US1320726A - adams - Google Patents

Description

AJ. H. ADAMS.

PROCESS FOR THE CONVERSION 0F LIOUIDS, FLUIDSI AND OILS. APPLICATION FILED DEC.3I. I9I4.

l ,320,726. vPatented N ov. 4, 1919.

RES .L -mfom [NVE IV TOR.

l. H. ADAMS. PROCESS FOR THE CONVERSION 0F LIQUIDS, FLUIDS, AND OILS.

- APPLICATION FILED 050.31. 1914.

1,320,726. Patented N ov. 4, 1919.

2 SHEETS-SHEET 2.

Y EIs.

. NVENTOR.

WJTNESSES 'ramas sans time,

JOSEPH H'. ADAMS, OF BROOKLYN, NEW YORK, ASSIGNOR T0 THE TEXAS COMPANY, OF HOUSTON, TEXAS, A CORPORATION OF TEXAS.

Specicaton of Letters Patent.

Patented Nov. et, 1919.

Application led December 31, 1914. -Serial No. 879,907.

To all whom t may concern.'

Be it known that I, JoslPH H. `ADAMS, a citizen of the United States, residing at Brooklyn, in the county of Kingsand State of New York, have invented anew and useful Process for the Conversion of Liquids, Fluids, and Oils, and of which the following is a specification.

My invention relates broadly to the art of convertingoils and distillates of the plain hydro-carbon series, as well as those of the aromatic series, into more volatile products resembling light oils, gasolenes, 'benzins and naphthas which are characterized by lower specific gravities'and boiling points, with the object in view of meeting the great demand for internal combustion engine fuels, gasolcnes, oils and spirits of the aromatic series and naphthas for manufacturing and other industries; and to augment the gradually diminishing supply of the natural product.

It is also within the scope of this invention to treat the various crude petroleums and their products having asphalt or tar i bases in such a manner that the oils driven oif in vapors and those drawn off in liquid form, when collected, will'have greater volume and lower specific gravity than the product obtained from similar oils by any of the known and commonly practised methods of fractional distillation.

The object of this invention is to formulate and carry out in a continuous manner a process for bringing about the conversion and transformation of oil by means of eX- ternally applying a high degree ofheat to a chamber, the whole or a part of which is .composed of heat enduringv material, and,

while containing hydro-carbon or other oils, heating the walls of the chamber to a temperature of sutlicient intensity to locally crack and convert the said oil into oils and spirits essentially different from the original untreated oil.

This invention is based on the fact that petroleum oils and distillates can be successfully cracked and broken into those of lower specific gravities and boiling points by means of properly applied intense heat without unduly converting them into large quantities of fixed gases; and that these oils, when transformed by decomposition and synthetic reconstruction, form new chemical compounds, or products of a more valuable nature than the original untreated oils as set forth in my Patent 976,975, November 29, 1910, and pending applications 17,7145 530,852 and 618, 011.

By my process, however, it becomes quite feasible to convert a high specific gravity oil into those of lower specific gravities such as benzol, toluol, benzin, naphtha and gasolene, by subjecting the oil or mixtures of oils to the powerful influence of properly applied external incandescent heat and decomposing temperature of not less than one thousand degrees, Fahrenheit (1000O E), and from a visible cherry red in color to a full white heat, according to the character of the oil to be treated.

My object in general is to provide a new method and process for successfully breaking up the hydro-carbon' oils such as the low naphthas, kerosenes and fuel oils into those of greater commercial value comprising the lighter naphthas and gasolenes, benzols and toluols to augment the natural supply now obtained by known methods of crude oil separation.

Broadly stated, my improved process, which is in contra-distinction from mere fractional distillation methods, consists in subjecting hydro-carbon oil to a form of dccomposition and reconstruction under the influence of intense heat and self-generated vapor pressure, whereby the product obtained, when condensed, collected and separated, will have greater commercial advanwhich wllserve to illustrate a common form of heater and the correlated parts of apparatus.

Fig. 3 shows more clearly a form of re-f lease valve and vapor or liquid collector.

Fig. 4 is atop plan of the crown which is los .elevated with respect to the converter C, so4

that the gravity tendency of the oil may augment its flow into the converter underl the iniuence of the contained weight of o il, or

the ease with which it may be withdrawnl and forced into the converter C by means of pump 5.

The {iuid oil may be suppliedlto the container A through pipe 1, whileat the same time the displaced air can escape through pipe 2, or this pipe may be connected with an air compressor which will maintaina a suflicient pressure over the surface of the oil to force it through discharge valve 3, pipe 4 and through the regulating feed valve 6,

to the pre-heater B, of which 7 represents a" pipe coil through which the oil Yflows and is heated before entering the cracln'ng chamber 9, of converter C, through pipe 8. n

For obviousvreasons, it is best to pre-heat the oil before it is admitted to the converter C, so that the heat in that 4part of the apl paratus maybe conserved for themore important function of cracking, splitting the molecules of and rapidly vaperizing the converted oils; and therefore the heater B, is provided wherein the qil to be treated may be brought to any desired temperature within the coils 7,' by any economical means of heating.

This oil heater B, is placed in the pipingv system between the source of oil supply A, and the converter C, in a manner conducive to the best methods of admitting oil to the cracking chamber'of the converter C.

The drawing shows one of the many diverse forms which the converter Cpmay assume, and such converter here shown comprises a chamber 9 of oil containing capacity having a Vheat enduring bottom plate 10,

l located r`directly over a heating medium or furnace 11. I

The chamber 9, 1s connected by a pipe or neck 12 directly with an inclosed expansion dome 13, intended to contain Iboth liquid. 'and'vapor, and closed at the top by means of cap 14.

A gage glass 15 and thermometer 16 can bearranged on the vapor and liquid dome n 13, for the inspection of oil quantities and temperatures, which are re lated by thel flow of oil through supply plpe 4, and c011- troller valves 6.

The furnace 11 is provided and located 4under the liquidl containing parts of converter C, as a means of generating Intense heat by known methods of gas, fuel oil, coal or electricity, and this furnace is supported on legs or piers, if necessary, so that in the use of gas or fuel oil, the piping system, valves and controllers 17 'can be the more readily operated.y

' A pyrometer element 16 is arrangedI to extend through the walls of the furnace in order that temperature may be determined, which, in` this-'process is a very important feature.

Inasmuch as the vapors rising into and lling the upperl part of the expansion dome 13 may, at any time, be so rapidly evolved as to exert undue pressure; I have placed a .collecting tank 18 and pop valve 19, in relation with the upper part of dome 13by means of the pipe 20,' so-that any sudden pressure above a given number of pounds necessary to carry on theI process under normal conditions, will cause the pop valve 19 to act rapidly and relieve the excessive pressure.

A feature of primary importance is the meansy for externally applying heat of intense temperature to` the heat enduring plate 10, for the purpose of bringing about amore or less complete conversion of oil.

Preferably this feature is operated by gas or .fuel oil and air or steam under pressure, and comprises one or more jets 17, through which elements of combustion are forced A into an inclosed furnace or retort 11, composed of a shell or container 11 as shown in Fig. 2, lined with frebrick 21 arid asbestos or magnesia filling 58, which together are intended to retain the heat as long as possible, for the purpose of maintaining the plate 10 at the proper and uniform temperature. In the shown form this furnace 11, ,with its intake pipes 17, and outlet or exhaust flue 21,' passing through stack 51,'is made up in circular form to properly heat the round plate 10, located at its top in the formof ,a cap; and while the design of heater maybe varied to conform to the different shapes and styles of converters,

this form is well adapted for the economical` I may here state that when operating upon certain oils it is desirable to localize the application of heat so as to prevent the spread of the heat in a lower degree of intensity than is necessary to efficiently crack the oil, but of a suiicient intensity to cause evaporation of undue amounts of oil at a distance from the intensely heated walls of the cracking plate 10, without bringing about the desired conversion.

To this end in the `embodiment of the apparatus shown in Fig. 1, I have provided a crown plate 22, to which the cracking plate 10 is made fast with bolts drawn against a gasket at its outer edge, and spaced them so that only a thin layer of oil comes in close proximity to the intensely heated surface of the plate 1() which, as shown at Fig. 5, is provided with slotted holes 52, having parallel edges radiating from the center of the plate, so that as eX- pansion or contraction takes place in the plate, a means is provided to prevent upsetting the anchorage bolts or breaking the cracking chamber crown 22.

A more comprehensive idea of this crown .can be had by referring to the drawing, Fig.

4, where in three ports 37, and three oil supply1 pipes 8 are definitely located to facilitate operation. This drawing also shows the series of ribs 59 radiating from the ceni ter, and which lend strength to this part of the apparatus.

The slight tube 22 provides a means of inspecting the incandescence of the cracking plate 10, or the molten metal 10 (Fig. 2) while the converter is in operation; and also affordsa port through which pieces of metal or alloy can be Placed in the chamber 9, preparatory to its being melted.

To protect the plate 10 from burning out, or the destruction of the oil over its surface and its complete transformation into xed gases, with a consequent heavy and clogging deposit of carbon, I employ a metal or alloy having a melting point consistent with the required cracking temperature for the oil to be treated; which, when brought to the proper degree of heat, becomes a fluid metal 10 (Fig. 2) flowing over the top surface of the plate 10, where it can be seen through inspection sight 2-2, and remaining so during the process of oi l conversion while y the furnace heat is maintained at the proper degree of intensity.

In this manner the oil does not come in direct Contact with the heated plate 10, but is affected by indirect heat absorbed through the molten metal, and which treats it as required, but without the undesirable accumulation of carbon which is destructive to the heat enduring plate 10.

Alternately', and for the treatmentof certain oils, the molten metal or alloy can be omitted from the apparatus, when in operation, so that the oil may come in direct contact with the intensely heated surface of plate 10; and the choice between these two methods of oil contact is largely a matter of judicious oil practice over which no set rules can govern.

In order to prevent furious agitation within the chamber 9, and dome 13, while the process is in operation, perforated bafile plates 23, are located on the rod 24, and made fast so that they occupy a position within the connecting neck or pipe 12, and lare held in place by means of a nut and gland 25, at the top of dome 13, through which it passes.

Owing to the excessive quantity of heat employed in this process, and the consequent volatilization of unconverted oils under ordinary atmospheric conditions, I have, by a series of valves and collecting tanks, provided a means of carrying on the conversion process under a pressure of several atmospheres, if necessary, by setting the pop valves to operate at certain pressures, as may be indicated by gages 35and 36, bothfor the release of vaporized oil from the top of dome 13 through pop valve 19 and chamber 18, and liquid oil from the bottom of said dome throu-,gh pop valve 26 and collecting tank 27.

In this manner I am able to reduce the undesirable vaporization without conversion to a minimum, and as a consequence the evolved oils are, in a large proportion cracked and otherwise converted in chalacter.

In addition to the intense heat employed for the purpose of conversion, I also may use superheated steam forced into the body'of oil through pipe 8 and a Small jet at its point of entry 8 into the chamber 9, and regulate the supply of steam in proportion to the amount of oxygen required to combine With a certain quantity of carbon contained in the oil, and thusfreeing the resultant vapors, the product of conversion, from a portion of undesirable carbon.

In Fig. 3, a detailed drawing shows a form of liquid or vaportrap, wherein 27 is the container or expansion tank, provided with a tightly fitting cover 27 held on with bolts and a gasket at itsouter edge.

The pop valve 26 is arranged centrally on an elbow of pipe 43, and made fast to the container with flanges or lock nuts 43.

The pop valve can be regulated for various pressures by meansof the rod and cross head 26', which projects through the cap 27 and is properly sealed by a stufiing box or land. g

il or vvapor escaping through the pop valve 26, and collected within the chamber 27, is then discharged through pipe and valve 45 to its destination.

By the proper means ofv propulsion, the

oil will be'constantly flowing'toward and into contact with the intensely heated lower surfaces of the cracking chamber 9, to take the place of that already vapor-ized from above, or that drawn from below the surface line of oil maintained inthe dome C, as indicated by the dotted line X.

Newly admitted oil will in turn be cracked and changed in the apparatus into lighter and more volatile products, which will pass off in the form of vapors through'the tank 18 and gooseneck 28, into the pipe coils 29 of 'condensing apparatus D; and having been condensed inthe usual manner the condensate is discharged into collecting tank E, through trap tank 30, valve 30 and pipe 31; or through pop valve 32 and tank 33, then conducted through pipe 34, according'to'the method to be employed for operation with the apparatus under partial or complete compression.

During the operation of the process for oil conversion by this' method, the raw nonconverted oils will be relieved of a certain portion of free carbon, of which they are in part composed, as Well as some of the foreign substances which it is desirable to A eliminate.

This, ofcourse, alters their chemical character and converts them from one 'or more of the hydro-carbon series into others of an essentially dierent character.

The carbon `and other sediment remaining on the top surface of plate 10, or the molten metal 10 aboveit, can be removed from time to time by cooling down the furnace, withdrawing the oil, and o peningV the ports 37 in the cap 22; which are 'more clearly shown in Figs. 2, and 4, and with a narrow scraper'or long slicing chisel,-the refuse may be removed.

Inasmuch as the precise degree of temperature at which the plate 10, should be maintained in practice, will largely depend upon, and be varied with particular conditions, it will be sufficient to state that the temperature of the plate will generally vary from a cherry red to a full white heat, ac-

cording tothe nature of the oil to be treated, 50I

and thatat no time in the process of conversion will the plate 10 be below a temperature of one thousand degrees Fahrenheit, (1000o E).

,When operating, it has been observed that apparently only a certain part of the luid vaporized co`mes in direct contact with the intensely heated surface of the cracking plate 10, for the reason that the intensity of heat evaporates a certain portion of the oil ata lower temperature than is required for kcracking7 the oil.

Accordingly, the vapors passingI into the dome will be composed not only of the oil which has been'transformed; but will also contain a certain portion of the unchanged original oil in the form of vapors which,

oil, rise to the top of dome 13, and pass out through pipe 20, and condense before 'pass heavy molecules or spray of unconverted i ing through valve 19, the condensate is led, i

down through column 40, and into neck pipe 12, through pipe 39. y

In this manner the already condensed un-` converted oil may be passed into the system again to mingle, and possibly become converted, with the new supply of oil continually flowing into the cracking chamber 9.

The above specically described 'apparat-us may, of course, be modified greatly and yet be well adapted to carry out one or more of the essential correlated steps of my process which, having now described a form of apparatus, is carried on in thefollowing manner When operating under atmos heric conditions, and without pressure in t e systems, oil A is admitted to container A through pipe 1, the displaced -air in the container passing out through pipe 2, until a sufficient amount of oil is stored for progressive work.'

The system is then supplied with oil from the container lthrough valve 3, and pipe 4,

lpassing pump 5, whichis cut out by closing valve 4', thereby 'allowing the oil to pass through valve 5 and precision valves 6, into the coils 7 of pre-heater-B.

The oil circulating through these coils, where it is heated, is then passed through pipe 8, into cracking chamber 9, of the converter C, where it is brought into contact with intense heat maintained in plate 10.

The oil is held at a uniform level in dome 13, as indicated by the dotted line X, for

the purpose of supplying weight to hold the body of oil down against cracking plate 10, or molten metal 10', and also to provide a medium VTfor the partial arrest of up-lowing converted vapors, which are rapidly evolvedv by `the treatment of oil subjected to in-v tensely high temperature.

As the vapors rise through pipe neck 12, to escape into the upper part of liquid and vapor dome 13, an intense. agitation is carried on withinpthispipe 12, which would cause undue disturbance over the surface of the oil'at line X; therefore perforated baffle plates 23, are made fast to rod 24, which is attached to thetop 14, of the dome 13,

by means of a nut and gland 25 and the lower end screwed into crackingplate 10, where it is held securely in place.

As the oil rapidly becomes heated and volatilized, and would expand to unreasonable bounds if conned in the dome for any length of time, the overflow pipes 41, are provided to carry olf the surplus unconverted oil which Hows down through them into collecting chamber 42 and out through pipe 43 and valve 44, to pipe 45, through which it is admitted tothe bottom of preheater B, and flows out of the top through pipe 46, to the overflow tank 47, from which it is withdrawn by pump 48, and delivered through pipe 49, to container A.

This returned oil may then be supplied again to the converter through the system just described. y

A certain small portion of oil having been cracked, converted and vaporized, rises to the top of dome 13 and passes out through pipe 20, pop valve 19, in container 18, which is opened and made a free passage to goose-4 neck pipe 28.

It then passes through condensing coils 29, immersedV in water contained in tank D, and flows through trap tank 30, valve 30, and pipe 31, into collecting tank E, from which the condensate may be drawn o through Valve 50. A

An important tfeature of pre-heater B, is the vent pipe 53, at the upper end of pipe v 46, through which air and gases may pass to avoid vacuuml or pressure within the container B, and which would interrupt the proper flow of hot oil through that apparatus. y

When operating under complete pressure brought about by the expansion, Vaporization and partial retention of oil and vapors in dome 13, due to the applied heat to plate 10, as in agsteam boiler, valve 5 in pipe 4 is closed. Valve 44 in pipe 43 is also closed, as well as valve 30 in pipe 31.

rlhe pop valve 26 inY container 27, is set to the proper release pressure, also pop valve 19 in container 18, and 32 inl container 33.

The valve 56, at the end of coil 29, is open, while the valve .57, in pipe 38 is closed; thus eflectually sealing the system against operation under atmospheric pressure.

Oil Ais then withdrawn from -container A, through valves 3 and 4, by`pump 5, which forces it through pipe 4 and valves 6, to the re-heater coils 7, and pipe 8, into the crac ing ,chamber 9.

A certain portion of unconverted oil overflows from the surface level X, in the dome 13, and is conducted through pipes 41 to chamber 42, thence through pipe 43, to pop valve. 26, in container 27, where, by the self generated vapor pressure maintained over the surface of oil in the dome 13, the

pop valve 26 in tank 27, is caused to release and allow a portion of the oil to How through pipe 45, into the lower part of prelieater B, and escape from the upper part of said container through pipe 46, to the overflow tank 47.

The residue oil may then be returned to tank A, as heretofore described.

That certain portion of oil which, having come in contactwith the hot plate 10, or molten metal 10 lying above it, and becomes vaporized; rises through neck 12, and body of oil contained in the lower part of dome 13, and expanding into the upper part of l the said dome, is driven olf through pipe 20, pop valve 19, and into the condensing coils 29, through pipe 28.

Popl valve 32, in container 33, is set at a pressure sufficient to check the rapid flow of condensateC from the coil, and is therefore an adjunct in maintaining vapor pressure within the entiresystem from pump 5, to the release valve 32. Distillate can also be accumulated under vapor pressure, in trap tank 30, then released through valve 30" and pipe 31. 'The oil, having passed the last checking point, then flows by gravity into the collecting tank E.

If a partial pressure only, is required 1n the system, the valve 56 and pop valve 32,

also valve 30 in pipe 31 are opened, thus giving a free run of vapor and condensate, at atmospheric pressure only, from the container I18, to the collecting tank E, at the foot of the pipe train.

Gases which maybe resent 1n the distillate, or fixed gases ma e in the process of conversion, can escape through valve 54 and pipev55, leading out from container 33, or through valve 54 leading out from trap tank'30.

As the condensate collected in tank E, is of a comple-X nature composed of converted and un-converted original oil, it may be withdrawn and separated by any of the ,methods of fractional distillation and the remainder' returned to container A, for retreatment as before.

From the foregoing disclosures it 1s apparent that 1 have succeeded in formulating a process well suited to the several objects in view, and that as a result I have made 1t possible, within commercial limits, to convert inexpensive available oils into products of greater value. f

1n viewpof these disclosures, it is obvious to those skilled in the art, that my process may be carried out with different fluids by varied steps, and accordingly I intend that all matter contained in this description shall be taken asillustrative and not in a limited sense.

I desire it to be ,understood also, that the language adoptedin the following claims is intended-to cover all of the generic and speciic features of this invention, and all statements of the scope thereof which, as a matter ofv language, might be. said to fall therebetween. j

The apparatus described .in the foregoing specification is not claimed herein, but forms the subject matter ofa process for accomplishing the required results, and, having now described my invention, whatl claim as new, and desire to secure by Letters Patent i chamber, maintaining. aportion of said'. oil

relatively separatev and distinct, subjecting said separate portion of oil to a cracking and converting temperature, maintaining superatmospheric vapori pressure on said body of oil, auf1 introducing superheatedsteam into said body of oil.

' 3. The herein disclosed process 0f converting high boiling point hydrocarbons into lower boiling point products whichconsists in confining a body of Oil in: an inclosedr chamber, maintaining a portion off said oil relatively separate and distinct, subjecting said separate portion of oil toa cracking and converting temperature, introducing superheated steam into said oil. where said cracking temperature is applied, conden'sin theconverted vapor products generated a, Y

maintaining self-generated' vapor pressure y on said oilv undergoing treatment ando said vaporswhile being condensed.

4. The herein disclosed' process ofcouvertingl high boiling pointhydrocarbons'finto lower boiling pointy products which consists inconflning a body of'oil under vapor pres- Sura-maintaining a portion of said oil relativelyfseparateand distinct, subjecting said separate portion o fsaidoil to laeracki-ng and converting temperature, continuously introducing oilandsuperheatedlsteam into said 'body of oil'ati the point where said cracking temperature is applied and continuously conducting awayv and condensing the 4 vapors generated.

5. Thezherein'disclosed -rocess of'converting high boiling point ydrocarbons-into lower; boiling point products which consists in confining'. a body of oil inV ariinclosed ing high boiling chamber, maintaining a portion of said oil relatively separate and distinct, subjecting said separate portion of oil to a cracking and converting temperature, continuously introducing oil and superheated steam into said body of oil at the point where said cracking temperature is applied, continuously conducting away and condensing the 'vaporsgenerated and maintaining lvapor pressure on said confined body of oil and on said vapors undergoing condensation.

6. The herein disclosed process of convertpoint hydrocarbons into lower boiling point products which consists in confining a body of oil within inclosed containers, subjecting a portion of said oil below the surface to a local cracking and converting', temperature, continuously intro: ducing oil into said body at the point where it is'. subjected to the local cracking temperature at a rate greater than that at which the oil is converted, withdrawing oil from the upper portion of said body' at such a rate as to maintain a substantially constant' volume and level of oil and condensing the converted products. f

7. The herein disclosed process of converting high boiling point hydrocarbons-into lower boiling'` point products whichy consists in confining a body of oil, subjecting a portion of said oil below the surface toa-local.

cracking and convertingtemperature inexcess of their volatilizing points, continuously introducing oil into said body at= the` point where it is subjected to the local cracking temperatureat a rate greater than that at which the oil'vis converted, withdrawing oil from the upper portion of said body atsuch a rate asto maintain a substantially constant volume and.. leveloft oil,..condensing the converted products, and maintaining self generatedvapor pressure on said. bodyl of oil and on said' vapors `during condensation.

- 8. The. herein disclosed process of converting` high boiling point hydrocarbons v' into lower boiling point. products which consists in confining a body o-foilf, subjecting a portion of said oil below the surface to adocal cracking and convertingl temperature,- continuously introducing preheated; oil

-andsuperheate'd'steam into said-body offoil f below theI surface, withdrawing oil from vthe upper portion of said body at such-a rate as to maintain av substantially constant.

volume' and level of oil; condensingf* the vapors. of convertedfoil in free communication with saidbody of oil andlxnaintaining self generated vapor pressure onl said oil during conversion and ing. condensation.

. 9.' The herein disclosed process pf. converting oils. which consi-sts in coniningz a body of oil of considerable volume, subjectinga limited portion of said 'oilatf the lowerl on. said vapors durpart of the body to a local cracking temperature, continuously supplying preheated oil and superheated steam to said limited portion subjected to said cracking temperature, drawin off oil from the upper portion of said bo y to maintain a substantially constant volume of oil and condensing. the vapors of the converted oil.

l0. The herein disclosed process of converting oils which consists in comining a body of oil of considerable volume, subjecting a limited portion of said oil at the lower part of the body to a local cracking temperature, continuously supplying preheated oil and superheated steam to Said limited portion subjected to said cracking temperature, drawing off oil from thev upper portion of Y said body to maintain a substantially constant volume of oil, drawing oi the converted vapors under pressure from above said oil and condensing them under pressure.'

11'. The herein disclosed process consisting in subjecting high boiling point hydrocarbons to an externally applied heat of intense temperature while contained in a heat enduring chamber, maintaining a self generatedl Vapor pressure only in the chamber and to and through the condenser in free communication with said chamber, introducing superheated steam under high pressure into the body of oil undergoing transformation, locally cracking and converting the same into loW boiling products essentially diierent from the original untreated oil, separating out the lighter and retreating the heavier residues..

In testimony whereof I aiiix my signature in the presence of two witnesses.

JOSEPH H. ADAMS.

Witnesses:

JOEL S. DE SELDING, A. CArs'rIoK.

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