"Y drogenation of the Banded FUSAIN
To obtain information on the behavior of the banded constituents of coal during liquefaction by hydrogenation, the hurcau has undrrtaken to study the relation between coal petrography and hydrogenation. This paper presents the results obtained M far on the hydrogenation characteristics of fusain; data on anthraxylons, attrital matter, and spores will he given in later papers. Theexperiments weremade a t 400', 415', 0~430'C. with a beginning (cold) hydrogen pressure of 1,OOO pounds per square inch in the presence of tetrahydmnaphthalene and stannous sulfide. Of the seven fuwains thus far hydrogenated, appreeiable liquefaction was effected in all instanecq, and two samples were liquefied to the extent of about 25 per cent. merefore, the view that fusain is completely inert is unsound. Liquefaotion yields oan be predicted roughly from the proximate and ultimate analyses. Since hydrogenation proceeded readily to a certain point and thou hecame difficult, it is believed that fusain comprises two main components, one of which is readily hydrogenatod. The hydrogenation residues had higher eorhonhydrogen ratios hut less translucent matter than the original fusains. If the more resistant component of fusain is not appreciably hydrogenated, these residues should he very similar to, or identical with, the inert component, fusinite. The oils and pitohes produced were similar to those obtained previously by hydrogenation of a Pittsburgh seam coal.
C. €1. FISHER, GEORGE C. SPRUNK, ABNER EISNER, LOYAL CLARKE, A N D f I . 11. STORCH Central Experiment Station, 17. S. Bureau of M i n q Pittsburgh, Pa.
elareins, which were hydrogenated in good yield, are well characterized by both Seyler's formula and Figure 1. The two durains differed tremendously in hydrogenation yield (Table I); it is unfortunate that analyses are not available for both samples. On hydrogenation the two fusains also gave considerably different yields, but in both instances the yields were low; this agreed with the prevailing opinion (17,29) that fusain is diffcult to hydrogenate. From the position of the more inert sample (fusain 1, Table I) in Figure 1 a t point E, it appears likely that other fusains would give higher yields on hydrogenation (most fusains contain more volatile matter and have lower carbon-hydrogen ratios). This prediction is borne out by the results obtained with fusain 2, Table I, and by the present work. Bakes (3)observed that bright coals, which contain large amounts of vitrain and clarain, react more readily with hydrogen and give higher liquefaction yields than do dull coals, which are composed largely of durain. This is in agreement with the claim of Gordon (18) and with the results of Petrick, Gaigher, and Groeuewoud (19)who hydrogenated several South African bright and dull coals. According to Francis (IS), vitrains, clarains, resins, hydrocarbons, and plant skins are readily hydrogenated, hut fusains and durains, which contain large proportions of opaque matter, arc unsuitable.
LTHOUGH numerous investigations have been devoted to coal hydrogenation (S6), little attention has been given to hydrogenation of the handed constituents and the relation between ease of hydrogenation and petrography. Furthermore, the little information available is c o f i c t i n a and has led to few deiinite conclusions. The earliest and most extensive published studies of hydrogenation of coal constituents were made in England (14, i6,83). These resuits are descrihed most conveniently with their petrographic nomenclature, although the Bureau of Mines nomenclature (26') is used later in discussing the authors' experiments. The vitrain and clarain samples were found to hydrogenate satisfactorily with one exception. Since the ultimate and proximate analyses of the vitrain sample giving a poor yield (vitrain 1 in Table I) do not satisfy the criterion of vitrain proposed hy Seyler (SZ?),
A
volatile matter
=
10.6113
- 1.24C + 84.15
or fall on the vitrain fine (9) in Figure 1 (constructed from data in the Iitersture, S,4,5,7,8, 18,8O,dl, 28,84,67), the quality of this vitrain om be questioned. .It is intemting that the
Dsscommuous HYDROGENATION EQUIPMBNT (OUTSXDEOF BARRICMB) UBEDEN F n s m EXPERIXENT~ 190
Constituents of Coal - .. I
1,200-cc. converter, the air was removed by flushing with nitrogen and hydrogen, and hydrogen was introduced until the pressure a t room temperature was 1,000pounds per square inch (70.3 kg. per sq. cm.). The time and temperatures are given in Table IV. When the hydrogenation lasted over 3 hours, the stepwise procedure previously described (IO) was employed. Experiments made with Bruceton coal show that the conditions employed in the present work are sufficiently drastic to obtain virtually maximum liquefaction. Stannous sulfide was not added to the charge in experiment 1A (Table IV), but the walls of the converter (18-8 stainless steel) probably had a catalytic effect (6). Tables I1 and I11 give analyses of the fusains hydrogenated and of their parent coals. The fusains were separated by hand from 0.3-3 cm. layers in the coal, and great care was taken to exclude other material. The apparent rank of these fusains is not always proportional to the rank of the coal. Before hydrogenation, sample 4 (Sharon fusain) was pulverized to pass a 60-mesh sieve; the other samples were ground to 200-mesh. The charge in experiment 1D consisted of 100 grams tetrahydronaphthalene, 0.4 gram stannous sulfide, 67 grams residue from experiment l B , and 33 grams residue from 1A; the time of hydrogenation was 6 hours (two 3-hour periods). The charge (hydrogenated for 3 hours) in experiment 5B was 153.6 grams tetrahydronaphthalene, 0.15 gram stannous sulfide, and 46.4 grams of the residue obtained in experiment 5.4. The original plan was to hydrogenate Sharon fusain for two 3-hour periods in experiment 4A (Table IV). A leak developed in the second period, and the experiment was terminated a t the end of 1 hour, making the total time of hydrogenation 4 hours. Because of temporary difficulty with equipment, close control of the temperature could not be maintained throughout experiment 4B. The centrifuge residues were washed six to eight times with acetone. The firfit three acetone washings and the centrifuged oil were distilled; the fraction collected from 150' C. t o the distillation end point was considered recovered vehicle and analyzed for tar acids, bases, and neutral-oil components (Table XI). The distillation residues were viscous oils or pitches (Table V). The acetone-insoluble residues were extracted in a Soxhlet apparatus with benzene for a t least 24 hours until the extract was colorless. Since small manipulative losses of these residues must have taken place, the liquefaction yields of Table IV, calculated from residue yields, are probably about 3 per cent high.
Hovers, Koopmans, and Pieters (16) hydrogenated a coal rich in vitrain and claimed that only the vitrain portion had been attacked readily, whereas Wright and Gauger (29),using American coals, believed that all banded constituents other than fusain were completely liquefied. In a later paper (28) these authors reported that another constituent, probably opaque attritus, offered some resistance to hydrogenation. Fisher and Eisner (IO) showed that some constituent of a Pittsburgh-bed coal other than fusain is difficult to hydrogenate. Much of the lack of agreement in hydrogenation of coal constituents can be attributed to differences in experimental conditions, technique, and the quality and rank of the constituents used.
TABLEI. HYDROGENATION OF BANDED CONSTITUENTS (ENGLISH INVESTIGATIONS) Constituent Vitrain 1
Volatile matter,
%
41.1
2 3
Clarain 1 2
..
79.83
.. ..
13.9
..
... ...
5.74
39.1 35.4
81.25 84.19
5.27 5.47
15.4 15.4
..
3 Durain 1 2 Fusain 1 2
Dry, Ash-Free Basis Car- Hydrobon, gen, Ratio % % C/H
34.5
.. 6.1 ..
... 82.44 ...
5.08
94.96
1.99
...
*. *.
..
Conversion,
Yo
.. .. 16.2 .. 47.5 ..
Reference
51.2 78.1 78.2 83.6 82.9 62.5
($3) (9%) (16)
Negligible Negligible
(14,B) (16)
26.7
The present paper describes part of the work on the hydrogenation of coal macroconstituents a t the Bureau of Mines, where such work has long been attractive because of the pioneer work of Reinhardt Thiessen and his associates on the petrography of coal. Only the results obtained with fusain (7, 24) are reported here; data on the hydrogenation of anthraxylon, opaque and translucent attritus, and spores have been obtained and will be presented in later papers.
Hydrogenation Procedure The hydrogenation equipment and procedure previously described (10) were employed with few changes. Unless otherwise indicated, 100 grams fusain, 100 grams tetrahydronaphthalene, and 1 gram stannous sulfide were placed in the
TABLE11. ANALYSESOF FUSAINS -Proximate,
Per Cent by Weigbt-Dry, Aab-FreeBasis -As-ReceivedCalcd. c-Vola- Fixed Vola- volaH, Mois- tile cartile tile ture matter bon Ash matter matter1 %
No. State 1 Penna. 2 Penna.
County Allegheny Fayette
Bed Pittsburgh LowerKittanning
3 4
Penna. Ohio
Allegheny Jackson
Upper Freeport Sharon No. 1
5
W. Va.
Raleigh
Beokley
6
Ky.
Pike
7
Ohio
Jackson
Warfield or Pond M~jestio Creek Sharon Sun
6
Calculated volatile matter
-
Mine Bruceton Indian Creek No. 1 Wildwood JacksonIron& Steel Co. Winding Gulf No.
1
0.6 0.5
13.8 77.2 9.1 8 4 . 6
8.4 5.8
0 . 4 13.8 72.8 1 . 9 6 . 9 87.7
-
Ultimate (Dry, Ash-Free Basis) Avail- Cnlorifio N, 0, S, C/H able value % % % % ratio Hh G.-cal:
C,
15.2 10.9 9.7 11.5
2 . 8 92.6 0 . 4 3 . 7 0 . 5 33.1 2 . 2 2 . 9 93.0 0 , s 0 . 6 3.0 32.1 2.7
8,261 8,461
13.0 3.5
15.9 7.3
12.2 13 6
3 . 0 92.6 0.6 0 . 3 3 . 6 30.9 2 . 8 3 . 1 89.5 0 . 7 6 . 4 0 . 3 28.9 2 . 1
8,417
14.1
3.3
2.9
8,606
10.1 86.2
3.3
105
0.5
14.5 78.1
6.9
15.6 14.4
3 . 3 92.0 0 . 6 3.7
0 . 4 27.9
2.7
8,361
1.6
17.3 74.3
6.8
18.9 17.2
3 . 5 88.1
1 . 9 25.2 2.6
8,139
* + 2.3 (citation 9 ) .
b
Available hydrogen = % ' H -
191
-3
93.5 0 . 5 2 . 4 0 . 3 28.3
...
0.4
%W
0.7 5.8
(T),
INDUSTRIAL AND ENGINEERING CHEMISTRY
192
VOL. 31. NO. 2
Liquefaction Data COALS TABLE 111. ANALYSES OF PARENT -As-ReceivedCoal Mois- Volatile Fixed Volatile No.a ture matter aarbon Ash matter H r % by weight 1.6 35.7 56.4 2.8 25.6 67.4 2.8 36.1 54.2 10.7 34.8 49.6 2.7 18.0 75.6 59.0 3.0 33.2 9.9 35.1 47.4
Dry, Ash-Free Basis
I
a
C
N
S
0
.
Calorific C/H value ratio G.-cal.
15.0 17.0 14.5 15.4 19.3 15.7 15.2
Table I1 gives source of coals.
TABI,EIV. LIQUEFACTION-YIELD DATA Experiment No.
Tem-Productspera- Total Li uids, ture Time a%ds Gases Loss C. Hours f f r a m s fframs Grama 1.0 8.2 3 192.1 1 410 1Ab 3 194 1.6 6.2 400 1 18 6 180.2 4.8 400 IC 9 188.8 About 6 400 1D 3 192.8 2.4 6:s 2 430 2 3.0 10.5 3 189 430 3 3 4 .. 400 4A 4 415 About 6 183:7 4B 4 3:4 6:2 3 192.4 430 56 6 194.3 5B 430 3 191.1 i:6 9:s 430 6 6 3 194 430 3.3 5.3 7 7 3 191.7 5.5 5.8 Il(10) Bruoeton 400 coal 11.4 7.1 6 186.5 H2(10) Bruaeton 416 coal
from. LiqueCentn- faction fuge Yielda
%
%
184 169 182 182 175 165 179
16 18 17 13 23 30 3 6
188 178 177 174.8
20 14 78
9.8 11.0 15.6 15.1 11.7 19.6 26.3 27.2 10.4 18.7 15.7 24,4 89.4
176.9
84
92.9
185
..
!
Oil
Oil Centrifuged Grams
Fusain Used
..
...
!
66d
Dry ash-free basis. No &talyst used in this experiment. Resistant residue (100 grams) from experiments l A and 1B was hydrogenated further for two 3-hour periods. d Resistant residue (46.4 grams) from experiment 5A was hydrogenated in presence of 158.6 grams vehicle and 0.15 gram stannous sulfide. 0
b
c
TlBLE
No.
Yielda
1A
8.8 9.3 7.3
% 1B
1c
1D 2 3 44 4B 58 6 7 a
8:5 11.5 9.0 8.5 8.5 10.8 14.7
H
C
% 7.3 7.3 7.7 7.9 6.8 8.1 7.6 8.3 6.9 7.7 7.5
v.
N
PITCHES
0
S
2.6 2.6 0.4 1.3 1.7 1.6 0.4 0.9 0.6 1.4 2.6
0.3 0.2 0.1 0.1 0.4
C/H Available Ratio H
bg weigh-
88.8 89.0 91.5 90.2 90.3 89.4 91.6 90.3 91.5 89.9 88.8
1.0 0.9 0.3 0.5 0.8 0.8
0.3 0.5 0.8
0.9 1.0
0.1
0.1 0 0.2 0.1 0.1
12.2 12.2 11.9 11.4 13.3
6.8 6.8 7.6 7.6 6.4 7.7 7.5
11.0
12.1 10.9 13.3 11.7 11.8
8.1
6.6 7.3 7.0
Calorific Vdue G.-cal. 9,056 9,406 9,794 9,630 9,360 9,661 9,767 9,772 9,455 9,555 9,471
Dry, ash-free basis.
OF INSOLUBLE RESIDUES TABLEVI. COMPOSITION
-Insol.
ResiduCalcd. from ash No. Solvent“ Found oontent Grams Grams 91.1 94.3 A 1A 91.1 93.2 B 1B A 91 ... B 100 86.8 87.8 1C A 87.3 90.3 B 1D A 87.3 87.8 B 87.3 88.6 2 B 90 88.4 3 B 84.1 95.2 4A A 76.1 77.6 B 76.1 77.6 4B A 77.0 83.4 B 75.3 83.4 54 A 94.1 91.5 B 91.0 87.8 5B A 83.W 74.2 6 B 86.5 90.8 7 B 78.6 78.8
...
--
C
i:4 ...
84:4
6:3
i:i
0:5
2.4
83:s
0:Z
3:6
01%
2.3
83:6
b:Z
3:i
0:4 ’
2.4 2.4 .2.3
83:2 86.1 80.0
0:2
3:O 1.2 0.2
0:6 2.2 2.4
2.8
88:l
013
2:f
0:3
2:9
8715
0:5
315
0:2
2.9 3.0 2.8 3.0
8911 87.7 85.0 81.9
0:4
2:3
0:4
0:4 0.5
215 3.2
0:6
...
... . ..
...
N
0
8
Ash
Volatile Matterb
8.9 9.0
14.3 14.7
914 10 7 10:4 10.7 10.6 7.7 14.7 5.8 5.8 5.4 5.4 4.7 4.9
1?::’6 14.8 14.4 16.3 16.0 9.4 17.6 10.4 10.9 11.7 11.6 13.5 11.1 10.9 14.4 17.3
%
% bv weight (dw)-------
0.4 0.4
b Dry, !sh-free basis. Calculated on the basis of 100 grams fusain.
a A = acetone; B = benzene. c
H
1.5
5.8
8.7 9.9
Table IV shows that the fusain samples were liquefied to an extent that is astonishing (15 to 27 per cent) in view of the widely held opinion that fusain is almost completelyresistant to hydrogenation. Of the nine fusains thus far hydrogenated (Tables I and IV), appreciable liquefaction was effected with one exception, and three samples gave yields as high as about 25 per cent. The one fusain that offered most resistance to hydrogenation has a high carbon-hydrogen ratio and a very low content of volatile matter; from its position in Figure 1 this fusain should be most difficult to hydrogenate. Although positive conclusions cannot be formulated until more data are available, the foregoing facts indicate t h a t appreciable liquefaction of most fusains can be expected. Therefore, the view that fusain is completely inert and the practice of calculating hydrogenation yields on a fusain-free basis are unsound. The degree of liquefaction of fusains caused by hydrogenation can be predicted roughly (Figure 2 ) by properties such as carbon and hydrogen contents, carbonhydrogen ratio, volatile-matter content, and position on the upper line in Figure 1. From the results thus far available it appears that the relative ease of liquefaction of fusains can be predicted better from the carbon-hydrogenratio and hydrogen content than from the volatile-matter content. Data obtained previously (10) with a bright coal under similar conditions are given in Table I for comparison. It is significant that liquefaction under the conditions used in the present work proceeded readily to a certain point and then became difficult; this probably suggests that fusain is composed of two main constituents that differ greatly in their amenability to hydrogenation. From petrographic and other work Seyler (29) concluded that fusain is composed of two fundamentally different components which he termed “fusinite” and “vitrinite.” Fusinite, the main component, is opaque and is undoubtedly the component resistant to hydrogenation. Vitrinite, similar to vitrain in reactivity and volatile-matter content, is the component liquefied by hydrogenation. The nature and rank of the vitrinite, as well as the proportion, undoubtedly affect the hydrogenation of fusain. If the vitrinite is vitrain (or anthraxylon) of suitable rank, its hydrogenation and removal from the fusinite should be readily accomplished. Liquefaction of the vitrinite should be more difficult when it is composed of high-rank anthraxylon, opaque matter, or similar intermediate material. For some unknown reason there was considerable difference in the extent of hydrogenation of the vehicle in the
FEBRUARY, 1939
INDUSTRIAL AND ENGINEERING CHEMISTRY
Bruceton and Sharon fusain experiments. The differences in final (cold) pressures, gas volumes, hydrogen absorbed, specific gravity, and saturated hydrocarbon content of the distillates indicate that the vehicle was attacked appreciably in experiment 1C and possibly in experiments 4A and 4B. It is interesting that liquefaction of Bruceton fusain (experiment 1A) was nearly as great in the absence of catalyst. However, the presence of stannous sulfide caused a slight increase in liquefaction, the consumption of more hydrogen (Table X), and the formation of larger amounts of methane and ammonia (Table IX) ,
Nature of Products
193
TABLEVII. ULTIMATE ANALYSESOF INSOLUBLE RESIDUES BASIS) (DRY,ASH-FREE NO.
K %
%
%
%
%
1A IB 1c 1D 2 3 4A 4B 5A 6 7
2.6 2.6 2.5 2.7 2.6 2.6 2.9 3.0 3.1 3.0 3.3 4.9 4.8 4.8
92.7 93.2 94.3 93.8 93.6 94.3 95.4 93.5 94.1 94.2 91.7 92.5 92.5 92.0
0.3 0.2 0.2 0.2 0.4 0.4 0.3 0.5 0.4 0.5 0.6 1.7 1.9 2.2
4.1 3.7 2.7 3.1 3.0 2.3 1.1 2.8 2.1 2.0 4.1 0 2 0.1 0.3
0.3 0.3 0.3 0.2 0.4 0.4 0.3 0.2 0.3 0.3 0.3 0.7 0.7 0.7
L4 a
I4a H4"
C
N
--
0
S
C/H Ratio 35.6 35,9 37.7 34.8 36.0 36.3 32.9 30.8 30.3 31.4 27.8 18.9 19.3 19.2
Table V describes the composition of the pitches and viscous Tb 2 23 95.9 1.87 ... 43 0 oils that remained after the centrifuged oils had been disa Residues from hydrogenation of bright coal. (10). b Seyler's fusinite ($9). tilled to about 215' c. to remove the vehicle, Probably the analyses were affected by the fact that it was difficult to distill the last traces of vehicle from the pitches obtained from the fusains in low yield. As was the case with hydrogenation having high carbon-hydrogen ratios and a low content of volapitches obtained in previous work (IO), the calorific values tile matter, are not necessarily fusinite or similar in composiwere proportional to the carbon-hydrogen ratios, hydrogen tion. The composition of fusinite estimated by Seyler (28) content, and available hydrogen. In all instances the caris given for comparison ( T in Table VI1 and Figure 1). bon-hydrogen ratios were lower than those of the original Analyses for sulfur forms made by the modified method of fusains and were similar to the carbon-hydrogen ratios of Abernethy, Cooper, and Tarpley ( I ) show that sulfide and orpitches prepared from a column sample of Bruceton coal (IO). ganic sulfur predominate in the residues obtained by hydrogenating fusain (Table VIII). It is important to determine The composition of the insoluble residues (Tables VI and sulfur forms in hydrogenation residues by a modified method, VII) is of extreme interest. The residues are the chief products, and if hydrogenation of the inert component of fusain (fusinite) can be excluded, their composition should approach that of pure fusain or fusinite. Although the possibility of hydrogenation of the fusinite cannot be definitely excluded, extensive hydrogenation appears unlikely because the carbon-hydrogen ratios of the residues are higher than those of the original fusain samples. If hydrogenation and liquefaction of the fusinite are negligible, hydrogenation should provide a new and important method for estimating and isolating fusinite. In this connection it is interesting that the resistant residues are more similar in volatile-matter content and ultimate composition than are the original fusains. W h e t h e r or n o t t h e analyses of the fusain residues in Table VI1 represent fusinite, they are quite different from the analyses of the residues obtained from opaque att r i t u s (11) a n d from a column sample of Bruceton coal (IO). This indicates VOLATILE MATTER, PERCENT that the organic residues obtained by hydrogenating FIGURE1. RELATION BETWEEN VOLATILE MATTERAND CARBON-HYDROGEN RATIOSOF coal, although similar in BANDED CONSTITUENTS OF COAL(DRY,ABH-FREE BASIS)
FIouRm 2.
i
1
VOL.31, NO. 2
INDUSTRIAL AND ENGINEERING CHEMISTRY
194
RELATION BETWPlEN YIELDS AND PROPERTIES OB
FosfdNs
since the standard method gives high results for organic sulfur. The insoluble residues are similar in appearance to the original fusains. There is no detectable difference under the microscope by reflected light. However, with transmitted light it was possible microscopically to distinguish between the residues and fusains by the difference in their content of translucent matter. Although the fusains contained about 10 per cent, the residues contained only traces of translucent matter. This observation also agrees with the view that fusain is comprised of two main components, one of which is liquefied by hydrogenation.
The volatile matter in hydrogenation residues (10, 11) is roughly proportional to their ash content, owing, probably, to the presence of volatile inorganic matter. It is noteworthy that several of the residues contain more volatile matter than the parent fusains. For example, hydrogenation of Sharon fusain (volatile matter, 7.3 per cent) gave an insoluble residue containing about 11 per cent volatile matter. Unfortunately, the presence of volatile mineral matter (1, 11) makes it very difficult to calculate the composition of the organic material in the residues. Parr's well-known method of converting analyses to the mineral-matter-free basis cannot be used; in some instances the total thus obtained is considerably greater than 100. Table I X gives the composition of the hydrogenation gases obtained in the last 3 hours of each experiment. Several trends observed in previous stepwise hydrogenations (10) were noted in the present work. With minor exceptions the yields of carbon dioxide, methane, ethane, and hydrogen sulfide decreased as the hydrogenation progressed, and the yield of ammonia increased. Only traces of carbon monoxide and unsaturated hydrocarbons were found. As was to be 'expected, the fusains absorbed less hydrogen than the Bruceton coal previously studied (10). The small amounts of nitrogen consistently indicated in the hydrogenation gases are not included in Table IX. Table X gives the gas volumes, hydrogen consumed, and the maximum and final (cold) pressures. The centrifuged oil was distilled to recover the vehicle; the fraction collected from 150' to about 215' C. was analyzed by the procedure previously described (10) to obtain the data in Table XI. Apparently the vehicle was little changed during hydrogenation. In spite of shortcomings in the analytical method, the data indicate that the yields of tar acids are proportional to the total liquefaction yields, All the neutral oils contained 2 to 3 per cent olefins, as determined by a sulfuric acid extraction method. Small quantities of saturates were found in some of the distillates.
,
TABLE X. HYDROGEN ABSORPTION, MAXIMUM PRESSCRE, AND PRESSURE DROP No. 1A
1B
IC
ID 2 3 4A
i TABLE VIII. No. 1A 1B
FORMS IN BENZENE-INSOLUBLE RESIDUES (PER CENTBY WEIGHT)
SULFUR
Sulfide 0.118 0.230 0.285
ID
Pyritio
Sulfate 0.032 0.048 0.040
Organic 0.283 0.310 0.169
0.033 0.032 0.041
1
4B SA 58 6 7
Hydrogenation Hydrogen Period Consumed
Hours
Qrams
0-3 0-3 0-3 3-6 3-6 6-9 0-3 0-3 0-3 8-4 0-3 3-6 0-3 3-6 0-3 0-3
0.5 0.75 110 016 0.94 1.47
....
2:o 0.8 1:57 1.59
Pressure Maximum Pressure Drop Lb./aq. in. Ko./sq. cm. KgJsq. em. 2520 177.3 1.41 2500 175.8 6.62 2630 185.0 14.07 2720 191.3 10.55 2580 181.5 0 2640 185.7 0.70 2600 182.8 7.73 2400 168.8 14.77 2840 199.8 21.10 2860 201.1 2660 i:i4 187.0 191.3 2720 11.26 2700 189.0 2.81 2670 187.8 1.41 2200 154.7 19.69 2540 178.7 16.88
Volume at 00 c. Liters 64.0 60.6 53.3 47.6 62:9 67.2 52.9 46.7 64:4 51.2 60.3 70.2 49.8 51.5
TABLEXI. COMPOSITION OF DISTILLATES TABLE IX. COMPOSITION OF GASESFROM FINAL STAGE OF HYDROGENATION EXPERIMENTS (GRAMS) No.
1A 1B IC 1D
2 3 4B" 6A
6B
6
7 0
HZ 5.72 5.2 4.0 5.62 5.00 4.55 5.43 5.01 5.19 4.39 4.39
GO 0 0
0 0
0.1 0.2 0.1 0 0 0
0.1
CiH4 0 0 0 0 0.1 0 0 0 0 0 0
CHI 0.2 0.9 0.8 0 0.6 0.7 0.6 0.1 0.1 0.6 1.3
CiHa 0.6 0.6
2.3 0.4 1.1 1.6 2.4 3.0 3.2 0.6 1.2
COa 0.21 0.13 0.03 0.07 0.09 0.09 0.11 0.10 0.10 0.42 0.48
HpS 0.017 0.010 0.002 0.002 0.361 0.443 0.002 0.002 0.003 0.003 0.250
About 15 per aent of gas esoaped at end of experiment.
NHI 0 0.004 0.033 0.004 0.001 0.006
0.007 0,007 0.002 0.002 0.002
Distn. --Distillate Neutral OilEnd Sp. gr. Tar SP.p. No. Point Amount (15.6' C.) bases Phenols (15.6 C.) Saturates c. co. % b y uol. % by vol. 91 0.7 0.1 0.967 1A 0 0.2 0.1 0.967 91 0 1AB 0,947 0.1 73 0.4 1AC 1.5 0,966 93 0.4 0 1AD 0 0.964 96 0 2 0.3 o:i 0.965 0.1 95 3 0.958 0.4 0.7 74 0.9 4A 0.964 0 1.2 84 4B 1.2 0.968 0.2 88 0:sss 0.3 0 6A 0.6 164" 0.973 0 5B o:ii9 94 0.969 0.3 0.6 0.2 6 0.971 0 0.96Q 89 1.4 7 0.7 a 153.6 grams tetrahydronaphthalene used in this experiment. I
...
...
FEBRUARY, 1939
INDUSTRIAL AND ENGINEERING CHEMISTRY
Acknowledgment The authors are indebted to H. hL Cooper, F. R. Abernethy7 and Other members Of the Section for analyses of the coals, fUSainS, insoluble residues, and Pitches.
Literature Cited AbernethY, F.9 Cooper, M.1 and TarPleY, E * c.2 IN=. ENC.CHEM.,Anal. Ed., 10, 389 (1938). Bakes, W. E.1 DePt. sei. Ind. Research, Tech. Paper 37 (1933). Beel, A. E., Fuel, 3, 390 (1924). Bone, A.7 and Bard, B. J. A.1 PrOC. Roy. SOC. (London), 162A, 495 (1937). Boosere, M. de, Fuel, 5, 522 (1926). British Fuel Research Lab., Rept. for Year Ended March 31, 1937. Davis, J. D., Fuel, 8, 375 (1929). Finn, C. P., Trans. Inst. Mining Engr8. (London), 80, 283 (1930-31). Fisher, C. H., IND. ENG. CHEM.,Anal. Ed., 10, 374 (1938). Fisher, C. H., and Eisner, A., IND. ENO.CHEM.,29,1371 (1937). Fisher, C. H., Sprunk, G. C., Eisner, Abner, Clarke, Loyal, and Storoh, H. H., to be published. Francis, W., J . Inst. Fuel, 6, 301-8 (1933). Gordon, K., Trans. Inst. Mining E n g ~ s .(London), 82 (Pt. 4), 348-63 (1931). Graham, J. G., and Skinner, D. G., J . SOC.Chem. Ind., 48, 129T (1929).
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(15) Horton, L., Williams, F. A., and King, J. G., British Fuel Research Tech. Paper 42 (1935). (16) Hovers, T., Koopmans, H., and Pieters, H. A. J., Fuel, 15, 233 (1936). (17) Legrand, C., and Simonovitch, M., Ibid., 17, 145-60 (1938). (18) Macrae, J. c . , and Wandless, A. M., Ibid., 15. 68 (1936). (19) Petrick, A. J., Gaigher, B., and Groenewoud, P., J . Chent. Met. Minino Soc. S. Africa. 38, 122-4 ( S e d . 1937). (20) Rittmeisier, W., Glkckauf, 64, 624 (1928). (21) Selvig, W. A., and Seaman, H., Bur. Mines, Cooperative Bull. 43 (1929). (22) Seyler, C. A,, Colliery Guardian, 155, 990, 1046, 1087, 1137, 1231 (1937). (23) Shatwell, H. G., and Graham, J. I., Fuel, 4, 25, 75, 127, 252 (1925). (24) Sprunk, G. C., and Thiessen, R., IKD.ENG.CHBM.,27, 446 I1 51. ,-9 -x--, Storch, H. H., Ibid., 29, 1367 (1937). Thiessen, R., and Francis, W., Bur. Mines, Tech. Paper 446 (1929) ; Fuel, 8, 385-405 (1929). Wandless, A. M., and Macrae, J. C., Fuel, 13, 4 (1934). . . Wright, C. C., and Gauger, A. W., Am. Mining Congress, Yearbook, pp. 381-3 (1937). (29) Wright, C. C., and Gauger, A. W., Penna. State Coll., Tech. Paper 31 (Oct., 1936). RECEIVZD September 19, 1938. Presented before the Division of Gas and Fuel Chemistry at the 96th Meeting of the American Chemical Sooiety, Milwaukee, Wis., September 5 to 9, 1938. Published by permieaion of the Director, C.8.Bureau of Mines. (Not subject to oopyright.)
Glacial Acetic Acid in Petroleum Refining Glacial acetic acid has been found to have selective extraction characteristics for the removal of the undesirable materials present in petroleum fractions. It will remove by selective extraction materials which cause smoking in the burning of kerosene, and undesirable constituents in lubricating oil stocks. Experiments toward this end are reported, pilot-plant work is described, and a flow sheet of a plant erected is given.
T
HE use of selective solvents solvent for removhg unsaturated, S. S. BHATNAGAR &VD p. J. WARD for improving the quality naphthenic, and aromatic hydroUniversity of the Punjab, Lahore, India of aetroleum fractions has carbons (11. With intensive treatbecome Lwell-established practice ment, kerosene of the highest quality may be obtained from the stocks examined, and very in the refining industry during recent years. The first high yields of oils of moderate quality have been demonprocess Lo be adopted was that of Edeleanu (4) for prostrated with a relatively small percentage treatment. In the ducing high-grade kerosene from inferior stocks by extyaclatter case the excellent solvent powers of acetic acid for tion with liquid sulfur dioxide. More recently the prinresins and resin-forming compounds will produce an imciples of solvent extraction have been applied to lubricating provement in quality with respect to wick incrustation oil stocks to remove or reduce those constituents which are without excessive loss during treatment. responsible for poor temperature-viscosity characteristics The main and most reliable criterion of kerosene quality and bodies which form gummy and carbonaceous deposits in the cylinders of internal combustion engines. Usually is furnished by the smoke tendency test. The conditions for measuring smoke point have been fully described (8), a single solvent phase is employed such as Chlorex ( I @ , and the maximum flame height without smoke of a kerosene furfuraldehyde (g), or phenol (S),but in some cases a double may be accurately recorded by means of the smoke point solvent scheme is used as in the Duosol (11) or sulfur dioxidelamp used. Subject to other requirements such as viscosity, benzene @)processes. I n the course of an investigation on the properties of volatility, wick incrustation, etc., the determination of smoke various Indian and Burma kerosene fractions, one of the point serves to differentiate clearly between kerosenes of different qualities. writers found that glacial acetic acid is a particularly effective
