Indian Patents. 279409:HYDROCARBON THERMAL CRACKING USING ATMOSPHERIC RESIDUUM

Title of Invention	HYDROCARBON THERMAL CRACKING USING ATMOSPHERIC RESIDUUM
Abstract	A method for thermally cracking a hydrocarbonaceous feed wherein the feed is first gasified in a vaporization unit. A significant component of the feed is residua from the atmospheric thermal distillation of crude oil.

Full Text	HYDROCARBON THERMAL CRACKING USING ATMOSPHERIC RESIDUUM BACKGROUND OF INVENTION FIELD OF INVENTION This invention relates to the thermal cracking of hydrocarbons using a vaporization unit in combination with a pyrolysis furnace wherein at least a preponderance of the liquid hydrocarbonaceous feed to be cracked in the furnace is first vaporized in the vaporization unit. More particularly, this invention relates to the use of atmospheric residuum as a significant liquid hydrocarbonaceous feed component for the vaporization unit and furnace. DESCRIPTION OF THE PRIOR ART Thermal (pyrolysis) cracking of hydrocarbons is a non-catalytic petrochemical process that is widely used to produce olefins such as ethylene, propylene, butenes, butadiene, and aromatics such as benzene, toluene, and xylenes. Basically, a hydrocarbon containing feedstock is mixed with steam which serves as a diluent to keep the hydrocarbon molecules separated. The steam/hydrocarbon mixture is preheated in the convection zone of the furnace to from about 900 to about 1,000 degrees Fahrenheit (°F or F), and then enters the reaction (radiant) zone where it is very quickly heated to a severe hydrocarbon thermal cracking temperature in the range of from about 1,400 to about 1,550F. Thermal cracking is accomplished without the aid of any catalyst. This process is carried out in a pyrolysis furnace (steam cracker) at pressures in the reaction zone ranging from about 10 to about 30 psig. Pyrolysis furnaces have internally thereof a convection section (zone) and a separate radiant section (zone). Preheating functions are primarily accomplished in the convection section, while severe cracking mostly occurs in the radiant section. After thermal cracking, depending on the nature of the primary feed to the pyrolysis furnace, the effluent from that furnace can contain gaseous hydrocarbons of great variety, e.g., from one to thirty-five carbon atoms per molecule. These gaseous hydrocarbons can be saturated, monounsaturated, and polyunsaturated, and can be aliphatic, alicydics, and/or aromatic. The cracked gas can also contain significant amounts of molecular hydrogen (hydrogen). The cracked product is then further processed in the olefin production plant to produce, as products of the plant, various separate individual streams of high purity such as hydrogen, ethylene, propylene, mixed hydrocarbons having four carbon atoms per molecule, fuel oil, and pyrolysis gasoline. Each separate individual stream aforesaid is a valuable commercial product in its own right. Thus, an olefin production plant currently takes a part (fraction) of a whole crude stream or condensate, and generates therefrom a plurality of separate, valuable products. Thermal cracking first came into use In 1913 and was first applied to gaseous ethane as the primary feed to the cracking furnace for the purpose of making ethylene. Since that time, the industry has evolved to using heavier and more complex hydrocarbonaceous gaseous and/or liquid feeds as the primary feed for the cracking furnace. Such feeds can now employ a fraction of whole crude or condensate which is essentially totally vaporized while thermally cracking same. The cracked product can contain, for example, about 1 weight percent (wt.%) hydrogen, about 10 wt.% methane, about 25 wt.% ethylene, and about 17 wt.% propylene, all wt.% being based on the total weight of that product, with the remainder consisting mostly of other hydrocarbon molecules having from 4 to 35 carbon atoms per molecule. Natural gas and whole crude oil(s) were formed naturally in a number of subterranean geologic formations (formations) of widely varying porosities. Many of these formations were capped by impervious layers of rock. Natural gas and whole crude oil (crude oil) also accumulated in various stratigraphic traps below the earth's surface. Vast amounts of both natural gas and/or crude oil were thus collected to form hydrocarbon bearing formations at varying depths below the earth's surface. Much of this natural gas was in close physical contact with crude oil, and, therefore, absorbed a number of lighter molecules from the crude oil. When a well bore is drilled into the earth and pierces one or more of such hydrocarbon bearing formations, natural gas and/or crude oil can be recovered through that well bore to the earth's surface. The terms "whole crude oil" and "crude oil" as used herein means liquid (at normally prevailing conditions of temperature and pressure at the earth's surface) crude oil as it issues from a wellhead separate from any natural gas that may be present, and excepting any treatment such crude oil may receive to render it acceptable for transport to a crude oil refinery and/or conventional distillation in such a refinery. This treatment would include such steps as desalting. Thus, it is crude oil that is suitable for distillation or other fractionation in a refinery, but which has not undergone any such distillation or fractionation. It could include, but does not necessarily always include, non-boiling entities such as asphaltenes or tar. As such, it is difficult if not impossible to provide a boiling range for whole crude oil. Accordingly, whole crude oil could be one or more crude oils straight from an oil field pipeline and/or conventional crude oil storage facility, as availability dictates, without any prior fractionation thereof. Natural gas, like crude oil, can vary widely in its composition as produced to the earth's surface, but generally contains a significant amount, most often a major amount, i.e., greater than about 50 weight percent (wt. %), methane. Natural gas often also carries minor amounts (less than about 50 wt. %), often less than about 20 wt. %, of one or more of ethane, propane, butane, nitrogen, carbon dioxide, hydrogen sulfide, and the like. Many, but not all, natural gas streams as produced from the earth can contain minor amounts (less than about 50 wt. %), often less than about 20 wt. %, of hydrocarbons having from 5 to 12, inclusive, carbon atoms per molecule (C5 to C12) that are not normally gaseous at generally prevailing ambient atmospheric conditions of temperature and pressure at the earth's surface, and that can condense out of the natural gas once it is produced to the earth's surface. Ail wt.% are based on the total weight of the natural gas stream in question. When various natural gas streams are produced to the earth's surface, a hydrocarbon composition often naturally condenses out of the thus produced natural gas stream under the then prevailing conditions of temperature and pressure at the earth's surface where that stream is collected. There is thus produced a normally liquid hydrocarbonaceous condensate separate from the normally gaseous natural gas under the same prevailing conditions. The normally gaseous natural gas can contain methane, ethane, propane, and butane. The normally liquid hydrocarbon fraction that condenses from the produced natural gas stream is generally referred to as "condensate," and generally contains molecules heavier than butane (C5 to about C20 or slightly higher). After separation from the produced natural gas, this liquid condensate fraction is processed separately from the remaining gaseous fraction that is normally referred to as natural gas. Thus, condensate recovered from a natural gas stream as first produced to the earth's surface is not the exact same material, composition wise, as natural gas (primarily methane). Neither is it the same material, composition wise, as crude oil. Condensate occupies a niche between normally gaseous natural gas and normally liquid whole crude oil. Condensate contains hydrocarbons heavier than normally gaseous natural gas, and a range of hydrocarbons that are at the lightest end of whole crude oil. Condensate, unlike crude oil, can be characterized by way of its boiling point range. Condensates normally boil in the range of from about 100 to about 650F. With this boiling range, condensates contain a wide variety of hydrocarbonaceous materials. These materials can include compounds that make up fractions that are commonly referred to as naphtha, kerosene, diesel fuel(s), and gas oil (fuel oil, furnace oil, heating oil, and the like). Naphtha and associated lighter boiling materials (naphtha) are in the C5 to C10, inclusive, range, and are the lightest boiling range fractions in condensate, boiling in the range of from about 100 to about 400F. Petroleum middle distillates (kerosene, diesel, atmospheric gas oil) are generally in the C10 to about C20 or slightly higher range, and generally boil, in their majority, in the range of from about 350 to about 650F. They are, individually and collectively, referred to herein as "distillate," "distillates," or "middle distillates." Distillate compositions can have a boiling point lower than 350F and/or higher than 650F, and such distillates are included in the 350-650F range aforesaid, and in this invention. Atmospheric residuum (resid or residua) typically boils at a temperature of from about 650F up to its end boiling point where only non-boiling entities such as asphaltenes and tar are left. Atmospheric resid is formed by processing crude oil/condensate in an atmospheric thermal distillation tower. Atmospheric resid is not the same as vacuum residuum which is formed in a vacuum assisted thermal distillation tower, and has a boiling range of from about 1,000F up to its end boiling point where only non-boiling entities remain. The olefin production industry is now progressing beyond the use of fractions of crude oil or condensate (gaseous and/or liquid) as the primary feed for a cracking furnace to the use of whole crude oil and/or condensate itself. Recently, U.S. Patent Number 6,743,961 (hereafter "USP '961") issued to Donald H. Powers. This patent relates to cracking whole crude oil by employing a vaporization/mild cracking zone that contains packing. This zone is operated in a manner such that the liquid phase of the whole crude that has not already been vaporized is held in that zone until cracking/vaporization of the more tenacious hydrocarbon liquid components is maximized. This allows only a minimum of solid residue formation which residue remains behind as a deposit on the packing. This residue is later burned off the packing by conventional steam air decoking, ideally during the normal furnace decoking cycle, see column 7, lines 50-58 of that patent. Thus, the second zone 9 of that patent serves as a trap for components, including hydrocarbonaceous materials, of the crude oil feed that cannot be cracked or vaporized under the conditions employed in the process, see column 8, lines 60-64 of that patent. Still more recently, U.S. Patent 7,019,187 issued to Donald H. Powers. This patent is directed to the process disclosed in USP '961, but employs a mildly acidic cracking catalyst to drive the overall function of the vaporization/mild cracking unit more toward the mild cracking end of the vaporization (without prior mild cracking) - mild cracking (followed by vaporization) spectrum. U.S. Patent Number 6,979,757 to Donald H. Powers is directed to the process disclosed in USP '961, but that invention removes at least part of the liquid hydrocarbons remaining in the vaporization/mild cracking unit that are not yet vaporized or mildly cracked. These liquid hydrocarbon components of the crude oil feed are drawn from near the bottom of that unit and passed to a separate controlled cavitation device to provide additional cracking energy for those tenacious hydrocarbon components that have previously resisted vaporization and mild cracking. Thus, that invention also seeks to drive the overall process in the vaporization/mild cracking unit more toward the mild cracking end of the vaporization-mild cracking spectrum aforesaid. The disclosures of the foregoing patents, in their entirety, are incorporated herein by reference. U.S. Patent Application Serial Number 11/219,166, filed September 2, 2005, having common inventorship and assignee with USP '961, is directed to the process of using whole crude oil as the feedstock for an olefin plant to produce a mixture of hydrocarbon vapor and liquid. The vaporous hydrocarbon is separated from the remaining liquid and the vapor passed to a severe cracking operation. The remaining liquid is vaporized using a quench oil to minimize coke forming reactions. U.S. Patent Application Serial Number 11/365.212, filed March 1, 2006, having common inventorship and assignee with USP '961, is directed to the use of condensate as the dominant liquid hydrocarbonaceous feed for the vaporization unit and furnace. U.S. Patent Application Serial Number 11/584,722, filed October 20, 2006, having common inventorship and assignee with USP '961, is directed to the integration of the vaporization unit/furnace combination with a crude oil refinery. During periods of increased gasoline demand the gasoline supply (pool) can be increased by subjecting various crude oil fractions, including distillates, to various refinery catalytic cracking processes such as fluid catalytic cracking. Thus, the quantity of gasoline/naptha produced from a barrel of crude oil can be increased if desired. This is not so with distillates as defined above. The amount of distillate recovered from a barrel of crude oil is fixed and cannot be increased as it can with gasoline. The only way to increase distillate production to increase the distillate supply for the distillate pool is by refining additional barrels of crude oil By this invention valuable distillates that are in short supply are saved for the distillate pool, and not consumed in the cracking process. SUMMARY OF THE INVENTION In accordance with this invention, the aforesaid combination of a vaporization unit/cracking furnace is operated with its feed containing a significant amount of residuum from at least one atmospheric thermal distillation column, i.e., atmospheric resid. DESCRIPTION OF THE DRAWING Figure 1 shows a simplified flow sheet for the whole crude oil/condensate cracking process described hereinabove. DETAILED DESCRIPTION OF THE INVENTION The terms "hydrocarbon," "hydrocarbons," and "hydrocarbonaceous" as used herein do not mean materials strictly or only containing hydrogen atoms and carbon atoms. Such terms include materials that are hydrocarbonaceous in nature in that they primarily or essentially are composed of hydrogen and carbon atoms, but can contain other elements such as oxygen, sulfur, nitrogen, metals, inorganic salts, and the like, even in significant amounts. The term "gaseous" as used in this invention means one or more gases in an essentially vaporous state, for example, steam alone, a mixture of steam and hydrocarbon vapor, and the like. Coke, as used herein, means a high molecular weight carbonaceous solid, and includes compounds formed from the condensation of polynuclear aromatics. An olefin producing plant useful with this invention would include a pyrolysis (thermal cracking) furnace for initially receiving and thermally cracking the feed. Pyrolysis furnaces for steam cracking of hydrocarbons heat by means of convection and radiation, and comprise a series of preheating, circulation, and cracking tubes, usually bundles of such tubes, for preheating, transporting, and cracking the hydrocarbon feed. The high cracking heat is supplied by burners disposed in the radiant section (sometimes called "radiation section") of the furnace. The waste gas from these burners is circulated through the convection section of the furnace to provide the heat necessary for preheating the incoming hydrocarbon feed. The convection and radiant sections of the furnace are joined at the "cross-over," and the tubes referred to hereinabove carry the hydrocarbon feed from the interior of one section to the interior of the next. In a typical furnace, the convection section can contain multiple sub-zones. For example, the feed can be initially preheated in a first upper sub-zone, boiler feed water heated in a second sub-zone, mixed feed and steam heated in a third sub- zone, steam superheated in a fourth sub-zone, and the final feed/steam mixture split into multiple sub-streams and preheated in a lower (bottom) or fifth sub-zone. The number of sub-zones and their functions can vary considerably. Each sub-zone can carry a plurality of conduits carrying furnace feed there through, many of which are sinusoidal in configuration. The convection section operates at much less severe operating conditions than the radiant section. Cracking furnaces are designed for rapid heating in the radiant section starting at the radiant tube (coil) inlet where reaction velocity constants are low because of low temperature. Most of the heat transferred simply raises the hydrocarbons from the inlet temperature to the reaction temperature. In the middle of the coil, the rate of temperature rise is lower but the cracking rates are appreciable. At the coil outlet, the rate of temperature rise increases somewhat but not as rapidly as at the inlet. The rate of disappearance of the reactant is the product of its reaction velocity constant times its localized concentration. At the end of the coil, reactant concentration is low and additional cracking can be obtained by increasing the process gas temperature. Steam dilution of the feed hydrocarbon lowers the hydrocarbon partial pressure, enhances olefin formation, and reduces any tendency toward coke formation in the radiant tubes. Cracking furnaces typically have rectangular fireboxes with upright tubes centrally located between radiant refractory walls. The tubes are supported from their top. Firing of the radiant section is accomplished with wall or floor mounted burners or a combination of both using gaseous or combined gaseous/liquid fuels. Fireboxes are typically under slight negative pressure, most often with upward flow of ffue gas. Flue gas flow into the convection section is established by at least one of natural draft or induced draft fans. Radiant coils are usually hung in a single plane down the center of the fire box. They can be nested in a single plane or placed parallel in a staggered, double-row tube arrangement. Heat transfer from the burners to the radiant tubes occurs largely by radiation, hence the thermo "radiant section," where the hydrocarbons are heated to from about 1,400°F to about 1,550°F and thereby subjected to severe cracking, and coke formation. The initially empty radiant coil is, therefore, a fired tubular chemical reactor. Hydrocarbon feed to the furnace is preheated to from about 900°F to about 1,000°F in the convection section by convectional heating from the flue gas from the radiant section, steam dilution of the feed in the convection section, or the like. After preheating, in a conventional commercial furnace, the feed is ready for entry into the radiant section. The cracked gaseous hydrocarbons leaving the radiant section are rapidly reduced in temperature to prevent destruction of the cracking pattern. Cooling of the cracked gases before further processing of same downstream in the olefin production plant recovers a large amount of energy as high pressure steam for re- use in the furnace and/or olefin plant. This is often accomplished with the use of transfer-line exchangers that are well known in the art. With a liquid hydrocarbon feedstock downstream processing, although it can vary from plant to plant, typically employs an oil quench of the furnace effluent after heat exchange of same in, for example, the transfer-line exchanger aforesaid. Thereafter, the cracked hydrocarbon stream is subjected to primary fractionation to remove heavy liquids, followed by compression of uncondensed hydrocarbons, and acid gas and water removal therefrom. Various desired products are then individually separated, e.g., ethylene, propylene, a mixture of hydrocarbons having four carbon atoms per molecule, fuel oil, pyrolysis gasoline, and a high purity hydrogen stream. Figure 1 shows one embodiment of a cracking process that uses whole crude oil and/or condensate as the dominant {primary) furnace feed. Figure 1 is very diagrammatic for sake of simplicity and brevity since, as discussed above, actual furnaces are complex structures. Figure 1 shows a liquid cracking furnace 1 wherein a crude oil/condensate primary feed 2 is passed in to an upper feed preheat sub-zone 3 in the upper, cooler reaches of the convection section of furnace 1. Steam 6 is also superheated in an upper level of the convection section of the furnace. The pre-heated cracking feed stream is then passed by way of pipe (line) 10 to a vaporization unit 11 (see USP '961), which unit is separated into an upper vaporization zone 12 and a lower vaporization zone 13. This unit 11 achieves primarily (predominately) vaporization of at least a significant portion of the naphtha and gasoline boiling range and lighter materials that remain in the liquid state after the pre-heating step. Gaseous materials that are associated with the preheated feed as received by unit 11, and additional gaseous materials formed in zone 12, are removed from zone 12 by way of line 14. Thus, line 14 carries away essentially all the lighter hydrocarbon vapors, e.g., naphtha and gasoline boiling range and lighter, that are present in zone 12. Liquid distillate present in zone 12, with or without some liquid gasoline and/or naphtha, is removed there from via line 15 and passed into the upper interior of lower zone 13. Zones 12 and 13, in this embodiment, are separated from fluid communication with one another by an impermeable wall 16, which can be a solid tray. Line 15 represents external fluid down flow communication between zones 12 and 13. In lieu thereof, or in addition thereto, zones 12 and 13 can have internal fluid communication there between by modifying wall 16 to be at least in part liquid permeable by use of one or more trays designed to allow liquid to pass down into the interior of zone 13 and vapor up into the interior of zone 12. For example, instead of an impermeable wall 16, a chimney tray could be used in which case liquid within unit 11 would flow internally down into section 13 instead of externally of unit 11 via line 15. In this internal down flow case, distributor 18 becomes optional. By whatever way liquid is removed from zone 12 to zone 13, that liquid moves downwardly into zone 13, and thus can encounter at least one liquid distribution device 18. Device 18 evenly distributes liquid across the transverse cross section of unit 11 so that the liquid will flow uniformly across the width of the tower into contact with packing 19. Dilution steam 6 passes through superheat zone sub-20, and then, via line 21 in to a lower portion 22 of zone 13 below packing 19. In packing 19 liquid and steam from line 21 intimately mix with one another thus vaporizing some of liquid 15. This newly formed vapor, along with dilution steam 21, is removed from zone 13 via line 17 and added to the vapor in line 14 to form a combined hydrocarbon vapor product in line 25. Stream 25 can contain essentially hydrocarbon vapor from feed 2, e.g., gasoline and naphtha, and steam. Stream 17 thus represents a part of feed stream 2 plus dilution steam 21 less liquid distillate(s) and heavier from feed 2 that are present in bottoms stream 26. Stream 25 is passed through a header (not shown) whereby stream 25 is split into multiple sub-streams and passed through multiple conduits (not shown) into convection section pre-heat sub-zone 27 of furnace 1. Section 27 is in a lower, and therefore hotter, section of furnace 1. Section 27 is used for preheating stream 25 to a temperature, aforesaid, suitable for cracking in radiant zone 29. After substantial heating in section 27, stream 25 passes by way of line 28 into radiant section 29. Again, the multiple, individual streams that normally pass from sub-zone 27 to and through zone 29 are represented as a single flow stream 28 for sake of brevity. In radiant firebox 29 of furnace 1, feed from line 28, which contains numerous varying hydrocarbon components, is subjected to severe thermal cracking conditions as aforesaid. The cracked product leaves radiant firebox 29 by way of line 30 for further processing in the remainder of the olefin plant downstream of furnace 1 as described hereinabove and shown in USP '961. When using crude oil and/or condensate as the significant components; or feed 2, substantial amounts of distillates are ultimately passed into furnace 1 and cracked thereby converting such distillates into lighter components. Accordingly, these distillates are lost as a source of distillate supply for jet fuel, diesel fuels and home heating oils. Pursuant to this invention, feed 2 contains, as a significant component thereof, residuum obtained from the atmospheric thermal distillation of at least one crude oil and not the crude oil/condensate feed of the prior art. Although one or more atmospheric residua can be essentially the sole component of feed material 2, this invention is not so limited so long as atmospheric residuum is a significant constituent in feed 2 and line 10. Note that this invention does not apply to vacuum resid or catalytic cracking. For purposes of this invention, feed 2 can enter furnace 1 at a temperature of from about ambient up to about 300F at a pressure from slightly above atmospheric up to about 100 psig (hereafter "atmospheric to 100 psig"). Feed 2 can enter zone 12 via line 10 at a temperature of from about ambient to about 700F at a pressure of from atmospheric to 100 psig. Stream 14 can be essentially all hydrocarbon vapor formed from feed 2 and is at a temperature of from about ambient to about 700F at a pressure of from atmospheric to 100 psig. Stream 15 can be essentially all the remaining liquid from feed 2 less that which was vaporized in pre-heater 3 and is at a temperature of from about ambient to about 700F at a pressure of from slightly above atmospheric up to about 100 psig (hereafter "atmospheric to 100 psig"). The combination of streams 14 and 17, as represented by stream 25, can be at a temperature of from about 600 to about 800 F at a pressure of from atmospheric to 100 psig, and contain, for example, an overall steam/hydrocarbon ratio of from about 0.1 to about 2, preferably from about 0.1 to about 1, pounds of steam pa- pound of hydrocarbon. In zone 13, dilution ratios (hot gas/liquid droplets) will vary widely because the compositions of atmospheric resid and condensate vary widely. Generally, the hot gas, e.g., steam and hydrocarbon at the top of zone 13 can be present in a ratio of steam to hydrocarbon of from about 0.1/1 to about 5/1. Steam is an example of a suitable hot gas introduced by way of line 21. Other materials can be present in the steam employed. Stream 6 can be that type of steam normally used in a conventional cracking plant. Such gases are preferably at a temperature sufficient to volatilize a substantial fraction of the liquid hydrocarbon 15 that enters zone 13. Generally, the gas entering zone 13 from conduit 21 will be at least about 650F, preferably from about 900 to about 1,200F at from atmospheric to 100 psig. Such gases will, for sake of simplicity, hereafter be referred to in terms of steam alone. Stream 17 can be a mixture of steam and hydrocarbon vapor that has a boiling point lower than about 1,200F. Stream 17 can be at a temperature of from about 600 to about 800F at a pressure of from atmospheric to 100 psig. Steam from line 21 does not serve just as a diluent for partial pressure purposes as is the normal case in a cracking operation. Rather, steam from line 21 provides not only a diluting function, but also additional vaporizing and mild cracking energy for the hydrocarbons that remain in the liquid state. This is accomplished with just sufficient energy to achieve vaporization and/or mild cracking of heavier hydrocarbon components in the atmospheric resid and by controlling the energy input. For example, by using steam in line 21, substantial vaporization/mild cracking of feed 2 liquid is achieved. The very high steam dilution ratio and the highest temperature steam are thereby provided where they are needed most as liquid hydrocarbon droplets move progressively lower in zone 13. The atmospheric resid feed employed in this invention can be from a single or multiple sources, and, therefore, can be a single resid or a mixture of two or more residua. Atmospheric resid useful in this invention can have a wide boiling range, particularly when mixtures of residua are employed, but will generally be in a boiling range of from about 600F to the boiling end point where only non-boiling entities remain. Pursuant to this invention, light materials such as light gasoline, naphtha, and gas oils boiling lighter (lower) than about 1,000F, all as defined hereinabove, remaining in the atmospheric residuum feed will be vaporized in unit 11 and removed by way of either line 14 or 17 or both and fed to furnace 1 as described hereinabove. In addition, hydrocarbonaceous entities heavier than the lighter entities mentioned above in this paragraph can. at least in part, be mildly cracked or otherwise broken down in unit 11 to lighter hydrocarbonaceous entities such as those mentioned above, and those just formed lighter entities removed by way of line 17 as feed for furnace 1. The remainder of the residuum feed, if any, is removed by way of line 26 for disposition elsewhere. Atmospheric resid bottoms from an atmospheric thermal distillation tower (atmospheric tower) are primarily composed of a gas oil component boiling in the range of from about 600 to about 1,000F and a heavier fraction boiling in a temperature range of from about 1,000F up to its end boiling point where only non- boiling entities remain. A vacuum assisted thermal distillation tower (vacuum tower) typically separates this gas oil component from its associated heavier fraction aforesaid, thus freeing the gas oil fraction for separate recovery and beneficial use elsewhere. By the process of mis invention, the need for a vacuum tower to recover the gas oil component contained in atmospheric resid is eliminated, without eliminating the function thereof. This is accomplished in this invention by using atmospheric resid as a significant portion of the feed 2 (and 10) to stripper 11 of Figure 1. In section 13 of stripper 11 the counter current flow of downward moving hydrocarbon liquid and upward flowing steam 21 enables the heaviest (highest boiling point) liquids to be contacted at the highest steam to oil ratio and with the highest temperature steam at the same time. This creates an efficient operation for the vaporization and mild cracking of the atmospheric resid thereby forming additional lighter materials from that resid, and freeing the gas oil component of that resid, all for recovery by way of line 17 as additional cracking feed for furnace 1. It can be seen that this invention utilizes for breaking down atmospheric resid, energy in stripper 11 that is normally utilized in the operation of furnace 1, while eliminating the energy cost of operating a separate vacuum tower. Similarly the capital and other costs for a vacuum tower are eliminated without loss of the function of that vacuum tower in breaking down atmospheric resid and separating the useful gas oil component thereof. The amount of atmospheric resid employed in feed 10 pursuant to this invention can be a significant component of the overall feed 2. The atmospheric resid component can be at least about 20 wt.% of the total weight of the feed, but it is not necessarily strictly within this range. Depending on the specific physical and chemical characteristics of the atmospheric resid added to feed 2, other materials can be added to that feed. Such additional materials can include fight gasoline, naphtha, natural gasoline, and/or condensate. Naphtha can be employed in the form of full range naphtha, light naphtha, medium naphtha, heavy naphtha, or mixtures of two or more thereof. The light gasoline can have a boiling range of from that of pentane (C5) to about 158F. Full range naphtha, which includes light, medium, and heavy naphtha fractions, can have a boiling range of from about 158 to about 350F. The boiling ranges for the light, medium, and heavy naphtha fractions can be, respectively, from about 158 to about 212F, from about 212 to about 302F, and from about 302 to about 350F. If light materials, as aforesaid, are added to the atmospheric resid in feed 2, it can be preferable, again depending on the specific characteristics of this resid feed in line 2, that lighter fractions such as light gasoline and light naphtha be added to that resid feed, thereby leaving medium and/or heavy naphtha fractions for addition to the gasoline pool. The amount of light materiaS(s) thus deliberately added to the atmospheric resid in feed 2 can vary widely depending on the desires of the operator, but the resid in feed 2 will remain a significant component of the feed in line 10 to vaporization unit 11. The deliberate re-mixing of already separated light materials with atmospheric resid is counter intuitive and not done in the art. However, the addition of one or more of these light materials to the atmospheric resid is highly useful in this invention because they help lift the gas oil from the atmospheric resid in stripper 11. Depending on the characteristics of the resid in line 2, the amount of residua added to line 2, and present in line 10, after addition of one or more light materials thereto as aforesaid, can be less than 20 wt. % and still be within the spirit of this invention. It can be seen, that, with this invention, the distillates that are removed by the atmospheric tower are preserved for separate use such as for diesel fuel and kerosene, and a novel combination of atmospheric resid and lighter material in stripper 11 is used to form additional cracking feedstock from atmospheric resid that would otherwise be lost for this purpose. EXAMPLE An atmospheric residuum characterized as Skikda atmospheric resid from Algeria is mixed in equal parts by weight with natural gasoline, and fed directly into the preheat section 3 of the convection section of pyrolysis furnace 1. This feed is at 260F and 80 psig. In this convection section this residuum feed is preheated to about 690F at about 60 psig, and then passed into vaporization unit 11 wherein a mixture of gasoline, naphtha and gas oil gases at about 690F and 60 psig are separated in zone 12 of that unit. The separated gases are removed from zone 12 for transfer to the convection preheat sub-zone 27 of the same furnace. The preheated stream is then passed to radiant section 29. The hydrocarbon liquid remaining from residuum feed 2, after separation from accompanying hydrocarbon gases aforesaid, is transferred to lower section 13 and allowed to fall downwardly in that section toward the bottom thereof. Preheated steam 21 at about 1,050F is introduced near the bottom of zone 13 to give a steam to hydrocarbon ratio in section 13 of about 1. The falling liquid droplets are in counter current flow with the steam that is rising from the bottom of zone 13 toward the top thereof. With respect to the liquid falling downwardly in zone 13, the steam to liquid hydrocarbon ratio increases from the top to bottom of section 19. A mixture of steam and vapor 17 which contains the gas oil fraction at about 760F is withdrawn from near the top of zone 13 and mixed with the gases earlier removed from zone 12 via line 14 to form a composite steam/hydrocarbon vapor stream 25 containing about 0.4 pounds of steam per pound of hydrocarbon present. This composite stream is preheated in sub-zone 27 to about 1,000F at less than about 50 psig, and then passed into radiant firebox 29 for cracking at a temperature in the range of 1,400°F to 1,550°F. Bottoms product 26 of unit 11 is removed at a temperature of about 900 F, and pressure of about 60 psig, and passed to the downstream processing equipment to produce fuel oil therefrom. I claim: 1. A method comprising: (a) providing a feed comprising a significant amount of at least one atmospheric residuum formed from the atmospheric thermal distillation of a crude oil; (b) directing said feed to a first zone of a vaporization unit and separating a portion of said feed in said first zone into a first gaseous stream and a first liquid stream; (c) passing said first vapor stream to a cracking furnace (d) passing said first liquid stream to a second zone of said vaporization unit; (e) contacting said first liquid stream with counter-current steam in said second zone of said vaporization unit so that said first liquid stream intimately mixes with said steam to cause vaporization and mild cracking to produce a second vapor stream arid a second liquid stream; (f) passing said second vapor stream to a cracking furnace; and (g) recovering said second liquid stream from said second zone of said vaporization unit and disposing of said, second liquid stream other than in a cracking furnace. 2. The method of claim 1 wherein said first gaseous stream and the second gaseous stream are passed to the same cracking furnace. 3. The method of claim 1 wherein said feed is composed of a mixture of at least two differing residua. 4. The method of claim 1 wherein said feed has a boiling range of from 600F to its boiling end point. 5. The method of claim 1 wherein there is added to said feed to said vaporization unit at least one of light gasoline, at least one naphtha fraction, natural gasoline, and condensate. 6. The method of claim 5 wherein said light gasoline boils in the range of from the boiling point of pentane to 158F, said naphtha fraction boils in the range of from 158 to 350F, and said condensate boils in a range of from 100 to 650F. 7. The method of claim 6 wherein said naphtha fraction comprises at least one of light naphtha, medium naphtha, and heavy naphtha. 8. The method of claim 7 wherein said light naphtha boils in the range of from 158 to 212F, said medium naphtha boils in the range of from 212 to 302F, and said heavy naphtha boils in the range of from 302 to 350F. 9. The method of claim 1 wherein said feed comprises at least 20 wt.% atmospheric residuum based on the total weight of said feed. A method for thermally cracking a hydrocarbonaceous feed wherein the feed is first gasified in a vaporization unit. A significant component of the feed is residua from the atmospheric thermal distillation of crude oil.

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HYDROCARBON THERMAL CRACKING USING ATMOSPHERIC RESIDUUM
BACKGROUND OF INVENTION
FIELD OF INVENTION
This invention relates to the thermal cracking of hydrocarbons using a
vaporization unit in combination with a pyrolysis furnace wherein at least a
preponderance of the liquid hydrocarbonaceous feed to be cracked in the furnace is
first vaporized in the vaporization unit. More particularly, this invention relates to the
use of atmospheric residuum as a significant liquid hydrocarbonaceous feed
component for the vaporization unit and furnace.
DESCRIPTION OF THE PRIOR ART
Thermal (pyrolysis) cracking of hydrocarbons is a non-catalytic petrochemical
process that is widely used to produce olefins such as ethylene, propylene, butenes,
butadiene, and aromatics such as benzene, toluene, and xylenes.
Basically, a hydrocarbon containing feedstock is mixed with steam which
serves as a diluent to keep the hydrocarbon molecules separated. The
steam/hydrocarbon mixture is preheated in the convection zone of the furnace to
from about 900 to about 1,000 degrees Fahrenheit (°F or F), and then enters the
reaction (radiant) zone where it is very quickly heated to a severe hydrocarbon
thermal cracking temperature in the range of from about 1,400 to about 1,550F.
Thermal cracking is accomplished without the aid of any catalyst.
This process is carried out in a pyrolysis furnace (steam cracker) at pressures
in the reaction zone ranging from about 10 to about 30 psig. Pyrolysis furnaces have
internally thereof a convection section (zone) and a separate radiant section (zone).
Preheating functions are primarily accomplished in the convection section, while
severe cracking mostly occurs in the radiant section.
After thermal cracking, depending on the nature of the primary feed to the
pyrolysis furnace, the effluent from that furnace can contain gaseous hydrocarbons
of great variety, e.g., from one to thirty-five carbon atoms per molecule. These
gaseous hydrocarbons can be saturated, monounsaturated, and polyunsaturated,
and can be aliphatic, alicydics, and/or aromatic. The cracked gas can also contain
significant amounts of molecular hydrogen (hydrogen).
The cracked product is then further processed in the olefin production plant to
produce, as products of the plant, various separate individual streams of high purity
such as hydrogen, ethylene, propylene, mixed hydrocarbons having four carbon
atoms per molecule, fuel oil, and pyrolysis gasoline. Each separate individual
stream aforesaid is a valuable commercial product in its own right. Thus, an olefin
production plant currently takes a part (fraction) of a whole crude stream or
condensate, and generates therefrom a plurality of separate, valuable products.
Thermal cracking first came into use In 1913 and was first applied to gaseous
ethane as the primary feed to the cracking furnace for the purpose of making
ethylene. Since that time, the industry has evolved to using heavier and more
complex hydrocarbonaceous gaseous and/or liquid feeds as the primary feed for the
cracking furnace. Such feeds can now employ a fraction of whole crude or
condensate which is essentially totally vaporized while thermally cracking same.
The cracked product can contain, for example, about 1 weight percent (wt.%)
hydrogen, about 10 wt.% methane, about 25 wt.% ethylene, and about 17 wt.%
propylene, all wt.% being based on the total weight of that product, with the
remainder consisting mostly of other hydrocarbon molecules having from 4 to 35
carbon atoms per molecule.
Natural gas and whole crude oil(s) were formed naturally in a number of
subterranean geologic formations (formations) of widely varying porosities. Many of
these formations were capped by impervious layers of rock. Natural gas and whole
crude oil (crude oil) also accumulated in various stratigraphic traps below the earth's
surface. Vast amounts of both natural gas and/or crude oil were thus collected to
form hydrocarbon bearing formations at varying depths below the earth's surface.
Much of this natural gas was in close physical contact with crude oil, and, therefore,
absorbed a number of lighter molecules from the crude oil.
When a well bore is drilled into the earth and pierces one or more of such
hydrocarbon bearing formations, natural gas and/or crude oil can be recovered
through that well bore to the earth's surface.
The terms "whole crude oil" and "crude oil" as used herein means liquid (at
normally prevailing conditions of temperature and pressure at the earth's surface)
crude oil as it issues from a wellhead separate from any natural gas that may be
present, and excepting any treatment such crude oil may receive to render it
acceptable for transport to a crude oil refinery and/or conventional distillation in such
a refinery. This treatment would include such steps as desalting. Thus, it is crude oil
that is suitable for distillation or other fractionation in a refinery, but which has not
undergone any such distillation or fractionation. It could include, but does not
necessarily always include, non-boiling entities such as asphaltenes or tar. As such,
it is difficult if not impossible to provide a boiling range for whole crude oil.
Accordingly, whole crude oil could be one or more crude oils straight from an oil field
pipeline and/or conventional crude oil storage facility, as availability dictates, without
any prior fractionation thereof.
Natural gas, like crude oil, can vary widely in its composition as produced to
the earth's surface, but generally contains a significant amount, most often a major
amount, i.e., greater than about 50 weight percent (wt. %), methane. Natural gas
often also carries minor amounts (less than about 50 wt. %), often less than about 20
wt. %, of one or more of ethane, propane, butane, nitrogen, carbon dioxide,
hydrogen sulfide, and the like. Many, but not all, natural gas streams as produced
from the earth can contain minor amounts (less than about 50 wt. %), often less than
about 20 wt. %, of hydrocarbons having from 5 to 12, inclusive, carbon atoms per
molecule (C5 to C12) that are not normally gaseous at generally prevailing ambient
atmospheric conditions of temperature and pressure at the earth's surface, and that
can condense out of the natural gas once it is produced to the earth's surface. Ail
wt.% are based on the total weight of the natural gas stream in question.
When various natural gas streams are produced to the earth's surface, a
hydrocarbon composition often naturally condenses out of the thus produced natural
gas stream under the then prevailing conditions of temperature and pressure at the
earth's surface where that stream is collected. There is thus produced a normally
liquid hydrocarbonaceous condensate separate from the normally gaseous natural
gas under the same prevailing conditions. The normally gaseous natural gas can
contain methane, ethane, propane, and butane. The normally liquid hydrocarbon
fraction that condenses from the produced natural gas stream is generally referred to
as "condensate," and generally contains molecules heavier than butane (C5 to about
C20 or slightly higher). After separation from the produced natural gas, this liquid
condensate fraction is processed separately from the remaining gaseous fraction
that is normally referred to as natural gas.
Thus, condensate recovered from a natural gas stream as first produced to
the earth's surface is not the exact same material, composition wise, as natural gas
(primarily methane). Neither is it the same material, composition wise, as crude oil.
Condensate occupies a niche between normally gaseous natural gas and normally
liquid whole crude oil. Condensate contains hydrocarbons heavier than normally
gaseous natural gas, and a range of hydrocarbons that are at the lightest end of
whole crude oil.
Condensate, unlike crude oil, can be characterized by way of its boiling point
range. Condensates normally boil in the range of from about 100 to about 650F.
With this boiling range, condensates contain a wide variety of hydrocarbonaceous
materials. These materials can include compounds that make up fractions that are
commonly referred to as naphtha, kerosene, diesel fuel(s), and gas oil (fuel oil,
furnace oil, heating oil, and the like).
Naphtha and associated lighter boiling materials (naphtha) are in the C5 to
C10, inclusive, range, and are the lightest boiling range fractions in condensate,
boiling in the range of from about 100 to about 400F.
Petroleum middle distillates (kerosene, diesel, atmospheric gas oil) are
generally in the C10 to about C20 or slightly higher range, and generally boil, in their
majority, in the range of from about 350 to about 650F. They are, individually and
collectively, referred to herein as "distillate," "distillates," or "middle distillates."
Distillate compositions can have a boiling point lower than 350F and/or higher than
650F, and such distillates are included in the 350-650F range aforesaid, and in this
invention. Atmospheric residuum (resid or residua) typically boils at a temperature
of from about 650F up to its end boiling point where only non-boiling entities such as
asphaltenes and tar are left. Atmospheric resid is formed by processing crude
oil/condensate in an atmospheric thermal distillation tower. Atmospheric resid is not
the same as vacuum residuum which is formed in a vacuum assisted thermal
distillation tower, and has a boiling range of from about 1,000F up to its end boiling
point where only non-boiling entities remain.
The olefin production industry is now progressing beyond the use of fractions
of crude oil or condensate (gaseous and/or liquid) as the primary feed for a cracking
furnace to the use of whole crude oil and/or condensate itself.
Recently, U.S. Patent Number 6,743,961 (hereafter "USP '961") issued to
Donald H. Powers. This patent relates to cracking whole crude oil by employing a
vaporization/mild cracking zone that contains packing. This zone is operated in a
manner such that the liquid phase of the whole crude that has not already been
vaporized is held in that zone until cracking/vaporization of the more tenacious
hydrocarbon liquid components is maximized. This allows only a minimum of solid
residue formation which residue remains behind as a deposit on the packing. This
residue is later burned off the packing by conventional steam air decoking, ideally
during the normal furnace decoking cycle, see column 7, lines 50-58 of that patent.
Thus, the second zone 9 of that patent serves as a trap for components, including
hydrocarbonaceous materials, of the crude oil feed that cannot be cracked or
vaporized under the conditions employed in the process, see column 8, lines 60-64
of that patent.
Still more recently, U.S. Patent 7,019,187 issued to Donald H. Powers. This
patent is directed to the process disclosed in USP '961, but employs a mildly acidic
cracking catalyst to drive the overall function of the vaporization/mild cracking unit
more toward the mild cracking end of the vaporization (without prior mild cracking) -
mild cracking (followed by vaporization) spectrum.
U.S. Patent Number 6,979,757 to Donald H. Powers is directed to the process
disclosed in USP '961, but that invention removes at least part of the liquid
hydrocarbons remaining in the vaporization/mild cracking unit that are not yet
vaporized or mildly cracked. These liquid hydrocarbon components of the crude oil
feed are drawn from near the bottom of that unit and passed to a separate controlled
cavitation device to provide additional cracking energy for those tenacious
hydrocarbon components that have previously resisted vaporization and mild
cracking. Thus, that invention also seeks to drive the overall process in the
vaporization/mild cracking unit more toward the mild cracking end of the
vaporization-mild cracking spectrum aforesaid.
The disclosures of the foregoing patents, in their entirety, are incorporated
herein by reference.
U.S. Patent Application Serial Number 11/219,166, filed September 2, 2005,
having common inventorship and assignee with USP '961, is directed to the process
of using whole crude oil as the feedstock for an olefin plant to produce a mixture of
hydrocarbon vapor and liquid. The vaporous hydrocarbon is separated from the
remaining liquid and the vapor passed to a severe cracking operation. The
remaining liquid is vaporized using a quench oil to minimize coke forming reactions.
U.S. Patent Application Serial Number 11/365.212, filed March 1, 2006,
having common inventorship and assignee with USP '961, is directed to the use of
condensate as the dominant liquid hydrocarbonaceous feed for the vaporization unit
and furnace.
U.S. Patent Application Serial Number 11/584,722, filed October 20, 2006,
having common inventorship and assignee with USP '961, is directed to the
integration of the vaporization unit/furnace combination with a crude oil refinery.
During periods of increased gasoline demand the gasoline supply (pool) can
be increased by subjecting various crude oil fractions, including distillates, to various
refinery catalytic cracking processes such as fluid catalytic cracking. Thus, the
quantity of gasoline/naptha produced from a barrel of crude oil can be increased if
desired. This is not so with distillates as defined above. The amount of distillate
recovered from a barrel of crude oil is fixed and cannot be increased as it can with
gasoline. The only way to increase distillate production to increase the distillate
supply for the distillate pool is by refining additional barrels of crude oil
By this invention valuable distillates that are in short supply are saved for the
distillate pool, and not consumed in the cracking process.
SUMMARY OF THE INVENTION
In accordance with this invention, the aforesaid combination of a vaporization unit/cracking furnace is operated with its feed containing a significant amount of
residuum from at least one atmospheric thermal distillation column, i.e., atmospheric
resid.
DESCRIPTION OF THE DRAWING
Figure 1 shows a simplified flow sheet for the whole crude oil/condensate
cracking process described hereinabove.
DETAILED DESCRIPTION OF THE INVENTION
The terms "hydrocarbon," "hydrocarbons," and "hydrocarbonaceous" as used
herein do not mean materials strictly or only containing hydrogen atoms and carbon
atoms. Such terms include materials that are hydrocarbonaceous in nature in that
they primarily or essentially are composed of hydrogen and carbon atoms, but can
contain other elements such as oxygen, sulfur, nitrogen, metals, inorganic salts, and
the like, even in significant amounts.
The term "gaseous" as used in this invention means one or more gases in an
essentially vaporous state, for example, steam alone, a mixture of steam and
hydrocarbon vapor, and the like.
Coke, as used herein, means a high molecular weight carbonaceous solid,
and includes compounds formed from the condensation of polynuclear aromatics.
An olefin producing plant useful with this invention would include a pyrolysis
(thermal cracking) furnace for initially receiving and thermally cracking the feed.
Pyrolysis furnaces for steam cracking of hydrocarbons heat by means of convection
and radiation, and comprise a series of preheating, circulation, and cracking tubes,
usually bundles of such tubes, for preheating, transporting, and cracking the
hydrocarbon feed. The high cracking heat is supplied by burners disposed in the
radiant section (sometimes called "radiation section") of the furnace. The waste gas
from these burners is circulated through the convection section of the furnace to
provide the heat necessary for preheating the incoming hydrocarbon feed. The
convection and radiant sections of the furnace are joined at the "cross-over," and the
tubes referred to hereinabove carry the hydrocarbon feed from the interior of one
section to the interior of the next.
In a typical furnace, the convection section can contain multiple sub-zones.
For example, the feed can be initially preheated in a first upper sub-zone, boiler feed
water heated in a second sub-zone, mixed feed and steam heated in a third sub-
zone, steam superheated in a fourth sub-zone, and the final feed/steam mixture split
into multiple sub-streams and preheated in a lower (bottom) or fifth sub-zone. The
number of sub-zones and their functions can vary considerably. Each sub-zone can
carry a plurality of conduits carrying furnace feed there through, many of which are
sinusoidal in configuration. The convection section operates at much less severe
operating conditions than the radiant section.
Cracking furnaces are designed for rapid heating in the radiant section
starting at the radiant tube (coil) inlet where reaction velocity constants are low
because of low temperature. Most of the heat transferred simply raises the
hydrocarbons from the inlet temperature to the reaction temperature. In the middle of
the coil, the rate of temperature rise is lower but the cracking rates are appreciable.
At the coil outlet, the rate of temperature rise increases somewhat but not as rapidly
as at the inlet. The rate of disappearance of the reactant is the product of its
reaction velocity constant times its localized concentration. At the end of the coil,
reactant concentration is low and additional cracking can be obtained by increasing
the process gas temperature.
Steam dilution of the feed hydrocarbon lowers the hydrocarbon partial
pressure, enhances olefin formation, and reduces any tendency toward coke
formation in the radiant tubes.
Cracking furnaces typically have rectangular fireboxes with upright tubes
centrally located between radiant refractory walls. The tubes are supported from
their top.
Firing of the radiant section is accomplished with wall or floor mounted
burners or a combination of both using gaseous or combined gaseous/liquid fuels.
Fireboxes are typically under slight negative pressure, most often with upward flow
of ffue gas. Flue gas flow into the convection section is established by at least one
of natural draft or induced draft fans.
Radiant coils are usually hung in a single plane down the center of the fire box.
They can be nested in a single plane or placed parallel in a staggered, double-row
tube arrangement. Heat transfer from the burners to the radiant tubes occurs largely
by radiation, hence the thermo "radiant section," where the hydrocarbons are heated
to from about 1,400°F to about 1,550°F and thereby subjected to severe cracking,
and coke formation.
The initially empty radiant coil is, therefore, a fired tubular chemical reactor.
Hydrocarbon feed to the furnace is preheated to from about 900°F to about 1,000°F
in the convection section by convectional heating from the flue gas from the radiant
section, steam dilution of the feed in the convection section, or the like. After
preheating, in a conventional commercial furnace, the feed is ready for entry into the
radiant section.
The cracked gaseous hydrocarbons leaving the radiant section are rapidly
reduced in temperature to prevent destruction of the cracking pattern. Cooling of the
cracked gases before further processing of same downstream in the olefin
production plant recovers a large amount of energy as high pressure steam for re-
use in the furnace and/or olefin plant. This is often accomplished with the use of
transfer-line exchangers that are well known in the art.
With a liquid hydrocarbon feedstock downstream processing, although it can
vary from plant to plant, typically employs an oil quench of the furnace effluent after
heat exchange of same in, for example, the transfer-line exchanger aforesaid.
Thereafter, the cracked hydrocarbon stream is subjected to primary fractionation to
remove heavy liquids, followed by compression of uncondensed hydrocarbons, and
acid gas and water removal therefrom. Various desired products are then
individually separated, e.g., ethylene, propylene, a mixture of hydrocarbons having
four carbon atoms per molecule, fuel oil, pyrolysis gasoline, and a high purity
hydrogen stream.
Figure 1 shows one embodiment of a cracking process that uses whole crude
oil and/or condensate as the dominant {primary) furnace feed. Figure 1 is very
diagrammatic for sake of simplicity and brevity since, as discussed above, actual
furnaces are complex structures.
Figure 1 shows a liquid cracking furnace 1 wherein a crude oil/condensate
primary feed 2 is passed in to an upper feed preheat sub-zone 3 in the upper, cooler
reaches of the convection section of furnace 1. Steam 6 is also superheated in an
upper level of the convection section of the furnace.
The pre-heated cracking feed stream is then passed by way of pipe (line) 10
to a vaporization unit 11 (see USP '961), which unit is separated into an upper
vaporization zone 12 and a lower vaporization zone 13. This unit 11 achieves
primarily (predominately) vaporization of at least a significant portion of the naphtha
and gasoline boiling range and lighter materials that remain in the liquid state after
the pre-heating step. Gaseous materials that are associated with the preheated feed
as received by unit 11, and additional gaseous materials formed in zone 12, are
removed from zone 12 by way of line 14. Thus, line 14 carries away essentially all
the lighter hydrocarbon vapors, e.g., naphtha and gasoline boiling range and lighter,
that are present in zone 12. Liquid distillate present in zone 12, with or without some
liquid gasoline and/or naphtha, is removed there from via line 15 and passed into the
upper interior of lower zone 13. Zones 12 and 13, in this embodiment, are separated
from fluid communication with one another by an impermeable wall 16, which can be
a solid tray. Line 15 represents external fluid down flow communication between
zones 12 and 13. In lieu thereof, or in addition thereto, zones 12 and 13 can have
internal fluid communication there between by modifying wall 16 to be at least in part
liquid permeable by use of one or more trays designed to allow liquid to pass down
into the interior of zone 13 and vapor up into the interior of zone 12. For example,
instead of an impermeable wall 16, a chimney tray could be used in which case
liquid within unit 11 would flow internally down into section 13 instead of externally of
unit 11 via line 15. In this internal down flow case, distributor 18 becomes optional.
By whatever way liquid is removed from zone 12 to zone 13, that liquid moves
downwardly into zone 13, and thus can encounter at least one liquid distribution
device 18. Device 18 evenly distributes liquid across the transverse cross section of
unit 11 so that the liquid will flow uniformly across the width of the tower into contact
with packing 19.
Dilution steam 6 passes through superheat zone sub-20, and then, via line 21
in to a lower portion 22 of zone 13 below packing 19. In packing 19 liquid and steam
from line 21 intimately mix with one another thus vaporizing some of liquid 15. This
newly formed vapor, along with dilution steam 21, is removed from zone 13 via line
17 and added to the vapor in line 14 to form a combined hydrocarbon vapor product
in line 25. Stream 25 can contain essentially hydrocarbon vapor from feed 2, e.g.,
gasoline and naphtha, and steam.
Stream 17 thus represents a part of feed stream 2 plus dilution steam 21 less
liquid distillate(s) and heavier from feed 2 that are present in bottoms stream 26.
Stream 25 is passed through a header (not shown) whereby stream 25 is split into
multiple sub-streams and passed through multiple conduits (not shown) into
convection section pre-heat sub-zone 27 of furnace 1. Section 27 is in a lower, and
therefore hotter, section of furnace 1. Section 27 is used for preheating stream 25 to
a temperature, aforesaid, suitable for cracking in radiant zone 29.
After substantial heating in section 27, stream 25 passes by way of line 28
into radiant section 29. Again, the multiple, individual streams that normally pass
from sub-zone 27 to and through zone 29 are represented as a single flow stream 28
for sake of brevity.
In radiant firebox 29 of furnace 1, feed from line 28, which contains numerous
varying hydrocarbon components, is subjected to severe thermal cracking conditions
as aforesaid.
The cracked product leaves radiant firebox 29 by way of line 30 for further
processing in the remainder of the olefin plant downstream of furnace 1 as described
hereinabove and shown in USP '961.
When using crude oil and/or condensate as the significant components; or
feed 2, substantial amounts of distillates are ultimately passed into furnace 1 and
cracked thereby converting such distillates into lighter components. Accordingly,
these distillates are lost as a source of distillate supply for jet fuel, diesel fuels and
home heating oils.
Pursuant to this invention, feed 2 contains, as a significant component thereof,
residuum obtained from the atmospheric thermal distillation of at least one crude oil
and not the crude oil/condensate feed of the prior art. Although one or more
atmospheric residua can be essentially the sole component of feed material 2, this
invention is not so limited so long as atmospheric residuum is a significant
constituent in feed 2 and line 10.
Note that this invention does not apply to vacuum resid or catalytic cracking.
For purposes of this invention, feed 2 can enter furnace 1 at a temperature of
from about ambient up to about 300F at a pressure from slightly above atmospheric
up to about 100 psig (hereafter "atmospheric to 100 psig"). Feed 2 can enter zone
12 via line 10 at a temperature of from about ambient to about 700F at a pressure of
from atmospheric to 100 psig.
Stream 14 can be essentially all hydrocarbon vapor formed from feed 2 and is
at a temperature of from about ambient to about 700F at a pressure of from
atmospheric to 100 psig.
Stream 15 can be essentially all the remaining liquid from feed 2 less that
which was vaporized in pre-heater 3 and is at a temperature of from about ambient
to about 700F at a pressure of from slightly above atmospheric up to about 100 psig
(hereafter "atmospheric to 100 psig").
The combination of streams 14 and 17, as represented by stream 25, can be
at a temperature of from about 600 to about 800 F at a pressure of from atmospheric
to 100 psig, and contain, for example, an overall steam/hydrocarbon ratio of from
about 0.1 to about 2, preferably from about 0.1 to about 1, pounds of steam pa-
pound of hydrocarbon.
In zone 13, dilution ratios (hot gas/liquid droplets) will vary widely because the
compositions of atmospheric resid and condensate vary widely. Generally, the hot
gas, e.g., steam and hydrocarbon at the top of zone 13 can be present in a ratio of
steam to hydrocarbon of from about 0.1/1 to about 5/1.
Steam is an example of a suitable hot gas introduced by way of line 21. Other
materials can be present in the steam employed. Stream 6 can be that type of
steam normally used in a conventional cracking plant. Such gases are preferably at
a temperature sufficient to volatilize a substantial fraction of the liquid hydrocarbon
15 that enters zone 13. Generally, the gas entering zone 13 from conduit 21 will be
at least about 650F, preferably from about 900 to about 1,200F at from atmospheric
to 100 psig. Such gases will, for sake of simplicity, hereafter be referred to in terms
of steam alone.
Stream 17 can be a mixture of steam and hydrocarbon vapor that has a
boiling point lower than about 1,200F. Stream 17 can be at a temperature of from
about 600 to about 800F at a pressure of from atmospheric to 100 psig.
Steam from line 21 does not serve just as a diluent for partial pressure
purposes as is the normal case in a cracking operation. Rather, steam from line 21
provides not only a diluting function, but also additional vaporizing and mild cracking
energy for the hydrocarbons that remain in the liquid state. This is accomplished
with just sufficient energy to achieve vaporization and/or mild cracking of heavier
hydrocarbon components in the atmospheric resid and by controlling the energy
input. For example, by using steam in line 21, substantial vaporization/mild cracking
of feed 2 liquid is achieved. The very high steam dilution ratio and the highest
temperature steam are thereby provided where they are needed most as liquid
hydrocarbon droplets move progressively lower in zone 13.
The atmospheric resid feed employed in this invention can be from a single
or multiple sources, and, therefore, can be a single resid or a mixture of two or more
residua. Atmospheric resid useful in this invention can have a wide boiling range,
particularly when mixtures of residua are employed, but will generally be in a boiling
range of from about 600F to the boiling end point where only non-boiling entities
remain.
Pursuant to this invention, light materials such as light gasoline, naphtha, and
gas oils boiling lighter (lower) than about 1,000F, all as defined hereinabove,
remaining in the atmospheric residuum feed will be vaporized in unit 11 and removed
by way of either line 14 or 17 or both and fed to furnace 1 as described hereinabove.
In addition, hydrocarbonaceous entities heavier than the lighter entities mentioned
above in this paragraph can. at least in part, be mildly cracked or otherwise broken
down in unit 11 to lighter hydrocarbonaceous entities such as those mentioned
above, and those just formed lighter entities removed by way of line 17 as feed for
furnace 1. The remainder of the residuum feed, if any, is removed by way of line 26
for disposition elsewhere.
Atmospheric resid bottoms from an atmospheric thermal distillation tower
(atmospheric tower) are primarily composed of a gas oil component boiling in the
range of from about 600 to about 1,000F and a heavier fraction boiling in a
temperature range of from about 1,000F up to its end boiling point where only non-
boiling entities remain. A vacuum assisted thermal distillation tower (vacuum tower)
typically separates this gas oil component from its associated heavier fraction
aforesaid, thus freeing the gas oil fraction for separate recovery and beneficial use
elsewhere.
By the process of mis invention, the need for a vacuum tower to recover the
gas oil component contained in atmospheric resid is eliminated, without eliminating
the function thereof. This is accomplished in this invention by using atmospheric
resid as a significant portion of the feed 2 (and 10) to stripper 11 of Figure 1. In
section 13 of stripper 11 the counter current flow of downward moving hydrocarbon
liquid and upward flowing steam 21 enables the heaviest (highest boiling point)
liquids to be contacted at the highest steam to oil ratio and with the highest
temperature steam at the same time. This creates an efficient operation for the
vaporization and mild cracking of the atmospheric resid thereby forming additional
lighter materials from that resid, and freeing the gas oil component of that resid, all
for recovery by way of line 17 as additional cracking feed for furnace 1. It can be
seen that this invention utilizes for breaking down atmospheric resid, energy in
stripper 11 that is normally utilized in the operation of furnace 1, while eliminating the
energy cost of operating a separate vacuum tower. Similarly the capital and other
costs for a vacuum tower are eliminated without loss of the function of that vacuum
tower in breaking down atmospheric resid and separating the useful gas oil
component thereof.
The amount of atmospheric resid employed in feed 10 pursuant to this
invention can be a significant component of the overall feed 2. The atmospheric
resid component can be at least about 20 wt.% of the total weight of the feed, but it
is not necessarily strictly within this range.
Depending on the specific physical and chemical characteristics of the
atmospheric resid added to feed 2, other materials can be added to that feed. Such
additional materials can include fight gasoline, naphtha, natural gasoline, and/or
condensate. Naphtha can be employed in the form of full range naphtha, light
naphtha, medium naphtha, heavy naphtha, or mixtures of two or more thereof. The
light gasoline can have a boiling range of from that of pentane (C5) to about 158F.
Full range naphtha, which includes light, medium, and heavy naphtha fractions, can
have a boiling range of from about 158 to about 350F. The boiling ranges for the
light, medium, and heavy naphtha fractions can be, respectively, from about 158 to
about 212F, from about 212 to about 302F, and from about 302 to about 350F.
If light materials, as aforesaid, are added to the atmospheric resid in feed 2, it
can be preferable, again depending on the specific characteristics of this resid feed
in line 2, that lighter fractions such as light gasoline and light naphtha be added to
that resid feed, thereby leaving medium and/or heavy naphtha fractions for addition
to the gasoline pool.
The amount of light materiaS(s) thus deliberately added to the atmospheric
resid in feed 2 can vary widely depending on the desires of the operator, but the
resid in feed 2 will remain a significant component of the feed in line 10 to
vaporization unit 11.
The deliberate re-mixing of already separated light materials with atmospheric
resid is counter intuitive and not done in the art. However, the addition of one or
more of these light materials to the atmospheric resid is highly useful in this invention
because they help lift the gas oil from the atmospheric resid in stripper 11.
Depending on the characteristics of the resid in line 2, the amount of residua
added to line 2, and present in line 10, after addition of one or more light materials
thereto as aforesaid, can be less than 20 wt. % and still be within the spirit of this
invention.
It can be seen, that, with this invention, the distillates that are removed by the
atmospheric tower are preserved for separate use such as for diesel fuel and
kerosene, and a novel combination of atmospheric resid and lighter material in
stripper 11 is used to form additional cracking feedstock from atmospheric resid that
would otherwise be lost for this purpose.
EXAMPLE
An atmospheric residuum characterized as Skikda atmospheric resid from
Algeria is mixed in equal parts by weight with natural gasoline, and fed directly into
the preheat section 3 of the convection section of pyrolysis furnace 1. This feed is at
260F and 80 psig. In this convection section this residuum feed is preheated to
about 690F at about 60 psig, and then passed into vaporization unit 11 wherein a
mixture of gasoline, naphtha and gas oil gases at about 690F and 60 psig are
separated in zone 12 of that unit.
The separated gases are removed from zone 12 for transfer to the convection
preheat sub-zone 27 of the same furnace. The preheated stream is then passed to
radiant section 29.
The hydrocarbon liquid remaining from residuum feed 2, after separation from
accompanying hydrocarbon gases aforesaid, is transferred to lower section 13 and
allowed to fall downwardly in that section toward the bottom thereof. Preheated
steam 21 at about 1,050F is introduced near the bottom of zone 13 to give a steam
to hydrocarbon ratio in section 13 of about 1. The falling liquid droplets are in
counter current flow with the steam that is rising from the bottom of zone 13 toward
the top thereof. With respect to the liquid falling downwardly in zone 13, the steam
to liquid hydrocarbon ratio increases from the top to bottom of section 19.
A mixture of steam and vapor 17 which contains the gas oil fraction at about
760F is withdrawn from near the top of zone 13 and mixed with the gases earlier
removed from zone 12 via line 14 to form a composite steam/hydrocarbon vapor
stream 25 containing about 0.4 pounds of steam per pound of hydrocarbon present.
This composite stream is preheated in sub-zone 27 to about 1,000F at less than
about 50 psig, and then passed into radiant firebox 29 for cracking at a temperature
in the range of 1,400°F to 1,550°F.
Bottoms product 26 of unit 11 is removed at a temperature of about 900 F,
and pressure of about 60 psig, and passed to the downstream processing equipment
to produce fuel oil therefrom.
I claim:
1. A method comprising:
(a) providing a feed comprising a significant amount of at least one
atmospheric residuum formed from the atmospheric thermal distillation of
a crude oil;
(b) directing said feed to a first zone of a vaporization unit and separating a
portion of said feed in said first zone into a first gaseous stream and a
first liquid stream;
(c) passing said first vapor stream to a cracking furnace
(d) passing said first liquid stream to a second zone of said vaporization unit;
(e) contacting said first liquid stream with counter-current steam in said
second zone of said vaporization unit so that said first liquid stream
intimately mixes with said steam to cause vaporization and mild cracking
to produce a second vapor stream arid a second liquid stream;
(f) passing said second vapor stream to a cracking furnace; and
(g) recovering said second liquid stream from said second zone of said
vaporization unit and disposing of said, second liquid stream other than in
a cracking furnace.
2. The method of claim 1 wherein said first gaseous stream and the second
gaseous stream are passed to the same cracking furnace.
3. The method of claim 1 wherein said feed is composed of a mixture of at least
two differing residua.
4. The method of claim 1 wherein said feed has a boiling range of from 600F to
its boiling end point.
5. The method of claim 1 wherein there is added to said feed to said
vaporization unit at least one of light gasoline, at least one naphtha fraction, natural
gasoline, and condensate.
6. The method of claim 5 wherein said light gasoline boils in the range of from
the boiling point of pentane to 158F, said naphtha fraction boils in the range of from
158 to 350F, and said condensate boils in a range of from 100 to 650F.
7. The method of claim 6 wherein said naphtha fraction comprises at least one
of light naphtha, medium naphtha, and heavy naphtha.
8. The method of claim 7 wherein said light naphtha boils in the range of from
158 to 212F, said medium naphtha boils in the range of from 212 to 302F, and said
heavy naphtha boils in the range of from 302 to 350F.
9. The method of claim 1 wherein said feed comprises at least 20 wt.%
atmospheric residuum based on the total weight of said feed.

A method for thermally cracking a hydrocarbonaceous feed wherein the feed is first gasified in a vaporization unit.
A significant component of the feed is residua from the atmospheric thermal distillation of crude oil.

Documents:

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Patent Number

279409

Indian Patent Application Number

3650/KOLNP/2009

PG Journal Number

04/2017

Publication Date

27-Jan-2017

Grant Date

20-Jan-2017

Date of Filing

20-Oct-2009

Name of Patentee

EQUISTAR CHEMICALS, LP

Applicant Address

ONE HOUSTON CENTER, 1221 MCKINNEY STREET, HOUSTON, TEXAS 77010 UNITED STATES OF AMERICA

Inventors:

#	Inventor's Name	Inventor's Address
1	POWERS, DONALD, H.	14502 SOUTHERN MAGNOLIA CIRCLE, HOUSTON, TEXAS 77044 UNITED STATES OF AMERICA

PCT International Classification Number

C10G9/00; C10G7/00; C10G9/00

PCT International Application Number

PCT/US2008/004875

PCT International Filing date

2008-04-14

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	11/803,905	2007-05-16	U.S.A.