Solvent De-Asphalting With Cyclonic Separation (MEG Corp.)

CATEGORY: DEASPHALTING
PATENT
Solvent De-Asphalting With Cyclonic Separation (MEG Corp.)
Pub. No.:    WO/2013/044346    International Application No.:    PCT/CA2011/001106
Publication Date:  04.04.2013
Applicants:  MEG ENERGY CORP. [CA/CA]; 11th Floor 520 - 3rd Avenue SW Calgary, AB T2P 0R3 (CA) (For All Designated States Except US).
Inventors: 
BRUCE, Gerald; (CA).
DIDUCH, Greg; (CA).
HOCKING, Damien; (CA).
REMESAT, Darius; (CA)
Abstract: 
The present invention relates to a 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 by-product 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. The process comprises: (a) pre-heating a process fluid in a heater to a designed temperature; (b) moving the pre-heated process fluid to a reactor, and optimally converting asphaltenes in the process fluid within the reactor to produce a stream of thermally affected asphaltene-nch fraction( s), and a stream of non-condensible vapour and lighter liquid hydrocarbon(s); (c) deasphalting the thermally affected asphaltene-nch stream with a solvent extraction process into a stream of heavy deasphalted oil (DAO) and a second stream containing concentrated asphaltene; (d) separating dry thermally affected asphaltene solids from the second stream in a separation unit, recovering the process solvent; (e) a produced refinery feedstock comprising at least one of the produced streams.
Description
The present invention relates to a 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 by-product 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.
BACKGROUND OF THE INVENTION
Refining sweet crude resources require less capital input and have a much lower cost of processing than heavy sour crudes. However, the global availability of light, sweet crude to supply to refineries for the production of transportation fuels is on the decline making the processing of heavy sour crude an increasingly important option to meet the world's demand for hydrocarbon-based fuels.
Most (if not all) commercial upgraders for processing heavy crude have been built to convert heavy viscous hydrocarbons into crude products that range from light sweet to medium sour blends. Heavy oil upgraders basically achieve this by high intensity conversion processes which either release up to 20% by weight of the feedstock as a coke byproduct and another 5% as off-gas product, or require hydro-processing such as hydrocracking and hydro-treating to maximize the conversion of the heavy components in the feedstock to lighter, lower sulfur liquid products and gas.
Description of Prior Art
Processes have been disclosed to convert and/or condition Oil Sands bitumen into pipeline transportable and refinery acceptable crude. Of note, thermal cracking, catalytic cracking, solvent deasphalting and combinations of all three (for example, visbreaking and solvent deasphalting) have been proposed to convert bitumen to improve its characteristics for transport and use as a refinery feedstock.
Thermal Cracking
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 19).
There are two basic visbreaking configurations, the coil-only visbreaker and the coil-and-soak visbreaker. Both require heaters to heat the crude, with the coil-only style employing cracking only in the heater tubes. 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. In the coil-and-soak visbreaker, 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.
Examples of such visbreaking methods are described in Beuther et al., "Thermal Visbreaking of Heavy Residues", The Oil and Gas Journal. 57:46, Nov 9, 1959, pp. 151-157; Rhoe et al., " Visbreaking: A Flexible Process", Hydrocarbon Processing, January 1979, pp. 131 -136; and US Pat. No. 4,233, 138. The yield structure is approximately same for either configuration: 1-3% light ends, 5%(wt) naphtha and 15%(vt) gas oil. The remainder remains as heavy oil or bitumen. The products are separated in a distillation column for further processing or blending.
A concern with standard visbreaking schemes is that for Canadian Bitumen, the operating temperatures are above the limit (around 700°F-720°F) where significant coking impacts operability (Golden and Bartletta, Designing Vacuum Units (for Canadian heavy crudes), Petroleum Technology Quarterly, Q2, 2006, pp. 105). In addition, heat is added over a short period of time in the heater, so local heat fluxes are not uniform and can peak well above coking initiation limits; and the heat is not maintained consistently allowing for condensation reactions to occur. Attempting to apply conventional visbreaking to Canadian Bitumen is limited due to the propensity for coking and inability of these systems to manage this issue.
In the first part of US Pat. No. 6,972,085 and in patent application US2008/0093259 an attempt is made to address the desire for a constant and sustained application of heat to the crude over an extended period of time. Essentially, the heater and the holding vessel are merged into one vessel to create a continuous heated bath for the crude. Multiple heating levels are applied to the crude at various times. This is an improvement over standard visbreaking but does not eliminate hot spots within the processed crude, permitting coking due to temperature peaks above optimal levels for cracking.
Combination of Thermal/Catalytic Cracking and Solvent Deasphalting
In 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. The U.S. Ό23 patent provides a means for upgrading lighter hydrocarbons (API gravity> 15) than Canadian Bitumen but is burdened by the misapplication of the thermal cracking technology that will over-crack and coke the hydrocarbon stream, and by the complexity and cost of a two-stage solvent deasphalting system to separate the resin fraction from the deasphalted oil. In addition, the need to recycle part of the resin stream increases the operating costs and complexity of operation.
In U.S. Pat. No. 4,191 ,636, heavy oil is continuously converted into asphaltenes and metal-free oil by hydrotreating the heavy oil to crack asphaltenes selectively and remove heavy metals such as nickel and vanadium simultaneously. The liquid products are separated into a light fraction of an asphaltene-free and metal-free oil and a heavy fraction of an asphaltene- and heavy metal-containing oil. The light fraction is recovered as a product and the heavy fraction is recycled to the hydrotreating step. Catalytic conversion of Canadian heavy bitumen (API gravity<10) using this '636 process is a high-intensity process that tends to have reliability issues with rapid catalyst deactivation impacting selectivity and yield.
In U.S. Pat. No. 4,428,824, a solvent deasphalting unit is installed upstream of a visbreaking unit to remove the asphaltenes from the visbreaking operation. In this configuration, 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. However, the yield of the bitumen is greatly reduced (by 10-15%) since the early removal of the asphaltenes in the process prevents thermal conversion of this portion of the crude into a refinable product.
As in 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. 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.
In 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. However, PAT Ό28 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.
In U.S. Pat. No. 5,601,697 a process is disclosed 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.
In U.S. Pat. 6,533,925, a process is described involving the integration of a solvent deasphalting process with a gasification process and an improved process for separating a resin phase from a solvent solution comprising a solvent, deasphalted oil (DAO) and resin. A resin extractor with the solvent elevated in temperature above that of the first asphaltene extractor is included in the '925 invention. The asphaltene stream is treated but removed prior to any thermal conversion eliminating the possibility of
obtaining a value uplift into useable refinery feedstock. The impact is a reduction in the potential overall yield of the crude stream.
In 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. As stated with Pat' 023 above, visbreaking faces the challenges of early coke generation. Specifically, 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. In addition, additional energy is required in the distillation steps with most of the separated components being recombined for pipeline transport.
Treatment of SDA generated Asphaltene-Rich Stream
In US Patent# 4,421 ,639 a solvent deasphalting process uses a 2nd asphalt extractor to concentrate asphaltene material (and recovery of more deasphalted oil). The concentrated asphalt stream is sent through a heater to get to 425oF at 18 psia and uses a flash drum and stream stripper to separate solvent (in this case propane) from the asphalt stream. 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.
In US Patent# 3,847,751 , 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.
In US Patent# 4,278,529, a process for separating a solvent from a bituminous material by pressure reduction without carry-over of bituminous material is illustrated. The fluid-like phase comprising bituminous material and solvent is reduced in pressure by passage through a pressure reduction valve and introduced into a steam stripper. The pressure reduction vaporizes part of the solvent and also disperses a mist of fine bituminous particles in the solvent. The concern with this approach is that the remaining asphaltene remains wet and sticky and has not enough solvent left to keep the heavy bituminous phase (with many solids) flowable.
In US PAT# 4,572,781 a solvent deasphalting process for separating substantially dry asphaltenes of high softening point from heavy hydrocarbon material using a centrifugal decanter to separate a liquid phase from a highly concentrated slurry of solid asphaltenes is described. This process attempts to handle a rich asphaltene stream that has solid particles but is a highly costly process since the separation of the solids is done through a solid/liquid separation with additional solvent needed to make the material flow to the decanter. Invariably, the separated solid material is still relatively wet and needs another drying step to recover the solvent as a vapour. The solvent vapour needs to be condensed for re-use, another high energy step.
In US Patent# 7,597,794, a dispersion solvent is introduced into the asphalt phase after separation by solvent extraction and the asphalt phase undergoes rapid phase change in a gas-solid separator and is dispersed into solid particles while the solvent vaporizes, resulting in low temperature separation of asphalt and solvent with adjustable size of the asphalt particles. The challenge with flash/spray driers using liquid solvent as the transport media is the propensity for the asphaltenes generated in this integrated process to remain wetted before, during and after the flash drying phase. In addition, with this integrated process, the asphaltene continues to liquefy at elevated temperatures. A wetted asphaltene sticks to all surfaces and fouls and plugs the equipment readily. The reduced reliability from using this approach makes this operation costly for heavy crudes with high asphaltenic content.
In US Patent# 7,964,090 a method for upgrading heavy asphaltenic crudes using SDA and gasification is shared. Of interest in this patent, 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, 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.
SUMMARY OF THE INVENTION
It is to be understood that other aspects of the present invention will become readily apparent to those skilled in the art from the following detailed description, wherein various embodiments of the invention are shown and described by way of illustration. As will be realized, the invention is capable for other and different embodiments and its several details are capable of modification in various other respects, all without departing from the spirit and scope of the present invention. Accordingly the drawings and detailed description are to be regarded as illustrative in nature and not as restrictive.
Essentially, an improved process for producing a pipeline-ready crude and refinery feedstock from heavy crude oils, such as Canadian Oil Sands bitumen, 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).
Considering the relative complexity and high degree of side chains on the Canadian bitumen asphaltenes, under the operating conditions of the invention disclosed here, the side chains are preferentially cleaved from the core asphaltene molecule to make desired vacuum gas oil to light hydrocarbon range components. The remaining 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 vapour-solid separation like inertial separation (1 10).
Further, the heavier hydrocarbons in the bitumen are 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 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. 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 deasphalted, using a 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 a vapour-solid separation unit (e.g. inertial) 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; similarly, the sweep gas assists in the removal of reactor vapour products.
Deasphalting can be achieved using an open-art solvent extraction process; since the initial process fluid has been separated so that only the heavy asphaltene-rich fractions require deasphalting, extraction processes using high solvent-to-oil ratios are feasible and economical. Improved solvent-extraction performance, using lower 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 a vapour-solid separator such as a centrifugal collector, settling chamber or inertial separator to generate a dry, solid asphaltene by-product.
In one embodiment this invention provides an improved process for producing enhanced refinery feedstock and dry thermally-affected asphaltene solids from heavy hydrocarbon, said process comprising:
(a) Pre-heating the heavy hydrocarbon as a process fluid in a heater to a designed temperature;
(b) Moving the pre-heated process fluid to a reactor, and optimally converting asphaltenes in the process fluid within the reactor to produce a stream of thermally affected asphaltene-rich fraction(s), and a stream of non- condensable vapour and lighter liquid hydrocarbon(s);
(c) Deasphalting the thermally affected asphaltene-rich stream with a solvent extraction process into a stream of heavy deasphalted oil (DAO) and a second stream containing concentrated asphaltene;
(d) Separating dry thermally-affected asphaltene solids from the second stream in a separation unit, recovering the process solvent;
(e) the refinery feedstock comprising of at least one of the produced streams.
In another embodiment the invention provides a continuous process where the reactor is a single thermal conversion reactor with an overhead partial condenser operating within the following parameters:
(a) A uniform heat flux of between 7000-12000 BTU/hr sqft introduced to the process fluid within the reactor;
(b) A sweep gas of between 20-80 scf/bbl (gas/process fluid) is introduced within the reactor;
(c) Residence time of the process fluid within the reactor of between 40-180 minutes;
(d) A substantially uniform operating temperature of between 675-775 °F in the reactor;
(e) A near atmospheric operating pressure of <50 psig in the reactor.
In a further embodiment, the refinery feedstock comprises a blend of at least two of the produced streams to be pipeline ready, having an API of greater than 19 degrees gravity, and a viscosity less than 350 Cst at 8°C; one or more of the produced streams is treated to remove olefins.
In yet another embodiment, the refinery feedstock comprises one or more of the produced streams, suitable for diverse refinery types by virtue of its proportion of vacuum residue.
The invention further provides a process where the integrated process is applied to an existing coker-based bitumen upgrader or refinery by accepting as feedstock the upgrader's or refinery's virgin or processed heavy hydrocarbon streams and providing light liquid hydrocarbon, and heavy deasphalted hydrocarbon process streams to the upgrader or refinery.
In a further embodiment, the integrated process is applied to an existing residue hydrocracking upgrader or refinery by accepting as feedstock the upgrader's or refinery's virgin or processed heavy hydrocarbon streams and providing light liquid hydrocarbon, and heavy deasphalted hydrocarbon process stream to the upgrader or refinery.
In yet a further embodiment, the integrated process is applied to a new bitumen Upgrader, new "sweet crude" refinery or an existing "sweet crude" refinery in lieu of a coking process by accepting as feedstock the upgrader's or refinery's virgin or processed heavy hydrocarbon streams and providing light liquid hydrocarbon, and heavy deasphalted hydrocarbon process streams to the upgrader or refinery.
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