US2096210A - Conversion of hydrocarbon oils - Google Patents

Description

Oct. 19, 1937. K. swARTwooD CONVERSION OF HYDROCARBON OILS Filed June 28, 1935 Nm Ew ZmQZOU INVENTOR KENNETH SWARTWOOD ATTORNEY Patented Oct. 19, 1937 UNITED STATES acatar PATET CQNVERSION OF HYDRGCA-RBON OILS Application June 28,

9 Claims.

'Ihis invention refers to an improved process for the selective conversion of relatively low boiling and high boiling hydrocarbon oils accompanied by reduction of the residual liquid con- 5 version products of the process to coke in al high pressure coking zone of the system,` wherein the vaporous products from the coking operation are subjected to continued conversion time in a high pressure reaction chamber together with other l0 vaporous products of the process.

In one embodiment, the invention comprises subjecting low boiling components of the charging stock for the process, comprising a hydrocarbon oil of relatively Wide boiling range, to vaporization by introducing the charging stock into a vaporizing chamber to which hot conversion products of the process are supplied, withdrawing the commingled vaporous low boiling components of the charging stock and vaporous conversion products from the vaporizing chamber and subjecting the same to additional conversion time in a high pressure reaction chamber, withdrawing liquid conversion products and non-vapcrous high boiling components of the charging stock from the vaporizing chamber, subjecting the same to conversion conditions of cracking temperature and superatmospheric pressure in a heating coil and introducing the heated products into a coking chamber also maintained at substantial superatmospheric pressure, wherein their high boiling components are reduced to coke, withdrawing vaporous products from the coking chamber and introducing the same into said vaporizing chamber wherein they commingle with and eifect said vaporization of the low boiling components of the charging stock, and wherein any high boiling components are separated therefrom and commingled with the high boiling, non-vaporous components of the charging stock, separating vapor- 40 ous and liquid conversion products in the reaction chamber, returning the latter to the coking chamber without additional heating, subjecting the vaporous conversion products from the reactionl chamber to fractionation, whereby their insuiiiciently converted components are condensed as reflux condensate and separated into selected relatively low boiling and high boiling fractions, returning the high boiling fractions of the reflux condensate to said heating coil for further conversion, subjecting the low boiling fractions of the reflux condensate to independently controlled conversion conditions of cracking temperature and superatmospheric pressure in a separate heating coil, introducing the heated products from said separate heating coil into the reaction chamber to commingle with and supply additional heat to the vaporous products supplied to this zone from the vaporizing chamber, subject- 60v ing fractionated vapors of the desired end boiling 1935, serial No. 28,804

point to condensation ing distillate.

As an alternative method of operation to that above outlined, which is not to be considered equivalent, the vaporous products from the coking chamber may be supplied, all or in part, directly to the reaction chamber wherein they are subjected to additional conversion, in which case the heated products from the last mentioned heating coil, to which said low boiling fractions of the reflux condensate are'supplied, are introduced, all or in part, into the vaporizing chamber to effect said vaporization of the charging stock.

The features and advantages of the present invention will be more apparent with reference to the accompanying diagrammatic drawing and the following description thereof. The drawing illustrates one specic form of apparatus in which the process of the invention may be accomplished.

Referring to the drawing, heatingcoil i is located within a furnace 2 of any suitable form and the relatively high boiling oil supplied to this Zone, in a manner to be later more fully described, is subjected therein to the desired conversion conditions of elevated temperature and superatmospheric pressure by means of heat supplied from the furnace. The hot conversion products are discharged from heating coil l through line 3 and valve d into coking chamber 5.

The coking chamber is also maintained at a substantial superatmospheric pressure and the high boiling components of the hot conversion products supplied to this zone are reduced therein to substantially dry coke. 'I'he coke may be allowed to accumulate within the chamber to be removed therefrom, in any well known manner not illustrated, when the chamber has been substantially filled or after its operation has been completed for any other reason. It is specifically within the scope of the invention to employ a plurality of coking chambers, although only onev is illustrated in the drawing. When a plurality of such zones is employed the chambers preferably,` are alternately operated, cleaned and prepared for further operation in order that the duration of the operating cycle will not be limited by the capacity of the coking zone. Chamber 5 is provided with a suitable drain line i5 controlled by valve l, and this line may also serve as a means v of introducing steam, water or any other suit- 5 able cooling material into the chamber after its operation has been completed in order to hasten cooling and facilitate the removal of coke therefrom.

Vaporous conversion products are withdrawn from the upper portion of coking chamber 5 through line 8 and may be directed, all or in part, through valve 9 in this line into Vaporizing chamand recovering the resultber i0 or they may be diverted, all or in part, 6107iV from une s through une lland valve lz'into Y reaction chamber I3. y

"729 Spondingto the Vnohfvfaporous Vhigh-boilingcom- Simultaneously with the 'operation abo-ve de-Y scribed charging stock for the process, preferablyY comprising hydrocarbon oil of relatively; wide "boiling range lsuch as crude'petroleum, toppedj crude or the like, is suppliedY through line I4 and Valve I5 to pump I6, byy meansrof which it'is'fed e through line I'I'and valve I8 and introduced intom', Y Y

Y point are withdrawnytogether' with uncondensa- '10Q vaporizing chamber I l). The .chargin'gstock'thus o :supplied to thewfaprorizihgV chamber is cornmingrled,YV Y in this zone with'hot vaporous conversion prod-` ucts ofthe process from coking chamber 5 and/or from another source which will be later described,V whereby the low boiling components of the'chargf Qing' stocklare vaporized. YThe charging stock in turn serves to condense Y'and remove fvrornjtheV .ponents of Ythe charging stockpand thecommihgled relatively high-boiling liquids collect in -the lower portion of thelvaporizing chamber to'be 1 withdrawn therefromthrough line I9 and' valve Y I2ptopu1np 2I,'byfmeans of rwhich they are-Ysup-fi plied YVthrough lineY 22 and valve 23 to conversionV .in'heating'coil I', in the manner alreadyVY de-Y scribed.; v'I'heconversion products which Vremain Y thereof whereby Atheir heavy liquid Vcomponents *uncondensed in chamber I0 and the vaporous low ,Y boiling components Y' of 'the charging stock are Y withdrawn from the upper portion of this zne and directed through line24and Valve 25 into re-` action chamber I 3,Y wherein theyfare `subjected Y L loto ladditionalV conversion time under thecondir,

tions maintained in this zone.

Y Reaction chamber I3 is also operated at a 'sub-'V stantialV superatmospheric pressure,v andV prefer- Y ably Vthe commingled-materials supplied to this zonegareldirected by means `of a suitable spreader Y flange'or spray arrangement, such asindicated, for example, at 26, against the Virriteriorrsurface of the walls of the chamber, in the upperportion comejin contactwith the chamber walls andare 'fY VV55V Y v Qreduction to, coke; while lthe,ivapo'rous.A products arewithdrawn from YaV suitablepoint inthe'lower Ydirected rapidly downward thereover, while their lower boiling rvaporous components pass Vdown-` Ward Vthrough vthe1vapor space inthe chamber line VA21 and valve 28 to .pumpl 29, byV means of which they arerdirected through line 30 o and valve 3l to coking'chamber 5for furthertreatment'and portionof lthechamber,A abovethe point of 're- 'moval of :the liquid products; Y ,andY VareV directed' ,throughline 32- and valve '33 ftofractionation in'` ,fractionator Y34. Itis, of coursepalso within'Y the scope of the' invention, althoughnot here-illus-l trated,f`tointroduce the conversion Vproducts'into .i Ythe lower Yportion fof :chamber I3, in'owhichca'se ,Y more rapid separationof their liquid components VYwill be effected in this zone, Ytobe directed therefrom, as previously described, to the coking chamber, while the vaporous products willrbersubjected 'tocontinued conversion as,VV they pass upwardr Y l V'through the reaction chamber, to beV directed from Y the 'upper portion thereof to fractionation in fractionatorspj Y y *Y *The componentsY Y Y 2,096,210 Y' Ycooling in condenser 31. K and gas passes through line Y38,;andY valve `39 tot 15 4 ofthe` vaporous conversion' products supplied toffr,ac'ztionatcr 34 boiling above f the range ofthe desired unal iight distillate product of the process are condensed Within this zone as reflux condensate andtherefluxrcondgnsate is Y'separated by fractional distillation into selected y jrelatively,lowlboilihg andhigh boiling fractions which arejseparately subjected to further conf L version within thesame system, as will be later ,j

'more fully described, Y, l

Eractionated vapors of the desired end boilingY ble gas produced bythe processfrom the 'upper through line 35 and valve 36 to condensation and The resulting'distill'ate collection Vand `separation in receiverll. Un-Y condensable gas may be released from the receiver through line :4I l.andlval've;V 42. Distillatei may beiwithdrawnffrom receiver'40 through line' H5."s'ahdvalve'44 tostorage ortoany` other desired 2o 'Y l further treatment.V When desired a.Y regulated Y portion of ther distillate collected in receiver V4I! may be circulated'by well known means notiillusu Y trated intherdrawing, Vto the upper portion,y off fractionatorv 3 4 to serveV as -a cooling and reux-lY fing,medium'V for` assisting vfractionation of vrthe apors; and tomaintain SthefdesirerdY vapor outlet,

jtemperature from the'fractionator,

,YI-The high boiling fractions ofthe 'reuxlcon` I y Vdensatefformed in fractionator 34are withdrawn Soi l I from the'lower portion ofthis zone throughline Y 4.5 ,andvalve 46 to pump-41, by means ofwhich theyjare fed through line 48-and1may b'edirected,`Y 'as desired, either through valve 49Y in VthislinegjY i and line 22to further conversion in heating coilV ,-I,or, in case the boiling range and/or Vcracking?` characteristics ofthe `high boilinggrefluxcon-V Vdensate arematerially different 'than those fof the liquid products supplied'to heating coil Il from' chamber` I0, as previously described, the high boilingV reflux condensate may berr'directed lfrom' g line 48 through line 56 and VvalveSI' to further Vconversion under independentlylcontrolled conditions in heating coilr52.

When heating' coil 52 is utilized the oil'suppliedfY thereto is subjected to the Ydesiredconversion conditions ofY elevated temperature' and super--V `atmospheric pressure by means of heat supplied from a furnace 53 `ofany suitable form,`and th'evf hot conversion products areY discharged from this zone through line'54 andV valve 55Y intoljcokingy n' chamber 5,`V,-w1"iereink they comminglerwithglthe conversion products fromkh'eating coil'I and Vwherein theirrhigh Yboiling components are re-r -duf2edto1coke. f Y' Y e selected lowboiling kfractions of` thereilincV 1, 'r1 V.condensate formed inV fractionator34 may be re- ,Y "moved from one ora plurality of Y suitable'inter-YV mediate'points in 'this one;-provisionbeingrnade-Y in the case hereillustrated for directing thisma-r terial through line Y56 and, valve 5'IV to Vpump 558, j

Y:byfmeans of which it i'si'supplied through Vlir`1e59A` Y, o v

andivalve 60 Atojfwurther conversion in heatingV coll 6I. 'fA' furnacej62 of anyV suitablefofrm supplies?" Y the required-heatto the oil passing'throughheat-V G5 Y Y Y ing rcoil Y6I to subject'thesame tothe desired con-fiY 'f V*version conditions of elevatedteVmperatureV and superatmospheric pressure, and the,V ,heated productsV are Y discharged from the heating coil through line 63 and may be directed, all vor in part as desired,reither through valve Y64 in this linefand through lines 21| andfII into reaction chamber I3, or through line-65 and valve 66`into .Y vaporizing changlberJIl),` VInr casethetotal:vapor-V Y Y ous `products frorn'coking chamheri are' directed Y in the manner previously indicated to chamber I3,

at least a regulated portion of the hot conversion products. from heating coil 6i is introduced into chamber I0 in order to eiect the desired vaporization of the charging stock in this zone. On the other hand, when the total or a substantial portion of the'vaporous products from chamber 5 is supplied to chamber I 0 the heated products from heating coil BI may be introduced, as desired, into either chamber I0 or chamber I3, or in part toboth. When all or a substantial portion of the heated products from heating coil 6I is introduced into chamber I0 the vaporous vproducts from chamber 5 are preferably supplied direct to chamber I3, although they may when desired be introduced, all or in part, into chamber I0. By means of these alternative methods of operation the degree of vaporization to which the charging stock is subjected in chamber I0 may be controlled to suit requirements depending upon the characteristics of the charging stock and the other operating conditions of the process.

In the operation of the process of the present invention as it may be accomplished in an apparatus of the character illustrated and above described the preferred range of operating conditions may be approximately as follows: The first mentioned heating coil to which the high boiling fractions ofthe charging stock and liquid conversion products from the vaporizing chamber are supplied may utilize an outlet conversion temperature ranging for example from 800 to 950 F., preferably with a superatmospheric pressure at this point in the system of from 100 to 500 pounds or more per square inch. When a separate heating coil is employed for conversion of the high boiling reflux condensate conversion conditions within substantially the same range may be employed in this zone, although the specific conditions employed are preferably different from those employed in the iirst mentioned heating coil. 'Ihe coking chamber is operated Yat a substantial superatmospheric pressure, which may be either substantially equalized or somewhat reduced relative to the pressure employed in the communicating heating coil utilizing the lowest pressure. The reaction chamber is preferably operated at substantially the same pressure as that employed in the coking chamber, although the pressure employed in the reaction chamber may be somewhat reduced when desired. The vaporizing chamber may be operated at substantially the same or at a higher pressure than that employed in the reaction chamber. The fractionating, condensing and collecting portions of the system may utilize substantially the same pressure as that employed in the reaction chamber or may be operated at substantially reduced pressures. The heating coil to which the selected low boiling fractions of the reiiex condensate are supplied may utilize an outlet conversion temperature ranging Yfor example from 900 to 1050 F., preferably with a superatmospheric pressure in this zone of from 200 to 800 pounds or more per square inch.

As a specific example of one of the many possible operations of the process of the present invention, the charging stock, which comprises a California crude of Yabout 26 A. P. I. gravity, containing approximately 5% of material boiling up to 286 F., and approximately 18% at 400 F., is introduced into the vaporizing chamber, wherein its components boiling below approximately 660 F., which comprise aboutl 50% of the charging stock, are Vaporized. The non-vaporare supplied, together with the liquid conversionr Y products which accumulate in the vaporizing` chamber, to a heating coil wherein the com-V pressure of aboutV 250 pounds per square inch',v

and the heated products from both heating coils is also maintained at substantially the same pres-v sure. v'I'he vaporous products withdrawn from: the coking chamber are introduced into the reaction chamber, which is also maintained at a superatmospheric pressure of about 250 pounds per square inch. Residual liquids are returned from the reaction chamber to the coking chamber, and the vaporous products from this zone are subjected to fractionation for the formation of light and heavy reflux condensates. 'I'he low boiling reflux condensate, approximately of which boils within the range of 400 to 600 F., is subjected in a separate heating coil to an outlet conversion temperature of approximately 970 F., at a superatmospheric pressure of about 400 pounds per square inch. A suilicient portion of. the highly heated products from this heating coil is introduced into the vaporizing chamber to effect the desired vaporization of the charging stock, and the remainder is introduced into the reaction chamber. This operation will produce per barrel of charging stock approximately 64% of motor fuel of good anti-knock value and approximately 65 pounds of coke, the remainder being chargeable to uncondensable gas. Y

I claim as my invention:

l. A process for the conversion of hydrocarbon oils which comprises, contacting charging stock for the process, comprising an oil of relatively wide boiling range, with hot vaporous conversion products of the process in a vaporizing chamber, withdrawing the resulting vaporous low boiling components of the charging stock and the commingled vaporous conversion products from the vaporizing chamber, introducing the same into a reaction chamber maintained under cracking conditions of temperature and pressure and ous, high-boiling fractions'of'the charging stock;

are introduced into'the coking chamber, which f with, separating vaporous and liquid conversion products in the reaction chamber, returning the latter to the coking chamber, subjecting vaporous jformedr, by said' fractionation it@ Jindepen'zinuy controlled conversion conditions of cracking temi: .perature and sl'iperatniospheric` pressure in a'sep-f arate heating coil, and introducing at least a reg,-

, ulated'portionof the'heated products froml the;V

saidv separate heating coil' into'the Vaporizing porization of the charging stoclr.V Y j c Y:2. Aprocessrfor the conversion of hydrocarbon oils 'which' comprises Vcontacting charging stock 4 chamber toY commingle Ywith and effect 'saidivaf-v i components of the Vcharging stock andthe com- Y mingled vaporous conversion products"froinffthev vaporizingchamber and introducing thelsarneintoz;

`Y aV reactionY chamber Vwherein they aresubjectedto appreciable- Yconversion, withdrawing non-vapori ousxhighboiling components of the charging` Y stockand'c'cmmingled liquid conversion products M from fthevaporizi'ng chamber, subjecting 4the same Y tof conversion 'conditions' of cracking temperature s and `superatrnosph.eric'pressure in a heatingV coil;

Y *'turning'the latterirtc the coking chamber, sub-Y intro'ducingthe heated products 'intofa coking chamber wherein their high boiling components.

are Vreduced'to coke,` withdrawing vaporousprod- Y ucts from the coking chamber, introducing the sarneqinto said reaction chamber to commingle with the Vaporousproducts from the Ivaporizing chamber 'and be subjected YtoV continued Vconver- Y sioni therewith, Vseparating"Vv'aporous andrliquid conversion products inthe reaction chamber; re-

jecting"vaporous products fromV the? reaction chamber Ytorfr'actionation for the formation of reilux condensate, subjecting fractionatedivapors Y Y of the desired end boiling rpoi'ntvto condensation; i recovering'the resulting distillate', returningrse-` lectedlhigh vboiling fractions Vofj the Yreflux con#v j densate formed bysaidffractionation to: the firstv V'mentioned heating coilff'or further',conversion,-V

subjecting'selected low boiling Yfractions. of Ythe reilux condensate formed by said fractionation to independently controlled conversion conditions of cracking` temperatur'efand VsuperatrnosphericY pressure in a separate heating coil, and introducr ing/at` least a regulated portion of the heated products from the said separate heatingcoil Ainto the vaporizving chamber to Vcornmingle with and V`effect said vaporization 'of the charging stock. :i

3.V A process for the conversion of hydrocarbon Y Voils Ywhich comprises; contac'zting charging'lstock AV:rfvorthe process, comprising an oil of`rerlat'ivelyr- Y products'of 'the'processin a vaporizing chamber,"

Y oo

wideboiling' range, with hot'yaporous 'conversion withdrawing vthe Y resulting vaporous low boiling components of the charging Ystock and the come; 1 mingled ivaporous'conversion products fromftheff v ,Y

'Vicoking VZonefarre introduced'togthegvaporizing zone-Y Y V`toiassist'distillationof the:chargingoiltherein. e

8.' VVThe'process asdenedin-daini 4' further Vaporizing chamber,` introducing the-l same intoY a reaction chamberv wherein they are subjected t'o .Y

Yappreciable conversion, withdrawing non'evapo'r` ous high boiling components of the charging stock and commingledliquid conversion products from the vapori'zingrchamber, subjecting'the same to conversion conditions! ofV cracking temperature andsuperatmospheric pressurefina heating coil, i introducing'the'heatedrproducts 'into a cokingV chamberWhereintheir high boiling' components are reduced 1to1 coke, withdrawing Vaporous'products `Vfrom the coking chamber; :introducingrthe Ysame into said reaction chamber tocornmingleY `Vpressure in' af separate heating coil; and introduci- .gingthe resulting heated products into thepoking g 'f jhamber"y subjecting selected low boiling fractionsY Y ofthe v'rei-luxc'ondensateformed by'sai'd fractiongff ation to independently controlled conversion{cron-IV from,Y heating the lightV Vrefiuzr Ycondensate Vto Ycharacterized in that-said unvaporize'd'goil andV g' 5o Vtemperature While flowing" in admixturej through:WAY VasecondheatingV coil. 5?*2 i 't 6." The Vprocess as'denedin claimflfurther Yconversion 'temperature prior to` thei Withthe Vaporous products Vfrom the vaporlzingeAV `chamber and be subjectedV to continuedconvier-` Y sion therewithgseparati'ng"vaporous andliquid;l Y g i y conversion products inthe reaction chamberre-` Y ,turning the latter to Vthe crokingf-chamberg'sub-V f5 'jecting vaporousr products from lthe reaction chamber to-fractionation fonthe formation' ofi4 reflux condensate; subjecting fractionatedv'aV 1po'rs of the desired end boiling point'gt'o condensa.-n tion; .recovering the resulting-distillate, subjecting selected high boiling fractions ofthe reilux con' densate iormedrby said fractionation to inde-jv Y pendently 'con'trolled conversion; conditions, off cracking temperature* andYV superatmospheric ditionscf cracking temperature and superatmo's-` c into the" vaporizin'g Achamber'tor commingle with' @and effect said vapori'zatl'on of thechargin'g'stock; -5Y

4. Aihydrocarbc'n'oil conversion process .which Y Vcomprises .ractionating crackedrvapors, vformedn ,Y

as` 'hereinafter "set Aforthyfan'd` separatingrela-YY tively heavyfand lightireilux condensatesrrtheref crackingtemperaturegunder pressure ina heating coil'and`-dischargingresultantYheatedgproducts a into ava'porizing Zonefintroducing gehargingoll for theprocess to said vvraporizing'zone and there- Y ing the unvaporized oil andthe heavy reflux cone:Y v densate to conversion temperaturevunder'pressure independently of lthe lightY reflux ,condensate and distillingthe `same torcokelin a coking zonepa'ss vaporous, conversion-products from fthereaction-v zonetowthe fractionatingistep as Ysaid cracked-vapors, Yfand Y.finally .condensing the', fractionated' vapors. f *c 5.` 'The process as definedinl claim i4 furtherv heavy reuxucondensate ,arerheated to conversion characterizedin Vthat `said un'vaporizredoil Vand heavy reflux condensate'are separately l'ieatedftoY tionfto thecoklngzione@` ,Y A j Y `i 1:7.1`The' processi as ldencd, in 'claim 4 characterizedin that additional' vaporsfrom,thei` characterized in that additionallfeated `products'YV :from said Vcoil lare 'discharged dlrectlyintothe reaction zone. Y Y Y m* 9. The process asdenedinrclaimlv'furtherf' Vcharacterizedfin Ythat, additional heated products "from said coil are-discharged directly into there-,1 "action zoneand liquid conversion products from the 'reaction@one` supplied'to Y the coking Vz cne.'V i

1 i SWARTWOOD! V2() Y pheric pressure in another separate,heatingrcollv and introducing at' least aportion offtheheated` Yproducts;fromV the. last mentioned heatingVY coil in separating vapors: from "unvaporized oil, heat-1 A 35 further i

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