Патент USA US2107269код для вставки
' Feb. 8,‘ 1938.- 2,107,269 J. B. BARNES HYDROCARBON OIL CONVERSION Original Filed Ma‘rch 16, 1951 FURNACE 25 ' FRACTIONATOR FURNACE 56 INVENTOR > JOHN B. BARNES BY F ozf?ééy! ATTORNE Patented Feb. 8, 1938 ' 2,107,269' UNITED STATES PATENT" OFFICE 2,107,269 HYDROCARBON OIL CONVERSION John B. Barnes, Chicago, Ill., assignor, by mesne assignments, to Universal Oil Products Com‘ pany, Chicago, 111., a corporation of Delaware Application March 16, 1931, Serial No. 522,865 Renewed March 4, 1936 2 Claims. This invention relates to the treatment of hydrocarbon oils andrefers more particularly to the conversion of relatively heavy hydrocar bon mixtures into mixtures containing material 5 amounts of hydrocarbons boiling within the range of motor fuels. ' More speci?cally the invention contemplates the treatment under elevated temperatures and pressures of relatively heavy hydrocarbon frac 10 tions from petroleum and other naturally occur ring hydrocarbons to produce therefrom sub stantial yields of motor fuel fractions of superior quality as regards their tendency to burn with out “knocking” in the cylinders of internal com 15 bustion engines. In one speci?c embodiment the invention com, prises passing heavy hydrocarbon oils through'a heated zone, discharging the heated material into an enlarged reaction zone in which separation 20 (Cl. 196-60) to the primary heating zoneand the line leading the products from the primary heating zone to the primary reaction zone. To assist-in more clearly de?ning the inven" tion and describing any operation comprised 5 within its scope, the attached drawing is pro~ vided which shows diagrammatically a side'ele vational view of an arrangement of equipment which may be used in e?ecting some of its aims and objects.v 1O Raw oil charging stocks typi?ed by heavy hydrocarbon oil mixtures such as, for example, those obtained as residues when crude oils are stripped of their lighter fractions or relatively heavy distillates produced from similar crudes may be taken from line I by pump 3 through valve 2 and discharged into line 4 containing valve 5 or line 6 containing valve 1. Line 4 leads to secondary fractionator $6,v hereinafter to be of vapors and nonvaporized liquids is effected, 7 described more in detail, and such portions of _ discharging the nonvaporized liquids into a va porizing chamber under reduced pressure where in further separation of vapors and nonvaporized liquids is e?ected, ‘discharging the nonvaporized liquids from the process, passing the vapors from thesecondary vaporizing zone to a primary frac tionating zone to produce liquid re?uxes to be returned to the primary heating zone and vapors which are combined with the vapors from the 30 primary reaction zone to form a mixture which is further heated in a secondary heating zone, discharging the products of the second heating into a second reaction zone, again separating vapors and nonvaporized liquids which may be 35 returned in part to the primary heating zone for further conversion and in part to a succeed ing. secondary fractionating zone, passing the vapors from the secondary reaction zone into the secondary fractionating zone designed to pro duce vapors of desired boiling point range which may be cooled, condensed and collected and a plurality‘ of higher boiling intermediate frac— tions to be utilized as material for blending with the liquid products discharged from the vaporiz ing zone or returned in part to the primary heat ing zone for further conversion. The invention further comprises the injection of relatively cold raw oil at suitable points in the line of flow to reduce temperatures, such points of injection including the lower portions of the secondary fractionating zone, the line discharging re?uxes from this equipment to the primary heating zone, the primary fractionating equipment, the liquid discharge line between the primary reaction. zone and the vaporizing zone, the combined feed line the raw oil as- are admitted fromHthisline-may assist in fractionating the cracked-vapors from the secondary reaction zone of the process and be themselvespreheatedv and discharged through line ‘l0 ‘containing valve "in admixture with 25 re?ux condensates from the cracked vapors. Line 6 constitutes a raw oil header having branch line 8 ‘containing valve 9, line l0 contain~ ing valve II and line 12 containing valve I3. Line 8 containing valve 9 leads to line 10' containing valve ‘H’ on the suction side of pump l6 which pump is preferably employed to return heavy liquid re?uxes from secondary reaction chamber 59 and fractionator ??vto primary heating zone 24. Line 60 containing valve 6| may provide a means of discharging nonvaporize'cl liquids from reaction chamber 59 into suction line 10' and line 10 containing valve ‘H enables the admis sion of liquid r'e?uxes from. secondary frac tionator 66. Line 68 containing valve 69 may i lead from collecting pan 6‘! (typifying one of. any number of such devices that may be used at dif ferent levels in fractionator 66) to line 10 and 7B’ and thus to the suction side of pump l6. Line 62 containing valve 63 may branch from line 60 containing valve BI and enable the transfer- of liquid residuals either in whole or in part vfrom reaction chamber 59 to the bottom of fraction‘ ator G6 to assist in reboiling. Pump I6 which may be designated as the reflux pump for the secondary cracking stage of the process dis charges through line ll containingvalve [8 into line 26 on'the discharge side of. combined feed pump I9. . Line l0 containingevalve H may permit the 2 2,107,269 introduction of relatively cold charging oil into primary fractionator 40, the raw oil being pre heated and stripped of its lighter portions and the effectiveness of fractionator 40 being in creased. Line l2 containing valve l3 may join with line 38 containing valve 3| conveying the liquid products from primary reaction chamber 28 to vaporizer 32, the introduction of raw oil in some instances serving to cool the discharge liq 10 uids to a degree sufficient to prevent continued reactions resulting in the deposition of coke in the line and evaporator. Line 14 containing valve l5- may branch from line [3 and convey cool raw oil to line 26 through which the prod 15 ucts from the primary heating element 24 are passing, thus effecting a control of temperature at this point and providing a means of inhibiting undesirable side reactions which otherwise might occur in reaction zone 28. Combined feed pump I9 preferably takes suction on primary fraction ator 40v through line 4| containing valve 42, heavy nonvaporized portions of the products en tering this fractionator being thereby returned to the heating element for further conversion though a portion of this material may be di verted into reaction zone 28 through line 22 con taining valve 23 to control coking reactions and insure the ejection of substantially liquid resi dues from reaction zone 28. Pump l9 discharges 30 preferably into line 29 containing valve 2| so that a mixture of raw oil from line 6, reflux conden sates from secondary reaction zone 59 and sec ondary fractionator 66 and re?ux from primary fractionator 40 may pass in varying proportions 35 into heating element 24 disposed in furnace 25, Heating element 24 may be composed of tubu lar elements connected to produce a continuous coil and furnace 25 may be of any type found suitable for the transmission of heat thereto. it) During passage through the primary heating ele ment temperatures necessary for cracking are 12 containing valve 14 as will also be described later. The vapors from vaporizer 32 may pass through line 38 containing valve 39 and enter primary fractionator 40 which preferably sep arates intermediate re?uxes for further heat treatment which may be discharged through line 4| containing valve 42 topump l9 as already in dicated, Vapors from this fractionator may pass through line 43 containing valves 44 and 49 un der slightly superatmospheric pressure and pass 10 either through line 41 containing valve 48 to join with the vapors coming from reaction zone 28 through line 45 or pass through valve 49 to pump 59 which may discharge into line 53 containing valve 54 leading to secondary heating element 55 disposed to receive heat from furnace 56. Pump 58 is preferably provided for raising the pressure on the vapors from fractionator 40 to any point. desired for the secondary conversion stage but not above that pressure on the vapors in line 20 45 which pass into- line 5| containing valve 52 and join line 53 prior to its junction with the heating element. In heating element 55 pressures v‘maintained may be substantially lower than those main tained on primary element'24 being, for example, of the order of 100 pounds per square inch more or less. and temperatures employed may be sub stantially higher, being, for example, of the or der of from 900° to 1200° R, such changed con 30 ditions being in general conducive to the forma tion of relatively large amounts of hydrocarbon compounds of a cyclic or closed ring character, which compounds have notably high anti-knock ratings when used as motor fuel. ' The heated materials from element 55 pass preferably through line 51 containing valve 58 to secondary reaction zone 59 in which time for reconversions and reformations may be given, liquid portions being withdrawn. through line 60 40 as already indicated and vapors leaving through line 64 containing valve 65 to secondary frac tionator 66. This fractionator may be of a con struction known as “bubble tray” construction 1000° F. more or less, at the exit of the heating element, the heated products passing preferably and be designed to effect an ef?cient separation 45 through line 26 containing valve 21 to primary‘ of low boiling hydrocarbon fractions. Raw oil may be admitted from line 4, refluxes withdrawn reaction zone 28 which may be any arrangement through line 18 and intermediate or side cuts of enlarged equipment in- series or parallel en abling the employment of prolonged reaction taken off through line 68 as previously described. Vapors of desired boiling point range may pass 50 time in the conversion process. Pressures de veloped during the conversion period may be of through line 15 containing valve 16 to condenser the order of approximately 100 to‘ 500 pounds ‘H which may cool and partially liquefy the entering products, these passing through line 18 per square inch in reaction zone28, suitable dif ferentials being maintained at the entrance to containing valve 19 to receiver 80 in which liquids and gases may be segregated, the former being the heating element to cause ?ow. withdrawn to storage through line 83 containing The reaction chambers of zone 28 may be pro valve 84 and the latter released through line 8| vided with removable manheads 29 and 29’ to permit cleaning at intervals andare preferably containing valve 82. The gas release may fur; preferably acquired by the oil mixtures, such temperatures being, for example, from 800 to well insulated to conserve heat necessary for con 60 version reactions. The elements of reaction zone 28 are preferably provided with bottom outlet lines 30 cotaining valves 3| which release pres sure so that vaporization may be effected in va porizer 32 under substantially atmospheric pres sure conditions. The vapors from reaction zone 28 mayv pass through line 45 containing valve 46 with or without pressure reduction to a second ary heating zone to be described more fully later. Vaporizer 32 preferably effects the separation of relatively heavy portions of the cracked prod ucts, these being released throughyline 33 con taining valve 34 and passed through cooler 35, the cooled residue passing through line 36 con taining valve 31 and passing to storage not shown after mixing with second stage re?uxes from line nish a convenient method of controlling pressure on preceding portions of the equipment. 60 To assist in controlling the boiling point range of the vapors issuing from fractionator 66, a pump 81 may be provided to take suction on a suitable portion of the end product liquids through line 85 containing valve 86 and discharge the same into the top of fractionator 66 through line 88 containing valve 89. A portion of the intermediate fractions produced as side cuts and bottom Vrefluxes in fractionator 66 may pass through line 10 to blending pump ‘I2 as permitted by the opening of valve 10", pump ‘I2 discharg 70 ing through line 13 containing valve "to the residuum run-down line 36. ' The foregoing detailed description will serve to indicate the general operations characteristic of 75 2,107,269 Ch 3, the process of the invention but since many other that their benzol equivalent as determined in test types and arrangements of equipment may be employed the speci?c description is not to be con motors may be as high as 65 to. 70% or higher depending on the inherent character of the sidered in a limiting manner. As an example of an operation that may be process. conducted according to the process of the inven tion and results obtainable therefrom, the case of a 24 A. P. I. gravity Mid-Continent topped crude may be taken. The feed of this charging 10 stock may be split so that approximately 20% of the same is admitted to the secondary fractiona tor, 75% to the primary fractionator and the remaining 5% to the line leading from the primary heating element to the primary reaction zone. The temperature maintained at this last named point may be approximately 945° F. which is immediately cooled to approximately 900° F. before the products enter the primary reaction zone. Pressures maintained on the primary re 20 action zone may be 250 pounds. per square inch, the nonvaporized liquids being reduced to sub stantially atmospheric pressures for vaporization and the vapors reduced in pressure to‘ approxi mately 100 pounds per square inch before ad mission to the secondary or substantially vapor phase conversion zone, in which case the vapors from the primary fractionator may be compressed to an equivalent degree. Temperatures employed in the secondary conversion zone may be of the 30 order of 1050 to 1100° F. more or less and there may be produced as an overall yield a fraction of gasoline boiling point range equal to 60% of the raw oil charged. At the same time there charging oil and the details of operation of the The above example is given merely for purposes of illustration and is not intended as a limitation of my invention. I claim as my invention: 1. A hydrocarbon oil cracking process which 10 comprises subjecting the oil to cracking condi~ tions of temperature and pressure and separat ing the same into vapors and unvaporized oil, ?ash distilling the unvaporized oil by pressure reduction, dephlegmating the flashed. vapors and returning resultant re?ux to the cracking step, combining the ?ashed vapors uncondensed by the dephlegmation with the first — mentioned vapors, heating the commingled vapors to- vapor phase cracking temperature,Vdephlegmating the thus heated vapors to condense heavier fractions thereof, blending such condensed fractions with the residue of the ?ash distillation and recover ing the resultant blend as a product of the process, and ?nally condensing the deplhlegmated vapors. 2. A process for cracking hydrocarbon oil to product low boiling products comprising passing the oil through an initial heating coil wherein it is raised to a cracking temperature, thence pass- - ing the oil in succession through a series of vapor releasing chambers, uniting vaporous fractions taken off from said chambers, subjecting the may be produced a yield of low viscosity fuel oil residuum equal to 20% of the charging oil, the same to vapor phase cracking in an independent heating zone, separating the products of the .. remaining 20% being represented by losses in gas vapor phase cracking step into vapors and residue, and directly returning the residue thus obtained and coke, the latter being formed in minimum or negligible amounts. The gasoline fractions produced may be of a highly aromatic nature so to the initial heating zone. JOHN B. BARNES.