CA2446889A1 - A method for converting a liquid feed material into a vapor phase product - Google Patents
A method for converting a liquid feed material into a vapor phase product Download PDFInfo
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- CA2446889A1 CA2446889A1 CA002446889A CA2446889A CA2446889A1 CA 2446889 A1 CA2446889 A1 CA 2446889A1 CA 002446889 A CA002446889 A CA 002446889A CA 2446889 A CA2446889 A CA 2446889A CA 2446889 A1 CA2446889 A1 CA 2446889A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1818—Feeding of the fluidising gas
- B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/36—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed through which there is an essentially horizontal flow of particles
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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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
- C10G9/32—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material according to the "fluidised-bed" technique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01B—BOILING; BOILING APPARATUS ; EVAPORATION; EVAPORATION APPARATUS
- B01B1/00—Boiling; Boiling apparatus for physical or chemical purposes ; Evaporation in general
- B01B1/005—Evaporation for physical or chemical purposes; Evaporation apparatus therefor, e.g. evaporation of liquids for gas phase reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00823—Mixing elements
- B01J2208/00858—Moving elements
- B01J2208/00867—Moving elements inside the bed, e.g. rotary mixer
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- General Chemical & Material Sciences (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
A liquid feed material such as a heavy hydrocarbon feed in liquid form is contacted with a fluidized bed of heated solid particles which have a bulk horizontal velocity which is generally perpendicular to the flow of a fluidizing medium. The liquid feed material reacts on the solid particles to produce a vapor phase product, which vapor phase product is collected in a vapor collection apparatus.
Description
A METHOD FOR CONVERTING A LIQUID FEED MATERIAL INTO A VAPOR PHASE
PRODUCT
FIELD OF INVENTION
A method for converting a liquid feed material into a vapor phase product using a cross-flow fluid bed.
BACKGROUND OF THE INVENTION
A number of processes for upgrading heavy hydrocarbons involve spraying a liquid feed onto a fluid bed. Fluid beds are well suited for providing the heat and mass transfer requirements associated with the thermal cracking reactions of the upgrading process. At lower gas velocities, the fluidized bed will have a free surface. In this operating regime the bed exhibits fluid behavior. As the gas velocity is increased, the fast fluidization or dilute phase transport regime is approached and the particles become entrained in the gas. In this regime, there is no identifiable free surface.
Examples of fluid bed processes which have been used for the upgrading of heavy hydrocarbons include riser coking, fluid coking and LR coking. All of these processes are directed at leveraging the inherent advantages of a fluid bed reactor, including but not limited to heat and mass transfer, to create a process that maximizes the value of the products created from a heavy hydrocarbon feedstock. Some of these technologies operate in the fast fluidization or dilute transport regime, while others make use of a low velocity bed of fluidized solids which has a free surface.
In general, with any heavy hydrocarbon upgrading process, one goal is to promote conditions that allow molecules contained in the feed to react to the point of becoming a valuable product then stop reacting. Ideally, the resulting products of the primary cracking reaction are withdrawn and quenched before any subsequent reactions can take place. A
second is to provide all molecules contained in the feed sufficient time at reactor conditions so that they can react fully and all of the potential product has escaped into the vapor phase of the reactor. All designs require a compromise between these two goals.
For processes in which liquid hydrocarbon is sprayed onto hot fluid bed particles that provide the heat for reaction the ideal sequence of events would be as follows:
1. a liquid feed droplet comes into contact with a solid fluid bed particle;
PRODUCT
FIELD OF INVENTION
A method for converting a liquid feed material into a vapor phase product using a cross-flow fluid bed.
BACKGROUND OF THE INVENTION
A number of processes for upgrading heavy hydrocarbons involve spraying a liquid feed onto a fluid bed. Fluid beds are well suited for providing the heat and mass transfer requirements associated with the thermal cracking reactions of the upgrading process. At lower gas velocities, the fluidized bed will have a free surface. In this operating regime the bed exhibits fluid behavior. As the gas velocity is increased, the fast fluidization or dilute phase transport regime is approached and the particles become entrained in the gas. In this regime, there is no identifiable free surface.
Examples of fluid bed processes which have been used for the upgrading of heavy hydrocarbons include riser coking, fluid coking and LR coking. All of these processes are directed at leveraging the inherent advantages of a fluid bed reactor, including but not limited to heat and mass transfer, to create a process that maximizes the value of the products created from a heavy hydrocarbon feedstock. Some of these technologies operate in the fast fluidization or dilute transport regime, while others make use of a low velocity bed of fluidized solids which has a free surface.
In general, with any heavy hydrocarbon upgrading process, one goal is to promote conditions that allow molecules contained in the feed to react to the point of becoming a valuable product then stop reacting. Ideally, the resulting products of the primary cracking reaction are withdrawn and quenched before any subsequent reactions can take place. A
second is to provide all molecules contained in the feed sufficient time at reactor conditions so that they can react fully and all of the potential product has escaped into the vapor phase of the reactor. All designs require a compromise between these two goals.
For processes in which liquid hydrocarbon is sprayed onto hot fluid bed particles that provide the heat for reaction the ideal sequence of events would be as follows:
1. a liquid feed droplet comes into contact with a solid fluid bed particle;
2. molecules in the feed droplet begin to thermally crack;
3. products of the thermal cracking reaction that evolve as vapor from the surface of the heat carrier (i.e., the fluid bed particles), are swept away by the fluidizing gas, and are quenched before subsequent reactions can take place; and 4. the residual liquid remaining on the heat carners from which no product can be derived is provided a residence time equal to that required to form dry solid.
Failure to cater to item four Leads to operational difficulties related to the stickiness imparted by the residual reactant hydrocarbon. The current art for spraying a heavy liquid hydrocarbon onto a fluid bed represent attempts at achieving this idealized mode of operation that have not been entirely successful.
A schematic depicting a Fluid Coking reactor is shown in Figure 1. Fluid Coking is a low-velocity fluid bed process where hot solids enter the reactor in the freeboard region above the surface of the fluid bed, near the top of the reactor. Feed is injected into the fluid bed at several different elevations. Solids are generally well mixed within this feed zone. >3efore exiting the reactor, the solids pass through a stripping zone that is designed to recover unreacted liquid from the heat carriers. The stripping zone is designed to produce a solids residence time distribution (RTD) that is closer to plug flow. The additional residence time provided to the solids in the stripping section, together with stripping steam, allows the recovery of additional product from the surface of the fluidized particles. Solids exit the reactor after passing through this stripping zone. The solids RTD of the Fluid Coking process in the feed zone, which is well mixed, has an important impact on achieving the two primary goals of the process as set out above.
_2_ With a solid's RTD approaching that of a continuous stirred tank reactor (CSTR), it is necessary to tailor the designed solids holdup (as it relates to minimizing the loss of unconverted feed and production of "dry" solid particles) to the portion of solids that exit the reactor first. As a result, a fraction of the solid particles remain at reactor conditions much longer than is necessary to achieve the goals of the process. Solids with a plug flow residence time distribution would be less affected by this.
Practical considerations associated with the design of fluid coking reactors require that significant bed depth be used in combination with increasing vessel diameter to provide the design solids holdup. Due to the increased bed height required to meet the solids holdup requirement, the vapor phase residence time is increased which may cause product vapors to react further, contrary to the first goal of the process It is noted that although the stripping zone of the Fluid Coking reactor attempts to create a plug flow condition for the solids, there is a requirement that the solid particles enter the stripping zone of the reactor with little unconverted feed present. Failure to meet this condition results in fouling of the stripper internals by the wet solids and circulation of solid particles is impaired. The stripping zone therefore does little to mitigate the need for a Fluid Coking reactor to be designed with an average solids holdup that is much greater than what would be required if solid particles flowed through the entire reactor under plug flow conditions.
It is also noted that for all intents and purposes of this application, a Flexi-Coking reactor differs little from a Fluid Coking reactor.
A schematic depicting riser, or transfer line coking is given in Figure 2. The fluid bed for these processes is typically characterized as fast-fluidization or dilute phase transport.
The solid carrier is contacted with feed at one end of the riser or pipe and transported to the opposite end of the pipe at a speed equal to the speed of the gas phase less the slip velocity between the solid and gas phases. Vapor and solid phase RTDs are closely linked in this type of reactor. Short vapor phase residence times can be achieved but because of the link between _3_ .. CA 02446889 2003-10-27 solids and gas phase RTDs, the time required to ensure the feed has completely reacted is compromised.
A schematic depicting an LR coking reactor is given in Figure 3. In LR Coking, the force required to counter gravity and fluidize the solid particles is imparted mechanically through rotation of the auger-like internal of the reactor. The solids RTI~
approaches plug flow and the absolute vapor phase residence time is relatively short. High capital costs, and limited throughput relative to other fluid bed processes, have practical design implications that limit the ratio of solids to feed that may be attained using LR coking processes. In LR
coking processes, as in other fluid bed processes, reactor temperatures must typically be higher since the solids-to-oil ratios are lower. As a result, the high reactor temperatures of an LR
coking reactor relative to other fluid bed processes and the high capital costs associated with LR coking processes offset the benefits of the relatively short absolute vapor phase residence times.
The present invention is directed at a method for converting a liquid feed material into a vapor phase product using a cross-flow fluidized bed. The present invention is also directed at an apparatus comprising a cross flow fluid bed reactor.
The liquid feed material may be any suitable material. In a preferred embodiment, the liquid feed material is comprised of a heavy liquid hydrocarbon. The vapor phase product may be comprised of a single product, or substance, or may be comprised of a plurality of products or substances. The term "vapor phase product" as used herein means that the product is or behaves as a vapor phase under the conditions of the conversion method, although the product may ultimately be condensable to a liquid phase or even a solid phase.
In one aspect the invention is a method for converting a liquid feed material into a vapor phase product comprising the following steps:
_q._ (a) providing a fluid bed comprising solid particles and a fluidizing medium, wherein the fluidizing medium is moving in a substantially vertical fluidizing direction;
(b) moving the solid particles in a substantially horizontal solid transport direction;
(c) contacting the liquid feed material with the solid particles in order to convert the liquid feed material into the vapor phase product;
(d) collecting the vapor phase product in a vapor collection apparatus; and {e) collecting the solid particles in a solid collection apparatus.
In a second preferred aspect of the invention, a fluidizing medium such as a gas is introduced into a reactor to fluidize a bed of solid particles such that the fluidizing medium is moving in a substantially vertical fluidizing direction. The solid particles are transported substantially horizontally in a solid transport direction from a solids inlet at one end of the reactor to a solids outlet at the opposite end of the reactor, preferably but not necessarily by the force of gravity. As the solid particles move through the reactor they are contacted by a liquid feed material comprising a liquid hydrocarbon. The solid particles are at a temperature which facilitates the reaction of the liquid hydrocarbon to produce one or more upgraded hydrocarbon products as a vapor phase product. The vapor phase product is collected in a vapor collection apparatus, preferably with the fluidizing medium. The solid particles are collected in a solid collection apparatus and are preferably regenerated for re-use.
The selection and design of the solid particles, vapor collection system, freeboard and fluidizing mechanism may be made so that vapor phase residence time is short relative to competing technologies and so that the residence time distribution of the solid particles approaches plug flow conditions despite significant evolution of product within the fluid bed.
The invention permits relatively high ratios of solids to liquid feed, which aids in achieving lower reactor temperatures.
Failure to cater to item four Leads to operational difficulties related to the stickiness imparted by the residual reactant hydrocarbon. The current art for spraying a heavy liquid hydrocarbon onto a fluid bed represent attempts at achieving this idealized mode of operation that have not been entirely successful.
A schematic depicting a Fluid Coking reactor is shown in Figure 1. Fluid Coking is a low-velocity fluid bed process where hot solids enter the reactor in the freeboard region above the surface of the fluid bed, near the top of the reactor. Feed is injected into the fluid bed at several different elevations. Solids are generally well mixed within this feed zone. >3efore exiting the reactor, the solids pass through a stripping zone that is designed to recover unreacted liquid from the heat carriers. The stripping zone is designed to produce a solids residence time distribution (RTD) that is closer to plug flow. The additional residence time provided to the solids in the stripping section, together with stripping steam, allows the recovery of additional product from the surface of the fluidized particles. Solids exit the reactor after passing through this stripping zone. The solids RTD of the Fluid Coking process in the feed zone, which is well mixed, has an important impact on achieving the two primary goals of the process as set out above.
_2_ With a solid's RTD approaching that of a continuous stirred tank reactor (CSTR), it is necessary to tailor the designed solids holdup (as it relates to minimizing the loss of unconverted feed and production of "dry" solid particles) to the portion of solids that exit the reactor first. As a result, a fraction of the solid particles remain at reactor conditions much longer than is necessary to achieve the goals of the process. Solids with a plug flow residence time distribution would be less affected by this.
Practical considerations associated with the design of fluid coking reactors require that significant bed depth be used in combination with increasing vessel diameter to provide the design solids holdup. Due to the increased bed height required to meet the solids holdup requirement, the vapor phase residence time is increased which may cause product vapors to react further, contrary to the first goal of the process It is noted that although the stripping zone of the Fluid Coking reactor attempts to create a plug flow condition for the solids, there is a requirement that the solid particles enter the stripping zone of the reactor with little unconverted feed present. Failure to meet this condition results in fouling of the stripper internals by the wet solids and circulation of solid particles is impaired. The stripping zone therefore does little to mitigate the need for a Fluid Coking reactor to be designed with an average solids holdup that is much greater than what would be required if solid particles flowed through the entire reactor under plug flow conditions.
It is also noted that for all intents and purposes of this application, a Flexi-Coking reactor differs little from a Fluid Coking reactor.
A schematic depicting riser, or transfer line coking is given in Figure 2. The fluid bed for these processes is typically characterized as fast-fluidization or dilute phase transport.
The solid carrier is contacted with feed at one end of the riser or pipe and transported to the opposite end of the pipe at a speed equal to the speed of the gas phase less the slip velocity between the solid and gas phases. Vapor and solid phase RTDs are closely linked in this type of reactor. Short vapor phase residence times can be achieved but because of the link between _3_ .. CA 02446889 2003-10-27 solids and gas phase RTDs, the time required to ensure the feed has completely reacted is compromised.
A schematic depicting an LR coking reactor is given in Figure 3. In LR Coking, the force required to counter gravity and fluidize the solid particles is imparted mechanically through rotation of the auger-like internal of the reactor. The solids RTI~
approaches plug flow and the absolute vapor phase residence time is relatively short. High capital costs, and limited throughput relative to other fluid bed processes, have practical design implications that limit the ratio of solids to feed that may be attained using LR coking processes. In LR
coking processes, as in other fluid bed processes, reactor temperatures must typically be higher since the solids-to-oil ratios are lower. As a result, the high reactor temperatures of an LR
coking reactor relative to other fluid bed processes and the high capital costs associated with LR coking processes offset the benefits of the relatively short absolute vapor phase residence times.
The present invention is directed at a method for converting a liquid feed material into a vapor phase product using a cross-flow fluidized bed. The present invention is also directed at an apparatus comprising a cross flow fluid bed reactor.
The liquid feed material may be any suitable material. In a preferred embodiment, the liquid feed material is comprised of a heavy liquid hydrocarbon. The vapor phase product may be comprised of a single product, or substance, or may be comprised of a plurality of products or substances. The term "vapor phase product" as used herein means that the product is or behaves as a vapor phase under the conditions of the conversion method, although the product may ultimately be condensable to a liquid phase or even a solid phase.
In one aspect the invention is a method for converting a liquid feed material into a vapor phase product comprising the following steps:
_q._ (a) providing a fluid bed comprising solid particles and a fluidizing medium, wherein the fluidizing medium is moving in a substantially vertical fluidizing direction;
(b) moving the solid particles in a substantially horizontal solid transport direction;
(c) contacting the liquid feed material with the solid particles in order to convert the liquid feed material into the vapor phase product;
(d) collecting the vapor phase product in a vapor collection apparatus; and {e) collecting the solid particles in a solid collection apparatus.
In a second preferred aspect of the invention, a fluidizing medium such as a gas is introduced into a reactor to fluidize a bed of solid particles such that the fluidizing medium is moving in a substantially vertical fluidizing direction. The solid particles are transported substantially horizontally in a solid transport direction from a solids inlet at one end of the reactor to a solids outlet at the opposite end of the reactor, preferably but not necessarily by the force of gravity. As the solid particles move through the reactor they are contacted by a liquid feed material comprising a liquid hydrocarbon. The solid particles are at a temperature which facilitates the reaction of the liquid hydrocarbon to produce one or more upgraded hydrocarbon products as a vapor phase product. The vapor phase product is collected in a vapor collection apparatus, preferably with the fluidizing medium. The solid particles are collected in a solid collection apparatus and are preferably regenerated for re-use.
The selection and design of the solid particles, vapor collection system, freeboard and fluidizing mechanism may be made so that vapor phase residence time is short relative to competing technologies and so that the residence time distribution of the solid particles approaches plug flow conditions despite significant evolution of product within the fluid bed.
The invention permits relatively high ratios of solids to liquid feed, which aids in achieving lower reactor temperatures.
For example, whereas there are significant constraints on the flow of solid particles a single LR coking reactor can process, arid whereas significant costs associated with LR coking require that the process adopt relatively low solids-to-oil ratios, the amount of solid particles a cross flow coking reactor can process is virtually limitless. This feature allows the S invention to employ higher solids-to-oil ratios than may be employed with some competing processes, such as the LR coking processes.
Furthermore, whereas the LR coking process is forced to adopt a relatively high operating temperature to compensate for low solids-to-oil ratios, no similar requirement exists for the current invention. In the practice of the invention a relatively high solids-to-oil ratio is used with feed and product recovery zones that are staged such that solid particle residence times may be tightly controlled.
BRIEF DESCRIPTION OF DRAWINGS
Embodiments of the invention will now be described with reference to the accompanying drawings, in which:
Figure 1 is a schematic drawing of a Fluid Coking reactor;
Figure 2 is a schematic drawing of a riser, or transfer line coking reactor;
Figure 3 is a schematic drawing of an LR coking reactor;
Figure 4 is a schematic drawing of a cross-flow reactor according to a preferred embodiment of the present invention;
Figure 5 is an alternate schematic drawing of a cross-flow reactor according to a preferred embodiment of the present invention depicting spraying of the liquid feed material within the fluid bed.
DETAILED DESCRIPTION OF THE INVENTION
In general, the present invention relates to a method or process for converting a liquid feed material into a vapor phase product. In a preferred embodiment, the present invention relates to a method for converting a heavy hydrocarbon feedstock material into value added reaction products. The method or process of the invention is herein referred to as "cross flow conversion" process or "XFC" process.
The central process unit in the XFC design is a cross-flow fluidized bed reactor.
As in most fluidized bed processes, a fiuidizing medium, preferably a gas, is introduced into the bottom of the reactor base and exits at the top of the reactor so that the fluidizing medium moves in a substantially vertical fluidizing direction.
A significant difference between the XFC design and a conventional fluid bed process is that the solid particles in the fluid bed move substantially perpendicularly to the gas phase in the fluid bed. Solid particles enter at one end, flow along the length of the reactor under the influence of gravity, and are removed at the opposite end. Since the solids and gas flows are generated by independent driving forces, the two are essentially independent.
This provides for a significant increase in flexibility, which will be discussed in detail in the description that follows.
This description teaches a method for designing an XFC reactor to produce a solid particle RTD that approaches plug flow, allowing for evolution of a vapor phase product within the fluid bed. This is an important feature of the present invention. Eenefits accruing from this solid particle RTD together with those inherent in the type of fluidized bed reactor proposed can be leveraged by a person skilled in the art to provide significant advantages over the current art.
For example, it is well understood by those individuals skilled in the art how to manipulate operating and design conditions such as increased solids-to-feed ratios and the ability to deliver feed in a more controlled and uniform fashion to enhance operability and yield at typical reaction temperatures. The hydrodynamics of the XFC reactor have been studied with cold flow physical models, using dimensional analysis to establish a tie to typical process operating conditions.
1. XFC Reactor Vessel The XFC reactor is divided into a number of zones, each having a different function:
1. Solid feed zone 2. Liquid feed zone 3. Reaction zone 4. Solid withdrawal zone 5. Gas distribution zone 6. Freeboard zone Figure 4 and Figure 5 both depict a schematic which demonstrates the different zones of the XFC reactor.
The length of the reactor vessel is typically greater than its width. This design feature ensures the solids are well mixed across the width of the vessel, and helps to maintain plug flow characteristics in the moving solid phase. The impact of plug flow on the characteristics of the process is described below.
Gas is introduced as a fluidizing medium through a distributor located on the bottom of the reactor vessel. The gas distributor can vary in complexity.
Bubble cap and perforated plate designs have been tested, but any design capable of adequately fluidizing the solids is acceptable. The fluidization gas, along with any product vapor generated by the xeaction, will typically exit at the top of the reactor vessel.
_g_ p CA 02446889 2003-10-27 The height of the reactor vessel is designed to accommodate both the fluidized bed contained in the vessel and the height required for solids disengagement in the freeboard region (see below).
To provide effective contact between liquid feed and solid heat earner and to take advantage of high solids-to-feed ratios it will generally make sense to provide an amount of solid particles substantially in excess of what is required for the given feed zone.
By staging several of the units depicted in Figure 4 in series, the bulk of the solid particles will be contacted in a more uniform fashion. To increase capacity, the width of the reactor can be increased, an option not available in many commercial configurations.
2. Solids Particle Characteristics The solid particles in the XFC reactor provide the surface area upon which the conversion reaction occurs. In addition, the solid particles provide a heat source or sink for the reaction, depending upon whether the reaction is endothermic or exothermic.
They may also possess catalytic activity, although this is not a requirement. The most critical attribute is that the particles fluidize well. Based on the Geldart classification (Kunni D. and Levenspiel, O.
Fluidization Engineering Zed. Butterworth-Heinemann 1991), only the following two types of particles are suitable for the XFC reactor:
1. Geldart A type particle: Aeratable particles or materials having small mean particles size (<40 microns) or low particle density (<1400 kg/m3). Fluidized Cracking Catalyst is an example of particles of this type.
2. Geldart B type particles: Most particles of size 40 microns to 500 microns and density 1400 kg/m3 to 4000 kg/m3. Sand is an example of this type of particle.
These two particle types characterize the typical particles used in industrial fluidized beds. When fluidized, they provide the positive characteristics that are most often associated with fluidized bed reactors: uniform temperature, high rates of heat and mass transfer, and high specific surface area. In addition, Geldart A and B particles will be fluid enough to allow for smooth horizontal flow.
All remaining particles fall into either the Geldart C (cohesive powders) or Geldart D (large coarse particles) classifications and are not typically suitable for use in the XFC
process unless they make up a relatively small fraction (<10%) of the particles, with the majority being either Geldart A or Geldart B.
The other factors to consider when choosing the solid particle material are the heat storage and transfer characteristics, attrition rates and cost.
3. Bed Characteristics The fluidized bed will preferably be operated in the bubbling bed regime or, in the case of Geldart A particles, may be operated in the smooth fluidization regime below the bubbling fluidization velocity but above the minimum fluidization velocity.
In the bubbling bed regime the fluidized bed resembles a boiling liquid with bubbles forming at the gas distributor, rising through the bed quickly then bursting at the surface of the bed. For descriptive purposes the fluid bed can be thought to have two phasesn 1. Emulsion phase containing both solids and gas 2. Bubble phase containing primarily only gas Gas exits the bed almost exclusively in the bubbles. Gas in the emulsion phase must therefore first enter the bubbles in order to exit the fluid bed. The transfer of gas between the bubbles and the emulsion can occur by diffusion in the bed, or by mixing in the turbulent region in the vicinity of the gas distributor.
4. Freeboard Region The freeboard is the solids lean region of the reactor vessel above the surface of the fluidized bed. Solids are ejected from the fluidized bed by the action of bubbles bursting at its surface. The freeboard region is required for the solid particles to disengage from the gas so that they are not carried out of the reactor vessel.
The optimum freeboard height is that which allows all of the solid particles with terminal velocities less than the superficial gas velocity to disengage.
Extending the freeboard above this height will not reduce the solids carryover and will only add to the cost of the vessel and to the residence time of the gas.
Even for a very large freeboard region, solid particles will be earned out of the reactor because they have been entrained in the gas or because of large eruptions of bubbles at the surface of the bed which can potentially eject solids to the roof of the reactor vessel. If the downstream gas processing units can not tolerate the presence of solids then a unit must be installed to separate the solids from the gas stream. Proven technologies, such as cyclones, will be sufficient for this purpose.
Reducing the height of the freeboard region will reduce the residence time of the gas phase, which will in turn limit the severity of the gas phase reactions.
However, inadequate height of the freeboard region can result in an excessive amount of solids carryover, requiring larger solids handling units outside the reactor to separate the solids from the gas.
The optimum freeboard height will be dependent on the type of particles, the fluidization velocity and the effects of the feed on the cohesive forces between particles. The residence time distribution of the gas in this zone has been shown to be substantially plug flow.
5. Fluidization Velocity The solid particles are fluidized by the gas that enters through the gas distributor at the base of the vessel. The velocity of the fluidizing gas can be between the minimum fluidization velocity and the turbulent fluidization velocity of the solids.
If the gas velocity is below the minimum fluidization velocity of the particles, then the bed will not fluidize and the solids will not flow across the bed. At fluidization velocities larger than the turbulent tluidization velocity, the carryover of solids will be too great for a solids handling system of a reasonable size.
The range of gas velocities that would function in the bed for Geldart B and Geldart A particles is from approximately 0.01 m/s to 1 m/s. there the liquid feed is viscous, a safety margin should be added to the operating fluidization velocity to manage agglomeration of the wet particles.
The fluidization velocity has an impact on many characteristics of the reactor. As the velocity is increased the gas phase residence time will decreases, but the concentration and height of solid particles in the freeboard region will increase. Solid mixing also increases within the bed when the fluidization velocity is increased. This reduces the plug-flow nature of the solids flow, but increases the resistance of the bed to defluidization, which is of concern when processing a viscous liquid feed. All of these factors must be considered when choosing the fluidization velocity.
6. Solids Throu~h~ut Solids particles will be fed into one end of the reactor and withdrawn at the opposite end. The solid particles preferably flow in a substantially horizontal direction. The fluidized solids behave hydrodynamically like a continuous fluid and can be made to flow across the bed under the influence of gravity. This flow could be simply induced by the difference in bed depth caused by feeding the solids into one end, or by tilting the reactor vessel in the direction of flow. Tilting the reactor has the advantage of maintaining a more uniform bed depth and allows for greater solids flowrates. In either case, the depth of the bed may be maintained through the use of a weir at the solids withdrawal end.
The solids flux through the reactor will likely be the primary factor in determining the capacity of the reactor to accept liquid feed. This will be the case when the heat or surface area requirements of the reaction are limiting. If required, it is possible to increase the mass flow of solid particles through the reactor at a constant flux by increasing the cross-section of the bed.
Furthermore, whereas the LR coking process is forced to adopt a relatively high operating temperature to compensate for low solids-to-oil ratios, no similar requirement exists for the current invention. In the practice of the invention a relatively high solids-to-oil ratio is used with feed and product recovery zones that are staged such that solid particle residence times may be tightly controlled.
BRIEF DESCRIPTION OF DRAWINGS
Embodiments of the invention will now be described with reference to the accompanying drawings, in which:
Figure 1 is a schematic drawing of a Fluid Coking reactor;
Figure 2 is a schematic drawing of a riser, or transfer line coking reactor;
Figure 3 is a schematic drawing of an LR coking reactor;
Figure 4 is a schematic drawing of a cross-flow reactor according to a preferred embodiment of the present invention;
Figure 5 is an alternate schematic drawing of a cross-flow reactor according to a preferred embodiment of the present invention depicting spraying of the liquid feed material within the fluid bed.
DETAILED DESCRIPTION OF THE INVENTION
In general, the present invention relates to a method or process for converting a liquid feed material into a vapor phase product. In a preferred embodiment, the present invention relates to a method for converting a heavy hydrocarbon feedstock material into value added reaction products. The method or process of the invention is herein referred to as "cross flow conversion" process or "XFC" process.
The central process unit in the XFC design is a cross-flow fluidized bed reactor.
As in most fluidized bed processes, a fiuidizing medium, preferably a gas, is introduced into the bottom of the reactor base and exits at the top of the reactor so that the fluidizing medium moves in a substantially vertical fluidizing direction.
A significant difference between the XFC design and a conventional fluid bed process is that the solid particles in the fluid bed move substantially perpendicularly to the gas phase in the fluid bed. Solid particles enter at one end, flow along the length of the reactor under the influence of gravity, and are removed at the opposite end. Since the solids and gas flows are generated by independent driving forces, the two are essentially independent.
This provides for a significant increase in flexibility, which will be discussed in detail in the description that follows.
This description teaches a method for designing an XFC reactor to produce a solid particle RTD that approaches plug flow, allowing for evolution of a vapor phase product within the fluid bed. This is an important feature of the present invention. Eenefits accruing from this solid particle RTD together with those inherent in the type of fluidized bed reactor proposed can be leveraged by a person skilled in the art to provide significant advantages over the current art.
For example, it is well understood by those individuals skilled in the art how to manipulate operating and design conditions such as increased solids-to-feed ratios and the ability to deliver feed in a more controlled and uniform fashion to enhance operability and yield at typical reaction temperatures. The hydrodynamics of the XFC reactor have been studied with cold flow physical models, using dimensional analysis to establish a tie to typical process operating conditions.
1. XFC Reactor Vessel The XFC reactor is divided into a number of zones, each having a different function:
1. Solid feed zone 2. Liquid feed zone 3. Reaction zone 4. Solid withdrawal zone 5. Gas distribution zone 6. Freeboard zone Figure 4 and Figure 5 both depict a schematic which demonstrates the different zones of the XFC reactor.
The length of the reactor vessel is typically greater than its width. This design feature ensures the solids are well mixed across the width of the vessel, and helps to maintain plug flow characteristics in the moving solid phase. The impact of plug flow on the characteristics of the process is described below.
Gas is introduced as a fluidizing medium through a distributor located on the bottom of the reactor vessel. The gas distributor can vary in complexity.
Bubble cap and perforated plate designs have been tested, but any design capable of adequately fluidizing the solids is acceptable. The fluidization gas, along with any product vapor generated by the xeaction, will typically exit at the top of the reactor vessel.
_g_ p CA 02446889 2003-10-27 The height of the reactor vessel is designed to accommodate both the fluidized bed contained in the vessel and the height required for solids disengagement in the freeboard region (see below).
To provide effective contact between liquid feed and solid heat earner and to take advantage of high solids-to-feed ratios it will generally make sense to provide an amount of solid particles substantially in excess of what is required for the given feed zone.
By staging several of the units depicted in Figure 4 in series, the bulk of the solid particles will be contacted in a more uniform fashion. To increase capacity, the width of the reactor can be increased, an option not available in many commercial configurations.
2. Solids Particle Characteristics The solid particles in the XFC reactor provide the surface area upon which the conversion reaction occurs. In addition, the solid particles provide a heat source or sink for the reaction, depending upon whether the reaction is endothermic or exothermic.
They may also possess catalytic activity, although this is not a requirement. The most critical attribute is that the particles fluidize well. Based on the Geldart classification (Kunni D. and Levenspiel, O.
Fluidization Engineering Zed. Butterworth-Heinemann 1991), only the following two types of particles are suitable for the XFC reactor:
1. Geldart A type particle: Aeratable particles or materials having small mean particles size (<40 microns) or low particle density (<1400 kg/m3). Fluidized Cracking Catalyst is an example of particles of this type.
2. Geldart B type particles: Most particles of size 40 microns to 500 microns and density 1400 kg/m3 to 4000 kg/m3. Sand is an example of this type of particle.
These two particle types characterize the typical particles used in industrial fluidized beds. When fluidized, they provide the positive characteristics that are most often associated with fluidized bed reactors: uniform temperature, high rates of heat and mass transfer, and high specific surface area. In addition, Geldart A and B particles will be fluid enough to allow for smooth horizontal flow.
All remaining particles fall into either the Geldart C (cohesive powders) or Geldart D (large coarse particles) classifications and are not typically suitable for use in the XFC
process unless they make up a relatively small fraction (<10%) of the particles, with the majority being either Geldart A or Geldart B.
The other factors to consider when choosing the solid particle material are the heat storage and transfer characteristics, attrition rates and cost.
3. Bed Characteristics The fluidized bed will preferably be operated in the bubbling bed regime or, in the case of Geldart A particles, may be operated in the smooth fluidization regime below the bubbling fluidization velocity but above the minimum fluidization velocity.
In the bubbling bed regime the fluidized bed resembles a boiling liquid with bubbles forming at the gas distributor, rising through the bed quickly then bursting at the surface of the bed. For descriptive purposes the fluid bed can be thought to have two phasesn 1. Emulsion phase containing both solids and gas 2. Bubble phase containing primarily only gas Gas exits the bed almost exclusively in the bubbles. Gas in the emulsion phase must therefore first enter the bubbles in order to exit the fluid bed. The transfer of gas between the bubbles and the emulsion can occur by diffusion in the bed, or by mixing in the turbulent region in the vicinity of the gas distributor.
4. Freeboard Region The freeboard is the solids lean region of the reactor vessel above the surface of the fluidized bed. Solids are ejected from the fluidized bed by the action of bubbles bursting at its surface. The freeboard region is required for the solid particles to disengage from the gas so that they are not carried out of the reactor vessel.
The optimum freeboard height is that which allows all of the solid particles with terminal velocities less than the superficial gas velocity to disengage.
Extending the freeboard above this height will not reduce the solids carryover and will only add to the cost of the vessel and to the residence time of the gas.
Even for a very large freeboard region, solid particles will be earned out of the reactor because they have been entrained in the gas or because of large eruptions of bubbles at the surface of the bed which can potentially eject solids to the roof of the reactor vessel. If the downstream gas processing units can not tolerate the presence of solids then a unit must be installed to separate the solids from the gas stream. Proven technologies, such as cyclones, will be sufficient for this purpose.
Reducing the height of the freeboard region will reduce the residence time of the gas phase, which will in turn limit the severity of the gas phase reactions.
However, inadequate height of the freeboard region can result in an excessive amount of solids carryover, requiring larger solids handling units outside the reactor to separate the solids from the gas.
The optimum freeboard height will be dependent on the type of particles, the fluidization velocity and the effects of the feed on the cohesive forces between particles. The residence time distribution of the gas in this zone has been shown to be substantially plug flow.
5. Fluidization Velocity The solid particles are fluidized by the gas that enters through the gas distributor at the base of the vessel. The velocity of the fluidizing gas can be between the minimum fluidization velocity and the turbulent fluidization velocity of the solids.
If the gas velocity is below the minimum fluidization velocity of the particles, then the bed will not fluidize and the solids will not flow across the bed. At fluidization velocities larger than the turbulent tluidization velocity, the carryover of solids will be too great for a solids handling system of a reasonable size.
The range of gas velocities that would function in the bed for Geldart B and Geldart A particles is from approximately 0.01 m/s to 1 m/s. there the liquid feed is viscous, a safety margin should be added to the operating fluidization velocity to manage agglomeration of the wet particles.
The fluidization velocity has an impact on many characteristics of the reactor. As the velocity is increased the gas phase residence time will decreases, but the concentration and height of solid particles in the freeboard region will increase. Solid mixing also increases within the bed when the fluidization velocity is increased. This reduces the plug-flow nature of the solids flow, but increases the resistance of the bed to defluidization, which is of concern when processing a viscous liquid feed. All of these factors must be considered when choosing the fluidization velocity.
6. Solids Throu~h~ut Solids particles will be fed into one end of the reactor and withdrawn at the opposite end. The solid particles preferably flow in a substantially horizontal direction. The fluidized solids behave hydrodynamically like a continuous fluid and can be made to flow across the bed under the influence of gravity. This flow could be simply induced by the difference in bed depth caused by feeding the solids into one end, or by tilting the reactor vessel in the direction of flow. Tilting the reactor has the advantage of maintaining a more uniform bed depth and allows for greater solids flowrates. In either case, the depth of the bed may be maintained through the use of a weir at the solids withdrawal end.
The solids flux through the reactor will likely be the primary factor in determining the capacity of the reactor to accept liquid feed. This will be the case when the heat or surface area requirements of the reaction are limiting. If required, it is possible to increase the mass flow of solid particles through the reactor at a constant flux by increasing the cross-section of the bed.
7. Liquid Feed Delivery The liquid feed material is sprayed onto the bed of fluidized solids using conventional nozzles. The zone of the bed used to accept the atomized feed will be jusl; after the solid feed zone.
The feed system should maximize the distribution of liquid feed over the solids particles that pass through the feed zone. The optimum situation would be to have every droplet of feed hit and engulf a different solid particle. This would maximize the surface area over which the reaction occurs which reduces any mass transfer limitations.
To maximize the spread of liquid feed and minimize mass transfer limitations, the droplet size should preferably be less than or equal to the solid particle size, which will allow the I S droplet to form a thin film over the solid particle. This will be limited by the wetting properties of the solid and the liquid. If the feed droplets are too large they can potentially cause the agglomeration of the bed solids, and if they are too small they can be entrained in the rising gas.
The feed nozzles are preferable oriented so that the feed material is sprayed in a spraying direction which is substantially perpendicular to the solid transport direction. The feed nozzles can be oriented vertically, pointing downward through the surface of the bed.
Alternatively, the nozzles can be oriented horizontally, through the walls of the vessel or in through the base of the vessel. There is an advantage to spraying the feed into the bottom of the fluidized bed since this is an area of good mixing between the bed solids and the gas. For any nozzle orientation, the aim is to penetrate the bed with feed without impacting the bottom or sides of the vessel.
The feed system should maximize the distribution of liquid feed over the solids particles that pass through the feed zone. The optimum situation would be to have every droplet of feed hit and engulf a different solid particle. This would maximize the surface area over which the reaction occurs which reduces any mass transfer limitations.
To maximize the spread of liquid feed and minimize mass transfer limitations, the droplet size should preferably be less than or equal to the solid particle size, which will allow the I S droplet to form a thin film over the solid particle. This will be limited by the wetting properties of the solid and the liquid. If the feed droplets are too large they can potentially cause the agglomeration of the bed solids, and if they are too small they can be entrained in the rising gas.
The feed nozzles are preferable oriented so that the feed material is sprayed in a spraying direction which is substantially perpendicular to the solid transport direction. The feed nozzles can be oriented vertically, pointing downward through the surface of the bed.
Alternatively, the nozzles can be oriented horizontally, through the walls of the vessel or in through the base of the vessel. There is an advantage to spraying the feed into the bottom of the fluidized bed since this is an area of good mixing between the bed solids and the gas. For any nozzle orientation, the aim is to penetrate the bed with feed without impacting the bottom or sides of the vessel.
8. Bed D~th A shallow bed has the advantages of reduced gas phase residence time, increased gas solid contacting, reduced axial solids mixing and a reduced concentration of solids in the freeboard region. All of these effects will be advantageous for most of the reaction systems that will operate in the cross-flow reactor.
There are two operational issues that will determine the minimum depth of the fluidized bed in the reactor:
1. The required solids throughput 2. The liquid feed jet penetration The maximum solids throughput is dependent upon the maximum horizontal solids velocity and the bed cross-section perpendicular to the flow. ~Nhile operating with a smaller bed depth can have many advantages (see below), reducing the bed depth will reduce the solid particle capacity of the reactor.
The liquid feed nozzles should deliver the liquid feed material to the fluid bed without creating liquid droplets of a size that will be entrained in the upward rnovin g gas. To accomplish this, adequate momentum is imparted to the feed droplets to allow some penetration of the liquid into the fluidized bed. The bed should be deep enough relative to the momentum imparted to the feed droplets so that the feed material does not impact on the base of the gas distributor. This limit on bed depth can be avoided if the liquid feed material is sprayed horizontally into the fluidized bed. This will then place the constraint on the minimum bed width in order to avoid the feed material impacting upon the sides of the reactor vessel. Through adequate design, the feed delivery system can be engineered to provide the required performance.
There are two operational issues that will determine the minimum depth of the fluidized bed in the reactor:
1. The required solids throughput 2. The liquid feed jet penetration The maximum solids throughput is dependent upon the maximum horizontal solids velocity and the bed cross-section perpendicular to the flow. ~Nhile operating with a smaller bed depth can have many advantages (see below), reducing the bed depth will reduce the solid particle capacity of the reactor.
The liquid feed nozzles should deliver the liquid feed material to the fluid bed without creating liquid droplets of a size that will be entrained in the upward rnovin g gas. To accomplish this, adequate momentum is imparted to the feed droplets to allow some penetration of the liquid into the fluidized bed. The bed should be deep enough relative to the momentum imparted to the feed droplets so that the feed material does not impact on the base of the gas distributor. This limit on bed depth can be avoided if the liquid feed material is sprayed horizontally into the fluidized bed. This will then place the constraint on the minimum bed width in order to avoid the feed material impacting upon the sides of the reactor vessel. Through adequate design, the feed delivery system can be engineered to provide the required performance.
9. Temperature The temperature of the reactor will be dependent upon the requirements of the reaction. The temperature drop across the reactor will be dependent on the heat requirements of the reaction and the heat capacity and mass flow of solids.
10. Pressure Slight positive pressure (0.5-10 psig) is desirable in that there is expense involved with providing fluidizing gas which, at constant superficial velocity, will decrease as the pressure is reduced. In addition, the rectangular shape of the reactor is less suited to pressure containment than cylindrical designs which again make low operating pressures desirable.
Downstream gas processing requirements will likely set the Iower boundary for system pressure.
Downstream gas processing requirements will likely set the Iower boundary for system pressure.
11. Process advantages Via) Approach to PIu~ Flow of Solid Phase Residence Time Distribution The assumption of plug flow is an ideal case where every solid particlf; has the same axial velocity. The solid particles move along the length of the reactor in uniform plugs that are well mixed in the radial direction. Since every particle has the same horizontal velocity, there can be no mixing along the length of the reactor. In the current process of the invention, the solids RTD approaches the plug flow ideal since the bulk rate of solids flow along the length of the bed is much larger than the rate of solids mixing in the same direction. In engineering terms, this is equivalent to stating that the Peclet (Pe) number is relatively large.
The plug flow characteristics of the solid phase takes greater advantage of the reactor volume than a fluidized bed that is well mixed. This is because the residence time distribution of the solid particles is much narrower than in a fiuidized bed reactor that is well mixed. This allows for many advantages all of which are related to the narrow residence time distribution:
1. Greater capacity in a smaller reactor, thus reducing capital costs;
2. Larger ratio of dry solids to feed material, allowing more feed material to be added to the bed without risking agglomeration of the bed solids, a condition known as "bogging". In many cases, this allows the reactor to be operated at lower temperatures, as more severe conditions are not required to address bogging issues';
3. Reduced loss of liquid feed material by preventing solid particles from short circuiting through reactor vessel. In well mixed reactors, short circuiting of wetted solids force operation at higher reaction severity;
4. Reduced incidence of solid particles with excessive residence times (seventies).
(b) Flow Characteristics of the Gas Phase in the Freeboard Re ion The gas exiting the free surface of the fhuidized bed has also been shown to exhibit substantially plug flow characteristics, with relatively little mixing in the direction of flow. As a result, the time that the gas spends under reactor conditions is minimi:~ed, and subsequent reactions that can downgrade the vapor phase product are minimized.
A further benefit to tr.e plug flow nature of the gas is that the product gas streams generated at the various locations along the length of the reactor can bc~
collected independently.
This allows for tailoring of the gas recovery system for different gas flow-rates and allows the downstream gas processing units to 1=re tailored for different gas compositions.
(c) Substantial I~ecoupling of Gas and Solid Phase Residence Times The cross-flow design allows the residence times of the solid phase and the gas phase to be adjusted independently. The solid phase residence time is set by the solid particle bulk horizontal velocity and the reactor length. The gas phase residence time is ccmtrolled primarily by the bed depth and th~,e fhuidization velocity. This allows for the independent optimization of the gas phase and solids phase, and hence independent control of the reaction severities associated with the gas and liquid phases, offering a significant advantage over technologies based on dilute transport.
~d, High Rate of Vertical Mixing in the Bed The high rate of vertical solids mixing in the fluidized bed increases the efficiency with which the feed material is distributed throughout the bed solids. This attribute is dramatic when compared to other technologies that incorporate a moving bed of non-fluidized particles.
The high rate of vertical mixing in the fluidized bed allows for a deeper bed as opposed to a non-fluidized bed which must be made shallow. Furthermore, the: superior feed distribution has a positive impact on product formation in cases were mass transfer through the reacting liquid phase is in issue, as the liquid films t:hicknesses are kept to a minimum.
(e) Amenability to Small Scale Field Application The XFC process is rwell suited for scale down. Therefore, it can be used in field applications to process relatively small volumes of feed material, on the order of 1000 barrels per day.
(f) Ability to Design Solids Holdu~Without Affecting Vapor Please Severity When a viscous liquid feed material is sprayed into a fluidized bed, there is the danger that the particles will agglomerate, and the bed will defluidize. This condition is referred to as "bogging". The tendency for bogging can be addressed '~y increasing the amount of dry solid particles onto which the feed is introduced. This parameter is fixed during the design phase. With a well-mixed reactor, increased solid particle circulation necessitates increased reactor residence time to accommodate additional product short circuiting. Due to mechanical and other practical constraints, it is not possible to increase reactor volume without increasing the reactor height. As a result, increasing solid particle circulation increases the gas phase residence time, and hence product losses through the increase in reactor severity. T:he XFC
reactor does not suffer from these design issues, as solid particle throughput can be increased at constant bed height by increasing the width of the reactor.
Once a reactor is in operation, avoiding bogging in a conventional well-mixed Fluid Coker is usually accomplished by increasing severity, which ensures that the liquid quickly reacts to completion. This operating strategy can be undesirable for many reactions, as the products may be degraded to less valuable chemicals under the increased severity.
fig) Discrete Zones with Ability to T:~ilor Fluidizing Gas to These Zones Because feed zones and product recovery zones are distinct, fluidizing gas rates and fluid bed properties can be tailored to the requirements of the specific zones. For example, to manage bogging, more fluidizing; gas can be used in the region where the fluid bed accepts feed.
~h) Fluid Bed Volume Near gas entry point is a Significant Fraction of Total Volume It has been shown that exchange of product vapour from emulsion to bubble phase is much better near the gas entry point a fluid bed reactor than anywhere else in the bed.
This region is often termed the "grid zone". Given that the proportion of the fluid bed of the XFC
reactor in this region is much higher than current art this provides an advantage to the quick evolution of product vapour.
The plug flow characteristics of the solid phase takes greater advantage of the reactor volume than a fluidized bed that is well mixed. This is because the residence time distribution of the solid particles is much narrower than in a fiuidized bed reactor that is well mixed. This allows for many advantages all of which are related to the narrow residence time distribution:
1. Greater capacity in a smaller reactor, thus reducing capital costs;
2. Larger ratio of dry solids to feed material, allowing more feed material to be added to the bed without risking agglomeration of the bed solids, a condition known as "bogging". In many cases, this allows the reactor to be operated at lower temperatures, as more severe conditions are not required to address bogging issues';
3. Reduced loss of liquid feed material by preventing solid particles from short circuiting through reactor vessel. In well mixed reactors, short circuiting of wetted solids force operation at higher reaction severity;
4. Reduced incidence of solid particles with excessive residence times (seventies).
(b) Flow Characteristics of the Gas Phase in the Freeboard Re ion The gas exiting the free surface of the fhuidized bed has also been shown to exhibit substantially plug flow characteristics, with relatively little mixing in the direction of flow. As a result, the time that the gas spends under reactor conditions is minimi:~ed, and subsequent reactions that can downgrade the vapor phase product are minimized.
A further benefit to tr.e plug flow nature of the gas is that the product gas streams generated at the various locations along the length of the reactor can bc~
collected independently.
This allows for tailoring of the gas recovery system for different gas flow-rates and allows the downstream gas processing units to 1=re tailored for different gas compositions.
(c) Substantial I~ecoupling of Gas and Solid Phase Residence Times The cross-flow design allows the residence times of the solid phase and the gas phase to be adjusted independently. The solid phase residence time is set by the solid particle bulk horizontal velocity and the reactor length. The gas phase residence time is ccmtrolled primarily by the bed depth and th~,e fhuidization velocity. This allows for the independent optimization of the gas phase and solids phase, and hence independent control of the reaction severities associated with the gas and liquid phases, offering a significant advantage over technologies based on dilute transport.
~d, High Rate of Vertical Mixing in the Bed The high rate of vertical solids mixing in the fluidized bed increases the efficiency with which the feed material is distributed throughout the bed solids. This attribute is dramatic when compared to other technologies that incorporate a moving bed of non-fluidized particles.
The high rate of vertical mixing in the fluidized bed allows for a deeper bed as opposed to a non-fluidized bed which must be made shallow. Furthermore, the: superior feed distribution has a positive impact on product formation in cases were mass transfer through the reacting liquid phase is in issue, as the liquid films t:hicknesses are kept to a minimum.
(e) Amenability to Small Scale Field Application The XFC process is rwell suited for scale down. Therefore, it can be used in field applications to process relatively small volumes of feed material, on the order of 1000 barrels per day.
(f) Ability to Design Solids Holdu~Without Affecting Vapor Please Severity When a viscous liquid feed material is sprayed into a fluidized bed, there is the danger that the particles will agglomerate, and the bed will defluidize. This condition is referred to as "bogging". The tendency for bogging can be addressed '~y increasing the amount of dry solid particles onto which the feed is introduced. This parameter is fixed during the design phase. With a well-mixed reactor, increased solid particle circulation necessitates increased reactor residence time to accommodate additional product short circuiting. Due to mechanical and other practical constraints, it is not possible to increase reactor volume without increasing the reactor height. As a result, increasing solid particle circulation increases the gas phase residence time, and hence product losses through the increase in reactor severity. T:he XFC
reactor does not suffer from these design issues, as solid particle throughput can be increased at constant bed height by increasing the width of the reactor.
Once a reactor is in operation, avoiding bogging in a conventional well-mixed Fluid Coker is usually accomplished by increasing severity, which ensures that the liquid quickly reacts to completion. This operating strategy can be undesirable for many reactions, as the products may be degraded to less valuable chemicals under the increased severity.
fig) Discrete Zones with Ability to T:~ilor Fluidizing Gas to These Zones Because feed zones and product recovery zones are distinct, fluidizing gas rates and fluid bed properties can be tailored to the requirements of the specific zones. For example, to manage bogging, more fluidizing; gas can be used in the region where the fluid bed accepts feed.
~h) Fluid Bed Volume Near gas entry point is a Significant Fraction of Total Volume It has been shown that exchange of product vapour from emulsion to bubble phase is much better near the gas entry point a fluid bed reactor than anywhere else in the bed.
This region is often termed the "grid zone". Given that the proportion of the fluid bed of the XFC
reactor in this region is much higher than current art this provides an advantage to the quick evolution of product vapour.
12. Application Case 1-Application to the Uneradin~ of Heavy Oil The following description describes the specific application of the XFC
process to the upgrading of heavy oil, such as t~.thabasca bitumen. In this application, four reactor units are used in series (i.e. the solid particles will flow from one reactor into the next). Each unit has been designed to process feed at a rate of 250 bbl/day making the total capacity 1000 bbl/day.
The design specifications and operating conditions for this application are listed in Table 1. The specifications listed in Table 1 are for a single reactor unit, and are based on an extensive piloting exercise designed for this purpose. The following is a brief explanation of the rationale behind the numbers in Table 1.
Table 1 Operating Condition and Design Ranges for a Single Reactor Unit Specific to Bitumen where the Goal is to Maxirruze Liquid Yield.
Broadest Preferred Optimal Vessel Length3m - 6m 4m - Sm 4.2rn Vessel Height2m - 7m 3rn - 4m 3.7Sm Vessel WidthO.Sm - 2m 0.75m -1.Sm 0.75m Solid Particle50 microns - 400 120 microns - 240 microns Size Coke microns microns coated sand) Bed Depth 0.5 m - 2m O.Sm - 2m 0.75m Freeboard lm - Sm 2m -3m 2.Sm Height Reaction 2.Sm - 3.Sm 2.Sm - 3.5m 3.2m Zone Feed Zone 0.5 m - lm O.Sm - 1 m 1 m Superficial0.1 m/s - 0.7 0.2 mls - 0.6 0.45 m/s mls m/s Gas Velocity Solids Bulk0.02 m/s - 0.2 0.05 m/s - 0.15 0.1 m/s m/s m/s Horizontal Velocity Mean Reactor440C - 540C 460C-500C 484C
Temperature The solids particles selected for this application are sand particles with a mean particle size between 150 and 250 microns. During operation a coke layer will form on the sand particles. The average coke layer will be between 10 and 40 microns thick.
This will increase both the mean and variance of the particle size distribution. Small particles will also be formed by the attrition of larger particles.
The freeboard height is 2.Sm. This is larger than the optimal freeboard height, but will ensure that solids carryover is kept to a minimum.
The fluidized bed depth for the bitumen feed will be between 0.75 and 1.25 m.
This brings the total required vessel height to 3-4 m. The bed depth was set by considering the gas phase residence time while still maintaining a sufficient reactor cross section for solids throughput.
Due to the viscous nature of the feedstock a minimum fluidization velocity of 0.2 mls is provided to maintain proper fluidization.
In this application, the horizontal solid particle velocity through the reactor will be between 0.05 and 0.15 m/s. This velocity is based on the heat and surface area requirements of the system. It may be necessary to tilt the bed in the direction of solids flow to achieve the required bulk horizontal velocity.
To produce the desired reaction, the minimum operating temperature of the reactor will be about 460°C. Solid feed temperatures to the reactor will be 490°C. A heat balance for the overall system indicates that the temperature drop across each reactor unit will be about 12°C making the mean reactor temperature 4~4°C. This application of the XFC operates at moderate pressures (5 psig).
A partial oxidation gasifier may be used to provide heat to the reactor. This technology is readily available from a number of vendors. The solids particles will be heated in this unit before they are returned to the main reactor unit. The gasifier will use the coke that is formed in the reactor as a fuel source, and the gas formed in the combustor will be used to fluidize the main reactor.
Most of the evolved vapor phase product, which may comprise more than one substance or product, will be generated in the emulsion phase of the fluid bed. Due to the rapid vertical mixing of solid particles the products will be formed at all heights within the fluid bed.
. CA 02446889 2003-10-27 Due to the fluid mechanics associated with the bed, the gas contained. in the emulsion phase of the fluid bed will generally flow downwards, in opposition to the upward flow of gas in the bubble phase. Vapor phase products will be transferred from the emulsion phase to the bubble phase mainly through the mixing of the gas from these two phases in the grid zone of the reactor.
Reducing the height of the bed increases the portion of the bed occupied by the grid zone, and also reduces the time it takes for the evolved products to reach the bottom of the bed and be mixed into the escaping bubbles. The bubbles can then rise to be collected in the vapor collection apparatus at the top of the reactor vessel.
The invention provides quantifiable economic advantages over competing fluid bed technologies that have well mixed solids and confounded gas and solid phase residence times. dVhere the desire is to maximize the yield of condensable overhead vapors, three main advantages are noted:
I S l . Reduced reactor operating temperatures. As mentioned above under point (f~, in a well mixed reactor, lower reactor temperatures increase the risk of bogging.
This concern is managed in the XFC design through increased solids throughput, enabling lower operating temperatures, and increased yields;
2. Decreased losses of unreacted product. A well mixed reactor will also result in the loss of unreacted feed, due to the residence time distribution of the solid particles. This does not occur in the XFC unit; and 3. Decreased over-cracking of gaseous products. The shallower bed allows for a reduced gas phase residence time so that valuable products are not downgraded due to high seventies.
Issues 1 and 2 can be addressed for a process incorporating a well mixed fluid bed reactor by making the vessel significantly larger. However, this ~~ill significantly increase capital costs. In the current example, a well mixed reactor would require 16.5 times the solid particle holdup in order to ensure 95% of the solid particles are retained for a sufficient amount of time for the reaction to go to completion. Furthermore, this apparent remedy will only serve ., CA 02446889 2003-10-27 to exacerbate the problem outlined in 3, offsetting any incremental benefit associated with the increased reactor size.
As a conservative estimate of incremental yields, the XFC is expected to have the capacity to increase the yield of condensable products by 2-3%, on an absolute basis. Tlhis value is very significant in the industry, where yield increments ors the order of 0.1% are seen as significant, and have formed the basis for major capital expenditures. As a result, the XFC
process has the additional benefit of making better use of the natural resource. This is significant given environmental concerns that have received worldwide attention and general endorsement.
process to the upgrading of heavy oil, such as t~.thabasca bitumen. In this application, four reactor units are used in series (i.e. the solid particles will flow from one reactor into the next). Each unit has been designed to process feed at a rate of 250 bbl/day making the total capacity 1000 bbl/day.
The design specifications and operating conditions for this application are listed in Table 1. The specifications listed in Table 1 are for a single reactor unit, and are based on an extensive piloting exercise designed for this purpose. The following is a brief explanation of the rationale behind the numbers in Table 1.
Table 1 Operating Condition and Design Ranges for a Single Reactor Unit Specific to Bitumen where the Goal is to Maxirruze Liquid Yield.
Broadest Preferred Optimal Vessel Length3m - 6m 4m - Sm 4.2rn Vessel Height2m - 7m 3rn - 4m 3.7Sm Vessel WidthO.Sm - 2m 0.75m -1.Sm 0.75m Solid Particle50 microns - 400 120 microns - 240 microns Size Coke microns microns coated sand) Bed Depth 0.5 m - 2m O.Sm - 2m 0.75m Freeboard lm - Sm 2m -3m 2.Sm Height Reaction 2.Sm - 3.Sm 2.Sm - 3.5m 3.2m Zone Feed Zone 0.5 m - lm O.Sm - 1 m 1 m Superficial0.1 m/s - 0.7 0.2 mls - 0.6 0.45 m/s mls m/s Gas Velocity Solids Bulk0.02 m/s - 0.2 0.05 m/s - 0.15 0.1 m/s m/s m/s Horizontal Velocity Mean Reactor440C - 540C 460C-500C 484C
Temperature The solids particles selected for this application are sand particles with a mean particle size between 150 and 250 microns. During operation a coke layer will form on the sand particles. The average coke layer will be between 10 and 40 microns thick.
This will increase both the mean and variance of the particle size distribution. Small particles will also be formed by the attrition of larger particles.
The freeboard height is 2.Sm. This is larger than the optimal freeboard height, but will ensure that solids carryover is kept to a minimum.
The fluidized bed depth for the bitumen feed will be between 0.75 and 1.25 m.
This brings the total required vessel height to 3-4 m. The bed depth was set by considering the gas phase residence time while still maintaining a sufficient reactor cross section for solids throughput.
Due to the viscous nature of the feedstock a minimum fluidization velocity of 0.2 mls is provided to maintain proper fluidization.
In this application, the horizontal solid particle velocity through the reactor will be between 0.05 and 0.15 m/s. This velocity is based on the heat and surface area requirements of the system. It may be necessary to tilt the bed in the direction of solids flow to achieve the required bulk horizontal velocity.
To produce the desired reaction, the minimum operating temperature of the reactor will be about 460°C. Solid feed temperatures to the reactor will be 490°C. A heat balance for the overall system indicates that the temperature drop across each reactor unit will be about 12°C making the mean reactor temperature 4~4°C. This application of the XFC operates at moderate pressures (5 psig).
A partial oxidation gasifier may be used to provide heat to the reactor. This technology is readily available from a number of vendors. The solids particles will be heated in this unit before they are returned to the main reactor unit. The gasifier will use the coke that is formed in the reactor as a fuel source, and the gas formed in the combustor will be used to fluidize the main reactor.
Most of the evolved vapor phase product, which may comprise more than one substance or product, will be generated in the emulsion phase of the fluid bed. Due to the rapid vertical mixing of solid particles the products will be formed at all heights within the fluid bed.
. CA 02446889 2003-10-27 Due to the fluid mechanics associated with the bed, the gas contained. in the emulsion phase of the fluid bed will generally flow downwards, in opposition to the upward flow of gas in the bubble phase. Vapor phase products will be transferred from the emulsion phase to the bubble phase mainly through the mixing of the gas from these two phases in the grid zone of the reactor.
Reducing the height of the bed increases the portion of the bed occupied by the grid zone, and also reduces the time it takes for the evolved products to reach the bottom of the bed and be mixed into the escaping bubbles. The bubbles can then rise to be collected in the vapor collection apparatus at the top of the reactor vessel.
The invention provides quantifiable economic advantages over competing fluid bed technologies that have well mixed solids and confounded gas and solid phase residence times. dVhere the desire is to maximize the yield of condensable overhead vapors, three main advantages are noted:
I S l . Reduced reactor operating temperatures. As mentioned above under point (f~, in a well mixed reactor, lower reactor temperatures increase the risk of bogging.
This concern is managed in the XFC design through increased solids throughput, enabling lower operating temperatures, and increased yields;
2. Decreased losses of unreacted product. A well mixed reactor will also result in the loss of unreacted feed, due to the residence time distribution of the solid particles. This does not occur in the XFC unit; and 3. Decreased over-cracking of gaseous products. The shallower bed allows for a reduced gas phase residence time so that valuable products are not downgraded due to high seventies.
Issues 1 and 2 can be addressed for a process incorporating a well mixed fluid bed reactor by making the vessel significantly larger. However, this ~~ill significantly increase capital costs. In the current example, a well mixed reactor would require 16.5 times the solid particle holdup in order to ensure 95% of the solid particles are retained for a sufficient amount of time for the reaction to go to completion. Furthermore, this apparent remedy will only serve ., CA 02446889 2003-10-27 to exacerbate the problem outlined in 3, offsetting any incremental benefit associated with the increased reactor size.
As a conservative estimate of incremental yields, the XFC is expected to have the capacity to increase the yield of condensable products by 2-3%, on an absolute basis. Tlhis value is very significant in the industry, where yield increments ors the order of 0.1% are seen as significant, and have formed the basis for major capital expenditures. As a result, the XFC
process has the additional benefit of making better use of the natural resource. This is significant given environmental concerns that have received worldwide attention and general endorsement.
Claims (19)
1. ~~A method for converting a liquid feed material into a vapor phase product comprising the following steps:
(a) providing a fluid bed comprising solid particles and a fluidizing medium, wherein the fluidizing medium is moving in a substantially vertical fluidizing direction;
(b) moving the solid particles in a substantially horizontal solid transport direction;
(c) contacting the liquid feed material with the solid particles in order to convert the liquid feed material into the vapor phase product;
(d) collecting the vapor phase product in a vapor collection apparatus; and (e) collecting the solid particles in a solid collection apparatus.
(a) providing a fluid bed comprising solid particles and a fluidizing medium, wherein the fluidizing medium is moving in a substantially vertical fluidizing direction;
(b) moving the solid particles in a substantially horizontal solid transport direction;
(c) contacting the liquid feed material with the solid particles in order to convert the liquid feed material into the vapor phase product;
(d) collecting the vapor phase product in a vapor collection apparatus; and (e) collecting the solid particles in a solid collection apparatus.
2. ~~The method as claimed in claim 1 wherein the step of providing the fluid bed is comprised of introducing the solid particles at an upstream horizontal position and wherein the step of collecting the solid particles is comprised of collecting the solid particles at a downstream horizontal position.
3. ~~The method as claimed in claim 2 wherein the step of providing the fluid bed is comprised of introducing the fluidizing medium at a lower vertical position below the solid particles.
4. ~~The method as claimed in claim 3, further comprising the step of collecting the fluidizing medium in the vapor collection apparatus.
5. ~~The method as claimed in claim 4 wherein the vapor collection apparatus is located at an upper vertical position above the solid particles so that the fluidizing direction is substantially upward.
6. ~~The method as claimed in claim 5 wherein the step of providing the fluid bed is further comprised of providing the solid particles at a conversion temperature which is suitable for facilitating the conversion of the liquid feed material into the vapor phase product.
7. ~~The method as claimed in claim 6 wherein the step of contacting the liquid feed material with the solid particles is comprised of spraying the liquid feed material so that the liquid feed material contacts the solid particles as droplets.
8. ~~The method as claimed in claim 7 wherein the liquid feed material is sprayed within the fluid bed so that the droplets penetrate the fluid bed.
9. ~~The method as claimed in claim 7 wherein the liquid feed material is sprayed so that the droplets contact the solid particles from a spraying direction which is substantially perpendicular to the solid transport direction.
10. ~~The method as claimed in claim 9 wherein the spraying direction is a substantially vertical direction.
11. ~~The method as claimed in claim 10 wherein the spraying direction is substantially opposite to the fluidizing direction.
12. ~~The method as claimed in claim 6 wherein the vapor phase product is comprised of a plurality of substances.
13. ~~The method as claimed in claim 6, further comprising the step of quenching the vapor phase product after collecting the vapor phase product in order to minimize further conversion of the vapor phase product.
14. ~~The method as claimed in claim 6, further comprising the step of separating the vapor phase product and the fluidizing medium after collecting the vapor phase product and the fluidizing medium.
15. ~~The method as claimed in claim 6, further comprising the step of regenerating the solid particles for re-use after collecting the solid particles.
16. ~~The method as claimed in claim 15 wherein the step of regenerating the solid particles is comprised of heating the solid particles.
17. ~~The method as claimed in claim 16 wherein the step of regenerating the solid particles is comprised of heating the solid particles to the conversion temperature.
18. ~~The method as claimed in claim 6 wherein the solid particles are moved in the solid transport direction at a rate which is significantly larger than a rate of mixing of the solid particles in the same direction.
19. ~~The method as claimed in claim 6 wherein the liquid feed material is comprised of liquid hydrocarbon.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002446889A CA2446889A1 (en) | 2003-10-27 | 2003-10-27 | A method for converting a liquid feed material into a vapor phase product |
| EP04789783A EP1680483A4 (en) | 2003-10-27 | 2004-10-26 | A process for converting a liquid feed material into a vapor phase product |
| AU2004284119A AU2004284119B2 (en) | 2003-10-27 | 2004-10-26 | A process for converting a liquid feed material into a vapor phase product |
| US10/535,487 US20050279671A1 (en) | 2003-10-27 | 2004-10-26 | Process for converting a liquid feed material into a vapor phase product |
| CA002505632A CA2505632C (en) | 2003-10-27 | 2004-10-26 | A process for converting a liquid feed material into a vapor phase product |
| CN2004800316121A CN1875085B (en) | 2003-10-27 | 2004-10-26 | A method for converting a liquid feed material into a vapor phase product |
| BRPI0415963-2A BRPI0415963A (en) | 2003-10-27 | 2004-10-26 | process for converting a liquid feed material into a vapor phase product |
| PCT/CA2004/001876 WO2005040310A1 (en) | 2003-10-27 | 2004-10-26 | A process for converting a liquid feed material into a vapor phase product |
| RU2006118319/15A RU2359008C2 (en) | 2003-10-27 | 2004-10-26 | Method of converting initial liquid material into vapour-phase product |
| MXPA06004689A MXPA06004689A (en) | 2003-10-27 | 2004-10-26 | A process for converting a liquid feed material into a vapor phase product. |
| US13/428,778 US20120211402A1 (en) | 2003-10-27 | 2012-03-23 | Process for converting a liquid feed material into a vapor phase product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002446889A CA2446889A1 (en) | 2003-10-27 | 2003-10-27 | A method for converting a liquid feed material into a vapor phase product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2446889A1 true CA2446889A1 (en) | 2005-04-27 |
Family
ID=34468729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002446889A Abandoned CA2446889A1 (en) | 2003-10-27 | 2003-10-27 | A method for converting a liquid feed material into a vapor phase product |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20050279671A1 (en) |
| EP (1) | EP1680483A4 (en) |
| CN (1) | CN1875085B (en) |
| AU (1) | AU2004284119B2 (en) |
| BR (1) | BRPI0415963A (en) |
| CA (1) | CA2446889A1 (en) |
| MX (1) | MXPA06004689A (en) |
| RU (1) | RU2359008C2 (en) |
| WO (1) | WO2005040310A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10703979B1 (en) | 2019-02-12 | 2020-07-07 | Syncrude Canada Ltd. | Liquid yield from fluid coking reactors |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7862707B2 (en) * | 2007-02-18 | 2011-01-04 | David Rendina | Liquid fuel feedstock production process |
| MX359613B (en) * | 2010-12-23 | 2018-10-02 | Etx Systems Inc | Method for feeding a fluidized bed coking reactor. |
| CN115406804B (en) * | 2022-09-13 | 2023-05-12 | 台州学院 | Method for measuring influence of jet bubble crying on turbulent flow of gas-liquid bubbling fluidized bed |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2064715A (en) * | 1933-03-29 | 1936-12-15 | Gasoline Prod Co Inc | Coking liquid hydrocarbons |
| US2686710A (en) * | 1945-07-07 | 1954-08-17 | Kellogg M W Co | Catalytic conversion of hydrocarbons |
| US2717867A (en) * | 1949-11-26 | 1955-09-13 | Kellogg M W Co | Hydrocarbon conversion |
| US2670322A (en) * | 1951-05-01 | 1954-02-23 | Standard Oil Dev Co | Naphtha reforming process |
| US2698284A (en) * | 1951-05-17 | 1954-12-28 | Standard Oil Dev Co | Coking of heavy hydrocarbonaceous residues |
| BE508628A (en) * | 1951-05-19 | |||
| BE508568A (en) * | 1951-06-09 | |||
| US2723949A (en) * | 1951-10-31 | 1955-11-15 | Universal Oil Prod Co | Method and apparatus for converting a hydrocarbon oil stream in the presence of a relatively thin moving particle bed |
| US2895906A (en) * | 1957-05-10 | 1959-07-21 | Phillips Petroleum Co | Fluidized solids process and apparatus |
| FR1293023A (en) * | 1961-03-27 | 1962-05-11 | Improvements to fluidization devices for the treatment of divided products | |
| FR1426349A (en) * | 1964-12-17 | 1966-01-28 | Siderurgie Fse Inst Rech | Process for the treatment of powdery materials |
| FR1504435A (en) * | 1965-11-24 | 1967-12-08 | Siderurgie Fse Inst Rech | Improvements in fluidization treatment processes and implementation device |
| US3503184A (en) * | 1968-03-07 | 1970-03-31 | Aluminum Co Of America | Treatment of gases evolved in the production of aluminum |
| US3713781A (en) * | 1970-10-21 | 1973-01-30 | W Dunn | Cross-flow fluid bed reactor |
| US3734850A (en) * | 1971-09-08 | 1973-05-22 | Shasta Beverages Div Of Cons F | Wastewater treatment system |
| US4409101A (en) * | 1981-11-16 | 1983-10-11 | Moskousky Institut Stali I Splavov | Fluidized bed apparatus |
| US4445919A (en) * | 1983-03-14 | 1984-05-01 | Thermo Electron Corporation | In situ rapid wash apparatus and method |
| US5714056A (en) * | 1995-07-17 | 1998-02-03 | Exxon Research And Engineering Company | Process for deasphalting residua (HEN9511) |
| US5658455A (en) * | 1995-07-17 | 1997-08-19 | Exxon Research & Engineering Company | Fluidized bed coking process |
| US5919352A (en) * | 1995-07-17 | 1999-07-06 | Exxon Research And Engineering Co. | Integrated residua upgrading and fluid catalytic cracking |
| US6596242B1 (en) * | 1996-09-30 | 2003-07-22 | Shell Oil Company | Reactor riser of a fluidized-bed catalytic cracking plant |
| CN2350119Y (en) * | 1998-10-30 | 1999-11-24 | 中国科学院化工冶金研究所 | Multilayer moving fluid-bed reactor |
-
2003
- 2003-10-27 CA CA002446889A patent/CA2446889A1/en not_active Abandoned
-
2004
- 2004-10-26 MX MXPA06004689A patent/MXPA06004689A/en active IP Right Grant
- 2004-10-26 US US10/535,487 patent/US20050279671A1/en not_active Abandoned
- 2004-10-26 EP EP04789783A patent/EP1680483A4/en not_active Withdrawn
- 2004-10-26 AU AU2004284119A patent/AU2004284119B2/en not_active Ceased
- 2004-10-26 RU RU2006118319/15A patent/RU2359008C2/en not_active IP Right Cessation
- 2004-10-26 WO PCT/CA2004/001876 patent/WO2005040310A1/en active Application Filing
- 2004-10-26 CN CN2004800316121A patent/CN1875085B/en not_active Expired - Fee Related
- 2004-10-26 BR BRPI0415963-2A patent/BRPI0415963A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10703979B1 (en) | 2019-02-12 | 2020-07-07 | Syncrude Canada Ltd. | Liquid yield from fluid coking reactors |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1875085A (en) | 2006-12-06 |
| BRPI0415963A (en) | 2007-01-23 |
| EP1680483A4 (en) | 2008-12-03 |
| AU2004284119B2 (en) | 2010-10-28 |
| EP1680483A1 (en) | 2006-07-19 |
| RU2006118319A (en) | 2007-12-10 |
| CN1875085B (en) | 2010-05-12 |
| MXPA06004689A (en) | 2007-05-23 |
| AU2004284119A1 (en) | 2005-05-06 |
| US20050279671A1 (en) | 2005-12-22 |
| RU2359008C2 (en) | 2009-06-20 |
| WO2005040310A1 (en) | 2005-05-06 |
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