US1322878A - Low-boilina oil esom hicrhek-boilihg petroleum ob belated oil - Google Patents

Description

names! is. com, or :rEnsEY crrnnaw JERSE Assrenon r0 STANDARD on. COMPANY,

or BAYONNE, nEw JERSEY, A conroan'rxon or NEW JERSEY.

ammo Low-Bourneon. mom HIGHER-BOILING PETROLEUM on RELATED on.

aeaaets.

l lo Drawing.

To all whom it may camera:

Be it known that I, ERNEs'r B. COBB, a citizen ofthe United States, residing at Jersey City, in the county of Hudson and State of New Jersey, have invented certain new and useful Improvements in Making Low-Boilin Oil from Higher-Boiling Petroleum or elated Oil, of which the following is a specification.

his invention relates to obtaining 011s which arecomposed mainly at least of hydescription which are mainly at'least composed of hydrocarbons with viscosities too low for normal constituents of other than li ht grades of lubricants (say with viscosities under one hundred and seventv seconds at 100 F. with an Engler viscosimeter with which water exhibits a viscosity of fiftythree seconds at 60 F.) such as the inferior grades of burning oil (kerosene) (either finished or untreated) and the oils commonly disposed of as gas oil or fuel oil on account of their being unfit on the one hand for burning oil (kerosene) and on the other for medium and heavy lubricants; for which products there is usually a good demand at higher prices than those of gas oil or fuel oil.

In accordance with the invention, pe-

troleum in appropriate form is distilled with anhydrous aluminum chlorid (Al Cl in solution in (combination with) a part of the oil operated upon (useful proportions hereinafter indicated) at temperatures sufficient to split up component hydrocarbons of the oil; and the products of such distillation are fractionated to obtain oils of such grades as may be desired and obtainable.

Said distillation with anhydrous aluminum chloridis continued to such extent as may be desired. By continuing it until a Specification of Letters Patent.

Patented Nov. 25, 1919,.

Application filed April 25, 1914. Serial No. 884,344.

dry or nearly dry residue remains in the still, practically the entire carbon content of the oil operated upon, except the portion which escapes as gas or as uncondensed vapors or is otherwise lost, is obtained'in the forms of distillate from distilling in the presence of anhydrous aluminum chlorid and of coke respectively.

Should the distillation be terminated previously, that is to say, while the residual material is yet liquid as a whole or in substantial proportion, the carbon content of theoil operated upon can also be obtained 11 said forms respectively, by separating the oily portion of the residual material from the aluminum chlorid thereof and (if desired) also from the solid carbonaceous matter (1f any) which may be present therein, and subjecting the hydrocarbons of said oily portion to distillation with anhydrous alumlnum chlorid. The so separated oily portion can be distilled at once with anhydrous aluminum chlorid, but it would best be distilled by itself to dryness or nearly so, and the resulting distillate then be distilled with anhydrous aluminum chlorid.

The said oily portion can, however, be disposed of otherwise as may be preferred; in case it should not be desired to distil its component hydrocarbons with anhydrous aluminum chlorid.

In distilling with anhydrous aluminum chlorid the activity of the latter diminishes with the progress .of the distillation; and of the temperature of the oil in distillation should be kept approximately constant, after a suitable flow of the distillate has been established, the delivery is liable to diminish down to an impracticably slow rate, andeventually to cease altogether; and this diminution (or cessation) of distillation, in distilling at constant temperature,

occurs sooner the less the proportion of an-- more than ten per cent. by weight of the original charge of oil operated on (less than I ten percent. in fact) will exert its activity continued to dryness or approximately so.

The aluminum chlorid is easily separated temperature, and allowing the resulting:

substantiallyto the end of a run, which-is in its entirety from its original solution in a part of'the oil operated upon, by washing such solution with water at say atmospheric num'in a sample after the latter has been I boiled say for ten minutes in water.

By further distillation at increasing temperature, less and less of the aluminum chlorid is found to be separable in this manner; so that eventually the major portion of the aluminum chlorid will be retained. The union with carbonaceous matter may in fact become so strong that little 4 (if any) of the aluminum chlorid can be extracted from the residual material by boiling water as aforesaid.

In case, therefore, the aluminum chlorid is to be recovered by washing out, it is desirable not to proceed too far with the distillation; but, in view of the fact that the farther the distillation is carried, the greater the conversion effected by a given amount of aluminum chlorid, it is desirable on this account to proceed at least until the residual material attains approximately the lowest point at which practically all of the aluminum chlorid can be washed out with water.

Any ordinary or suitable distilling apparatus can be used. An ordinary still of horizontal cylindrical form holding say six hundred barrels of forty gallons each and an ordinary watercooled condenser connected with said still by a vapor pipe will answer. The following examples are given by way of illustration and not as restricting the invention to them or to details of them.

Such a still may well receive a charge of about four hundred barrels of the gas oil or fuel oil mentioned, and a limited proportion;

not more than about ten per cent. by weight of anhydrous aluminum chlorid. The temperature isgradually raised until distillate commences to flow from the condenser outlet (which may be 'in say six or eight hours or there about from the commencement of firing); and the fires are regulated to give barrels an,

tion increases gradually, as is required in order to distil at an industrially; practicable rate. The run is terminated sooner or later, according to It may, for example, be carried on until the contents of the still constitute an at least approximately dry residue; or it may be terminated while the residual material is liquid in whole or in asubstantial proportion. It may be terminated while the stlll contents are of a character to permit the practicable separation ofaluminum chlorid from the remaining material by washing out; or it can be carried so far that the'separation, 1f any, which can thus be effected is not enough to be practicable.

Atthe close of the run, the heating is discontinued, and later, when the running (if any) from the condenser outlet has ceased, the residual material is removed from the still preparatory to charging the still for a a new run; If said residual material is sufliand the aluminum chlorid therein (or its elements) can-be recovered and disposed of, in any appropriate way. The oily or other carbonaceous matter in said resldual material can also be recovered and disposed of I as preferred. For example, by combustion of the residual material (in whatever condition) an ash consisting almost wholly of alumina is obtained, and also gases containing hydrochloric acid. If the residual material is of a character to allow a practicable separation of aluminum chlorid by washing out, it is advantageously washed with water of appropriate temperature, say at or above 150 F., using as little water as will suflice, say about twenty five per cent. of the residue, or possibly a smaller amount; especially if the washing is conducted in a systematic manner by transferring the wash water from a previously washed residue to residue whichhas not been washed to the same extent, if at all. An aqueous solution of hydrated aluminum chlorid is thus obtained, which can be disposed of in any appropriate way. By evaporation of it' to dryness, alumina is obtained as residue and hydrchloric, acid passes OK with the water vapor. If the residual material is liquid in whole or in substantial proportion, washing aqueous solution of hydrated aluminum chlorid. The so recovered oil is advanaluminum chlorid. The coke from distillin the recovered oil to dryness can be dispos of as may be preferred. The recovered oil I can be distilled at once with anhydrous aluminum chlorid, although not so advanmasses means from hydrochloric. acid) is passed over an incandescent mixture of coke and alumina.

Returning to the distillation of the petro-' leum (gas oil as mentioned) with anhydrous aluminum chlorid, it suflices to collect the distillate all in one receiver. Any solution of anhydrous aluminum chlorid which may come over with distillate is allowed to settle out and is separated for. future 'use. The condenser and a liquid separator intermediate the condenser and the distillate receiver may well be elevated above the still, and the bottom of the separator be connected with the still by a suitably trapped pipe for conducting the aluminum chlorid solution back to the oil in distillation; while the upper part of the separator is connected with the distillate receiver.

The distillate may be washed with water and then fractionated with partial or with complete distillation by means of dry heat; or the fractionation may be performed by partial distillation in a steam still, in whic case the water of condensation serves to wash the distillate. Washing the distillate with water can precede the steam stilling, if preferred; and the residual oil from partial distillation with dry heat or in the steam still can be fractionated by dry. heat, or can be disposed of otherwise, as may be preferred. Iii-some cases at least it may be best to agitate the washed distillate with sufficient alkali (caustic soda lye) to neutralize any remaining acid (hydrochloric acid) therein before fractionating by distillation. In fractionation, cuts are made to obtain oils of the desired grades, all of which may well be composed at least mainly of hydrocarbons with boiling oints not exceeding 450 F. and also to o tain, if desired, higher boiling oils. The low boiling oils, say various grades of naphtha, may be finished for use or sale by giving them the customary treatment with sulfuric acid and alkali; and the burning oil (kerosene) distillate can be similarly finished. The higher boiling oils, as a whole or in such part as may be preferred, can be distilled anew with aluminum chlorid; or ,they can be disposed of otherwise, as may be preferred.

Good results have been obtained in a small way with an amount of anhydrous aluminum chlorid equal to about seven per cent. by weight of the oil operated upon; nine per results. The proportlon can cent. by Weight would probably give betteg e varle within wide limits. Reduction of the proportion of anhydrous aluminum chloridtends to lower the yield. of hydrocarbons with boiling points below 450 F. Increase in the proportion of anhydrous aluminum chlorid tends to increase the proportion of such hydrocarbons; but it Will probably not be worth while to exceed about ten per cent. by weight in any case. If this percentage be aluminum chlorid dissolves at appropriately elevated temperature in a part of such d s-- agitation, The anhydrous aluminum ch10 ridcan be added to the oilin thestill in solid state or in solution; or it can beplaced added to petroleum distillate (gas oil or fuel ,oil or, other .distillate) the; anhydrous in the still before charging the same with i' oil. When the still is heated the aluminum chlorid dissolves gradually in a part of the oil when the temperature sufiices. Probably if enough aluminum chlorid were employs the whole of the oil might form a solution thereof; but it is'not be ieved that so large a proportion would be desirable, practicable.

From gas oil or fuel oil containing some parafiin wax and of a gravity of 33.8 B.,

which consisted of over ninety per cent. by

volume of hydrocarbons with boilin points above 450 F. and which, if distilled in the usual Way in a laboratory flask, would give first runnings equal to five per cent. by

volume with a gravity of 48 3, an amount of naphtha (distilling ove'r up to 302 F.) of 67 B. equal to about twenty anda half per cent. by volume of said gas oil or fuel oil and water white burning oil (kerosene) of 45:6" B. equal to twenty nine per cent. by volume of said gas oil or fuel oil have been obtained, using about 7% by weight of anhydrous aluminum chlorid and working in a small way. These oils consisted the naphtha wholly and the kerosene mainly of hydrocarbons with boiling points not exceeding 450 F. The first 5% runnings of the distillate had a gravity of 80.7 B. The naphtha hydrocarbons have been found to be mainly at least of a saturated character, exhibiting small heating effect, as compared with naphtha produced in the ordinary crackingof crude petroleum, when shaken up 20 7 low grade and about 45.3" B. gravity" obfree from paraffin wax and having a gravity of 403 B., which consisted over thirty per cent. of hydrocarbons with boiling oints above 450 F. and which, if distilled 1n the usual way in a laboratory flask, would give first runnings equal to five per cent. by volume having a gravity of 51.9 B. there has 'been obtained (using about 7% by weight of anhydrous aluminum chlorid and work- 'ingin a small way) a yield of nearly twenty seven percent. by volume of naphtha of 57.7 B. gravity, composed wholly of hydro carbons with boiling pointsup to 302 F. (first runnings equal to five per cent. by volume of the oiloperated upon having a gravity of;71 B.) and about sixty per cent. of burning oil (kerosene), distillate over ninety five per cent. of whose hydrocarbons had boiling points not exceedin 4 50. F.

From finished burning oil erosene) of tained mostly from Pennsylvania and Limacrude petroleum (in part from each), using about 7% by Weight of aluminumc-hlorid and working in a small way, about 24.5% by volume of naphtha of 687 B. distillin over up to 302 F. (first 5% runningsof 603 B.

' The temperatures of the oil in distillation and other things will vary consider ably, according to the character of. the starting material and other circumstances. In

a small scale test run (which was made sub-' sequentlyto the filing of the application for the present patent by way of example in order to illustrate a particular case in detail 16 and in which a charge of 2,500'cubic' centi- -meters of a gas oil of 344 B. gravity was distilled with anhydrous aluminum chlorid to dryness) the oil inflistillationshowed a temperature of 315 F. when distillate commenced to flow from the condenser outlet (about an hour and twenty five minutes after commencement of firing)" and a temperature of nearly 700 F. when less than one per cent. of obtainable distillate remained in the still (about eleven hours and forty five minutes later). vThe observed temperature of the vapors passing over to be condensed as distillate. was 200 F. when distillate commenced to flow from the condenser outlet and 470 F. when the oil had been distilled to. the. above mentioned state of approximate dryness. lnthis testrun one hundred and fifty grams of anhydrous aluminum chlorid (equal to seven per cent.

the start.

the vapors which were condensed as distillate. The first of the following tables by Weight of the original still charge) were 1 I employed, the whole being introduced at" The distillate was collected in sixteen fractions, each equal to five per cent.

(Table 'A) shows the gravities of the sev- I eral fractions, the respective temperatures of the oil in distillation and the vapors passing over to be condensed as distillate at the,

close of each collection, and the time oc-jfcupied in each collection. The second table I (Table B) gives the results of assays of the j 1 several 5% fractions of distillate and shows 1.. j.

the percentages of each fraction with boiling points up to 302 F., 350 F.,1450 F. and 572 F.,'respectively. This table also shows (1) the final temperatureof the]; pors in the flask neck in each assay in which such final temperature was below 572 -'F.Q, (2) the percentage ofoilremaining inthe flask at the close of the assay in each case y I in whichthe vapors in the flask neck. at-" tained a temperature of 572 F., and (3) the percentage of loss 1n each assay.

Table A.

. Fractiors (laistillalatejper gfi gfg tolill 1 225;; Time,

. 11 m 5 s i 0e y v0 u e B over .F minutes 00.1 402 31s 40 63.8 434 320 35 59.2 472 340 4 30 57.5 502 35s 35 56.1 534 376 40 55.0 557 505' 50 54.5 500 390 40 54.2 570 420 35. 53.8 572 420 40 55. l 581 424 40 55.5 500 434 45 55.5 500 440 50 54.1 515 450 55 54.2 035 475 55 53.0 050 475 50 55.9 002 470 05 54.8 000+ 480 55 Table B.

Fractions distillate, Sper 302 350 450 572 Final, Bot- L cent. by vol- F. F. F. F. T. toms.

ume.

Perot. Perct. Perot. Perot. Perot. Perot. Perot. 75.0 83.0 89.0 91.0 490 0. 70.0 20.0 86.5 02.0 543 s. 57.0 71.0 85.0 93.0 550 7. 49.0 63.5 82.0 93.5 560 6. 43; O 57. 0 78. 0 94. 0 560 6. 42.0 55.0 75.5 00.5 558 0. 36. 0 4S. 0 74. O 95. 0 565 5. 35.0 47.0 07.5 94. 5. 570 5. 33. 0 43. 5 64. 0 94. O 2. 0 4. 35.0 45.0 53.0 05.0 558 5. 39. 0 49.0 68. 0 93. 0 3. 0 4. 36. 0 46.0 66.0 95. 0 570 5. 32.0 41.0 57.0 91.0 7.0 2. 31. 0 40. 0 55. 0 89. O 9. 0 2. 30.0 38.5 50.0 73.0 25.0 2. 35.0 45.0 58.0 74.5 23.5 2.

An assay of a specimen of the gas 011 haaaere charged (344 B. gravity) showed the following percentages:

may be made of petroleum in undistilled forms, reduction (partial distillation) of crude petroleum with or without injection of superheated steam into the oil; but it is considered less advantageous to operate upon un distilled petroleum than upon distillates on account of the larger proportion of carbon in the former.

' Gas oil yields more carbon oil (kerosene). A considerable amount of gas and light vapors, which would escape condensation in the ordinary water cooled condenser, would also be formed in any case.

Distillates of higher boiling hydrocarbons than those of the gas oil or fuel oil mentioned (such as heavy paraffin distillate or pressed paraflin distillate, or even residue from partially distilling pressed distillate). can be operated upon; but it is considered that to do so would be less advantageous than to operate on gas oil or fuel oil, or low grade burning oil (kerosene) (finished oil or untreated distillate). The distillates obtained in reducing pressed paraffin distillate can be operated upon; and, in fact, the lighter portion of such distillate (when available) commonly forms part of the gas oil or fuel oil mentioned. So-called acid oil, obtained in known ways from acid sludge from treating burning oil (kerosene) distillate and lubricant stock (one or other, or both) with sulfuric acid (usually acid of 66 13., sometimes stronger) can be operated upon, alone or in mixtures. Hydrocarbon oils which are not forms of petroleum, but have a suitably close relation thereto, such as shale oils and the like, canbe operated upon.

The fractionation of the distillate from the distillation with anhydrous aluminum chlorid, instead of being performed wholly in a distinct distillation, may be performed at least in part in the distillation with anhydrous aluminum chlorid by means of a partial condensation or a series of partial condensations of the vapors. Condensate or one or more condensates from such partial condensation or condensations can be re-.

turned to the oil in distillation or can be col lected as distillate, as may be preferred. -The partial condensers (one or more) may be air cooled or liquid cooled. They may receive the vapors at or near the bottom, so

as crude petroleum, or residues from than burning oil (kerosene) or other that these pass in tact with retrograding condensate; or they may receive the vapors at or near the top, so that the, vapors, as well as the condensate, travel downward.

The distillation with anhydrous aluminum chloridis not necessarily performed by charging a still and then running off the charge. less continuous manner. Oil might be supplied to the charge in the still while the distillation is going on, with or without addition thereto of anhydrous aluminum chlorid,

It maybe performed in a more oropposite directions in conand with or without the withdrawal of residual oil during the run. Continuous stills of any known or suitable form can be used.

Distillate from the distillation with anhydrous aluminum chlorid can be treated with sulfuric acid and alkali prior to fractionation by further distillation; but it is considered better to apply such treatment to fully fractionated oils.

Other materials not inconsistent with the action of the aliiminum chlorid on hydrocarbons can, ofcourse, be used in addition thereto. Anhydrous perchlorid of iron (Fe Ol if used inaddition to the anhydrous aluminum chlorid, is believed to comchlorid of iron and aluminum; which acts similarly to the aluminum chlorid; a difference in reaction has been observed; and probably a number of other substances would act similarly. In naming aluminum chlorid, therefore, in the hereinafter written claims, it will be understood that double chlorid of iron. and aluminum and other similarly actingsubstances are intended to be included and'not excluded by such recital.

In stating in the hereinafter written claims that the petroleum or related oil is to be in' any appropriate form, it is to be understood that gas oil or fuel oil, burning like form is primarily but not necessarily exclusively intended. In consequence of oflicial requirement of division, an application (oflicially numbered 186,542), for part of the subject-matter set forth hereinabove, was filed August 16, 1917, as a division andcontinuation of the application for the present patent.

On. July 14 and October 4, 1919, applications (officially numbered 310,875 and. 328,578, respectively) were also filed for part of the subject-matter herein above set forth. Each of them is a continuation of the application for the present patent; and each of them, moreover, has been made under section 4897, Revised Statutes, for the invention or discovery of my said divisional appication No. 186,542, allowed October 6, 191

I claim as my invention or discovery: 1. The process of making low boiling oil although bine with thelatter and so to form a double from higher boiling petroleum or related oil,

consisting in distilling petroleum or related oil in any appropriate form with anhydrous aluminum chlorid in solution in a part of the oil operated upon, and conducting operations in such manner that practically the entire carbon content of the oil operated. upon, except the portionwhich escapes as gas or as uncondensedvapors or is otherwise lost, is obtained the main part thereof in the form. of distillate from distillation in the presence of said anhydrous aluminum chlorid and the remaining smaller part of said carbon content in the form of coke, substantially as described;

2. The process of makinglow boiling oil from higher boiling petroleum or related oil, consisting in distilling petroleum or related oil in any appropriate form with anhydrous aluminum chlorid in solution in a part of the oil operated upon at least until the residue approximates the lowest point at which it can be freed from aluminum by boiling with water, substantially as described. I

3. The process of making low boiling oil from higher boiling petroleum or related oil, consisting in distilling petroleum or related oil in any appropriate form with a limited proportion, not more than about ten per cent. by weight, of anhydrous aluminum chlorid in solution in a part of the oil operated upon, conducting the distillation with such regulation of the fires as to maintain a good flow of distillat from the condenser outlet by reason of the rising temperature of the oil operated upon, and continuing the distillation with rising temperature in said oil at least until the residue approximates the lowest point at which it can be freed from aluminum by boiling with water, substantially as described.

4. The process of making low bolling oil from higher boiling petroleum or related oil,

consisting in distilling petroleum or related oil in any appropriate form with anhydrous aluminum chlorid in solution in a part of the oil operated upon until the residue is reduced to an at least approximately dry condition, substantially as described.

5. The process of making low-boiling oil cent. by weight, of anhydrous aluminum chlorid in solution in a part of the oil operated upon, conducting the distillation with such regulation of the fires as to maintain a good flow of distillate from the condenser outlet by reason of the rising temperature of the oil operated upon, and continuing the distillation with rising temperature in said oil until the residue is reduced to an at least approximately dry condition, substantially as described.

6. The process of making low-boiling oil from higher boiling petroleum or related oil, consisting in distillingpetroleum or related oil in any appropriate form with anhydrous aluminum chlorid in solution in a part of the oil operated upon, conducting the distillation with such regulation of the fires, as

to maintain a good fiow of distillate from the condenser outlet by reason of the rising temperature of theoil operated upon, and continuing the distillation with rising temperature insaid oil until at least approxi mately the end of the run, substantially as described.

7. The process of making low-boiling oil from higher boiling petroleum or related oil, consisting in distilling petroleum or related oil in any appropriate form with a limited proportion, not more than about ten per cent. by weight, of anhydrous aluminum chlorid in solution in a part of the oil operated upon, conducting the distillation with such regulation of the fires as to maintain a good flow of distillate from the condenser outlet by reason of the rising temperature of the oil operated upon, and continuing the distillation with rising temperature in said ERNEST B. COBB.

l/Vitnesses:

C. M. FORREST, CORA H. TRACY.