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TABLEIV-SELBCTED DATAFOR COMPARISONS OF RESULTS INCREASESIN ORGANIC MATTER INSOLUBLE INCREASES IN FIXED CARBON -Volatilization 1 6 3 O C.-Exfioswe-Volalilisafion 163’ C.-Exfiosure-Volatilization 163 C.-Ezfioswe-Loss ConsisLoss ConsisINCREASE INCREASE VALUE VALUE NO. Hrs. Per cent tency Mo. Per cent tency Hrs. Calc. Actual M o . Calc. Actual Hrs. Calc. Actual Mo. Calc. Actual 6320 ...... 5 27.19 6’ 0” 8 27.62 41 5 4 . 6 4 11.63 6 4 . 3 4 17.98 5 2.10 4.39 4 2.23 4 . 0 5 15 31.18 98 6 25.57 99 10 5 . 1 8 13.85 8 4 . 9 4 21.12 10 3 . 0 0 5 . 1 0 10 2 . 7 4 5 . 9 9 6 3 3 5 . . .... 5 25.69 4‘ 46” 6 24.96 35 5 3.07 8.95 6 2 . 9 5 25.73 5 1.67 3 . 7 3 6 1.61 4.71 10 28.31 242 10 26.60 13 10 3 . 5 0 10.74 10 3 . 2 2 31.27 10 1.91 4 . 3 0 10 1 . 7 6 5 . 8 0 13.29 22” 4 7.04 22” 5 1.14 0.99 6 1.05 6.75 6122.. , , , 5 5 0.64 0.35 6 0 . 5 2 1.57 10 0 . 9 9 1 . 3 3 10 0 . 8 3 2 . 9 8 1, 5 ” 9.79 6121 . . . . . . 5 10 9.57 50” 5 1.25 3.85 10 1.22 8.68 5 0 . 7 4 1.36 10 0 . 7 2 1 . 8 6 6336 . . . . . . 5 6.32 18: 6 6.20 48” 5 0.04 0.66 6 0.04 7.88 5 0.10 0.57 6 0 . 1 0 1.49 10 13.02 27 4 3.30 24“ 15 0 . 1 2 2.00 10 0 . 0 6 13.43 15 0 . 2 7 1 . 3 3 12 0 . 1 8 2 . 3 5 5857 15 15.36 117 4 6.09 83 5 1.30 6.54 8 0 . 8 5 28.69 5 0.73 2.02 10 0 . 5 8 4 . 5 9 6321 ...... 5 19.27 106 4 20.94 41 5 0.58 5.39 4 0.51 6.51 .......... 10 30.78 3 8 27.38 3 15 1 . 1 0 7.49 8 0 . 9 2 11.52 LOSS AND CONSISTENCY O F RESIDUES
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petroleums (Kos. 6320 and 6335), in which t h e resi- more pronounced t h a n those obtained in t h e routine dues from volatilization were too fluid for a penetra- laboratory test. tion test, while after losing approximately t h e same The above d a t a corroborate a n d amplify all amount on exposure they yielded residues having previous d a t a t o t h e effect t h a t bituminous materials penetrations of 41 a n d 35, respectively. Samples upon exposure undergo changes t h a t are due t o some6320 a n d 6122 also offer interesting comparisons, thing more t h a n mere loss of volatile matter. Such since t h e consistencies in two instances are identical. changes occur in samples when subjected t o t h e volaI n t h e case of t h e first material, however, i t required tilization test in a laboratory oven, although t h e changes a loss of 3 I . 81 per cent b y volatilization i n a n oven are greater when t h e exp0sure.k made under atmospheric t o produce a residue of t h e same consistency as t h a t influences. These changes differ in both character obtained through a loss of 2 5 . 5 7 per cent on exposure, a n d degree with different types of fluid bitumens, as while in t h e case of Xo. 61 2 1 i t required losses of 13. 29 would be expected from our knowledge of t h e varying a n d 7 . 0 4 per cent t o bring about t h e same result. chemical character of bituminous materials. Hubbard T o show t h e relation between t h e increase in actual and Reeve in reviewing their work on semi-solid overcalculated organic matter insoluble in samples bitumens indicated t h a t t h e increase in insoluble tested b y laboratory methods a n d exposure, samples organic matter might be due to oxidation, and t h a t for comparison were selected a t periods when t h e cal- t h e products might actually contain oxygen or be t h e culated increases based on t h e loss in weight were result of nucleus condensation brought about by t h e approximately equal. It is shown t h a t in practically reaction of oxygen with two or more hydrocarbons every instance t h e increase in organic matter as a re- originally present in t h e bitumens. The conclusions sult of exposure is several times greater t h a n t h a t pro- in t h a t case were based almost entirely on t h e results duced through heating in a laboratory oven. The of atmospheric exposure, while in t h e present d a t a Texas residual petroleum (No. 6336) shows t h e most t h e authors have included results obtained through noticeable differences b y t h e two methods where t h e t h e laboratory routine volatilization test. T h e fact calculated increase for 6 months’ exposure is identical t h a t t h e organic matter insoluble also increases mawith t h a t for 5 hours in t h e oven, whereas t h e actual terially in a closed oven where t h e changes of oxidaincrease b y t h e former method is 1 2 times t h e actual tion are reduced t o a minimum, would tend t o indiincrease obtained in t h e oven-heated sample. The cate t h a t other causes might be responsible for t h e t w o Trinidad products (Nos. 6335 a n d 5 8 j 7 ) also changes which occur. While oxygen plays its part show similar marked differences in t h e increases ob- in t h e changes which occur, t h e authors are led t o t h e conclusion t h a t polymerization a n d intermolecular tained by t h e two methods. It will be noted t h a t t h e oil-asphalt cut-back KO. reactions induced b y heat a n d possibly increased b y 6122 offers t h e only instance in which t h e actual in- t h e action of light are also very largely responsible for crease was less t h a n t h e calculated. This occurs in such changes, in addition t o those which are accounted t h e residue from t h e 5-hour volatilization and t h e sam- for b y simple evaporation. OFFICEOF PUBLICROADSAND RURALENGINEERING ple shows a similar peculiarity in t h e results of fixed WASHINGTON, D. C. carbon increases which were selected on a similar basis t o t h a t adopted for t h e other groups in Table THE OXIDATION OF MINERAL OILS BY AIR IV. T h e d a t a show t o some extent t h e same rela- I-THE EFFECT OF SULFUR ON THE OXIDATION OF tions between t h e results of oven a n d atmospheric HYDROCARBONS WITH PARTICULAR REFERENCE exposure, although t h e differences between t h e fixed TO ASPHALT carbon increases are not as marked as those €or orBy BENJAMIN T. BROOKSAND IRWIN w. HUMPHREY ganic matter insoluble. Received May 15, 1917 It has sometimes been contended t h a t t h e volatilIt has long been known t h a t on heating sulfur and ization test a t 163’ C. was too severe, a n d t h a t it paraffin, hydrogen sulfide is evo1ved.l Lidoff2 made subjected materials under test t o changes t h a t would hydrogen sulfide b y adding a petroleum “naphtha” t o not occur under ordinary conditions of exposure. hot sulfur a t 350’ t o 400’ C. a n d in 1892 Dubbs obT h e results above cited show t h a t such a n assumption tained a patent in t h e United States for a process of is not altogether well taken, a n d t h a t as a matter of 1 Galletly, Chem. N e w s , Z4 ( 1 8 i l ) , 162. 2 Chem. Zentr., 1882, 22. fact t h e effects of atmospheric exposure are much
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T H E JOURNAL OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
manufacturing asphalt by heating heavy oils or residuums with sulfur. According t o Richardson, asphalt made in this way differs markedly from natural asphalts a n d also from t h a t made merely b y blowing air through t h e hot residuums, t h e product of t h e Dubbs' process being cheesy in structure and lacking in ductility a n d hardness. Willstaetter a n d Sonnenfeld' have recently shown t h a t t h e oxidation of olefines by air takes place very rapidly a t ordinary temperatures in t h e presence of phosphorus, b u t t h a t elementary sulfur, under t h e same conditions, was without effect. T h e work here described indicates t h a t a t more elevated temperatures sulfur accelerates t h e oxidation of petroleum hydrocarbons by air. The ease with which many organic compounds containing sulfur, for example t h e mercaptans a n d sulfides, are oxidized b y air or oxygen is well known. We have noticed t h a t t h e petroleum oils of both t h e saturated t y p e such as natural gasoline, and 'bcracked" gasoline containing unsaturated hydrocarbons which contain sulfur compounds, deteriorate TABLE I-EFFECT OF SULFUR
O N OXIDATION OF PETROLEUM RESIDUUMS B Y AIR No. 9 Agitated with Natural Gas Instead of Air TREATPER PROPERTIES O F PRODUCT SOVRCE O F MENT CENT PeneSULFUR traRESIDUUMS Oil * Be. No. C. Hrs. Added Final tion(o) REMARKS Kansas 18.5 1 205 16 5 . 0 2.16 58 ...... lb 215 96 None . . 42.2 ...... 2 210 14 None . . Harder than No. 9 3 210 14 5 . 0 . . 83 Texas 14.0 4 210 14 None * Harder than No. 9 5 210 14 5 . 0 19.0 6 210 16 5 . 0 2 : i 8 23.0 Illinois 18.5 7 205 16 5.0 3 . 5 3 112 8 210 16 5.0 ,. 44.0 86 210 100 None . . 42.5 More fluid than No. 10 9 210 16 5 . 0 .. 10 210 16 None . . Mexicantb) 11 216 16 5 . 0 8.26 13 ( a ) No. 2 needle, 100 gram weight, 5 seconds a t 25' C. (b) 4 . l i per cent sulfur in original residuum. Too soft for measurement. ** Supplied with more air than h-0. 8
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by air oxidation a t ordinary temperatures much more rapidly t h a n portions of t h e same oils which were desulfurized by lead or copper oxides or metallic sodium. Whether t h e oxidation of t h e compounds of sulfur of unknown constitution occurring in petroleum can also effect simultaneously t h e oxidation of other substances through t h e initial formation of peroxides after t h e manner of Engler's theory is not known. However, t h e effect of sulfur as noted in our work indicates t h a t such may be t h e case, since heating petroleum residuums with small amounts of sulfur and agitating with natural gas instead of air has very little effect as compared with t h e product obtained by air-blowing t h e sulfur-oil mixture. I t is probable t h a t when petroleum oils are heated with sulfur, complex sulfur compounds are first formed a n d t h a t these compounds are more or less completely decomposed on continued heating, since in t h e case of t h e artificial asphalts described in this paper t h e final products contained from 2 t o 9 per cent sulfur. We have found t h a t cracked oils and unsaturated hydrocarbons, such as limonene a n d pinene, slowly combine with sulfur a t about 160' C. without t h e formation of hydrogen sulfide, forming heavy, viscous, yellow oils, markedly soluble in alcohol, a n d 1
Ber., 47 (1914), 2801.
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t h a t heating these sulfur compounds t o higher temperatures results in decomposition with evolution of hydrogen sulfide. These products were not further investigated. They are probably very similar t o t h e so-called thiozonide of linalool which Erdmannl prepared by t h e direct combination at 160' C. of sulfur a n d t h e unsaturated alcohol linalool. I n t h e case of saturated hydrocarbons, direct elimination of hydrogen probably occurs, as BruZ showed t h a t on heating sulfur and glycerine t h e compound CS.OH.CHOH.CHzOH is formed. The readiness with which sulfur and unsaturated hydrocarbons react explains the fact t h a t after heating paraffin or a saturated petroleum oil with one mol of sulfur t h e oil distilled from t h e mixture in vacuo contained no olefine groups; in other words, unsaturated oils cannot be made by eliminating hydrogen from t h e m by heating with s ~ l f u r . ~ I n t h e case of paraffin t h e possibility suggested itself t h a t perhaps paraffin would be converted, by heating with one mol of sulfur, t o a naphthene, b u t distillation of t h e resulting TABLE 11-EFFECT OF AIR-BLOWING TEXASRESIDUUM(12' B%.) WITH DIFFBRENTAMOUNTS OF SULFUR FOR 10 HOURS S o . 4 blown 7 hrs. Per cent Per cent PER CENT Flowing Pene- Soluble Fixed SULFUR T p p . Point tra- in86'BB. Carbon NO. Added Final C. O C. tion(a) Gasoline in Bitumen 1. . . . . . . . 4 1.95 210 73 61 72.5 ... 2 ........ 6 210 109 28 67.7 ... 3 8 2:42 210 148 l? 65.0 ... 4 . . . . . . . . 20 .. 210 192 59.8 ... ~
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4 210 i3 61 72.5 ... 4.3 ... 225 108 6 ........ 4 .. 10 62:1 ... 235 176 i........ 4 .. 8 ........ 8 .. 180 68 60 75.7 9 . . ...... 8 195 86 46 68.6 18:03 10. . . . . . . . 8 .. 210 148 17 65.0 20.21 11 ........ 8 .. 215 167 1.3 12 . . . . . . . . 8 .. 225 171 io 6i:o 2i:ii ( a ) No. 2 needle, 100 gram weight, 5 seconds at 25' C. XOTE-NOS. 8 to 12. No coke was formed for these products were over 99 per cent soluble in carbon bisulfide.
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reaction mixture in vacuo yielded paraffin of t h e same melting point as t h e original material. Although t h e tendency of organic sulfur compounds t o "polymerize" and form extremely complicated substances of high molecular weight, as in t h e case of t h e sulfur black dyes, is well known, t h e facts already cited indicate t h a t oxidation is necessary t o induce t h e polymerization t o asphalt. Engler and Zaloziecki concluded t h a t polymerization is the main factor in the formation of asphalt and very recently Staudinger4 has called attention t o the fact t h a t in t h e polymerization of certain unsaturated hydrocarbons a very small amount of air has a very marked effect. I n determining t h e effect of added sulfur two experiments were made a t one time, every condition, such as air, agitation, temperature and exposed surface, being made as nearly identical as possible. I n each 14nn., 363 (19081, 133. French Patent 455.124, Feb. 15, 1913. 3 We find that in order to employ this reaction as a cheap source of HsS and evolve 80 to 85 per cent of the sulfur as HzS a large excess of oil is required. Although much coke is deposited, nothing like the results 25S-25C 25HzS can be atexpressed by the equation CxHa tained. Two or more parts of oil to one of sulfur give excellent results and an oil should be selected boiling above 200' C. When heavy fuel oil is employed and normal prices are reckoned hydrogen sulfide can be made in this way for about one-fifth the cost by the iron sulfide and sulfuric acid method. 4 Chern.-Zlg.. 1918, 1188; 1913, 379. 2
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case two pounds of residuum were placed in a glass The presence of mannans in various woods has been flask and two or more such flasks heated in a large shown by several investigators. Tollensl and assosand bath, the temperature of the sand bath and t h e ciates found mannose in sulfite liquor, the raw material temperature of t h e residuum being noted a t frequent generally employed being Picea excelsa Lk. T h e intervals . presence of mannan in the wood of about a dozen T h a t asphalts of exceptional hardness and high conifers was shown by Bertrand,2 who also made melting point can be made by t h e combined action of several quantitative determinations. Kimoto3 found air and sulfur is shown by the fact t h a t on air-blowing 6 . 3 5 per cent mannan in Cryptomeria japonica Don. a sample of Mexican residuum, t o which 8 per cent of A study of several American species was made by sulfur had been added, for 3 1 hrs. a t 220-230' C., a S t ~ r e r ,but ~ only two quantitative determinations product was obtained which had a flowing point of were reported; the mannose hydrazone was identified 185' C. (366' F.) and a penetration of 7 mm. a t 25' C. microscopically. (100g. weight and No. 2 needle, I O seconds). Another Bertrand5 considers t h e source of the mannose product made by air-blowing a sample of the same from wood as a mannocellulose. This classification residuum, t o which 1 2 per cent of sulfur had been is not justified on account of t h e ease of hydrolysis added, a t 230-235' C. for 3 1 hrs. showed a flowing of the parent carbohydrate, t h e latter falling properly point of 200' C. (392' F.) and a penetration a t 25' C. into t h e class of hemicelluloses created by Schulze. of 5 mm. (100g. weight and No. 2 needle, I O seconds). The presence of mannan in woods is of technical I n practice, it is seldom desirable to produce products significance. According t o Schwalbe6 waste sulfite as hard as this, b u t t h e addition of much smaller liquors may be considered t o contain sufficient amounts, 3 t o 5 per cent of sulfur, had a marked effect fermentable sugar t o give 60 liters of ethyl alcohol per in producing hard asphalts in much less time t h a n is "tonne" ( 2 2 0 0 lbs.) of pulp, which is equivalent t o required by the usual air-blowing method. This is 108 lbs. of alcohol per t o n (zoo0 lbs.) of dry pulp. well indicated by Experiments Ib and 8b in Table I as On t h e basis of a yield of 45 per cent of pulp, about compared with t h e results obtained with t h e same 2.5 per cent of the dry wood is recovered as alcohol. residuums under t h e same conditions b u t with t h e addi- The results obtained by Krause' show t h a t mannose tion of 5 per cent sulfur. It will be noted t h a t t h e time constitutes about 6 0 per cent of the total fermentable required t o produce an asphalt of medium degree of sugars in sulfite liquor. hardness is reduced, by t h e addition of j per cent The various woods examined contain sufficient sulfur, t o about one-sixth of the time necesSary when mannan alone t o furnish 2 t o 4 per cent alcohol so no sulfur is added. It is t o be expected, therefore, t h a t t h a t considerable mannose is evidently destroyed during residuums naturally containing relatively large amounts t h e cooking process. It is plain, however, t h a t mannan of sulfur will give hard asphalts by air-blowing in t h e must be considered t h e chief source of t h e ethyl alcohol. least time. By t h e hydrolysis of white spruce Kressmans obtained 6 . 8 t o 8 . 3 per cent of absolute alcohol. This MELLONINSTITUTE OF INDUSTRIAL RESEARCH UNIVERSITY OF PITTSBURGH species contains 7.12 per cent mannan from which i t is theoretically possible t o obtain 3 . 5 per cent alcohol. It is difficult, however, from available d a t a THE CHEMISTRY OF WOOD t o determine how much alcohol is derived from the 111-MANNAN CONTENT OF THE GYMNOSPERMS mannose. Mannoseg is apparently as stable when By A. W. SCHORGER heated with acids as dextrose b u t it is probable t h a t Received April 14, 1917 considerable mannose is destroyed during t h e cooking A marked difference between t h e conifers (Gymnospermae) and hardwoods (Afigiospevmae) occurs not since all t h e mannan would be hydrolyzed a t t h e beonly in the structure but also in the chemical composi- ginning of the reaction. Yeasts t h a t ferment dextrose will usually ferment mannose equally well b u t tion of t h e wood. I n a previous communication' i t was pointed out t h a t water-soluble galactans oc- exceptions occur. curred in many of t h e conifers. The present paper has a special bearing on t h e relative amounts of mannan present in t h e various species. So far as is known, carbohydrates yielding mannose on hydrolysis have been found in only one hardwood. Fromherz2 obtained mannose from Populus tremula L. The lignocellulose purified b y treatment with acid a n d alkali was heated with water in a n autoclave at 150'. The aqueous solution, after boiling with sulfuric acid, was found t o contain mannose. T h e writer, employing hydrolysis a t atmospheric pressure, examined six species of hardwoods, among t h e m Populus tremuloides Michx., b u t in no case was mannose detected. 1 2
Schorger and Smith, THISJOURNAL, 8 (1916). 494. Z . physiol. Chem., 60 (1906), 237.
E XP ERI M E " F A L
The method of determining mannan was t h e following: The wood, cut into sawdust, was so ground as t o pass through a 40-mesh sieve. A portion was removed for determining moisture. Ten grams of t h e fine material with 150 cc. of hydrochloric acid, sp. gr. 1.025, were placed in a n Erlenmeyer flask connected with a reflux conde.nser and boiled for three a n d one-half hours. The contents were then filtered into a 500 cc. flask, and t h e sawdust washed back into t h e Erlenmeyer with about I O O cc. of disI 2 8
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Ber., 23 (1890), 2990; Z. angew. Chem.. 6 (1892), 155; Ann., 267 (1892), 349. Compt. rend., 129 (1899), 1027. 1 Chem. Ind., 29 (1901), 217. Bull. Coll. Agr. Tokio, 5 (1902), 254. 8 THISJOURNAL, 7 (1915), 920. Bussev Inst. Bull.. 3 (1902). 32. @ Fischer and Hirschberger. Bcr.. Comp;. rend., 129 (1899). 1025. 22 (1889). 365. Z . angev. Chcm., 23 (1910). 1540.
