US1428311A - Oil-converting process for the conversion and transformation of oils - Google Patents

Description

J. H. ADAMS.

OIL CONVERTING PROCESS FOR THE CONVERSION AND TRANSFORMATION OF OILS.-

APPUCATION FILED JUNE 25,1918. v

PatentedSept. 5, 1922.

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mm UM mm u mm+ Ehtmk S INVENTOR WIT SSES ATTORNEYS I J.H.ADAIVIS. OIL CONVERTING PROCESS FOR THE CONVERSION AND TRANSFORMATION OF OILS.

I MPUCATIQN FILED JUNE 25' 19H? 1,428,3"1 1 I Pat-e t p 5, 1922.

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IN vEMEI ATTORNEYS D S i JOSEPH H. ADAMS, FLATBUSH, NEW YORK, ASSIGNOR TO THE TEXAS COMPANY, OF HOUST'ON, TEXAS, A CORPORATTON OF TEXAS.

OIIPCON-VERTING' PROCESS FOR THE CONVERSIDN AND TRANSFORMATION OF OILS.

Application filed June 25,

T 0 all whom it may concern:

Be it known that I, JOSEPH H; ADAMS, a citizen of the United States, residin at Flatbush, in the county of Kings and tate of New York, have invented a new and useful Oil-Converting Process for the Conver vsion and Transformation of Oils, and of which the following is a specification.

This invention relates broadly to the art 154 of converting fluids such as oils into prod-' ucts of dissimilar character from the original untreated oils.

In its more intense aspect this invention consists in-a thermal'and high vapor pressure method of converting the vapors of semiand more or less refined mineral oils such as those of the kerosene, non-viscous neutral, gas, fuel and coal tar oils into more volatile and lower boiling hydro-carbons such as gasolene, naphtha, benzine, kerosene, benzol, toluol and other light oils and oily spirits of both the plain and aromatic series.

The apparatus illustrated and to be described as adapted for use in carrying out my process was invented by me but is not herein claimed since it istmade the subject matter of another application Serial No. 241,837, filed of even date herewith.

One object of this invention is to formulate a process of a commercially practical and economical nature for carrying on the conversion of oils by. heating the oils to or above their boiling points while held under supe1=atmospheric vapor pressure, then volatilizing the oil in the presence of high temperature super-heated steam while under self-built up vapor pressure assisted by the admission of the steam for the purpose of cracking the oily vapors into those which, when condensed, will result in the desired products and also, if desired, bringing the expanded vaports into close proximity with an applied source of cracking heat prior to condensation. r

This invention is clearly distinguished from the ordinary process of fractional distillation since it breaks up or converts a large part of the oil being treated into lower boiling products as above indicated and does not merely have. the effect of separating out the lighter and lower boiling compounds already existing in the oil.

According to my process, the vapors which have been transformed by the cracking heats of steam at temperatures exceeding 800 to 1918. Serial No. 241,836.

1000 F while maintained under pressure as above stated, are then expanded, the lighter parts separated out and condensed, and I prefer to carry on this condensing operation under pressure with the condenser in free communication with the converter so that the vapors undergoing the cracking operation will be in com'municationwith those undergoing condensation whereby there will be vapor pressures to and through the condenser and in this manner the' lighter parts of converted vapors will be condensed under pressure and held in liquid form whereas the distillates of converted vapors condensed under atmospheric pressure would not contain such a high percentage of the lighter parts.

I In carrying out my invention the oils are heated and sprayed in vaporous form under presssure intothe same enclosed vessel in which the vapors are subjected to the hightemperature super-heated steam for transformation, the vessel or vessels being in open communication with the expander, separator and condenser, and the super-atmospheric vapor pressure is maintained at the desired number of pounds by controlling the discharge of liquids and of fixed gases from the ap aratus. v y properly controlling the flow of ingoing oil and steam and the discharge of distillates and generated gases the process may be operated continuously'and as the apparatus is designed for such operation the lighter vapors will be automatically separated from the heavier matter and the preci itation of the latter may cause an accumu ation until it becomes necessary for its removal while the heavy unconverted oils may be returned to the converter again for re-treatment.

This process may be employed for oils of various kinds either of a crude or semi-refined nature and by proper regulation of the superheated steam temperatures and the vapor pressures maintained in the system, in accordance with the characteristics of the particular oil undergoing treatment, the oil .may be broken or cracked and transformed into products covering a wide range of lower boiling point and lower specific gravity products quite different from and of higher commercial value than the original material,

By this process it is possible to transform oils of one series into those of an entirely and essentially different series as the plain into the aromatic or the chain into the ring series. For example, a kerosene or gas oil distillate yielding no gasolene or naphtha by fractional distillation may, by this vaporization-heat-pressure method, be transformed into gasolene and naphtha, the heavy coal tar oils into benzol, toluol and other light oils, while under different conditions, that is higher steam heats and vapor pressures, petroluem oils may be transformed into aromatic compounds as benzene, benzol, toluol and other light oils of the ring or aromatic series.

By the herein disclosed process discovered by me, it is quite feasible to convert high boiling oils into lower boiling products and to more than double the yield of any of the lighter desirable products such. as gasolene, naphtha and other hydro-carbon spirits and convert the less valuable petroleum products into those in greatest demand and of higher commercial value.

Apparatus suitable for practicing my improved process is shown in the accompanying drawings in which: I

Fig. 1, is an elevationand partly sectional drawing of an apparatus used by me in experimentally demonstrating the process and:

Fig. 2, is a side and partly sectional elevation of a commercial type of apparatus more complete in detail.

The same reference characters designate like or corresponding parts throughout both figures of the drawings.

Referring now to the simple form of apparatus shown in Fig. 1, the reference character A, represents an oil supply tank from which the oil is supplied to the apparatus for the conversion process. from this tank A, through pipe 5, precision feed valvesfiand pipe 7, toheater B, is heated to or above its boiling point and preferably to a temperature above 600 F., within the coils 8, of this heater. This hot oil is then admitted through pipe 9, to the spray nozzle 10,;located at one end of a mixing chamber 11.

Oil is admitted to the tank A, through pipe 1, controlled by valve 2, and displaced air may escape through pipe 3 controlled by valve 4c, when the tank is filled at first, but subsequently and during the process oil may be forced in through pipe 1, at greater pressure than that maintained by compressed air over the surface of contained oil; such compressed air being furnished from an outside source through pipe 3 controlled by valve 4,

I and such pnessure being recorded on gauge 13, while a glass sight gauge 12, is pro vided on this tank so as to be informed as to the height of oil therein.

The heater B may be of any suitable form such as a feed water heater, a small boiler or other form of heater whereby the oil may The oil passing.

into coils 18, of the super-heater B, is raised 1 in temperature above 800' to 1000 F., and then flows through pipe 19, being mingled with the heated oil and discharged from thg nozzle 10. The oil molecules are thus broken up and transformed from high boi ing oil into lower boiling products within the mixing chamber 11 and ,expander D.

Both the oil and steam may be controlled in amount and in proportion to each other as-they are discharged through the nozzle 10, by valves 9 and 19 which permit a close regulation to be obtained.

Located within the expander C, and opposite the mixing chamber 11, a curved plate 20, of metal such as hardened steel, nickel. hard alloys or other substance capable of withstanding high temperatures, is made fast at an angle so as to deflect the incoming spray or vaporous oil in an upwardly direction or toward a plurality of perforated disks 21, through which the lighter co1l verted vapors will pass as they rise within the dome D, and flow through the pipe 25 over into the condenser E.

Arranged within 22, may be supported on insulators and supplied with current through cables 23 and 2 1.

This heater is preferably constructed of a series of resistors through which low voltage high amperage current may flow to i so that the I incoming mingled oil and steam vapors may be kept at high temperatures while expand- I maintain cracking temperatures,

ing in order to obtain thereby the greatest yield of the desired low boiling products. 1 The heater B, is preferably composed of a steel shell lined with fire brick having inthe shell and lini sulating material between ing, for confining the heat .and any suitable and economical means such as the burn ers to consume gas or fuel oil may be utilized for producing the heat in this chamber.

I prefer making the heater coils 8 and the super-heater coils 18, in tubular form so that there will be a large heating surface presented as compared to the volume of oil and ,steam passing through them. This heater is intended only to heat the oil sufliciently to cause its easy volatilization when admitted to the mixing chamber 11 and expander C, and is not intended to perform the expander C, and beif low the deflectmg plate 20, an electric heater The oil and oily vapors, after being sub jected to the high temperature in the coils 8, pass out through the nozzle 10, and into the chamber 11, and expand in receptacle C, where the lighter converted vapors rise and flow through the perforated battle plates 21, in the dome D, then pass out from the top and through the vapor pipe 25, to the coils 26 of the condenser E. It will be seen that the condenser E, is in free communication with the expanderand dome 0-D, and

that any pressure maintained in the apparatus C-D, will extend through the condenser E, as well.

The heavier unconverted vaporscoming in contact with the perforated baflie lates 21, and being thrown down will be a ected by the high temperature of the electric heater 22, and a large part of such vapor may be broken up under this heat and pressure influence into finer vapors to again pass up and through the plates 21, to and through the condenser E.

From the condenser, the distillates of condensation pass freely through pipe 27 into a trap tank F, from which they may be withdrawn through pipe 28, controlled by.

valve 29, and the fixed gases may escape through pipe 30 controlled by needle valve 31. The vapor pressure in the system may be recorded on gauge 32, located at the top of running trap tank F, and 33 on a tank G,

'and by means of the withdrawal of both liquid and gases from tank F, a constant pie-determined vapor pressure may be maintained. within'the system.

Since some of the unconverted heavier vapors may fall to the bottom of the apparatus C-D, they will pass into the heavy bottoms chamber 34, located below the expander C, and in their passage they will carry any particles of coke or carbon which may result from this transformation process and which may fall or precipitate to the lower part of the chaa nber C. Such carbon or fore gn solid matter which may be caught in this chamber 34:, can be removed from time to time as occasion requires throu h the bottom, by suspending operation, witdrawing oil from the converter, removing the cap plate 35 and clearing out the chamber. then replacing the cap and proceeding with the process.

Any accumulation of hot oil in this chamber will overflow through pipe 36, into the tank G, from which it can be reni'oved as required through pipe 37 controlled by a valve.

Both the distillate tank F and hot overflow oil tank G, are provided with glass sight gauges 38 and 39, so that the operator to withdraw oil to make room for that which will be constantly flowing into these tanks.

The continual feeding of new quantities of hot oil to be broken into spray or vapors on admission to the mixing chamber 11 and expander C, together with the super-heated steam and the tendency of the super-heated oil to greatly expand when released, willbuild, up or. raise the vapor pressures in the converter and consequently throughout the condenser, so that the vaporsundergoing the cracking operation will at all times be under super-atmospheric vapor pressures while. being subjected to the cracking heats of the steam and if the electric heater is used, to the internal heat maintained at cracking temperatures thereby.

would be lost and the efliciency of this process lowered-or rendered ineffective. Obviously, in its broad aspect the invention is not restricted to the particular manner in p which the vaporized oil and the steam are mixed. 1

Fig. 2, presents a partly sectional elevation of an apparatus adapted to carry out my process on a comme-rclal scale, and this apparatus embodies all of the above described features in connection with added parts for more perfect continuous operation.

As may be seen by this drawing thesource of supply or oil tank A, is 'provided with a suction and force pump 40, which draws the oil to be converted from tank A, forces it against a back or vapor pressure into the converter C-D, through the precision valves 6, pipe 7, heating coils 8, pipe 9 and nozzle 10. i

.As it is not possible to so perfectly regulate the speed of a pump as to accurately deliver a given amountof oil into the converter at all times and at a given pressure, a pipe 41 and an enclosed release valve 42, are provided to return any excess oil to tank A, so that in this manner only the desired amount of oil may pass into the converter as regulated by the precision valves 6. In this manner oil to be delivered into the system against a back pressure of say seventy five pounds to the square inch will be forced by the pump 40, against the 70 may be informed as to when it is necessary release valve 42, set at one hundred pounds pressure, and in such regulation the oil will be delivered into the system under a head pressure of twenty five pounds to thesquare inch, or sufficient to become properly ato mized by the admixture of super-heated steam, l

The steam employed in this system for assisting in the process is generated outside the apparatus in a boiler, as H, and is admitted into the system through pipe 14 controlled by valve 15, and highly super-heated in the heater B, before co-mingling with the pre-heated oil in nozzle 10, of the mixing chamber 11,

In this form of apparatus the converter C-D, is made in two separate parts connected by the neck 43, and in this arrangement the vapors will have ample space to expand then rise through this neck into the separating dome D, where, coming in contact with the perforated baffle plates 21, the heavier oily vapors will fall and come in contact with the electric heater 22, which in this form is located above the deflecting plate 20, instead of below as in the former apparatus shown in Fig. 1. The heat from this heater will affect the partially transformed or un-converted vapors in a more efficient. manner than if placed at the lower part of expander C.

As the overflow hot oil may accumulate rapidly in the operation of a battery of converters. the pump 44, is connected with the tank G, and the oil may be continuously withdrawn through pipe 37 and returned to y the supply tank A. through pipe 45.

As a means of safety in this high temperature and pressure process a release blow off or pop valve 46, is preferably located at adistance away from the converter, usually at the end of the vapor line 25, and just above the condenser E, as indicated in both figures of the drawings.

In COIIlll'lQl'Cltll practice waere it is desirable to convert oil on a large scale it will be necessary to employ a -number of units of moderate size rather than large cumbersome and expensive converters, and in the event, of such units being arranged in battery form they should be so connected by the vapor lines leading to the condensers or by other compensating pipes that the vapor pressure from each will be transmitted to the others, thus operating all units under the same uniform pressure; and in this manner any drop or increase in pressure in any one converter will be compensated for by the pressure from the others and in this way more perfect ation of pressure can be secured by releasing fixed gases from the foot of or beyond the condenser as heretofore explained.

While I do not herein claim this battery feature and freely connected converter units one with another, this principle was de assen scribed in connection with my co -pending application 530.852 filed Dec. 1, 1909.

It will, of course, be understood by those skilled in the art that thetemperature necessary in the heater B, and converter C, as well as the temperature of the super-heated steam for conversion purposes and the pressure of the vapors and steam in the converter and condenser as well as in the enclosed running trap tank located beyond the condenser, will vary with the character of the particular oil being treated and therefore it is not possible to state any definite figures which would cover all of the various oils susceptible to treatment by this process.

The operator may determine when he has the proper temperatures and pressures by the character of the product coming from the condenser, and as an illustration of the adaptability of my process for use with oils of widely different boiling points and characters I may state that kerosene distillate with an initial boiling point of 300 to 350 F., can be converted into distillates having an initial boiling point below 100 F., and heavier distillates such as gas oil and nonviscous neutral oils having initial boiling points above 400 to 500 F., can be transformed into distillates with initial boiling points below 100 F.

As it is not possible to lay down any fixed rules with regard to temperatures and pre sures that would apply to all grades and natures of oils susceptible to transformation by this process, the temperature and pres-' sure would naturally have to vary to a certain degree but as an illustration of these necessary features to obtain the best results from a kerosene or gas oil distillate it may be said that a temperature from 700 to 900 1 and pressures from 50 to 100 pounds to the square inch above atmospheric pressure will influence the production of very satisfactory distillates and that large yields of low boiling products particularly the naphthas are among the principal products desired, for, by fractional distillation of the resultant condensate, large percentages of the more valuable gasolene are obtained.

lileritorious products of the gasolene and naphtha types can be obtained in large quan tities from original oils and distillates having initial boiling points ranging above 500 l*., by the application of-temperatures above 900 F., while held under pressures of from T0 to-90 pounds to the square inch, and in some instances I have employed temperatures from 1000 to 1500 F, in the superheated steam and converters and pressures up to 300 pounds to the square inch in the vapors but have found that the lower temperatures and pressures are more satisfactory, excepting however, in the production of aromatic compounds which require higher temperatures and pressures.

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It will be apparent to those skilled in the art that the breaking up of the oily vapors into finer molecules and a possible re-arrangement of the series by the] intensely heated steam will have the desired effect in rendering a product very lightin color and as clear as spring water as well as sweet in odor when compared to distillates from the result of applying dry cracking heats to original oils; and it will be undertood as well, that the influence of the high temperature super-heatedsteam will have a tendency to free the resultant product of this conversion process from more or less of the carbon which will be taken on in the form of fixed gases. v

It is noticeable that the product "withdrawn from the collecting trap tank at the foot of or beyond the condenser is almost water white in color and requires but very slight treatment to de-odorize it for commercial purposes. V y,

It will be apparent also that by condensing the converted vapors under high superatmospheric vapor pressure instead of under atmospheric pressure only, that a certain percentage of the very light and valuable converted vapors will be condensed and held in liquid form instead of .passing'off with the fixed gases through thecond-enserwhere the pressure is released between the converter and condenser as disclosed in other processes and shown in the several forms of apparatus adapted for such uses.

This process is. of course, not limited to the use of a specific apparatusand it may be performed in various ways, but I believe the fundamental steps of the process as set forth to be broadly new and it is my intention to cover the process in its broadest aspect by the language employed in the following claims, i

Having described my invention what I claim as new and desire to secure by Letters Patent is: I

1. The process of producing lower boiling hydrocarbons from higher boiling hydrocarbons that consists in discharging the higher boiling hydrocarbons in the-form of vapor into a closed chamber and therewith steam superheated to a sufficiently high temperature to roduce cracking, passing the resulting lig ter products through a con denser, and supplying additional heat to crack the remaining heavier products in the closed chamber, while maintaining-m substantially uniform superatmospheric pressure being maintained throughout the closed.

chamber and the condenser.

2. The process of producing lower boiling hydrocarbons from higher boiling hydrocarbons thatconsists in discharging the higher boiling hydrocarbons imthejform of vapor into a closed chamberand mixing therewith steam superheated to a sufiiciently chamber having high temperature to roduce cracking, passing the resulting lig ter products through a, condenser, supplying additional heat to crack the remaining heavier products in the closed chamber, while maintaining a sub stantially uniform superatmospheric pressure being maintained throughout the closed chamber and the condenser, and continu ouslysupplying oil and steam 'and'withdrawing products from the condenser without relieving pressure under which theprocess is carried on.

3. A process of producing-lower boiling hydrocarbons from higher boiling hydrocarbons that consists in preheating higher boiling hydrocarbons to a temperature as high as their boiling point, superheating steam to approximately 1000 F., atomizing and mixing the heated hydrocarbons and the steam in a closed. chamber, whereby the Vaporized hydrocarbons are cracked in the vapor phase by the direct action of the superheated steam, condensing the lighter products in free communication with the cracking chamber, cracking the heavier roducts in said chamber by subjecting them to additional heat at a cracking temperature,

and maintaining a substantially uniform super-atmospheric pressure throughout the cracking and condensing steps of the process.

4. A process of producing lower boiling hydrocarbons from higher boiling hydrocarbons that comprises spraying into a chamber a'mixture of hot oil and steam superheated to a suflicient temperature to crack the oil when mixed therewith, withdrawing the lighter converted vapors from the chamber, subjecting the heavier vapors unconverted by the superheated steam to additional cracking heat, and condensing the withdrawn vapors under superatmospheric pressure.

5. A process of producing lower boiling hydrocarbons from higher. boiling hydrocarbons that comprises spraying into a chamber, having spaced end portions connected by a restricted passage, a mixture of hot oil and steam superheated to a sufficient temperature to largely crack the oil by the direct action thereof, withdrawing thelighter products from the upper end of the chamber, subjecting the heavier products as they rise from the lower end portion of the chamber to additional cracking heat, andcondensing the withdrawn vapors, while maintaining a superatmospheric pressure throughout the conversion and condensation steps.

6. A process of producing lower boiling hydrocarbons from higher boiling hydrocarbons that comprises spraying hot oil and steam into the lower end portion of a communicating upper an lower end port ons, the steam being superheated to a sufiicient temperature to largely crack the oil by its direct action, subjecting the evolved vapors as they rise into the upper end portion to additional cracking heat to augment the cracking process, withdrawing the lighter products from the upper endportion, and condensing them in free communication therewith, while maintaining a uniform superatmospheric; pressure throughout the cracking and the condensation steps.

7. A process of producing lower boiling hydrocarbons from higher boiling hydrocarbons that comprises spraying a mixture of hot oil and steam into a chamber, the steam being superheated to a suflicient temperature to largely crack'the oil by direct contact therewith, subjecting the unconverted portions in said chamber to additional cracking heat to augment the conversion process, withdrawing the evolved va )ors, separating out the heavier portions and returning them into the chamber; and condensing the lighter vapors while maintaining superatmospheric pressure throughout the conversion and condensation steps.

8. A process of producing lower boiling hydrocarbons from higher boiling hydrocarbons that comprises spraying a mixture of hot oil and steam into a chamber, the. steam being superheated to a temperature sufficient to crack the oil by its direct action as it is commingled therewith, separating out and collecting the heavy residue in the lower portion of the chamber, withdrawing the collected residue, and'taking ofi and condensing the evolved vapors from the upper portion of the chamber.

9. A process of producing lower boiling hydrocarbons from higher boiling hydrocarbons that comprises spraying a mixture of hot oil and steam into a chamber, the steam

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