EP2804930A1 - Low complexity, high yield conversion of heavy hydrocarbons - Google Patents
Low complexity, high yield conversion of heavy hydrocarbonsInfo
- Publication number
- EP2804930A1 EP2804930A1 EP12866398.6A EP12866398A EP2804930A1 EP 2804930 A1 EP2804930 A1 EP 2804930A1 EP 12866398 A EP12866398 A EP 12866398A EP 2804930 A1 EP2804930 A1 EP 2804930A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reactor
- solvent
- stream
- asphaltene
- process fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/003—Solvent de-asphalting
Definitions
- the present invention relates to an optimized method of improving a heavy hydrocarbon, such as bitumen, to a lighter more fluid product and, more specifically, to a final hydrocarbon product that is refinery-ready and meets pipeline transport criteria without the addition of diluent.
- a solid asphaltene byproduct is created for easy handling and further processing.
- the invention is targeted to enhance Canadian bitumen, but has general application in improving any heavy hydrocarbon.
- a low complexity, high yield integrated process has been developed, tested and enhanced to improve the viability and economics of converting heavy viscous hydrocarbons into desired refinery feedstock.
- the concept for this integrated process has been previously described in US PAT APP# 13/037185 and US PAT APP# 13/250935, and has been validated through pilot plant (5 BPD) and demonstration scale ( 500 BPD) facilities. Improvements to the integrated process through shear mixing have been disclosed in US PAT APP# 61/548915.
- This invention describes the optimal operating conditions to achieve the lowest complexity and highest yield for the described integrated process.
- the integrated process operates at temperatures, pressures, heat fluxes, residence times, sweep gas rates and solvent to oil ratios outside any open art processes.
- Visbreaking or viscosity breaking a form of thermal cracking, is a well known petroleum refining process in which heavy and/or reduced crudes are pyrolyzed, or cracked, under comparatively mild conditions to provide products that have lower viscosities and pour points, thus reducing required amounts of less-viscous and increasingly costly to obtain blending hydrocarbons known as diluent to improve fluidity of the crude, and make the crude meet minimum transport pipeline specifications (minimum API gravity of 9).
- Coil-only visbreakers operate at about 900°F at the heater outlet with a residence time of about 1 minute. Gas oil is recycled to quench the reaction.
- a vessel is used at the outlet of a furnace to provide additional residence time for cracking of the crude. The crude sits and continues to crack/react as the temperature slowly reduces.
- the coil-and-soak visbreaker runs at heater outlet temperatures of 800°F. The soaker drum temperature reduces down to 700°F at the outlet with aggregate residence times of over 1 hour.
- U.S. Pat. No. 4,454,023 a process for the treatment of heavy viscous hydrocarbon oil is disclosed, the process comprising the steps of: visbreaking the oil; fractionating the visbroken oil; solvent deasphalting the non- distilled portion of the visbroken oil in a two-stage deasphalting process to produce separate asphaltene, resin, and deasphalted oil fractions; mixing the deasphalted oil ("DAO") with the visbroken distillates; and recycling and combining resins from the deasphalting step with the feedstock initially delivered to the visbreaker.
- DAO deasphalted oil
- a solvent deasphalting unit is installed upstream of a visbreaking unit to remove the asphaltenes from the visbreaking operation.
- the visbreaking unit can now operate at higher temperatures to convert the heavier molecules to lighter hydrocarbon molecules without fouling, since the asphaltenes are removed from the product stream entirely.
- the yield of the bitumen is greatly reduced (by 10- 5%) since the early removal of the asphaltenes in the process prevents thermal conversion of this portion of the crude into a refinable product.
- U.S. Pat. 4,428,824, U.S. Pat No 6,274,032 disclosed a process for treating a hydrocarbon feed source comprising a fractionator to separate the primary crude components, followed by a Solvent Deasphalting (SDA) unit to work on the heavier crude asphaltene rich component, and a mild thermal cracker for the non-asphaltene stream.
- SDA Solvent Deasphalting
- the asphaltene rich stream is processed in a gasification unit to generate syngas for hydrogen requirements.
- Placing an SDA unit upstream of a thermal cracker reduces the overall yield of the bitumen as refinery feed, since the asphaltene portion of the crude, comprising up to 15% of Canadian bitumen, is removed from consideration for inclusion in some format as crude. This loss in product yield is not compensated for by the increased cracking in the visbreaker.
- U.S. Pat. No. 4,686,028 a process for the treatment of whole crude oil is disclosed, the process comprising the steps of deasphalting a high boiling range hydrocarbon in a two-stage deasphalting process to produce separate asphaltene, resin, and deasphalted oil fractions, followed by upgrading only the resin fraction by hydrogenation or visbreaking.
- the U.S. Pat. No. 4,686,028 invention applies visbreaking to a favourable portion of the whole crude stream to minimize coke generation.
- PAT ⁇ 28 is limited by missing a large part of the crude that could benefit from optimal conversion and thus a large portion of the crude does not end up as pipeline product without the need of transport diluent.
- a process for the treatment of topped crude oil, the process comprising the steps of vacuum distilling the topped crude oil, deasphalting the bottoms product from the distillation, catalytic cracking of the deasphalting oil, mixing distillable catalytic cracking fractions (atmospheric equivalent boiling temperature of less than about 1 100 degrees F.) to produce products comprising transportation fuels, light gases, and slurry oil.
- U.S. Pat. No. '697 is burdened by the complexity, cost, and technical viability of vacuum distilling a topped heavy crude to about 850°F and catalytic cracking the deasphalted oil to produce transportation fuels.
- U.S. Patent application 2007/0125686 a process is disclosed where a heavy hydrocarbon stream is first separated into various fractions via distillation with the heavy component sent to a mild thermal cracker (visbreaker).
- the remaining heavy liquid from the mild thermal cracker is solvent deasphalted in an open art SDA unit.
- the asphaltenes separated from the SDA are used as feed to a gasifier.
- the deasphalted oil is blended with the condensed mild thermal cracker vapour to form a blended product.
- visbreaking faces the challenges of early coke generation.
- the '686 patent application explains that the intent of this mild thermal cracker is to crack the non-asphaltene material exclusively, which is also not practical with Canadian bitumen.
- the mild thermal cracker operates at elevated pressures unnecessarily increasing coke formation, and thus yield.
- additional energy is required in the distillation and extraction steps with most of the separated components being recombined for pipeline transport.
- US Pat #8,048,291 a process is described where the bottoms from an atmospheric column and/or vacuum column is treated in a solvent deasphalting unit and then by some form of thermal or catalytic cracking. The objective of this patent is to reduce the cost of cracking the DAO stream by putting an SDA upstream of the cracker.
- the multiple extraction steps and operating conditions of the SDA increase the cost of the entire process offsetting some of the savings from a smaller cracking unit, with the integrated process providing a lower overall yield unless significant costs are incurred to add hydrogen to increase yield.
- the SDA unit removes the heavy asphaltenes which comprised over 15% of heavy bitumen streams, thus limiting overall yield to less than 85% unless expensive catalytic processes are employed. The overall result of this process is uneconomic with the limit of feed being processed being greater than 5 API through the SDA.
- a solvent deasphalting process uses a 2 nd asphalt extractor to concentrate asphaltene material (and recovery of more deasphalted oil).
- the concentrated asphalt stream is sent through a heater to get to 425°F at 18 psia and uses a flash drum and stream stripper to separate solvent (in this case propane) from the asphalt stream.
- solvent in this case propane
- Asphalt product, in liquid form, is pumped to storage. This arrangement only works if the asphalt rich stream is liquid at these conditions. It is burdened by plugging if any appreciably solid asphaltenes are present as in asphaltene-rich streams like bitumen.
- the concentrated asphaltene product from the SDA unit is mixed with solvent to transport as a liquid solution to a spray dryer.
- the spray nozzle design and pressure drop dictates the size of liquid droplets that are formed.
- the smaller the light hydrocarbon (solvent) droplet the faster it will flash completely to vapour.
- the smaller the heavy hydrocarbon (asphaltene) particle the more surface area available for heat transfer to cool the heavy droplets down with the goal of producing a dry, non-sticky solid particle.
- Additional cold gas is added to the bottom of the spray dryer to enhance cooling by additional convective heat transfer as well as increasing the droplet residence time by slowing its descent rate (via upward cooling gas flow) in order to reduce the size of the vessel (which tend to be extremely large). This arrangement is not required if the asphaltene particles that have settled out in the extractor are in a solid form in the solvent at the process operating temperature.
- Patent# 5,009,772 a method is shown relating to a continuous, relatively low temperature deasphalting process in which a heavy hydrocarbon feedstock material and an extraction solvent are contacted, at elevated subcritical temperatures and superatmospheric pressures, in an extraction zone to produce a light extract phase and a heavy phase rich in higher molecular weight hydrocarbon components, Conradson carbon precursors and heavy metals.
- Pat# 5,009,772 comprises continuously effecting a reduction in the pressure upon the first light extract phase produced within the extraction zone suggesting there are benefits of operating at less than supercritical conditions in the SDA unit.
- further improvements in the overall process can be used to allow for more heavier crudes to processed in a simpler, less costly fashion.
- a method for transporting and upgrading heavy oil or bitumen comprising: diluting the heavy oil or bitumen at a production site with a diluent comprising a hydrocarbon having from 3 to 8 carbon atoms to form a mixture; transporting the mixture from the production site to a solvent deasphalting unit; deasphalting the mixture in the solvent deasphalting unit to recover an asphaltene fraction, a deasphalted oil fraction essentially free of asphaltenes, and a solvent fraction; separating water and salts from the asphaltene fraction, the deasphalted oil fraction, and the solvent fraction at the solvent deasphalting unit; and conveying at least a portion of the solvent fraction to the production site to dilute the heavy oil or bitumen and form the mixture.
- a method for upgrading heavy asphaltenic crudes using SDA and gasification is disclosed.
- a stream to a gasifier is generated by mixing a hydrocarbon comprising one or more asphaltenes and one or more non-asphaltenes with a solvent, wherein a ratio of the solvent to the hydrocarbon is about 2: 1 to about 10: 1 .
- the asphaltene rich stream is transferred out of the SDA to a gasifier as a liquid stream.
- the large quantities of solvent used in transport are consumed in the gasifier, and are downgraded in value to a fuel gas equivalent. Since the asphaltenes tend to be liquid, using a solvent to transport the material in the quantities stated is feasible. For a solid asphaltene, this method would require 10-20 times more solvent to transport and this quantity of expensive solvent would be consumed and its value reduced.
- an improved process for producing a pipeline-ready crude and refinery feedstock from heavy crude oils is described, with said process consisting of: (1 ) optimal asphaltene conversion with minimum coke and offgas make in a full bitumen stream within a reactor to produce a thermally affected asphaltene-rich fraction, a minimum non- condensable vapour stream, and an increased refinery-feed liquid stream; (2) deasphalting said thermally affected asphaltene-rich fraction into a refinery-feed liquid stream and a concentrated asphaltene stream; (3) Selectively hydrotreating specific hydrocarbon components as required for pipeline specification, and finally blending of all the liquid streams to produce a refinery feed; and (4) inertial separation of the concentrated solid asphaltene stream for conversion in a gasifier, power or asphalt plant.
- the bitumen is thermally treated to remove and convert/crack selected asphaltenes, which are then sufficiently separated in a more efficient solvent extraction process, reducing production of coke and isolating undesirable contaminants (like metals, MCR, and remaining asphaltenes).
- undesirable contaminants like metals, MCR, and remaining asphaltenes.
- the side chains are preferentially cleaved from the core asphaltene molecule to make desired vacuum gas oil to light hydrocarbon range components.
- thermally affected polyaromatic asphaltene cores remain solid at elevated temperatures and pressures above operating conditions and thus separate more readily than non-thermally affected asphaltenes resulting in improved separation processes, such as solvent deasphalting (50) and inertial separation (110).
- bitumen is also mildly cracked to vacuum gas oil, gasoline and distillate boiling range components, all desirable for separation and conversion in refineries. Any major deviations in temperature and heat flux within the bitumen pool in the reactor will lead to coking and increased gas yield and a reduction in the overall crude yield of the original bitumen, and reduced reliability of the operation, increasing the operating cost of the facility.
- the invention provides an improved apparatus and method for producing a pipeline-ready and refinery-ready feedstock from heavy, high asphaltene crudes (for example, Canadian bitumen) and feedstocks, with utility for any virgin or previously processed hydrocarbon stream, the process and apparatus comprising a pre-heater for pre-heating a process fluid to a design temperature at or near the desirable operating temperature of a reactor; moving the process fluid into a reactor for conversion of the process fluid by controlled application of heat to the process fluid in the reactor so that the process fluid maintains a substantially homogenous temperature throughout the reactor to produce a stream of thermally affected asphaltene-rich fractions, and a stream of liquid hydrocarbon vapour with minimal non-condensable vapour.
- a pre-heater for pre-heating a process fluid to a design temperature at or near the desirable operating temperature of a reactor
- moving the process fluid into a reactor for conversion of the process fluid by controlled application of heat to the process fluid in the reactor so that the process fluid maintains a substantially homogenous temperature throughout
- the stream of vapour is separated into two further streams: of non-condensable vapour, and of light liquid hydrocarbons.
- the thermally affected asphaltene-rich fraction is first mixed using a high-shear mixer, then is deasphalted using a single-stage solvent extraction process into streams of deasphalted oil liquid and concentrated asphaltene, respectively.
- the deasphalted oil liquid and the light liquid hydrocarbons produced in the processes are blended to form a pipeline and refinery-ready feedstock.
- the concentrated asphaltene is processed in an inertial separation unit to create a dry solid asphaltene by-product.
- a sweep gas can be deployed in the reactor, and can be preheated to provide a heat flux source other than the reactor's heaters; the sweep gas may also assist in the removal of reactor vapour products.
- Deasphalting is achieved using a minimum of one extraction step (more steps may be used) and a low pressure stripper at conditions outside any open-art solvent extraction process. Since the initial process fluid has been thermal-affected, the heavy asphaltene-rich fractions can be further separated using a high shear mixer and a lower complexity single stage extraction process using a combination of lower solvent-to-oil ratios, temperatures and pressures than typically found in similar upgrader operations. Even further improved solvent-extraction performance, using even lower overall solvent to oil ratios and improved DAO yield can be achieved by further concentrating the asphaltene rich fraction before a final extraction step.
- the process improves on open-art solvent deasphalting utilizing an additional solvent extraction column (rinse column) operating on the asphaltene-rich stream from the primary solvent extraction column to increase pipeline crude recovery and quality.
- the SDA process may allow for some portion of the heavy asphaltene-rich hydrocarbon stream to be recycled and blended with the fresh feed to the reactor.
- the resulting concentrated thermally-affected asphaltenes can be successfully processed in an inertial separator such as a centrifugal collector or settling chamber to generate a dry, solid asphaltene by-product.
- Fig. 1 is a process diagram for forming a pipeline transportable hydrocarbon product from a heavy hydrocarbon feedstock
- Fig. 2 is a process diagram pertaining specifically to a cracking process and liquid separation process and a solids separation process
- FIG. 3 depicts an illustrative application of an integrated mild thermal cracking and improved solvent deasphalting process with appropriately placed shear mixing devices within an existing upgrader or refinery with a vacuum and/or coking unit according to one or more embodiments described.
- FIG. 4 depicts a specific illustrative application from FIG. 3 of an integrated mild thermal cracking and improved solvent deasphalting process fed a vacuum bottoms stream from an existing upgrader or refinery with the various products from the integrated cracker/SDA sent to hydrocracking, residual hydrocracking and gasification units according to one or more embodiments described.
- DETAILED DESCRIPTION OF VARIOUS EMBODIMENTS
- FIG. 1 is a process flow diagram depicting a process 10 for forming a hydrocarbon product 160 from a hydrocarbon feedstock 12, where the final hydrocarbon product 160 has sufficient characteristics to meet minimum pipeline transportation requirements (minimum API gravity of 19) and is a favourable refinery feedstock.
- a process fluid 14 formed from a feedstock 2 of heavy hydrocarbon can be routed through a heater 20 to heat the process fluid 14 to a desired temperature level before it is routed to a reactor 30 where the process fluid 14 is controlled and maintained while it undergoes a mild controlled cracking process. After the mild cracking process, a light top fraction 32 can be routed from the reactor 30 to a gas liquid condensing separator process 40 and a heavy bottom fraction 34 can be routed to a high performance solvent extraction process 50.
- Some of the outputs 44 from the gas liquid separation process 40 can be blended with some of the outputs 52, 54 of the high performance solvent extraction process 50 to result in a hydrocarbon product 160 that has sufficient physical characteristics to enable it to meet the required pipeline transport criteria without having to mix the final hydrocarbon product 160 with diluents from external sources, or requiring much reduced volumes of such diluent.
- the feedstock 12 can be a heavy hydrocarbon (virgin or a previously processed stream), such as the heavy hydrocarbon obtained from a SAGD (steam assisted gravity drainage) process, for example Canadian Oil sands bitumen, or from any other suitable source of heavy hydrocarbon.
- the feedstock 12 can have an API gravity in the range of 0 to 14.
- a recycled portion 70 of the resin stream 54 output from the high performance solvent extraction process 50 can be blended with the incoming feedstock 12 to form the process fluid 14 that passes through process 10.
- the resin stream may be added to the process fluid in instances in which further crude yield, and/or lighter crude, and/or asphaltene suppression is desired in order to meet treated product characteristic targets.
- the resin recycle provides the operator with flexibility, through an adjustable flow parameter, to meet production specifications, and allows the plant to handle feedstock variations robustly.
- the resin product 54 from the solvent extraction process 50 will typically have a relatively low API gravity.
- the API gravity of the resin product 54 can have an API gravity between 0 and 10.
- the resulting process fluid 14 can have a range of characteristics and particularly a range of API gravities.
- the process fluid 14 (obtained entirely from the feedstock 12 or formed as a blend of feedstock 12 and resin product 54 from the solvent extraction process 50) can be routed to the heater 20 where the process fluid 14 can be heated to a desired temperature as it passes through the heater 20 before being routed to the reactor 30 to undergo mild thermal cracking.
- Reactor 30 maintains a consistent fluid temperature through a uniform application of heat through-out the reactor to allow for mild thermal cracking to occur without coking being a concern or detrimental to the operation and/or performance of the reactor.
- the heater 20 will heat the process fluid 14 to a temperature between 675-775°F before the process fluid 14 is introduced into the reactor 30.
- the process fluid 14 (heated to between 675- 775°F by the heater 20) undergoes a mild controlled cracking process.
- Appropriately located heaters are provided in this reactor 30 to maintain the desired constant temperature generated in heater 20 and to apply uniform heat flux for the fluid 14.
- the heaters provide heat through any source readily available (electric, heat transfer fluid, radiant etc.).
- the reactor 30 can be operated in a manner, through optimizing primarily five inter-related process variables (Temperature, Pressure, Residence Time, Sweep Gas and Heat Flux), so as to reduce or even prevent coke from forming during the reaction, and minimizing gas production, while also providing optimal conversion of the part of the asphaltene portion of the heavy hydrocarbon to refinery-ready feedstock components.
- the first and second variables involve applying a uniform heat flux between 7000-12000 BTU/hr sq.ft to the entire pool of process fluid in the reactor and maintaining a single operating temperature in the reactor between 675- 775°F. This may be achieved by the presence of appropriately sized and located heating devices in the reactor.
- the number of heaters will be set by calculating the optimal dispersion of heat between any two heaters so as to have a uniform temperature throughout the pool and to avoid peak or spot temperatures significantly higher than the target temperature in the reactor.
- the third reactor variable, residence time can be between 40-180 minutes in the reactor.
- the fourth reactor variable, operating pressure can be maintained at near atmospheric pressure, in any case to be less than 50 psig, with standard pressure control principles used for consistent performance.
- the pressure range is controlled on the low end to prevent excessive, premature flashing of hydrocarbon, essentially bypassing the reactor, and limited on the high end to reduce secondary cracking and consequent increased gas yields.
- the fifth reactor variable, hot sweep gas 36 in the same temperature range as the process fluid (675-775°F) 21 , is added to the process fluid 14 in the reactor 30 in the range of 20-80 scf/bbl.
- the sweep gas 36 can be natural gas, hydrogen, produced/fuel gas from the process, steam, nitrogen or any other non-reactive, non-condensable gas that will not condense to a liquid in the reactor environment.
- Sweep gas in the dosage of 20-80 scf/bbl of feed is provided to remove the "lighter" hydrocarbon products (i.e. methane to ⁇ 750°F boiling point hydrocarbons) as soon as they are formed in the reactor 30 so that there is a minimum of secondary cracking which could increase gas make and potentially increase olefinic naphtha/distillate production.
- the sweep gas may also allow the reactor to operate closer to the desired operating pressure ( ⁇ 50 psig) and temperature.
- the sweep gas 36 can also be used to provide additional heat and/or mixing to the process fluid 14 in the reactor 30.
- the heat energy stream 36, for reactor 30 is uniformly (7000-12000 BTU/hrsq.ft) applied throughout the hydrocarbon residence time (40-180 minutes) in the reactor at the desired temperature (675-775 °F) and pressure (less than 50 psig) to minimize any local peak fluid temperatures which can initiate coking, and thereby allowing an increased thermal transfer of heat at a higher bulk temperature improving the conversion of hydrocarbons within reactor 30.
- reaction kinetics favour optimum conversion of the asphaltenes that preferentially cleaves the outlying hydrocarbon chains creating desirable hydrocarbons (VGO and diesel range hydrocarbons) for the refiner without causing coking or increased gas production in the reactor.
- Table 1 illustrates different configurations of asphaltenes for different types of crudes.
- the proposed operating conditions of reactor 30 factor in the relative complexity and high degree of side chains on different crudes.
- Table 1 Average molecular structures representing asphaltene molecules from different sources: A, asphaltenes from traditional heavy crudes; B, asphaltenes from Canadian bitumen (Sheremata et al., 2004). Each variable may be changed independently, within the ranges suggested, based on the quality of feedstock provided or based on the quality of output desired. Since the 5 noted process variables are inter-related, a multi- variable process control scheme with a prescribed objective function (for example maximum yield to meet minimum product specifications) will be beneficial to ensure the process operates at an optimal point when any one of the variables is changed or the feed/product situation or goal is altered.
- A asphaltenes from traditional heavy crudes
- B asphaltenes from Canadian bitumen (Sheremata et al., 2004).
- Each variable may be changed independently, within the ranges suggested, based on the quality of feedstock provided or based on the quality of output desired. Since the 5 noted process variables are inter-related, a multi- variable process control scheme with a prescribed objective function (for example maximum yield to meet
- a light overhead fraction 32 and a heavy bottoms fraction 34 can be removed from the reactor 30.
- the light overhead fraction 32 of the output from the reactor 30 can contain non-condensable vapor products, light liquid hydrocarbon and heavier liquid hydrocarbon.
- the vapor products can be vapors released from the process fluid 14, such as sour gas, while undergoing thermal cracking, as well as introduced and unconverted or unused sweep gas 36 that has passed through the reactor 30.
- the overhead liquid fraction 32 will have a much higher API gravity than the bottom fraction 34.
- the overhead liquid fraction 32 could typically have an API gravity of 26 or greater.
- the overhead fraction 32 can be directed to a gas liquid separation unit 40, which can comprise a cooler 41 and separation drum 42, as an example, in which a portion of the overhead fraction 32 that is a condensable liquid product containing naphtha and heavier hydrocarbons can be separated from the gaseous components of the overhead fraction 32.
- An off-gas line 43 containing undesirable gases such as sour gas can be provided at the separation drum 42 for those gases to be disposed of, recycled, or subjected to further treatment.
- One or more liquid hydrocarbon streams can be produced from separation drum 42.
- Stream 44 a heavier hydrocarbon than stream 46, can be sent to product blending, while stream 46 can be considered for further bulk hydro-treating prior to product blending.
- the bottom fraction 34 can contain hydrocarbons, and modified asphaltenes. Although the characteristics of the bottom fraction 34 taken from the reactor 30 will vary depending on the process fluid 14 input into the reactor 30 and the reactor's operating parameters, in one aspect the bottom fraction 34 can have an API gravity ranging between -7 and 5.
- Controllable process variables allow an operator to vary the performance of the reactor 30 to meet the needs of the final product based on changing characteristics of the incoming process fluid 14.
- the controllability of the five inter-related variables, residence time, sweep gas, heat flux, temperature and pressure in the reactor 30 allow an operator to vary the performance of the reactor 30.
- the five inter-related process variables can be optimized to avoid the production of coke and minimize the production of non-condensable vapors are produced in the reactor 30.
- the operator can vary the residence time of the process fluid 14 in the reactor 30 based on the characteristics of the process fluid 14 to obtain the desired yields and/or quality of the outputs 32, 34.
- the operator can vary the sweep gas, temperature or pressure to achieve similarly tailored outcomes.
- the process variables are inter-related and the minimization of coke and avoidance of excess gas make is challenging and is best determined by pilot operations, which may be done without undue experimentation.
- the bottom fraction 34 from the reactor 30 can be fed to a high performance solvent extraction process 50 that can produce a thermally affected asphaltene stream 58, an extracted oil stream 52 and a resin stream 54.
- the reactor 30 is operated in a manner that significantly limits and even prevents the formation of coke and reduces gas production while converting asphaltenes into more suitable components for downstream processing. Consequently, modified asphaltenes and other undesirable elements remain in the bottom fraction 34 that is removed from the reactor 30.
- the bottom fraction 34 from the reactor 30 must be further treated using, for example, a high performance solvent extraction process 50.
- the treatment of the bottom fraction 34 by solvent extraction process 50 allows the reactor 30 and the solvent extraction process 50 to be used in conjunction to produce a suitable full range refinery feedstock crude.
- the solvent extraction process 50 can comprise any suitable solvent extraction process. In one aspect, it can be a three stage super-critical solvent process that separates the asphaltenes from the resins in the bottom fraction 34.
- the output of the solvent extraction process 50 can be an asphaltene stream 58, an extracted oil stream 52 and a resin stream 54.
- the asphaltene stream 58 is typically undesirable and is removed from the process 10.
- the extracted oil stream 52 can be of a relatively high quality, with an API gravity range of 9 to 15.
- the resin stream 54 is typically of a lower quality than the extracted oil stream 52, with an API gravity lower than the extracted oil stream 52.
- the resin stream 54 can have an API gravity in the range of 0 to 10 API gravity.
- the extracted oil stream 52 and the resin stream 54 from the solvent extraction process 50 can be blended along with the liquid product stream 44 obtained from the liquid gas separator 40 to form a final hydrocarbon product 160 meeting the specifications of the pipeline and/or refinery-ready.
- this final hydrocarbon product 160 would have an API gravity greater than 19.
- the final hydrocarbon product 160 would have a viscosity of 350 CentiStokes (“cSt") or less.
- the resin stream 54 is typically of a lesser quality than the extracted oil stream 52.
- the recycle portion 70 of the resin stream 54 can be blended with the feedstock 12 to be reprocessed in order to form the final hydrocarbon product 160. As a result, this recycling portion of the resin stream will improve the quality of the final hydrocarbon product 160.
- the optimal solvent deasphalting and solid separation scheme is illustrated when integrated with reactor 30 operated with the five inter-related variables set accordingly for maximum yield.
- a shear mixer 25 and a single asphaltene extractor 50 is provided to separate the solid asphaltenes in stream 58 from the oil and solvent, stream 51 .
- a single low pressure solvent stripper processing stream 41 is economical and effective to separate the product deasphalted oil 52 and the recovered solvent as stream 101 .
- Stream 58 the concentrated asphaltene solid stream, is processed in an inertial separator 60 separating a solvent vapour stream 62 and a dry solid asphaltene stream 61.
- Stream 62 is condensed 1 10 and the solvent is recirculated for use in the process again.
- the dry solid is sent to dry solid storage 130 or otherwise handled.
- the inertial separation unit 1 10 separates the asphaltene solids from the gas remaining solvent in stream 58 using a combination of forces such as centrifugal, gravitational, and inertial. These forces may move the asphaltene solid to an area where the forces exerted by the gas stream are minimal.
- the separated solid asphaltene may be moved by gravity into a hopper where it is temporarily stored.
- Unit 1 10 can be either a settling chamber, baffle chamber or centrifugal collector; a device that provides inertial separation of solid and gas. Centrifugal collectors can either be single or multi-staged cyclones.
- stream 58 can be injected with suitable low molecular weight gas (ex. Natural gas, or nitrogen) to provide pneumatic conveyance to the asphaltene solids that otherwise would be provided by flashing remaining process solvent in the line.
- suitable low molecular weight gas ex. Natural gas, or nitrogen
- a pneumatic conveying system may transport solids up to approximately 50 mm particle size. The solid must be dry, with no more than 20% moisture and not sticky. The thermally-affected asphaltene solids meet the above criteria and thus the process benefits from the ability to use an inertial separation unit, 1 10.
- a high-performance solvent extraction process 50 could include an optional supplemental extraction process step 55, with another shear mixer 235.
- the additional solvent extraction step on the asphaltene-rich stream by second extractor 55 uses standard liquid-liquid extraction with the same solvent used in the primary extractor.
- the placement of this standard liquid-liquid column on the asphaltene-rich stream may be beneficial since the solvent to oil ratio can be economically increased within this column up to 20:1 to increase the recovery of deasphalted oil, while the overall solvent use is reduced.
- Overall solvent use to achieve high hydrocarbon recovery in stream 52 can be 25% less than using comparable open art processes. The result is a significant reduction in energy consumption compared to a state of the art 3-stage extraction process.
- the resulting asphaltene stream 58 can be processed in a 20% smaller asphaltene separation unit 1 10.
- the core portion of the remaining concentrated thermally-affected asphaltenes are solid even at elevated temperatures (above 700oF) with the side hydrocarbon chains removed, resulting in less volume for the asphaltene separation unit to handle.
- the modified nature of the asphaltenes provides for the opportunity for more effective metals reclamation and better feedstock for a clean energy conversion technology (eg. gasification, catalytic gasification, oxy-combustion for enhanced SAGD production).
- Process 10 in figure 1 provides a crude feedstock that is pipeline compliant and is optimal for high conversion refiners.
- Stream 160 has low metals ( ⁇ 20 wppm Ni+V), low asphaltenes ( ⁇ 0.3 wt%), a very low TAN number ( ⁇ 0.3 mg KOH/mg), no diluent, and is high in VGO range material (30-50% of crude).
- the distillation quality of the crude produced in stream 160 will improve utilization of the highest profit- generating units while filling out the remaining units.
- Table 2 shows the percentage of each boiling range material that comprises a barrel of oil for various representative heavy oil crude streams in comparison to stream 160 of process 10.
- HVGO heavy vacuum gas oil
- LVGO light vacuum gas oil
- AGO atmospheric gas oil
- Another illustration of improved performance is the reduced energy requirement of 3.93 GJ/tonne feed when compared to a delayed coking process that requires an energy input of 4.70 GJ/tonne feed to operate. This is a 16.4% reduction in energy intensity compared to a delayed coking process.
- GSG greenhouse gas
- process 10 When compared to a coking upgrading process and standard reactor and solvent extraction process, process 10 provides a significant improvement in yield by minimizing by-products (Coke and non-condensable hydrocarbons) as noted in Table 3.
- figure 3 shows an illustrative application of the disclosed integrated controlled thermal cracker and improved SDA of this invention to an existing upgrader.
- the proposed integrated process, reactor 30, simplified SDA 50, and asphaltene recovery, 1 10 can be placed upstream of a refiner' s/upgrader's coking unit.
- the benefit to a refiner/upgrader is the ability to debottleneck the vacuum and coking unit and accept more heavy crude to the unit. More barrels processed on existing equipment equates to larger profits and economic returns on invested capital.
- the operating severity can be decreased, increasing the life of the coker by increasing the cycle time for the coker (from 12 to 24 hours), and producing less gas and coke and more product.
- Capital costs to replace equipment can be delayed and an increased yield can be realized (approx. 2-3%).
- the solid asphaltenes captured in the SDA have a readily available disposition, stream 302, the existing coke gathering and transport systems making the addition of the proposed integrated process more cost effective and highly profitable.
- Stream 12 can be the bottoms streams from an atmospheric column, vacuum column, or a catalytic cracking unit, noted as unit 200 in Figure 3.
- the integrated cracker and SDA process produces a DAO stream 52 that can be further processed into transportation fuels of stream 401 in a hydrocracking and hydrotreating complex unit 400.
- the integrated cracker and SDA process also can produce a resin quality stream 54 that can be sent to a coking, FCC (fluidized catalytic cracking) and/or an asphalt plant for further processing into finished products.
- FCC fluidized catalytic cracking
- the solid asphaltenes generated as stream 61 can either be mixed with the coke generated in unit 300 or sent off-site for further processing (energy generation and/or sequestration).
- Figure 4 shows a specific embodiment for a new design or revamp opportunity for a refinery and/or upgrader.
- Unit 200 is a vacuum unit and the bottoms stream 12 is sent to the integrated cracker/SDA process, units 20,30,40,50, 60, and 1 10.
- the DAO stream, 52 is sent to the hydrocracking and hydrotreating unit 400 along with stream 205 from the vacuum unit.
- a resin stream 54 is produced from unit 50, and sent to a residue hydrocracking unit 500. With less asphaltenes, that are highly exothermic when reacted, sent to unit 500, the residue hydrocracker can run at higher conversions (+8-15%) producing more material as final transportation fuel product.
- the solid asphaltene stream 61 from unit 1 10 can be sent to the gasification unit for hydrogen generation.
- the benefits of adding the integrated unit in figure 4 may include: maximum yield of incoming crude to plant debottlenecking, if existing, or reduction of coking unit size; debottlenecking, if existing, or reduction of residue hydrocracking size; debottlenecking, if existing, or reduction of gasification unit size; overall carbon footprint reduced for complex.
- the integrated process in figure 2 can also can help sweet, low complexity (hydro-skimming) refiners take heavier, cheaper crudes which are more readily available, and thus reposition assets to capture more value.
- the integrated process can be placed at the front of the refinery to provide the initial conditioning of the heavier crude.
- novel arrangement and features of the integrated process of the invention may provide an opportunity to operate in a region not previously possible in any specific prior art process thereby creating a technically feasible and economically favourable/superior solution for treating heavy hydrocarbons down to API's of 0.
- DAO volume yields in the 89-91 % range and with solvent losses less than 2% this low complexity integrated process, resulting in low operating and capital costs, creates an economical (based on rates of return) solution to create a pipeline ready and refinery feedstock.
- Table 4 provides a comparison of some representative existing patents with the present invention. The items in bold indicate conditions that directly limit or disadvantage the prior art when compared to process 10. None of the compared technologies achieve the same yields as the illustrated process for heavy hydrocarbon feeds in the 0 to 7 API density range.
- the comparison includes integrated cracker and SDA units, and also SDA only schemes. Since this invention borrows some concepts of a thermal cracker process outlined in US PAT# 7976695 for part of its operation, a comparison to thermal cracker processes is not provided. Of note in Table 4, the unique combination of operating conditions for the thermal cracker allows for a simplification of the SDA that can run with a unique combination of operating conditions and the use of an inertial separator handling strictly asphaltene solids and solvent vapour.
- the SDA unit 50 can accept feeds with an API in the range of -5 to 0 reliably.
- the use of sweep gas (not used in other similar processes), a uniform heat flux (not maintained in other processes), low operating pressures and temperatures allow for mild, favourable reactions to shift heavier hydrocarbons to the light gas oil range suitable for pipeline transport along with the existing hydrocarbons in this range.
- Minimal coke formation, and light gas formation keeps a majority of the hydrocarbons (>90% of crude barrel) as desireable product. Asphaltenes have also been converted from "sticky" molecules to "crunching" molecules.
- the modified asphaltene rich stream at API densities of -7 to 0, can be processed in a simplified SDA process with a novel combination of operating conditions.
- a single extraction step and a low pressure solvent stripper with an inertial solids separator may be all that is needed to obtain the stated high yields.
- the solvent to oil mass ratio can be in the range of 2 to 4 : 1 for preferred solvents in the C6 and C7 range.
- the temperature in the single extraction column is well below critical, as is the pressure. At these low operating conditions, energy use is greatly reduced, and a single low pressure stripper is only needed. There is a lot less physical equipment of less expensive materials and configurations required, making the overall investment cost lower than other concepts.
- the solvent for deasphalting heavy crude needs to be heavy enough (high enough molecular weight) to just precipitate out the necessary asphaltenes while keeping the DAO in solution with the solvent.
- the solvent must be light enough to flash during the transfer of the asphalt extractor bottoms (solid asphaltenes plus solvent) without requiring large quantities of energy.
- the operating temperature has to be cool enough to encourage DAO solubility in the solvent and warm enough so there is enough heat to flash the solvent during transport of the solid asphaltenes. For this process, solid asphaltene precipitation out of solution is mostly insensitive to solvent selection.
- Table 5 provides a comparison of the solvents to be considered when processing heavy viscous hydrocarbons (-7 to 0 API to the SDA).
- C6 and C7 provide a high yield (89-91 %) and with the reduced complexity of the process creates a novel and economically viable process.
- Asphaltene - asphaltenes are the material in crude oil that is (1 ) insoluble in n-pentane (or n-heptane) at a dilution ratio of 40 parts alkane to 1 part crude oil and (2) re-dissolves in toluene.
- Bitumen - shares the attributes of heavy oil but is yet more dense and viscous. Natural bitumen is oil having a viscosity greater than 10,000 cP and an API typically ⁇ 10.
- Canadian Heavy Crudes comprises of both conventional heavy oil and bitumen with API ⁇ 20.
- Deasphalted oil (DAO) Portion of heavy oil that has majority of asphaltenes removed with a boiling range of nominally 500+ °F.
- Heavy oil - is an asphaltic, dense (low API gravity ⁇ 20 API), and viscous oil (limit of 100 cP) that is chemically characterized by its content of asphaltenes (very large molecules incorporating most of the sulfur and perhaps 90 percent of the metals in the oil).
- Light ends - Hydrocarbon that consists of 5 carbon chains and less, typically comprising of pentanes, pentylenes butanes, butylenes, propane, propylene, ethane, ethylene and methane Includes all material found in crude oil and bitumen with Boiling points below 100°F at atmospheric conditions.
- MCR means micro carbon residue.
- Resin- Portion of Heavy Oil that is in the 800+°F boiling range and can contain asphaltenes.
- SDA means “solvent deasphalter” or “solvent deasphalting” and refers typically to a SDA unit, which is a processing apparatus (or step) for solvent deasphalting (removal of asphalt from a process fluid using solvent).
- Syngas - a gaseous mixture primarily comprised of hydrogen, methane, carbon monoxide, and contaminants generated from the destructive distillation of hydrocarbons.
- Topped crude oil - A portion of the crude stream remaining after the removal by distillation or other means of an appreciable quantity of the more volatile components of crude petroleum (eg. Light ends).
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Abstract
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PCT/CA2012/000049 WO2013106897A1 (en) | 2012-01-17 | 2012-01-17 | Low complexity, high yield conversion of heavy hydrocarbons |
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JP (1) | JP6378094B2 (en) |
KR (1) | KR101930580B1 (en) |
CN (1) | CN104114677A (en) |
AU (1) | AU2012366724B2 (en) |
BR (1) | BR112014017582A8 (en) |
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CN106010629A (en) * | 2016-07-16 | 2016-10-12 | 辽宁石油化工大学 | Technology method for deeper cracking and shallow coking of oil sand bitumen |
US11149213B2 (en) * | 2019-12-27 | 2021-10-19 | Saudi Arabian Oil Company | Method to produce light olefins from crude oil |
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US4454023A (en) * | 1983-03-23 | 1984-06-12 | Alberta Oil Sands Technology & Research Authority | Process for upgrading a heavy viscous hydrocarbon |
JPS60130682A (en) * | 1983-12-19 | 1985-07-12 | Toyo Eng Corp | Improved method for treating heavy oil |
US4572781A (en) * | 1984-02-29 | 1986-02-25 | Intevep S.A. | Solvent deasphalting in solid phase |
FR2602783B1 (en) * | 1986-08-12 | 1989-06-02 | Total France | PROCESS FOR DEASPHALTING A HEAVY HYDROCARBON LOAD |
GB8828335D0 (en) * | 1988-12-05 | 1989-01-05 | Shell Int Research | Process for conversion of heavy hydrocarbonaceous feedstock |
CN1167770C (en) * | 2001-09-26 | 2004-09-22 | 石油大学(北京) | Solvent extraction technology for removing high softening point asphalt in petroleum slag and its equipment |
ITMI20022713A1 (en) * | 2002-12-20 | 2004-06-21 | Enitecnologie Spa | PROCEDURE FOR THE CONVERSION OF HEAVY CHARGES SUCH AS |
CN100513520C (en) * | 2005-07-05 | 2009-07-15 | 中国石油大学(北京) | Method for realizing heavy oil deep-step separation by coupled residue granulating |
WO2007117919A2 (en) * | 2006-03-29 | 2007-10-18 | Shell Oil Company | Improved process for producing lower olefins from heavy hydrocarbon feedstock utilizing two vapor/liquid separators |
CA2732919C (en) * | 2010-03-02 | 2018-12-04 | Meg Energy Corp. | Optimal asphaltene conversion and removal for heavy hydrocarbons |
EP2760974B1 (en) * | 2011-09-30 | 2019-02-13 | Meg Energy Corp. | Solvent de-asphalting with cyclonic separation |
SG11201401623SA (en) * | 2011-10-19 | 2014-05-29 | Meg Energy Corp | Enhanced methods for solvent deasphalting of hydrocarbons |
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CN104114677A (en) | 2014-10-22 |
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WO2013106897A1 (en) | 2013-07-25 |
KR20140120313A (en) | 2014-10-13 |
MX2014008571A (en) | 2016-01-29 |
BR112014017582A8 (en) | 2017-07-04 |
BR112014017582A2 (en) | 2017-06-13 |
AU2012366724A1 (en) | 2014-07-24 |
JP6378094B2 (en) | 2018-08-22 |
JP2015507685A (en) | 2015-03-12 |
AU2012366724A8 (en) | 2014-10-23 |
RU2014133552A (en) | 2016-03-10 |
KR101930580B1 (en) | 2018-12-18 |
SG11201404054QA (en) | 2014-08-28 |
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