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Percentage results of Distillation under Pressure.
Number I. II. III. IV. Volatile impurity, consisting of air and water,
12.5 1st. Pressure Distillation of crude material,
87.66 82-86 72:20 Coke and loss at do.,
9:- 12:34 17:34 15:50 1st Fractionation of sp. gr. 43° B. = .810,
42:- 56.72 40:33 16.70 Leaving Heavy Residue for re-distillation,
49:- 30.94 42:33 55:30 Which yielded, by 2d Pressure Distillation,
44.15 27.84 58:09 49.80 2d. Fractionation of sp. gr. 43° B. =:810,
12.25 6.96 9.52 12:40 Total crude Illuminating Oil,
54.25 62-68 49.85 29 10 Loss in treatment of do., 18.
1.62 1.88 1:49 .90 Total yield of Refined Oil,
51.25 60.70 48:36 23:20 Total crude Lubricating Oil,
31.85 20.88 28.57 37:40 Loss in treatment of do., jo
.85 1:10 Total Refined Lubricating Oil,.
30 90 20.26 27.72 36-30 Yield of Refined Illuminating Oil, sp. gr. 43° B., -- 51.25 60.70 48 36 28:20 Yield of Refined Lubricating Oil, sp. gr. 23°-25° B., 30.90 20.26 27:52 36-30 Loss in treatment,-
2.61 2:50 2:34
2:00 Coke and loss in Distillation,
18:24 16:51 21:58 33:50 Yield of Illuminating Oil by ordinary process, -
15.00 20.00 3.00 2:50
Dr. Hirsch criticises these experiments as not being executed under circumstances “parallel to the distillation on a large scale." He then states, that during the distillation of hydrocarbons on the large scale,“ the process of cracking' always takes place in some degree,” as “all hydrocarbons of high boiling points contained in such mixtures are, during distillation, exposed to varying degrees of temperature below
their own boiling point, as long as those hydrocarbons of lesser gravity and lower boiling point have not been removed by distillation. He further states, that “it is this exposure to a lower degree of heat than corresponds to the distilling point of an oil of definite gravity, which comprises the operation of cracking.' Again he states, that during slow distillation in the enormous stills now being introduced, “cracking” takes place without any “special efforts” to produce such a result, while only a small portion distills over as paraffine oil, that being due to over-heating.” He next states, that by rapid distillation of a small quantity, the different hydrocarbons which make
the petroleum come over unchanged, and that the difference between this last named distillation and the former, is the same as the one between distilling coal for the production of illuminating gas, and that for producing coal oil; the former producing a dense tar, being carried on in small low retorts, and the latter, in revolving retorts of large capacity. “In these the oily vapors are exposed to a cooler temperature than their own with every revolution of the retort, and are in this manner broken up into oils of lighter gravity.”
He then gives a number of rules, the result of his own experience.
‘lst. *** the more the temperature of the actual boiling point of oil of definite gravity is above the temperature to which the same oil is raised, the greater is the quantity of light oil obtained
“2d. The gravity of distillate resulting from reduction of temperature will be directly proportionate to said reduction. **** In distillation, the temperature, therefore, should always be reduced to the boiling point of the oil of the specific gravity desired.
“ 3d. The difference between the temperatures of the two boiling points, viz: of the oil being subjected to distillation, and of the derived distillate, is in direct proportion to the height of the still employed, or to the facility for cooling the upper portions of the stiil.
• 4th. The intensity of the process of 'cracking' is proportionate to the suddenness with which the oil vapors are condensed before leaving the still.
“ 5th. The difference in gravity between that of the oil distilled, and the desired distillate, is in direct proportion to the quantity of water produced in the process.
“ These laws are the same with hydrocarbons distilled under the ordinary atmospheric pressure, as with those distilled in a vacuum, or under increased pressure.”
It is very rarely that as many errors are included within as little space, and the entire discussion exhibits in a remarkable degree to what totally erroneous conclusions the results of close observation and experience may lead, when explained upon a false hypothesis.
The operation of "cracking," as conducted by Mr. Downer, consists in a slow distillation of oils of high specific gravity, and high boiling point, in a still furnished with a high dome, the outer surface of which is freely exposed to radiation. As distillation proceeds, those oils which are condensed at the temperature at which the dome is maintained, instead of passing into the worm and thence into the receiver, collect in drops upon the surface of the dome, and fall back upon the surface of the oil beneath, which has meantime become heated above their boiling points. Mr. Young distills the oils under pressure, thereby vaporizing them at a temperature above their normal boiling points.
It is therefore obvious, that the primary and essential condition of “ cracking" is simply to subject the oils to a temperature above their boiling points, or in other words, to super-heat their vapors. It will be found that for oils of the same density,
per square inch.
the higher the temperature to which they are raised, or at which they are distilled, the lighter will be the product; and that to produce an oil of given density, the heavier oil must be raised to a certain fixed temperature, the intensity of heat depending on the lightness of the oil required.
Now it is evident that Prof. Silliman could not subject five or ten gallons of Maltha to experiment strictly analogous to Mr. Downer's process, the two elements of time and large capacity of apparatus being practically unattainable when manipulating so small a quantity. He could, however, follow Mr. Young's process strictly, using from 10 to 15 pounds pressure
My own results were obtained by using from 30 to 40 pounds pressure per square inch, and operating upon only 1,500 cubic centimeters at a time.
Dr. Hirsch is correct in stating that during the distillation on the large scale, this process always obtains action in some degree, but his reasoning is utterly at fault. So, too, is his explanation of the fact, that "cracking” takes place in large stills without any special effort to secure such a result. The real explanation lies in the fact, that the upper portion of stills in ordinary use is generally exposed to atmospheric currents and radiation. With such an arrangement it is impossible, upon Mr. Downer's plan, to prevent more or less condensation upon the dome, and consequent "cracking,” especially toward the end of the operation, in stills of the enormous capacity of 40,000 gallons, where all the conditions essential to his process are present. It was in stills set in this manner that the heavy California oils were first distilled, and in which they were "cracked” to an oil of medium density; but when the sides and domes of the stills were surrounded with brick-work, the vapors were no longer condensed, and they passed unchanged into the receiver.
Dr. Hirsch is again in error, in supposing that paraffine oils are produced by a high temperature. I am told that Mr. Downer has made illuminating oils, by “cracking” solid paraffine wax by means of his process. The paraffine lubricating oils of commerce are now most successfully produced from coals, by distilling the material in large kilns, in which combustion takes place at the upper surface, and the draft is conducted downward, insuring the expulsion of the volatile products at the very lowest temperature possible.
He is yet again in error, in the analogy which he assumes to exist between rapid and slow distillation of petroleum, and the distillation of coals, in small retorts to produce illuminating gas, and in revolving retorts to produce oil. Rapid distillation "cracks” the oil, because it necessitates increased temperature to force the vapors from the still. Such has been my experience repeatedly on both the large and small scale. Slow distillation yields the hydrocarbons unchanged, provided the vapors have ready egress from the still, because distillation is then carried on at the lowest temperature attainable. Small retorts are used for the manufacture of gas, in order that the coal may the sooner be raised to the red-heat, and the greatest possible' “ cracking" effect be experienced, while revolving retorts are used in the manufacture of oil, not that the charge may be repeatedly cooled, but in order that it may be uniformly heated, avoiding the necessity of over-heating the portion next the fire, in order that the upper portion may be heated sufficiently.
His first and second rules, when reduced to plain English, assert that “cracking" may be produced by refrigeration. Following their lead, in order to produce from paraffine wax the lightest member of the naphtha series isolated by Prof. Warren, and boiling at 0° C., the paraffine should be immersed in melting ice. According to these rules, the best method of producing illuminating gas from crude petroleum would be, to subject the oils to the action of a refrigerating mixture of solid carbonic acid and ether, instead of allowing them to drip upon red-hot coke.
His third rule is correct, as the lower the temperature at which the top of the still is maintained, the lower will be the boiling point of the liquid resulting from the condensation of the vapors that escape.
His fourth rule is too obscure in its signification to admit of criticism.
His fifth rule is of the most extraordinary character. Chemistry is not yet ready for the announcement of the transmutation of one element into another, and such transmutation must certainly take place if WATER can be produced by distillation of volatile HYDROCARBONS, with exclusion of oxygen. So, to is it almost equally difficult to imagine how any general laws can be “the same” for two processes so diametrically opposed as distillation in a vacuum and under pressure.
I desire in this connection to note a few suggestions which have occurred to me in reference to this subject. In the last edition of Prof. Dana's Mineralogy (1868), he has classified the results obtained by Profs. Warren and Storer, and arranged the hydrocarbons isolated by them in three groups, viz: the Naphtha and Beta-naphtha series, and the Pittoleum group. The first two are isomeric, the last contains more carbon in proportion to its hydrogen. The members of the Pittoleum group at present isolated are doubtless the lower members of a large group, the higher members of which have very high boiling points; or perhaps there is still another group containing a still larger proportion of carbon. As the different members of these groups decrease in density, the proportion of hydrogen increases, and as they increase in density, the proportion of. carbon increases. The process of "cracking” Pennsylvania oils, therefore, is simply subtraction of carbon ; and it appears from the results of experiment and analysis, that each additional atom of carbon is held by a feebler affinity than the last, consequently the stability of the members increases as the proportion of carbon decreases. The lower the member is in the series, the stronger is the affinity of the hydrogen for the carbon, and consequently, the higher is the temperature required for the production of the member next below it. Thus it is that over-heating dense paraffine oils produces medium or illuminating oils ; over-heating illuminating oils produces still lower and more volatile liquids ; at a still higher temperature the products become gaseous, and at an excessively high temperature, light rather than heavy carburetted hydrogen gas is produced.
In the absence of actual demonstration by fractionation, I am led to believe from the behavior of California petroleums, that they do not contain either the Naphtha or Beta-naphtha series in appreciable quantity ; nor do they contain the members of the Pittoleum group yet isolated in large proportion, but are doubtless made up of the higher members of that group, or a still more highly carbonized and unstable group not yet described, with which is mingled one or more nitrohydrocarbons yet more easily decomposed. Be this fact or fancy, the appearance and physical properties of the refined pressure distillate from these oils, lead to the opinion that it is made up of the same members of which refined Pennsylvania petroleum is composed. The lightest oils existing in crude California petroleum change in a few weeks, after treatment, to a dirty yellow color, even when tightly corked and exposed only to the light. A bottle of refined pressure distillate in my possession has now been prepared nearly two years, yet its color has scarcely changed perceptibly.
By Prof. Warren's process of fractionation only a trace was eliminated from any of my samples of crude California oil under 150° C., yet in one instance, when my valve accidentally stuck so that the pressure was very considerably increased above 40 pounds, the vapors when they escaped passed through the worm uncondensed at 8° C., and melted the lead pipe at its point of connection with the retort ; proving that as in the case of the heavy paraffine oils, decrease in the density of the