NOVEMBER, 1935
INDUSTRIAL AND ENGINEERING CHEMISTRY
Literature Cited (1) Allen, C. H., and Sprinkel, K. M., Drugs, Oils,Paints,Oct., 1934; IND. ENG. CHEM., News IM.,12, 392 (1934); Federation Paint Varnish Production Clubs, Oficizl Digest, 143, 54-65 (1935): Ibid., 144, 111-24 (1935). ( 2 ) Barry, T. H., “Natural Varnish Resins.” London, Ernest Benn Ltd., 1932. (3) Barry, T. H., and Dunster, G. W., “Varnish Making,” London, Leonard Hill Ltd.. 1934. (4) Coffignier, Ch., “Tarnishes, Their Chemistry and Manufacture,” London, Scott, Greenwood and Son, 1923.
( 5 ) Krumbhaar, Wilhelm, J . Oil Colour Chen. Assoc., 17 (1731, 413-36 (1934). (6) McIntosh, J. G., “Manufacture of Varnishes and Kindred Industries,’’ 2nd ed., Vol. I1 (1908), Vol. I11 (1911), London, Scott, Greenwood and Son; Livache, A , and McIntosh, J. G., Ibid., 3rd ed., Val. I (1919). (7) Rangaswami, M., J . Oil Colour C h e w dssoc., 13, 287 (1930). (8) T a n De Koupel, C., “De Handel in het Nederlandsch-Indische copal (Manila-copal) en het gebruik er van voor verschillende industrieele doeleinden,” Buitenzorg, Java, 1934. RECEIVED J u n e 18, 1935. Presented before t h e Division of Paint and Varnish Chemistry a t t h e 89th l f e e t i n g of t h e American Chemical Society, New York, 3 . Y., hpril 22 t o 2 6 , 1935.
Volatile Matter of Pennsvlvania J Anthracite H. G. TURNER
AND
1373
The composition of the volatile matter of Pennsylvania anthracite was determined by treatment of thirty-six bed samples selected from points throughout the anthracite region, The proximate and ultimate analyses for the samples used and the proximate analyses for prepared coals from all parts of the region are given. The samples tested were heated slowly a t temperatures from 70’ F. to 1900’ F. (21’ C. to 1036’ C.) in a nichrome tube connected to 12 or 15 liters of space evacuated to less than 1 mm. pressure. Hydrogen sulfide appeared in small quantities in every sample of evolved gas. No illurninants were detected. No tar was emitted by any of the coals. The gas contained 75 to 89 per cent hydrogen (average 83 per cent); the average volume of hydrogen was about 5000 cubic feet per ton of coal under standard conditions.
W. L. KEENE‘
Anthracite Equipment Corporation, New York, N. Y.
HE apparatus consisted essentially of a
ENGINEERS TAKINGSAMPLES IN A PENR’SYLVANIA AKTHRACITE MINE FOR EXPERIMENTATION
0.75-inch nichrome tube mounted in an electric furnace and connected to a Hyvac pump. Provision was made for the control and measurement of temperatures and the collection, measurement, and sampling of gases. The anthracite was sized to 10 X 16 mesh and dried 24 hours a t 110’ C.; 50 cc. were measured into a graduated cylinder and then weighed. The coal was placed on a bed of broken silica so situated in the nichrome tube as to bring the sample into the middle part of the furnace. The upper end of the tube was sealed and the lower end \vas connected to a condenser and buret. Both ends of the tube were protected against heat by mean5 of copper coils through which flowed a stream of cold water. The partially dried gas passed from the condenser through a calcium chloride drying tube, through a flowmeter, t o a 12liter sealed flask which was connected to a mercury nianometer and Hyvac pump. ,111 connections were sealed, and the entire system was evacuated t o the capacity of the Hyvac pump, about 1 mm. of mercury. 1
Present address, Rustles8 Iron Corporation of America, Baltimore, M d .
INDUSTRIAL AND ENGINEERING CHEMISTRY
1374
GRADIENT AND TEMPER.4TURE TABLEI. TEMPERATURE 0.75-INCH DIAMETER NICHROME TUBE Time Min. :sec. 0
85 95 130 205 335 555 775 965 1120 1275 1435 1580 1730 1895
1:55 3:15 5:05 7:40 11: 10 15: 10 19:35 24: 10 29: 40 37: 10 46:30 61:15 94:30
Modifications of Standard Test L.4G I N
-
Several tests were made in which the gas was samded and analyzed at various temperatures from room temperature to the maximum furnace temperature. Table I11 shows the variation of the composition of volatile matter and gas volumes with coal temperatures. The low-temperature treatment' evidently releases adsorbed air from the surface of the coal; the intermediate temperature, 335" to 1125" F. (168" to 604" C.), evidently causes a combination of oxygen with carbon to form carbon dioxide and releases hydrogen and methane (if present as such) ; the high-temperature treatment chiefly releases hydrogen. The actual mechanism of these reactions has not been determined.
Outside Couple" F. 0 c.
Inside Couplea F. c. 29 35 54 96 168 290 413 518 604 689 779 860 942 1033
85 245 375 515 650 780 910 1040 1175 1310 1450 1590 1745 1910
29 11s 191 268 343 415 487 560 634 708 787 864 950 1041
u Chrornel-alumel couples; inside couple embedded i n 50-cc. coal sample; outside coupie against tube wall.
TABLE 11.
ULTIMATE
AXALYSESAND
Volatile matter
Hz
c
43.6 44.7 44.2 40.2 46.8 45.3 44.8 43.7 47.0 47.2 47.0 44.8 41.9 41.8 44.7
2.9 3.0 3.1 3.2 3.3 3.6 3.7 3.9 4.0 4.1 4.1 4.1 4.4 4.6 4.7
1.9 l.Y 1.8 2.0 1.9 2.0 2.0 2.1 1.8 1.8 2.0 2.0 2.5 2.6 2.1
86.0 90.3 89.7 88.8 86.5 82.3 85.1 82.7 80.3 83.9 85.3 86.4 89.9 86.7 84.6
0.7 0.8 0.7 0.8 0 6 0.6 0.9 0.9 0.7 0.7 0 8 1.2 0.9 0.9 0.7
1.6 1.4 1.2 0.9 1.6 1.3 1.6 1.3 1.2 1.6 1.5 1.1 1.1 2.3 2.6
44.5
3.8
2.0
85.6
0.8
1.4
KO.
Grams 097 087 100 401 071 395 085 405 076 073 064 488 948 533
663
A\,.
VOLATILE MATTER ANALYSES ARR.4SGED I S ORDER O F INCREASING VOLATILE C O N T E S T A S SHOWN BY PROXIM-4TE ANALYSES
-
D r y Coal Analyses
7
Sample
VOL. 27, NO. 11
Voiatiie &latter H20 Gas vol Grams Cc. Lou-Volatile Anthracite
~
N1 Per c e n t
0 2
9
0.5 0.7 0.5 0.5 0.5 1.1 0.8 0.7 0.5 0.6 0.5 0.5 0.9 0.7 0.6 0.6
Ash
12.r 9.6 12.3 15.5 11.4 9.9 8.8 4.7 6.8 9.4
0.3 0.1 0.1 0 .3 0.4 0.3 0.3 0.3 0.2 0.3 0.4 0.3 0.7 0.7 0.8
9.6
0.4
9.3 4.9 6.1 7.0
8.2
Gas Analysle H1 N2 Per cent
,
co
CHI
5 9 9 4 2.8 7.6 1.5 11.8 8.4 3.6 2 4 5.8 3.0 7 9 0 8 1.2 0.0
7.1 4.2 4.7 4.1 4.7 4.2 4 Y 4.3 3,2 4.5 4.2 3.3 3.6 2.3 3.6
1.5 1.9 1.8 4.5 3.8 3.4 2.4 2.8 3.4 5.3 3.8 4.3 5.6 6.7 4.6
83.2
4.8
4 2
3.7
0.6 0.6 1.3 0.8 1.4 2.0 2.1 1.0 1.0 1.1 1.1 0.7 0.8 0.6 1.6 0.8
87.5 86.0 86.0 87.9 86.0 80.4 (8.0 85.4 83.0 84.9 86.4 77.6 85.4 86.0 81.4 85.0
0.7 1.8 3.3 1.0 1.2 6.1 9.5 2.0 3.6 0.9 1.0 2.7 0.6 1.1 5.3 0 7
4.7 3.8 3.1 3.2 4.1 4.5 3.3 4.5 4.4 3.7 3.7 5.9 5.1 3.8 3.2 4.4
4.9 6.1 5.0 5.5 5.5 4.5 5.0 5.7 6.6 8.1 6.4 5.7 6.7 7.4 6.1 7.5
2.0
1.1
84.2
2.6
4.1
6.0
-
C02
0 2
1.5 2.2 2.6 1.6 2.1 1.9 1.3 1.6 2.1 2.4 2.2 1.2 1.1 1.0 1.9
2.0 1.7 5.1 1.6 1.3 3.8 3.2 8.1 0.9 1.0 0.8 2.4 1.7 0.6 1.0
82.0 80.6 83.0 80.6 86.6 74.9 79.8 79.6 88.0 81.0 86.0 80.9 87.2 88.2 88.9
1.8
2.3
1.6 1.7 1.3 1.6 1.8 2.5 2.1 1.4 1.4 1.3 1.4 7.4 1.4 1.1 2.4 1.7 8,495
7,003
-
.\Iedium-Volatile Anthracite 943 Y71 664 8Y2 665 661 485 n. i g ~ 654 534 471 890 970 504 658 525
dv.
.
1.7 0.6 0.8 0.8 2.0 0.7 0.5 0.8 0.9 0.9 1.1 1.2 1.0 1.2 0.2
44.7 41.5 41.7 42.1 43.2 45.9 44.2 42.3 42.5 42.4 42.5 45.5 43.5 40.4 42.0 42.9
4.8 4.9 5,l 5.1 5.2 5.3 5.3 5.6 5.7 5.8 5.8 6.0 6.1 6.3 6.4 6.5
2.3 2.7 2.5 2.6 2.3 2.2 2.2 2.7 2.6 2.7 2.8 2.2 2.5 3.1 2.7 2.8
83,s 85.8 87.0 86.8 85.6 82.3 84.6 83.7 77.8 83.2 82.4 80.1 79.3 86.9 86.1 77.9
0.8 1.0 1.0 0.9 0.9 0.8 0.8 1.0 0.9 0.9 1.1 0.7 0.9 1.1 1.0 1.1
1.5 2.1 2.5 2.4 2.3 2.5 1.3 1.6 2.3 2.0 2.0 2.3 1.4 2.7 2.4 2.0
1.1 0.9 0.9 0.7 0.6 0.9 0.7 2.0 1.6 1.0 0.9 1.1 2.6 0.8 0.8 2.5
10.8 7.5 6.1 6.6 8.3 11.3 10.4 9.0 14.8 10.2 10.8 13.6 13.3 5.4 7.0 13.7
O.,
42.9
5.6
2.6
83.3
0.9
2.1
1.2
9.9
1.0
High-Volatile h n t h r a c i t e 731 667 153 156 890
Av.
0.5
9.6 10.6 10.3 7.4 133
1.3 0.4 0.7 0.3 0 3
8,090 9,330 10,660 10,290 9,290
1.6 1.6 2.2 2.1 3.5
0.8 0.8 1.0 1.3 1.2
86.2 84.0 85.5 83.1 79.0
0.4 3.1 0.9 2.8 2.7
4.4 3.3 3.5 3.0 6.2
6.6 7.2 6.9 7.7 7.4
0 7
10.2
0.6
9,518
2.2
1.0
83.6
2.0
4.1
7.1
41.6 42.0 41.Y 41.1 43.2
6.6 7.3 7.6 8.1 8.5
2.7 3.0 3.1 3.1 2.7
82.5 82.2 82.6 85.6 80.2
1.0 1.1 1.0 1.1 1.0
3.2 2.2 2.4 2.2 2.3
1.0 0.9 0 6
42.0
7.6
2.9
82.6
1.1
2.5
0.6
The furnace and sample were heated to the temperatures and a t the rates indicated in Table I. The temperatures given are those indicated by chromel-alumel thermocouples, one located in the center of the coal sample and the other against the outside wall of the nichrome tube. After these temperature relationships were established, the outside thermocouple was used to indicate temperatures of coal sample. l h e sample was held a t the top temperature until gas evolution ceased. The gas collected in the large flask and was registered on the manometer. From the known capacity of flask, manometer reading, barometric pressure, and room temperature, the volume of gas was calculated to standard conditions. Samples were taken from the flask for analyses. This test routine was adopted as a standard and used on the thirty-six samples listed in Table 11.
TABLE111. VARIATIONOF COMPOSITION OF VOLATILE MATTER WITH C0.4L TEMPERATURE (SAMPLE 890) Temperature:
F.
70-335 21-168
335-1120 168- 604
72
330
Ha
1.9 23.7 0.8
CH4 Na (difference)
1.1 72.5
18.8 3.3 24.4 7.2 35.4 10.9
c.
1120-1895 604-1033
Vol. a t 0" C. a n d 760 mrn. from 50 cc. of 10 X 16
m. coal, cc. Analyses, 70: COa OS
co
0.0
7520 1.3 1.2 80.6
3.8 5.7 7.4
Several tests were made whereby the same sample was subjected to repeated standard runs to see whether or not the standard test removed all of the volatile matter. The re-
NOVEMBER, 1935
INDUSTRIAL AND ENGINEERING CHEMISTRY
sults of a typical test of this kind on a sample containing 5.7 per cent' volatile matter and 11.0 per cent ash are as follows: Test Standard Second Third Fourth (estd.) Total gas emitted, N. T . P.
Vol. from 50 Cc. of 10 X 16 M. Coal, Cc 8480 640
85
8 -
9213
92 per cent of the gas was removed under the standard test conditions-that is, heating t,he sample to a suitable temperature while connected to an evacuated space. The 92 per cent thus liberated might be considered a "commercial yield." The total amount would he considered the "theoretical yield." A few tests TTere made to learn the volume and composition of gas that is liberated at atmospheric pressure. In these tests the gas was taken off in an automobile inner tube from which the air was removed by means of an aspirator with 17 inches (432 mm.) of water pressure. The same aspirator was used to pull the gas from the t'ube through a gas meter for measurement of volume. The fol!owing figures show the comparative results with the same sample under standard test conditions: Standard Vacuum Test Analysis, per cent:
cot 02
Hl
co
CH1
N?
Volume ( N . T . P.), CC.
'
.itmospheric Pressure
2.2
2 ,5
1.5
1.5 80.1 5.1 5 .0
83.0 4.6 6.0 2.7 8480
4 . !3
7890
93 per cent of the gas liberated under standard vacuum conditions was released a t atmospheric pressure or 85.5 per cent of the theoretical yield. These figures also may be of commercial int'erest.
MANOMETER
1375
A test was made on a composite sample from the Northern field to learn what happens to the coal during the standard test procedure. The results are shown in Table IV. It is impossible to tell how much of the reduction in particle size is due to breakage and how much to shrinkage. ___.
TABLE Iv. RESULTS ON
NORTHERN
FIELDCOMPOSITE
R u n in vacuum t o 1910° F. (1015' C.!; held 10 minutes ( t o t a l time 100 minutes): 5.5 per cent volatile matter 9.8 per cent ash; harometer, 700 mm: room temperature 24' C. (75' F:J. 40 grams coal t a k e n , volume of gas i t 700 mm. and 24O C. (7.5' F.),2 . 2 pe'r cent, loss of weight, 2.6 per c e n t ; of volume, 20.8; specific gravity before,'l.556; a f t e r , 1.715. Screen .inalysis-------. Before .Ifter 93 % ._ 100 10 X 14 65.5 ... 1 4 X 16 33.2 0.5 16 X 20 . . . . 0.8 20 x 0 Total 100 100.0
7 -
Mesh
-
Gas .Inalysia, Per C e n t
GO? Oi H?
CO CHr u ..
1.9 1 5 83.5 5 0 5 4
2.7
Comments on Analyses The anthracite samples used in this study were a part of a collection made by the U. S.Bureau of Mines in cooperation nith the Anthracite Institute. All analyses were made by the Bureau of Xines and are used here with their permission. .4n attempt was made to select thirty-six sample. representative of anthracites from the whole area. The average of breaker coal analyses shown in Table I' is very close to the average of the face samples taken in the mines and used in this study, as shown in Table VI. Therefore, the average gas composition and yield from prepared coal probably would be about the same as the average of Table VII. The analyses in Table I1 are divided into three groups arbitrarily chosen to represent l o w , medium-, and high-
INDUSTRIAI. AND ENGIYEEHING CHEMISTRY
1376
TABLE
v.
PREPARED SIZES FROM NINETEEN COLLIERIES IN ANTHnnCrTE FIELDS, ON h DnY cO.kL I$hSIs
ANALYSES OF
AVERAoE
. . vuiatiie maLtei,
c,
V(JI.. 27, NO. 11
75
5.0 85.5 9.5 0.7 133.614 2.789
Fixed 70 inb. % s.. % .. Rest vslue, B. t . u . SoiLening temp., * Y.
9.9 0.7
0.7
133,553
13.395 2,826
2.812
" Prum eig1ttesn coiiieriea.
5 .3 x2.5 12.2
5.0 84.3 10.7
5.0 85.1
81.0 13.7
1a.s
0.7
0.7
12.926 2,847
12,895 2,840
0.7 18.168
2,848
5.2 80.9 13.9 0.7
5.3
5.2 X I .:3
DIFFEWEiYT
5.1 n2.9 11 9 0.7 13,'201 2.829
12.85R 2,855
e Bran, BeVBntee" euilieries.
'l'.kBLE
VI.
PEoXrMATB ANALYSESOF FACESAXPLES FGoM
Vola-
No.
tile 'Mstter
097
2.9 8.0
Sample
% as7
Pired G %
Aeh %
lieat veiue H . 1. tA.
87.8 r2.1 90.8
9.3 4.9 0.1 7.0
I:UID I~.ISO 13,930 15.870
sample
'remp.
No.
8
70 0.6
661
2~90
0.7 0.5 0.5
485 019 654
471 890 970
5.8
89.8 87.8
8.9
18,630
2700
0.5
395 085 405 076 073
3.6 3.7
m.7
12.7 9.0 12.3
ia.010 13.180 13.100
2730 2890 2880 2600 2580
1.1
80.7 a.8
15.5
84.5
11.4
12,500 13,140
4.1 4.1 4.4 4.0 4.7
86.0 87.1
9.9 8.8 4.7
13,430
943 971
4.8
84.4
4.9
87.6
004 892 665
5.1
88.8
7.5 0.1
5.2
86.5
8.3
044 488 948
533 662
5.1
80.5
90.9 88.0
88.3
29s0
0.7
%
2910 2830
0.9 0.7
% 11.3 10.4
5.0
85.4
13.760 13,860
10.2
2770 2960
1.6
13,500
10.8
13,460 12.800
2982
0.0 6.1
83.4 80.4 80.6
2300
13.010
2260
0.9 1.1 2.0 0.8 0.8
9.0
14.6 13.3
2510
5.4 7.0
14,420 14,110
2900 2490
0.5
525
13.7
13.090
2570
731
6.5 0.6
79.8
0.5
BB7
7.3
9.0 10.6
13.540
0.9 0.7
1.1
2870 2982
0.9
153
150
Av.
2.0
14.8
6.4
890
5
79.5 84.0
86.6
3020
83.8
7.0 8.1 8.5
82.1 83.1 84.5 78.2
5.1
85.3
7.4
13.600 13.760 14.m
9.0
13.556
10.3
18.100
13.3
2690 2740
2430 2180
2100 2766
1.0
2.5
1.0 0.9 0.6
0.0 0.5 0.9
0.9
0.7
300L 2980
13.730
'P.
% W.4 84.3
88.3
13270 14,010
B.L.u. 13.100 13,370
% 5.3 5.3
0.3
10.8
14,110
Vaiuo Hest
501
0.6
14:OJO
Ash
658
9.4
ASB B.4818
Ash Sp!teaing lemp.
0.0
0.5
2830 2900 2940 2950 2900
6.0
c
5.7 5.8
J34
0.8
14,460 14,130 13,450
13,580
0.8
85.9
2790
Fired
tile Matter
x'.
3.2
3.9 4.0 4.1
vola-
2950
3.1
3.3
FlELuS I N PEXNSYLVANLA ANTERACITE REoIoN, D H Y
Soitanrug
100 401
071
hLL
Ash
0.6 ~
TABLEVII. AvEnAoEs OF ,Voi*tiIe matter ,~
~
Ilr . ..
c
Nn
Or ~-~p,'erce,i(~~.~~~
2.0 85.6 x5.8 5.8 2.6 2.9 RZ.6 7.6 Av. 2.5 83.8 Ciao "0I""Xe eorreoced t" 44.5 ~~~~~~~
ANALYSES AND VOLATILE
Dry Coal A " s l y a e 8 - . - - - - - . - - -
3.8
0
ULTIIMhTE
-
0.8 0.9
1.4
1.1
2.1 2.5
0.9
2.0
S
.-~.
0.6 1.2
9.0
0.7 O.S
Asli
MAWEB
Vulatile Matter Gas >I& "01. (irams CC. 7.003 0.4
-.-.
0.7
8.632
This work was undertaken with the purpose of increasing our knuwledge of the volatile matter of Pennsylvania anthracite. Tho information brought out may assist in the support of various theories as to the origin, oomposition, and combustion characteristics of anthracite. Such discussion, however, is heyorid the scope of this paper. The information has been used in the design of a reliable slide rule for the determination of the R. t. u. content of anthracite based on dry volatile matter and dry ash. The possibility of making commercial hydrogen from anthracite has been suggested. Rough calculations indicate that a good-welding hydrogen and possibly a hydrogen for hydrogenation can be made at a cost lower than that of
2.3 1.5
10.008
Conclusion
1.8
2.2 2.0
1.0
volatile anthracite. This arrangement places inore like coals in the m n e group than would be possible by listing the analyses according to geographiaal fields. Table VI1 shows that the total yield of gas increases u4th increase of volatile matter and that the niethane content of the gas increases in the same manner. The rather constant hyrlnigen content, regardless of increasing volatile matter and regardless of increasing hydrogen in the ultimate analyses, is not so logical. No explanation is offered for the marked decrease of the nitrogen of the gas with the increase of volatile matter and increase uf nitrogen in the ultimate analyses.
~~~
1.1
0.6
~
~
0 1
2.0
9.9
~~~
..
COn
8.811
10.2 9.9
gr"'L18.
ANALYSESFOH TUE
~
_
~~~~
_
~..
1.0
.
' h I K E E VOLATILE
Cia,? inslyaos
Ni -I'm crrit 8 3
83.2
84.2
83.0 85.7 ~~
4.8 2.6 2.0 3.1
..
Gnouw
- .
Glrs
CO
ClL
4.2
.
Volume
cu. f w o n
8.7
4.1 4.1
6.0 7.1
5041 6342 7258
4.1
5.0
0233
~~~~~~
~
.. .- -
electrolytic hydrogon. If the gas can be remuved witliout weakening tho coal or inaterially irnpairirrg its usefulness a8 a domest,ic fuel, it will provide a soiirce of hydrogen a t a cost lower than that of any known mettiod (if production. nEceivkoApril 25, 1ws. Presented ns p w t of the .Antlireaita Sympuaiuni before the Division of Gas snd Fuel Clmmintry at the 89th Meeting of t l i C Ameriesri Cireinionl Sooiety, New Y v i k N. Y . . h i d 22 to 26, 3935.
-._-. .__ .
