WO2020256880A1 - Réacteurs à lit à garnissage rotatif et procédés associés - Google Patents

Réacteurs à lit à garnissage rotatif et procédés associés Download PDF

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Publication number
WO2020256880A1
WO2020256880A1 PCT/US2020/033740 US2020033740W WO2020256880A1 WO 2020256880 A1 WO2020256880 A1 WO 2020256880A1 US 2020033740 W US2020033740 W US 2020033740W WO 2020256880 A1 WO2020256880 A1 WO 2020256880A1
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catalyst
catalyst bed
reactor
rotating
product
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PCT/US2020/033740
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English (en)
Inventor
Matthew S. IDE
Guang Cao
Bryan A. Patel
Eric B. Shen
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Exxonmobil Research And Engineering Company
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Publication of WO2020256880A1 publication Critical patent/WO2020256880A1/fr

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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
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
    • B01J8/0407—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds
    • B01J8/0411—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds the beds being concentric
    • 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
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
    • 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
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00203—Coils

Definitions

  • the present disclosure relates to a rotating packed bed reactors and methods of producing hydrocarbons using rotating packed bed reactors.
  • molecular weight growth reactions are of interest in producing higher value products from low cost hydrocarbon starting materials.
  • Some examples of molecular weight growth reactions include: methanol to gasoline, alkylation, olefin oligomerization or polymerization, LAO productions, Fischer-Tropsch synthesis, and gasoline to diesel processes.
  • these reactions produce a product molecular weight distribution that is difficult to deviate from with fixed or packed bed reactors.
  • Packed bed reactors are used in industry for multiphasic reactions, such as distillation, absorption, desorption, catalytic reactions, or air-stripping.
  • the packed bed reactor may be built as a large cylinder (e.g., several meters in height or greater).
  • the packed bed reactor is frequently equipped with a large amount of packing material for increasing contact area between gaseous and liquid phases.
  • the mass transportation between the gaseous and liquid phases can be prone to slow progress of the liquid, small contact area, low mass transportation as well as the necessity of employing a packed bed of large volume to achieve reaction efficiency.
  • the efficiency of the packed bed reactor may also be affected by flows, density and viscosity of interchanging fluids and/or gases, which may, in turn, be affected by temperature and pressure. Furthermore, the characteristics of the packing materials, packing conformation, specific surface area, porosity, mixing, and gravitational force may also affect the reaction rates and product throughput.
  • packed bed reactors rely on gravity or pressurization to move reactants into the catalyst bed and reactants out of the catalyst bed. In some instances the reactors (or catalyst beds) are rotated to provide a force greater than the force of gravity (at the earth’s surface). Even at forces greater than the force of gravity, the production often results in a molecular weight distribution of products similar to those found at normal gravity and fails to provide the ability to tailor molecular weight distributions.
  • the present disclosure relates to a process for producing a hydrocarbon product.
  • the process includes introducing reactants in the vapor phase to a reactor having a catalyst bed including catalyst under reaction conditions to produce a liquid product and separating the liquid product from the catalyst by rotating the catalyst bed, where rotating the catalyst bed creates a slip velocity of about 0.95 or less.
  • the present disclosure also relates to reactors having a rotatable catalyst bed including catalyst with an average pore size gradient that decreases as radius from a center point increases.
  • FIG. 1 depicts an embodiment of a rotating fixed bed reactor.
  • FIG. 2 depicts changes in product distribution from rotation of a reactor at sufficient angular velocity to overcome the surface tension of liquid product droplet smaller than the catalyst pore size.
  • FIG. 3 depicts the bubble point of 1-decene and the dew point of 1-pentene at a constant temperature and varied pressure.
  • FIG. 4 depicts the effect that product and reactant molecular weight has on the force exerted on the product at a radius from the rotor.
  • FIG. 5 depicts rotations per minute versus average pore size distribution with a line showing a reactor with a set rotational speed.
  • the present disclosure fulfills the need for molecular weight distribution selectivity in molecular weight growth reactions. It has been discovered that the use of a rotating packed bed (RPB) reactor may provide the ability to adjust molecular weight distribution of products of molecular weight growth reactions.
  • the reaction in a RPB reactor may be affected by the temperature and pressure of the system, which in turn affects the dew point of liquid products.
  • the rotational velocity in conjunction with catalyst pore size affects the flow of liquefied product out of the packed bed, eliminating or reducing further reactions on liquid product. The balance of these varying parameters allows for fine tuning of reactions involving molecular weight growth.
  • the rotating packed bed has various advantages, especially small size, high efficiency, low energy consumption, and short retaining time leading to higher throughput and thus may be widely used in processes controlling, for example, distillation, absorption, desorption, air-stripping or gaseous-liquid reaction with diffusion control.
  • the rotating packed bed may also drastically reduce space for a plant compared with plants that use a packed bed tower.
  • the rotating packed bed can generate force exerted on the reaction components greater than the force of gravity, and rotational reactors may be called high gravity reactors, or super gravity reactors for this reason.
  • the force greater than the force provided by gravity alone may aid in separation of reaction components by their density and affects multiphasic reactions accordingly.
  • the gaseous components are less dense and experience comparatively less force as the reactor is rotated.
  • liquid components are denser and feel comparatively greater force as the reactor rotates.
  • the force on the components in a RPB reactor increases the further they are from the center of rotation. It has also been discovered that a balance of higher than gravity force and catalyst pore size is relevant to liquid removal from a solid catalyst surface.
  • A“fixed bed” means a substantially packed bed of solid catalyst or reactant and is used to realize a multi-phase reaction process in a reactor.
  • the solid catalyst may be in particulate form and may remain stationary in relation to the reactor wall or an internal catalyst retainer.
  • the fixed bed may be an annular bed.
  • the term“Molecular Weight Growth Reaction” means any chemical reaction where the product has molecular weight greater than the reactants.
  • the term“reactant” means a chemical that takes part in and undergoes a change during the molecular weight growth reaction.
  • the term“dew point” means the pressure at which condensation of a component in the gaseous reactor effluent stream first begins. The dew point pressure is temperature dependent. As the temperature in the reactor is increased the dew point pressure will increase. Also, the dew point takes into account temperature, pressure and physical properties of other gases in the gaseous medium. At a pressure at or below the dew point of a component in the gaseous medium, a component in the liquid phase may not evaporate or vaporize into the gaseous medium. On the other hand, the component may vaporize or evaporate if the pressure of the gaseous medium is above the dew point.
  • bubble point means the pressure at which vaporization of a component in a liquid first begins, essentially, the converse of the dew point discussed above, with similar attributes regarding its dependencies.
  • the single phase fluid may become (at least temporarily) a two phase fluid (i.e. a gas/liquid mixture).
  • Tip speed is the circumferential distance traveled by the tip of the rotor per unit of time. Tip speed is thus a function of the rotor diameter and the rotational frequency. Tip speed (in meters per minute, for example) may be calculated by multiplying the circumferential distance transcribed by the rotor tip, 2nR, where R is the radius of the rotor (meters, for example) times the frequency of revolution (for example revolutions per minute, rpm). The frequency of revolution may be greater than 250 rpm, greater than 500 rpm, greater than 1000 rpm, greater than 5000 rpm, greater than 7500 rpm, greater than 10,000 rpm, greater than 13,000 rpm, or greater than 15,000 rpm.
  • the rotational frequency, flow rate, and temperature may be adjusted to get a certain product profile. If channeling should occur, and some reactants pass through unreacted, the rotational frequency may be increased to reduce or eliminate channeling.
  • Pore volume distribution of the catalyst material is defined by or determined with ASTM D4284-12.
  • a fixed bed comprising a catalyst
  • the present disclosure is applicable also to reactors having a fixed bed of particulate or granular material which is intended to interact with a liquid and/or gaseous material flowing through said reactor.
  • the actual chemical reaction occurring within the system may be, for instance, an alkylation, and olefin oligomerization or polymerization, a Fischer-Tropsch synthesis, or other molecular weight growth reactions.
  • the design, operation, and diagnosis of a three-phase reaction in a fixed bed reactor may provide a convenient tool to increase gas-liquid-catalyst interaction over the full length and diameter of the reactor.
  • the fixed bed catalytic reactor may provide, among other attributes, sufficient volume and residence time to provide molecular weight growth, provide sufficient mass transfer rate of reactants and products through the gas-liquid interface and through the liquid film formed as products condense within catalyst pores or on the surface of catalyst particles, provide effective use of substantially all of the catalyst particle and active sites throughout the cross section of particles in the bed, provide uniform flow distribution over substantially all of the width and length of bed to utilize all of the catalyst, allow for conditions where all the catalyst is adequately wetted such that both reactants are present and heat is transferred effectively from substantially all zones in the reactor, provide an effective method for controlling temperature in a safe operating window or effective range to improve reaction selectivity, product quality, catalyst life, and the like. See for instance H. Hofmann:“Multiphase Catalytic Packed Bed Reactors”, Catal. Rev. Sci. Eng. 17 (1978) 71-117.
  • At least one of temperature or pressure may be modified so as to obtain specific hydraulic conditions. If modification of pressure and/or temperature does not provide the targeted result, then other modification can be made including: changing the composition of at least one of the gaseous or liquid feeds (e.g., adding diluents such as inert gases or liquids, partially recycling product, adding more reactant gas and/or liquid, adding surfactants, and the like), catalyst bed particle size or shape, or catalyst bed void fraction, or diameter, length and/or number of beds, or a combination of these parameters. It will be recognized that a temperature range, pressure range, and catalyst composition are usually determined based on chemistry and pilot plant data prior to the design of the commercial reactor, which places a practical limit on the preferred options.
  • Pressure and temperature are hydraulic parameters that may be adjusted in meeting the reaction conditions within the reactor. Other variables may include catalyst particle size and shape, liquid velocity, gas velocity, and bed void fraction.
  • bed void fraction may be conveniently determined by extrapolation based on first principles and visual observations in a transparent laboratory reactor using water and air. Combinations of two or more of the hydraulic variables including: average catalyst pore size, gas hourly space velocity, liquid velocity, pressure, or a combination thereof may be adjusted to provide particular molecular weight distributions.
  • an embodiment of reactor 100 may include: reactor housing 102 and a catalyst bed 104.
  • Catalyst bed 104 may contain a plurality of zones containing varying catalysts or a single catalyst with varying characteristics (e.g. pore size). Zones within catalyst bed 104 are represented by 104a, 104b, and 104c, but may be greater or fewer in number than shown.
  • Catalyst bed 104 is defined by inner catalyst retainer 106 and outer catalyst retainer 108, which may include concentric tubular members having a common axis 110 (which is the center point for determining radius). Axis 110 may be vertical, horizontal, or at another angle in relation to earth’s surface.
  • Catalyst bed 104 may have an annular shape, or alternatively may include other shapes, e.g. elliptical, oblong, toroidal, etc., that are weight balanced across common vertical axis 110.
  • the inside of inner catalyst retainer 106 defines a central chamber 112, and an outer chamber 114 is defined between outer catalyst retainer 108 and the reactor housing 102.
  • Retainers 106 and 108 may have a specific radius, so long as the difference is wide enough to contain a predetermined amount of catalyst.
  • bed 104 may vary in height.
  • central chamber 112 can be replaced with an alternative gas distribution device that allows gas to flow radially outward through the full height of the catalyst bed at substantially uniform pressure.
  • Catalyst bed 104 may include a first end 116 and a second end 118, with first end 116 also closing one end of central chamber 112.
  • Catalyst bed 104 may be packed with a suitable catalyst system, which may include supported or bulk catalyst provided in a form having a predetermined porosity, for example: saddles, rings, stacked layers of mesh, sponge, particles, or the like.
  • Inner catalyst retainer 106 and outer catalyst retainer 108 may be perforated or include a mesh so as to allow the passage of gas and/or liquid while containing the catalyst packing.
  • Various other modifications to the embodiments can be made including removal of the retainers where the catalyst includes a binder that allows the formulation to hold its shape.
  • outer retainer 108 may be constructed to include grooves or channels that direct liquids leaving the catalyst bed 104 to a localized area and could further include gas permeable membranes to allow for efficient vapor/liquid separation.
  • Reactor 100 further includes a feed gas inlet 120, a liquid outlet 122, and a gas recycle line 124.
  • Feed gas inlet 120 opens into one end of central chamber 112.
  • a rotating seal 126 may be included between the stationary gas inlet 120 and the rotating annular catalyst bed 104.
  • the gas recycle line 124 and liquid outlet 122 are in fluid connection with outer chamber 114 and may be connected (as shown) or be separate connections through reactor housing 102. In another embodiment, gas recycle line 124 is connected through reactor housing 102 at the opposite end from liquid outlet 122.
  • Catalyst bed 104 is mounted on a bearing (not shown) so as to be rotatable around axis 110.
  • the system may include a motor 128 engaging bed 104 for driving rotation of bed 104.
  • motor 128 as shown is mounted at one end of the reactor 100, the position of motor 128 is not important to operation of the present system and could be placed in other locations, e.g. the side of the reactor connected by gears or belts, or the other end of the reactor.
  • Reactor 100 may include a heat exchange system 130, which may include at least one heat exchange tube 132 in thermal contact with outer chamber 114.
  • Heat exchange tube 132 may include a coiled tube that spirals around the circumference of chamber 114, as shown, or can be another configuration that is suitable for effective heat exchange between the cooling system and the contents of outer chamber 114.
  • a heat exchange medium such as water, may enter heat exchange tube 132 at heat exchange inlet 134 and exit at heat exchange outlet 136 after exchanging heat with outer chamber 114.
  • Heat exchange system 130 may take other forms, including a suitable device capable of exchanging heat from the system without interfering with the catalytic reaction, including multiple tubes, cooling fins, heat sinks, etc.
  • reactor 100 includes rotating seal 126
  • the rotating seal may be cooled using any suitable technique.
  • the reactor 100 may include a shaft in the center (not shown) which may be used to control the temperature within reactor 100 or within catalyst bed 104.
  • a water- cooled shaft may be used to moderate and extract heat produced by exothermic reactions.
  • heat may be added to reactor 100, via the center shaft, heat exchange system 130, or elsewhere, to promote the reaction.
  • An inert liquid may be introduced into the rotating packed bed reactor, either together with the gaseous reactants or separately, which may become vaporized during a molecular weight growth reaction and provide control of (e.g., lower) reactor temperature.
  • Catalyst bed 104 is rotated at a determined rotation rate, which is set by reactor and reaction conditions including product density, catalyst pore size, and distance from the center of the reactor.
  • a feed gas stream comprising reactants may enter central chamber 112 via inlet 120.
  • Inlet 120 may be at a higher pressure than outer chamber 114, and therefore the gas flows radially outward through the catalyst retainers and the catalyst within catalyst bed 104.
  • the reaction forms a liquid product, according to the mechanism of a molecular weight growth reaction.
  • the annular configuration and substantially radial gas flow may produce a substantially uniform residence time for the gas in the catalyst bed.
  • Catalyst bed 104 may rotate with sufficient angular velocity to generate a centrifugal force as great as the force of gravity or greater.
  • a force greater than the force of gravity is sometimes referred to as“high gravity.” Because the radial acceleration resulting from rotation of the reactor can be calculated and controlled, the radial acceleration can be factored into production rates, with other factors including porosity, pressure, temperature, and surface tension. Therefore, the residence time of the produced liquids in the reactor may be controlled.
  • the angular velocity co that generates a force equal to the acceleration of gravity (980 cm/s 2 ) is about 1.57 revolutions/second.
  • the angular velocity co that generates a force at equal to twice the gravitational force is about 2.23 revolutions/second.
  • V is the volume
  • R is the radius
  • co is the angular velocity in revolutions per second.
  • the rotation of catalyst bed 104 need not be at a constant angular velocity, but can be increased or decreased as reaction conditions change.
  • Some conditions that may affect the rotation rate include pressure and temperature, as either temperature or pressure increase the angular velocity may decrease to offset the decrease in surface tension that comes with increased temperature or pressure.
  • the rate of rotation varies within predetermined values, with a lower value including zero rotation.
  • rotation is controlled by feedback from the reactor itself. For example, measurement of the production rate of liquid product versus the gas reactant flow rate could signal alterations in the angular velocity.
  • angular velocity may be controlled by a timer, with the length of time a certain speeds being independently predetermined.
  • the catalyst pore size may be inversely related to the radius from the rotor and may include a factor that correlates the droplet size and surface tension.
  • a catalyst may have a pore size in nm greater than 500 times the inverse of the radius in m from the rotor in a range of angular velocities, such as about 0.5 rotations/second or greater.
  • a drop radius may be defined that will allow the liquid drop to escape from the solid surface inside of a pore.
  • the determination of drop size also relates to pore sizes used in the catalyst bed, because a drop larger than a catalyst pore cannot pass through the pore and out of the catalyst bed. Therefore, catalyst pore size can be determined based on the surface tension relating the liquid product to the catalyst bed.
  • equations I through IV may be used to determine the minimum droplet radius to start moving the droplet at a given rotation speed.
  • materials of construction may limit the rotational speed, especially for larger reactors.
  • a limit on rotational speed can set a lower limit on catalyst pore size at a given radius from the rotor.
  • the catalyst used for a reaction might permit certain ranges of pore sizes, which may lead to the desire for higher rotational speeds or larger radii from the rotor.
  • a catalyst may have a pore size distribution from about 100 nm to about 1000 nm based on the class of materials of which the catalyst is made. While the catalyst material may have a defined pore size distribution, the pore sizes used in the rotating bed reactor may be calculated from the equations (I) to (IV).
  • Some example pore size distributions may include, from about 1 nm to about 2000 nm, from about 5 nm to about 1800 nm, from about 10 nm to about 1500 nm, from about 15 nm to about 1200 nm, or from about 20 nm to about 1000 nm.
  • catalyst bed 104 contains zones, shown as 104a, 104b, and 104c in FIG. 1. Zones may include catalyst with pore sizes that decrease as radius from the rotor increases, for example, catalyst in zone 104a may have larger pore size than the pore size of catalyst in zone 104b, which may have a larger pore size than the pore size of catalyst in zone 104c.
  • the number of zones within catalyst bed 104 need not be limited to three, e.g., there can be greater or fewer zones than those shown in FIG. 1.
  • the bed may contain catalyst of a single pore size, or catalyst of varying pore sizes.
  • the variation in pore size may form a gradient of larger to smaller pore size as the radius from the rotor increases.
  • the gradient may be stepwise (e.g. a number of zones) or gradual, e.g. such a large number of zones that a single zone is no longer distinguishable from adjacent zones, but the zones together form a gradient of catalysts having larger to smaller pore sizes.
  • a zone may include a pore size greater than or equal to the pore size calculation for the inner bound of that zone.
  • zone 104b may contain a pore size greater than or equal to the calculated pore size for the border of zones 104a and 104b.
  • the rings defined by the tips of the rotor/stator contain no openings (i.e. teeth or grooves) such that substantially all of the reactants are forced through the pores of the catalyst bed, rather than being able to bypass the catalyst by passing through openings or grooves which may be present in dispersers. In this manner, a reactant will be forced through the catalyst bed, and is more likely to come in contact with catalyst.
  • a gaseous or vapor phase reactant may be converted into a liquid phase product.
  • Vapor phase reactants may include syngas, methane, carbon monoxide, carbon dioxide, hydrogen, or Cl -Cl 2 hydrocarbons (saturated or unsaturated).
  • the conversion from vapor phase reactant to liquid phase product yields an opportunity to separate product from the catalyst bed at a sufficient rate to affect the molecular weight distribution of the product.
  • the pressure and temperature may be selected to maintain one or more reactants in the vapor phase allowing the vapor phase reactants to reach the catalyst, while also reaching the product bubble point at relatively low concentrations of liquid product.
  • the pressure/temperature combination may condense liquid product at about 50 mol% or less, about 40 mol% or less, about 30 mol% or less, about 30 mol % or less, or about 10 mol% or less.
  • the pressure and temperature ranges may be broad for vapor phase reactants that are gaseous at a wide range of temperatures and pressures and readily form high molecular weight products (e.g. conversion of syngas to liquid).
  • the pressure and temperature ranges may be more narrow for other molecular weight growth reactions where the vapor phase reactants are less volatile and/or the dissimilarity between the reactants and products is small (e.g. pentene dimerization).
  • a pressure that is too low may not lead to a product forming a liquid phase until the product is at a higher mol%, which may not provide increased mass transfer of the liquid phase out of the catalyst bed.
  • a pressure that is too high may be too near the dew point of a reactant causing reactant condensation and decreased access to the catalyst.
  • a suitable pressure is one that allows for condensation of liquid product at a low (less than 50) mol% while not nearing (within 10 psia) a reactant’s dew point.
  • a similar or identical assessment could be performed at a constant pressure and varied temperature to define a range of reactor conditions that would achieve a similar effect. For certain reactants and products, pressure and temperature may be adjusted to allow for greater separation of liquid product from vapor phase reactants.
  • a method for determining separability of products and reactants is the slip velocity.
  • the slip velocity (S) is defined as the velocity of the gas divided by the velocity of the liquid.
  • the slip velocity relating the flow of the gas and liquid phases increases at increased force, e.g. gravity, or high gravity.
  • the radial acceleration is one factor among many that affects the rate at which liquid product exits the catalyst bed and is used in determining the slip velocity of liquid product in relation to reactant gas.
  • the slip ratio is by definition 1, but experimentally the velocity of the gas and the velocity of the liquid may be significantly different.
  • the slip velocity at normal gravity is greater than 1 because the velocity of the gas is higher than the velocity of the liquid. At forces greater than gravity, the higher density of the liquid lowers the slip velocity, therefore, S may be useful in determining the angular velocity at which to rotate the catalyst bed or reactor.
  • the one-dimensional slip velocity can be represented by equation
  • S is the slip velocity
  • ms is the velocity of the gas
  • pL is the velocity of the liquid
  • pG is the ideal gas density at a given temperature and pressure
  • pL is the density of the liquid
  • c is the gas quality
  • a is the void fraction.
  • the slip velocity may be a factor used in determining the angular velocity for a reaction, but its effectiveness may be limited by the pressure at feed gas inlet 120, and by the rate of formation and molecular weight distribution of liquid products.
  • the slip velocity may be a good measure of how efficiently the liquid products are being removed from the reactor if other factors are also considered, for example, pore size, droplet size, and surface tension.
  • the calculation of slip velocity demonstrates that liquid products may be removed from the catalyst bed more efficiently in a rotating reactor than by using gravity alone to remove the liquids.
  • a weight average molecular weight (M w ) can be defined.
  • the product distribution curve and its M w will be lower (shift to the left) at forces higher than the force of gravity.
  • the ratio of the M w at forces greater than the force of gravity and the M w at the force of gravity will be less than 1.
  • the term“relative M w ” is defined as the ratio of 1) M w of a product distribution formed at a force greater than the force of gravity (at the earth’s surface) and 2) M w of a product distribution formed under the same reaction conditions, except formed at the force of gravity.
  • the molecular weight growth reactions for a single component ex.
  • the ratio of the M w of a product formed at forces greater than the force of gravity to the M w of a product formed at the force of gravity will be less than 1, if the combination of catalyst pore size, product density, and product surface tension allows efficient removal of product from the catalyst bed.
  • the ratio of the M w of a product formed at forces greater than gravity to the M w of a similar product formed at the force of gravity may be about 0.95 or less, about 0.9 or less, about 0.85 or less, or about 0.8 or less, and may be about 0.05 or more, 0.1 or more, 0.15 or more, or about 0.2 or more, such as from about 0.05 to about 0.95, from about 0.1 to about 0.9, or from about 0.2 to about 0.9.
  • FIG 2. is a graph illustrating product distribution dependence on the ratio of the M w of a product formed at forces greater than gravity to the M w of the product of the same reaction, but formed at the force of gravity. In FIG.
  • line 202 represents a ratio of 1, meaning that is the distribution expected at the force of gravity, and is also the distribution expected by Flory-Schulz calculation of single component step growth reactions.
  • the product distribution represented by line 202 may be formed in a stationary reactor under the force of gravity, or in a rotating reactor with a small pore size and not overcome by the force created by the angular velocity.
  • Point 204 represents the M w of the distribution represented by line 202.
  • Line 206 represents a distribution where the ratio of the M w at forces greater than gravity and the M w at the force of gravity is about 0.9, and point 208 is the M w for that distribution.
  • the distribution represented by line 206 may be formed by rotation of a reactor at sufficient angular velocity to overcome the surface tension of liquid product droplets smaller than the catalyst pore size.
  • line 210 represents a distribution where the ratio of the M w at forces greater than gravity to the M w at the force of gravity is about 0.2, and point 212 is the M w for that distribution.
  • the distribution represented by line 210 may be formed similarly to the distribution represented by line 206, but with increased rotation, larger pore size, or decreased surface tension.
  • the disclosed systems and methods may be used to produce liquid products such as higher alcohols, oxygenates, and liquid hydrocarbons from syngas (a combination of carbon monoxide and hydrogen which may also include methane and carbon dioxide) or light gases, such as carbon dioxide, methane, ethane, propane, butane, methanol and ethanol.
  • syngas a combination of carbon monoxide and hydrogen which may also include methane and carbon dioxide
  • light gases such as carbon dioxide, methane, ethane, propane, butane, methanol and ethanol.
  • Higher molecular weight hydrocarbons including alkanes and alcohols may be produced.
  • light gas may be converted to hydrocarbons and/or organic oxygenates, including intermediate products, such as methanol or dimethyl ether.
  • the overall processes includes the conversion of gas selected from carbon dioxide, methane, ethane, propane, butane, pentane and combinations thereof to hydrocarbons with carbon numbers greater than 2, such as C5-C10 hydrocarbons and/or oxygenates, such as methanol.
  • Olefin oligomerization may include the reaction of light olefins, such as C2 to C8 olefins with an oligomerization catalyst.
  • Oligomerization catalysts may include solid acids such as solid phosphoric acid (SPA), mixed metal oxides such as silica-alumina, W/Zr02, and zeolites, such as ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-48, or ZSM-57.
  • Oligomerization catalysts may also include metal catalysts, which may optionally be supported, such as Ni, Co, Pt, Pd, Ru, Rh, or Fe.
  • Olefin oligomerization may be performed at a temperature of about 100 °C or greater, such as about 125 °C or greater, or about 150 °C or greater, such as from about 100 °C to about 400 °C, from about 125 °C to about 300 °C, or from about 150 °C to about 250 °C.
  • Olefin oligomerization may be performed at a pressure of about 50 psig or greater, such as about 100 psig or greater, about 200 psig or greater, or about 300 psig or greater.
  • the olefin oligomerization pressure may be from about 50 psig to about 1000 psig, such as about 100 psig to about 800 psig, or about 200 psig to about 600 psig.
  • Olefin dimerization may include the reaction of light olefins, such as C3 to CIO olefins with an oligomerization catalyst.
  • Dimerization catalysts may include solid acids including zeolites, such as ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-48, or ZSM-57 or metal catalysts, which may optionally be supported, such as Ni, Pt, Pd, Ru, Rh, or Fe.
  • Olefin dimerization may be performed at a temperature of about 100 °C or greater, such as about 125 °C or greater, or about 150 °C or greater, such as from about 100 °C to about 400 °C, from about 125 °C to about 300 °C, or from about 150 °C to about 250 °C.
  • Olefin dimerization may be performed at a pressure of about 50 psig or greater, such as about 100 psig or greater, about 200 psig or greater, or about 300 psig or greater.
  • the olefin dimerization pressure may be from about 50 psig to about 1000 psig, such as about 100 psig to about 800 psig, or about 200 psig to about 600 psig.
  • systems and methods described may include the use of large pore sizes within a rotating bed reactor for the direct conversion of syngas to organic oxygenates (alcohols) and other liquid hydrocarbons.
  • the conversion of syngas may be accomplished using any suitable catalyst, such as group 8-10 metals, such as iron, cobalt, or manganese catalysts.
  • the catalysts for conversion of syngas may include promoters, such as copper or zinc.
  • the syngas conversion catalyst may be supported on a refractory oxide, such as alumina, silica, silica-alumina, chromia, titania, zinc oxide, or Group 4 oxides.
  • the catalyst may further include a promoter, such as ruthenium, platinum, palladium, rhenium, cerium, hafnium, zirconium, lanthanum, copper, or combination(s) thereof.
  • the syngas conversion produces an alcohol product which includes methanol.
  • Methanol synthesis may take place at a temperature of about 100 °C or greater, such as about 125 °C or greater, or about 150 °C or greater, such as from about 100 °C to about 500 °C, from about 125 °C to about 400 °C, or from about 150 °C to about 350 °C.
  • Methanol synthesis may take place at a pressure of about 250 psig or greater, such as about 300 psig or greater, about 400 psig or greater, or about 500 psig or greater.
  • the olefin dimerization pressure may range from about 250 psig to about 1500 psig, such as about 300 psig to about 1300 psig, or about 400 psig to about 1200 psig.
  • a syngas conversion process may be used to convert methanol and/or syngas to higher molecular weight alcohols and hydrocarbons.
  • the products include C4-C20 hydrocarbons.
  • Hydrocarbon synthesis may be performed at a temperature of about 100 °C or greater, such as about 125 °C or greater, or about 150 °C or greater, such as from about 100 °C to about 500 °C, from about 125 °C to about 400 °C, or from about 150 °C to about 350 °C.
  • Methanol synthesis may be performed at a pressure of about 250 psig or greater, such as about 300 psig or greater, about 400 psig or greater, or about 500 psig or greater.
  • the olefin dimerization pressure may be from about 250 psig to about 1500 psig, such as about 300 psig to about 1300 psig, or about 400 psig to about 1200 psig.
  • the systems and methods described may be used to produce ethyl acetate from a carbonyl reactant and ethanol.
  • the carbonyl reactant may include acetic acid, acetic anhydride, acetaldehyde, or combination(s) thereof.
  • the production of ethyl acetate may be catalyzed by any suitable catalyst, such as metal catalysts including Pd, Ti, or Ru, or zeolites, or combination(s) thereof.
  • Ethyl acetate production may be performed at a temperature of about 100 °C or greater, such as about 125 °C or greater, or about 150 °C or greater, such as from about 100 °C to about 400 °C, from about 125 °C to about 300 °C, or from about 150 °C to about 250 °C.
  • Ethyl acetate production may be performed at a pressure of about 50 psig or greater, such as about 100 psig or greater, about 200 psig or greater, or about 300 psig or greater.
  • the ethyl acetate production pressure may be from about 50 psig to about 1000 psig, such as about 100 psig to about 800 psig, or about 200 psig to about 600 psig.
  • the systems and methods described may also be used to produce glycerol via hydroxylation of allyl alcohol.
  • the production of glycerol may include reactants including a peroxide and an olefmic alcohol.
  • the peroxide may include hydrogen peroxide, ethylbenzyl hydroperoxide, t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide, 2-methyl-2-hydroperoxy-methyl proprionate, 2-methyl-2-hydroperoxy propanoic acid, pyrrolehydroperoxide, furan hydroperoxide, 2-butylhydroperoxide, cyclohexyl hydroperoxide, and 1-phenyl-ethylhydroperoxide, or combination(s) thereof.
  • the olefmic alcohol may include allyl alcohol, methallyl alcohol, cinnamyl alcohol, methyl vinyl carbinol, dimethyl allyl alcohol, oleyl alcohol, methyl vinyl carbinol, crotyl alcohol, methyallyl alcohol, cyclohexenol, or combination(s) thereof.
  • the production of glycerols may be catalyzed by a hydroxylation catalyst, which is selected from a metal oxide, a tungstic catalyst, an osmium catalyst, or combination(s) thereof.
  • the hydroxylation catalyst may include transition metals such as zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, rhenium and uranium.
  • suitable catalysts include metal oxides, such as tungsten oxide or molybdenum oxide.
  • Glycerol production may be performed at a temperature of about 100 °C or greater, such as about 125 °C or greater, or about 150 °C or greater, such as from about 100 °C to about 400 °C, from about 125 °C to about 300 °C, or from about 150 °C to about 250 °C.
  • Glycerol production may be performed at a pressure of about 50 psig or greater, such as about 100 psig or greater, about 200 psig or greater, or about 300 psig or greater.
  • the glycerol production pressure may be from about 50 psig to about 1000 psig, such as about 100 psig to about 800 psig, or about 200 psig to about 600 psig.
  • Table 1 shows the critical rotational speed, N, that moves a water droplet (on an alumina surface) of a given droplet size (defined using drop radius) and radius from the rotor.
  • Table 2 lists the water droplet radius that is needed to start moving the droplet on alumina at a given radius from the rotor if the angular velocity is 100 rot/min. Consistent with the results above, the drop radius to start moving the droplet decreases with increasing radii from the rotor due to the higher radial acceleration imparted on the liquid droplet.
  • the wetted area of the droplet, B is estimated as approximately half of the surface area of the spherical drop.
  • FIG. 3 depicts the bubble point of 1-decene (line 302) and the dew point of 1-pentene (line 304) at a constant temperature of 200 °C and varied pressure in the oligomerization of pentene to decene.
  • the bubble point 302 and dew point 304 can be predicted for a wide range of pressures.
  • the 100% pentene feed goes in as a gas and forms a liquid product at just 6 mol% or 11 wt% decene.
  • a pressure of 100 psia was chosen, then the product would not form a liquid phase until 81 mol% or 90 wt% decene.
  • FIG. 4 depicts the effect that product and reactant molecular weight has on the force exerted on the product at a radius from the rotor.
  • the centrifugal force (Fc) can be determined for each molecule at a rotational speed of 100 rot/min at a given distance from the rotor up to 5 meters for the pentene 402 oligomerization to decene 404, pentadecene 406, and eicosene 408.
  • FIG. 5 is a graph illustrating rotations per minute versus average pore size distribution, depicting an example calculation for determining catalyst pore size based on a reactor with a set rotational speed.
  • the example reaction for the calculation is the oligomerization of C3-C4 olefins with a solid acid catalyst.
  • Line 502 represents a rotational speed of 35 rotations per minute.
  • Line 504 represents the force needed for product removal based on rotations per minutes and pore size for a catalyst bed with an inner diameter of 1 m.
  • Line 506 represents the force needed for product removal based on rotations per minute and pore size for a catalyst bed with an inner diameter of 3 m.
  • Line 508 represents the force needed for product removal based on rotations per minute and pore size for a catalyst bed with an inner diameter of 5 m.
  • a reactor spinning at 35 rotations per minute with three catalyst zones at 1 m, 3 m, and 5 m may have an average catalyst pore size in the first zone (1 m) of about 550 nm or more, in the second zone (3 m) of about 200 nm or more, and in the third zone (5 m) of about 125 nm or more.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production d'un produit hydrocarboné. Le procédé comprend l'introduction de réactifs dans la phase vapeur dans un réacteur ayant un lit de catalyseur comprenant un catalyseur dans des conditions de réaction pour produire un produit liquide et la séparation du produit liquide du catalyseur par rotation du lit de catalyseur, où la rotation du lit de catalyseur crée une vitesse de glissement d'environ 0,95 ou moins. La présente invention concerne également des réacteurs ayant un lit de catalyseur rotatif comprenant un catalyseur ayant un gradient de taille de pore moyen qui diminue à mesure que le rayon à partir d'un point central augmente.
PCT/US2020/033740 2019-06-18 2020-05-20 Réacteurs à lit à garnissage rotatif et procédés associés WO2020256880A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN113842841A (zh) * 2021-09-11 2021-12-28 唐山三友硅业有限责任公司 树脂法制备二甲基硅油的方法及制备用反应釜
CN114082391A (zh) * 2021-11-12 2022-02-25 武汉科技大学 一种自稳定折流式超重力旋转床

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US20020086910A1 (en) * 2000-12-13 2002-07-04 Trinh Sinh Han Rotating annular catalytic reactor

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US20020086910A1 (en) * 2000-12-13 2002-07-04 Trinh Sinh Han Rotating annular catalytic reactor

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113842841A (zh) * 2021-09-11 2021-12-28 唐山三友硅业有限责任公司 树脂法制备二甲基硅油的方法及制备用反应釜
CN114082391A (zh) * 2021-11-12 2022-02-25 武汉科技大学 一种自稳定折流式超重力旋转床
CN114082391B (zh) * 2021-11-12 2023-04-07 武汉科技大学 一种自稳定折流式超重力旋转床

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