888
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING CHEJMISTRY
are just as compatible a n d just as reliable as results f r o m longer periods. I n cases when a comparatively stable condition of t h e sample has been reached between t h e fifth a n d tenth d a y without exhaustion of the available oxygen, t h e 24-hour results are a b o u t 40 per cent of t h e whole.”. . . . . . “ I t seems t h a t we can hardly d o better t h a n t o a d o p t a dilution t h a t will leave a 3 0 per cent t o 60 per cent residual oxygen in j d a y s as t h e English do, for it is certain t h a t too high a concentration would interfere with t h e life of t h e oxidizing organisms.” Mr. Hoover would prefer t h e t e r m “dissolved oxygen consumed’’ t o “biochemical oxygen demand.” Prof. Phelps finds t h e work not very satisfactory a n d i t is his intention t o develop some method which will take us entirely away from oxygen determinations. Notwithstanding t h e shortcomings of t h e methpd, i t is of some advantage t o be able t o know even approximately t h e 24-hour a n d total oxygen consumption of t h e sewage. -4s long as we lack proven methods which will give us this information accurately, the introduction of t h e “hiodified English Incubation Test” as a provisional method a t t h e next annual meeting of the American Public Health Association ought t o serve some useful purpose. A method developed b y me for t h e determination of t h e oxygen demand consists in t h e addition of saltpeter, t h e oxygen of which is utilized during incubation just as t h e oxygen in diluting water is used. T h e method has been published in t h e M a y number of t h e Journa2 of Infectious Diseases. T h e method has since been simplified b y me a n d has given satisfaction in determining t h e strength of sewages in polluted waters. Various chemists are employing t h e method a t present a n d their criticism a n d results will help t o decide whether t h e method is of sufficient value t o supplant the one discussed a t length in this paper, or whether i t is t o serve ‘as a m a t t e r of choice. It is also t o be hoped t h a t Prof. Phelps will be successful in his endeavor t o originate a reliable method for t h e determination of t h e oxygen demand a n d t h e ratio of oxygen absorption. It is t h e intention t o present t h e provisional procedure as t h e “Modified English Incubation Test” for t h e determination of t h e biochemical oxygen demand in t h e following form: “A definite volume of sewage or effluent is mixed with aerated distilled water or t a p water, free from nitrites a n d nitrates, in such proportion t h a t between 30 a n d 60 per cent of t h e available oxygen is consumed a t the end of I O d a y s incubation a t 2 0 ’ C. Care should be t a k e n t o store t h e diluting water for some t i m e (one or t w o days) a t t h e constant temperature of 2 0 ” C., previous t o t h e preparation of t h e mixture. T h e sewage a n d even t h e bottles which are t o be incubated should be of the same temperature t o obtain satisfactory results. T h e sewage m a y be added directly into t h e bottles or else a larger quantity of t h e mixture may be prepared a n d t h e mixture siphoned into t h e bottles, care being t a k e n t o avoid aeration. A bottle of 2 j0 cc. capacity with a seal such as is often used for t h e methylene blue putrescibility test is employed. It is necessary t o establish t h e ratio of ab-
Vol. 6, NO.
II
sorption in a definite concentration for each particular dry weather flow sewage before resorting t o short time incubation. Having established t h e per cent ratio of absorption for I , j a n d I O d a y s a t t h e proper concentration a t various times, i t may then suffice t o incubate t h e mixture for 24 hours a t 20’ C. T h e results after incubation of 24 hours can be converted into approxim a t e results obtainable after j a n d I O days incubation b y multiplying b y the proper factors. I t is assumed t h a t a Io-day period of incubation coincides with t h e complete oxidation of the sewage mixture, which is correct for all practical purposes. Results should be expressed in “milligrams of oxygen absorbed per liter of crude sewage or effluent.” For purposes of comparison with other sewages, i t is desirable t o state the pxygen consumption in milligrams for 2 4 hours a n d T h e Io-day consumption figure m a y either I O days. be actually determined or obtained by calculation with t h e factor established in the initial experiments.” T h e writer wishes t o t h a n k heartily all those who have cooperated in this work b y actual experiment a n d b y suggestions. On t h e whole, the results of the experimental work have not been very satisfying to, the collaborators, including myself. Even though we did not decide on a method which promises t o be of a permanent character, I feel t h a t we shall be able a t least t o obtain more uniform results by establishing a standard concentration, incubation temperature a n d period. If all those who are interested sufficiently in this test will establish t h e approximate ratio of oxygen exhaustion in their sewage during a Io-day period, the results obtained in various places ought t o be fairly comparable with each other. THE S A N I T A R Y 39TH
DISTRICT
ST. A N D
LAKE
OF CHICAGO
FRONT
NOTES ON THE COMPOSITION OF MIDCONTINENTAL PETROLEUM’ By F. W. BUSRONG Received August 14, 1914
T h e crude oil from which the products described herein were derived came from the wells of t h e Alluwe Oil Company in Oklahoma. It is a typical Oklahoma oil of specific gravity2 0.8j13 a t I j o / I j o . Although the writer is firmly convinced t h a t a thorough series of fractional distillations begun on a factory scale a n d carried out t o t h e highest limit of efficiency would richly reward t h e immense labor involved b y opening u p a new world of possibilities in the way of chemical products t o be manufactured from petroleum he keenly feels his helplessness in t h e face of t h e enormity of such a n undertaking. T h e time a t his disposal permitted only a series of four distillations. Two 8-liter portions of t h e crude oil were subjected t o distillation from a copper retort until t h e temperature of t h e vapors reached 31 j ’ C. T h e distillates were collected in I O fractions of j per cent each by volume. The redistillations were carried out in Jena 1 This work was done under the J. R. Greenlees Temporary Industrial Fellowship, established under the direction of the late Dr. Robert Kennedy Duncan, in the University of Kansas, 1908. % T h e r ewas a loss of gasoline during shipment. The oil a t the well is lighter.
NO\.., 1914
T H E J O L - R S d L OF I-YDCSTRIA4L A S D ESGINEERILVG C H E M I S T R Y
glass flasks. I n t h e case of t h e gasoline fractions a LeBel-Henninger dephlegmator was employed. Twelve-degree fractions were collected in t h e second distillation, four-degree fractions in t h e third. a n d two-degree fractions in t h e fourth. S a t u r a l gas \$-as used a s t h e source of heat in t h e first three distillations, b u t in t h e final distillation electricity was employed in t h e following manner: T h e distilling flask was mounted upon a n electric flask heater which was so regulated as t o heat t h e oil nearly t o its boiling point. A coil consisting of about five meters No. 24 German silver wire was held in place in t h e form of a ring within t h e distilling flask b y means of two stout copper wire terminals which passed u p through t h e cork stopper in t h e neck of t h e flask. T h e q u a n t i t y of current passed through this coil in order t o efiect t h e distillation of t h e preheated oil was small, a n d was controlled b y outside resistance. This arrangement permitted easy control a n d constancy of distillation, a n d did not require a great difference between t h e tem.perature of t h e heating coil a n d t h a t of t h e oil. Tables I a n d I1 show t h e fractions t h u s collected, their relative quantities, densities a n d indices of refraction. TABLE I-GASOLINE FRACTIOXS Fraction Below 40: 40 to 50 50 to 60'
60 to 62' 62 o t 64' 64 t o 66' 66 to 68' 68 t o 70' 70 t o 7 2 0 !2 to 740 1 4 t o 76' 76 t o 78: 78 to 80 80 to 820 82 t o 84O 8 4 t o 86O 86 to 88' 88 to 90' 90 to 92' 92 t o 94: 94 t o 96 96 t o 98' 98 to 100: 100 t o 102 102 t o 104O 104 to 106O 106 t o 1 0 8 O 108 to 110; 110 t o 112 112 t o 1 1 4 O 114 t o 116O 116 t o 118O 118 to 1200 120 to 1220 122 t o 124' 124 t o 126O 126 t o 128O 128 t o 130° 130 t o 132O 132 to 134' 114 t o 136: 136 to 138 138 to 140° 140 t o 142O 142 to 144O 144 to 146' 146 to 148' 148 to 1500
Bar. pr. mm. 739 739 739 739
744 744 744 744 744 744 ' 740
Percentage by vol. 0.5 0.12 0.35 0.08 0.08
0.10 0.34 0.29 0.27 0.22 0.18
740
0.07
z40
0.19 0.13 0.11 0.11 0.36 0.31 0.26
I40 740
74c 740 740
740 i40 740 740 7 40
731 731 73 1 73 1 731 731 731 73 1 73I
744 i44
744 744 744 744 748 748
748 750
0.44
0.39 0.93 0.31 0.41 0.29 0.28 0.13 0.15 0.31 0.29 0.36 0.36 0.37 0.43 0.46 0.34 0.40
0.25 0.32 0.24
0.35 0.31 0.27
750 750 750 750
0.33
750
0.14 0.22
7i o
TOTAL GASOLISE
0.27 0.40
Sp, gr 15 ,150
Ref index 15' C
0.6296 0.6448 0.6608
....
.... ....
0.6867 0.6926 0.6976
...,
o:jiii
0 . ,211 0.7221 0.7261 0.7260 0.7273 0.7286 0.7291 0,7306 0.7331 0.7364 0.7391 0.7407 0.7430 0.7432 0.7436
0.7440
0.7438 0.7433 0,7435 0,7443 0.7450
0.7467 0.7485
0.7526 0.7557
0.7600 0.761, 0.7652 0.7666 0.7679 0,7684 0.7679 0.7682 0.7686 0.7687
13.77
Results of analysis of some of t h e untreated higher kerosene fractions are here s h o v n : Fraction 290 to 292' 292 t o 294' 294 to 296' 296 t o 298'
Per cent C 86.07 85,96 86.24 85.80
Per cent H 13.31 13.03 13.18 13.06
Per cent 0 (dif.) 0.62 1.01 0.58 1.14
__
AVERAGE.. ,,,.. . . . 86.02 13.14 0.84 Fractions dried b y means of metallic sodium, a n d filtered, were found t o have the following composition: ~
~
Fraction 252 to 254: 272 t o 274 292 to 294; 296 t o 298
889
Per cent C 86.58 86.39 86.65 86.29
Per cent H 13.41 13.43 13.46 13.26
Several fractions were treated with ozone, in t h e cold. After separating t h e resinified ozonides, b y settling, t h e residual oils had t h e following composition: Fraction Per cent C 302 t o 304' 84.19 83.88 300 t o 302' 83.73 298 t o 300' 296 t o 298O 84.54 Same after drying with N a 84.84
Per cent H 13.13 12.88 13.31 13.35
Per cent 0 (dif.) 2.68 3.24 2.96 2.11
13.67
1.49
The residual oil from t h e 302 t o 304' fraction, after refining with successive portions of concentrated TABLE11-KEROSENE FRACTIOKS Fraction 150 to 152' 152 t o 154; 154 to 156 156 t o 158O 158 t o 160' 160 t o 162' 162 to 164' 161 to 166' ( a ) 166 t o 168'1 168 to 1 7 0 ° li0 t o 172' 172 to 174' 174 t o 176' 176 t o 178: 178 to 180 180 t o 1820 182 to 184' 184 to 186O 186 to 188O 188 t o 190: 190 t o 192 192 t o 194' 194 t o 196O 196 t o 198' 198 t o 200; 200 to 202 202 t o 204' 204 t o 206' 206 t o 208' 208 to 210' 210 t o 2120 212 t o 214' 214 to 216' 216 to 218O 218 t o 220° 2 2 0 to 2220 222 t o 224O 224 t o 226O 226 to 228O 228 t o 230° 230 t o 232' 232 t o 234O 234 t o 236O 236 to 238' 238 t o 240' 240 t o 242' 242 t o 244O 244 t o 246O 246 t o 2 4 8 O 248 t o 250' 250 to 252' 252 t o 254O 254 to 256O 256 to 258' 2 5 8 t o 260' 260 to 262' 262 t o 264' 264 t o 266' 266 t o 268; 268 t o 270 270 t o 272O 272 t o 274: 274 t o 276 276 to 278' 278 to 280; 280 to 282 282 to 2 8 4 O 284 to 286O 236 to 2880 288 t o 290; 290 t o 292 292 t o 294O 294 to 296O 296 t o 298O 298 t o 3003
Bar. pr . mm. 738 738 739 739 739 739 i3i 7 44
738 733 733 733 736 736 736 735 734 734 734 734 734 734 734 73 1 738 738 738 738 736 736 733 733 733 732 730 730 730 730 730 730 742 742 i42 742 742 741
741 741 741
741 740 740 7 40
738 7.38
i38 i37 737 735 735
733 733 736 i36 741 741 741 740
740 739 739 739 739
.Percentage by vol.
Sp. gr. 15°i150
Ref. index 15' C .
0.20
0.7z15
1,4320
0.50
O.ij30
0.36 0.49 0.31
0.7744
0,7762 0.7784
I , 4330 I , 4338 1 ,4350
0.55
0 . 7800
0.60 0.37 0.36
0.7818
0.40
0.56 0.52 0.35 0.44
0.41 0.24 0.44
0.20 0.48 0.40
0.51 0.32 0.30
0,7844
0.7849 0.7868 0.7884 0.7897 0.7910 0.7920 0.7930 0.7944 0.7957 0.7969 0.7980 0.7997 0.8006 0.8026 0.8030
0.50
0,8050
0.33 0.43 0.51 0.37
0.8075
0.8064 0.8094 0.8105
0.51
0.8118 0.8129 0.8138 0.8154 0.8160
0.28
0.8175
0.40 0.50 0.38
0.8184 0.8190 0.8207 0.8219 0.8230
0.47
0.43 0.51 0.47
0.45
0.41 0.33 0.41 0.37 0.40 0.40
0.42 0.42 0.34 0.30 0.31 0.39 0.51
0.24 0.39 0.40
0.34 0.37 0.46 0.43
0,8244 0.8252
0.8264 0.8270 0.8290 0.8306 0.8322 0.8329 0.8339 0.8355 0.8360 0.8381 0.8388 0.8398 0.8410 0.8418 0.8434 0.8440
0.8449
0.45
0.8455
0.27
0.8462 0.8469
0.44 0.23 0.41 0.38 0.43 0.23 0.33 0.40 0.28 0.29 0.37 0.22 0.28 0.28
-
1.4359 1.4372 1.4384 1,4393
0,8480
0.8483 0.8483 0.8595 0,8500
0.8498 0,8508
0.8508 0.8510
0.8513 0.8518 0.8525 0.8530
TOTALKEROSEKE 28.80 300 to 302O 739 0.8533 ... 0,8540 739 302 t o 304O ... ( a ) Mercury column of thermometer became shattered.
1.4761 1 ,4765
sulfuric acid, washing i n t h e usual manner a n d drying over calcium chloride, gave t h e following analysis:
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
890
8 5 . 8 4 per cent C and 13.99 per cent H
The residual oil of t h e 300 t o 302' fraction (after separation of t h e ozonide) was refined b y means of liquid sulfur dioxide, according t o t h e method of Ede1eanu.l T h e oil t h u s refined, washed a n d dried, h a d t h e refractive index 1.4712 a t 14', a n d was found t o contain 85.42 per cent C 85.62 per cent C
Calculated for C,H,,
14.12 per cent H 14.38 per cent H
T h e oil extracted therefrom b y the liquid sulfur dioxide, after washing, etc., h a d the refractive index 1 . 5 2 2 2 a t 1 6 ' a n d contained 8 2 . 4 2 per cent C
10.31 per cent H
7.27 per cent 0 (dif.)
T h e 296 t o 298' fraction, weighing 58.34 g. after t r e a t m e n t with sodium, a n d filtration, was treated in t h e cold with ozonized air for five successive days. T h e ozonide was washed with a b o u t 2 5 cc. of light gasoline, t o which it gave only a slight color. After evaporation of t h e residual gasoline in a current of per natural gas there remained 5.8 g. of ozonide-Io cent of t h e weight of oil. Some of this ozonide was treated with anhydrous ether, yielding a red colored solution, which was poured off from a brick-red insoluble powder. After the evaporation of t h e ether there remained a transparent red syrup which hardened slowly like a varnish. A portion for analysis was spread in a film over t h e inner surface of a porcelain boat a n d dried in a desiccator. Its weight became constant a t 0.4122 g. On combustion this gave 0.9623 g. COZ a n d 0.2336 g. H 2 0 . Found 63.67 per cent C 6 . 3 4 per cent H Calculated for CirHzoOa 63.72 per cent C 6 . 3 0 per cent H 2 9 . 9 8 per cent 0
This is in accordance with t h e results obtained b y Molinari a n d Fenaroli2 with distillates from Roumanian a n d Russian petroleums. T h e 2 5 2 t o 254' fraction-the largest of t h e upper kerosene-after drying over sodium, was refined with liquid sulfur dioxide. A-The refined oil h a d a specific gravity of 0.8240 Its a t 15' a n d t h e refractive index 1.4660 a t 15'. composition was found t o be 85.29 per cent C
1 3 . 9 8 per cent H
B-The sulfur dioxide extract, after washing, etc., had t h e refractive index 1.5412 a t 12' a n d t h e composition Calculated for CISHzo
88.94 per cent C 10.19 per cent H 0.87 per cent 0 (dif.) 10.07 per cent H
89.93 per cent C
This extract, B, was t h e n treated with ozonized oxygen, in t h e cold. It yielded a n ozonide which when freshly precipitated was flaky a n d almost white, b u t slowly resinified. It was t a k e n up in absolute ether a n d shaken with successive portions of a dilute aqueous solution of potassium hydroxide until freed from acids. It was then washed, a n d dried over calcium chloride. After evaporation of the ether a thick resinous syrup remained. 0.4681 g . of t h e dry substance gave 1 . 2 7 1 2 g. COz a n d 0.2884 g. HzO. Found Calc. for ClsHlaOs
74.06 per cent C 6 . 8 9 per cent H 73.73 per cent C 6 . 6 1 per cent H
19.66 per cent 0
Molinari a n d Fenaroli isolated from t h e petroleum 1
U. S. Pat. 911,553. Feb. 2, 1909; Chcm. Abs.. 8, 1082.
* Bcrichtc, 41 (1908). 3407.
Vol. 6, No.
11
of Velleja, Italy, a flaky white ozonide having t h e composition C15H1606, which t h e y believe t o have been formed from t h e hydrocarbon C1bH16 b y t h e addition of t w o 0 3 groups t o t w o double bonds. Possibly our original product also may have been the same double ozonide, which on t r e a t m e n t with alkali lost half of its oxygen. I n the excellent work "Wissenschaftliche Grundlagen der Erdolbereitung," b y Dr. L. Gurwitsch, Berlin, 1913, pp. 34-35) t h e significance of t h e suggestion of hlolinari a n d Fenaroli regarding t h e preexistence of hydrocarbons of t h e series in kerosene is critically discussed, a n d i t is pointed out t h a t oxidation may precede the ozonide formation. T h e analysis of t h e sulfur dioxide extract of t h e unoxidized 2 5 2 t o 254 ' fraction shows approximately t h e same hydrogen content as t h e hydrocarbon Cl6Hza. Since, however, the extraction method cannot effect complete separation of t h e t w o classes of hydrocarbons i t is very probable t h a t this extract may consist essentially of t h e hydrocarbon C15H16, contaminated by small residual quantities of ordinary naphthenes. T h e ozone reaction has given us a valuable working tool for detecting new constituents of petroleum. T h e extraction method of Edeleanu enables us t o remove these constituents from the main body of t h e petroleum, in concentrated form a n d apparently unaltered condition. I n t h e opinion of t h e writer, however, t h e proof of t h e chemical composition of these reactive constituents awaits t h e development of a n independent method of attacking t h e problem. 3447 PARKVIBW Arm. PITTSBURGH, PA.
EFFECT OF PRESSURE ON YIELDS OF PRODUCTS IN THE DESTRUCTIVE DISTILLATION OF HARDWOOD By R. C. PALMER Received August 5, 1914
INTRODUCTION
A study of the effect of pressure on yields was conducted a t t h e Forest Products Laboratory as a part of a series of experiments t o devise methods of increasing t h e amounts of valuable products obtained in t h e destructive distillation of hardwoods. It is generally known t h a t certain primary reactions occur in t h e action of dry heat on wood substance in t h e absence of air, resulting i n t h e primary products: acetic acid, methyl alcohol, a very complex t a r , charcoal, a n d such gases as carbon dioxide, carbon monoxide a n d methane. From a theoretical standpoint, i t is possible t o produce secondary reactions between these primary products such as zCH3COOH = CH3COCHa C02 HzO, resulting in a decrease in CH,COOH = CH3COOCH3+ acetic acid, or CHaOH HzO, giving a decrease in both alcohol a n d acetic acid. T h e decomposition reactions of wood which result in t h e formation of t a r are a t present too little understood even for speculation b u t undoubtedly a relation exists between t h e t a r a n d charcoal, both products containing a high carbon content,' a n d a relation between acid or alcohol a n d t a r is certainly not impossible
+
1 Ultimate
+ +
analysis of birch tar has been given as CaeHaOis. Rlason.
Arch. j . Kemic Min. and Geol.. Vol. 6, No. 7.
