US1986593A

US1986593A - Treatment of hydrocarbon oils and coal

Info

Publication number: US1986593A
Application number: US537233A
Authority: US
Inventors: Jacque C Morrell
Original assignee: Universal Oil Products Co
Current assignee: Universal Oil Products Co
Priority date: 1931-05-14
Filing date: 1931-05-14
Publication date: 1935-01-01
Anticipated expiration: 1952-01-01

Description

' Jan. 1, 1935. J. (#MORRELL 1,986,593

TREATMENT OF HYDROCARBQN OILS AND GOAL Filed May 14, 1931 INVENTOR I JAcQUE Q. MORRELL BY Z MQ ATTORN 10 under tities of relatively Patented Jan. 1 1935 Jacque C. 'Morrell, Chicago, 111., assignor to Universal Oil Products Company, Chicago, 111., a corporation of South Dakota Application May 14, 1931, Serial No. 537,233

6 Claims.

This invention relates to the treatment of hydrocarbon'oils and coal and particularly refers to the simultaneous conversion of relatively heavy oils and coal into lighter and more valuable liquid products and carbonaceous residue.

It has been proposed, as an economic process in localities where coal is plentiful, to convert mixtures or a suspension of pulverized or powdered coal in a relatively heavy hydrocarbon oil, elevated temperatures and substantial superatmospheric pressures, into lighter and more valuable hydrocarbon liquid products, such as, for example, motor fuel. and substantially dry carbonaceous residue. Difliculties have been encountered in suchprocesses under someconditions of operation by carbonization of the 'heatmg element through which the coal and oilfnixture is passed when conversion temperatures sufliciently high to effect the production of maximum quanlight desirable products such as motor fuel are employed. The present invention overcomes this difficulty by providing a secondary charging stock which preferably comprises a hydrocarbon oil which is not so easily coked or carbonizedas the coal and oil mixture, said secondary charging stock being subjected to higher conversion temperatures than those to which the coal and mixture of oil is subjected. The two streams of heated material are commingled, either in the coking zones of the system, or prior to their introduction thereto, the relatively highly heated oil serving as a means of increasing the temperature of the coal and oil mixture to the desired degree, after passage of the latter through the heating element.

A specific embodiment of the present invention may comprise: subjecting a mixture of hydrocarbon oil and pulverized or powdered coal to conversion conditionsin a heating element, introducing the heated products into a reaction zone wherein vaporous and non-vaporous conversion products may be reduced to a substantially dry carbonaceous residue, subjecting vapors from said reaction zone to fractionation, subjecting. the desirable components of the vapors to condensation and cooling and collecting the resulting products, returning the relatively heavy insufiiciently converted components of the vapors which may be condensed in the fractionating zone to further conversion in the same cracking system and subjecting a secondary charging stock to independently controlled conversion conditions in a secondary heating element under a higher conversion 1 temperature than that to which the coal and oil mixture has been subjected, thence commingling the stream of heated secondary charging stock with the heated coal and oil mixture and introducing the stream of commingled materials into said reaction zone. 5

As a feature of the present invention the insufficiently converted intermediate products of the process, which may becondensed from the vapors during fractionation thereof, may be returned for further treatment either with the coal and oil mixture or with the secondary charging stock and except in cases where the secondary charging stockis a relatively light distillate such as, for example, a light gas oil, kerosene distillate, naphtha or straight-run motor fuel, said intermediate products are preferably returned for retreatment, together with said secondary charging stock. When naphtha or gasoline is employed as a secondary. charging stock, it is among the objects of the invention to reform the same to improve the anti-knock value.

The attached diagrammatic drawing illustrates one form of apparatus embodying the principles v of the present invention. A mixture of coaland oil, the coal preferably being finely dispersed and suspended in an oil sufliciently heavyto function as a carrying medium, may be supplied through line 1 and valve 2 to pump 3 from which it may be fed through line 4 and valve 5 intoheating element 6 which is located within any, suitable form 'of furnace 7 capable of supplying the required heat to the material undergoing treatment. The heating element is preferably of such form that the mixture is passed therethrough at relatively high velocity and preferably the mixture is maintained in a turbulent state during heating to prevent deposition of coal-in the heating element. The coal and oil mixture, after being heated to the desired temperature, preferably under a substantial super-atmospheric pressure, may be discharged through line 8 and valve 9 and may pass either thri ugh line 10 and valve 11 into reaction chamber 12 or through line 10' and valve 11' into reaction chamber 12' or may be discharged, in part, into both of these chamberssimultaneously. The temperature and pressure conditions employed in heating element6 may be within or somewhat below the range of conversion conditions and, preferably the conditions under which the oil and coal mixture is subjected to treatment in this zone are suflicient to initiate and effect substantial conversion of' said coal and oil mixture but are not sufliciently severe to cause any substantial deposition of carbouau Ousmaterial prior to the introduction of the stream of heated material into the reaction zone.

Reaction chambers 12 and 12' are similar zones preferably maintained under substantial supera other is being used, or, if desired, the two chambers may be operated simultaneously, the purpose in either case being to prolong the operating cycle. It-will be understood that while two reaction chambers are illustrated only one chamber or, if desired, more than two chambers may be employed without departing from the spirit of the invention. Drawoff lines 13 and 13' controlled by valves 14 and'14' respectively, are provided on chambers 12 and l2" respectively, to permit the removal of water and/or of any liquid residual product, when desired. Vapors may be withdrawn from chamber 12 through line 15 and valve 16 while vapors may be withdrawn from chamber 12 through line 15 and valve 16. The vapors from the reaction zones may pass through line 1'7 and valve 18 to fractionation in fractionator 19, which may be of any suitable and well known form capable of separating the relatively light desirable components of the vapors from their heavier insufliciently converted components.

The relatively light desirable compone'ntsof the vapors may pass from iractionator 19 through line 20 and valve 21, may be subjected to condensation and cooling in condenser 22, uncondensable gas and distillate from which may pass through line 23 and valve 24 to be collected in receiver 25. Uncondensable gas may be released from the receiver through line 26 and valve 27.

Distillate may be withdrawn from the receiver through line 28 and valve 29. A portion of the distillate may, if desired, be withdrawn from receiver 25 through line 26 and valve 27' to pump 28' by means of which it may be recirculated through line 29' and valve 30 to the upper portion of fractionator 19, wherein it may serve as a cooling and refluxing medium, assisting fractionation of the vapors and controlling their outlet temperature.

The relatively heavy insufliciently converted components of the vapors, which may be condensed in fractionator 19, may pass therefrom through line 31 and valve 32 to pump 33 by means of which they may be returned to the cracking system for further conversion, passing through line 34 and either through line 35, valve 36 and line 4 into heating element 6 or, preferably,

through line 37, valve 38 and line'39 into a separate heating element 47 or, ii desired, this oil may be directed, in part, to each of the heating elements 6 and 4'7. That portion, if any, of the re-- flux condensate from fractionator 19 which is returned to heating element 6 is subjected to retreatment therein together with the coal and oil mixture supplied to the process. That portion, if any, of the reflux condensate from fractionator 19, which is returned for retreatment to heating element '47, is subjected to conversion conditions in this zone, together with a secondary charging stock, preferably comprising an oil which is not easily coked or carbonized under conversion conditions somewhat more severe than the conditions employed in heating element 6. The secondary charging stock may be supplied through line 40 and valve 41 to pump 42, being fed therefrom through line 39 and valve 43 to heating element 47. This secondary charging stock may correspond in characteristics to the reflux condensate from fractionator 19 or may possess different characteristics and said reflux condensate may be subjected to retreatment together with the coal and oil mixture, depending upon which said secondary charging stock or together with of the conversion conditions, those employed in heating element .6 or those employed in heating element 47, are best suited to effect further conversion of said reflux condensate into maximum yields of the desirable products. For example, if

the reflux condensate and the secondary charging stock are both relatively light; low boiling oils possessing similar characteristics with respect to their ideal conversion conditions they are preferably commingled and subjected to conversion in heating element 4'1. 0n the other hand if for example, the secondary charging stock is a relatively light distillate such as naphtha or straight-run gasoline and the reflux condensate is a heavier oil which might be over-cracked into excessive yields of gas and coke if subjected to the conversion conditions desirable for the secondary charging stock, saidreflux condensate is preferably returned for retreatment together with the primary charging stock. It may be desirable to blend a portion of the reflux condensate with each of the two streams of charging stock in order to somewhat alter the character thereto is preferably subjectedto conversion conditions more severe than the conditions employed in heating element 6. A substantial super-atmospheric pressure is preferably employed in heating element 4'7, although substantially atmospheric or relatively low super-atmospheric. pressures may be employed in this zone, ifdesired. The stream of heated oil may be discharged from heating element 47 through line 45 and-valve 46, conmiingling with the stream of heated coal and oil mixture discharged from heating element 6, serving to increase the temperature of the latter for the purpose of eflecting its further conversion and passing therewith either through line 10 and valve 11 into reaction chamber 12 or through line 10' and valve 11 into reaction chamber 12 or partially to both of these zones, wherein conversion of the commingled materials may continue and where, as'already described, the residual conversion products may be reduced to-a substantially dry carbonaceous material. It will be readily understood that the two streams of heated material may be commingled either within or prior to their introduction into the coking or reaction chamber, although for the sake of simplicity, no alternative is shown in the drawing.

Pressures employed within the system may range from substantially atmospheric to superatmospheric pressures as high as 2000 pounds per square inch or more. Temperatures employed in F. more or less. The

the heating elements may range from 650 to 1200 heating element in which the coal and oil mixture is treated may employ temperatures below the conversion range or.rel-- atively mild conversion temperatures, said temperatures ranging preferably from 650 to 900 F. or thereabouts, depending primarily upon the percentage and type of coal and its degree of dispersion or suspension in the oil, the type of oil which the coal is admixed with, and upon the pressure conditions employed. Preferably substantial super-atmospheric pressures of the order of.100 to 500 pounds per square inch are employed in the primary heating element. Substantial super-atmospheric pressures of about this same range may also be employed in the reaction chambers although the reaction chambers may; if desired, be operated under reduced pressure relative to that employed in theprimary heating element and, if desired, may employ substantial ly atmospheric or relatively low super-atmospheric pressures. Preferably, substantially higher temperatures of the order of 900 to 1200" F. are employed in the heating element in which the secondary charging stock is treated and pressures ranging from substantially atmospheric to super atmospheric pressures as high as 500 pounds per square inch or more may be employed in this zone. In general, relatively low pressures are used with the higher temperatures and vice-versa. If a relatively low pressure is employed in the secondary heating element substantially the same or lower pressures must, of course, be employed in the reaction chambers. The fractionating, condensing and collecting equipment may be maintained under any desired pressure ranging from substantially atmospheric to 500 pounds per square inch or more super-atmospheric.

As a specific example of the operation of the process .of the present invention, the primary charging. stock comprises a fuel oil of about 16- A. P. I. gravity with. which has been mixed about 50% by weight of the raw oil, of pulverized bituminous 'coal. The coal and oil mixture is subjected in the primary heating element to a. temperature of about 850 F. under a super-atmospheric pressure of about 500 pounds per square inch. Reflux condensate from the fractionator of the system is returned tothe primary heating element for further treatment, together with the coal and oil'mixture- A secondary charging stock comprising a straight-run gasoline of low anti-knock value is subjected in the secondary heating element to a temperature of about 1000 F., under a super-atmospheric pressure of about 400 pounds per square inch. The stream of heated oil from the secondary heating element is commingled with the stream of heated material from the primary heating element and the commingled streams are introduced to alternatereaction or coking chambers maintained under a super atmospheric pressure of about 300 pounds per square inch. A substantially equalized superatmospheric pressure of about 100 pounds per square inch is maintained in the fractionating, condensing and collecting portions of the system. This operation may yield about 70% of premium motor fuel having an anti-knock value equivalent to a blend of about 75% iso-octane in normal heptane. The only other products ofthe process are about 100 pounds of carbonaceous material per barrel-of both primary and secondary charging stock and about 400 cubic feet of .comprises about 25% uncondensable barrel system.

As another typical example of an operation which. may be employed by the process of the present invention, the

material charged to the by weight of pulverized bituminous coal in admixture with about 75% by weight of a 22 A. P. I. gravity fuel oil. The coal and oil mixture is subjected, in the primary heating element, to a temperature of about 870 F. under a super-atmospheriepressure of about 500 pounds per square inch. The secondary charging stock is a. Pennsylvania distillate of about 34 A. P. I. gravity which is subjected, together with reflux condensate froin the fractionator of the system, to a temperature in the secondaryheating element, of about 1000 F. under a super-atmospheric pressure of approximately 100 pounds per square inch. The two streams of heated materials are commingled and introduced into alternate coking chambers maintained under a super-atmospheric pressure of approximately 60 pounds per square inch which pressure is substantially equalized in the fractionating, condensing and collecting portions of the system. This operation may yield approximately 50% of motor fuel having an octane number of about 72, the only other products of the system being about 150 pounds of carbonaceous material per barrel of combined charging stock and about 300 cubic feet of uncondensable gas per barrel of material charged to the system.

It will be evident that the examples given are only illustrative of some of the many operations which may be practiced in accordance with the principles of the presentinvention and therefore donot limit the invention in anysense.

By the term bituminous as used in the claims- I intend to include coal, lignite, peat, gilsonite, and similar materials.

I claim as my invention:

1. A process for the conversion of hydrocarbons into products of greater value, which comprises forcing a stream of solid bituminous material such as coal and relatively heavy hydrocarbon charging oil through a heating zone where it is raised substantially in temperature to at least 650 F., but without any substantial carbon. deposition, discharging the heated mixprimary charging stock ture into an enlarged reaction zone where separation takes place between'vapors and nonvaporous residue, subjecting the vapors to partial condensation-to condense the heavier fractions thereof, collecting the vapors remaining uncondensed after passage through the dephlegmating zone as the distillate product of the process, returning a stream of reflux condensate from said dephlegmating zone and merging same with the stream of oil being passed through the heating zone, simultaneously forcing a second stream of hydrocarbon charging oil from a source outside the process and of lower boiling point than said heavy charging oil through a second independently controlled zone and raising said latter stream to a temperature higher than the temperature to which the stream passing through the first heating zone is raised and discharging sa-idsecond heated stream into said enlarged reaction zone.

from the dephlegmating zone is admixed with the stream of oil being forced through the second heating zone.

4. A process for the conversion of hydrocarbons into products of greater value, which comprises forcing a stream of solid bituminous materialsuch as coal and relatively heavy hydrocarbon charging oil through a heating zone densed after passage through the dephlegmating zone as the distillate product of the process, returning a stream of reflux condensate from said dephlegmating zone and merging same with the stream-of oil being passed through the heating zone, simultaneously forcing a second stream of hydrocarbon charging oil from a source outside the process and of lower boiling point than said heavy charging oil through a second independently controlled zone and raising said latter stream to a temperature higher than the temperature to which the stream passing through the first heating zone is raised and discharging said second heated stream into said enlarged reaction zone. I

5. A process which comprises passing a mixture of heavy charging oil and ,lid bituminous material such as coal in a re tricted stream through a heating zone and h ating the same therein to at least 650 F. without substantial carbon deposition, simultaneously passing charging oil of lower boiling point than said heavy oil and from a source outside the process through a second heating zone maintained at higher temperature than the first-mentioned heating zone and heating the same to cracking temperature therein, discharging the heated products from both said heating zones into an enlarged distilling zone and commingling the same therein whereby heat is transferred from the lighter oil to said mixture, distilling the mixture substantially to coke in the distilling zone, and removing and condensing the vapors.

6. A process which comprises passing a mixture of heavy oil and solid bituminous material such as coal in a restricted stream through a heating zone and heating the same therein to at least 650 F. without substantial carbon deposition, simultaneously passing an oil of i -wer boiling point than said heavyoil and containing gasoline hydrocarbons of low anti-knock value through a second heating zone maintained at higher temperature than the first-mentioned heating zone and heating the same to cracking temperature therein,-discharging the heated products from both said heating zones into an enlarged distilling zone and commingling the same therein whereby heat is transferred from the lighter oil to said mixture, distilling the mixture substantially to coke in the distilling zone, dephlegmating the vapors to condense heavier fractions thereof, supplying resultant reflux condensate to said second heating zone, and finally condensing the dephlegmated vapors.

JACQUE C. MORRELL.