THE EFFECT OF OXYGEN AND CARBON DIOXIDE ON 
 THE CARBONIZATION OF COAL 
 
 BY 
 
 FLOYD BEATTY HOBART 
 B. S. University of Illinois, 1920 
 
 THESIS 
 
 Submitted in Partial Fulfillment of the Requirements for the 
 
 Degree of 
 
 MASTER OF SCIENCE 
 
 IN CHEMISTRY 
 IN 
 
 THE GRADUATE SCHOOL 
 , OF THE 
 
 UNIVERSITY OF ILLINOIS 
 
 1921 
 
V2>2.\ 
 
 UNIVERSITY OF ILLINOIS 
 
 THE GRADUATE SCHOOL 
 
 July. 29 , 1 92L 
 
 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY 
 
 SUPERVISION BY Floyd. Bea_tty Hobart.. __ 
 
 ENTITLED The Effect o f O xyge n a nd C arbon Dioxide on 
 
 the Carbonization of Coal . 
 
 BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR 
 
 Recommendation concurred in* 
 
 Committee 
 
 on 
 
 Final Examination* 
 
 ^Required for doctor’s degree but not for master’s 
 
Digitized by the Internet Archive 
 in 2015 
 
 https://archive.org/details/effectofoxygencaOOhoba 
 
This investiation v/as undertaken at the 
 suggestion of Dr. T. E. Layng. He has given 
 valuable advice, help and instruction on all 
 occasions during the investigation and I am 
 deeply indebted to him, not only for his as- 
 sistance in this particular problem, but also, 
 for the deeper appreciation of research that 
 he has inspired, and I wish to sincerely 
 thank him. 
 
 I wish, also, to thank Prof. 3. Vi". Parr 
 for the interest he has shown towards this 
 investigation. 
 

 
 
 
 
 
 
 
 
 
 
 
 
Table of Contents 
 
 pages 
 
 I. Introduction. 
 
 1. nature of the Problem 1 
 
 2. Historical 1 
 
 3. Outline of the Present Investigation.... 8 
 
 II. Experimental. 
 
 1. Apparatus 9 
 
 2. Temperature Control and lie a sure me nt 12 
 
 3. Operation of Apparatus 13 
 
 4. Determination of Products and Analysis.. 14 
 
 5. Types of Coal Used 15 
 
 III. Results. 
 
 1. The Effect of Carbon Dioxide... 16 
 
 2. The Effect of Oxygen 18 
 
 IV. Discussion and Conclusions 32 
 
 V. Summary 36 
 
 VI. Bibliography 37 
 
' 
 
 
 
 
1 . 
 
 THE EFFECT CF OXYGEN AND CARBON LIOXILE 
 ON THE CARBONIZATION OF COAL. 
 
 I. Introduction. 
 
 1. Nature of the Problem: 
 
 This problem is one of a series of closely related problems 
 which are being studied in this laboratory, with a purpose of 
 learning mor6 about the carbonization of coal. Luring previous 
 work it was observed that the gases, obtained from the carboniza- 
 tion of non-coking and poorly coking coals, held large percentages 
 of carbon dioxide. It was thought at the time that this carbon 
 dioxide was responsible, in part at least, for the non-coking of 
 these coals. Accordingly this problem was undertaken as a means 
 of learning whether or not carbon dioxide is responsible for the 
 non-coking of certain coals. After some investigation it was 
 learned that it would be advantageous to study along with the ef- 
 fect of carbon dioxide, the effect of oxygen; as it appeared that 
 the carbon dioxide, formed during carbonization, was a result of 
 oxygen present in the coal. 
 
 2. Historical: 
 
 There is nothing in the literature concerning the effect of 
 
 carbon dioxide on the coking constituents of coal. Anderson and 
 
 1 
 
 Roberts, during tests on a large number of coals to determine the 
 cause of coking in some of them and not in others, "heated these 
 coals (from the Clyde Basin) to a temperature of 500° C. for three 
 hours in an atmosphere of dry carbon dioxide, instead of gaining 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 ' 
 
 
 
 
 
 
 
 
2 . 
 
 in weight as they did when heated in air to between 100“’ and 150' C., 
 they lost in weight. The non-coking coals lost the most and the 
 coking coals the least, that is to say, the humus bodies were even 
 at this temperature beginning to decompose. The same experiment 
 showed that after this treatment the percentage of coke was in- 
 creased (probably fixed carbon is meant, as only three of the coals 
 coked), and that in the feebly-coking coals the power of coking 
 was entirely destroyed, but only impaired in the true coking coals! 
 The authors conclude, n that in all the coals resinoid bodies ex- 
 ist, which can be saponified by caustic potash, and which alone 
 are accountable for the coking of semi-coking coals. In addition 
 to these, in the true coking coals there is a constituent not so 
 easily, if at all, acted on by alkalies, oxidisable in air, but 
 not volatile at 300° C." They find also "that the true coking 
 coals melt in an atmosphere of carbon dioxide at 317 C.", and this 
 they take to be the melting point of the constituent referred to. 
 
 It is evident that Anderson and Roberts saw nothing in the 
 behavior of coals, when in an atmosphere of carbon dioxide, to 
 cause them to believe that carbon dioxide had a deleterious effect 
 
 upon their coking constituents. 
 
 2 
 
 According to Anderson, the first one to investigate the ef- 
 fect of heating coal in air, or in oxygen, was Prof. Richter, who, 
 in 1870, found that coal heated in air absorbed oxygen, and that 
 on further heating the percentage of fixed residue was increased 
 extraordinarily. He also knew that some of the ?as coals resisted 
 the absorption of oxygen for some tine. Anderson investigated 
 the effect of oxygen on Scotch coals with the idea of determining 
 the nature of the coking constituent. He proved the validity of 
 

 
 
 
 
 
 
 
 
 
 
 « 
 
 
 
 
 
 , ’ 
 
 
 
 
 
 
 
3. 
 
 Richter's work, and that the effect of oxygen was a destruction 
 of the coking properties, especially in the weakly-coking coals. 
 
 fhe effect of oxygen, that is in the original combination of 
 the coal and that which has been absorbed by weathering, has pro- 
 bably been noted by every authority who has studied the carboniza- 
 tion of coal since Richter's publication of 1870, and was no doubt 
 noted by some even before this time. The earlier investigation 
 along this line was undertaken with the idea of learning more a- 
 bout spontaneous combustion and v/eathering, and their causes. On- 
 ly recently has the study been carried on to a great extent with 
 
 the effect on coking as the important object. 
 
 3 
 
 White claims, that the coking qualities of coal depend upon 
 the presence of certain gelatinous algae, that those coals which 
 contain the greatest quantity of micro-algae shov; hydrogen and 
 oxygen in almost the same proportion as exists in bitumen, that 
 is, they have the highest hydrogen and lowest oxygen content. He 
 therefore concludes that coals high in volatile matter and whose 
 analysis show sufficiently high bituminization will coke by the 
 ordinary, or bee-hive process, and that the degree of bituminiza- 
 tion in these coals is indicated by the relative excess of hydro- 
 gen as compared with the diminished oxygen in dry coal, expressed 
 by the ratio of hydrogen over oxygen(E:0). 
 
 White examined and compared the results from a large number 
 of American coals, and an examination of his results shows that be- 
 low the highest of the semi-bituminous coals, which are approaching 
 the anthracite stage, those coals with a H:Q ratio, or percentage, 
 of 59 or more, but with one or two exceptions, make coke by the 
 ordinary commercial process. Nearly all of those below 59 and a- 
 

 
 
 
 * • • Um I 
 
 
4 
 
 bove 55, so far as tested, make a coke, and among those with a ra- 
 tio of between 55 and 50 a large percentage make coke. A few of 
 the coals, tested, with a slightly lower, ratio also make coke, 
 but those cokes made from coals with a H:0 ratio of less than 55 
 are usually very poor and apt to be dark and brittle. The best 
 cokes are made from coals in which the H:0 ratios are 60 or more. 
 Other factors need to be considered, the most important being the 
 fixed carbon content. White’s results point to the fact that 
 coals of less than 79 per cent, fixed carbon, on the pure coal ba- 
 sis, will give a true index of their coking qualities on applica- 
 tion of the H:0 ratio. 
 
 In coals of greater than 79 per cent, fixed carbon it is gen- 
 erally possible to produce a coke if the qunatity of carbon in 
 the volatile matter is relatively large. Also, most coals in 
 which the H:0 ratio is high, but which refuse to coke, are distin- 
 guishable by their clearly defined calorific deficiency with re- 
 ference to the carbon : oxygen f ash ratio. White further states 
 that, "the changes of coal on exposure or weathering are indicated 
 in the analysis by reduced H:0 ratios; by reduced available hydro- 
 gen; and in many cases by reduced volatile carbon ratios. Weath- 
 ering can in most cases be detected by the change in the oxygen- 
 hydrogen relations and by the marked calorific deficiencies.” 
 Considerable data relating to the absorption of oxygen by 
 
 zi 
 
 coal is available. Anderson; in 1898 found that at temperatures 
 below 160° C. atmospheric oxidation of Scottish coals progressed 
 rapidly during the first 12 to 24 hours, but afterwards fell off 
 considerably. Nevertheless the coal increased slowly in weight 
 for a long time, the period varying for different coals. 
 

 
 . ... 
 
 ' 
 
 v 
 
 
 
 
 
 
 
 
 
 
 
5 
 
 Bone mentions that, "the Doncaster workers had been puzzled 
 to find that 'in the oxidation of coal at low temperatures oxygen 
 disappears but scarcely any carbon dioxide is formed 1 , but this 
 fact was surely well known before to chemists (S.W.Parr in parti- 
 cular), and need cause no surprise to any one familiar with the 
 
 phenomena of surface combustion generally." 
 
 G 
 
 Bone has experimented on the absorption of oxygen at temper- 
 atures between 45 and 120* 0. on a Durham coking coal and a Barns- 
 ley hard steam coal. He found that at temperatures below 80 Q G. 
 the absorption was in each case rather slow, even under increased 
 pressure. In the nieghborhood of 80^ G. the reaction became de- 
 cidedly quicker and at above 100° C. it was marked by a regular 
 and simultaneous production of the two oxides of carbon, and steam, 
 these evidently resulting from the decomposition of some unstable 
 body, or bodies, primarily formed by the absorption of the oxygen. 
 These tests were made by circulating dry oxygen continuously over 
 the previously dried coal. Bon6 gives quantitative results of 
 the tests made on both coals at 107 to 109° C. which are, in part, 
 as follows; 
 
 Durham Coking Coal. 
 
 Temperature 
 
 100' 
 
 200 * 
 
 300 6 
 
 400 * 
 
 500 
 
 0 P absorbed 
 
 34.40 
 
 57.90 
 
 84.00 
 
 9 7.40 
 
 110.00 
 
 COp evolved 
 
 4.27 
 
 6.94 
 
 9.30 
 
 11.32 
 
 
 GO evolved 
 
 1.92 
 
 2.78 
 
 3.63 
 
 4.27 
 
 

 
 
 
 
 
 
 
 
 . 
 
 
 
 
 
 
 
 
 
 
 • 
 
 
 
 ♦ 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
6 . 
 
 Barnsley Hard Stean: Coal. 
 
 Temperature 
 
 100" 
 
 200 ' 
 
 300 * 
 
 400° 
 
 o 
 
 500 
 
 Op absorbed 
 
 57.50 
 
 81.20 
 
 96.00 
 
 108.30 110.10 
 
 COg evolved 
 
 7.60 
 
 12.00 
 
 14.40 
 
 15.90 
 
 
 CO evolved 
 
 5.90 
 
 5.30 
 
 5.76 
 
 5.76 
 
 
 Note. The volumes of gas 
 
 are in c.c. 
 
 per gram 
 
 of coal. 
 
 
 Bone says 
 
 that , "the 
 
 whole process is one 
 
 of 'surface 
 
 combustion 1 which, the writer's researches have shown, is subject 
 to special conditions which do not apply in homogenous gaseous 
 combustion. It is abundantly evident that the oxygen is first of 
 all ’’absorbed" by the coal substance, possibly in some 'activated' 
 form , then incorporated in some way (it may only be loosely, or, 
 on the other hand, it may be, as S.W.Parr suggested, in some defi- 
 nite form), and as the temperature rises, it finally is expelled 
 in gaseous products (HgO and oxides of carbon). And between its 
 initial absorption and its final expulsion a whole series of com- 
 plex phenomena may be involved, which have hitherto received lit- 
 tle attention." 
 
 7 
 
 Porter and Ralston have recently done considerable research 
 on the effect of oxygen and air on coal. They used a Pittsburgh, 
 a West Virginia and an Illinois coal and also a Wyoming lignite. 
 They determined the total amount of oxygen absorbed by these coals 
 at various temperatures and pressures and the amount of exothermic 
 heat (roughly) from this absorption. They also passed air over 
 the Illinois and Wyoming coals at different temperatures and de- 
 termined the weight of carbon dioxide, carbon monoxide and water 
 formed and the change in weight of the coal, but did not determine 
 the amount of oxygen that was actually used during the tests. 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 , 
 
 - 
 
 
7 . 
 
 Porter and Ralstons' s conclusions are in part as follows: 
 
 "The effect of weathering or of perliminary moderate heating on 
 the coking quality of coal is explained as an effect of oxidation 
 whereby the fusible organic constituents of the coal are decomposed 
 or altered. The alteration does not occur in a nonoxidizing at- 
 mosphere. It is known that weathering of coal causes an increase 
 of ”eombined"water ; that is, of water that is not in the normal 
 free stat6 and that has at any given temperature a vapor pressure 
 lower than the normal. This water remains in the coal after 
 "air drying." Its increase by weathering is due to oxidation and 
 to the formation thereby of a complex easily decomposed by heat 
 to form water." 
 
 Katz® has shown that coal will absorb any gas until an equil- 
 ibrium with that gas is reached, the volume required depending 
 upon the gas used. He concludes from his work that, "In so far as 
 investigated, the absorption of gases by Pittsburgh coal is close- 
 ly analogous to the absorption of gases by charcoal." 
 
 The study of oxidation or weathering of coal is not a new to- 
 pic. The first investigations were carried on in an attempt to 
 learn something of deterioration and spontaneous combustion of 
 coal and wer6 of little value otherwise. At the present time the 
 same motives favor investigation, the desired result being greater 
 efficiency from the storage and use of coal for power production. 
 The effect of oxygen on the coking qualities of coal has usually 
 been noted, but in many cases given but slight consideration. 
 
 White seems to have associated the oxygen content of coal 
 with its coking qualities more closely than any one previously, 
 and his H:0 ratio is quite applicable as a means of determining 
 
. 
 
 
 
 
 
 
 
 
 
 
 
 ' 
 
 
8 . 
 
 the coking qualities of most coals. 
 
 Bone, and Porter, and Ralston, give considerable quantitative 
 data on the absorption of oxygen oy coal, but their results may 
 be slightly erroneous due to partial combustion, since th6y passed 
 a continuous stream of oxygen over heated coal. 
 
 Bone advances the idea that the oxygen may be held in an "ac- 
 tivated form” whil6 Katz suggests that coal behaves similiarly to 
 charcoal towards gases. Thus both hint at the plausibility of the 
 oxygen being held to the coal mechanically as a molecular conden- 
 sation or in an adsorbed condition. 
 
 Porter and Ralston explain the effect of oxidation of coal 
 as destroying the coking constituent by altering or decomposing 
 
 the fusable organic compounds in the coal. 
 
 9 
 
 Parr and Olin sum up the situation rather well in the fol- 
 lowing: "It has been proved that oxygen absorption goes on rapid- 
 ly when fresh coal is exposed to the atmosphere. It has been 
 shown further that this absorption weakens or destroys altogether 
 any coking properties that the original coal may have. In other 
 words a high H:0 ratio marks the absence of fusibility and cemen- 
 tation. The organic compounds of the coal which furnish the ce- 
 menting material for the cok6 are apparently attacked by oxygen. 
 They yield, on oxidation, humic acids of varying composition which 
 decompose into powdery residues.” 
 
 Outline of the Present Investigation: 
 
 The initial portion of the investigation consisted in a study 
 of the effect of carbon dioxide on the coking qualities of various 
 coals. The coal used was either saturated with carbon dioxide and 
 

 . 
 
 
 
 . 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 . 
 
 
 
 
 
 
 
 
 
9 . 
 
 carbonized, or it was carbonized in a current of carbon dioxide. 
 
 In either case the carbon dioxide used v/as measured and the total 
 gas evolved, also measured and analyzed, and the gain or loss in 
 carbon dioxide noted. 
 
 In studying the effect of oxygen on the coking properties, 
 the coal v/as in each case saturated with the oxygen before the 
 carbonization began. This made it necessary to determine the tem- 
 perature best suited for the saturation, and the time necessary 
 
 for complete saturation. The data from these preliminary oxida- 
 
 6 
 
 tion tests conforms very well with that of done and fairly well 
 
 7 
 
 with that of Porter and Ralston. Blank or straight carbonization 
 tests were made on each of the coals and the products determined. 
 These were followed by tests in which the coal v/as previously sat- 
 urated v/ith oxygen and again, the products were determined. The 
 resultant gas was analyzed, in both cases, and the difference in 
 its constituents , due to the added oxygen, noted. 
 
 II. Experimental. 
 
 Apparatus : 
 
 The complete apparatus is shown in Figure 1. For measuring 
 and storing the gas that v/as added to the coal two sets of aspir- 
 ator bottles and a 200 c.c. gas burette v/ere used. These bottles 
 (A & B) were of four and two liter capacity and were always filled 
 to the same level at atmospheric pressure. The burette (G) was 
 used to measure volumes less than the capacity of the smaller bot- 
 tle. The bottles and burette were connected so that either of 
 the three could be filled or emptied as desired, and they were u- 
 sed, not only for measuring the gas passing into the retort, but 
 
/ 
 
 . 
 
 
 . 
 
 
 
 
10 . 
 
 also for that evolved by the coal. The wash bottles (D & E) con- 
 tained sulfuric acid for drying the used gas and also to show the 
 rate of flow of the gas as it was being used. The gas passed in- 
 to the bottom of the retort (F), under a slight pressure measured 
 by the manometer (G). 
 
 The retort used was made of pyrex tubing 50 mm. in diameter 
 and 45 cm. long. At the lower end a 10 mm. tube was sealed on and 
 a second 10 mm. tube or side arm was sealed on at about 10 cm. 
 from the top of the retort. The retort was placed in the furnace 
 (T) in a vertical position with the upper 15 to 20 cm. exposed. 
 
 The top of the retort was closed with a one hole rubber stopper 
 carrying a pyrex thermocouple tube (P). Heat was held away from 
 the stopper by two aluminum discs (Q) placed on the thermocouple 
 tube. The retort was in reality a modified distilling flask with 
 a side arm long enough to act as a condenser. Over the end of 
 the side arm v/as placed a 50 c. c. distilling flask (H) in which 
 the tar and water were collected. The evolved gas passed out 
 through the side arm of the small distilling flask into a small 
 bulb filled with glass wool, used to remove the tar fog. The man- 
 ometer (G) measured the pressure of the evolved gas. 
 
 The U tube (K) contained dilute sulfuric acid for th6 removal 
 of ammonia from the gas. Hext in the train was a CaCls tub6 (L) 
 for removing the last traces of water. The gas next passed into 
 a KOE bulb (!I) (used for determining C0 o in organic combustions, 
 but here filled with a weakly acid solution of CdSC> 4 ) w bich re- 
 moved the hydrogen sulfide. Prom here the gas passed directly in- 
 to the 12 liter aspirator bottle (IT) where it was stored until 
 ready to be measured in the previously mentioned bottles (A & B). 
 
. 
 
 
 
 
 * 
 
 

 
 
12 . 
 
 Temperature Control and Measurement: 
 
 The furnace used for heating the retort and charge of coal 
 was built in this laboratory. It consisted of a Chromel heating 
 element, h6ld on an Alundum core of about 14 by 4 inches, and in- 
 sulated with Sil-O-Cel. The outside container was an ordinary 
 can of approximately 16 inches in diameter and depth. The heat- 
 ing element was connected in series with an external resistance, 
 by means of which the temperature of the furnace could be held at 
 any desired point up to 800 * C. , or could be brought from room 
 temperature to 600° C. at an uniform rate and in about two hours 
 
 a. 
 
 if desired. In all of these tests 600 to 625° C. were the maxi- 
 mum temperatures used. 
 
 Temperature readings of the furnace and of the center of the 
 charge were taken each 15 minutes. Ordinary thermometers we re 
 used for temperatures up to 250 or 300° C., one being suspended in 
 the furnace between its wall and the retort and the other being 
 hung in the pyrex tube (?) which passed through the stopper and 
 down to the center of the charge of coal. For temperatures above 
 300°C. two Chromel -Alum© 1 thermocouples (0), made of number 16 
 wire, were used. These were connected as shown in Figure l,.to 
 a Weston Direct Current Millivoltmeter (3). They were standar- 
 dized against the freezing points of Bureau of Standards Aluminum 
 and Tin. The couples we re exact duplicates and the same curve was 
 used for both. The temperatures could be read from the curve to 
 within two degrees and the couples were accurate to the same de- 
 gree. ITo external resistance was needed. 
 

 
 
 
 
 
 
 
 
 
 , . 
 
 
 
 
 
 
 
 
 
 
 , . 
 
 
 
 . 
 
 . 
 
 
 . 
 
 
 
 
 
13. 
 
 Operation of Apparatus: 
 
 The bottom of the pyrex retort was covered with glass wool; 
 
 100 grams of coal, usually ground to 60 mesh, wer6 poured in and 
 the stopper and thermocouple tube inserted. The retort and con- 
 tents were weighed and placed in the furnace. The small flask 
 was placed over the side arm and the various connections made. 
 
 All pieces of the train for collecting the products were weighed 
 before being placed in position. Thus on a second weighing, after 
 the 1 6 st was completed, the weights of the products we re available., 
 
 In nearly all of the tests using carbon dioxide, the gas was 
 passed continuously through the retort. This was easily accom- 
 plished since it was possible to fill either aspirator bottle while 
 the other was being emptied. In all the tests using oxygen, the 
 coal was saturated before the carbonisation began. The tempera- 
 ture at which the coal was saturated was varied as desired in the 
 different tests. In some cases, after the desired amount of oxy- 
 gen had been added, the retort was swept out with nitrogen before 
 the carbonization began, while in others this was thought unneces- 
 sary and neglected. 
 
 A number of tests were made in which no gas was added to or 
 passed through the coal. These were termed blank tests and were 
 made in order that the effect of the added gas could be more dis- 
 tinctly noted. The apparatus did not need to be altered for these 
 tests. 
 
 In order to easily control the flow of gas, both into the re- 
 tort and from it, the auxiliary aspirator bottles (A, B & II) were 
 suspended by means of cords and pulleys (not shown in Figure 1.). 
 
 In this manner the bottles could be held at any desired height and 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 , 
 
 
 
 . . 
 
 
 . 
 
 
 
 
 . 
 
 
 
 
 
14 
 
 the pressure in the retort easily controled. 
 
 The time of preliminary treatment of the coal with oxygen 
 or carbon dioxide varied and did not require close attention. The 
 time of carbonization also varied but was usually about three 
 hours . 
 
 Determination of Products and Analysis: 
 
 The most important products from the carbonization tests W 6 re 
 the coke residues and the evolved gases. The amount of residue, 
 in the retort, was determined by weighing the coal used and the 
 retort and contents before and after the t 6 st. The coke was then 
 taken from the retort and stored in small glass jars. The gas 
 collected in either or any of the bottles A, B, or K, and was 
 measured by means of the bottles A and B, and the burette G. The 
 volume of gas was in each case corrected to 60° P. and 30 inches 
 
 of mercury. The evolved gas was analyzed in a Modified Orsat Ap- 
 
 10 
 
 paratus, designed and built in this laboratory. The constituents 
 were determined as follows: COg by absorption in KOK, Og in al- 
 kaline pyrogallol, GgH A in bromine water, and CgHg in fuming 
 Hp,S0^. Hp and CO were burned in a copper oxide furnace at 300^ G. ; 
 the Hg determined by contraction and the CO by absorption of the 
 resultant CO 2 in KOH.CH 4 and CgHg were burned in oxygen over mer- 
 cury in a glass bulb and the two gases diferentiated according to 
 Earnshaw , s' 1 method. ilg was taken as the difference between the 
 total of the above mentioned constituents and the original volume. 
 The original volume taken was always 100 C.C. and thus the values 
 obtained were in percentage by volume. 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 ■ 
 
 
 
 
15 
 
 The water and tar, collected in the flask (H) wer6 v/eighed 
 together, centrifuged, and the volumes determined. Thus the 
 weights of each were obtainable . II o attempt was made to analyze 
 
 the tar. 
 
 The apparatus as designed would also permit the determination 
 of the ammonia and hydrogen sulfide formed, but as these had no 
 direct bearing on the problem and since their determination re- 
 quired considerable time, none were made on the ammonia and only 
 a few were made on the hydrogen sulfide. In most of the tests 
 these products were not collected. Probably very little ammonia 
 was formed at the temperatures attained and the amount of hydro- 
 gen sulfide depended upon the coal carbonized. Hydrogen sulfide 
 was observed to be first liberated at 275 to 300° G. In the tests 
 where the hydrogen sulfide was not removed as cadmium sulfide, it 
 remained in the gas and was determined as carbon dioxide. Thus, 
 although the carbon dioxide values for the gases analyzed were 
 high, they were uniformly so and the ultimate results were unef- 
 fected. 
 
 Types of Coal Used: 
 
 Two types of coal we re used for these tests, one was an Eas- 
 tern Bituminous Goal of the High Volatile type, from the Consoli- 
 dated Goal Company of Fairmount, West Virginia, and the other 
 type consisted of several coals from the Illinois field. These 
 were from Saline, Perry, Franklin, and Moultrie Counties. The 
 Saline and Perry County coals were mainly used, the former being 
 a good coking and the latter a weakly coking coal. The analysis 
 of these two and the West Virginia coal are as follows: 
 

 . 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 . 
 
 
 
 
 
 
 
 
 . . 
 
 
16 . 
 
 Proximate 
 
 Nest 
 
 Saline 
 
 Perry 
 
 
 Virginia 
 
 County 
 
 County 
 
 Moisture 
 
 1.34 
 
 4.27 
 
 5.30 
 
 Volatile Matter 
 
 35.76 
 
 35.93 
 
 35.91 
 
 Fixed Carbon 
 
 56.92 
 
 53.17 
 
 49.85 
 
 Ash 
 
 5.98 
 
 6.63 
 
 8.96 
 
 Ultimate 
 
 
 
 
 Carbon 
 
 78.43 
 
 71.88 
 
 68.00 
 
 Hydrogen 
 
 5.06 
 
 4.83 
 
 4.94 
 
 Oxygen 
 
 6.91 
 
 8.32 
 
 10.00 
 
 Nitrogen 
 
 1.50 
 
 1.03 
 
 1.66 
 
 Sulfur 
 
 0.78 
 
 3.04 
 
 1.14 
 
 Ash 
 
 5.98 
 
 6.63 
 
 8.96 
 
 Moisture 
 
 1.34 
 
 4.27 
 
 5.30 
 
 
 III 
 
 . I\6 Suit S 
 
 
 The Effect of Carbon Dioxide: 
 
 
 
 The results 
 
 from the tests 
 
 where carbon 
 
 dioxide was used dur- 
 
 ing the carboniz 
 
 ation were all 
 
 of a negative 
 
 character. Those 
 
 given in Table 1 
 
 . show that carbon dioxide has apparently no effect 
 
 on the coking constituents of Illinois or Eastern Bituminous coal. 
 
 The first tests with carbon dioxide were 
 
 made on the West Vir- 
 
 ginia coal and when the results 
 
 were found to 
 
 be negative it was 
 
 decided that the 
 
 younger coals 
 
 of Illinois might be more easily 
 
 effected. Accordingly, tests were next made 
 
 on a Saline County 
 
 coal. Here again negative results were obtained. The results of 
 
 these tests are 
 
 shown in Table 
 
 1. as tests 3, 
 
 4 and 5. In these 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 . 
 
 
 ' 
 
 
 
17 
 
 and other tests (data not shown) the conditions were varied so as 
 to attack and destroy th6 coking constituent in the coal. In test 
 number 5 the coal w as held at its decomposition point for four 
 hours and carbon dioxide passed continuously through the retort, 
 but nevertheless, a residue of coke was obtained. 
 
 In test number 6 the residue was a powder. The coal used in 
 this test, from Franklin County, had been in the laboratory for 
 some time and was in a more or less weathered condition. A second 
 test, number 7, was made on fresh Franklin County coal and a good 
 coke obtained. This proved that the results of test number 6 were 
 due to the weathered condition of the coal and not to the carbon 
 dioxide , 
 
 In all these tests the carbon dioxide was passed through the 
 retort in a continuous stream during the period of decomposition. 
 
 It was laser learned that if the coal, in a powdered condition, 
 was heated slightly above 100 C. and evacuated it could be made to 
 "adsorb" gases in a similiar manner as activated charcoal. There- 
 fore test number 23 was made on a weakly coking coal from Perry 
 County, in which the coal was heated to about 180 P C., evacuated, 
 and carbon dioxide admitted. The coal was then allowed to stand 
 in this carbon dioxide atmosphere for several hours to insure com- 
 plete saturation. It was hoped that the "adsorbed" carbon dioxide 
 would be combined sufficiently with the coal to have a deleterious 
 effect upon the coking constituents. However nearly all of this 
 added carbon dioxide was delivered with the gas that came from the 
 coal below 400 *0. and the resultant coke was even better than 
 that obtained from one of the blank tests (Humber 18.) on this 
 
 sam6 coal 
 
. , 
 
 
 
 
 
 
 
 
 
 . 
 
 
 
 
 . 
 
 
 
 
 
 
 
 , 
 
 
 - 
 
 
 
 
18 
 
 All of this data SG6ras to prove, then, that carbon dioxide 
 does not have a deleterious effect upon the coking coals. And 
 the carbon dioxide that is obtained in the gas from coking tests 
 on non-coking coals must b6 a product of decomposition and not in 
 itself responsible for the non-coking of the coal. However this 
 carbon dioxide, coming as it does from the reaction of oxygen with 
 carbon, may be an index of the state of oxidation, or better, the 
 weathered condition of the original coal. And in this ?/ay the 
 study of the effects of the two gases is connected. 
 
 The Effect of Oxygen: 
 
 The addition of oxygen continuously during a coking test is 
 not advisable since combustion would take place when a temperature 
 of about 300° C. was reached. Therefore in the study of the ef- 
 fect of oxygen on the carbonization of coal, the coal was satura- 
 ted with the oxygen before the carbonization was attempted. In 
 order to determine at which temperature oxygen would be most readi- 
 ly adsorbed, a series of tests were made on Saline County coal, to 
 determine quantitatively the volume taken at different temperature q, 
 and the time of apparent saturation. Temperatures from 30 to 330*0, 
 were used and it was found that the coal took more oxygen in a 
 short time at a temperature slightly above 100 * C. The results of 
 these tests are shown in Figure II. The method employed was to 
 heat the coal to the desired temperature, evacuate as low as possi- 
 ble, and admit the oxygen from a graduated container. The oxygen 
 did not pass through the retort in which the coal was held but 
 merely replaced the vacuum, more oxygen being free to enter as 
 needed. As has been mentioned. Bone, and Porter, and Ralston, have 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
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 61 
 
Table II 
 
 
 
 
 
 
 
 . 20. 
 
 DATA FRO!? 
 
 TESTS 
 
 OK P3REY COUaTY COAL. 
 
 
 
 
 Tost o* 18 
 
 
 
 
 
 
 
 
 height Coal 
 
 
 100 gme 
 
 . Carbon Dioxide a ide 3 
 
 Iiono 
 
 
 Residue 
 
 67 rt 
 
 Time 
 
 of addition 
 
 
 — 
 
 
 Tar 
 
 
 10 
 
 Carbonisation Tenr. 
 
 616° 
 
 C. 
 
 Water 
 
 
 13 " 
 
 Ti 0 
 
 of Carboni s 
 
 at ion 
 
 3:45 
 
 bra. 
 
 Type of Re 3 i due : Poor c o he 
 
 f due to tine of carbonisation. 
 
 
 Gas Data: 
 
 
 
 Fractions 
 
 
 
 
 
 
 I 
 
 
 II 
 
 III 
 
 Total 
 
 
 
 $ 
 
 c.o. 
 
 c.o . 
 
 c.c . 
 
 % 
 
 c.c. 
 
 
 Total Gas 
 
 
 1550 
 
 3030 
 
 4770 
 
 
 9360 
 
 
 Temperature 
 
 
 420* 
 
 515 0 
 
 615" 
 
 
 616 e 
 
 
 COo 
 
 18.1 
 
 280 
 
 8.6 260 
 
 C.O 286 
 
 8.9 
 
 826 
 
 
 02 
 
 7.3 
 
 113 
 
 0.9 27 
 
 0.2 10 
 
 1*6 
 
 150 
 
 
 c ? h 4 
 
 3.2 
 
 50 
 
 3.5 106 
 
 0.3 14 
 
 1,Q 
 
 170 
 
 
 c|hS 
 
 3.0 
 
 46 
 
 2.3 770 
 
 0.2 10 
 
 i, ' 
 
 126 
 
 
 Hg 
 
 2.4 
 
 37 
 
 14.7 445 
 
 36.3 1730 
 
 ■ * 'Jl 
 
 2212 
 
 
 CO 
 
 2.4 
 
 37 
 
 2,7 81 
 
 10.3 492 
 
 6.5 
 
 610 
 
 
 ch 4 
 
 16.0 
 
 248 
 
 44.0 1330 
 
 42.9 2-1/45 
 
 38.3 
 
 3623 
 
 
 c?h 6 
 
 17.0 
 
 263 
 
 18.0 548 
 
 2.0 96 
 
 9,7 
 
 904 
 
 
 ■s 
 
 30.6 
 
 474 
 
 5.3 160 
 
 1*3 86 
 
 7.7 
 
 720 
 
 
 Remarks!? Air 
 
 in rot 
 
 ort at 
 
 start - 120 
 
 c.c. and 460 
 
 c.c. 
 
 »2* 
 
 
 ■a- 
 
 * 
 
 * 
 
 * 
 
 * » 
 
 * # 
 
 
 
 
 Test Do# 23 
 
 
 
 
 
 
 
 
 height Coal 
 
 
 100 p'i\ s. Carbon Di 02 d.de 
 
 -4.de d 
 
 1630 
 
 c « c. 
 
 Residue 
 
 71 " 
 
 Tiro of addition 
 
 10:00 
 
 hr a* 
 
 Tar 
 
 
 10 " 
 
 Carbonisation Temp 
 
 61; 
 
 0 ej 
 
 Water 
 
 
 10 " 
 
 Tir e of Carboni 
 
 sat ion 3:15 
 
 hr a 
 
 Type of Residue: Poor ooke but slightly better f ■ 
 
 . 1 n in 
 
 Test 18 
 
 • 
 
 Gao Dj.it a 
 
 
 
 Fractions 
 
 
 
 
 
 
 
 I 
 
 II 
 
 111 
 
 Total 
 
 
 
 ■ 
 
 c.o. 
 
 't c.o. 
 
 C .0 . 
 
 € 
 
 c.c. 
 
 
 Total Gas 
 
 
 2660 
 
 3160 
 
 4850 
 
 106 7 0 
 
 
 Temperature 
 
 
 420" 
 
 516* 
 
 61; ° 
 
 
 615 
 
 
 C02 
 
 55.8 
 
 1485 
 
 9.0 284 
 
 6.5 315 
 
 19.5 
 
 2084 
 
 
 0*5 
 
 0.3 
 
 8 
 
 0.3 9 
 
 0.3 14 
 
 0.3 
 
 31 
 
 
 c 0 i4 
 
 5.2 
 
 136 
 
 4.5 142 
 
 0.2 10 
 
 2.7 
 
 290 
 
 
 c 6 h* 
 
 0.4 
 
 11 
 
 0.8 25 
 
 0.4 19 
 
 0.5 
 
 56 
 
 
 si 
 
 3.0 
 
 80 
 
 16.4 518 
 
 37.1 1800 
 
 22.4 
 
 2398 
 
 
 CO 
 
 1.4 
 
 37 
 
 2.4 76 
 
 9.7 471 
 
 5.5 
 
 584 
 
 
 CH 4 
 
 13.1 
 
 351 
 
 44.4 14 2 
 
 38.6 1872 
 
 33.9 
 
 3626 
 
 
 CgH 6 
 
 15.3 
 
 407 
 
 18,2 575 
 
 4*0 194 
 
 11.0 
 
 1176 
 
 
 n 2 
 
 5.3 
 
 207 
 
 4,0 126 
 
 3.2 166 
 
 4.6 
 
 488 
 
 
 - Re; arks: Dearly all 
 
 of added COo accounted for by 
 
 analysis. 
 
 

21 . 
 
 investigated the absorption of oxygen by coal to some extent, but 
 their method was to pass the oxygen or air continuously over the 
 coal and thus it would seem that, at temperatures of 100° C. or 
 higher, they were favoring at least a partial combustion of the 
 coal, while in the method as used by the writer there seems to be 
 no combustion on the addition of oxygen, except at the higher tem- 
 peratures (250 to 350° C.). 
 
 A second point of note is that, in the method used, the com- 
 plete saturation of the coal seems to take place in a comparitive- 
 ly short time. In two different tests at 115 to 120° C. one of 
 two and one half and the other of eleven and one half hours dura- 
 tion, the former adsorbed 19.9 and the later 21.5 c.c. of oxygen 
 per gram of coal used. However oxygen would probably continue to 
 slowly enter the coal for some time. With the Eastern coal it 
 was necessary to oxy eiate for 100 hours before its coking proper- 
 ties were destroyed and in this length of time each gram of coal 
 adsorbed 53.9 c.c. of oxygen. It seems, though, that the Eastern 
 coal does not take oxygen as rapidly as does an Illinois coal. 
 
 Having learned how to oxy 'e iate coal to the best advantage , 
 carbonization tests were made on the following coals: A weakly 
 
 coking coal from Perry Gounty, and a good coking coal from Saline 
 County, Illinois, and, a bituminous coal from West Virginia. 
 
 Blank tests were made on each of these coals to determine the pro- 
 ducts evolved, two being made on the Perry County coal (tests 18 
 and 19) to determine the accuracy of the method. The results of 
 these tests and of others to be discussed are given in tables II, 
 III, IV and V. The blank tests were duplicated on each coal with 
 charges that had been oxidized at about 110* C. The evolved gas 
 was fractionally collected and analyzed in each test, the frac- 
 

 
 
 
 
 
 
 
 . . 
 
 
 
 
 
 
 
 
 
 ■ 
 
 , 
 
 ♦ • * 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
22 . 
 
 tions being taken each time at as near the same temperatures as 
 
 possible . 
 
 The results of the tests are shown by the tables and graphs. 
 With both the Illinois coals, the residue after treatment with ox- 
 ygen was a powder with no indication of coke structure. In the 
 first attempt to coke the oxiginated West Virginia coal the resi- 
 due was partly coked and partly a powder. In this test the coal 
 had adsorbed about 20 c.c. of oxygen per gram. A second test 
 was made in which the coal was treated with oxygen at 110° C. for 
 100 hours and adsorbed 53.9 c.c. per gram. The residue from the 
 carbonization of this sample was similiar to those from Illinois 
 coals and showed no evidence of softening or fusing. 
 
 rr 
 
 e) 
 
 YJhite classifies coals as to their coking qualities by the 
 H:0 ratio. If the H:0 ratios of the coals used in these tests 
 are calculated they are found to be as follows: 
 
 Test Ho. 19 
 
 20 
 
 21 
 
 22 
 
 24 
 
 25 
 
 26 
 
 Coal Perry Perry 
 
 Saline 
 
 Saline 
 
 W.Va. 
 
 W.Va. 
 
 W.Va 
 
 Treatment Blank 
 
 Oxgd . 
 
 Blank 
 
 Oxgd. 
 
 Blank 
 
 Oxgd. 
 
 Oxgd 
 
 Type Residue Ccke 
 
 Pw'd. 
 
 Cole 
 
 Pw'd. 
 
 Coke 
 
 Coke 
 
 Pw'd 
 
 H:0 Ratio 49.4 
 
 36. 
 
 8 58.0 
 
 45.8 
 
 73.2 
 
 51.3 
 
 33.' 
 
 These calculated ratios show themselves to be very good in- 
 dices of the coking qualities of the coal after treatment with 
 oxygen. The residue from Test 25. would be expected to make a 
 poor coke from inspection of the ratio, 51.3, as it approaches 
 the lower limit for coking coals. As a matter of fact this resi- 
 due was not completely coked and the portion near the wall and 
 near the bottom of the retort was a powder that had evidently ne- 
 ver softened, but the residue in the center of th6 retort was 
 

 
 
 
 
 
 
 . 
 
 • • 
 
 
 
 
 
 
 
 
 
 
 
 
 . 
 
 
 
 
 
 
 
 
 
 . 
 
 
 
 
 
 
 
 
 
 
 
23 
 
 hard dense coke. Evidently the oxygen entering the coal had not 
 diffused thoroughly through it and the oxygen content was not uni- 
 form. Thus the ratio, 51.3, would not hold for all portions of 
 the coal in the retort. 
 
 The above H:0 ratios are calculated from the ultimate analy- 
 sis of the coal on the air dry basis, while White calculates them 
 on the dry basis. But since in this laboratory it is customary 
 to consider the moisture as one of the constituents of the coal; 
 it is reported, along v/ith the other constituents, in the ulti- 
 mate analysis. Therefore the H:0 ratio, here calculated on the 
 air dry basis, is the same as if it was calculated on the dry 
 basis as proposed by White. 
 

 
 , • . CiJ "X 
 
 . 
 
 
 
 
 
 . 
 
 
 , ■ 
 
 
 
■ Ta h-I^^RLX 
 
 Teat Ho. 
 
 DATA 
 
 10 
 
 FRO’* T30T 
 THS 
 
 on ?srry oo*;::;y 
 MAJESTIC HI IFF 
 
 COAL. PROM 
 
 Weight Coal 100 gme. 
 
 Real due 68 M 
 
 Tar 11 M 
 
 Vator 13 
 
 Carbon Dioxide added 
 Tine of addition 
 Carbonisation Temp. 
 Tine of Carbonisation 
 
 24. 
 
 None 
 
 615 ° C. 
 3:10 hr s. 
 
 Type of Residue: Coke, fair quality. 
 
 
 
 
 
 Gas Data: 
 
 
 
 Fraoti ons 
 
 
 
 
 
 
 I 
 
 
 II 
 
 III 
 
 Total 
 
 
 dl 
 
 P 
 
 C .0. 
 
 % 
 
 o . c « 
 
 % 
 
 C.C. 
 
 
 0.0 • 
 
 Total Gas 
 
 
 1560 
 
 
 3030 
 
 
 4680 
 
 
 9260 
 
 Temperature 
 
 
 425° 
 
 
 515 ° 
 
 
 615 ° 
 
 
 615 c 
 
 COo 
 
 16.8 
 
 260 
 
 7.7 
 
 234 
 
 4.9 
 
 230 
 
 7.8 
 
 724 
 
 02 
 
 4.0 
 
 74 
 
 0.5 
 
 15 
 
 0.4 
 
 19 
 
 1.2 
 
 108 
 
 OgH/i 
 
 3.2 
 
 50 
 
 3.9 
 
 113 
 
 0.5 
 
 23 
 
 1,3 
 
 181 
 
 C 6 H 6 
 
 3.7 
 
 57 
 
 2.1 
 
 64 
 
 0.2 
 
 9 
 
 1.4 
 
 130 
 
 Hp 
 
 3.1 
 
 40 
 
 13.2 
 
 397 
 
 36.0 
 
 1685 
 
 23.0 
 
 2130 
 
 CO 
 
 1.8 
 
 28 
 
 3.8 
 
 .115 
 
 8.6 
 
 402 
 
 5.9 
 
 545 
 
 OIL 
 
 16.8 
 
 260 
 
 44.7 
 
 156 i 
 
 41.0 
 
 1920 
 
 38.1 
 
 3534 
 
 C ? H 6 
 
 17.5 
 
 271 
 
 19.2 
 
 682 
 
 4 .1 
 
 192 
 
 11.3 
 
 1045 
 
 
 32.3 
 
 600 
 
 5.0 
 
 152 
 
 4.3 
 
 8 06 
 
 9.3 
 
 050 
 
 Remarks : Air 
 
 in retort at 
 
 start 
 
 e Tuals 
 
 120 
 
 cc Om and 450 
 
 oc n g 
 
 Tent JSTo. 20 
 
 height Coal 
 
 100 gme. 
 
 T ot il Oxy ne n ad \ e L 
 
 2320 c.e. 
 
 Residue 
 
 71 " 
 
 Tine of addition 
 
 2:00 , 
 
 Tar 
 
 10 ,T 
 
 Car b on i s a t i o n Te nr > . 
 
 6600 
 
 Tater 
 
 12 " 
 
 Time o £ Garb oni sa 1 on 
 
 3:30 
 
 Type of Residue: PowderGd, no evidence 
 
 \ of softening 
 
 or cakin'- • 
 
 Gas Data: 
 
 
 
 Fractions 
 
 
 
 
 
 
 * ' 
 
 I 
 
 II 
 
 
 III 
 
 
 Total 
 
 
 c.c. 
 
 % 
 
 c.c. 
 
 % 
 
 c #c « 
 
 % 
 
 c.c. 
 
 Total Gas 
 
 
 1740 
 
 
 3036 
 
 
 4840 
 
 
 5616 
 
 Temperature 
 
 
 426" 
 
 
 * 
 
 
 m> * 
 
 
 620 s 
 
 co g 
 
 45.2 
 
 740 
 
 11,3 
 
 346 
 
 7.1 
 
 344 
 
 14.8 
 
 1430 
 
 °2 
 
 7.4 
 
 129 
 
 0.4 
 
 12 
 
 0.3 
 
 15 
 
 1.6 
 
 156 
 
 G g H 4 
 
 4.1 
 
 71 
 
 4.5 
 
 134 
 
 0,5 
 
 24 
 
 2,4. 
 
 229 
 
 ^6% 
 
 1.3 
 
 23 
 
 1.0 
 
 30 
 
 0.3 
 
 15 
 
 0.8 
 
 68 
 
 Hg 
 
 2.7 
 
 47 
 
 13.8 
 
 420 
 
 33.5 
 
 1620 
 
 21.7 
 
 2087 
 
 CO 
 
 4.1 
 
 71 
 
 2.2 
 
 67 
 
 10.4 
 
 540 
 
 7.4 
 
 670 
 
 CH 4 
 
 4.7 
 
 82 
 
 31.4 
 
 952 
 
 36.6 
 
 1757 
 
 28.9 
 
 2791 
 
 CgH 6 
 
 20,0 
 
 384 
 
 24*6 
 
 746 
 
 6.6 
 
 319 
 
 14.7 
 
 1413 
 
 ilg 
 
 13.3 
 
 230 
 
 11.0 
 
 334 
 
 4.8 
 
 232 
 
 0.3 
 
 756 
 
 Remarks : 1666 
 
 c.c. 
 
 added 
 
 Og not 
 
 accounted for 
 
 by analysis 
 
 = 1.96 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
gable IV 
 
 25 
 
 BATA FROi* TS T 3 OS 3A *11? JUIITI 
 
 goat Ho. 21 
 Weight Coal 
 
 100 gms, 
 
 !o&‘ .1 Oxyren /Idod 
 
 Ilono 
 
 Residue 
 
 70 ” 
 
 Time of addition 
 
 mum 
 
 Tar 
 
 10 ” 
 
 Carbon! sat i on Tern. 
 
 620' C. 
 
 Water 
 
 10 " 
 
 fine of Carbonization 
 
 3: If hr a. 
 
 *.f Residue: 
 
 Coke, hard 
 
 and dense. 
 
 
 Gao Data: 
 
 Fractions 
 
 
 
 I 
 
 
 II 
 
 
 III 
 
 Total 
 
 
 * 
 
 c.c. 
 
 % 
 
 c.c. 
 
 
 C e 0 
 
 . ?-• c.c. 
 
 Total Gas 
 
 
 1550 
 
 
 3024 
 
 
 6,50 
 
 10624 
 
 Temperature 
 
 
 425* 
 
 
 5 0* 
 
 
 620 
 
 ° 
 
 CO* 
 
 10.0 
 
 244 
 
 0.6 
 
 262 
 
 *• 
 
 0 
 
 .6 399 
 
 8.9 955 
 
 °2 
 
 0.7 
 
 11 
 
 0.3 
 
 9 
 
 0 
 
 .4 24 
 
 0.4 44 
 
 c 2 H l 
 
 4.2 
 
 65 
 
 4.0 
 
 122 
 
 0 
 
 .6 36 
 
 2.1 283 
 
 C r ,H 6 
 
 0.4 
 
 6 
 
 1.0 
 
 55 
 
 0 
 
 .4 24 
 
 ir.- 
 
 co 
 
 CD 
 
 e 
 
 o 
 
 Hg 
 
 6*0 
 
 93 
 
 14.3 
 
 436 
 
 iW . *' c> 8 2 U 
 
 25.8 2749 
 
 C0„ 
 
 1.0 
 
 16 
 
 0.0 
 
 24 
 
 3.3 199 
 
 2.3 239 
 
 CH 4 
 
 c»h| 
 
 17.5 
 
 271 
 
 42.2 
 
 1287 
 
 37 
 
 .0 2246 
 
 35.6 3798 
 
 21.1 
 
 327 
 
 21 • 3 
 
 649 
 
 8 
 
 .2 496 
 
 13.8 1472 
 
 Hfi 
 
 30.1 
 
 467 
 
 6.7 
 
 p ; A 
 
 6 
 
 *8 418 
 
 10.2 183 
 
 Remarks : Retort swept with Tip at start 
 
 . Do 
 
 iG 
 
 in retort 
 
 568 c.c. 
 
 * 
 
 
 45 
 
 m 
 
 * 
 
 * 
 
 
 * 
 
 Teat Ho. 22 
 
 
 
 
 
 
 
 
 Weight Coal 
 
 100 
 
 * 
 
 Total OXw 
 
 iron added 
 
 2525 c *3, 
 
 lie si due 
 
 71 " 
 
 
 Time 
 
 of addition 
 
 13:00 his 
 
 Tar 
 
 
 9 " 
 
 
 Carbonisation Temp 
 
 620* C. ! 
 
 Water 
 
 
 10 w 
 
 
 Time 
 
 o f Garb ni z a tion 3 i 45 hr a 
 
 Type of Re si 
 
 duo: Powdered 
 
 , no evidence 
 
 of softening 
 
 S’ 
 
 T} 
 
 O 
 
 o 
 
 & 
 
 o 
 
 O&s Data: 
 
 
 Fractions 
 
 
 
 
 
 1 
 
 
 II 
 
 III 
 
 Total 
 
 
 i 
 
 c.c. 
 
 % 
 
 c.c. 
 
 % 
 
 c.c. 
 
 c.c. 
 
 Total Gas 
 
 
 2150 
 
 
 3100 
 
 
 6160 
 
 11420 
 
 Temperature 
 
 
 
 
 500" 
 
 
 680 d 
 
 680 " 
 
 GOg 
 
 37.2 
 
 800 
 
 10.1 
 
 313 
 
 8.0 
 
 493 
 
 14.1 1606 
 
 °2 
 
 11.2 
 
 241 
 
 0*6 
 
 18 
 
 0.5 
 
 31 
 
 2.5 290 
 
 c. b h 
 
 5.0 
 
 107 
 
 3.2 
 
 99 
 
 0.3 
 
 18 
 
 2*0 224 
 
 g 6 H 5 
 
 0.4 
 
 9 
 
 1.9 
 
 59 
 
 0.5 
 
 31 
 
 0.9 99 
 
 Ho 
 
 3.4 
 
 73 
 
 14.5 
 
 450 
 
 32,2 
 
 8830 
 
 84.1 2753 
 
 CO ' 
 
 9.8 
 
 . 10 
 
 3.5 
 
 108 
 
 7. ) 
 
 453 
 
 6.6 750 
 
 C*3$ 
 
 13.6 
 
 294 
 
 44.2 
 
 1360 
 
 36,6 
 
 82255 
 
 34.3 3917 
 
 13*4 
 
 288 
 
 18.0 
 
 558 
 
 6.0 
 
 370 
 
 10.6 1216 
 
 *2 
 
 6.0 
 
 129 
 
 4.0 
 
 124 
 
 4.9 
 
 302 
 
 4.9 555 
 
 Re? arks: 1330 c.o. 
 
 of added Og 
 
 unacc 3 unted 
 
 for by analysis, * 
 
 1.61 ;• 
 
table V*. 
 
 26, 
 
 DATA FROM 
 
 TJS3T0 
 
 05 V.T:oT V X :l INIA C fa . 
 
 Test No. 24 
 
 Y. 7 elght Coal 
 
 100 gms 
 
 • Total Oxy ren added 
 
 Hone 
 
 Residue 
 
 76 ” 
 
 Time of addition 
 
 
 — 
 
 Tar 
 
 15 ” 
 
 Cart) oni a at ion T 
 
 ; enp 
 
 
 605 * C. 
 
 flator 
 
 4 " 
 
 Tine of Carbon! 
 
 b: vt i on 
 
 3 
 
 :16 hr a. 
 
 Type of Residue 
 
 : Coke, sli jhtly por us, avide 
 
 noe of 
 
 swelling* 
 
 Oao Data: 
 
 
 Fractions 
 
 
 
 
 
 .. I 
 
 II . Ill 
 
 
 Total 
 
 
 fo C.C. 
 
 % c.c . 
 
 » < : . 
 
 <1 
 
 c.c. 
 
 Total Gas 
 
 1606 
 
 3820 
 
 5600 
 
 
 10605 
 
 Temperature 
 
 415* 
 
 496" 
 
 6 ° 
 
 
 005° 
 
 COp 
 
 15.8 216 
 
 6.1 196 *3.9 
 
 218 
 
 6.5 
 
 680 
 
 o* 
 
 5*8 56 
 
 025 16 1*0 
 
 56 
 
 1.2 
 
 128 
 
 %H4 
 
 5599 99 
 
 6,1 196 0.5 
 
 28 
 
 3.0 
 
 323 
 
 C.H. 
 
 2.4 40 
 
 1.6 51 0.6 
 
 34 
 
 1.3 
 
 125 
 
 *4 
 
 4.5 76 
 
 9.9 318 33.5 
 
 1875 
 
 25.6 
 
 8269 
 
 CO 
 
 0.6 10 
 
 0.0 26 3.9 
 
 218 
 
 2.4 
 
 254 
 
 oh* 
 
 11.2 189 
 
 44.2 1420 46.2 
 
 2586 
 
 40.0 
 
 4195 
 
 
 26.3 4«'k> 
 
 21.8 ®02 6.4 
 
 3359 
 
 14.4 
 
 1513 
 
 »8 
 
 29.5 417 
 
 9.0 290 4.0 
 
 224 
 
 9.7 
 
 1011 
 
 Remarks : Air in 
 
 retort at 
 
 start - 120 c.e. 0£ 
 
 and 45C 
 
 > c.c. 
 
 Ho. 
 
 * 
 
 m * 
 
 #e * * 
 
 4f * 
 
 \ 
 
 
 Test Ho, 26 
 
 
 
 
 
 
 Weight Coal 
 
 100 3Q8 . 
 
 Total Oxygen added 
 
 5395 c.c. 
 
 Residue 
 
 72 u 
 
 Time of addition 
 
 100: 
 
 0 hrs. 
 
 Tar 
 
 12 " 
 
 Carbonisation T 
 
 or ip. 
 
 616° C 
 
 Water 
 
 6 M 
 
 Tiro of Carbonization 
 
 3:6 
 
 0 hrs. 
 
 Type of Residue 
 
 : Powdered, no evidence of softenin 
 
 of coking. 
 
 Gas Data : 
 
 
 Fractions 
 
 
 
 
 
 I 
 
 II III 
 
 j* 
 
 
 Tot 1 
 
 
 % c.c. 
 
 c.c • 
 
 c.c. 
 
 jtv 
 
 c.c. 
 
 Total (las 
 
 1730 
 
 3140 
 
 6260 
 
 
 11030 
 
 Temperature 
 
 416° 
 
 6 >0 d 
 
 615 * 
 
 
 615° 
 
 43.5 
 
 2.1 
 
 5.5 
 
 1.3 
 
 2.3 
 14.9 
 10.8 
 
 3.? 
 
 5.9 
 
 4 
 
 36 
 
 95 
 
 22 
 
 40 
 
 £58 
 
 18? 
 
 151 
 
 9.4 
 1.0 
 6.2 
 
 1.5 
 9.1 
 6.3 
 
 45.4 
 
 16.1 
 
 4*0 
 
 286 
 30 
 189 
 46 
 277 
 191 
 1 00 
 .439 
 122 
 
 5.3 
 
 0.3 
 
 0.3 
 
 0,6 
 
 50.0 
 
 6.0 
 
 44.5 
 
 6.6 
 
 6,5 
 
 332 
 
 19 
 
 19 
 
 38 
 
 1880 
 
 376 
 
 2786 
 
 407 
 
 407 
 
 IS. 2 
 0.8 
 2.8 
 1.0 
 20*0 
 
 7.5 
 39.6 
 
 9.5 
 5.7 
 
 3468 
 
 85 
 
 303 
 
 106 
 2197 
 825 
 4362 
 1 47 
 631 
 
 Remarks: 1000 c.c. added Op in evolved gas. Undetermined 437603. 
 

27 
 
 The volumes of oxygen, carbon dioxide, hydrogen and carbon 
 monoxide are plotted in Figures IV, V and VI against the tempera- 
 tures of fractional collection. Each graph represents the tests 
 on one coal. Thus the differences in the constituents evolved by 
 each coal under different conditions are shown. The oxygen added 
 to the coal is shown to be given off, in part, as carbon dioxide 
 and carbon monoxide, the former predominating at the lower temper- 
 atures and the latter increasing as the temperature rises. This 
 must be due in part to the reduction of carbon dioxide to the mon- 
 oxide at high temperatures, by carbon. The oxygen added does not 
 seem to effect the volume of hydrogen evolved nor does it effect 
 the volume of oxygen, except in the first fraction of gas taken. 
 However it is impossible to account for all of the oxygen added 
 by an analysis of th6 evolved gas. In all probability the oxygen 
 lost is in part retained in the residue, and would at higher tem- 
 peratures b6 evolved as carbon monoxide, and is in part held in 
 the tar. There is also the probability that the water of decompo- 
 sition, from the tests in which oxygen was added, is in greater 
 proportion than in the blank tests but it was impossible to detar - 
 mine this accurately in these tests. However the formation of 
 water of decomposition should decrease the volume of hydrogen in 
 the gas and as the curves do not show this to be true it would 
 seem that the probability, of a greater amount of water of decom- 
 position, is erroneous. 
 
 Figure III shows a comparison of the adsorption of carbon 
 dioxide, oxygen and nitrogen by Saline County coal at ordinary 
 temperatures. Time is the only variable, since the pressure and 
 temperature remained constant during the test. 
 

 
 . 
 
 
 , 
 
 . 
 
 
 
 
 
 
 
 
 
 
 
 
 -S--> 
 
 . 
 
 
 
 
 
 
 
 
vu/urne m cuo/c Leor/merers Volume in Cubic Centimeters 
 
 
 
 otion 
 
 temperatures 
 
 Centimeters 
 
 i 
 
\ 
 

 Carbpn 
 
 Carbon 
 
 Monoxide 
 
 grams 
 
 carbonization . 
 
 W200 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
2000 
 
 <?.vo)vi\ 
 
 gram. 
 
 feat con 
 
 T S£idi 
 
. 
 
2000 
 
 C\ioxid&, 
 
 Carbon 
 
 Pmm 
 
 hydrogen, 
 
 valued 
 
 100 grams 
 
 1800 
 
 Carboniza. 
 
 moo 
 
IV. Discussion and Conclusions. 
 
 52 . 
 
 Carbon dioxid6 lias no effect upon the coking constituent of 
 
 coal. Its presence in the gas from coal is a result of the reac- 
 tion of carbon with the oxygen hold in the coal. The gas from 
 non-coking and weathered coals contains large amounts of carbon 
 dioxide, due to the high oxygen content of these coals. 
 
 All coal as mined contains some oxygen, chemically combined. 
 The amount varies with the different ranks of coal and seems to be 
 a determining factor which governs the coking of the coal. 7, 'hen 
 oxygen is present beyond certain proportions as compared to the 
 hydrogen present, it is known that the coking quality of the coal 
 will be impaired. White has proposed a H:0 ratio which is quite 
 accurate and which serves as an excellent index for the coking 
 qualities of nearly all coals. 
 
 Lump coal will, on exposure to gases, absorb them to a cer- 
 tain extent. Finely divided coal absorbs gases more rapidly but 
 does not necessarily have a greater capacity for them. Coal shows 
 a marked avidity for oxygen, and its behavior towards oxygen, and 
 
 other gases, may be compared similiarly to that of activated char- 
 
 14 
 
 coal. Then the added oxygen which is held by the coal may be 
 assumed to b6 in two forms; first, as a molecular condensation on 
 the particles of coal, considered as an "adsorbed" condition, and 
 second, as a carbon-oxyg6n complex, essentially a stable solid 
 oxide or sub oxide of carbon, which is considered as "fixed oxygen" 
 The first from which is thought to be held mechanically should be 
 removed by moderate heating or evacuation. The second form should 
 be removed by heating to higher temperatures and should come off 
 as the two oxides of carbon. This seems to be confirmed by exper- 
 imental data as also does the tendancy of the adsorbed oxygen to 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
33 
 
 change in time to the fixed condition. 
 
 Coal may be divided into two portions by extraction with or- 
 
 1 2 
 
 ganic solvents, viz phenol . These portions should be termed 
 
 the residue and extract. It is this residue that shows the great- 
 
 13 
 
 est avidity for oxygen according to Cherry, and therefore resem- 
 bles activated charcoal in its behavior, while the extract con- 
 tains the coking constituents of the coal. The compounds in the 
 extract are not oxidizable at ordinary temperatures but are con- 
 sidered as easily oxidized, as they are h6ld by the coal, at or 
 
 13 
 
 near the softening or fusion point of the coal. 
 
 Then, in the case of oxiginated or weathered coal the resi- 
 due may be assumed to act as a carrier of oxygen to the extract 
 and liberate its adsorbed oxygen, during the coking process, at 
 precisely the temperature when it will be most reactive with the 
 extracted portion, thus destroying the coking properties of the 
 coal . 
 
 Just how the oxygen destroys the coking Qualities of coal is 
 
 9 
 
 a matter of speculation. According to Parr and Olin, the coking 
 constituent is an organic compound, of a complex nature, that has 
 a definite melting point and that during the coking process melts 
 and flows through the coal mass thus binding it together and form- 
 ing a coke. It is more probably a mixture oljbompounds , each with 
 a definite melting point. If these compounds are oxidized one 
 of two things probably takes place. Either the melting point of 
 the compound will be raised, due to the formation of higher mol- 
 ecular weight compounds, to such an extent that it will be decom- 
 posed by heat before its melting point is reached; or the oxida- 
 tion itself will decompose and break up the compounds into other 
 

 
 
 
 
 
 
 
 
 . 
 
 ' 
 
 
 
 
 
 
 
 
 
 
 , 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
34 
 
 unstable compounds of indefinite melting points. In either case 
 the final decomposition would give large amounts of carhon diox- 
 ide and the residue in the retort would show no sighs of fusion 
 or softening. In the event that the coal also holds fixed oxygen 
 an even greater volume of carbon dioxide would be evolved. 
 
 Then, from the above assumptions, in the case of high oxygen 
 coals, the melting point of the resinic portion, which is composed 
 of high molecular weight compounds, is so hi^h that in the coking 
 process decomposition takes place before it is reached, and this 
 accounts for the large volume of carbon dioxide given off up to 
 rather high temperatures. This carbon dioxide, then, is an effect 
 of the oxygen in the coal substance. 
 
 While, from the same assurftions, in the ease of low oxygen 
 coals the resinic portion is not easily oxidized at ordinary tem- 
 peratures. But on oxidation of the coal the c6llulosic portion 
 takes up the oxygen and holds it until, during the carbonization, 
 the temperature is reached where it will react with the resinic 
 portion. At this point then, the cellulosic part delivers to the 
 resinic part sufficient oxygen to cause it to change into a high- 
 er melting compound or to break up into compounds of indefinite 
 physical properties. And thus may be explained the mechanics of 
 the effect of adsorbed oxygen on the coking constituents of coal. 
 
 Whether the coal is originally high in oxygen or has had oxy- 
 gen added in the process of weathering seems to matter little anl 
 to all practical purposes the effects and results are the same. 
 
 The theories just proposed are tendered as plausible and pro- 
 bable explanations of the effect of oxygen on the carbonization of 
 coal. They are strengthened by the data obtained during this in- 
 

 
 
 
 
 
 . 
 
 •- • • >- 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 * 
 
 
 
 
 
 
 
 
35 . 
 
 vestigation and also from other sources. It is not the intention 
 of the writer to disprove other existing theories on carbonization 
 nor to propose these as proven facts, but as theoretical consi- 
 derations worthy of further study and investigation, and as such 
 it is hoped that they will prove to be of value. 
 

 
 
 
 
36 • 
 
 V. Summary. 
 
 Carbon dioxide adsorbed by coal or passed through the 
 retort during the carboni zation process has no effect upon 
 the coking qualities of coal. 
 
 A coking coal if saturated with sufficient oxygen will 
 refuse to coke. 
 
 The H:0 ration is an excellent index of the coking prop 
 erties of a weathered or oxidized coal as well as of a fresh 
 coal. 
 
 The oxygen adsorbed by coal is delivered during the 
 carbonization, mostly as oxides of carbon. That portion 
 unaccounted for must necessarily remain in the tar and the 
 residue . 
 
 Finely ground coal possesses an avidity for gases, and 
 especially oxygen, very similiar to that of activated char- 
 coal . 
 
 Adsorbed oxygen destroys the coking properties of coal 
 by apparently reacting with the phenol soluble portion during 
 the carbonization, and changing it, into compounds of such 
 high melting point that they decompose before this point is 
 reached, or into compounds of indefinite physical properties. 
 
 Carbon dioxide is a product of the decomposition of the 
 oxiginated phenol extract and the probable carbon-oxygen 
 complex (sub-oxides of carbon or fixed oxygen). 
 

 
 
 
 
 . 1 
 
 
37 
 
 Bibliography. 
 
 1. Anderson and Roberts, J. S. C. I. (1898) p 1013 
 (abstracted in Lewes text (1914) P 212) 
 
 2. Anderson and Roberts, J. 3. C. I. (1898) p 1005 
 
 3. Bureau of Mines Bulletin 29. by David White. (1911) 
 
 (The Effect of Oxygen in Goal) 
 
 4. Y/. A. Bone, text, "Goal and its Scientific Uses" p 152 
 
 5. W. A. Bone, text, " ” " " " p 157 
 
 6. W. A. Bone, text, ” M " " ’* p 158-62 
 
 7. Tech. Paper 65. Bur. Min. Porter and Ralston. (1914) 
 
 (A Study of the Oxidation of Goal) 
 
 8. Tech. Paper 170. Bur. Mines, by S.H.Katz. (1917) 
 
 (The Diffusion of Oxygen Through Stored Goal) 
 
 9. U of I Bulletin 60, by 3. W. Parr and H.L.Olin. (1912) 
 
 (The Coking of Coal at Low Temperatures) 
 
 10. S.W.Parr, text. The Chemical Examination of ’Water, Fuel, 
 Flue Gases and Lubricants. (1921) 
 
 11. J. of the Franklin Inst. 154 , pp. 161-76. (1898) 
 
 12. U of I Bulletin 76, by S.W.Parr and H.F. Hadley. (1914) 
 
 ( Th.6 Analysis of Goal with Phenol as a Solvent) 
 
 13. Thesis by 0. A. Cherry for B. 3. degree U of I (1920) 
 
 (The Effect of Oxygen on the Coking of Coal) 
 
 14. J.Am.Chem.Soc . _42, Ho. 7. pp. 1393 July 1920. 
 
 (Studies in the Adsorption of Charcoal)