ASPHALT OXIDATION STUDIES A T ELEVATED TEMPERATURES

. J . H U G H E S , Research and Development Department,

American O i l Go., Whiting, Ind.

Asphalt exposed to the weather is affected by many variables that can cause it to lose plasticity. Although absorption of oxygen by asphalt is well known, the mechanism is not fully understood. Thin-film oven oxidation and air-blowing of mid-continent asphalts were used to study the role of oxygen and the effects of depth in the asphalt, time, and temperature on the reaction. Oxygen from the air is required for thinfilm hardening; it reacts fastest a t the surface and very slowly below 0.07 inch into the asphalt. Conversion of resins to asphaltenes and of asphaltenes to insoluble polymeric material causes loss of plasticity and failure by cracking. Air-blowing apparently leads to the same reaction as thin-film oven oxidation. As temperature is increased, failure time indicates three different rate-controlling steps in the oxidation process.

A by temperature changes, heat. air, light, and moisture.

SPHALTS

under the influence of the weather are affected

to crack upon cooling, defined as "failure time," was measured and treated kinetically to shed light on oxidation mechanism.
Experimental Four mid-continent asphalts were used : three blown asphalts having a common origin and softening points between 180' and 200' F.. and an unblown material of like source with a softening point of 90' F. For the oven tests, samples were prepared in rectangular 3 X 6 inch aluminum trays with rounded corners. The amount of asphalt needed to give the desired depth was weighed into the tray, which was then heated until the asphalt formed a smooth layer. For the experiment to determine the need for external oxygen, similar thin films were prepared in 4-ounce tins; half of the tins were left open to the air and the other half were flooded with nitrogen, covered, and sealed with a n adhesive tape. Both the trays and the tins were allowed to cool to room temperature before use. I n each oven test, all samples were placed a t the same time in the oven. maintained within 2' F. of the selected temperature between 200' and 450' F. The thermometer bulb was placed close to the asphalt surfaces. to assure that the indicated temperature was actually that of the asphalt. T o observe the effects of time, trays were withdrawn at intervals; either they were examined for visible cracks upon cooling and replaced in the oven if none appeared, or they were used for analysis. In each air-blowing test. 600 grams of the unblown asphalt was blo\vn with 700 ml. of air per minute in a stirred steel reactor. At intervals, samples were withdrawn for analysis. For the empirical analyses, vertical cross sections from the asphalt trays were taken up in benzene. Material insoluble in

These factors harden the asphalt in time and cause it to lose its plasticity. Oxygen of the air appears to be one of the most important factors in the deterioration of asphalt. Asphalts in the absence of light absorb oxygen when heated (6) and when blown with air a t high temperatures (5). A thorough study of the kinetics of asphalt blowing has clarified engineering aspects of the oxidation process but has yielded little information on the mechanism (2). Changes in asphalt composition and properties during blowing have been measured (3) and, based on the results of earlier workers. a mechanism has been proposed to explain the effects of antioxidants on the adsorption of oxygen by asphalts ( 7 ) . A general mechanism of hardening of polymers by oxidative polymerization has been advanced ( 4 ) and may be applicable to asphalts. To establish further the role of oxygen in asphalt hardening, oxidation reactions have been carried out with blown and unblown asphalts. Both were subjected to oven tests to determine the need for external oxygen, the effect on oxidation of depth in the asphalt, and the effects of time and temperature. The effect of time on oxidation was also investigated during air-blowing of the unblown asphalt. All these effects were measured in terms of changes in asphalt composition, determined by empirical analysis for oils, resins. asphaltenes. and materials insoluble in benzene. and by elemental analysis I n addition, the reaction time needed to cause each asphalt
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l & E C P R O D U C T RESEARCH A N D D E V E L O P M E N T

benzene was dried and weighed as such. The benzene solution was passed through a n alumina-packed chromatographic column, from which oils were eluted with hexane and resins were eluted with 97y0 ethyl ether plus 3% eth>l alcohol. Asphaltenes were determined by difference. T h e elemental analyses were carried out by conventional methods. All results lvere expressed in weight per cent.
Results and Discussion

The difference in reaction in a thin film of blown asphalt when oxygen is present or absent is shown in Figure 1. Lt'ith a film 0.025 inch thick a t 375' F. in air, composition changed markedly; in nitrogen, little change occurred. Combined oxygen that may have been retained in blowing during manufacture was apparently not enough to cause appreciable reaction. By the time evidence of insolubles formation in nitrogen appeared, the tapes sealing the tins had begun to fail. The depth in the asphalt to which the oxidation reaction penetrates is indicated in Figure 2. In this experiment: trays cam)-ing different amounts of a blown asphalt \\-ere heated for 48 hours a t 375' F. Because vertical cross sections were analyzed, the composition at each thickness is actually the average composition to the depth indicated. Apparently little reaction takes place a t depths beyond 0.07 inch. Diffusion of oxygen is apparently much slo\ver at 375' F. than reaction of asphalt Lvith oxygen. To ensure that a large portion of the asphalt Ivould react, an asphalt thickness of 0.025 inch was used in subsequent oven tests. Effects of Time. The effect of time on the thin-film oxidation of unblown asphalt a t 375 F. is shown in Figure 3. Oils apparently do not reacl., but decrease slightly by evaporation. The resins change to asphaltenes, which later change to insolubles. M'hen the insolubles comprise 10% or more of the asphalt, the sample cracks or fails when cooled. Failure time seems to coincide with the maximum rate of formation of insolubles. Air-bloiving oxidation of the unbloivn asphalt a t 385" F. gave the data points plotted in Figure 4. These data show the same decline in resins and increase in asphaltenes observed

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in thin-film oxidation. If the curves of Figure 3 are superimposed on these data at one tenth the time scale here indicated, the resultant dashed curves fit the data points fairly well. The similarity of pattern suggests that the same reactions are taking place a t a rate governed by the amount of asphalt surface presented to the air. Effects of Temperature. The effect of temperature on thinfilm oxidation of asphalts is most readily seen from the formation of insolubles in bloivn asphalt and the elemental analysis of them. The pattern of insolubles formation at four temperatures is shown in Figure 5. As expected, insolubles form faster at high temperatures. Hoivever, the similarity of the curves suggests that the same type of reaction is occurring at all temperatures studied. Moreover, oxidation a t the loiver temperatures seems to result in ultimate formation of larger amounts of insolubles. Results of elemental analyses of the insolubles formed at the four temperatures are given in Table I. In each case? oxidation had been carried to the point where the percentage of insoluble material was leveling off. The data show no sig-

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nificant variations or trends except a t the lowest temperature. Here, a notably higher oxygen content suggests the formation of peroxy linkages. Because the insolubles are also insoluble in all common solvents, polar and nonpolar, they are probably the result of cross linking of the resins and asphaltenes.
Conclusions

taken to be equivalent to the time of a constant amount of reaction in all samples. Then
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where k is the reaction rate constant. Substitution for k kom the Arrhenius equation gives
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=

The combined effects of time and temperature are revealed by relating failure time to temperature. Such a relationship can be derived from the Arrhenius equation if failure time is

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+ constant

where Ea is the Arrhenius activation energy, R is the gas constant, and T i s the absolute temperature.

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Figure 6.
292
I&EC

Variation of failure time with reciprocal temperature for blown asphalt

P R O D U C T RESEARCH AND DEVELOPMENT

Table I.

Hydroqen Oxygen Nitrogen Sulfur

Elemental Analysis of lnsolubles Formed at Four Temperatures Composition. 70 260' F. 325' F. 375' F. 400"F. Carbon 79 5 81 1 82 1 76 3 _.

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25
9

32
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8 1

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7 4

1.7 0.097 1.17 0.073 1.18

1.4 0,072 1 13

1.7 0 075 1.16

M o l e Ratio

Oxygen-carbon Hydrogen-carbon

These values suggest that, belolv 300' F., decomposition of peroxides may be rate-controlling ; between 300' and 375' F. and above 450' F.. diffusion of oxygen may be ratecontrolling. Between 375' and 450' F., a reaction with higher energy-perhaps dehydrogenation-complicates the picture.
literature Cited (1) Beitchman, B. D.! J . Res. .\'atl.

A plot of log (failure time) against reciprocal temperature is 5 0 ' F. \\.ere shobvn in Figure 6. Data for temperatures u p to 4 obtained directly from oven tests. Those for higher temperatures were obtained by air bloiving to the same softening point as the 450' F. material. At least three different slopes indicatc that at least three phenomena occur. each rate-controlling in a different temperature range. Activation energies for the four temperature ranges were determined from the slopes:

Bur. Std. 64C, 13-7 (1960). (2) Holmgren. J. D., thesis, University of Florida, 1954. (3) Kleinschmidt. L. R.: Snoke. H. R., J . RPS..\'atl. Bur. Std. 60, 169-72 (1958). (4) Mark, H. F.! Mesrobian, R. B.. A n n . Recs. Phys. Chem. 1, 329-34 (5) Pfeiffer, J. P., "Properties of Asphaltic Bitumen," pp. 111-3, Elsevier. Amsterdam, 1950. (6) Van Oort. IV. P.: Ind. Eng. Chem. 48, 1196 (1956).
RECEIVED for review February 7, 1962 ACCEPTED July 23, 1962
i i 95ni \-'-",'

Division of Petroleum Chemistry. 138th Meeting, ACS. S e i c Yolk. N. Y . , September 1960.

XYLENE SEPARATION BY DEPOLYALKYLATION

J .

T. K E L L Y , l J .

R .

KIMG,2 AND H. M. K N I G H T 3

Citirs Sercicr Rrsrarch and Der'r/oprnent Co., Lake CharlPs, Lo.

High purity p-xylene can b e obtained from a mixture with m-xylene b y selective tsrt-butylation of the metaisomer, followed b y simple distillation. When using BFa monohydrate as catalyst, the reaction i s highly szlective, resulting in very low conversion of p-xylene and thus affording a convenient method of separating these isomers. Using a mole ratio of tert-butyl groups to m-xylene of 1.3, 99% conversion of m-xylene was attained. An unreacted xylene fraction containing 97.5y0p-xylene can b e recovered from this mixture b y fractionation. For higher m-xylene conversion and p-xylene purity, removal of alkylate b y distillation at selected points during the course of the reaction i s required, presumably to offset the alkylation-dealkylation equilibrium.

HE SEPARATION of m- and p-xylene by fractional distillation T i s extremely difficult because of the small difference in boiling points. This separation is done commercially by 7 5 ) . sulfonation ( 7 4 , and clathrafractional crystallization ( tion (8). but none of these processes gives clean separation togethn Tvith high recovery of both isomers. An alternate method of accomplishing this separation is by selective tprtbutylation of rn-s)-lene, folloxved by a distillation. The reaction of p-s)-lene with tPrt-butylating agents is extremelv slo~v because of steric factors, but m-xylene reacts rapidly to form 1,3-dirnethyl-5-tert-butylbenzene. The m-xylene can then be recovered in high purity by cleavage of the tert-butyl group over an acidic cracking catalyst o r by transalkylation. Since this method allo\vs recovery of both isomers in high yield and
1 Present address. Marathon Oil Co.. Denver Research Center, Littleton, Colo. * Present address, Louisiana State University, Department of Chemistry, Baton Rouge, La. 3 Present address, University of Texas Medical School: Galveston, Tex.

purity, it is potentially more attractive than knoivn commercial processes. Selective tert-butylation of CS aromatics has been reported by several v.orkers in the past 10 years (7-d, 9-13) and \vas mentioned as early as 1929 by a Japanese author (7). High p-xylene purities were obtained in some cases but only at high ratios of tert-butylating agent to aromatic. Corson and coworkers ( 3 ) recovered p-xylene of 947, purity from a 50 to 50 mixture of m- and p-xylene using isobutylene at a molar ratio of isobutylene to rn-xylene of 2. \Vhen tert-butyl chloride was employed under the same conditions, 99Yc p-xylene resulted. Siniilarly, Schlatter ( 9 , 72) obtained p-xylene of 96.27, purity by selective alkylation of a mixture of C S aromatics containing 18.97, p-xylene using a 1.7 molar ratio of tmt-butyl chloride to alkylatable aromatic. Since most of the excess tert-butylating agent is converted to polymeric and other degradation products and cannot be recovered and recycled, commercial operation under these conditions is probably not economically attractive.
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