US793026A - Process of separating sulfur from the sulfur-containing constituents of petroleum and making hydrogen carbid. - Google Patents

Description

N0. 793.026. PATENTED JUNE 20, 1905.

H. S. BLAGKMORE.

PROCESS OF SEPARATING SULFUR FROM THE SULFUR CONTAINING OONSTITUENTS 0F PETROLEUM AND MAKING HYDROGEN GARBID. APPLICATION FILED ooma. 1904.

alum" to:

Patented June 20, 1905.

UNITED STATES PATENT OFFICE.

' IIENhY SPENO ER. BLACKMORE, OF MOUNT VERNON, NEIV YORK, ASSIGNOR,

BY DIRECT AND MESNE ASSIGNMENTS, TO BLACK-FORD UTILITY OIL COMPANY, A CORPORATION OF THE DISTRICT OF COLUMBIA.

PROCESS OF SEPARATING SULFUR FROM THE SULFUR-CONTAINING CON STITUENTS OF PETROLEUM AND MAKING HYDROGEN CARBID.

SPECIFICATION forming part of Letters Patent No. 793,026, dated June 20, 1905.

Original application filed September '7, 1904, Serial No. 223,625. Divided and this application filed October 29,1904. Serial No. 230,550.

To (1, 11:71 m, it may concern:

Be it known that I, HENRY SPENCER BLACK- Moim, a citizen of the United States, residing at Mount Vernon, in the county of \Vestchester and State of New York, have invented certain new and useful Improvements in Processes of Separating Sulfur from the Sulf u r-Containing Constituents of Petroleum and Making llydrogen Oarbid, of which the following is a specification, being a division from my appli cation, Serial No. 223,625, filed in the United States Patent Office September 7, 190%.

The object of my invention is to separate sulfur from sulfur-containing petroleum and similar compounds and produce hydrogen carbids in such a manner as to facilitate purification, effect a saving in time and labor, thereby economixing the cost; and it consists in exposing the sulfur-containing petroleum to the action of an alkali-earth-metal carbid, such as calcium carbid, at a reacting temperature.

In carrying out my invention on a practical basis I proceed as follows, reference being had to the accompanyingdrawings, in which-- Figure 1 is a vertical transverse section through the line a a of Fig. 2, showing retorts partially filled with metal carbid. Fig. 2 is a vertical longitudinal section through the line ;1 1/ of Fig. l; and 3 is a front view of the purifying apparatus, showing outletpipes.

Similar letters of reference indicate like parts in the various views.

A designates a retort made of any suitable material and provided with the heads B and B, the said heads being held against the flange of the retort A by means of the screw-clamp O. Through the heads B pass the inlet-pipe I), provided at the inner end with a deflector or spreader v. The retort A is provided at or near the end closed by the head B with a suitable outlet-pipe b controlled by valves I, said pipes communicating with a common outlet K. Retorts A are preferably heated by means of gas-burners L, which are so arranged as to throw the flame dlrectly under the retorts, whereby the temperature may be regulated and maintained uniformly.

In employing the apparatus, as described, in the separation of sulfur from sulfur-containing petroleums I fill the retorts A with granulated calcium carbid about two inches deep over the entire bottom. I then close the retort or receptacle and introduce into and pass through the retort A a current of vaporized sulfur-containing petroleum from the inlet-pipe D, which is thrown upon the surface of the carbid by the extended depending spreader or deliector c. As the sulfur-containing petroleum passes over the calcium carbid the calcium absorbs the sulfur therefrom, producing a substance which is practically free from sulfur. The reaction which takes place may be illustrated by the following chemical formula or equation, which illustrates the action of calcium carbid on methyl sullid, a hydrocarbon compound containing sulfur, analogous in action to sulfur-containing petroleum:

GeiHeS GREG: 0: "i- CaS,

S+ CR0: 1 CH1;

It will be noted in the foregoing equations that the sulfur is removed from the hydrocarbon, forming calcium sullid, while the carbon of the calcium car-bid unites with a portion of the freed hydrocarbon, producing two molecules of hydrocarbon of less density than the one molecule of sulfur-containing hydrocarbon acted upon. It is found in the sulfurcontaining petroleums that the heavier products predominate over the lighter, the reason for which appears to be that the lighter hydrocarbons are condensed by the coupling or joining action of the sulfur combined therewith, upon removal of which by the action of a carbid, such as calcium carbid, the heavier product is transformed into hydrocarbons of lighter or less dense character. This does not appear to be the case where the sulfur is removed by such agents as. copper oxid or other simple sulfur-extracting or absorbing agents in which the hydrocarbon from which the sulfur is abstracted condenses upon itself, producing products of the heavier hydrocarbon type.

The advantage attained by the employment of a carbid, such as calcium carbid, will be seen when it is understood that the heavier sulfur-containing hydrocarbon products are transformed by the action of carbids, such as calcium carbid, into lighter hydrocarbons, such as kerosenes or illuminating-oils, from the otherwise more dense paraffin products.

After the sulfur has been abstracted from the sulfur-containing oils or petroleum products the purified vapor passes out of the retort or receptacle through the pipes b and the conduit K to a suitable reservoir. (Not shown.)

In starting the reaction it is sometimes advisable to heat the retort or receptacle by means of the burners L to about 360 Fahrenheit, the draft being controlled by the dampers It is found, however, that during the reaction between the sulfur of the sulfur-containing hydrocarbon and the carbid considerable heat is liberated internally, whereupon after inducing the reaction by means of the initial heating the burners L may be shut off and the reaction continued by the heat liberated during the transformation or purification.

I can use or employ any available sulfurcontaining hydrocarbon or sulfurous petroleum, either in a gaseous or vaporized condition or in a pure fluid condition, and I can employ any other alkali-earth-metal carbid in place of calcium carbid aforesaid, so long as the sulfur of the sulfur-containing hydrocarbon or sulfurous petroleum has such an affinity for the base of the carbid that it is withdrawn or separated therefrom when brought in contact therewith.

The term alkali-earth-metal carbid, as employed in this specification and claims, relates to a compound or union of carbon with an alkali-earth metal, be it a normal carbid, acetylid, or other union of carbon with the metal or metals aforesaid.

The processes devised in the prior art for the purification from or the removal of sulfur from sulfurous petroleum or its products have for their object the abstraction of the sulfur content with the destruction of the hydrocarbon to which the sulfur is joined without supplying any available ingredient in lieu of the sulfur abstracted, while in my process the hydrocarbons left after the abstraction of the sulfur content of the sulfurous petroleum.

are augmented or increased in value to the extent of the substitutlon of the carbon for the sulfur content removed, therebynot only removing the sulfur with the purification of the petroleum, but simultaneously producing an equivalent of hydrocarbon as a substitute for the sulfur eliminated, which hydrocarbon exists in a lighter form and is more available for illuminating purposes.

When the process is employed for the removal of sulfur from sulfurous petroleum, such as Lima oil, I prefer to first vaporize the oil by the action of heat and convey this vaporized mixture of hydrocarbon and sulfo-hydrocarbon in contact with the alkaliearth-metal carbid, as aforesaid; but I do not confine myself to this particular method of procedure, as the carbid may be introduced in the liquid of liquefied sulfur-containing hydrocarbon or petroleum, or brought in contact therewith, or exposed to the action thereof, in any convenient manner.

The term gaseous, as employed herein, is intended to include substances of vaporous nature or those which may be vaporized by the action of heat.

My process is not only available for the pnrification of gaseous, vaporous, or vaporized hydrocarbons or sulfo-hydrocarbons, (sulfurous petroleums,) but is applicable to the purification of the more solid constituents of the petroleumssuch as parafiin, petrolatum, &c. and 1 do not desire to confine myself to the purification of petroleum as a composite cornposition, but reserve the right to purify any individual product of the sulfur-containing petroleum which may be or may have been separated into its individual products by fractional distillation or otherwise prior to separating the sulfur therefrom, whereby the individual ingredients of the petroleum may be purified separately instead of collectively, as is the case where the petroleum is vaporized as a whole direct and purified by the abstraction of the sulfur before separation of the individual ingredients.

Having now described myinvention, what I claim as new, and desire to secure by Letters Patent, is-- 1. The process of removing sulfur from petroleum containing the same, which consists in exposing sulfur-containing petroleum to the action of an alkali-earth-metal carbid.

2. The process of removing sulfur from petroleum containing the same, which consists in exposing sulfur-containing petroleum to the action of calcium carbid.

3. The process of removing sulfur from the constituents of petroleum, which consists in exposing the sulfur-containing constituent to the action of an alkali-earth-metal carbid.

4. The process of removing sulfur from the constituents of petroleum, which consists in exposing the sulfur-containing constituent to the action of calcium carbid.

5. The process of removing sulfur from oil containing the same, which consists in exposing the sulfur-containing oil to the action of an alkali-earth-metal carbid.

6. The process of removing sulfur from oil containing the same, which consists in exposing the sulfur-containing oil to the action of calcium carbid.

7. The process of producing hydrogen carbid, which consists in exposing an alkaliearth-metal carhicl to the action of sul't'urous petroleum at a reacting temperature.

8. The process of producinghydrogen carhid which consists in exposing calcium carhid to the action of sulfurous petroleum at a reacting temperature.

9. The process of producing hydrogen carbid which consists in vaporizing sulfurous petroleum and exposing the same to the action of an alkali-earth-metal carbid.

10. The process of removing sulfur from sulfurous petroleum, which consists in exposing it to the action of an alkali-carth-metal carbid at a reacting temperature.

11. The process of purifying petroleum which consists in exposing the petroleum to the action of an alkali-earth-metal carbid.

12. The process of purifying petroleum which consists in exposing vaporized petroleum to the action of an alkali-carth-metal carbid.

In testimony whereof I allix my signature in presence of two witnesses.

HENRY SPENCER 1111A CKHOltll.

\Vitnesscs:

H. N. JENKINS, C. C. \Viueu'r.

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