The invention is directed to a method for cracking heavy oil. More particularly, the invention is directed to a method for cracking heavy oil using staging to convert the heavy oil feed to a cracked pitch product.
A recent review article [Hulet (2005)] examined the key features and configurations of short residence time cracking processes developed over the past 25 years. This work succinctly summarized the promise, key features, and challenges of short residence time processes:
“There is a strong economic incentive for considering short residence time cracking processes. Not only do such processes increase the yields of the more valuable liquid and gaseous products, but more compact designs would also decrease capital costs. Careful control of the vapor residence times appears to be crucial in order to prevent secondary cracking and yet allow for maximum cracking of the feedstock. Rapid and thorough mixing of the feedstock with the heat source, not just creating a uniform dispersion, is also a key design aspect to consider. Finally, rapid and complete separation must also be carefully considered; again, to help control product residence time and avoid secondary cracking but also from a heat balance point of view.”
These insights suggest short residence time cracking processes should rapidly heat the feed, rapidly separate products to control residence time of all products, rapidly cool the reaction products to avoid secondary cracking, and make productive use of the thermal energy. The most successful short residence time processes meet all these criteria. However, none of these processes fully meet all these criteria while treating asphaltic residual oils. Fully meeting these criteria with asphaltic residual oils is the goal for more effective deasphalting, thermal cracking, and hydrocracking processes.
Fluid catalytic cracking (FCC) is undoubtedly the most common and commercially successful short residence time cracking process. Typically, the FCC process intimately contacts a gas oil boiling range hydrocarbon feedstock with hot catalyst particles in an entrained flow, short-residence, riser reactor to produce more valuable cracked products, particularly gasoline and olefins, and less desirable dry gas and coke by-products. The FCC process developers have used improved feed nozzle designs to increase feed heating rate. The FCC feed nozzles improve the uniformity of the initial contact between the carbonaceous feed and the hot regenerated catalyst, which increases the feed heating rate and decreases the yield of the undesirable dry gas and coke FCC produces. For example, U.S. Pat. No. 6,387,247, summarizes a long standing effort to use feed injection nozzle improvements to increase the feedstock heating rate and improve the overall FCC reactor performance.
FCC process developers have also identified approaches to control the residence time. For example, U.S. Pat. No. 6,979,360, teaches methods for conducting short contact time hydrocarbon conversions in a FCC reactor with the rapid inertial separation of gas and solid FCC reactor products. U.S. Pat. No. 6,616,900 extends this concept by using a staged FCC riser reactor with interstage product removal. U.S. Pat. No. 5,762,882, teaches methods to remove reaction products from the spent catalyst via vaporization. With distillate feeds, the by-product coke production is roughly in balance with FCC process heat requirement. The higher coke yield associated with more asphaltic residual FCC feeds has a large adverse effect on the process performance. U.S. Pat. No. 4,415,438 teaches the use of a thermally stable catalyst and high catalyst regeneration temperature to increase the heavy oil feed heating rate and decrease coke yield. U.S. Pat. No. 5,271,826 achieves a similar result by increasing the regenerated catalyst to feed ratio to achieve an elevated riser initial temperature and then adding a quench liquid to temperature the riser temperature. Canadian Patent No. 2,369,288, teaches thermal cracking of residual oil feed with inert solids in an FCC reactor-type short contact time reactor to eliminate catalyst deactivation problems, but also results in an inferior product yield distribution, including coke production in excess of the process heat requirement. US Patent Application Publication No. 2006/0042999 teaches deasphalting of the FCC heavy oil feed to decrease the catalyst deactivation rate due to metals and coke precursors in the feed. U.S. Pat. No. 6,171,471 teaches the combination of mild hydrocracking and deasphalting of the residual oil FCC feed to decrease the catalyst deactivation rate due to metals and coke precursors. Despite these efforts to decrease the FCC process coke yield with residual asphaltic feeds, the coke yield far exceeds the amount required to preheat the regenerated catalyst or inert solids.
As a result, similar principles were used to develop successful short contact time fluid coking processes that maximize the conversion of asphaltic residual oil feeds to distillates. The fluid coking process typically comprises partial combustion of coke particles, rapid heating of the residual oil feed by intimate contact with a fluidized bed of hot coke particles, rapid separation of entrained by-product coke from the vapor product using cyclones, and a quench system to rapidly cool the vapor product to minimize secondary thermal cracking. U.S. Pat. No. 2,881,130 teaches atomization and distribution of the residual oil feed to prevent bogging of the fluidized coke bed and to increase the residual oil feed heating rate. The fluid coking process developers have also identified methods to control residence time. For example, U.S. Pat. No. 4,816,136 teaches sequentially contacting the feed with higher temperature coke particles in a riser reactor and then in a fluidized coke bed that operates at a lower temperature to increase the distillate yield. U.S. Pat. No. 5,658,455 describes a method for a short vapor residence time reactor to minimize secondary thermal cracking reactions. U.S. Pat. No. 4,497,705 teaches methods to solvent refine the recycle heavy oil to selectively remove less carbonaceous species to decrease undesirable secondary cracking of these valuable products. U.S. Pat. No. 4,587,010 teaches methods to strip valuable products from the coke prior to regeneration via partial oxidation. The fluid coking has many common features with the FCC process and has several advantages for treating carbonaceous residual oil feeds. The fluid coking process eliminates the rapid catalyst deactivation problem and need to burn very large quantities of coke that are associated with the FCC process treating asphaltic residual oil feeds. Since both the fluid coking and FCC processes require that all liquid products are produced by vaporization, neither process can operate with a short residence time for unconverted asphaltic residual oils.
U.S. Pat. No. 3,393,133 teaches high temperature and short residence time distillation processes to maximize distillate yield with minimum degradation of the residual oil due to thermal cracking reactions. However, solvent extraction [Altgelt (1994)] is the preferred method to produce residual oil fractions with much higher equivalent normal boiling points and essentially no thermal cracking degradation. Successful solvent refining processes have been developed, e.g. U.S. Pat. No. 4,810,367, to continuously produce deasphalted oil, resin, and asphaltene streams from an asphaltic residual oil feed. These processes require a large number, but simple and reliable, unit operations to contact and separate the residual oil from the solvents. In addition, the solvent and residual oil separation steps have a significant steam heat requirement. As a result, this process technique is particularly useful in petroleum refineries, where the required solvents, steam, and maintenance infrastructure are readily available. U.S. Pat. No. 6,357,526 teaches a solvent extraction field upgrader method to produce a deasphalted oil synthetic crude product and an asphaltic fuel to produce steam for bitumen extraction. For this remote application, a flash deasphalting process has many potentially desirable features. A very high temperature, very short contact time flash unit operation could produce the deasphalted oil and asphaltic streams in a compact and single unit operation without the need for a solvent. The thermal energy input could be used to separate the deasphalted oil and asphaltene products, produce steam for bitumen extraction, and produce a hot asphaltene stream that can be burned without the need for reheating or pelletization. Unfortunately, the earlier processes do not provide any method that can heat the bitumen feed, separate the deasphalted oil and asphaltene products, and cool the separated deasphalted oil and asphaltene products sufficiently rapidly to avoid excessive thermal cracking and degradation of the deasphalted oil product.
Resid hydrocracking is the most well established method to convert asphaltic materials to less carbonaceous materials and to reduce the metals and coke precursor concentration in the unconverted asphaltene species. U.S. Pat. No. 2,987,465 first introduced the ebullated bed hydrocracking reactor concept. An ebullated hydrogenation reactor utilizes up-flow of the carbonaceous asphaltic residual oil and hydrogen feeds to contact an expanded bed of particulate hydrotreating catalyst and or entrained colloidal hydrotreating catalyst. The expanded bed hydrotreating catalyst bed is much less susceptible to plugging than the previous fixed catalyst bed designs. U.S. Pat. No. 5,164,075 teaches methods to produce colloidal heavy oil catalysts that are particularly effective for hydrogenating asphaltic species. U.S. Pat. No. 6,511,937 teaches methods to recover and recycle colloidal heavy oil hydrocracking catalysts. All these resid hydrocracking process simultaneously hydrogenate and thermally crack the residual oil. U.S. Pat. No. 4,427,535 identifies a fundamental limitation with this approach. The thermal cracking reactions have higher activation energies than the hydrogenation reactions. Hydrogenation reactions retard polymerization reactions that produce coke precursors and ultimately coke. Therefore, a resid hydrocracker must be operated at a much lower temperature than a FCC or fluid coking unit in order to maintain operability.
US Patent Application Publication No. 2005241993 teaches the use of a colloidal molybdenum sulfide catalyst to increase the hydrogenation rate, particularly the rate of hydrogenation of asphaltic species. This innovation increases hydrogenation rate of asphaltic species and the maximum operable temperature, but does not alter the basic nature of this hydrocracker operating temperature limitation. Hydrogen donor diluent cracking processes substantially eliminates this temperature limitation by hydrogenating a naphthenic distillate at moderate temperatures to produce a hydrogen donor solvent and then thermal cracking the residual oil in the presence of the donor solvent to substantially reduce the rate of coke precursor formation. U.S. Pat. No. 4,698,147 teaches simultaneously increasing the hydrogen donor diluent cracking temperature and decreasing the contact time to monotonically increase the maximum resid conversion to distillates. U.S. Pat. No. 4,002,556 teaches that high temperature and short contact time hydrogen donor diluent cracking also substantially reduces the hydrogen consumption required to maintain operability. These high temperature and short contact time benefits seem to be only limited by the practical limits on the feed heating rate and the product cooling rate. The hydrogen donor diluent process requires sufficient pressure to maintain a liquid phase hydrogen donor solvent at the elevated thermal cracking temperatures.
The invention is able to address the concerns of these earlier processes by using a staging process to convert heavy oil into a cracked distillate.
The invention provides for advantages to the process of converting residual heavy oil. The invention improves control over the reactor composition. The staging process provides for prompt removal of cracked distillate product to inhibit secondary cracking and increases the solubility of coke precursor in the liquid phase. Thermal efficiencies are also realized by the invention.
The invention further provides for a method for cracking heavy oil comprising feeding residual heavy oil first to a heating stage comprising an atomizer, a contactor and an inertial vapor-liquid separator, and then to at least one stage selected from the group consisting of temperature maintenance stage comprising a reactor and an inertial vapor-liquid separator, and a second heating stage comprises an atomizer, a contactor and an inertial vapor-liquid separator
The invention provides for a method of cracking residual heavy oil comprising at least one heating stage and at least one or more of a stage selected from the group consisting of a heating stage and a temperature maintenance stage.
The heating stage is accomplished by three unit operations comprising an atomizer, a contactor and an inertial vapor-liquid separator.
The temperature maintenance stage is accomplished by two unit operations comprising a reactor and an inertial vapor-liquid separator.
The method of cracking residual heavy oil can be accomplished by any combination of the two stages can be employed so two heating stages may be employed or two temperature maintenance stages or one or more of each stage. Thus numerous combinations of heating stages and temperature maintenance stages can be employed as long as there is more than one stage used in the cracking process.
The heating stage starts with a feed of a heating gas formed from the reaction products of an oxygen-containing compound and a fuel. This reaction occurs in a heating pressurized combustor. The heating gas is fed to the atomizer along with a residual heavy oil feed.
The now atomized residual heavy oil is fed to a contactor where the residual heavy oil is maintained for sufficient residence time to achieve the desired conversion of residual oil to distillates via thermal cracking reactions.
The products from the contactor are then fed to the inertial vapor-liquid separator where the products are separated into vapor and liquid portions.
The vaporized gas and liquid distillate products are removed from the inertial vapor-liquid separator and the remaining residual oil liquid is fed to the second stage of the method, the temperature maintenance stage.
The first step of the temperature maintenance stage is the reactor step where the reactor receives the liquid product from the inertial vapor-liquid separator of the heating stage. The reactor will provide sufficient residence time to achieve the desired cracking.
The cracked reaction products are then fed to an inertial vapor-liquid separator where they will mix with the reaction products from a cracking pressurized combustor. The liquid portion and vapor portion are separated and the gas and cracked distillate product recovered.
The invention will now be described in more detail and with reference to the drawing figures.
The pressurized combustor on
Typical heavy oil atomizers are illustrated on
In the case of the conical nozzle (see
The vapor-liquid contactor or reactor 18 is illustrated on
The preferred inertial vapor-liquid separator is a cyclone.
An atomizer is advantageously used to increase the interfacial area of the hydrocarbon quench liquid 29. The hydrocarbon quench liquid preferably has a normal boiling point less than 350° C. The liquid product conduit 32 is used to remove the liquid product 33 from the inertial vapor-liquid separator. A liquid product conditioning stream 34 may be advantageously introduced via the liquid product conditioning stream conduit 35 to achieve the desired liquid product 33 properties. For example, one could advantageously use steam as the liquid product conditioning stream 34 to minimize the quantity of the vapor in the feed stream 26 that exits in the liquid product stream 33 and cools the liquid product stream 33 to control the thermal cracking rate. Alternatively, one could advantageously use the pressurized combustor product gas 7 on
This process description will describe the options to use these unit operations for a staged thermal cracking with the aid of
The stage cracking method (See
The asphaltic residual oil feed 37 typically contains more than 25 weight percent of species with normal boiling points greater than 975° F. (524° C.), more preferably greater than 50 weight percent, and most preferably greater than 75 weight percent. The residual oil feed typically has micro carbon and heptane insoluble contents between 5 and 40 weight percent. The more carbonaceous feeds typically exhibit higher micro carbon and heptane insoluble values. Typical sources for residual oil feed include petroleum atmospheric or vacuum residual oil, oil sands, bitumen, tar sand oils, coal tar, pyrolysis tars, or shale oils.
The residual oil feed 37 may also be partially hydrogenated prior entering atomization-heating nozzle 41. The optional residual oil feed hydrogenation step typically has a hydrogen consumption between 100 and 1500 standard cubic feet per petroleum barrel (SCF/bbl) or between 95 and 285 gram moles per cubic meter, more preferably between 150 and 1000 SCF/bbl, most preferably between 200 and 700 SCF/bbl. The optional hydrogenation step is preferably performed in an ebullated bed hydrotreating reactor with conventional cobalt-molybdate or nickel-molybdate on activated alumina supported hydrotreating catalyst and/or colloidal hydrogenation catalyst system, preferably a molybdenum sulfide colloidal catalyst.
The residual oil feed 37 is preheated in a conventional fired heater (not shown on
The 1st heating stage atomizing and heating gas 42 is typically produced in the heating stage pressurized combustor using air oxidant 44 with optional steam additions to prevent sooting and a convert fuel 45. Alternatively, one could use an O2-steam oxidant. The O2 flow rate in the oxidant 44 feed to the pressurized combustor 43 is typically between 90% and 100% of the theoretical flow rate required to convert the hydrogen and/or carbon in the fuel feed 45 to CO2 and H2O. The 1st heating stage atomizing and heating gas 42 typically is in the temperature range of 1300-1800° C. and the pressure range of 5 to 20 bar. The heating stage pressurized combustor fuel 45 may be any hydrocarbon fuel or hydrogen. The preferred fuel is a H2 and CO synthesis gas produced by gasification of the pitch product 40.
The 1st heating stage atomizer 41 (see
The 1st heating stage contactor product 47 is promptly fed to the 1st heating stage inertial separator 48 (see
The operation of the 2nd heating stage atomizer 52, contactor 54, and inertial separator 56 are similar to the operation of the corresponding unit operations in the 1st heating stage with some minor exceptions. First, the ratio of the flow rate of the atomizing and heating gas for the 1st stage 42 is typically substantially higher than the flow rate for the 2nd stage 53. Generally, these flow rates are adjusted such that the temperature of the 2nd heating stage inertial separator liquid product 59 has reached the desired thermal cracking temperature, typically in the 650 to 850° C. temperature range, and the vaporized distillate flow rates in streams 50 and 58 are roughly equivalent. In addition, the residence time in the 2nd heating stage contactor 54 is less than the 1st heating stage contactor in order to control the extent of thermal racking. As a result, the temperature difference of the vapor and liquid portion of the 2nd heating stage contactor product 55 is greater than the 1st heating stage contactor product 47.
1st cracking stage reheat and purge gas 60 is typically produced in the cracking stage pressurized combustor 61 using a steam-O2 oxidant 62 and a convent fuel 63. The O2 flow rate in the oxidant 62 feed to the cracking pressurized combustor 61 is typically between 90% and 100% of the theoretical flow rate required to convert the hydrogen and/or carbon in the fuel feed 63 to CO2 and H2O. The 1st cracking stage reheat and purge gas 60 typically is in the temperature range of 1000-1600° C. and the pressure range of 2-10 bar. The lower temperature and pressure of the 1st cracking stage reheat and purge gas 60 relative to 1st heating stage atomizing and heating gas 42 results from the fact that this stream must only provide sufficient thermal energy to compensate for modest heat losses and heat of cracking in order to maintain the desired thermal cracking temperature. This lower heating requirement also eliminates the need for an atomizer. The cracking stage pressurized combustor fuel 63 may be any hydrocarbon fuel or hydrogen. The preferred fuel is a H2 and CO synthesis gas produced by gasification of the pitch product 40. A water quench stream 64 may be advantageously used to obtain the desired 1st cracking stage reheat and purge gas 60 temperature.
The 1st cracking stage reheat and purge gas 60 in fed to the terminal reheating inertial separator 56 as shown on
As noted in
While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of the invention will be obvious to those skilled in the art. The appended claims in this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
This application claims priority from U.S. Provisional Application Ser. No. 61/223,885 filed Jul. 8, 2009.
Number | Date | Country | |
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61223885 | Jul 2009 | US |