US2102947A - Treatment of hydrocarbons - Google Patents

Description

Dec. 21, 1937. G. EATON 2,102,947

TREATMENT OF HYDROCARBONS Filed March 27, 1934 frzveni or Gerald LJZ'aion his Alforney Patented 21, 193? UNITED STATES PATENT. OFFICE TREATMENT OF HYDBQOAIIONB Gas. Eaton Philadelphia.

Process Corporation, Jersey City. poration of Delaware Application March at.

11 Claims.

This invention relates to the thermal conversion of hydrocarbons, and more particularly to the production'from low-boiling hydrocarbons of relatively liigherboiling point hydrocarbons including hydrocarbons boiling within the boiling range of commercial motor fuels and having .valuable anti-detonation characteristics and being otherwise suitable as motor fuel.

An object of this invention is to provide a 1. process whereby low-boiling hydrocarbons, in-

cluding especially hydrocarboi'is which are nor mally gaseous, such as occur in natural gas or in petroleum refinery gas, and particularly in gases from cracking still operations, may be conas constituents of motorv fuel. In accordance with this invention, the conditions created and maintained in the several steps-are so adjusted- .and related as to effect a maximum conversion of the hydrocarbons treated into desirable products and a minimum'conversion thereof into undesirable products. I

In the practice of this invention, the hydrocarham to be treated are compressed prior to being subjected to heat and are maintained under pressure during the cracking operation and the polymerizing operation. The pressure maintained in the polymerizing step is essential to the polymerisation desired; and compression before cracking avoids the necessity for compressing hot uses between the cracking and polymerizing.

steps, or, in the alternative, the hecessity for cooling, compressing, and reheating of the cracked gases at that point in the operation. Also, I have inventionI'the pressures. selected for promotion of polymerization are not'such as will deieteriously affect the progress and results of the, cracking operation; and the employ'mentof such pressures 1934, Serial In the practice of this invention, lower boiling.

bans and preierably into hydrocarbons suitable j found that in procedure in accordance with this a in the cracking operation appears to minimize,

assignor, by

the formation of hydrogen to such extent as to render unnecessary the removal thereof from products passing from the cracking operation to the polymerizing operation; Moreover the employment of: pressure minimizes the size of equip- 'ment necessary in apparatus employed in the practice of my process. The pressure employed depends-upon and must bear a more or less definite relation to other conditions adjusted in" accordance with the principles of this invention,

the requirements of the polymerizing step in this regard being of great importance. To this end, pressures of the order of from per sq. in., and more preferably pressures of the order of from 500 to 1500 lbs. per sq. inch, are employed in the practice ofthis invention.

In the practice of this invention, the conditions of temperature, pressure, and time employed inthe cracking operation areso co-ordinated as to give definite results of" a particular. nature, and are so co-ordinated with the conditions preserved 200 to 3000 its.

and results effected in the polymerizing step that maximum production of desirable products with minimum production oi waste is achieved. Thus, the temperature, and time of the cracking operation are so chosen that, under the existing pres- I su e conditions, the content of unsaturates and polymers in the products leaving the cracking operation will yield a maximum of desired polymers as a result of the polymerizing step, with minimum production of waste products. The

higher the temperature employed in the crack-- ing operation, the more rapid is the production oi fixed and inert gases and tar. The higher the temperature employed, the greater is the concentration attainable-of unsaturates plus polymers provided the durationof the high temperature is correctly adjusted. Thus; for example, with a cracking temperature of 1l00 F., em played in connection with a charge gas consisting principally of C: and C4 hydrocarbons", as high a content (percentage by weight) ,of unsaturates plus polymers cannot be achieved as can be achieved by employment of higher temperatures; at the lower temperature it is not necessary to adjust the time with great care in order 'to ob- 'tain the maximum concentration of unsat'urates plus polymers, any period of time within a relatively wide range giving such maximum concentration. On the other hand, when a temperature of i300 F. is-employed with such charge gas, the content of unsaturates plus polymers .rises' to a higher maximumflaut the time must be adiusted with care, because excessive time leads to rapid reduction of such content; and such exextends the production of waste products, such as inert gases and tar.

' Accordingly, in the practice of this invention the relation of time and temperature in the cracking operation is preferably so adjusted as to cause that operation to produce a maximum content of tion of benzol, whereas the preferable conditions in the practice of this invention are conducive to .the production of hydro-aromatic and cyclic hydrocarbons; and such hydro-aromatic and cyclic hydrocarbons have anti-detonation qualities, when actually blended with motor fuel,.which are in some respects equal to if not greater than those qualities of benzol.

Inthepracticeof thisinvention the temperatures attained in the cracking zone are within the range of from approximately 1000' F. to 1500 F., and

more preferably from about 1200 F. to 1400 F.,

whenthe pressure maintained is of the order of from-200 to 3000 pounds per sq. inch,"and the duration of the elevated temperature is adjusted as above pointed out and hereinafter more specifically exemplified, suitable cracking periods being of the order of, for example, from 0.2 to 0.5 second at 1350 F., or from 10 to 30 seconds while the temperature of the hydrocarbons ll being raised from 1050 F. to 1200 F., when, for instance,.a charge gas consisting principally of Ca and- C4 hydrocarbons is being converted. Inasmuch as the employment of temperatures above the minimum at which cracking begins, results in the occurrence of cracking while the temperature of the hydrocarbons is being raised fromsuch minimum to the maximum temperature employed, account must be taken of the time required for that rise in' temperature as well as of. the time during which the-hydrocarbons are at the maximum temperature. In practice it is frequently advantageous to raise the temperature to a predetermined value and thereupon effect the cooling between the cracking and polymerizing operations; thus making it necessary to take into accountonly the time during which the temperature is rising from a-temperature at which substantial cracking occurs, e. g. rising from 1050 F., up to. the predetermined maximum temperature. I

have found that the yield of unsaturates and the -yield of unsaturates plus polymers decreases when, for a given cracking temperature, the cracking time is extended for too long a period, or when, for apredetermined heating period, the temperature is increased beyond the optimum for that period. I have found that adjustment of the time and temperature, at the pressure employed, in such relation as to produce a maximum concentration of unsaturates in thehydrocarbons leaving the cracking operation, facilitates a max imum yield of desired polymers and a minimum yieldof waste products, such asine hydrogen as to render unnecessary the removal thereof from the system prior to the polymerizing operation. I

Having completed the cracking operation, which involves an endothermic reaction and requires addition of heat, the polymerizing operartor fixed gases and tarfand results in such low content of,

r cessive maintenance of high temperatures also tion, which exothermic, is carried out; but I reduce the temperature of the gases passing from the cracking operation to the polymerizing operation. This reduction of temperature slows down or annuls further cracking of the hydrocarbons treated and tends to minimize or prevent further.

degradation of valuable hydrocarbons into fixed.-

or inert gases and tar or other waste products. Preferably, the cooling is eil'ected in such manner as to preserve such .pressure as is desired in the subsequent polymerizing operation; and the cooling may be efiected by addition to the products passing from the cracking operation of a cooling, medium, such as naphtha, heavy oil; water, or inen. or hydrocarbon gas, or it may be effected by conventional heat exchange. The cooling will effect a reduction of temperature sometimes amounting to several hundred degrees, thus bringing the temperature of the products passing from the crackingzone at,,a temperature approximately within the range of from 1000" F. to 1500 F., down to a temperature approximately within the range of from 700 F. to 1200 F., and preferably.

within a range of mimetic" F. to 1050 n, the

pressure being maintained within the range of from approximately 200 to 3000 lbs. per sq. in.

The desired polymerization may be effected with or without the aid of a catalyst, and the carrying out of this operation in a separate zonefacilitates the adjustment of temperature, time, and pressure conditions. The pressure, being of the order of from 200 to 3000 lbs. per sq. in., the time and temperature are adjusted somewhat as a compromise between theoretical and practical considerations. A long period of time at a relatively low temperature minimizes degradation and promotes yield but requires apparatus of large capacity. At higher temperatures, polymerization can be effected more rapidly, but simultaneous degradation is promoted. Inany event,,the polymerization tends-to increase the content of p lymers and decrease the content of unsaturates.

For example, when reaction-accelerating catalysts are not employed, if the charge gas consists principally of Ca and C4 hydrocarbons, and such gas, under a pressure of substantially 1000 lbs. per sq. in., leaves the cracking zone with a 40% content by weight of unsaturates and the temperature. of the polymerizing zone is held at 1000" 1''., for a period of from 4 to 8 minutes, a yield of 15% to 17% by weight of motor fuel hydrocarbons results, whereas if that temperature is held at 950 F. for a period of 8 to 15 minutes a yield of 17% to 20% by weight of motor fuel hydrocarbons results; if that temperature is held at 900 F., for a period of from 20 to 40 minutes, a yield of 21% to 23% by weight of motor fuel hydrocarbons results; and if that temperature is held at 800 F. for a still longer period a still higher yield of such hydrocarbons results. The use of lower temperatures and longer times gives less production of. hydrogen, methane, ethane,

V and tar. This example serves to indicate the conditions afl e'cting the choice of temperatures and pressures in the polymerizing operation, but in any event thepolymerizing operation usually requires periods oftime measured in minutes as ends or, fractions of a second in the cracking operation. As a further example, when catalysts pressures of the order of 1000 lbs. per sq. in.,

whereas such time may be of the order of. from contrasted with periods of time measured in secamass? about 2 to aboutfl minutes for of about'1000 It, the pressure being the same.

' In adjusting the temperatureand time condi tions for the pressure employed, both in the cracking operation and the polymerizing operationiit' is to be recognized that conditions employed in connection with hydrocarbon gas 0f onecomposition must be adjusted to eilect comparable results in connection with hydrocarbon gas of a 'diilerent composition, higher content of hydrocarbons having a higher number of carbon atoms usually requiring lower temperatures and vshorter effective periods of time.

In the practice of this invention, the products passing from the polymerizing operation are subiected to cooling which condenses certain constituents thereof, and the products may be separated into 'various fractions, for example, iixed gases such as hydrogenand methane (and prefably-ethane), tar, desired polymers, and, gases suitable for recycling through the system.

7 At point it will appear that practice in accordance with this invention provides for the 'production'of desirable liquid or liqueflable polymers from hydrocarbon mixtures which are ,whollyor in major proportion normally gaseous;

the desired products.

that the yield of desired products is high and thedegradation of hydrocarbons isjminimized; that the advantages may flow from limitation of the conversion in the cracking operation while extending the conversion in the polymerizing operation; and that the co-ordination of the conditions in the cracking operation with those existing in the polymerizing operation leads to an avoidance of extensive production of hydrogen and inert gases and avoidance of resulting waste, and interference with proper procedure toward To assist further in an understanding of this invention, there is described herein aspecific ex-.

' ample oi the application-thereof, with the undervnection with the description thereof.

standing that this inventionis not limited thereto nor to the particular apparatus shown in con- Hydrocarbon gas, for example, such as that taken from an oil cracking unit, is passed from a source (not shown) through valve-controlled 'pipe' I tocompressor 2 wherein it is compressed to a pressure of the ,order or from 200 to 3000 lbs./sq.in., and delivered through valve-controlled pipe 3 totheicracking tubes 4 of memuses 0, Herein, the compressed gases are heated to a temperature of from about 1000 F. to about 4500 F., for a period of time suillc'ient to efiect a substantial conversion of the stable constituents of. the gas to polymerizable. :unsaturates. The heated products from the cracking tubes 4, at a temperature of from substantially 1000, F. to 1500 FL, and under a pressure of the order of from 200 to 3000 lbs./sq.in., are passed tostransforum 6, and thencaintqreaction chamber'll However, either during their passage through the transfer line or at their point of introduction into the reaction chamber, the heated products are cooled from a temperature of the order of from.

1000 F. to 1500 F., to a temperature of from substantially 700 F. to 1200 E, whereby further is substantially prevented. The step v oi! cooling may be accomplished in various ways.

example, -ajportion or the coyipressed' hydroam-mm; I. in closed may be passed through pipe ier ai-v ve-controuea pipe l0 and pipe u transfer- .line' 8, valves l2 and I! being recycle hydrocarbonsmay be intmduced'E' -into line I from valve-controlled 1 and pipe 28 may be redu d by means of valve 22, for example, from about 200 to'about. 3000 lbs./sq.in.,

pipe It, or a cooling medium such as, for example, inert gas, hydrocarbon gas, naphtha,

heavy oil, water or steam may be passed, under pressure, from a supply notshown, through valve-controlled pipe I! and pipe ilinto transfer line 6."; Cooling of the heated products from the cracking tubes [may be eilected, I: desired, by a the installation of conventional heat exchange,

apparatus in the transfer line 0. Regardless of the cooling means used, the temperature of the heated products is reduced to the order of from about-700915. to about 1200 F., at which temperature further cracking is substantially prevented and at which polymerization-is effected. .The thus cooled productsin thereactlon chamber I are maintained at a temperature of from a about 700 F. to about 1200 F. and under a pressure of from substantially 200 to 3000 lbs./sq. in.,

for a period of time suiiicient to eifect the most economical degree of conversion of.the unsaturates into desirable polymers. The products from the reaction chamber 1 are passed, by

'means of valve-controlled pipe I and pipe i5 into separator l6. In certain instances, it may and water vapor if present, are passed from the top of the separator W at a temperature prefer ably below 800 F., through valve 22', cooler 23 to water separator 25. Pressure to about 200 to 1000 lbs/sq. in., and the temperature of the vapors passing through cooler 23 may .be' reduced fromabout 800 F. or lss, to

' about from 35 F. to 250 F., thereby permitting 'the bulk oi the water, when present, to separate from the hydrocarbons, said water being withdrawn from the separator 25 through valve-comtrolled pipe 26. v

g The hydrocarbon mixture comprising polymers, unconverted hydrocarbons, fixed gases and a small quantity of-tar is passed from the water separator ,25 through pipe 21 into reflux column 28 provided adjacent its top with a refrigerating coil 29. In the column 28 the hydrocarbon liquids are freed or the fixed gases, i. e., hydrogen and 'methane (and preferably also ethane) which are removed from the top of the column by means of pipe 30 and vented through valve 3!, the coil 29 providing reflux which aids in the removal of,

higher boiling hydrocarbons from the gases. The hydrocarbon liquid withdrawn from .the' bottom of column 20 is forced, under a pressure of the order of from about 200 to 1000 lbs./sq. in. through heat exchanger", wherein-the temperature is raised to about from 100 to 500 F. The heated hydrocarbon mixture is passed from 'the' exchanger 32 through valve-controlled pipe 33 into fractionating column 04, provided with a heating coil 46. The pressure on the hydrocarbons introduced into column 34 is preferably reduced from about 200 to 1000 lbs/sq. in., to about 50 to 400 lba/sq. in., by means of valve 83', the temperature of the material introduced into the column being .within the range, for example, of from about 100 F. to about-500 1". 'Incol'umn.

34 the normally gaseous hydrocarbonsare fracf .tionated from thepolymers and tar, theformer being removed from the top 'of thecolumn 1 throughs-pipe l6 and passed into partial condenser 31, from which any liquid condensed is withdrawn and returned to column 34 by means of valve-controlled pipe 38, pump 39a and valvecontrolled pipe 38b, to' serve therein as reflux. The uncondensed gaseous hydrocarbons are removed from the top of partial condenser ll and v are passed through v ve-controlled pipe; 39 to compressor 40. The condensed gases are compressed therein to a pressure of the order of from about 200 to about 3000 lbs/sq. in., and may be a pressure of from atmospheric to 200 lbs/sq. in. 7

recycled by means of pipe 4! and valve 42' to the cracking tube 4 for further heat treatment, or they may be passed, under the aforesaid pressure.-

through pipe 43, cooler 44 and valve-controlled pipe i3 into transfer line 6 to function as a coolant for the heated products from the cracking coil 4.

In the event that the recycling of theunconverted hydrocarbon gases is not desired, said gases may be vented by means of valve-controlled pipe 39a.

The polymersand tar from the bottom of column 34 are passed under pressure, through pipe 45, valve 46, heat-exchanger 4'! and pipe 48 into 1 fractionating column 49, provided withheating coil 50. This column is operated preferably at a. temperature of from 200 F. to 500 FJ, and under Herein the polymers and tar are separated by fractionation. The polymers are removed as vapors from the top of the columnthrough pipe 51 and passed to condenser 52 wherein condensation is effected, a portion of the liquid polymers then being returned as reflux to column 49 bymeans of valve-controlled pipe 63, and the remiainder of the polymers being withdrawn to storage through valve-controlled pipe 54. Taris drawn from the bottom of column by means of valve-controlled pipe 55, and is removed from the system through pipe 20 and valve 2|.

While in the above illustration I have'shown a reflux tower (28) as a means of separating the fixed gases from the valuable hydrocarbons, I may substitute therefor, a flash drum wherein the un-' condensed gases, in equilibrium with the liquid hydrocarbons, may be separated therefrom,- under the proper conditions of temperature and prasure. Likewise, various modifications in the fractionating column 34 may be employed, or a different type of fractionating equipment, such as for example, an absorption system, may be utilized in place of columns and 34. In general. the separation of the. products of reaction may-v be accomplished by variousmeans familiar todefinedas that material boiling between 60 F.

and 400 F. Tar? is designated as material boiling above 400? F.

'; Example 1.-'-.1vo catalyst I Pressure perv. a (m/sq. im a.) Contact time cm cns 'maflhu- 1200 s 1 -10 206 0 r.

'Polym eri'zingzonam 900 I :90 wminut es.

Analyses Chsrgeto Leaving crack- Leavingpolycracking lone ing zone mcrizing zone Wt. .Vol. Wt. Vol. Wt. Vol. perperperpcrperper. cent cent cent cent cent cent ydrogen 0.2 2.7 0.2 as Methane l2. 0 26. 4 l4. 9 33. 6 Ethylene 5. 9 7. 4 2.2 2.8 Ethane 1.0 1.6 9.0 10.6 11.4 13.7 Propylene 12. 1 10. l 4. 3. 8 Propane... 64.0 69.5 37.3 29.9 33.6 27.5 Butylane Y 4.7 3.0 1. 7 1.1 Butane 35.0 28.9 12.8 7.8 11.5 7.1 Nnnhfim 0. 0 2. 0 17. 1 0. 3 Tar--- 0.4 0.1 3.0 0.0 'fotal 100.0 1000 100.0 1000 100.0 100.0 Total oinns...- 22.7 20.5 8.4 7.7

Example II.-No catalyst Temper'a- Pressure Contact ture (lbs/sq. in.-ga.) time F: g

Cracking zone. I 1300 500 0.4 second. Polymerizing zone-.. 900 600 50minutes.

Analyses Ghsrgetov Iaavingcrack- Leavlngpolycracking zone ing zone merlzing zone we v01. Wt. v01. Wt. v01. W- p 0 perp cent cent cent cent cent cent 02 4. 0 0. 2 4. s 1.1 5.4 1&0 8.7 23.0 I. 7 6.2 B. 6 1. 6 2.4 7.2 7.6 9.8 10.3 14.6 14.0 2Z9 19.2 5.2 6.2 46. 7 34. 9 39. 5 30. 9 29. 7 Butyiene---- 104 9.5 6.6 2.4 1.8 Butano 18. 9 8. 9 5. 9 7. 9 5. 8 Naphthn 0. 1 2. 4 2s. 0 12. 1 Tar.-. 0. s 0.1 4. a 1. 0 "Total. 100.0 100.0 100.0 100.0 1000 100.0 'lt oiiiolaanamua... 20.5 20. 30.0 314 0.2 0.4 3 J I In Example I the charge was of natural gas source, and contained no unsaturates. The obiect ofthe thermal treatment inthe cracking zone was to produce'the maximum percentage of ole ns'plus naphtha, with the minimum productio .of hydrogen, methane,- and ethane. The

contact time given isapproximately the optimum for the temperature employed. In this case the gas was heated continuously to a furnace outlet temperature of 1200 -F., and the contact time tabulated isthe time in which the gas was heating fr0m.1050 F.'to 1200 F. f I

Had the contact time at this temperature been either substantially less or substantially greater than that given, the conversion would not have been as satisfactory, since the amount of oleflns plus naphtha would have been less than that tabulated. Also, if the time had been longer, the

amount of hydrogen, methane, and ethane would have been greater. By cooling immediately to the polymerizing temperature, after .the proper cracking time, the production of naphtha in the process as a whole is markedly increased.

In Example II the charge was of refinery gas 7 merizing zone, and if recycling or these unconverted compounds is ed out quantitatively, in Example'I the ultimateyield of naphtha would be of theorder of 35% by weight as against a once thru yield of 17.1% by weight; whereas in Example 11, the ultimate yield of naphtha would be of the order of 47% by weight, as against aonce thru yield of 23% by weight.

One of the. major advantages of my process consists in the fact that the entire stock is treated under the optimum conditions, so that by con-. trolling the time of reaction the greatest ratio of valuable products to waste products is obtained. Under these conditions there remain considerable unconverted compounds which may again be passed through the apparatus to obtain the same high ratio of valuable to waste products.

' Had the conversion been carried on for-appreciably longer cracking times than the optimums disclosed herein, the once through yield of naphtha would have been slightly greater, but the ultimate yield would have. been very markedly reduced.

with regard to the function of pressure in the ,two stages of my process, I find, in the cracking zone, that pressure has relatively little eilect on the reaction other than itsefiect on contact time. In the polymerizing zone, however, the polymerization of unsaturatesto. naphtha. is very greatly aiiected by pressure, particularly in the range below 200 lbs/sq. in., and unless the pressure is above this figure only slightconversion is obtained, in the absence of catalysts.

For brevity, herein and in the appended claims, the term cooling medium is to be understood to comprehend such agents as hydrocarbon oil;- compressed hydrocarbon gases, water and steam. Also, when'in the appended claims the term a high superatmospheric pressure is employed, it

is to be understood to mean pressures of the order of 200 lbs/sq. in. or greater. What I claim is:

1. The process of converting predominantly paraillnic normally gaseous hydrocarbons into polymers, which comprises heating said hydrocarbons under a high superatmospheric pressure to a temperature at which at least a portion of said hydrocarbons will decompose to form substantial quantities of unsaturates, cooling the heated products to a temperatm'e to prevent further substantial decomposition and at which polymerization thereof takes place, introducingsaid cooled products without separation and while maintaining substantially the same pressure into a reaction zone wherein polymerization is eirected during the passage of substantially all or the cooled products therethrough, and removing the products of reaction from the zone last mentioned.

2. The process of converting predominantly polymers, which comprises heating said bydrocarbons under a high super-atmospheric pressure to-a temperatureat which at least a portion of tion'ed, iractionally' separating the products of re- [cooled products therethrough removing the. products oi. reaction from the zone last men action, and recycling. unconverted hydrocarbons for further heat treatment.

8. The process oi converting normally gaseous hydrocarbons into polymers, which comprises heating said hydrocarbons under a high superatmospherlc pressure to a temperature of the order of'trom 100051 to 1500' F., whereby at least a portion of said hydrocarbons will decompose to form substantial quantities of unsaturates,

cooling the heated-products to a temperature 0! the order of'from 700 F. to 1200 F., to prevent further substantial'decomposition and at which polymerization thereof takes placefiintroducing the cooled products without separation and whilemaintaining substantially the same pressure into a reaction zone wherein polymerization is eflected during the passage of substantially all or the cooled products therethrough, and removing the products oi. reaction from the zone last men.-

tioned. a

4. The process or converting predominantly paraflinic normallyigaseous hydrocarbons into polymers, which comprises heating said hydrocarbons under a high-superatmospheric pressure to a temperature at which at least a portion of said hydrocarbons will decompose to form subheated products to a temperature to prevent fur:- ther substantial decomposition and at which polymerization takes place by introducing-there-' into a cooling medium, passing said cooled products' without separation and while maintaining paraflinic normally gaseous hydrocarbons into polymers, which comprises heating said hydrocarbons under a high superatmospheric pressure 'stantial quantities of unsaturates, cooling the' to -a temperature of the .order of from 1000 F. to

1500 F., whereby at least a portion of said hydrocarbons will decompose to form substantial quantities of unsaturates, cooling the heated products to a temperature of the ordrbf from 700' I". to 1200 F., to prevent further substantial decomposition and at which polymerization takes place by introducing thereinto a cooling medium, passing the. cooled products without separation and while maintaining substantially the same pressure into a reaction zone wherein polymerization is effected during the passage of substantially all of the cooled products there-' polymers, which comprises heating said hydro carbons under a high superatmospheric pressure said hydrocarbons will decompose, to form substantial quantities of unsaturates, maintaining such temperature and pressure conditions for such time as will give in .-the products leaving I the cracking operation substantially the maximum content of. polymers plus unsaturates attainable at such temperature, cooling the heated products to a temperature to prevent further 'substantial decomposition and at whicly polymerization thereof takes place, introducing said cooled products without separation and while maintaining substantially the same pressure into a reaction zone wherein polymerization is effected during the of substantially all of the cooled products therethrough, and remov ing the products of reaction from the zone last mentioned.

7, The process of converting predominantly paraflinic normally gaseous hydrocarbons into polymers, which comprises heating said hydro-' carbons uiinder a high superatmospheric pressure to a te perature at which at least a portion of said hydrocarbons will cdecompose to form substantial quantities of unsaturates, introducing a part of the hydrocarbons from the same source asthose being heated into contact with heated products to cool them to a temperature to prevent further substantial decompositibn and at which polymerization thereof takes place, introducing said cooled products without separation and while maintaining substantially' the same pressure into a reaction zone wherein poly merization' is eifected'durins the e of substantially all. of the cooled. products therethrough, and removing the productsof reaction from the zone last mentioned.

8. The process of converting predominantly paraflinic normally gaseous hydrocarbons into polymers comprising motor fuel, which 'co'm-, prises heating saidhydrocarbons under a high to a temperature at which at least a portion of"? tained at a high superatmospheric pressure wherein polymerization is effected during the passage of substantially all of the thus cooled products therethrough, and removing the prod-' ucts of reaction from the reaction zone to recover polymers-therefrom.

9. The process of converting predominantly paramnic normally gaseous hydrocarbons into polymers, which comprises heating said hydrocarbons under a pressure in excess of about 500i stantially, the same pressure into a reaction zone wherein polymerization is effected during the passage of substantially all of the cooled products therethrough, and removing the products of reaction from the zone last mentioned.

10. The process of converting predominantly parafllnic normally gaseous hydrocarbons into polymers comprising motor fuel, which comprises heating said hydrocarbons under a high superatmospheric pressure at least as great as that later mentioned for the reaction zone to a temperature at which at least a portion of said hy-' "drocarbons will decompose to form substantial quantities of unsaturates, cooling the heated products to a temperature to prevent further substantial decomposition and at which polymerization thereof takes place, introducing substantially all of said cooled products without separation thereof into a reaction zone maintained at a pressure in excess of about 500' pounds per square inch*wherein polymerization thereof is effected during the e of substantially all of the thus cooled products therethrough, and removing the products of reaction from the reaction zone. to recover polymers therefrom.

rates.

' GERAID L. EATON.

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