development of the present theories of reaction mechanisms over such catalysts in terms of carbonium ions. D a t a on the thermal cracking of pure naphthenes are scanty. experiments have now been made by the authors with pure silica and pure alumina of high surface areas.. Aromatic rings are stable under thermal cracking conditions. Thus. 26.- Liquid hourly space velocity. there is considerable reluctance to crack a t the bond next t o the aromatic ring. the alkyl groups attached thereto.007 second-1 (11. Information is lacking on the liquid products of thermally cracking cyclopentane type naphthenes. To extend our knowledge of cracking reactions. . The latter render the catalyst inactive since no carbonium ions can then be formed.. this means t h a t protons (hydrogen ions) are present and available for reaction with even weak bases and with suitable hydrocarbons. 2 Moles product/100 Calcd. Total hydrocarbon 378 ' . . Obsvd.6 . The first order cracking rate constants are also similar. 500' C.T a .. This result was traced t o the presence of available protons in the combined silica-alumina structure.6-~entamethyIheptane). As may be seen in another work (33) the correspondence of the calculated and experimental results is considered fairly good in view of the complex structure of this hydrocarbon and the approximate nature of the parameters used in the R-K theory. . .0 . the statements regarding acidity of porous solids made herein rest on the findings of Tamele (31)which are supported by the work of Thomas (32)and refer particularly to the type of acidity denoted by the term "proton availability". These chains may be expected to tend t o crack within themselves in accordance with the rules of the R-K theory. which require available protons for their creation. Keetane = 0. which cracks very differently from its isomer. Definite experimental evidence has been obtained by Tamele (SI) for the strongly acidic character of silica-alumina. Decalin (30) appears to crack like a branched paraffin. I n addition. i t is also classified here as a nonacidic catalyst... .A -..05 . but t h a t otherwise there is no departure from the general prin-ciples of the R K theory implied in the observed results. CATALYTIC CRACKING The study of the catalytic cracking of pure hydrocarbons was undertaken to explore the chemistry of the industrial process. wt. and oxygen atoms that additional cations are required t o obtain electrostatic neutrality. The majority of the authors' published experiments have been made with a synthetic silica-zirconiaalumina catalyst designated as UOP cracking catalyst Type B. On the other hand.. manner of preparation. the cracking of petroleum aromatics is essentially confined t o the cracking of attached carbon chains which may be alkyl or cycloalkyl groups. The pure alumina used by the authors has been determined to be aweaklyacidic catalyst.Naphthenes and aromatics are of much importance in petroleum fractions. a classification which fits well with many circumstantial observations on its properties. atmospheric) Quartz Activated Carbon UOP-B Run C-590 C-708 C-579 L. their cracking behavior is determined by the combined effect of the cyclic group. (11)closely resembles that from cetane.November 1949 +3 h INDUSTRIAL AND ENGINEERING CHEMISTRY From Gault (8) the over-all product distribution from the thermal cracking of cetene a t 450 to 550 C. and catalytic activity. give a fairly similar product distribution and are also in commercial use. Thus. . accompanied by ring dehydrogenation to aromatics. and acidtreated clays. . respectively ( 5 ) .. 10. One publication (18) indicates t h a t scant aromatics came from cyclopentane or methylcyclopentane. or naphthenic portions of condensed ring systems. good qualitative correspondence between acidity so considered and catalytic cracking activity has been established. this has virtually the same cracking characteristics as the synthetic silica-alumina catalysts in general commercial use. the product distribution was calculated by the authors (33) for isododecane (presumably chiefly 2. which structure so distributes the valence charges of aluminum. The available data lead to the conclusion that aromatic production via dehydrogenation is an important reaction of cyclohexane type naphthenes.. Obsvd. the authors have made comparable experiments in some extensiveness with activated carbon of very high indicated B-E-T (Brunauer-EmmettTeller) ( 4 ) surface area. 10. Most of these cyclic hydrocarbons in petroleum are alkyl substituted. I n thermal cracking. because of the unique product distribution' obtained with this material. 2 4 . but also by the reaction of the dry solid with ammonia. "1 - .2... Throughout the text the relative activities of the catalysts for the cracking of pure hydrocarbons are computed by either of two methods. Catalysts prepared from natural clays.003 (33) and Koetene = about 0. silicon. The several catalytic agents will be discussed in approximate order of their transition from thermal to acid type of cracking. a basic gas.5 . I n general. The present commercial catalysts are effective agents for accelerating those cracking and secondary reactions which lead t o a product distribution of considerable economic value t o the petroleum refiner. On the whole. CRACKINGOF NAPHTHENESAND AROMATICS. and the nature of the bonds linking the side groups to the ring. and those protons which are available a t the surface are readily exchanged for other cations such as sodium.. although derived from silicic acid. 61 53 4" 11 c1 0 5 139 130 13 22 0 12 CZ 50 60 21 23 Ca 95 97 27 23 17 17 C4 97 102 15 9 20 13 CS 72 64 17 24 Ce 13 21 50 41 14 16 13 15 7 8 C7 12 13 13 9 C8 6 8 11 10 I3 18 5 3 CS 10 11 13 15 c10 4 3 9 9 13 14 4 2 CII 8 7 17 13 4 2 c12 8 4 7 CIS 21 7 2 7 5 C.6.. silicazirconia-alumina (UOP Type B cracking catalyst). This acidity is measured not only as pH of the material in contact with water. both synthetic and natural. Therefore. both of which accelerate the rate of cracking of most pure hydrocarbons with respect to the thermal rates observed over quartz chips. pressure.v. This behavior places these solids in t h e class of baseexchange agents.200 223 339 358 26 0 Hydrogen 0 17 0 12 . For further verification of the R-K theory. CALCULATED THERMAL AND CATALYTIC CRACKING OF CETANE (Temperature. which cannot dehydrogenate to aromatics without prior ring isomerization. this demonstrates that the double bond has no large effect on either the mechanism or rate of cracking. n-propyl and isopropyl benzenes give chiefly toluene and styrene.recalculated from 8) a t 500' C..

41.. Accordingly. a t a comparable extent of cracking.INDUSTRIAL AND ENGINEERING CHEMISTRY 2576 OF EXTENTS OF CRACKING ovan PVRE TABLE 11. and this radical cracks at the beta position.. L.8 27.2 n-Octenes 0.v./hr.7 0.? Cl4 5 9 24 18 13 10 11 9 k ClS Total hydrocarbon Hydrogen Olefin content of fractions. the relative activity of pure silica gel was very low. Table I11 shows a sixfold increase. To c. the cracking of cetane over activated carbon may' be explained as follows: A free radical is formed a t the catalyst surface by the removal of a hydrogen atom anywhere in the carbon chain. T o solve this dilemma. this difference can be assigned principally to the smaller production of CI. The results are shown in Table I1 together with data of Tainele (3'1) for t h e cracking of three other pure hydrocarbons. which suggests that free radical formation may be assisted a t a suitable solid surface. t o yield a normal alpha olefin and a primary free radical. T h e saturation .3 1. Pure silica gel has little catalytic cracking activity. as represented by present commercial production of synthetic silica-alumina catalysts in this country. % 42-99' C. atmospheric) Flow R a t e Amt.6 0 5 0 06" Liquid hourly spare velocity Process period. 4pproxi. The cracked products from C1 to CIS are seen to be rather evenly distributed over the entire range. T h e great acceleration of cracking observed with cetane may be ascribed t o the characteristics of the high surface area of the activated carbon. t h e authors calculated the product distribution shown in Table I. % 20. Cetane cracked from one to ten times as fast over activated carbon as over UOP-B catalyst. the authors have proposed that t h e cracking may start via free radicals and therefore should show the effect of different ty-pes of carbon-hydrogen bonds on the rate of cracking as postulated by the R-K theory. T o test t h e cracking properties of pure silica gel containing less than 0. mt. Moles/ Pure Hydrocarbon O C. It is concluded t h a t cetane cracks over pure silica gel by the same mechanism as over quarts chips-namely. which later enables hydrogen atoms t o combine with radicals from the first cracking step and thereby prevents their further cracking to small fragments. T h e high normal alpha olefin content and the lack of skeletal isomerization of olefins correspond to the thermal or free radical (R-K) mode of cracking. Cp. 60 270 Moles product/100 moles cracked 35 53 C1 104 130 C? 57 60 CS 23 30 C4 Cracking Surface . The flow rate for silica gel.. However. . %.6 0. 99-125" C. Over half of the normal olefins examined (C8. occupied by quartz chips. and the product contained more paraffins than olefins throughout the entire range.2 Decalin 0. this latter material catalyzed the cracking of cetane by increasing t h e rate several times relative t o the rate over quartz chips... Indeed. Temp. Silica Gel Quartz UOP-Rb Cetane 500 0. depending on the extent of cracking' this is equivalent t o a t least fifty times the thermal rate.3 40 450 4. On the basis of these simple assumptions. A slightly lower value for tertiary hydrogen is derived from the hexane tests but is not needed for the cetane calculation.s. a C TABLE 111.h. This was tested with the five hexane isomers. From these observations the authors have concluded that a carbonium ion mechanism could not explain the results. as with other catalysts. Aromatic content of fractions. PURE SILICAGEL.6 80 550 4. but the addition of very small amounts of alumina. The increased rate is attributed to the high surface area of the silica gel. wt. wherein encouraging agreement with t h e experimental results is found. and UOP-B catalyst. Cf. Tho hot free space was found to be roughly 45% of this volume. min. 155 moles less hydrocarbon were obtained per 100 moles cetane cracked. the authors have obtained reasonably good agreement with experimental data by using the R-K values for the relative reactivities of primary and secondary hydrogen atoms. Very little chain-branching was noted. and CIZ)were alpha isomers. quartz chips. The lower amounts of C1 and CZ over pure Vol. The addition of more alumina (about 10 t o 15%) makes a highly active and stable cracking catalyst. which is less by 187 moles. Virtually t h e same product distribution is obtained in both cases (Table 111).2 0. 1 3 0. but the relatively high saturation of the product (over 60'%) throughout the whole range and the lack of preferential formation of CI. may change rapidly with time. GS 42-74O C.7 20. COXPARISON SILICAGEL. A N D UOP-B C A T A L Y ~ T (Process period.. is based on t h e total catalyst volume. of 1600 square meters per gram specific surface.\VU (Temperature. The product distribution is shown in Table I in comparison with t h a t obtained thermally over quartz chips.08 78 nrc 90 .a l. as reported later in the text. Therefore.9 oa.2C 27. 11 silica gel represent a difference of less than 5$Z0 of the cetane cracked. 500' C.inclusive. Cracking over activated carbon may thus be characterized as a radjcal mechanism at an active surface. nrhich acts (a)t o remove hydrogen from the hydrocarbon to generate reactive free radicalq. such as the silica-alumina type. K t . 45 Cumene 500 ' 3. pressure. QUARTZCHIPS. * Liquid Estimated from d a t a a t other flow rates. 31). even a few hundredths of one per cent. all compared over pure silica gel.. also according t o R-K theory.8 . and the other the ratio of exten's of cracking a t equal flow rates. 1 h o w .01% by weight of alumina and with a specific surface of 531 square meters per gram.07 The flow rate for t h e thermal run is based on t h e total volume a t 500' * bo C. No. Cracked. I n comparison with thermal cracking. and CBdo not. little more than 2 moles of product were obtained per mole of cetane cracked over activated carbon in this experimenb. 5' C .1 80 hourly space velocity. atmospheric) Pnre Qnartz Silica Gel Chips C-930 C-590 Run Conversion. product distribution is of paramount interest for ascertaining the mode of cracking. the values cited here are those obtained for process periods of 15 minutes t o 1hour. This primary radical is rap dly saturated or quenched by the addition of a hydrogen atom a t the surface of the catalyst to form the corresponding normal paraffin which cracks no further unless it has high molecular weight (see discussion of n-CdT64). the authors used cetane. ACTIVATEDCARBOX. preqsure. all of which was a t 500' i. 19 C6 18 14 15 C8 c7 C8 10 CP Cro 7 10 c 1 1 7 C1e C. Cp.5 1. has given the authors results with cetane remarkably different both in cracking rate and product distribution from those observed thermally and over silica-alumina type catalysts. as in the R-K theory. Steam-activated carbon from coconut charcoal. CRACKING O F CETANE OVER QUARTZ CHIPS PURE SILICA GEL . The activity of a cracking catalyst. via free radicals according t o the R-K theory. Iso/normal utylenes ratio b 70 92 95 97 0. will raise the activity of pure silica gel t o a high value (7.9 81.2c 27. and CB. 196-217'C. I n comparison with UOP-B catalyst. mt.natelp. and conversely ( b ) to return hydrogen t o the radical derived from the cracking reaction t o convert it t o a normal paraffin.

the same bond division as in thermal Bpace velocity. and the production of methane and CS aromatics is found thermally (6) and over activated carbon. Normal p a r f f i s . These observations support the view t h a t cracking over as propylene is characteristic of acid type cracking. and 13. although was teated with cetane and cumene. i t seems quite believable a Assigned value of unity.) Cumene gave Cumene was cracked about 10% at 500" C. 1 hour.) t h a t this weakly acidic pure alumina displays 3-Methyl2-Methyl2. Obsvd. cracking over activated carbon. process period.54 0. a value of 11. 2-methylpentane fell out of line. Fairly even distribution of CI t o Cia C-708 Cetane At 500" C. intermediate t o t h a t products.a-DimethylCracked a mixed type of cracking. Obsvd.1 carbon radicals from the first cracking step are resaturated t o paraffins atoms under the conditions just given. than to the value for thermal cracking. respectively (19). which represent of total aliphatic products above the theoretical 50% may be many different carbon-carbon groupings within small paraffin correlated with the observed activity of this catalyst for hydrogen molecules. cetene. flow rate. both with reCARBON spect t o rate and product distribution. Another test of the proposed mechanism is the prediction of cracked products from the isomeric hexanes. The butylenes and c 4 17 24 28 22 24 29 21 20 12 0 amylenes were found t o be skeletally isomerized C E 5 5 5 28 12 21 6 13 19 37 to equilibrium. These calcuthe case for a Borneo wax of approximate average formula nlations offer further confirmation of the suggested mode of CzsH54.4.November 1949 INDUSTRIAL AND ENGINEERING CHEMISTRY 2577 activated carbon proceeds by a free radical. but considerably demonstrates the high dehydrogenation activity of activated lower than for UOP-B. atmospheric. Recracking of most of the material above Cla is indiin such close proximity t o one another in the hexane isomers. an interTABLE VI. 7.00a 1. The amount of each comtion of aromatics.00b 3-Methylpentane Table V. as shown in 1. secondary. cetene cracks far faster than cetane over acidio catalysts. as depicted in Table VI. and the postulate for activated carbon that some amount of normal paraffins and olefins of 16 t o n . Cz.66 was confirmed t o within 4% by (Temperature. inclusive. the mixed with small amounts of silica./Lr. 1 . This considerable saturation of product from an oleover pure alumina as over UOP-B. a property which falls in line with the reactions noted and 11. 3. (The release of hydrogen by aromatic formaponent is intermediate t o t h a t obtained over UOP-B and actition may also enter into the excess saturation-60yo instead of vated carbon. above. Calcd. and tertiary hydrogen atoms. Calcd. atmospheric) different reactivities of the three types of hydrogen-carbon bonds Compound Chief Products Run (primary.00 1 27 2-Methyfpentane 1:02b 1.9 liquid hourly methane and ethylbenzene. compared with about 1% over quartz chips or silica cracking but accompanied by saturation of the vinyl side chain.66. These products should and not recracked.0 for primary. cumene. The authors found this t o be exactly sults is obtained here. CATALYTIC CRACKING OF HEXANE ISOMERS OVY~RACTIVATED mediate type of cracking is evident. Considering the good 1. Cetene cracked a t about the same rate as cetane. 500° C.01 yo by trast. that removal of a hydrogen atom is the initial step in catalytic Experiments used t o determine *he rate ratio of tertiary to primary hydrogen removal. pressure. this demonstrated the existence of TABLE IV. Obsvd. CARBON An important postulate in the R K theory is t h a t of the (Temperature. Porous alumina in various forms. gel. Applying the relative rates of removal of 1. over strongly acidic oxides and activated carbon. transfer. Obsvd. The chief products cracking properties of the commercial silica-alumina catalyst from cetane. either alone or in combination with other substances. these are given as 1. Calcd. larger than cetane should yield the beta fission rule. C. %-Hexane Neohexane pentane pentane butane . The 2 t o 1 mole ratio of hydrocarbon product to cracked PUREALUMINA.66. fair agreement with the experimental rethen extensively recrack. I n cona sample prepared by the authors containing below 0. with t h e comparative product finic feed stock may be correlated with the simultaneous producdistribution shown in Table VII. which yielded 363 moles of hydrocarbon product per 100 cracking over activated carbon. is an important type of catalyst possible value of this ratio. The authors therefore cracked the five hexane isomers over activated carbon.. the data for normal and neohexane. CATALYTIC CRACKING OF HEXANEISOMERS OVER ACTIVATED CARBON primary reactivity ratio of 3. For tertiary hydrogen.56 0. whatever the source of the hydrogen may be.1 moles/l..0. 8% over activated carbon. 1 hour.\%ole% Obsvd. The Decalin was dehydrogenated t o naphthalene and showed a 200gas composition indicated a much higher ratio of Cs to methane fold acceleration of this important thermal reaction. CS. atmospheric. products..3iDimethylbutana for the rate of cracking of 2.and C6. pressure. Since removal of the entire alkyl group carbon. tural isomers. and tertiary) in aliphatic hydrocarbons. 500n C. and Decalin are shown in Table to some degree (20). cated./hr. I n each theoretical 50y0'o--of the products from cetane cracking. rather than a carCRACKING OF PURE HYDROCARBONS OVER ACTIVATED bonium ion mechanism. then these Hydrogen a n d naphthalene C-722 Decalin reactivities should be reflected in the rates of cracking of struca CI t o C4.) two kinds of bonds.. with high liquid/gas" C-721 Cetene If the first (and rate-controlling) step in catalytic cracking over ratio Methane a n d ethylbenzene C-686 Cumene activated carbon is the removal of a hydrogen atom. somewhat less saturated (about 55% unsaturation of the aliThe authors found that cetane cracked a t about half the rate phatics). fairly good agreement was obtained NeohexnnR 0. IV.98 1. T o observe the behavior of a pure alumina.08 2. When To characterize further the catalysis over activated carbon. but does of the latter cases the value is closer t o that for activated carbon not alter the concept of radical saturation a t the carbon surface. With this value. CI 15 5 27 28 25 21 13 13 36 37 with perhaps some accelerated thermal cracking cz 28 24 33 22 29 29 22 20 3 0 cs 35 42 7 0 10 0 39 34 20 26 entering to a small degree.. with the exception of CI.3-dimethylbutane.1 The authors have concluded from the foregoing moles/l. (Temperature. especially in view of the possible moles wax cracked at 44y0 conversion (run C-715) in these experidisturbing effects of different carbon atom groupings arranged ments. and 1. pressure. 500" C. many aluminas acquire the authors tested four other hydrocarbons.0 Ratios of Cracking Rates was computed from data on 3-methylpentane with respect to Hexane Isomer Calculated Observed n-hexane. 7.3. secondary. Calcd. Calod. which contain only these flow rate.02 n-Hexane agreement in four out of five cases. process period. with the result t h a t the secondary/ TABLEV. which than for thermal or activated carbon cracking. such as feed stock which was approached by cetane represents the lowest bauxite or precipitated alumina. weight silica with specific surface 180 square meters per gram The cracked products were similar to those from cetane. and 84% over UOP-B.

ACIDIC OXIDE CATALYSTS. h e common features of these: acid-catalyzed hydrocarbon reactions are the attack on the hydrocarbon. v > I I X .5 108 Resultant. I n general. - 199 12 16 17 4 Total hydrocarbon Hydrogen 11 18 116 113 Quartz C-590 0. The carbonium ion can be regarded as a simplified concept of a polarized state. Olefins: A proton will combine with an olefin by taking the two Pi electrons from the ethylenic double bond to form an ordinary hydrogen-carbon bond comprising one pair of electrons (36). CARBONIUM IONR E A C T I O ~ ST. CRACKING OF CETANEOVER PCREh . 4 AND OTHER CATlLYsTs (Temperature. or catalyst surface regions. Of much importance is the concept t h a t an olefin will attract a carbonium ion in t h e same sense as i t will attract a proton. liquid sulfuric. synthetic silica-alumina gel with 10 t o 15% by weight alumina and specific surface area ranging from 250 t o 600 square meters per gram. pressure. These latter catalyst's have much greater activity for cracking olefins than for cracking paraffins. unsaturates add a proton t o form a carbonium ion. quenched free radical-type cracking for the latter. These relative energy values are in accord with the modes ol formation. porous solids impregnated with acidic substances. The observed data may be correlated with the relatively weak acidity arid high surface area of the pure porous alumina. as suggested by the high butenes to butanes mtio.ures a r ~017tained : + >C=C< + >c-c< IT-+ I H :111d + >c-<r< + I I3 I n the case of unsymmetrical olefins.Industrial cataly-tic cracking of petroleum fractions utilizes porous solid acidic oxide cat'alystsfor example. tert-butyl ion is favored over isobutyl ion by 21 kg. groups.her low hydrogen transfer activity." as will be shown. including solid heteropoly acids. rearrangement. A comparison n-ith thermal (free radical-type) cracking \-.aiice and example t o these concept.-as made earlier in the paper. will be discussed next..7 moles cracked 29 44 58 53 22 11 15 11 12 11 A 3 a 50 32 7 5 5 4 3 2 1 1 13 26 28 26 28 16 24 13 20 16 10 14 7 4 4 53 130 60 23 9 24 16 13 10 11 9 7 8 5 206 . and hydrofluoric acids.5 1.her contributing factor t o high hydrogen production might be the stabilization of some of the free radicals from the first.C= C "ICHa HzC=C(CHa)z PI 152 178. No.ransferred t o and from. I n proper balance. sec-propyl ion is favored over n-propyl ion by 7 kg. the production of a carboniuni ion..470 zirconia. ways.05 31. 70 61. Furthermore. as well as with t h e manner of their addition l o nucleophilic moleculc~ssuch as olefins and aromatics.5 367 378 Does not include coke.: Olefin HIC=CH2 H. The large amount of hydrogen produced in cetane cracking can be partially attributed t o the rat. 0 68. and acidic mixtures of refractory oxides.C=CEI--CII*-CH1 H Hac-CII--CH~-CII. The formation of a carbonium ion from a hydroca. and i t has been proposed here t h a t cracking over the nonacidic cat'alysta. UOP Type R.INDUSTRIAL AND E N G I N E E R I N G CHEMISTRY 2578 TABLE VII. Somo of these rules are reviewed here for the sake of exposition of the concepts t o be applied t o catalytic cracking. 500" C.-cal. and activated carbon can be explained as t h e simple acceleration of thermal free radical-type cracking for t h e former and as an accelerated but modified. These relations easily account for the important catalytic cracking secondary reaction of' olefin double bond shift studied by t h e present authors ( 3 4 ) .. Then the weak acidic character of the pure alumina Tvould come into play and encoursge the cracking of the resultant large olefins according t o the carbonium ion mechanism t o be proposed for acidic oxide catalysts.hcr acid-catalyzed hydrocarbon reactions. craclring step by the removal of a second hydrogen atom to form an olefin and a n adsorbed hydrogen atom a t the surface of t h e catalyst. x i t h PIand P1 in kg. T o illustrate: + IT.he proton affinities (Pi) of the first rind swond carbon atoms as follows. and saturates lose a hydride ion t o form a carbonium ion (36). closely allied t o those hydrocarbon reactions which always require the presence of an acidic catalyst but which can occur a t lower temperatures. The authors believe t h a t protons ( H + j . For a symmetrical olefin. such as t h e present commercial cracking catalysts..nd ionization potentials.). Cracking over porous solid acidic catalysts appears to comprise a process of a very different kind. hydrideions (H-j.3y0alumina. These rules serve to emphasize the close relation of catalytic cracking t o many ot. --+ +H&-CH=CII-CIIa + H' in accordance with the lesser proton affinity of middle carbon atoms in most olefins. phosphoric. and carbonium ions ( R + )in the catalytic systems under discussion are always associated with.0 3. Anot. Most of our experiments have been made with a synthetic gel catalyst of virtually the same cracking characteristics-namely. t h e simplest and best-known set of reactions. and are t. wt. solid aluminum chloride with various promoters and supports. the other carbon atom will now carry a positive charge and may be designated the "carbonium ion carbon atom.9 6 8 . acidtreated clays.34. the proton Trill generally add preferentially to one of the two ethylenic carbon atoms.. and which had specific surface about 330 square meters per gram. molecules. involving the addition of a proton t o a n olefin. liquid organic complexes with aluminum Vol. in contrast t o the addition of a hydrogen atom to form a paraffin. pure silica gel. These substances all regisler acidity intrinsically or in contact with water and can be viewed a s the source of t h e protons required to convert hydrocarbons into reactive carbonium ions.rbon may occur in several different.4a Conversion. T o give subst. and dissociation of carbonium ions. 247 . They give t. atmospheric) Catalyst or surface Alumina UOP-B Carbon C-587 C-710 C-931 Run Liquid hourly space velocity 0. There- . coupled with considerable dehydrogenation activit. and 4. complementary electronegative or electropositive atoms. some carbonium ion or acid type activity. such a mechanism can account for a product distribut'ion for cetane over alumina intermediate to those observed over activated carbon and UOP-B catalysts. these values give quantitative expression to Markownikoff's rule. this has recently been given quantitative expression by Evans and I'olnnyi ( 6 ) .2% silica. 11 chloride. but a concept which usefully predicts reactions according to a definite set of rules. borofluohydrjc.-cal. Ethvl ser-Propyl teit-Butyl Ions Ethyl n-Propyl iso-Butyl Thus.5 189 Pz 152 168. Acidic catalysts exist in many forms.-cal. from bond energies a. as in t h e case of activated carbon.y t o form aromatics (as observed) and t o release molecular hydrogen. aqueous solutions of the foregoing. and the behavior of carbonium ions according t o specific rules (36). two equivalent struct. The behavior of over sixty pure hydrocarbons in t h e presence of this catalyst has beon reported ( 9. 41. which analyzed 86. This bond will be made with one of the h o carbon atoms sharing the original double bond.

and mater @I). even 0. respectively. to woctme. In conclusion. as first proposed by Whitmore (37). may dissociate to a smaller olefin and a carbonium ion. the small carbonium ions produced continue the reaction chainwise via the hydride ion exchange mechanism proposed by Bartlett (1) for the alkylation of olefins with paraffins. without specific calculation. Excellent consistency of product distribution by carbon number is seen to hold. There are no Pi. I S H +Hzc=LCH. H~c-cH-cH~-~-cH.or CHa. oxygen. which has been reported to occur in the absence of olefins or other promoters using HBr 3. a mode of initial formation of carbonium ions from saturates is required To avoid the step of removing a hydride ion therefrom directly by the catalyst to give a carbonium ion.+ in which a hydride ion (H. and hydrogen transfer are greatly influenced by experimental conditions. and naphthenes.or H:) is transferred from isopentane to the tertbutyl ion. the initial structure of a polymer ion can be directly p r e dicted. Other evidence (’3. Secondary reactions of olefins (34) play an important part in determining the composition of the final products of catalytic cracking. the high reactivity of olefins in catalytic cracking and other acid-catalyzed systems may be ascribed t o the high attraction of the ethylenic double bond for a proton. including the effects of hydrogen. Therefore. either directly or after rearrangement. Since the purpose of this work is to study the primary cracking reactions. There are many additional data bearing on this quastion.4) indicates need of a promoting agent. which are best explained as movement of a proton or methyl carbonium ion. electrons available for direct proton attack as in olefins. yielding tert-amyl ion and isobutane. It is the key step in the important secondary reaction of olefin skeletal isomerization ($4). These reactions are shown as follows: H H H. page 825. After cracking. The latter can then dissociate to a proton and an olefin. The same problem of the initiatory mechanism arises in the carbonium ion reaction of butane isomerization. as are those in aromatics (17). with only 5% deviation from the average total 361 moles of hydrocarbon product per 100 moles cetane cracked. thereby the effects of these secondary reactions are largely removed from view. 99) which will determine the structure of the final product. olefins. the results of cracking cetane will be discussed in detail. Using the principles set forth. isobutene dimer ion will be: C C-Cf I . 38. This provides a pattern more consistent with the energetics of the system than does the H . Saturates (Paraffins and Naphthenes): The catalytic cracking of petroleum saturates-namely.INDUSTRIAL AND ENGINEERING CHEMISTRY November 1949 fore. 3- c c c-c-c-c-c I I C c=c-c I --f ei d tert-Butyl Ion Isobutene “Iso-Octyl” Carbonium Ion with the Carbonium ion carbon atom in the beta position to the added positive group. AIBrs catalyst ($1. For example. I as in Eauation 1 H~C---~~--CH~ (2) I Here the sec-butyl ion becomes the more stable tertbutyl ion by skeletal isomerization via movement of a methyl carbonium ion. Aromatics: The catalytic cracking of aromatics differs greatly from that of paraffins. which results in the rapid formation of reactive carbonium ions. H+ H Primary Ion Olefin A NoC-+--CH8 --f + Proton (1) Secondary Ion in which n-propyl ion becomes sec-propyl ion via movement of a proton through ah intermediate resonance position (36).01% butenes suffice. an ole& nil1 accept a proton In a definite position. yielding a specific carbonium ion. Table IV). These data indicate that a uniform mechanism of primary cracking prevails in this system. Finally. which then become carbonium ions by simple proton addition. -+HaC-CH=CH$ i. nor are the hydrogen atoms rapidly exchanged for protons (or their isotopes) in dilute acids. This ion. it is logical to postulate the dow formation of a carbonium ion from cetane as the first step to establish a common point of departure for their subsequent reactions. Since cetane 2579 cracks in a manner similiar to cetene but much more slowly. but there are not yet adequate data to cover all cases. which lead to the conclusion that it is difficult to decide which of the several following possibilities initiates the attack of the acid catalyst upon butane: ( a ) direct attack of catalyst proton to remove hydride ion from paraffin. Thomas (8. These rearrangements are in general accord with the relative energies of the initial and rearranged ions as specified directly by.+--cH. Table VI11 presents a series of five new experiments the authors have made with cetane up to a twenty-five-fold increase of flow rate. These rearrangements will be seen later to have much influence upon the minimum size of the fragments produced in catalytic cracking. - -ic CHs H I + H~C-C-CH. for example. Reaction Mechanism for the Cracking of Cetane (or Any Kormal Paraffin): From the data in Table VI11 a mechanism based on the properties of carbonium ions has been devised to explain the cracking of cetane. paraffins and naphthenesposes a special problem. All these possibilities enter into the catalytic cracking of saturates. except that ( b ) may corraspond to olefinsderived from some thermal cracking and (e) becomes even more indefinite. ( d ) addition of catalyst proton to water to provide hydronium ion (H30+)which may attack paraffin as in ( a ) . Cracking qf Cetane over an Acidic Oxide Type Catalyst (UOP-B). other conditions were constant. among which reactions those of doublebond isomerization. as tert-CaHp+ + iso-C6HIZ--+ iso-CaHlo + tert-CaH1. and is the mechanism of depolymerization of olefins (by acid catalysts) for the special case of the cracked product being identical with the monomer. the same in many respects as that which Thomas (32) proposed. This reaction may be written. skeletal isomerization. Two of the most important rearrangements comprise a shift of hydrogen or a methyl group. This is the essence of the catalytic cracking of olefins. and that it should be possible to apply definite rules thereto with the aim of predicting product distr?oution. yielding molecular hydrogen (5). ( b ) addition of catalyst proton to traces of olefin to start paraffi-carbonium ion exchange. The steprvise process in a certain formalistic sense . and the percentage cracked varied from 11 to 68%. all products have been grouped according to carbon number. or by analogy with. It is discussed separately at the end of the text.2)proposed that saturates first undergo some thermal cracking to give olefins. Carbonium ions undergo several types of rearrangement (56. (e) formation of catalyst-promoter complex which provides a sufficiently activated proton to react as in (a). the Evans and Polanyi values. ( c ) dehydrogenation of p a r a f i by oxygen to yield olefin to react as in ( b ) . or double bond.shift proposed by Whitmore (36).

and then only frc one side to the other of the prospective ethylenic carbon atom the point of division. STAGE I f . The carbonium ion will split at a carbon-carbon bond in a beta position to the carbonium ion carbon atom. Any large olefins initially formed will tend to recrack because of their great reactivity over acidic oxide catalysts.4 Conversidn. eachCaor larger. The primary carbonium ion derived from cracking will in turn rearzange to a secondary carbonium ion a3 in stage I and crack beta to the carbonium ion carbon atom as before. a normal secondary CS carbonium ion. H Example: Cl& I + GHi+ +C6HlI-F-ClOHPI + C3Ha For simplicity. The extent of recracking of olefins wi! with the experimental conditions. The beta fission rule is not a purely arbitrary law. cracking to such small ions occurs to but a small extent. These govern the primary cracking reactions by the preferential formation of certain initial carbonium ions. at 11% conversion. 8‘7). of which 53 moles were isoparaffins. H Example: H J . with respect to product distribution is this: Secondary ions can give no olefins smaller than Cs. an alpha olefin is produced which rearranges. 500’ C.and data indicate that carbonium ions that cannot crack by this mechanism into two fragments. with the exception of hydrogen transfer. and paraffin and olefin isomers is thereby greatly altered from that of thermal cracking. the rearrangement of most primary to secondary ions. These become amall parafins by acquir hydride ion. a Cia was not determined in these tcsts.2 3 4 . Convincing evidence of this rearrangement is found in cetane cracking. There fore. STAGE11. include the isomerization of carbonium ions (both hydrogen shift and skeletal rearrangement) as an essential step. in accordance with the observed properties of carbonium ion systems.C ~ H I ~+HaC--C-GHls -r H HIC-C=CHZ --+ -i-H&-CSHii + This process will continue until a carbonium ion which cannot yield fragments of three or more carbon atoms is producedfor example. which need not be ascribed to thermal cracking. However./hr. ressure. all are considered equally. atmospheric. since a secondary carbonium ion carbon atom by definition must be at least in the 2 position with respect to the end of the chain. H-. I I shows parallelism to the R-X mode of thermal cracking. Thw. Continued crackin isomerization proceeds w described until all ions are reduc c 6 or smaller. secondary. and some secondary to tertiary ions. and the cracking of these ions into fragments not smaller than three carbon atoms each. the important rearrangement of Becondsry to tertiary carbonium ions has been omitted in this description. Example: STAGE111. No.. The cetane molecule first reacts with a proton or small carbonium ion at the surface of the catalyst to form cetyl carbonium ion by the loss of a hydride ion. some methane and CZ are formed. The product distribution d t h respect to carbon number. The two electrons from this bond will move to the original carbonium ion carbon atom and neutralize the single positive charge. since there are twenty-eight secondary and only six primary hydrogen atoms. w t . still leaving the carbonium ion Vol. Thus. 41. which corresponds to the large amounts of Cg and iso-C6 in the product.) The pri carbonium ion then isomerizes by proton shift to an equa tribution of all possible secondary ions. leaving a hydrogendeficient entity. the theory . Thus. I n some similar experiments one mole of CISproduct was obtained per 100 moles of cetane cracked. which then cracks at a carbon-carbon bond beta to the hydrogen-deficient carbon atom. paraffin to olefin ratio. the extensive skeletal isonierization of olefins. forming an olefin. Of course. this corresponds to their high electron impac appearance potentials (16) from their parent paraffins. Calculations v made on the following basis: 1. 11 carbon atom in at least the 2 position with respect to the end of the chain. which then becomes saturated by acquisition of hydrogen. as will be shown later. Beta fission ail1 then yield propylene as the smallest product olefin. Accordingly the following mechanism of cetane cracking is set forth: STAGEI. The example is the same as in stage I. Furthermore.ion of olefin double bonds. tertiary. catalyst UOP-B. and the saturation of olefins by hydrogen transfer. the significant is0 to normal ratio is then 53 to 16. producing an alpha ole& and a new hydrogen-deficient entity. To illustrate the applicability of these rules to cetane. Accordingly. 99 moles of total paraffins came from 100 moles cetane cracked (in nearly complete hydrogen balance). and CsHs. Since a tertiary carbonium ion is more stable than a secondary carbonium ion. The differences in energy of the isomeric forms of a given carbonium ion are determinative features of cracking over acid oatalysts. the smallest fragments in important yield from catalytic cracking are Ca and C. Since 30 moles were CHI. a primary carbonium ion. Secondary cetyl carbonium ions will immediately predominate. Finally.(Whenever altern bonds are available ior cracking. The significance of carbonium ion rearrangement. but to adequate activation of much less favored types of cracking. Beta fission in this case will yield isobutylene as the smallest product olefin. which gives large amounts of small isoparaffins. CzHe. and in a very characteristic and definable manner. a number of secondary ions will rearmnge to tertiary.INDUSTRIAL AND ENGINEERING CHEMISTRY 2580 TABLE VIII.0 53. hydrocarbons. any primary ions formed may rearrange to secondary ions before cracking. The final carbonium ion from stage 111reacts wit a new cetane molecule by hydride ion exchange to produce a sma paraffin and a new cetyl carbonium ion. applied to this generalized process are the definite.8 3.1. Their energies decrease and their stabilities increase in the order primary. simultaneously forming an ethylenic double bond. It is ar experimental fact that methyl and ethyl carbonium ions are harc to produce. hydrogen is first removed from the molecule. because most of the carbonium ion reactions dealt with here. but is description of that mode of molecular division which will yield neutral olefin and ti smaller carbonium ion without the rearrang ment of any carbon or hydrogen atoms within the ion during t cracking process. 85. half of these olefins are assur form carbonium ions which then crack according to thr outlined above. 1hoh7 Run C-614 C-679 C-578 C-613 C-587 Flow rate moles/l. The olefins formed in step 2 should react about j extent to be expected from the authors’ cracking tests wit’ olefin feeds. The secondary cetyl carbonium ion cracks at a bond to the carbonium ion carbon. This mode of behavior corresponds to I principle of least motion or the principle of least rearrangeme It has been shown in the analogous case of free radicals that SI a process should have a lower work of activation than any ot possible process (2. CATALYTIC CRACKING OF CETANE (Temperature. % (through Cir) 11. experimental and calculated product distributions by car number are shown in Table I and Figure 1. Cetane forms cetyl carbonium ion by random loss of dride ion from any secondary position.2 40.5 68. CI~--nH+33-z. 0 13 6 8. CnH2”. process pdiod. Only electrons are shifted. will crack but very little. 2. thereby propagating tE reaction chain. Therefore. These properties also govern many of the secondary reactions by the almost complete equilibrat. special properties of carbonium ions. and the latter are twice as slow to be removed. . The latter repeats the process until a small uncrackable group is left. and the other fragment becomes a primary carbonium ion. 3. viding that fragments Ca or larger are formed.0 S 17 87 103 53 35 17 9 7 3 3 2 1 1 343 12 5 12 97 102 64 60 8 8 3 3 2 2 2 4 16 112 116 43 38 7 8 7 4 3 1 1 1 12 11 113 116 18 115 113 29 32 7 18 60 9 5 4 SO 5 5 3 4 2 1 1 1 3 3 2 1 1 E 361 3% 367 Total hydrocarbon 12 9 12 14 Hydrogen .0 24.

as proposed by Bartlett (1. and this difference is believed t o be related to the preferential saturation of tertiary olefins in catalytic cracking (34). I n addition.29. and 13. and those calculated for activated carbon were 1. The experiments TABLEIX.32). IT (b) n . This is shown in run C-46.9) and has been left out of consideration. 32 31 21P:4S. Several secondary reactions of olefins. using the authors' data (9). the R K thermal values a t 500" C. Hexane Isomer 2 3-Dimethylbutane . Thus. An identical mechanism waa proposed by Thomas (Sf?). For comparison.0. The unique properties of the benzene ring with respect to protons are now reviewed in the light of well-known concepts. as exemplified by the saturation of olefins. and 20 for P. A similar calculation may be made for UOP-B catalyst a t 550" C. with good agreement of relative rates. the cracking of two octanes and two dodecanes is shown. as shown in Table IX. the determinative influence of the numbers and types of carbon-hydrogen bonds on the extent of cracking provides strong indication that the carbon-hydrogen bond is the critical point of attack in paraffins. Olefins: In accordance with the prior discussions of olefin and paraffi reactions.INDUSTRIAL AND ENGINEERING CHEMISTRY November 1949 ' I --. Naphthenes: The primary cracking reactions of naphthenes are expected to follow a pattern similar t o that of paraffins (IS. These experiments on the cracking of the five hexane isomers over activated carbon provided data for the calculation of the relative reactivities of primary ( P ) . (CHa)&=CH2 or. according to the mechanism of para& cracking set forth earlier in the text. that of hydrogen transfer. add up to the extent of cracking of a given hexane isomer. so t h a t only the ratios a / b are ekpected to agree.O o t a n ~ . which contribute to the ultimate product distribution in catalytic cracking. were 1. and T = 12. respectively. Decalin and 2.2 1.2-Dimethylbutitne Number and Type of C-H Bonds 12P 2T OP 8s + + 12P + 2s % Cracked 32 14 10 The relative values for the three types of C-H bonds are then close to 1. CATALYTIC CRACKING OF HYDROCARBONS AT 550' C.0 1. page 1536). since the six surplus (Pi) electrons are resonating among all the carbon-to-carbon bonds. As in the case of activated carbon.---. Thus. Aromatics: Alkyl-substituted aromatic hydrocarbons are highly reactive in catalytic cracking systems when the alkyl groups are Ca or larger. and tertiary ( T ) hydrogen.0. good agreement is obtained. This reaction is another example of hydride ion exchange. when multiplied by the number of C-H bonds of corresponding type. Wt. 2. Secondly. 3.-Hexane 2.1 1. 12s ratio a / b 1.4. n6 simple ethylenic double bond type of carbonium ion can be formed without altering the resonance energy of the benzene ring.3. Therefore.-_---- lo CARBON No. The very rapid addition reactions of proton to olefin (or of a small carbonium ion to an olefin to give a larger carbonium ion) account for the high response of olefins to acid catalysts.66. % of Numbers and Total Products Types of C-H Hydrocarbon Experimental Calculateda Bond Present (a) 2-Methylpentans 25 23 9 P 4 5 1T (b) 3-Methylpentane. However. The effect of molecular weight on extent of cracking is not simple (9. EOF PRODUCT Figure 1. 42 19 0 P .7-dimethyloctane (CIO hydrocarbons with two tertiary carbon atoms) showed similar conversions (runs C-641 and 642 in Table X). the characteristics of both the aromatic ring and the alkyl side chain are responsible for the ease of cracking of such compounds. but the values are different. proceeds by two steps. Table XI. 1T ratio a / b 1. will be shown. differing mainly in degree of saturation and extent of recracking of product olefins (11). 10. Of particular significance is the high value for tertiary hydrogen for cracking with an acidic oxide catalyst. Experimental.62. although the aromatic nucleus remains essentially intact. have already been discussed. the benzene ring has much affinity for protons in the sense of attracting them and exchanging the hydrogen (or deuterium) originally present . the addition of a proton to olefin to form a carbonium ion. The Carbonium ion is the common intermediate in both paraffin and olefin cracking. leading to the coefficients P = 0. the cracked products should in general be similar for paraffins and olefins of similar skeletal structure. Therefore. and T a t 550" C. These results indicate that the naphthene ring structure by itself may be of secondary importance in determining the rate of cracking over this acidic oxide catalyst. Tertiary carbonium ions are formed more readily (6) than secondary ions. and 11. OVER UOP-BCATALYST Conversion.3 (a) n-Dodecane 35 30 6P 2 0 s (b) Isododecane.0 ( a ) Isooctane 49 24 16P. 25 23 9P: 4s: 1T ratio a/b 1. First. S = 1.66. Naphthenes have been thought to be more reactive than paraffinsof a similar molecular weight ( I S ) . . but there are no ethylenic double bonds.3% of charge. These data lead to the conclusion that the relative rates of removal of hydride ions fall in the same order as those for the removal of hydrogen atoms. certain naphthenes and parafKns with the same number of carbon atoms and about the same number and types of carbon-hydrogen groupings more recently have been found by the authors to crack at similar rates (9).0 a Feed space rates were not the same for the digerent groups of isomers and other factors enter into the differences between the ex erimental and calculated absolute conversions of Cs and CIZ such as the e&ct of molecular weight. 2581 of Hansford (14) which show easier exchange of tertiary hydrogen (compared with secondary or primary) with deuterium incorporated in a silica-alumina cracking catalyst are in agreement with this view. and the transfer of hydride ion from a neutral donor molecule to give a saturate and a new carbonium ion derived from the donor. 2S. secondary (S).0. there is much unsaturation in the benzene ring. (CH3)sC+ + H + + (CHa)aC* + (CH&C=CH1 --+ (CH&CH + C&+ The donor may then lose a proton to become a 185s saturated molecule. S. Applying these numbers to the cracking of the two other hexane isomers. 24% conversion over UOP-B catalyst Cracking of the Five Hexane Isomers over UOP-B Catalyst. These coefficients. the formation of a carbonium ion is postulated to be the first step in their cracking. Cracking of Other Hydrocarbon Classes. I' l2 l3 l4 l5 Catalytic Cracking of Cetane at 500' C. One other important secondary reaction.

. for protons (or deuterons) in the vicinity. 69). .t -.'H where a n intermediate form is depicted to indicate the hypothetical transition state. . .. . and isopropylbenzenes. . at 500" C. . . . . . and 247 kg. followed by the dissociation of R + t o a n olefin and a proton. .. and i t is plain t h a t t h e rates of cracking of isomeric alkyl aromatics correspond t o t h e relative ease of formation of the several carbonium ions. . . by assuming t h a t a n alkyl carbonium ion plays the same part as a proton. . . ... .. . . . Thus H ii H H B H d ... . . . No. . This has been extensively reported (IS). isopropyl... . The authors believe that the same mechanism can be applied t o the alkylation of aromatics.. .. Ncld 0 + €1.i c. . These differences may be correlated with the relative extents of cracking (dealkylation) of methyl-. Thus. . . 11.. . . under the same ex- . . instead of cracking of a carbon-to-carbon bond within the side chain. . . . . 11 ati u . . 0. . and 8470. the energies of combination of methyl. . . .??R mm-ocy . . . 282.alyst.. . . The energy differences in this series are similar when a n alkyl group is substituted for hydrogen and may be assumed t o be correspondingly similar with respect t o a n aromatic nucleus.. . . 41. Vol.. .C 1 L R The distinctive characteristic of catalytic compared with thermal cracking of alkyl aromatics is the severance of the entire alkyl group from the ring.. . .INDUSTRIAL AND ENGINEERING CHEMISTRY 2582 3g 2 c o -1m09 B 6%" . . ..'y* .. . .o . and tertiary butyl positive ions with hydride ion (H-) are 319. demonstrated by Ingold and co-workers ( 1 7 ) with sulfuric acid a s cat. Suitable data are not available for computing the strength of attachment of a n alkyl carbonium ion t o an aromatic ring for comparison with the same covalent bond strength. 264. .. as follows: H H where R +is a n alkyl carbonium ion derived from the combination of an olefin and a proton. However. .N. ethyl-... which are 1. The cracking of aromatics over acidic catalysts is t h e exact reverse of this reaction.. . s ".ca:u?*'Ludi . . . . . respectively (26.. . . .. respectively.. . . . ethyl. .-cal..

3 0...8 36 2 61. Contained 86.e/g.6613.3 0.1 1..... Negative values si nify gain.C.7 75. AI less than O... .. The authors acknowledge appreciatively the earlier unpublished work (38) of Charles L.size 4-14.4 28.3753. From aluminum chloride by precipitation with ammonium hydroxide followed by washing. .Y November 1949 Hydrocarbon Catalyst Temperature.0 68. The work of F.3 78. . Phillips Petroleum Company.1 0.3-dimethy1-Pisopropylbenzene>pcymene > 1. N.983. C . % ' Moles product/100 moles cracked HZ CHI Cz H4 CzHa CUHS Ca He C4Ha dSO-CIH8 n-C& iso-C4Hio n-CIHio tert-CsHio sec-CsHlo i80-CsHit n-CsHiz Ce (74O)d c7 (990) C8 (125') Ce (152O) Cio (174') 2.1 1.3730.1 12.. SILICA(low alumina)..9 0. re- perimental conditions (13).. Z-METHYLPENTANE. 239 495 259 37.7 '2-686 C-1015 The CS.6-66.3 6. The work of P. and 4.7 0.2 88. UOP-B. upon an independent approach t o the problem in terms of carbonium ion theory and the intrinsic acidity of the catalysts employed. R . DATAON - THE CRACKING OF PUREHYDROCARBONS Cetane 7-CeteneWax -CarbonSilica Quartz" Alumina UOP-B -Carbon500 400 500 550 270 6 -090 . % of charge Gas below Ca Liquid boiling below feed Remainingliquid Coke on catalyst Loss Run Q TABLE XI.4 C-931 10.4 0.3% by weight. Bartlett ( I ) on the role of hydride ion in alkylation has supplied an essential step t o explain the cracking of saturates and the transfer of hydrogen t o olefins. Brewer. LacomblO.2 0. FEEDSTOCKS Feedstocks are arranged in order of carbon number.5 0.. Stock A. Rowe. Archibald. 33. . C ' C.2 7. .1 2... 0. 8 15 18 15 3 4 15 7.8 31. .9 3. . nv 1.4" C. Used in run C-822. Carbide and Carbon Chemicals Corporation.01%. Dried at 150" C.1 13 20 25 .8 17.2. Shell Oil Company Inc. Beeck.1 0. and D . ACTIVATEDCARBON.5 2 73 62 12 11 3 1 1 8 78 1 0 1 52 0 0 :} 6 0 0 1 0 0 0 100 29 24 20 19 20 15 17 14 11 12 7 378 11. Houston. chairman of the board of directors and former director of research. Thus.. C.0 53. The data and information supplied by the work of their colleagues. is..282. and Cr by spectrographic analysis...3 1 16 8 12.2 4. Calif.. dO : 0. W.. 2.3 0. a t only 400" C. TL-HEXANE. wt. their cracking rates decreased in the order: 1. l/a-inch pills. A2.3 -0. Loss on ignition a t 1000" C. Type B... (IS). Columbia Activated Carbon. Rice and A. Roberts.6 1:2b 2...8 3 0 10 19. Liquid. Stock A. . bromine No. are most appreciatively acknowledged. . respectively.0 40.. dO : 0. Calcined at 565" C..2 69. 0. E. Boiling range 59. 0.3759.. Ag. P. Spec& surface 531 m.3% alumina. J.5 12 12 5 7 5 76 21 0 26 39 25 12 25 17 16 6 50 8 8 3 3 2 2 2 14 4 9 7 85 27 1 28 40 32 15 14 10 13 6 38 7 8 7 4 9 12 10 12 11 9 9 81 34 1 20 31 44 17 16 26 11 16 13 33 17 53 77 53 47 5 11 6 68 19 0 29 41 22 11 23 14 11 5 35 17 9 7 3 3 2 . then of Universal Oil Products Company.0 62. This lot waa used for all runs except for those listed later.e/g.3-dimethy1-5-isopropylbenzene > cumene > p chlorocumene > trichlorocumene.0 26...03-0..7 90. and Cs fractions from cumene were cut a t 99O. bromine No. Kossiakoff on free radical cracking mechanisms has been applied with success t o the thermal cracking of relatively large paraffins and has proved t o be of much use in comparing different cracking systems. .2 55.' Cia ( 2 3 8 9 (255') Cia 273') ClS t2900) ci4 Total Material balance.... . which corresponds t o the order of decreasing electron density of the carbon atom bonded to the isopropyl group (89).6603.. Stevenson.7 15 3 3:9* 6.9 72.4 29. designated greater than 95% pure. for his interest and encouragement.. 125' and 150' C. D. 9. From hydrogenation of 2-methylpentenes. .9 37. ~ 23..7 -1. Sn.3 59.4 45.a/g. hourly space velocity Conversion wt. c UOP-B 60 .4 6. . Phillips Petroleum Company.. Whitmore on carbonium ion systems has provided basic concepts for the mechanism of reactions of hydrocarbons in the presence of acidic catalysts. 1 Upper cut points for Cn fractions from aliphatic feedstocks in epectively...2% silica..4 0. F e 0. . May. 355370 4.9 68.3 1. Ash content. C: Process period.0 24. Specific surface 1600 m..4 1 3 10 1 5 11 15 11 12 11 11.02%.. 375 1 . ..7 44.0" C.5 11. n? 1. -. 2. and tertiary butyibenzenes cracked 14.7 23.05 31. Ni. Carbon only. and traces of Cu.4 C-614 8 82 31 0 25 37 37 17 21 13 20 6 29 9 5 4 3 3 2 1 3 1 1 1 .. . Specific surface 180 m.5 49.5 20.. D.5 1.7 1 0 1.. .1 3..8 C-131 2.2 22. mesh. Further information can be obtained by changing the electron distribution in the benzene ring. Stock B.0 10. d i 0 0.0 0.. .1 1. Thomas. W. Boiling range wss 0. 0..0 10. 52. .. C.9 0. 385 379 249 263 373 13 2 2 16 1 2 3 6 0 0 24 16 13 10 11 9 7 8 5 .5 28.6 7.. Normal. Technical grade.9 0. 3.. 6 16 9 14 0 0 6 0 11 1 . as well as their helpful suggestions.8 0.CT...7 35. . Bittner. . W.6611. Used in run C-529..8 2.1 C-590 3. C.8 1.9 0. Bulk density 0.t%.. Tex. secondary. calcined a t 565' C.6 31. .4% zirconia.3 11.. . n v 1. UOP-B-2 used in run C-46. Grade S.. . ACKNOWLEDGMENT The pioneer work of F. and 84%..001-0..1%. 0.. proton attack a t the ring carbon atom which carries the vulnerable isopropyl group.UOP-B (R-51) used in runs C-139 and 140.9 3. M.7 57..5 1 33 20. R.I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTR.9 5.3 50. - - 24. Mo.. This is added evidence for the proposed cracking mechanism-namely.6 3..5 61.. Used in run (2-996.4 4.1 38.1 2583 9 8.OOl%.7 '2-46 C-721 C-715 . min..2 0.Tamele..8 89.2..9 20.2 C-579 C-578 C-613 C-587 '2-708 (2-710 C-930 36..9 31. 395 0.a/g.. P. SILICA-ZIRCONIA-ALUMINA.0 2. CATALYSTS ALUMINA (low silica). Made by Shell Development Compan Wilmington.7 199 29 24 20 42 16 0 17 26 3 7 Thermal run. Universal Oil Products Company. .. . M. Stock B. Ca.38.4 2. Used in run C-623. The relation of the ease of cracking t o the differences in energy of the carbonium ions is clearly apparent and provides support for the belief t h a t the reaction corresponds t o the carbonium ion mechanism. in an enlightening study by Roberts (88) of these laboratories on the cracking of cumenes substituted in particular manners.3. Three lots were used: 1. bromine No. Specific surface 346 m. Si 0. Mg. . The authors particularly thank A.. Gibson. 1 11 21 15 9 18 15 14 13 7 4 14 35 19 10 18 58 46 40 17 1 1 23 1 4 3 14 0 1 8 15 2 7 10 19 5 32 7 5 5 4 3 2 1 1 6 8 1 17 16 24 13 20 16 10 14 7 4 4 1 0 2 18 14 15 10 7 10 7 5 4 5 . Ca 0. H.0 6 7....010/0.0 13 21 7 20 17 16 0 0 10 0 13 1 15 25 31 29 27 19 1 1 14 1 12 8 1 42 7 23 10 16 17 10 12 11 10 7 73 7--CumeneUOP-B Carbon Alumina -500r 60 -1.

.ENG.O 1. John Wilev & Sons. Stock A. E. Eastman 1Codal< Company.). Trans. n9 1.ENG. Stock B. CHEM. ofice natl. 3.. F. 0. S. SOC. and Schmerling. H. n y 1.. Hipple. knp. 309 (1938). 209 (1924). Frost. and Stevenson. Am. 595 nso LITERATURE CITED (1) Bartlett. Soc. Y.26.. 3274 (1932). 5% and 95y0 distillation temperatures were 175. Phys.. ISD. 54.. N o . from cold acid polymerization of isobutene. 39. M. D. R. C. 1.. 1531 (1944). F. Rice.4886. 590 (1943). H..26.U.7822. SOC. . Ber. C. Whitmore. Chem. Y . A.5. dO : 0.M..8837. 668 (1948). Peski. Boiling range. 233--4.6492. Used in run C-46.7-DIMETHYLOCTANE." Baltimore.3690. CHEM. Boiling range 158-160" C. Henriques. J .. 5. TJsed in run '2-823..0. H... LEON 0. 1032 (1947). Raisin. I. chim.3. F. "The Aliphatic Free Radicals. ~ TEMPERATURE RANGE FROM 35" TO 77" C.3755. Brunauer. 1936. NEOHEXANE.. J . B. R. 67. J. ny 1. unpublished work. 6 . F.0" C. Kestern Waxed Paper Company.roleum Mij. T h e vapor pressure of maleic anhydride has been measured in the temperature range from 35" to 77" C. Pauling.7y0 cumene by infrared analysis). From isomerization of methylpentanes with AlCla catalyst. J .ENQ.. . d i o 0. K. and Teller. bromine No. L..8579.. H.. Faraday Soc. K. Phgs. bromine KO. 9/10... Chem. From alkylation of benzene with propylene. C.5. Good.. Emmett. . Stock C. 593 (1949). H. Emeryville.7742. H. New York 27. Inc. Sundgren. S. Used in runs '2-530 and 553.. p. d:" 0. New York. Phillips Petroleum Company. H. 0. 849 (1947).4908..8" C. 2. Whitmore. U.3925. 1 (1936).R. and Good.8' and 178. 94 (1934). C.. boiling range was 0. 1940. G.69.. F. Chem. 39.. F.. News. SOC. dzo 0... Ithaca.4. A. E.7-17.. H. S. BORNEO Wax. C. Several lots of similar properties were used.. J ..2" C. d i 0 0. F. melting point -9. combustibles liquides. 1564.. 0. Y .. O. Chem..05" C. (3) Bloch.4201.2. 1590. Used in run C-527. A . Am. D. F. (to Socony-Vacuum Oil C o .4089. A . E.. 37. G. I h i d . 60. bromine No. O... A . n2$ 1. Emeryville.. 1 Present address. d?" 0. and Altchidjian.4912. Inc. Ibid.. d:" 0. and Wackher. Oblad.. B. H . Greensfelder. Rice. F.. du Pont de Nemours & Company. Evans. Used in run C-686. 514 (1945). 3035 (1933). S. bromine no. A. Used in run C-131. CHEM. bromine No. Vapor pressure of Maleic Vol. S ... ESG. Trans. A . Reaearch Plant Khimgaz. Hydrogenated triisobutenes from Shell Oil Company. Range of properties: melting point _16.. Am. dqo 0. 2769 (1942). J. p.. B. 983. M .04. Good..64. H.3. dO : 0.01. Calif. and Voge.6542.ure of the Chemical Bond. 1944. 0.394.4" C. and Wilson. Eastman Kodak Company.4.. 2766. G. Voge. 0. W.. Delft. C . N. . C. Roberts.range . nZ. 199 (1939). G.4" C.CHEM. p. Soc. (U.. Holland. AM. de Bataafsche Pet.7813. ny 1..S.Eastman Kodak Company. L. 1023 (1934).. Shell Development Company. 489 (1938). IND. Ibid..and Greensfelder..3772. 1038. A . van (to Shell Development C o . Chem. Voge.S. A . ) .699. H.16. Emeryville. C .3-DIhlETHYLBUT. J. A.. 68. 1168. P. V.7248.8621...INDUSTRIAL AND ENGINEERING CHEMISTRY 2584 3-METHYLPENTANE. dqo 0. 68.. Farben. Ibid.. Rice. M.3978. Stock A. ISOOCTANE. A . p. 134. Phillips Petroleum Company. 822 (1946). and Plate.172.3732. y .. Whitmore.7025. a? 1. ng 1. IND. Patent 2. ( 2 ) Bawn. Am.. and co-workers. H. Whitmore. F. S. Z b i d . J . 1033 (1946) Wheland. d i 0 3. Ingold. and Stahly. 0. and Polanyi. H.. 1313-18 (1940). Linus. 2.. Kossiakoff. Calif.6" C. Soc. dO : 0. Voge. n'g 1.ENG.. Eastman Kodak Company. Used in run C-1015 (97. Boiling range 152153" C. Weiss and Down8 (6) determined this property a t higher teniperatures but they give only one value in the range of interest. E.4398.. Ibid. CUMENE.796 (1946).. Stock B. O. bromine No. Tamele. n y 1.68.. 847 (1934) .. d:" 0.6935. bromine No. Soc.. 95% from 150-152. Stock B. bromine No. J .. Dobryanskii. 71..65. 598 (1938). nag 1.2-0.4348. . Boiling point 217" C. 66.7474. and Katsman. ) . Stock A. Chem. K.. Greensfelder. ISODODECANE. bromine KO. Distilled from hydrogenated catalytically cracked gasoline from Standard Oil Company of New Jersey (Louisiana division).3. bromine h'o. ~-DODECANE. From alkylation of isobutane with ethylene. M . F. WINSTROM AND LAURENCE KULP' Allied Chemical and Dye Corporation. Chem. 1948. N . Chem. Kasanskii.9" C. 3. 4153 (1933). H. and SchneideI. S. and Teller. 1947. . "The Nat. N.... From lauryl alcohol from Eastman Kodak Company. Ibid.6619. J.Cornell University Press." pp.4409.. Marisic. CETANE. Used in run C-721. Shell Development Company. New York..7"C. O. and Greensfelder. Johns Hopkins Press. I (36) (37) (38) (39) RECEIYED August 2 . C.9.6603. Boiling.0 1.IND. Ann. CETENE. Boiling range 56. .. G. H.4216.3710.5-48. A new static method for the measurement of the vapor pressure of sublimable substances is described. E.7" C.228 (1938). 1643... unpublished work. p. Thomas.. 11 (1946). nY 1. Pines. B.. OCTANE. G. nSo 1. Voge. E. J.7486. 55. 0. G. Emeryville.. unpublished work. E. n2. n%?1. P. melting point 53. . Roiling range 124126.S.. .3' C. Chem.CHEM. d i 0 0. Kanep. Coliimbia University. Stock B. Hansford. Am.. and Rice. 153 (1946). V. C. Stock A. Chem.." 2nd ed... IND.98. Ann. S. L. URIKG the course of process development in expanding the production of maleic anhydride (Toxilic anhydride). E.3. 34.4KE. 55. Boiling range 48. Nature. 252... Chem.38. The only data available in the literature are those tabulated in Landolt-Bornstein (4) which refer t o unpublished data obtained from I. DECALIN. M.3. it became necessary t o know the vapor pressure of this substance a t temperatures near its melting point.. and Good. 41.4345-1..41. After silica gel treatment.7786.3. Soc. Inc. S. R. hf. 2. Condon. d ? O 0. 0. 2564 (1949). Am. V.35 (1930). 3. J.8629.. Dow Chemical Company. dZo 0. G. M. G. Pines. Ibid. J . B. and Rice. H.6638. 7. d i 0 0. A . C. bromine No. H. W.. H. Gault. M. Shell Oil Company. P. 915... n2$ 1. (10) 2. Shell Development Company. Melting point 4. bromine No. Soc. Am.4" C. Chem. n? 1. S. 0. bromine KO. pp. Ibid. K. and Gorin.38. 1938.4755.5-57. Used in runs C-821 and 998. molecular weight 368.7726-0.. Purified over silica gel. "The Theory of Resonance.T.4356. M.. Melting point 3. No. 14.Patent 2. bromine KO.