US1578235A - Gilsonitic product and its manufacture - Google Patents

Description

UNITED STATES.

CHARLES 1v. ronnns'r, or

mwn, HAROLD 'PATE NT OFFICE.

SHIP, MIDDLESEX COUNTY, NEW JERSEY, AND ORIN It. DOUT HETT, OF BEAVER FALLS, PENNSYLVANIA, ASSIGNOBS TO THE PHILADELPHIA, PENNSYLVAN A CORPORATION OF WEST VIRGINIA.

GILSONITIC PRODUCT AND ITS MANUFACTURE.

.No Drawing.

Z '0 all whom it, may concern:

Be it known that we, CHARLES N. FORREST, of Rahway, in the county of Union and State of New Jersey, HAROLD P. HAYDEN, of Raritan Township, in the county of Middlesex and State of New Jersey, and ORIN R; DoUTrrE'r'r, of Beaver Falls, in the county of Beaver and State of Pennsylvania, citizens of the United'States, have invented certain new and useful Improvements in Gilsonitic Products and Their Manufacture, whereof the following is a specification.-

Our invention relates to gilsonitic products and their manufacture, and more espe cially to products and materials obtainable from gilsonite through sulphona-tiontreatment and to processes and methods connected with such treatment. lVehave found that, by treatment of this character, there can be derived from, gilsonite andgilsonitic substances various new and useful products ofunique properties, and we-havedevised various novel processes, steps, and methods for accomplishing this to the best advantage. Certain of our processes and methods can .also be adapted and extended to hydocarbon substances or materials other than gilsonitic ones,-especially those of mineral origin. The various phases of our invention will be specifically described hereinafter in accordance with the best mode of applying them ina practical way at present known to us, while the real scope and essence of the inventionwill be indicated in our claims.

As a gilsonitic material to be treated, we ordinarily prefer gilsonite distillate to native gilsonite itself. Wehave obtaineda much greater yield of sulphonic products from the treatment by preparing the distillate some time in advance and allowedato age for a considerable period before being treated. Such distillate may be prepared as follows I Gilsonite as received from: the time is charged into an iron or steel still, fired with gas or oil (or otherwise suitably' heated), and connected to a suitable condenser,- such as an iron pipe condenser water-cooled.

' 7 Any convenient quantity of gilsonite may be chargech say 600 pounds to several tons.

"vapors under the single .ture approaches some 550 Application filed August 28, .1919. Serial No. 320,5}4.

The still being closed and. heat applied gradually, the gilsonite will liquefy and collect in the bottom of the still, and vapor and gas evolving from it will fill the top of the stlll and pass over into the condenser. As the heating progresses, temperature readings should be taken from time to time on the body of vapor in the upper portion of the still, as well as on the body of liquid beneath may be special octhem, we here andit; (Excepting as there casion for distinguishing hereinafter comprehen'd mingled gases and term vapor, for the sake of brevity; For convenience, we refer tovarious stages of operations by the corresponding vapor temperatures, unless otherwise specially noted.) The effect of the progressive heating of. the gilsonite is to gradually break it up and decompose it chemically,whence, mainly, the evolution of vapor. .The coming off of vapor from the still begins at a temperature of some 165 F., and continues up to or even beyond cokmg temperatures.

Up to the point where-the vapor tempera- F., the distillation may be carried out as rapidly as the contents of the still can bemade to absorb heat. At this point, however, some exothermic or other peculiar action occurs, so that the evolution of vapor in thestill tends 'to become excessively rapid. Unless, therefore, the previous heating has been laspecially slow, it is necessary to reduce the application of heating very greatly as this critical point is approached, in order that undistilled iquid may not be carried over into the condenser,and clog it up so as to render it unusuable. In practice, it will usually be found convenient to cut down the fire some 100" Earn advance of this temperature.

Once this critical point is well passed, the

fire'may be increased. and the distillation pushed on as rapidly as desired to its conclusion. In practice, the heating need not be carried further than a temperature of some850 F., measured on the solid coke product collecting in thebottom of the still.

. WYhile the vapor coming off from the still may all be led into the iron pipe condenser,

P, HAYDEN, OF RARITAN TOWN- IBARBER ASPHALT COMPANY; OF

as above suggested,.and all'of the strictly v length and providing-itwith a trap. With this arrangement, the heavier portion of the normally liquid products will be condensed bythe cooling effect of the atmosphere uponthe pipe (which thus acts as a sort of auxiliary condenser), and will collect in the trap,

. whence it can be drawn off from time to F.,t0 600 F.,subsequently time and added to the liquid products drawn from the condenser itself. The trap also affords ameasure of, protection againstthe effects of too rapid heating at thecritical temperature above mentioned.

'The crude distillate thus obtained contains some 2 to 5% water, which may be eliminated by settling it out in a settling tank.

We prefer not to treat the Water-freed primary, crude distillate thus produced directly, in ross, but to separate it into a plurality of different portions by fractionation'or reduction. The following examples (wherein the temperatures given are the vapor temperatures in the still, unless otherwise .stated) will sufiiciently illustrate the most-convenient met ods of redistillation:

(1) Condense separately the vapors coming from the still .up to 475 F. and from 4.7 5 drawing off as residuum the oil unvaporized at the latter temperature, or allowing it to remain and mix with the next charge of crude oil.

(2) Condense separately the vapors up to 475 n; from 475 F. to 650 F.; and

from 650 F. until the temperature of the material in the bottom of the still is about 850 F. By this procedure, an amount 0 coke equal to. about 2% of the crude oil charge will be produced.

In either of these cases, considerable destructive action, occurs in the productionof the higher fractions,especially the last.

(3) Three fractions nearly similar to those described under (2) may be obtained at temperatures some 100 F. lower than those mentioned by carrying out the redistillation as described in U. S. Patent 87 7 ,620, granted Jan. 28, 1908, to Wells, blowing carbon dioxide or other inert permanent gas through the liquid in the still. In this case, the destructive action is much less. It is advantageous to pass. the gas and vapor com-- ing off through a filter of fullers earth in the dome of the still, on its way to the condenser. A residuum of heavy oil will preferably be left in the still, as described under (1).

The gas tains ammonia, which can be segregated as ammonium sulphate by a sulphuric scrubbing operation. The coke from both distillations also has a nitrogenous content recoverable by a similar operation in connection With conversion thereof into fuel .gas

by incomplete combustion in a by-product gas-producer. the crude distillate also in solution, which may, if desired be also converted into ammonium sulphate. For these operations for recovery of ammonia may be used the unconsumed portion of the sulphuric reagent employed in the purification and sulphonation treatments hereinafter described.

Of the distillates contains ammonia thus produced, we gen.-

erally prefer to treat the intermediate one.

drior to sulphonation treatment, however, we prefer to sub cct the gilsomtic material to preliminary purifying treatment with a sulphuric reagent, thus removing therefrom organic bases, olefines, and other impurities that might alter or impairthe character and utility of the final products. This preliminary sulphuric' treatment may be carried out by agitation of the gilsonitic material with about 5% of sulphuric acid of oil of vitriol grade-d. e., about 66 Be.-for about onehalf hour. It is desirable to repeat the operation (using fresh acid) one or more times.

After this preliminary step,

sulphonation treatment may be carried out by subfrom the primary distillation con- I The water eliminated from' jecting the purified gilsonitic oil to the action of a sulphonating reagent, under the usual sulphonating conditions. The sulphonating reagents which we prefer to use are oil of vitriol, such as mentioned above, and fuming sulphuric acid Or oleum. It is desirableto conduct this treatment in a cast iron vessel, using mechanical agitation rather than air agitation in order to avoid f such contamination with atmospheric moisture as might interfere With the desired reaction. v

We have found that the quality of the final products is improved by carrying out this treatment progressively, with successive portions of reagent, and segregating the reaction products, as formed, from the material being treated, so that each of the successively acting portions of reagent shall be perfectly fresh and-untainted with such reaction products. Further improvement can be obtained .by starting with relatively weak reagent, and using more and more reactive or energetic reagent as the treatment progresses. This may be done in a succession, of separate operations upon a single lot of material with different portio s of reagent, rather than in one single operationsay four such with an amount of reagent equal to 20% ofthe material treated. Thus for the first treatment, the reagent may be oilof vitriol alone; for the "second, a mixture of 15 parts oil of vitriol and 5 parts oleum; for the third, a mixture of oil of vitriol and oleum in equalparts; for the fourth, a mixture of 5 parts oil of vitriol and 15 parts oleum. Each of these treatments may last about twohours.

If, on the other hand, it is desired to carry out sulphonation treatment all at once, in a single operation, rather than progressively; it may be done by mechanical agitation for some eight hours,.-.using, say, an amount of sulphonatin'g reagent equal to 80% of-the material treated and consisting of 50 parts oil of vitriol and 30 parts oleum.

At the end of each treatment or operation,-

the charge in the agitator is allowed to stand an hour or more, when it will be found to have. separated into two distinct layers; a top layer of residual or mother. oil, and a bottom layer of acid sludge. This latter should be drawn off an thus segregated prior to the next tre tment of the mother material.

The residual oil remaining after. the last treatment may be neutralized,.as with sodium hydrate solution (preferably of spe- I cific gravity greater than 30 B.,'in order to avoid emulsification). After the excess of caustic has been drawn oil, the resultant alkaline oil should preferably not be washed, on account of its emulsifying tendency; but it may instead be distilled" with steam, in order to improve its color, and filtered through fullers earth .for the same purpose. This gilsonitic sulphonation residual oil as thus purified is a thin, clear oil; substantially colorless, odorless, and tasteless; and suitable for about the same uses as hi hlv refined petroleum. If desired, the distllla- -tion above mentioned may be carried out fractional'ly, so as to yield different oils more specially suitable for particular pur- .oses.

r It is' preferable that the lots of sludge obtained from different sulphonation treatments be further treated or worked up individually, since the various treatments.

yield final products having somewhat different properties. This sulphonation sludge contains, as principal components, unconsumed sulphonating reagent, Water-soluble organic sulphonic products, and oil produced from the mother oil by chemical action incident to the sulphonationtreatment. It also contains, as impurity, an inconsider able amount of the mother oil itself (which may, if subsequently segregated, be neutreatments, each described, The top layer tralized along with that obtained :as above I described), and some small amount of other organic products. The proportions .of the the rest of the sludge-can be effected by addition thereto of asolvent of the sulphonating reagent; :for this purpose, the sludge may be diluted with an equal Weight of water. Preferably the Water is laced in a lead-lined, Water-jacketed vessel: and the sludge gradually introduced at such a rate that the temperature shall not rise excessively,110 F. being a perfectly safe limit. The operation is declcledly exot ermic, and

sulphur dioxide is copiously evolved. The

dilute sludge is allowed to stand some eight "to twelve hours,moreor less,-at a temperature of 150 F., or thereabout; During this period, separation into three distinct layers takes place, successively drawn offand thus segregated. The bottom layer is a dilute aqueous solution-of the excess of sulphonating reagent, discolored by some slight amount of orand these may be;

gan-ic impurity; the middle layer comprises the water-soluble organic sulphonic mate rial, contaminated with an inconsiderable amount of the solutionthat forms the bottom layer and with a small portion of the ingredlents of the top layer; and thetop layer contains the reaction oil component andthe residual mother-oil impurity, etc., mentioned above. (In some cases, as indicated above, the top layer may be entirely absent. Y

Comlng, now, to the further disposition or treatment of these separation products, the, dilute acid of the bottom layer may be used for the recovery of ammonia as above (when present) may be neutralized with sodium hydrate and washed with water until free from alkali. The resulting gilsonitic sulphonation sludge oil isa viscous liquid; of-slow-drying or semi-drying character; and usually'of dark, reddish-brown color and slight, inoffensive odor, Vaseline.

somewhat'suggesting that of It is soluble in benzole or naphtha and insoluble in. alcohol, when freshly I I also seems to render the fully dried linseed tougher and more elastic.

The water-soluble organic sulphonic material .of the middle layer gives an acid reaction, and has, in general, the useful properties of sulphonic acids. In appropri-. ate combinations, therefore,- its character istic radical or radicals constitute a useful agent for many different 1.)urposes-acting as hydrolyzer or saponifier for oils, "ate, and other glycerides or fatty substances, when employed in the usual manner, and having excellent detergent and emulsifying properties. For the first of these uses, at least, this sulphonie agent is serviceable in the impure acid form in which it exists in the middle layer, although its color characteristics and the efficiency of its hydrolyzing action are not so good as after purification. To purify it of the organic top layer material (the principal contaminating impurity), it may be neutralized, which has the effect of setting free this top layer material and allowing it to float to the surface and be readily removed. For hy'drelyzing purposes, the purified saltthus obtained may be reconverted (by means of sulphuric orother. acid) to yield the agent in purified free acid form; while for detergent or emulsifyingpurposes, the purified salt. form of the agent will ordi narily be preferred to the acid form. The 'sulphonic material of the middle layer can also be freed from organic contamination without neutralization, by merely diluting the middle layer with water freely,-whichwill allow the organic material to come to the surface as described above.

If desired, the salt form of the'reagent may be obtainedvfree from both organic material and sulphates- For this purpose, the middle layer may be diluted with water and barium sulphate precipitated therefrom (some little barium salt of the reagent being unavoidably thrown down also) by addition of barium carbonate in just sufficient amount to fully satisfy the sulphuric acid; this leaves the free acid reagent in solution. Y Af ter filtration, the organic material can be set free for. removal from the solution as before. v

In both purified and unpurilied states, the

sulphonic products from the later sulphonation treatments have greater hydrolyzing power than those from' the earlier treatments.

It is most convenient and desirable to handle, pack, and ship an agent of this sort in the'form of a dry, solid, stable salt, rather than in its more active free acid form,- which is, besides, in the present instance, more'diificult to dry. It is, of course, preferable that the particular salt that is to be so used commercially be produced at the outset, in the freeing of the agent from organic contamination as described in the precedphonic substances ing paragraphs. For detergent and emulsifying purposes, narily be preferable, on account of its relatively low cost. For saponifying or hydro: lyzing purposes, however, it is peculiarly advantageous to employ as the commercial material a salt with a volatile base, and to produce the active, free acid saponitier there from by acidulation when it is to be used,

either before or in the actual treatment of the glycerides,-on account of the facility thus ailorded for securing glycerine water free from sa-ponifier, acidulant, or other deleterious impurity. For this purpose, the ammonium salt form of the agent is especially suitable lVhen this is used, the glycerine water subsequently obtained will contain only acid saponiiier, acidulant, (usually sulphuric acid), and ammonium salt of the acidulant. By addition to this glycerine waterof a suitable base or salt (such as calcium hydrate or barium carbonate), insoluble salts of the acidulant and the saponifier vill be formed and precipitated. This will leave in solution in the glycerine water, as an impurity only an unstable combination (annnoui um hydroxide or carbonate) whose components can be volatilized and driven off by boi ing.

As to the general properties of these gilsenitic derivative sulphonic materials, it is to be observed that the alkali salts (i. e., both ainoniu n and alkali metal salts) are watersoluble, aswell as the acid; whi e the alkaline earth and the other metal salts general- 1y are wateninsoluble. (These properties, itwill be seen, specially adapt these materials'to the modes of use described in the preceding paragraph). As it exists in the middle layer, the acid, material is a thick, viscous fluid, dark or black, with a brown un-.

dertone in a thin film. Aside from the organic top' layer contamination, it is soluble in alcohol. The alkali salts are also soluble in aIcohol,'-which fact affords another convenient method of freeing them from sulhate contamination.

the sodium salt will ordi-' We have hereinbefore spoken of sulphonating reagents, sulphonation treatment, and sulphonation reaction or sulphonic products, etc, using these expressions in reference to the chemical character and mode of. use of the reagent employed in the principal treatment describedabove, or to the useful roperties of products resulting therefrom. lVe do not. however, mean by this language hat our sulphonic products are true 5111 in thevsense oflhaving sulphonic radicals, -since we are without clear evidence on .this point.

Returning,- now, to the residualoil remaining from the last sulphonat ion, we desire to call attention-:to a mode of dealing with it alternative to that above set forth. In this method,'the first step is to :wash

the excess of alkali. If desired, it may also.

be distilled, as'above; This mode of treatment; f greatly improves the color of the 'purifie d residual oil finally obtained.

/The organic material dissolved or. extracted from the residual oil by the, alcohol appears to be the cause of the emulsifying i property of the oil; for when recovered (by 'sulp purity.

distillation of the alcohol), it itself presents this same property. As thus obtained, this extract derivative is' an acid substance, brown to black. in color, and with slight odor. Appropriate combinations of its characteristic radical or radicals present useful roperties similar to those of our other lionic agent described abov'e,'-though' somewhat superior in degree,-and are serviceable for the same purposes and in the same way. -We have no proof, however, that it is a true sulphonic substance or sulphonation product, or that its characteristic radical is sulphonic. In both acid and salt forms, this gilsonitic sulphonic agent is similar to the other as regards water-solubilities; but with respect to organic solvents, it issharply distinguished. Thus both the acid and salt forms are soluble in most organic solvents,-such as benzole, alcohol, petroleum naphtha, or other distillates,' and both salt and acid forms are more freely soluble in such solvents than in water. The dissolution ofthe' acid material in water is peculiar (probably owin to impurity),

in that aswater is gradua added 'toythej' .material,-it'first gelatinizes and then goesv more freely into solution. Therelative hydrolyzin'g, detergent, and emulsifyingproperties of'these gilsonitic derivative sulphonic materials (i. e., acid and salts) are similar to those of the others.

Having thus described our invention, we claim 1. The process which consists in purifying gilsonltic material by sulphuric treatment; subjecting the purified product to the action of .a sulphonating reagent under sulphonating conditions and segregating the resultant sludge; se egating the sulphonic products in the slu ge from the remainder thereof; and freeing the segregated sul--- phonic products from contaminating im- 2. The process which consists in purifying gilsomticmaterial by sulphuric treatment; subjecting the purified product to the action of a sulphonating reagent under sulphonating conditions and segregating the,

resultant sludge; dissolving the unconsumed reagent in the sludge with a solvent, and thus causing reaction products in the sludge a the unconsumed sulphonatin to separate from one another andfrom the.

solution of reagent by gravity.

in the sludge from one another and from reagent by addition to the sludge of a so vent of such reagent.

4. The process which consists in treating gilsonitic material with a sulphonating reagent under sulphonating conditions, dissolving products of the reaction in an excess of such reagent; segregating the resultant sludge solution from the mother material; removing .the' excess of sulphonating re agent from said sludge solution by solution of such excess of sulphonating reagent with another solvent; and separating said reac fl" tion products from one another and from the solution of solvents by gravity.

5. The process of preparing sulphonation reaction products from gilsonitic material which comprises subjectin the gilsonitic material to sulphuric puri cation, thereby removing organic bases, olefines, or other impurities; and subjecting the thus purified material to the action of a sulphonating reagent under sulphonating conditions.

6. The process of preparing sulphonation reaction products from gilsonitic material which comprises purifying the gilsonitic material with oil of -vitriol grade sulphuric acid and subjecting the thus purified material to the action of a sulphonating reagent under sulphonating conditions.

7 7 The step in the manufacture of sulphonation reaction products from' hydrocarbon material which consists in subjecting said material to successive sulphonation treatments with different portions of sulphonating reagent, segregatingthe sludge of each treatment. from the mother material prior to the next treatment of said material.

8. The step. in the manufacture of sul- 9. The method which consists in subject- 1 inggilsonitic distillate oilto progressive sulphonation treatment with successive portions of fresh sulphonating reagent, each unta-inted with reaction products of such treatment.

10. The method which consists in subjecting gilsonitic material to progressive sulphonation treatment with fresh sulphonating reagent of greater and greater reactivity,

( segregating the reaction products, as formed,

' from the material being treated.

11. The method of manufacturing hydrocarbon sulphonation sludge products which consists 1n producing separate lots of-such sludge by a plurality of successive sulphonation treatments of a single lotof hydrocarbon material with different portions of sulphonating reagent, and further treating such lots of sludge individually.

12. The method ing up a plurality of lots of such sludge from a single lot'of gllsomtic material.

13. The method oi trcatmg g1ls0n1t1c sulphonation sludge which consists in segre-j ing the uneonsumed sulphonating reagent therein with a solvent, and separating the sulphonic and other reaction products in the sludge from one another and from the solution of reagent by gravity.

15. A gilsonitic snlphonic material; serviceable as an agent for the hydrolysis of glycerides; detergent: and characterized by a radical whose alkali= salts and free acid arew'atensoluble, but whose alkaline earth salts are water-insoluble.

16. A sulphonation product derived from gilsonite distillate; having generally the useful properties of true sulphonic substances; and characterized by a radical whose alkali salts and free acid are waterof manufacturing gilsomtlc sulphonation sludge products winch .consists 1n separately preparing and Worksoluble, but. whose alkaline earth and other metallic salts generally are water-insoluble.

17. A sulphonic material derived from gilsonitie sulphonation sludge as a watersoluble separation product; characterized by a radical whose alkali "salts and free acid are water-soluble, but whose alkaline earth salts are water-insoluble.

18. A sulpili'onie derivative of sulphurically purified gilsonitic material; having in general, the useful properties of true sulphonic substances.

19. A sulphonic derivative of the residual from antecedent sulpho-nation treatment of gilsonitic material;

stances; and characterized by superior hydrolyzing power as compared' with the corresponding product from such antecedent snlphonation treatment.

20. A sulphonie derivative of the residual "from antecedent sulphonation treatment of sulphurically purified gilsonite distillate.

21. A gilsonitic sulphonic material serviceable as an agent for the hydrolysis of glycerides; comprising a salt of a volatile base which yields, when acidulated, an active water-soluble saponifier.

22. A gilsonitic sulphonic material serviceable as an agent for. the hydrolysis of glycerides; comprising a water-soluble ammonium salt which yields, when acidulatcd an active water-soluble saponifier.

In testimony whereof,.we have hereunto signed our names at M'aurer, N. J this 25th day of August, 1919.

CHARLES N. FORREST. "HAROLD P. HAYDEN. ORIN R. DOUTHETT.

having, in general, the 'useful properties of true sulphonlc sub-