T H E J 0 C R S ; I L O F I i Y D L - S T R I d L A LVD E N G I N E E RI A-G C H E M I S T R Y
June. 1913
will decrease t h e gaseous hydrocarbon yields from a given a m o u n t of oil. Experimental results, shown in Table 111, have proven tLis correct. It was pointed o u t t h a t varying t h e pressure on t h e system would enable one t o better control t h e g u a n t i t y a n d quality of " t a r " obtained t h a n a t present where all t a r is made under atmospheric pressure. Experimental results indicate considerable flexibility. It has further been established t h a t t h e end products resulting from cracking oil i n a n atmosphere of a gas, such as H z , which reacts chemically with t h e e n d products of t h e cracking, are a function of both t h e composition a n d t h e q u a n t i t y of t h e gas admixed, per Table T'. Experiments, Table IT', have proven t h a t it is possible t o " c r a c k " oil a t a temperature of gooo C . witho u t depositing more carbon t h a n I per cent by rveight of t h e oil used.
iron ore found immediately over t h e coal in their mines a t Stearns, LIcCreary County. Kentucky. T h e ore occurs in a layer of about 18 inches maximum thickness, resting on t h e coal, a n d is capable of being mined with t h e coal. I t is seal-brcwn in color. has a horizontal lamination or banding with carbonaceous m a t t e r between t h e laminae, a n d breaks transversely t o t h e laminae, giving a rather smooth surface. On account of its structure a n d t h e presence of carbonaceous m a t t e r , i t is here classed as "Black Band" ore. though distinctly brown, not black, in color a n d containing much less carbonaceous m a t t e r t h a n is usual in black band. .In analysis b y I l r . J . S . I I c H a r g u e follows:
TABLE TI-SLMMARY OF GAS TABLES C , and 760 mrn p r e s u r e l Carbon
G.
Tar Cc.
CZHB
CHI
H:
L.
L
L.
Ill
L.
Total.. ......................... Total i r o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . T o t a l phosphorus.. . . . . . . . . . . . . . . . . . . . . . . .
Atmospheric Pressure Group (See Table 11)
900
15.0 15.0 15.0
650 i50 900
45.0 45.0 45.0
650 i50
3 18 115
135 206 382
163 80 11
13.8 10.15 Trace
45.5 84.5 178.1
12.1 39 6 I48 2
58.8 63.0 50.0
13.1 33.9 155 0
44.3 30. I 15.5
High Pressure Group (See Table 111)
8 26 165
145 194 310
133 Si 9
16.7 11.8 None
65.2 110.0 128.9
Low Pressure Group (See Tables I and I V j 750 850 900 950
0.75 0.75 0.75 0.75
146 211 234 235
1 3 3 12
153 100 60 58
..
7.16 3.0 Trace
.. 43.2 56.0 63.4
18.3 32.9 40.0 48.8
Hydrogen admixed
L.
L.
i50 800
15.0 15.0
358 412
50
--
15.4 18.0
125.0 116.0
308.0 335.0
?0 6 83.2
750 8 10 860 900 950
1.0 1.0 1.0 1.0 1.0
400 413 388 292 382
19 35 38 20 34
9.5
52.0 86.5 99.5 92.0 95.0
381.0 378.0 350.0 272.0 348.0
112.0 140.0 133.0 120.0 113.0
I ,
.. , . ..
..
P R O B A B L E COMBINATIONS. C.%LCULATED FROM ABOVE ANALYSIS Ferrous c a r b o n a t e . . . . . . . . . . . . . . . . . . . . . . . . . 83.50 per cent
.
Hydrogen shrinkage
Through a proper consideration of equilibrium a n d mass action conditions under various degrees of t e m perature a n d pressure, much can be expected in gaseous reactions. It soon becomes evident t h a t t h e single stage method wherein endothermic a n d exothermic, expansion a n d contraction reactions are combined i n a single a p p a r a t u s , is open t o cuestion. CHEMICAL ESCINEERINC LABORATORY ~ - E WYORK COLUMBIACNIVERSITY,
NOTE ON A BLACK BAND IRON ORE FROM THE STEARNS COMPANY'S COAL MINES AND ON THE CALCIUM-MAGNESIUM RATIO IN KENTUCKY CARBONATE ORES' By ALFRED hZ. PETER
I n September, 1913,t h e Stearns Coal Company sent t o this Experiment Station, for analysis, a sample of 1 Presented at the regular meeting of t h e Lexington Section of the American Chemical Society, F e b r u a r y 11. 1914.
100.00 40.87 0.035
Treatment with carbon disulfide extracted a n appreciable amount of brown. bituminous m a t t e r , t h e quant i t y of which was not determined. The figure for organic m a t t e r was obtained by digesting a portion of t h e ore i n HCl, filtering on a Gooch filter, washing, drying a t IOO', weighing a n d burning, t h e loss in weight being t a k e n t o represent organic matter.
82.0 111.5 122.0 110.0
Admixed Gas Group (See Table Vi
.
. x S A L Y s I S OF THE AIR-DRIED SAMPLE N O . 43255 Specific gravity (18' 18O) 3.268 Ferrous o x i d . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51.7; per cent Ferric oxid. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.85 Alumina. . . . . . . . . . . . . . . . . . . . . Manganousoxid . . . . . . . . . . . . . . Calcium o x i d . . . . . . . . . . . . . . . . . Magnesium o x i d . . . . . . . . . . . . . . . . . . . . . . . . . . 3 . 5 ; Phosphorus pentoxid.. . . . . . . . . . . . . . . . . . . . . . 0,08 Sulfur. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Trace Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . 1 6 Organic matter.. . . . . . . . . . . . . . . . . . . . . . . . . 2.7: Carbon dioxid. e t c . , by ditierence. . . . . . . . . . . . 3 6 . 6 9
(A11 based on 400 cc. oil and calculated t o 0' Pressure TemD. L b s Der Gas L. = c. sq. in
479
Alumina . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.60 Manganous carbonate.. . . . . . . . . . . . . . . . . . . . 1.29 Calcium c a r b o n a t e . . . . . . . . . . . . . . . . . . . . . . . . 3.30 Magnesium carbonate.. . . . . . . . . . . . . . . . . . . . . 7.49 Tricalcium phosphate. . . . . . . . . . . . . . . . . . . . 0 . l i Sulfate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Trace Silica.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 . !6 Organic matter. . . . . . . . . . . . . . . . . . . . . . . 2.I i Total.
............................
101.13
The analysis shon-s t h a t this is quite a pure iron ore, containing, however, considerable quantities of manganese, calcium a n d magnesium. A notable feature is t h a t there is more t h a n twice as much magnesium carbonate present as calcium carbonate. Calculating t o molecular proportions a n d including t h e manganese i n t h e comparison, gives I I I n C O s : 2.94 CaCOy : :.SI I l g C O y , or, in round numbers I : 3 : 8. T h e ratio of calcium carbonate t o magnesium carbonate is I CaC03 t o 2.66 1 l g c o 3 . Of course this m a y be only a chance relation. b u t there is room t o speculate why there is more magnesium carbonate t h a n calcium carbonate. Has it a relation t o t h e greater solubility of magnesium carbonate in carbonated water? Or is it because there was more magnesium t h a n calcium in t h e original material from which this ore w a s formed? N o answer is suggested, b u t a fact like this, in t h e hands of a well informed chemical geologist, might help t o explain t h e process b y which this kind of iron ore is formed. T o show t h a t magnesium usually predominates over calcium in t h e ferrous carbonate ores of Kentucky, all t h e analyses of such ores made for t h e first Kentucky
0
T H E JOUR-VAL O F I - V D U S T R I A L A N D E N G I Y E E R I A V G C H E M I S T R Y
480
Geological Survey, 18j6 t o 1860, b y Dr. Robert Peter, Chemist of t h e Survey, a n d published in t h e first four chemical reports, have been tabulated a n d compared. T h e total number of samples analyzed was 7 1 from 2 0 counties, as follows: B a t h 3, Bullitt 2, Butler z , Carter 3 . Crittenden 2, Edmondson I , Estill 4, Greenup 26, Hancock I, Hopkins 2, Laurel 4, Lincoln I, Slontgomery I, Morgan I, hluhlenberg 7 , Nelson 2 , Owsley 2, Powell I , Pulaski 2, Whitley 3. T h e geological formations represented were mainly t h e Coal Measures a n d t h e Devonian, with some from t h e "Sub-Carboniferous" of Owen, or Mississippian, a n d t h e Silurian. T h e kinds of ore were various, including kidney ore, oolitic ore, massive kinds, black b a n d ? block ore a n d t w o samples which would better have been classed a s ferruginous limestones. Probably most of t h e block ores should not have been included because, in these, t h e proportion of ferric oxid often exceeds t h a t of ferrous carbonate. T h e whole tabulation would occupy too much space here. Inspection of i t brings o u t t h e following facts:
A NOTE ON THE UTILIZATION OF MUDS AND SCUMS FROM SUGAR REFINERIES By R. F. G A R D I N E R ~ Received March 3, 1914
X description of t h e m u d s a n d scums in t h e sugar refining processes can be found in most works on industrial chemistry. T h o r p says t h a t "these m u d s have been thrown away." T h e possibility of their utilization is now being seriously considered b y some sugar producers, as is shown b y recent correspondence between this laboratory a n d a prominent American sugar producer, who says: " T h e m u d was thrown a w a y for quite a time a n d now we are trying some experiments in drying t h e same for t h e phosphoric acid content." Sample I was analyzed b y t h e a u t h o r ; t h e nitrogen determination was kindly made by 51r. T. C. Trescott, of t h e Bureau of Chemistry. The analysis of Sample 11, b y Plicque, is cited because i t also shows a considerable a m o u n t of water.2 TABLE I-SHOWING
tabulated.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 MgCO3 exceeds per cent CaCO8.. . . . . . . . . . . . . . 57 MgC03 equals per cent CaCOa.. . . . . . . . . . . . . . 1 MgCOs is less t h a n per cent C a C 0 8 . . . . . . . . . . . 13 Insoluble matter exceeds 10 per c e n t . , . . . . . . . . 4 5 CaCOa exceeds 10 per c e n t . , . . . . . . . . . . . . . . . . . 2
These last two, of course, are included in t h e thirteen which contain more C a C 0 3 t h a n 5 I g C 0 , . T h e large number containing more t h a n I O per cent insoluble m a t t e r shows t h a t t h e collection includes m a n y i m pure ores. T o gain a general idea of t h e composition of t h e samples in which t h e L'lgc03 predominated over t h e C a C 0 3 , t h e j 7 analyses of this class have been averaged, giving t h e figures in t h e following table, which includes also t h e extreme range of each constituent, all stated as per cent of t h e ore, dried a t 100' C.: COMPOSITION OF 57 SAMPLES Average 60.78 Ferrous carbonate, FeCO3.. . . . . . . . . Ferric oxid, Fez03. . . . . . . . . . . . . . . . . 8,09 Alumina, A1208.. . . . . . . . . . . . . . . . . . . 1.40 Calcium carbonate, CaCOs. . . . . . . . . 2. i 1 Magnesium carbonate, MgCO3.. , , , , 5.92 Manganous carbonate, MnCO3.. . . . . 1 , 57 Insoluble residue.. . . . . . . . . . . . . . . . . 16.36 Combined H20, bituminous matter and undetermined.. . . . . . . . . . . . 3.17 Total., .
Highest 87. 53 51.31 5.15
7.25 13.99 5.03 40.88
...
Lowest 20.19 Trace Trace Trace 0.83 0.12
I1 Plicque 52.70 3.50 3.72
...
...
4.77 26.07
In order t o economically recover t h e valuable fertilizer elements, such as phosphoric acid a n d nitrogen, i t will be necessary t o find some satisfactory drying process, for which modern improvements in drying processes m a y offer ultimate success in t h e utilization of' this potentially valuable fertilizer, now entirely lost. BUREAUO F
DEPARTMENT OF AGRICULTURE
SOILS,
VV'ASHINGTON
THE EFFECT OF HIGH TEMPERATURE ON YEAST By
c. B .
C O C H R A N 3 A N D J. H . PERKINS( Received October 17, 19 13
I n t h e esperiments recorded below, t h e yeast was added t o 30 cc. of simple syrup in sterilized test tubes plugged with cotton, raised t o t h e temperatures indicated a n d held there for t h e stated periods of time. T h e tubes mere then placed in a n incubator a n d k e p t a t a temperature of about 3 I O C RESULTING FERMEXTATION Fleischmann's ( b )
... SP. GR. AND
I t is seen th&t t h e proportion of magnesiclm carbonate is more t h a n twice t h a t of t h e calcium carbonate a n d t h a t t h e proportion of manganous carbonate is t h e smaller of t h e three. Calculated t o molecular proportions, t h e relation is I hlnCOa : z C a C 0 3 : j . 1 h l g C 0 3 . It is presumably only a n accident, however, in such a calculation as this, t h a t t h e molecular ratios are almost exactly whole numbers. T h e ratio of calcium carbonate t o magnesium carbonate is I C a C 0 3 to 2.55 M g C 0 3 , which does not differ very far from t h e ratio found in t h e Stearns sample, vis., I CaCOs to 2.66 MgCOa.
&IUD F R O M A S U G A R h I I L L
Percentages Gardiner HzO . . . . . . . . . . . . . . . . . . . . . . 67.32 Sugar. . . . . . . . . . . . . . . . . . . . . . Nitrogenous m a t t e r . . . . . . . . . . . . N . . . . . . . . . . . . . . . . . . . . . 1.14 KzO.. . . . . . . . . . . . . . . . . . . . . Trace P?Oj. . . . . . . . . . . . . . . . . . 8 . 3 3 Lime, silica, iron, etc.. . . . . . . . . .
4 .Si
. . . . . . . . . . . . . . . . . 100.00
KENTUCKY AGRICULTURALEXPERIMENT STATION LEXINGTON
COMPOSITIOX OF
I
S O .
Analyses Per cent Per cent Per cent Per cent Per cent
Yol. 6, No. 6
OF
SYRVP,
Prompt and vigorous
TIME
SP. GR., 1.125.. . . . TIME,5 m i n . . . . . .
$Tl;t Sone
SP. GR., 1.170.. , , . . TIME,30 m i n . . . . . . SP. G R . , 1.125.. . . . . T I M E ,30 min. . . . . SP. G R . , 1.126(a)... T I M E , 15 m i n . . . . . .
Magic(b)
I1,2&3
Active after 2 days h'one
Prompt and vigorous
Slow Slow ! 11,&22 & 3 65 io L'one None (3 70 None Slow I, 2 & 3 68 Sone None I, 2 & 3 72 Sone h70ne ( a ) I n these tests the heat was applied after leaving the yeast in the syrup for 24 hours a t a temperature of about 12' C. ( b ) T o each 30 cc. of syrup, 1 ' 3 2 of a Fleischmann's or 1/16 of a Magic yeast cake was added PHILADELPHIA
i
Scientist in Soil Laboratory Investigations. "Handbook for Planters and Refiners," Lock and Newlands Bros 1888, p. 489. 3 Chemist for T h e Dairy and Food Department of Pennsylvania. 4 Chief Chemist for T h e Charles E. Hires Company. 1
2
