WO2025001983A1 - 气体分布单元、鼓泡床反应器以及使用其的反应方法 - Google Patents

气体分布单元、鼓泡床反应器以及使用其的反应方法 Download PDF

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Publication number
WO2025001983A1
WO2025001983A1 PCT/CN2024/100542 CN2024100542W WO2025001983A1 WO 2025001983 A1 WO2025001983 A1 WO 2025001983A1 CN 2024100542 W CN2024100542 W CN 2024100542W WO 2025001983 A1 WO2025001983 A1 WO 2025001983A1
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WIPO (PCT)
Prior art keywords
gas
gas distribution
bed reactor
gas outlet
bubbling bed
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Ceased
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PCT/CN2024/100542
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English (en)
French (fr)
Inventor
周继鹏
何文军
戈军伟
王嘉华
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Publication of WO2025001983A1 publication Critical patent/WO2025001983A1/zh
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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
    • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
    • B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C07D317/38—Ethylene carbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the invention relates to the technical field of heterogeneous reactions, and in particular to a gas distribution unit, a bubbling bed reactor using the unit, and a reaction method.
  • Bubble bed reactor is widely used for gas-liquid reaction and gas-liquid-solid reaction.
  • gas-liquid reaction using bubbling bed reactor include the reaction of preparing terephthalic acid (TA) from p-xylene (PX), formaldehyde carbonylation reaction and the reaction of producing o- and p-halobenzaldehyde by selective oxidation of halogenated toluene.
  • gas-liquid-solid reaction using bubbling bed reactor include residual oil hydrogenation, Fischer-Tropsch synthesis, ethylene carbonate, propylene carbonate and butylene carbonate synthesis.
  • the main production methods of ethylene carbonate include phosgene method, transesterification method, urea alcoholysis method and addition method.
  • the addition method includes feeding carbon dioxide gas to a bubbling bed reactor, reacting with ethylene oxide liquid feed in the reactor in the presence of a catalyst bed formed by catalyst particles to form ethylene carbonate.
  • Chinese patent application CN106475017A discloses a gas-liquid-solid three-phase reactor for synthesizing ethylene carbonate from ethylene oxide and carbon dioxide, which includes a liquid discharge port, a liquid baffle, a gas feed port, a gas inlet distributor, a catalyst lower support sieve plate, a lower porcelain ball layer, a catalyst layer, an upper porcelain ball layer, a catalyst upper support sieve plate, a liquid feed port, a liquid feed distributor and a gas discharge port from bottom to top.
  • the gas and liquid feeds enter the catalyst bed radially and uniformly through the gas distributor and the liquid distributor, respectively.
  • the catalyst bed is fixed in the reactor by upper and lower porcelain balls and upper and lower support sieve plates. Multiple groups of baffles are arranged at the bottom of the reactor, and overflow weirs are arranged on both sides. This scheme achieves better separation of gas and liquid through the overflow weir. However, the presence of the overflow weir increases the liquid flow resistance, and the gas operation flux is small, which limits the production capacity of the reactor. In addition, the gas in the bed cannot be evenly distributed, which reduces the conversion rate and selectivity of the reactor. It is also easy for the local concentration of the gas-liquid-solid three-phase to be too high and the reaction to be highly exothermic, leading to catalyst deactivation.
  • the object of the present invention is to provide a gas distribution unit, a bubbling bed reactor and a reaction method.
  • the gas distribution unit of the present invention can make the gas-liquid raw material distribution more uniform and the gas-liquid raw material contact time longer.
  • the gas distribution unit is used in a bubbling bed reactor, it not only effectively improves the conversion rate and selectivity of the reaction in the reactor, but also can avoid the occurrence of excessive local concentration of raw materials, thereby avoiding violent reactions and avoiding catalyst deactivation.
  • the present invention provides a reaction method, which comprises the steps of: using the gas distribution unit according to the first aspect to inject gaseous reactants into a bubbling bed reactor to react with liquid reactants therein.
  • the present invention controls the gas outlet in the gas distribution unit to spray the gas obliquely downward into the bubbling bed reactor.
  • the gas entering the reactor moves obliquely downward and turns to move upward under the action of buoyancy.
  • the turning movement of the gas entering the reactor allows the bubbles to stay in the liquid feed longer, promotes gas-liquid mass transfer, and helps the reaction.
  • the turning movement of the gas entering the reactor increases the turbulence of the liquid phase. This can also promote gas-liquid mass transfer and help the reaction;
  • At least three gas outlets are provided from top to bottom, and the injection angles of the injected gas are controlled so that the injection angles decrease from top to bottom, and the reduction amplitude of the injection angles of two adjacent gas outlets increases from top to bottom. Unreacted gas feed will accumulate with increasing height. Correspondingly, the downward velocity component of the gas entering the reactor is reduced in an increasing manner from bottom to top in the structure of the present invention, so that the gas feed is more evenly distributed in the liquid feed throughout the bubbling bed reactor. This further improves the conversion rate and selectivity of the reaction carried out therein;
  • gas distributors at different heights are staggered. This can further increase the turbulence of gas and liquid, promote mixing, and improve the conversion rate and selectivity of the reaction carried out therein;
  • At least one catalyst bed layer may be provided in the bubbling bed reactor, preferably at least two catalyst beds are provided, and a bottom gas distributor is provided below each catalyst bed. This structure can increase the probability of avoiding back-mixing of catalysts in the two catalyst beds;
  • At least two catalyst beds are provided, and the bed at a higher position in the bubbling bed reactor contains catalyst particles with a larger average particle size, while the bed at a lower position in the bubbling bed reactor contains catalyst particles with a smaller average particle size.
  • the catalyst bed at a lower position in the bubbling bed reactor contains catalyst particles with a smaller average particle size, which allows more gaseous reactants to react, while fewer unreacted gaseous reactants rise along the reactor and leave the reactor.
  • the catalyst particles with a larger average particle size have a larger settling velocity in the liquid, and the reaction efficiency of the reactants thereon is lower.
  • a plurality of gas outlets are provided at different heights of the bubbling bed reactor, and the injection angle of the injected gas decreases from top to bottom in sequence, preferably from top to bottom in an increasing manner to reduce the injection angle.
  • This structure can gradually increase the horizontal velocity component of the gas entering the reactor from bottom to top, which increases the liquid phase and the catalyst.
  • the turbulence of the catalyst particles can offset the adverse effect of the larger average particle size on the reaction efficiency.
  • the structure of the catalyst layer and the structure of the gas distributor can lead to a synergistic effect, further improving the conversion rate and selectivity of the reaction.
  • FIG1 is a schematic structural diagram of a bubbling bed reactor according to one embodiment of the present invention.
  • FIG. 2 is a schematic structural diagram of a gas distributor according to an embodiment of the present invention.
  • FIG3 is a schematic cross-sectional view of a gas distribution pipe according to an embodiment of the present invention.
  • FIG. 4 is a schematic structural diagram of a bubbling bed reactor according to an embodiment of the present invention.
  • 1-bubbling bed reactor 11-catalyst bed, 11A-upper catalyst bed, 11B-lower catalyst bed, 12A-first gas distributor, 12B-second gas distributor, 12C-third gas distributor, 12D-bottom gas distributor, 120-gas outlet, 121-main pipe of gas distributor, 122-branch pipe of gas distributor, 13-liquid distributor, 14-catalyst supporting sieve plate, 15-cooling jacket, 16-reactor gas outlet, 17-reactor liquid product outlet.
  • spatial relative terms such as “below”, “beneath”, “down”, “above”, “above”, etc. may be used to describe the relationship between one element or feature and another element or feature in the accompanying drawings. It should be understood that the spatial relative terms are intended to include different orientations of the object in use or operation in addition to the orientation depicted in the drawings. For example, if the object in the figure is turned over, the element described as being “below” or “below” other elements or features will be oriented “above” the elements or features. Objects may also have other orientations (rotated 90 degrees, etc.) and the spatial relative terms used in this document should be interpreted accordingly.
  • the terms “above”, “above”, and “on” include an element or feature. Vertically above another element or feature and one element or feature obliquely above another element or feature, as long as the projection of one element or feature in the vertical plane is above the other element or feature. Accordingly, the terms “below”, “beneath”, and “below” include one element or feature vertically below another element or feature and one element or feature obliquely below another element or feature, as long as the projection of one element or feature in the vertical plane is below the other element or feature.
  • first”, second, third, etc. are used to distinguish multiple different elements or parts, and are not used to limit specific positions or relative relationships. In other words, in some embodiments, the terms “first”, “second”, “third”, etc. can also be interchangeable with each other.
  • the present invention provides a gas distribution unit, comprising at least one gas distribution pipe, wherein the at least one gas distribution pipe comprises from top to bottom at least one gas outlet A and at least one gas outlet B, wherein the gas outlet A sprays gas downward at an injection angle ⁇ A, and the gas outlet B sprays gas downward at an injection angle ⁇ B, wherein the injection angle is the angle between the gas injection direction and the vertical direction, and ⁇ A> ⁇ B.
  • the term "bubbling bed reactor” is also called “bubbling reactor” or “boiling bed reactor”, which refers to a reactor with liquid as continuous phase and gas as dispersed phase, which can be a gas-liquid two-phase reactor or a gas-liquid-solid three-phase reactor.
  • gas distribution unit refers to a device capable of introducing a gas feed into a reactor and dispersing it into a liquid feed.
  • gas distribution pipe refers to a device from which gaseous reactants are discharged.
  • the gas distribution pipe may have any structure and shape suitable for discharging gas feed in a bubbling bed reactor for reaction, such as annular, spherical, cylindrical, and irregular shapes.
  • the gas distribution pipe may be a folded pipe, annular, or straight pipe.
  • the gas distribution pipe is a straight pipe, wherein the cross-section of the straight pipe may be circular, elliptical, rectangular (including square), or polygonal, and is preferably circular.
  • the term "obliquely downward” refers to a direction having a downward component and forming an angle greater than 0° but less than 90° with the vertical direction.
  • vertical direction refers to a direction perpendicular to a horizontal plane.
  • injection angle refers to the angle between the gas injection direction and the vertical direction.
  • ⁇ A and ⁇ B are 10-85°, preferably 20-65°.
  • ⁇ A and ⁇ B are each independently 10°, 15°, 20°, 25°, 30°, 35°, °, 40°, 45°, 50°, 55°, 60°, 65°, 70°, 75°, 80°, or 85°.
  • the difference between ⁇ A and ⁇ B is 5-60°, preferably 5-45°.
  • the difference between ⁇ A and ⁇ B is 5°, 10°, 15°, 20°, 25°, 30°, 35°, 40°, 45°, 50°, 55° or 60.
  • the at least one gas distribution pipe also includes at least one gas outlet C, which is located below the gas outlet A and the gas outlet B, and sprays gas downward at an injection angle ⁇ C, and ⁇ A> ⁇ B> ⁇ C, preferably, the difference between ⁇ A and ⁇ B is smaller than the difference between ⁇ B and ⁇ C.
  • ⁇ C is 10-65°, preferably 20-50°.
  • ⁇ C is 10°, 15°, 20°, 25°, 30°, 35°, 40°, 45°, 50°, 55°, 60° or 65°.
  • the difference between ⁇ B and ⁇ C is 5-60°, preferably 5-45°.
  • the difference between ⁇ B and ⁇ C is 5°, 10°, 15°, 20°, 25°, 30°, 35°, 40°, 45°, 50°, 55° or 60°.
  • the difference between ⁇ A and ⁇ B is 1-30°, preferably 5-25°, smaller than the difference between ⁇ B and ⁇ C.
  • the difference between ⁇ A and ⁇ B is 1°, 2°, 3°, 4°, 5°, 6°, 7°, 8°, 9°, 10°, 11°, 12°, 13°, 14°, 15°, 16°, 17°, 18°, 19°, 20°, 21°, 22°, 23°, 24°, 25°, 26°, 27°, 28°, 29° or 30° smaller than the difference between ⁇ B and ⁇ C.
  • the gas distribution unit may include at least two, for example three or more, or four or more gas outlets at different heights, wherein the gas outlets are arranged from top to bottom, and the angle between the corresponding gas injection direction and the vertical direction, i.e., the injection angle, decreases from top to bottom.
  • the reduction amplitude gradually increases from top to bottom.
  • the term "height” refers to the vertical distance from the horizontal plane where the lowest point of the bubbling bed reactor is located.
  • the configuration of the present invention can offset the accumulation of unreacted gas feed with increasing height. This allows the gas feed to be more evenly distributed in the liquid feed throughout the bubbling bed reactor, thereby increasing the conversion rate and selectivity of the reaction conducted therein.
  • the gas outlet A and the gas outlet B may be located on the same or different gas distribution pipes of the at least one gas distribution pipe.
  • the gas outlet A is located on the first gas distribution pipe and the gas outlet B is located on the second gas distribution pipe, and more preferably, the first and second gas distribution pipes are arranged horizontally.
  • the horizontal arrangement of the gas distribution pipes means that the central axis of the gas distribution pipes is parallel to the horizontal plane.
  • the first and second gas distribution pipes each have a cross-section of a regular shape or an irregular shape, and each has a shape of a straight pipe, a curved pipe, and a circular pipe.
  • a plurality of the first and second gas distribution pipes are interconnected to form a gas distributor.
  • a plurality of the first gas distribution pipes are connected to form a first gas distributor, and a plurality of the second gas distribution pipes are connected to form a second gas distributor, wherein the first and second gas distributors are respectively arranged horizontally.
  • One of the plurality of gas distribution pipes connected to form a gas distributor is called a main pipe, and the others are called branch pipes.
  • the main pipe and the branch pipe can be connected in a common manner in the art.
  • the first and second gas distributors each include a main pipe in a horizontally arranged straight pipe shape and one or more branch pipes in a straight pipe shape connected to the main pipe, and the two main pipes of the first and second gas distributors are parallel to each other, and the projections of the two main pipes on the horizontal plane have an angle ⁇ , and the range of ⁇ is 0°-135°, preferably 20°-70°.
  • the first and second gas distributors are staggered. This can further increase the degree of gas-liquid turbulence, promote mixing, and improve the conversion rate and selectivity of the reaction carried out therein.
  • the gas outlet may be any device that can discharge gas, for example, an opening or a nozzle.
  • the term "opening" may have any shape suitable for outflowing gas, such as circular, elliptical, rectangular (including square) or polygonal, and preferably circular.
  • the size of the opening may be determined according to the shape and size of the gas distribution pipe in which it is located and the type of reaction, etc.
  • the ratio of the equivalent diameter of the opening to the equivalent diameter of the gas distribution pipe is 0.01-0.25, more preferably 0.02-0.15.
  • the "nozzle” may be in any form and have any structure, and its outlet is the same as the definition of the above-mentioned "opening".
  • the first and second gas distribution pipes are respectively straight pipes with circular cross-sections
  • the gas outlet A is an opening on the first gas distribution pipe
  • the gas outlet B is an opening on the second gas distribution pipe
  • the opening angles ⁇ A and ⁇ B are respectively equivalent to the gas injection angles ⁇ A and ⁇ B
  • the opening angle is the angle between the center point of the opening cross section and the straight line where the center point of the cross-section circle of the corresponding gas distribution pipe is located and the vertical direction
  • the first and second gas distribution pipes each have an open porosity of 1 ⁇ to 60 ⁇ , preferably 1 ⁇ -45 ⁇ , more preferably 5 ⁇ to 30 ⁇ .
  • the gas outlet A, the gas outlet B and the at least one gas outlet C are located on the same or different gas distribution pipes of the at least one gas distribution pipe.
  • the gas outlet A is located on the first gas distribution pipe
  • the gas outlet B is located on the second gas distribution pipe
  • the at least one gas outlet C is located on the third gas distribution pipe.
  • the first, second and third gas distribution pipes are arranged horizontally.
  • the first, second and third gas distribution pipes each have a regular or irregular cross-section, and each have a shape of a straight pipe, a curved pipe and a circular pipe.
  • a plurality of the first, second and third gas distribution pipes are interconnected to form a gas distributor.
  • a plurality of the first gas distribution pipes are connected to form a first gas distributor
  • a plurality of the second gas distribution pipes are connected to form a second gas distributor
  • a plurality of the third gas distribution pipes are connected to form a third gas distributor
  • the first, second and third gas distributors are each arranged horizontally
  • the first, second and third gas distributors each include a horizontally arranged straight pipe-shaped main pipe and one or more straight pipe-shaped branches connected to the main pipe, and more preferably the three main pipes of the first, second and third gas distributors are parallel to each other, and the projections of the three main pipes on the horizontal plane have an angle ⁇ , and the range of ⁇ is 0°-135°, preferably 20°-70°.
  • the adjacent two of the first, second and third gas distributors are staggered. This can further increase the degree of gas-liquid turbulence, promote mixing, and improve the conversion rate and selectivity of the reaction carried out therein.
  • each of the first, second and third gas distribution pipes is a straight pipe with a circular cross section
  • the gas outlet A is an opening on the first gas distribution pipe.
  • B is an opening on the second gas distribution pipe
  • the at least one gas outlet C is an opening on the third gas distribution pipe
  • the opening angles ⁇ A, ⁇ B, ⁇ C are respectively equivalent to the gas injection angles ⁇ A, ⁇ B, ⁇ C
  • the opening angle is the angle between the center point of the opening cross section and the straight line where the center point of the cross-sectional circle of the corresponding gas distribution pipe is located and the vertical direction
  • the first, second and third gas distribution pipes each have an open porosity of 1 ⁇ to 60 ⁇ , preferably 1 ⁇ -45 ⁇ , more preferably 5 ⁇ to 30 ⁇ .
  • the gas distribution unit further includes a bottom gas distribution pipe, which is located below all of the at least one gas distribution pipes, and the bottom gas distribution pipe has at least one gas outlet D, so as to spray gas upward at an injection angle ⁇ , wherein ⁇ refers to the angle between the injection direction and the vertical direction and is in the range of 0° to 80° or 10° to 80°, preferably 20° to 70°, and more preferably 30° to 60°.
  • a plurality of bottom gas distribution pipes are interconnected to form a bottom gas distributor.
  • the bottom gas distributor and the bottom gas distribution pipe have the same structure as the gas distributor and the gas distribution pipe described above, except that the former is inverted and the latter is arranged so that the gas injection direction is inclined upward.
  • the term "obliquely upward” refers to a direction having an upward component and forming an angle greater than 0° but less than 90° with the vertical direction.
  • the present invention provides a bubbling bed reactor, comprising the gas distribution unit according to the first aspect.
  • the height of the gas outlet A in the bubbling bed reactor is hA
  • the height of the gas outlet B in the bubbling bed reactor is hB
  • hA and hB are 10-90%, preferably 20-85% of the total height H of the bubbling bed reactor.
  • hA and hB are each independently 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% of the total height H of the bubbling bed reactor.
  • the difference between hA and hB is 5-70%, preferably 10-60%, of the total height H of the bubbling bed reactor.
  • the difference between hA and hB is 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70% of the total height H of the bubbling bed reactor.
  • the difference between hA and hB should be greater than the total height H of the bubbling bed reactor.
  • the jet length of the injected gas is shortened so that the gas injected from the gas outlet A does not touch the horizontal plane where the gas outlet B is located.
  • the total height H of the bubbling bed reactor can be 2-16 meters, for example 2 meters, 4 meters, 6 meters, 8 meters, 10 meters, 12 meters, 16 meters.
  • the ratio of the total height H of the bubbling bed reactor to the reactor diameter Dr is 1.2-10.5, preferably 2.5-7.
  • H/Dr is 1.2, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 10.5.
  • the height of the gas outlet C in the bubbling bed reactor is hC, wherein hC is 10-90%, preferably 20-85%, of the total height H of the bubbling bed reactor.
  • hC is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% of the total height H of the bubbling bed reactor.
  • the difference between hB and hC is 5-60%, preferably 10-50%, of the total height H of the bubbling bed reactor, wherein the difference between hB and hC is the same as or different from the difference between hA and hB.
  • the difference between hB and hC and the difference between hA and hB are each independently 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of the total height H of the bubbling bed reactor, but the sum of the difference between hB and hC and the difference between hA and hB should be less than or equal to 80% of the total height H of the reactor.
  • the difference between two gas outlets at adjacent heights should be greater than the injection length of the gas injected from the upper gas outlet, so that the gas injected from the upper gas outlet does not contact the horizontal plane where the lower gas outlet is located.
  • hA is 30-65%, preferably 30-55%, of the total height H of the bubbling bed reactor
  • hB is 10-40%, preferably 20-30%, of the total height H of the bubbling bed reactor.
  • hA is 50-85%, preferably 60-80%
  • hB is 30-65%, preferably 30-55%
  • hC is 10-40%, preferably 20-30%, of the total height H of the bubbling bed reactor.
  • the bubbling bed reactor comprises at least one catalyst bed, the at least one catalyst bed is composed of catalyst particles, wherein the gas distribution unit comprises a first and a second gas distribution pipe, and each of the first and second gas distribution pipes is independently located in the at least one catalyst bed.
  • the height of the first and second gas distribution pipes in the catalyst bed is 10-90%, preferably 20-85%, and more preferably 25-80% of the catalyst bed height.
  • the bubbling bed reactor comprises two catalyst beds, and the first and second gas distribution pipes are respectively located in the first and second catalyst beds.
  • the height of the first distribution pipe in the first catalyst bed is 10-90%, preferably 20-85%, more preferably 25-80% of the first catalyst bed.
  • the height of the second gas distribution pipe in the second catalyst bed is 10-90%, preferably 20-85%, more preferably 25-80% of the height of the second catalyst bed.
  • the first and second catalyst beds are each composed of catalyst particles, preferably spherical catalyst particles, wherein the average particle sizes of the catalyst particles in the first and second catalyst beds are P1 and P2, respectively, and P1>P2;
  • the bubbling bed reactor further comprises a bottom gas distributor.
  • the bottom gas distributor is located below all of the at least one gas distribution pipes.
  • the bubbling bed reactor includes at least one catalyst bed
  • the bubbling bed reactor comprises at least one bottom gas distributor, which is respectively located in the bubbling bed reactor space below each catalyst bed.
  • the bubbling bed reactor includes at least one catalyst bed, and a bottom gas distributor is located in the bubbling bed reactor space below all of the at least one catalyst bed.
  • the bubbling bed reactor comprises at least one catalyst bed, the at least one catalyst bed is composed of catalyst particles, wherein the gas distribution unit comprises first, second and third gas distribution pipes, and each of them is independently located in the at least one catalyst bed.
  • the height of the first, second and third gas distribution pipes in the corresponding catalyst bed is 10-90%, preferably 20-85%, more preferably 25-80% of the catalyst bed height.
  • the first, second and third gas distribution pipes are located in the first, second and third catalyst beds, respectively.
  • the height of the first distribution pipe in the first catalyst bed is 10-90%, preferably 20-85%, more preferably 25-80% of the height of the first catalyst bed.
  • the height of the second gas distribution pipe in the second catalyst bed is 10-90%, preferably 20-85%, more preferably 25-80% of the height of the second catalyst bed.
  • the height of the third distribution pipe in the third catalyst bed is 10-90%, preferably 20-85%, more preferably 25-80% of the height of the third catalyst bed.
  • the first, second and third catalyst beds are each composed of catalyst particles, wherein the average particle sizes of the catalyst particles in the first, second and third catalyst beds are P1, P2 and P3 respectively, and P1>P2>P3.
  • the bubbling bed reactor further comprises a bottom gas distributor.
  • the bottom gas distributor is located below all of the at least one gas distribution pipes.
  • the bubbling bed reactor includes at least one catalyst bed
  • the bubbling bed reactor includes at least one bottom gas distributor, which is respectively located in the bubbling bed reactor space below each catalyst bed.
  • the bubbling bed reactor includes at least one catalyst bed, and one bottom gas distributor is located below all of the at least A catalyst bed is located below the bubbling bed reactor space.
  • the bubbling bed reactor further comprises a liquid distribution pipe.
  • the height of the liquid distribution pipe in the bubbling bed reactor is greater than the height of all the at least one gas distribution pipes in the bubbling bed reactor.
  • the height of the liquid distribution pipe is greater than the height of all the at least one catalyst bed in the bubbling bed reactor.
  • the liquid distribution pipe inputs the liquid raw material into the bubbling bed reactor to submerge all the gas distribution pipes and the catalyst bed.
  • a plurality of liquid distribution pipes are connected to form a liquid distributor.
  • the liquid distribution pipe and the liquid distributor may have any shape and structure used in the field of bubbling bed reactors for introducing liquid reactants.
  • the liquid distributor has a plurality of openings for introducing liquid reactants and the opening rate is 1 ⁇ -65 ⁇ , preferably 5 ⁇ -60 ⁇ , more preferably 10 ⁇ -50 ⁇ .
  • the ratio of the equivalent diameter of the opening to the equivalent diameter of the liquid distribution pipe is 0.02-0.3, more preferably 0.05-0.2.
  • the bubbling bed reactor comprises two or more catalyst beds, preferably two catalyst beds, which are composed of catalyst particles, wherein the average particle size of the catalyst particles in each catalyst bed is greater than the average particle size of the catalyst particles in the catalyst bed below it.
  • the average particle size of the catalyst particles in the catalyst bed is independently 0.01 mm to 10 mm, preferably 0.1 mm to 5 mm, more preferably 0.3 mm to 3 mm.
  • the gas distribution unit comprises two catalyst beds, the average particle size P1 of the catalyst particles in the upper catalyst bed is greater than the average particle size P2 of the catalyst particles in the lower catalyst bed.
  • P1 is 0.1 mm to 10 mm, preferably 1 mm to 5 mm, more preferably 1 mm to 3 mm
  • P2 is 0.01 mm to 5 mm, preferably 0.1 mm to 2 mm, more preferably 0.3 mm to 1 mm.
  • the present invention provides at least one catalyst bed in a bubbling bed reactor, and installs at least one gas distributor of the present invention in each catalyst bed.
  • This structure can increase the uniform distribution of gas, increase the contact between feed and catalyst, and reduce the catalyst backmixing phenomenon, thereby improving the reaction rate, conversion rate and selectivity.
  • At least two catalyst beds are provided, and the bed located at a higher position in the bubbling bed reactor contains catalyst particles with a larger average particle size, while the bed located at a lower position in the bubbling bed reactor contains catalyst particles with a larger average particle size.
  • the bed at a lower position includes catalyst particles with a smaller average particle size.
  • the catalyst bed at a lower position in the bubbling bed reactor includes catalyst particles with a smaller average particle size, which allows more gaseous reactants to react, and fewer unreacted gaseous reactants rise along the reactor and leave the reactor.
  • the settling velocity of the catalyst particles with a larger average particle size in the liquid is larger, and the reaction efficiency of the reactant thereon is lower.
  • a plurality of gas outlets are provided at different heights of the bubbling bed reactor, and the injection angle of the injected gas is successively reduced from top to bottom, preferably from top to bottom in an increased amplitude mode to reduce the injection angle.
  • the structure can increase the horizontal velocity component of the gas entering the reactor from bottom to top, which increases the turbulence degree of the liquid phase and the catalyst particles, thereby offsetting the adverse effects of the larger average particle size on the reaction efficiency.
  • the structure of the catalyst layer and the structure of the gas distributor can lead to a synergistic effect, further improving the conversion rate and selectivity of the reaction.
  • the present invention provides a reaction method, comprising the steps of: using the gas distribution unit according to the first aspect to inject gaseous reactants into a bubbling bed reactor to react with liquid reactants therein.
  • the method comprises the following steps:
  • Reaction method can be used for carrying out the reaction of any gaseous reactant and liquid reactant, regardless of whether there is a catalyst, or the catalyst form is a homogeneous catalyst or a heterogeneous catalyst.
  • the reaction method is used for the synthesis of ethylene carbonate, propylene carbonate or butylene carbonate, wherein the liquid reactant ethylene oxide and the gaseous reactant carbon dioxide generate ethylene carbonate under the action of solid catalyst particles, the liquid reactant propylene oxide and the gaseous reactant carbon dioxide generate propylene carbonate under the action of solid catalyst particles, or the liquid reactant butylene oxide and the gaseous reactant carbon dioxide generate butylene carbonate under the action of solid catalyst particles.
  • the bubbling bed reactor 1 of the present invention is a columnar tank structure.
  • a cooling jacket 15 is wrapped around the outer wall of the bubbling bed reactor 1.
  • the bubbling bed reactor 1 includes a catalyst bed 11, a first gas distributor 12A, a second gas distributor 12B, a third gas distributor 12C, a bottom gas distributor 12D, and a liquid distributor 13.
  • the catalyst bed 11 is composed of catalyst particles between upper and lower supporting sieve plates 14.
  • the liquid distributor 13 is arranged above the catalyst bed 11.
  • the bottom gas distributor 12D is arranged below the catalyst bed 11.
  • the first gas distributor 12A, the second gas distributor 12B and the third gas distributor 12C are arranged in the catalyst bed 11 from top to bottom.
  • the height of the first gas distributor 12A is less than or equal to 80% of the height of the catalyst bed.
  • the bubbling bed reactor 1 also includes a reactor gas outlet 16 at the top and a reactor liquid product outlet 17 at the bottom.
  • the first gas distributor 12A, the second gas distributor 12B, the third gas distributor 12C, the bottom gas distributor 12D, the liquid distributor 13, and the supporting sieve plate 14 are all placed horizontally.
  • the liquid distributor 13 includes a horizontally arranged liquid distribution pipe as a main pipe and a branch pipe, wherein the branch pipe is connected to the main pipe and is perpendicular to the main pipe.
  • the liquid outlet on the liquid distribution pipe as the main pipe and the branch pipe is at least one row of openings, and the opening rate is 1 ⁇ -65 ⁇ .
  • the at least one row of openings is symmetrically distributed, and the opening direction is vertically downward or inclined downward.
  • the bottom gas distributor 12D includes a horizontally arranged bottom gas distribution pipe as a main pipe and a branch pipe, wherein the branch pipe is connected to the main pipe and is perpendicular to the main pipe.
  • the gas outlet on the bottom gas distribution pipe as the main pipe and the branch pipe is two rows of openings, wherein the two rows of openings are symmetrically distributed and have an opening angle ⁇ D inclined upward, wherein the opening angle is the angle between the center point of the opening cross section and the center point of the cross section circle of the corresponding gas distribution pipe and the vertical direction, wherein the opening angle ⁇ D is equal to the gas injection angle ⁇ , ⁇ is 10° to 80°.
  • the gas outlet on the bottom gas distribution pipe as the main pipe and the branch pipe is a row of openings, and its opening angle ⁇ D is equal to the gas injection angle ⁇ , ⁇ is 0° to 80°.
  • the third gas distributor 12C includes a horizontally arranged second gas distribution pipe as a main pipe 121 and a branch pipe 122, wherein the branch pipe 122 is connected to the main pipe 121 and is perpendicular to the main pipe 121.
  • the main pipe 121 and the branch pipe 122 each independently include two rows of openings as gas outlets, which are arranged symmetrically and have an opening angle ⁇ C inclined downward, wherein the opening angle is the angle between the center point of the opening cross section and the straight line where the center point of the cross section circle of the corresponding gas distribution pipe is located and the vertical direction.
  • the opening angle ⁇ C of the gas outlet is equal to the gas injection angle ⁇ C.
  • the main pipe 121 and the branch pipe 122 each independently include a row of openings
  • the holes are used as gas outlets, wherein the openings have an opening angle ⁇ C inclined downward.
  • the opening rates of the main pipe 121 and the branch pipe 122 are 1 ⁇ -60 ⁇ , preferably 1 ⁇ -45 ⁇ .
  • the third gas distributor 12C has the same structure as the bottom gas distributor 12D, and the main pipe 121 of the third gas distributor 12C is arranged to have an angle ⁇ with the horizontal plane projection of the main pipe of the bottom gas distributor 12D, and the angle ⁇ is in the range of 0°-90°, preferably 0-45°.
  • the first gas distributor 12A and the second gas distributor 12B have the same structure as the third gas distributor 12C, except that the opening angles of the openings on the gas distribution pipes of the first gas distributor 12A and the second gas distributor 12B are ⁇ A and ⁇ B, respectively, wherein ⁇ A> ⁇ B> ⁇ C, and preferably the difference between ⁇ A and ⁇ B is less than the difference between ⁇ B and ⁇ C.
  • the opening angles ⁇ A, ⁇ B and ⁇ C of the gas outlet are equal to the gas injection angles ⁇ A, ⁇ B and ⁇ C, respectively.
  • the horizontal plane projections of the two adjacent main pipes of the first gas distributor 12A, the second gas distributor 12B and the third gas distributor 12C each independently have an angle ⁇ , and the range of ⁇ is 0°-135°, preferably 20°-70°.
  • the bubbling bed reactor 1 of the present invention is a columnar tank structure.
  • a cooling jacket 15 is wrapped around the outer wall of the bubbling bed reactor 1.
  • the bubbling bed reactor 1 includes an upper catalyst bed 11A, a lower catalyst bed 11B, a first gas distributor 12A disposed in the upper catalyst bed 11A, a bottom gas distributor 12D 1 disposed between the upper catalyst bed 11A and the lower catalyst bed 11B, a second gas distributor 12B disposed in the lower catalyst bed 11B, a bottom gas distributor 12D 2 disposed below the lower catalyst bed 11B, and a liquid distributor 13.
  • the upper catalyst bed 11A and the lower catalyst bed 11B are each independently composed of catalyst particles between upper and lower supporting sieve plates 14, wherein the average particle size of the catalyst particles of the upper catalyst bed 11A is greater than the average particle size of the catalyst particles of the lower catalyst bed 11B.
  • the liquid distributor 13 is disposed above the upper catalyst bed 11A.
  • the bubbling bed reactor 1 further includes a reactor gas outlet 16 at the top and a reactor liquid product outlet 17 at the bottom.
  • the first gas distributor 12A, the second gas distributor 12B, the bottom gas distributors 12D1 and 12D2 , and the liquid distributor 13 have the structures mentioned in the description of the bubbling bed reactor shown in FIG. 1 , and will not be described in detail here.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide the reaction of synthesizing propylene carbonate from propylene oxide and carbon dioxide or the reaction of synthesizing propylene carbonate from propylene oxide and carbon dioxide are carried out.
  • the liquid phase (any liquid among ethylene oxide, propylene oxide and butylene oxide) enters the bubbling bed reactor 1 by the liquid distributor 13, so that the liquid phase submerges the catalyst bed 11.
  • the gas phase (carbon dioxide) enters the reactor 1 by the first gas distributor 12A, the second gas distributor 12B, the third gas distributor 12C and the bottom gas distributor 12D.
  • the liquid phase ethylene oxide and the gas phase carbon dioxide react in the catalyst bed 11 to generate ethylene carbonate, the liquid phase propylene oxide and the gas phase carbon dioxide react in the catalyst bed 11 to generate propylene carbonate, or the liquid phase butylene oxide and the gas phase carbon dioxide react in the catalyst bed 11 to generate butylene carbonate.
  • the reaction product flows out of the reactor 1 through the reactor liquid product outlet 17 in the form of liquid phase, and the unreacted carbon dioxide is discharged from the reactor 1 by the reactor gas outlet 16.
  • the present application may include the following implementations:
  • a gas distribution unit characterized in that it is applied to a gas-liquid-solid three-phase bubbling bed reactor, comprising:
  • a bottom gas distributor which is disposed below the catalyst bed and bubbles upward;
  • a first gas distributor is disposed inside the catalyst bed and bubbles downward.
  • the gas distribution unit according to claim 1 wherein the first gas distributor is arranged in 1 to 4 layers, preferably 2 layers, at different heights within the catalyst bed.
  • the gas distribution unit according to claim 4 is characterized in that the first air holes are arranged in two or more rows; when there are two rows of first air holes, the two air holes are symmetrically and tilted downward, and the angle ⁇ between the air hole direction and the vertical direction ranges from 25° to 65°.
  • the gas distribution unit according to claim 5 characterized in that when two layers of the first gas distributor are provided, the angle ⁇ of the first gas holes in the upper layer is greater than or equal to the angle ⁇ of the first gas holes in the lower layer.
  • the gas distribution unit according to claim 3 characterized in that the installation height of the first gas distributor in the uppermost layer is less than or equal to 80% of the height of the catalyst bed.
  • the gas distribution unit according to claim 1 is characterized in that the bottom air holes are arranged in two or more rows; when there are two rows of bottom air holes, the two air holes are symmetrically and inclined upward, and the angle ⁇ between the air hole direction and the vertical direction ranges from 30° to 60°.
  • the gas distribution unit according to claim 1 is characterized in that the bottom gas distributor and the first gas distributor are composed of a main pipe and multiple branch pipes that are perpendicular to each other, and the coverage of the branch pipes is adapted to the cross-section of the bubbling bed reactor; the porosity of the main pipe and the branch pipe is 1 ⁇ -45 ⁇ .
  • a bubbling bed reactor characterized in that it is applied to the gas distribution unit according to any one of claims 1 to 11.
  • the liquid distributor is arranged above the catalyst bed and is used to provide liquid phase feed for the reaction; the liquid phase feed immerses the solid catalyst bed.
  • the bubbling bed reactor according to claim 13 characterized in that the porosity of the liquid distributor is 1 ⁇ -65 ⁇ .
  • the catalyst bed is one layer or multiple layers.
  • the gas distribution unit is independently arranged in each bed.
  • the bubbling bed reactor according to claim 15 characterized in that supporting sieve plates are respectively provided at the upper end and the lower end of the catalyst bed.
  • the bubbling bed reactor according to claim 12 characterized in that the outer wall of the bubbling bed reactor is wrapped with a cooling jacket.
  • a reaction method characterized in that the bubbling bed reactor according to any one of claims 12 to 17 is used, comprising:
  • the liquid feed enters the reactor through the liquid distributor and establishes a liquid level that submerges the catalyst bed;
  • the gas feed is respectively sprayed through the bottom gas distributor and the first gas distributor, and the bubbles from the first gas distributor are turned back in the liquid phase at the catalyst bed;
  • reaction method according to claim 18 characterized in that the reaction method is used to synthesize ethylene carbonate.
  • reaction method according to claim 19 characterized in that the liquid feed is ethylene oxide and the gas feed is carbon dioxide.
  • the catalyst used in the following examples and comparative examples is commercial catalyst particles from Sinopec (Shanghai) Petrochemical Research Institute Co., Ltd., with a trade name of SEC-22.
  • a bubbling bed reactor 1 is provided.
  • the inner diameter of the bubbling bed reactor 1 is 1600 mm, and the reactor height is 6000 mm.
  • the bubbling bed reactor 1 includes a catalyst bed 11 (which is composed of the commercial catalyst particles), a first gas distributor 12A and a second gas distributor 12B arranged from top to bottom in the catalyst bed, a bottom gas distribution pipe 12D arranged below the catalyst bed 11, and a liquid distributor 13 arranged above the catalyst bed 11.
  • the first gas distributor 12A, the second gas distributor 12B and the bottom gas distributor 12D are each composed of a horizontally arranged gas distribution main pipe 121 and five gas distribution branch pipes 122, wherein the branch pipe 122 is connected to the main pipe 121 and is perpendicular to the main pipe 121.
  • the angle ⁇ between the horizontal plane projections of the main pipes of the first gas distributor 12A and the second gas distributor 12B and the main pipe of the bottom gas distributor 12D is 0°.
  • Two rows of symmetrically distributed and downwardly inclined openings are provided on the main pipes and branch pipes of the first gas distributor 12A and the second gas distributor 12B.
  • the installation height of the second gas distributor 12B is 25% of the height of the catalyst bed 11, and the installation height of the first gas distributor 12A is 50% of the height of the catalyst bed 11.
  • the porosity of the first gas distributor 12A, the second gas distributor 12B and the bottom gas distributor 12D is 25 ⁇ , and the porosity of the liquid distributor 13 is 45 ⁇ .
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide is carried out in the bubbling bed reactor 1.
  • the conversion rate and selectivity achieved in this example are 91.8% and 99.1%.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide is carried out in the bubbling bed reactor 1.
  • the conversion rate and selectivity achieved in this example are 93.5% and 99.8%.
  • Example 2 The difference between Example 2 and Example 1 is only the difference in injection angle: the difference in injection angle is 10° in Example 1 and 20° in Example 2. As the difference in injection angle increases, both conversion and selectivity are improved.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide was carried out in the bubbling bed reactor 1.
  • the conversion rate and selectivity achieved in this comparative example were 87.1% and 96.5%.
  • Example 2 Compared with Example 1 and Example 2, the injection angle difference of Comparative Example 1 is reduced to 0°, that is, the injection angle of the opening of the upper gas distributor is the same as the injection angle of the opening of the lower gas distributor. This significantly reduces the conversion rate and selectivity.
  • a bubbling bed reactor 1 is provided.
  • the inner diameter of the bubbling bed reactor 1 is 1600 mm, and the reactor height is 6000 mm.
  • the bubbling bed reactor 1 includes a catalyst bed 11 (which is composed of the commercial catalyst particles), a first gas distributor 12A, a second gas distributor 12B and a third gas distributor 12C arranged from top to bottom in the catalyst bed, a bottom gas distribution pipe 12D arranged below the catalyst bed 11, and a liquid distributor 13 arranged above the catalyst bed 11.
  • the first gas distributor 12A, the second gas distributor 12B, the third gas distributor 12C and the bottom gas distribution pipe 12D are each composed of a horizontally arranged gas distribution main pipe 121 and five gas distribution branch pipes 122, wherein the branch pipes 122 are connected to the main pipe 121 and are perpendicular to the main pipe 121.
  • Two rows of symmetrically distributed and inclined downward openings are provided on the main pipes and branch pipes of the first gas distributor 12A, the second gas distributor 12B and the third gas distributor 12C.
  • the installation height of the third gas distributor 12C is 25% of the height of the catalyst bed 11
  • the installation height of the second gas distributor 12B is 50% of the height of the catalyst bed 11
  • the installation height of the first gas distributor 12A is 70% of the height of the catalyst bed 11.
  • the opening rate of the first gas distributor 12A, the second gas distributor 12B, the third gas distributor 12C and the bottom gas distributor 12D is 25 ⁇
  • the opening rate of the liquid distributor 13 is 45 ⁇ .
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide is carried out in the bubbling bed reactor 1.
  • the conversion rate achieved in this example is 96.5% and the selectivity is greater than 99.9%.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide was carried out in the bubbling bed reactor 1.
  • the conversion rate and selectivity of this comparative example were 89.2% and 98.0%.
  • Comparative Example 2 and Example 3 The difference between Comparative Example 2 and Example 3 is that the injection angles (and their differences) of the openings of the three gas distributors are different.
  • the differences between the injection angles of Comparative Example 2 are all 0°.
  • the difference between the injection angles of the openings of the first gas distributor 12A and the second gas distributor 12B of Example 3 is 7°, and the difference between the injection angles of the openings of the second gas distributor 12B and the third gas distributor 12C is 23°.
  • the difference in the injection angles of the openings of two gas distributors at adjacent heights increases. Accordingly, relative to Example 3, the conversion rate and selectivity achieved in Comparative Example 2 are both reduced.
  • a bubbling bed reactor 1 is provided which is the same as the bubbling bed reactor 1 of Example 3, except that the opening angle ⁇ 12A of the opening of the first gas distributor 12A is 75°, and the second gas distributor 12B is 120°.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide was carried out in the bubbling bed reactor 1.
  • the conversion rate achieved in this comparative example was 94.1% and the selectivity was greater than 99.9%.
  • Comparative Example 3 the injection angle of the opening of the gas distributor gradually decreases from top to bottom, and the difference between the injection angles of the openings of two gas distributors at adjacent heights is the same, both of which are 15°. Compared with Comparative Example 2, the injection angle of Comparative Example 3 gradually decreases from top to bottom, and the conversion rate and selectivity are improved. Compared with Example 3, the difference between the injection angles of Comparative Example 3 is unchanged, and the conversion rate is reduced.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide was carried out in the bubbling bed reactor 1.
  • the conversion rate and selectivity of this comparative example were 92.2% and 99.3%.
  • Comparative Example 4 the injection angle of the openings of the gas distributor gradually decreases from top to bottom, and the difference between the injection angles also gradually decreases. Compared with Comparative Example 2, the injection angle of Comparative Example 4 gradually decreases from top to bottom, and the conversion rate and selectivity are improved. In contrast to Example 3, the difference between the injection angles of the openings of two gas distributors at adjacent heights in Comparative Example 4 gradually decreases from top to bottom, resulting in a decrease in conversion rate and selectivity.
  • a bubbling bed reactor 1 identical to the bubbling bed reactor 1 of Example 1 is provided, except that the angle ⁇ between the horizontal plane projections of the main pipe of the first gas distributor 12A and the main pipe of the bottom gas distributor 12D is 55°, and the angle ⁇ between the horizontal plane projections of the main pipe of the second gas distributor 12B and the main pipe of the bottom gas distributor 12D is 30°.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide is carried out in the bubbling bed reactor 1.
  • the conversion rate and selectivity achieved in this example are 92.7% and 99.6%.
  • Example 4 The difference between Example 4 and Example 1 is only that the angle ⁇ is different. It can be seen that the existence of the angle ⁇ will improve the reaction conversion rate and selectivity.
  • a bubbling bed reactor 1 identical to the bubbling bed reactor 1 of Example 4 was provided, except that only a first gas distributor 12A was provided in the catalyst bed.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide was carried out in the bubbling bed reactor 1.
  • the conversion rate and selectivity achieved in this comparative example were 82.0% and 93.5%.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide was carried out in the bubbling bed reactor 1.
  • the conversion rate and selectivity achieved in this comparative example were 86.1% and 95.1%.
  • a bubbling bed reactor 1 is provided.
  • the inner diameter of the bubbling bed reactor 1 is 1600 mm, and the reactor height is 6000 mm.
  • the bubbling bed reactor 1 includes a catalyst bed 11 (which is composed of the catalyst particles), gas distributors 12A and 12B arranged from top to bottom in the catalyst bed, a bottom gas distribution pipe 12D arranged below the catalyst bed 11, and a liquid distributor 13 arranged above the catalyst bed 11.
  • the first gas distributor 12A, the second gas distributor 12B and the bottom gas distributor 12D are each composed of a horizontally arranged gas distribution main pipe 121 and five gas distribution branch pipes 122, wherein the branch pipe 122 is connected to the main pipe 121 and is perpendicular to the main pipe 121.
  • the angle ⁇ between the horizontal plane projection of the main pipe of the first gas distributor 12A and the main pipe of the bottom gas distributor 12D is 45°, and the angle ⁇ between the horizontal plane projection of the main pipe of the second gas distributor 12B and the main pipe of the bottom gas distributor 12D is 0°.
  • Two rows of symmetrically distributed and downwardly inclined openings are provided on the main pipes and branch pipes of the first gas distributor 12A and the second gas distributor 12B.
  • the installation height of the second gas distributor 12B is 30% of the height of the catalyst bed 11, and the installation height of the first gas distributor 12A is 60% of the height of the catalyst bed 11.
  • the porosity of the first gas distributor 12A, the second gas distributor 12B and the bottom gas distributor 12D is 15 ⁇ , and the porosity of the liquid distributor 13 is 40 ⁇ .
  • a bubbling bed reactor 1 is provided.
  • the inner diameter of the bubbling bed reactor 1 is 1600 mm, and the reactor height is 6000 mm.
  • the bubbling bed reactor 1 includes an upper catalyst bed 11A and a lower catalyst bed 11B (each of which is independently composed of the commercial catalyst particles), a first gas distributor 12A arranged in the upper catalyst bed 11A, a second gas distributor 12B arranged in the lower catalyst bed 11B, a bottom gas distributor 12D 1 arranged in the middle of the catalyst beds 11A and 11B, a bottom gas distributor 12D 2 arranged below the lower catalyst bed 11B, and a liquid distributor 13 arranged above the upper catalyst bed 11A.
  • the first gas distributor 12A, the second gas distributor 12B, and the bottom gas distributors 12D 1 and 12D 2 are all composed of a horizontally arranged gas distribution main pipe 121 and five gas distribution branch pipes 122, wherein the branch pipe 122 is connected to the main pipe 121 and is perpendicular to the main pipe 121.
  • Two rows of symmetrically distributed and inclined downward openings are provided on the main pipes and branch pipes of the first gas distributor 12A and the second gas distributor 12B.
  • the installation height of the first gas distributor 12A is 25% of the height of the upper catalyst bed 11A
  • the installation height of the second gas distributor 12B is 25% of the height of the lower catalyst bed 11B.
  • the opening rate of the first gas distributor 12A, the second gas distributor 12B and the bottom gas distributors 12D1 and 12D2 is 25 ⁇
  • the opening rate of the liquid distributor 13 is 45 ⁇ .
  • the average diameter of the catalyst particles of the upper catalyst bed 11A is 1.4mm
  • the average diameter of the catalyst particles of the lower catalyst bed 11B is 0.5mm.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide is carried out in the bubbling bed reactor 1.
  • the conversion rate achieved in this example is 97.5%, and the selectivity is greater than 99.9%.
  • a bubbling bed reactor 1 was provided which was the same as the bubbling bed reactor 1 of Example 6, except that both the upper catalyst bed 11A and the lower catalyst bed 11B were composed of catalyst particles having an average diameter of 0.95 mm.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide was carried out in the bubbling bed reactor 1.
  • the conversion rate achieved in this comparative example was 95.4%, and the selectivity was greater than 99.9%.
  • Comparative Example 7 The only difference between Comparative Example 7 and Example 6 is that the upper catalyst layer and the lower catalyst layer are composed of catalyst particles with different average diameters. Compared with Example 6, the reaction performance of Comparative Example 7 is reduced.
  • a bubbling bed reactor 1 was provided which was the same as the bubbling bed reactor 1 of Example 6, except that the upper catalyst bed 11A was composed of catalyst particles having an average diameter of 0.5 mm, and the lower catalyst bed 11B was composed of catalyst particles having an average diameter of 1.4 mm.
  • the reaction of synthesizing ethylene carbonate from ethylene oxide and carbon dioxide was carried out in the bubbling bed reactor 1.
  • the conversion rate and selectivity achieved in this comparative example were 92.4% and 99.4%.
  • Comparative Example 8 The difference between Comparative Example 8 and Example 6 is that the upper catalyst layer and the lower catalyst layer are composed of catalyst particles with different average diameters. Compared with Example 6, the conversion rate and selectivity of Comparative Example 8 are reduced.

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Abstract

本发明涉及气体分布单元、鼓泡床反应器以及反应方法。本发明的气体分布单元包括至少一个气体分布管，所述至少一个气体分布管自上而下包括至少一个气体出口A和至少一个气体出口B，其中气体出口A以喷射角度εA倾斜向下喷射气体，并且气体出口B以喷射角度εB倾斜向下喷射气体，其中喷射角度为气体喷射方向与竖直方向的夹角，并且εA>εB。本发明的气体分布单元可使气液原料分布更为均匀并且气液原料接触时间更长。在鼓泡床反应器中使用该气体分布单元时，不仅有效提高反应器中的反应的转化率和选择性，而且能够避免出现原料局部浓度过高，进而避免反应剧烈和避免催化剂失活。

Description

气体分布单元、鼓泡床反应器以及使用其的反应方法 技术领域
本发明涉及非均相反应技术领域，特别涉及一种气体分布单元、应用该单元的鼓泡床反应器以及反应方法。
背景技术
鼓泡床反应器被广泛用于气液反应和气液固反应。使用鼓泡床反应器进行的气液反应的例子包括由对二甲苯(PX)制备对苯二甲酸(TA)的反应、甲醛羰基化反应和采用卤代甲苯选择性氧化生产邻、对卤苯甲醛的反应。使用鼓泡床反应器进行的气液固反应的例子包括渣油加氢、费托合成、碳酸乙烯酯、碳酸丙烯酯和碳酸丁烯酯合成。碳酸乙烯酯的主要生产方法有光气法、酯交换法、尿素醇解法和加成法。加成法包括将二氧化碳气体进料到鼓泡床反应器，在催化剂颗粒形成的催化剂床存在下，与反应器中的环氧乙烷液体进料进行反应，以形成碳酸乙烯酯。
针对鼓泡床反应器，如何提高气泡在液相中的接触时间以及均匀度是业内普遍关注的问题。中国专利申请CN106475017A公开了一种用于环氧乙烷与二氧化碳合成碳酸乙烯酯的气-液-固三相反应器，自下而上包括液体出料口、液体折流挡板、气体进料口、气体进口分布器、催化剂下支撑筛板、下部瓷球层、催化剂层、上部瓷球层、催化剂上支撑筛板、液体进料口、液体进料分布器以及气体出料口。气体和液体进料分别通过气体分布器和液体分布器径向均匀进入催化剂床层，催化剂床层由上、下部瓷球及上、下支撑筛板固定于反应器内，反应器下部设置多组折流挡板，并在两侧设置溢流堰。该方案通过溢流堰实现气液更好地分离。但溢流堰的存在增加了液体流动阻力，且气体操作通量较小，限制了反应器的产能。并且，床层内气体不能均匀地分布，降低了反应器转化率和选择性，而且容易发生气-液-固三相局部浓度过高、反应放热剧烈，进而出现催化剂失活现象。
因此，一直存在改造鼓泡床反应器的需求，以使气液接触时间更长并且分布更均匀，从而在反应中使用该鼓泡床反应器时可以实现更高转化率和选择性，并有效避免催化剂失活。
发明内容
为了克服现有技术中存在的问题，本发明的目的在于提供一种气体分布单元，鼓泡床反应器以及反应方法。通过控制气体出口的气体喷射角度，并任选控制催化剂层的构造，本发明的气体分布单元可使气液原料分布更为均匀并且气液原料接触时间更长。在鼓泡床反应器中使用该气体分布单元时，不仅有效提高反应器中的反应的转化率和选择性，而且能够避免出现原料局部浓度过高，进而避免反应剧烈和避免催化剂失活。
为实现上述目的，根据本发明的第一方面，本发明提供了一种气体分布单元，其包括至少一个气体分布管，所述至少一个气体分布管自上而下包括至少一个气体出口A和至少一个气体出口B，其中气体出口A以喷射角度εA倾斜向下喷射气体，并且气体出口B以喷射角度εB倾斜向下喷射气体，其中喷射角度为气体喷射方向与竖直方向的夹角，并且εA>εB。
根据本发明的第二方面，本发明提供了一种鼓泡床反应器，其包括根据第一方面所述的气体分布单元。
根据本发明的第三方面，本发明提供了一种反应方法，其包括步骤：使用根据第一方面所述的气体分布单元将气体反应物喷射到鼓泡床反应器中，与其中的液体反应物进行反应。
与现有技术相比，本发明具有如下有益效果：
1)本发明通过控制气体分布单元中的气体出口，以将气体倾斜向下喷射到鼓泡床反应器中。进入反应器内的气体倾斜向下运动，并在浮力作用下转为向上运动。进入反应器内的气体的转折运动使得气泡在液体进料内停留的时间更长，促进了气液传质，有助于反应的进行。并且，进入反应器内的气体的转折运动增加了液相的湍动程度。这也能够促进了气液传质，有助于反应的进行；
2)本发明通过设置气体分布单元中的气体出口，使气体出口自下而上以增大的喷射角度将气体倾斜向下喷射到鼓泡床反应器中。更大的喷射角度意味着进入反应器内的气体的向下运动分量更小。未反应的气体进料将随高度增加而累积。本发明的构造中位置更高的气体出口喷射进入反应器的气体的向下速度分量更小。这可以与未反应的气体进料的累积相匹配，使气体进料在整个鼓泡床反应器中均匀分布在 液体进料中。这提高了其中进行的反应的转化率和选择性；
3)在优选方案中，自上而下设置有至少三个气体出口，并控制其喷射气体的喷射角度，从而使喷射角度自上到下依次减小，并且相邻两个气体出口的喷射角度的减小幅度自上到下依次增大。未反应的气体进料将随高度增加而累积。与此相对应地，本发明的构造中自下而上以幅度增加的方式减少进入反应器的气体的向下速度分量，使气体进料在整个鼓泡床反应器中更均匀分布在液体进料中。这进一步提高了其中进行的反应的转化率和选择性；
4)在优选方案中，不同高度的气体分布器被交错设置。这能进一步增加气液湍动程度，促进混合，提高了其中进行的反应的转化率和选择性；
5)在优选方案中，在鼓泡床反应器中可以设置至少一个催化剂床层，优选设置至少两个催化剂床层，并且在每个催化剂床的下方设置底部气体分布器。该构造能增加避免两个催化剂床的催化剂发生返混的概率；
6)在优选方案中，本发明在鼓泡床反应器中设置至少一个催化剂床层，优选在各催化剂床层内安装至少一个本发明的气体分布器。该构造能增加气体均匀分布程度，增加进料与催化剂的接触，提高反应速率、转化率和选择性；
7)在优选方案中，设置至少两个催化剂床层，并且位于鼓泡床反应器中更高位置的床层包含平均粒径较大的催化剂颗粒，而位于鼓泡床反应器中更低位置的床层包含平均粒径较小的催化剂颗粒。一方面，由于反应物在平均粒径较小的催化剂颗粒内的扩散路径更短，并且平均粒径较小的催化剂颗粒的比表面积更大，因此反应物在平均粒径较小的催化剂颗粒上的反应效率更高。相应地，在位于鼓泡床反应器中更低位置的催化剂床层包含平均粒径较小的催化剂颗粒，这使更多的气体反应物进行反应，而更少的未反应的气体反应物沿反应器上升并离开反应器。另一方面，平均粒径较大的催化剂颗粒在液体中的沉降速度较大，反应物在其上的反应效率较低。如上所述，在鼓泡床反应器的不同高度设置有多个气体出口，其喷射气体的喷射角度自上到下依次减小，优选自上而下以幅度增加的方式减小喷射角度。该构造可以自下而上逐渐增加进入反应器的气体的水平速度分量，这增加了对液相和催 化剂颗粒的湍动程度，进而抵消了较大平均粒度对反应效率的不利影响。催化剂层的构造和气体分布器的构造可以导致协同作用，更进一步提高反应的转化率和选择性。
附图说明
图1是本发明一个实施方案的鼓泡床反应器的结构示意图。
图2是本发明一个实施方案的气体分布器的结构示意图。
图3是本发明一个实施方案的气体分布管的截面示意图。
图4是本发明一个实施方案的鼓泡床反应器的结构示意图。
主要附图标记说明：
1-鼓泡床反应器，11-催化剂床层，11A-上方催化剂床层，11B-下
方催化剂床层，12A-第一气体分布器，12B-第二气体分布器，12C-第三气体分布器、12D-底部气体分布器、120-气体出口，121-气体分布器的主管，122-气体分布器支管，13-液体分布器，14-催化剂支撑筛板，15-冷却夹套，16-反应器气体出口，17-反应器液体产物出口。
具体实施方式
下面结合附图，对本发明的具体实施方式进行详细描述，但应当理解本发明的保护范围并不受具体实施方式的限制。
除非另有其他明确表示，否则在整个说明书和权利要求书中，术语“包括”或其变换如“包含”或“含有”等将被理解为包括所陈述的元件或组成部分，而并未排除其他元件或其他组成部分。此外，术语“包括”或其变换如“包含”或“含有”等也可以排除其他元件或其他组成部分，即“由…组成”或“基本上由…组成”的情况。
在本文中，为了描述的方便，可以使用空间相对术语，诸如“下面”、“下方”、“下”、“上面”、“上方”、“上”等，来描述一个元件或特征与另一元件或特征在附图中的关系。应理解的是，空间相对术语旨在包含除了在图中所绘的方向之外物件在使用或操作中的不同方向。例如，如果在图中的物件被翻转，则被描述为在其他元件或特征“下方”或“下”的元件将取向在所述元件或特征的“上方”。物件也可以有其他取向(旋转90度，等等)且应对本文使用的空间相对术语作出相应的解释。同时，术语“上面”、“上方”、“上”包括一个元件或特征 在另一元件或特征的垂直上方和一个元件或特征在另一元件或特征的斜上方，只要一个元件或特征在竖直平面内的投影在另一元件或特征的上方即可。相应地，术语“下面”、“下方”、“下”包括一个元件或特征在另一元件或特征的垂直下方和一个元件或特征在另一元件或特征的斜下方，只要一个元件或特征在竖直平面内的投影在另一元件或特征的下方即可。
在本文中，术语“第一”、“第二”、“第三”等是用以区别多个不同的元件或部位，并不是用以限定特定的位置或相对关系。换言之，在一些实施例中，术语“第一”、“第二”、“第三”等也可以彼此互换。
在一个方面，本发明提供了一种气体分布单元，其包括至少一个气体分布管，所述至少一个气体分布管自上而下包括至少一个气体出口A和至少一个气体出口B，其中气体出口A以喷射角度εA倾斜向下喷射气体，并且气体出口B以喷射角度εB倾斜向下喷射气体，其中喷射角度为气体喷射方向与竖直方向的夹角，并且εA>εB。
在本文中，术语“鼓泡床反应器”又称“鼓泡反应器”、“沸腾床反应器”，是指以液相为连续相和气相为分散相的反应器，其可以为气液两相反应器或气液固三相反应器。
在本文中，术语“气体分布单元”是指能够将气体进料引入反应器并分散到液体进料中的装置。
在本文中，术语“气体分布管”是指气体反应物从中排出的装置。所述气体分布管可以具有适合在鼓泡床反应器中排出气体进料以进行反应的任何结构和形状，例如环形、球形、柱形和不规则形状。例如，所述气体分布管可以为折管、环形管或直管。在一个实施方案中，所述气体分布管为直管，其中所述直管的截面可以为圆形、椭圆形、矩形(包括方形)或多边形，并优选为圆形。
在本文中，术语“倾斜向下”是指具有向下的分量并与竖直方向形成大于0°但小于90°的夹角的方向。
在本文中，术语“竖直方向”是指与水平面垂直的方向。
在本文中，术语“喷射角度”是指气体喷射方向与竖直方向的夹角。
在优选的实施方式中，εA和εB分别为10-85°，优选20-65°。例如，εA和εB各自独立地为10°、15°、20°、25°、30°、35 °、40°、45°、50°、55°、60°、65°、70°、75°、80°或85°。
优选地，εA与εB的差为5-60°，优选5-45°。例如，εA和εB的差为5°、10°、15°、20°、25°、30°、35°、40°、45°、50°、55°或60。
在优选的实施方式中，所述至少一个气体分布管还包括至少一个气体出口C，其位于所述气体出口A和所述气体出口B的下方，并以喷射角度εC倾斜向下喷射气体，并且εA>εB>εC，优选εA与εB的差小于εB与εC的差。
优选地，εC为10-65°，优选20-50°。例如，εC为10°、15°、20°、25°、30°、35°、40°、45°、50°、55°、60°或65°。
进一步优选地，εB与εC的差为5-60°，优选5-45°。例如εB和εC的差为5°、10°、15°、20°、25°、30°、35°、40°、45°、50°、55°或60°。
更进一步优选地，εA与εB的差比εB与εC的差小1-30°，优选5-25°。例如，εA与εB的差比εB与εC的差小1°、2°、3°、4°、5°、6°、7°、8°、9°、10°、11°、12°、13°、14°、15°、16°、17°、18°、19°、20°、21°、22°、23°、24°、25°、26°、27°、28°、29°或30°。
根据本发明，所述气体分布单元可包括至少两种，例如三种或更多种，或四种或更多种高度的气体出口，其中所述气体出口自上而下设置，相应的气体喷射方向与竖直方向的夹角即喷射角度自上而下减小。优选地，减小幅度自上而下逐渐增大。在将所述气体分布单元用于鼓泡床反应器中时，在上方的相邻的两种高度的气体出口的所述喷射角度的差值总是小于在其下方的相邻的两种高度的气体出口的所述喷射角度的差值。所述“相邻的两种高度的气体出口”是指在鼓泡床反应器中，所述两种高度的气体出口之间没有第三种高度的气体出口。
在本文中，术语“高度”是指与鼓泡床反应器的最低点所在的水平面之间的垂直距离。
不希望束缚于任何理论，通过控制设置在鼓泡床反应器的不同高度的气体出口的喷射角度，使喷射角度自上到下逐渐减小，并且优选使相邻两个气体出口的喷射角度的差值(即减少的幅度)自上到下逐渐增大，本发明的构造可以抵消未反应的气体进料随高度增加而累积的现 象。这使气体进料在整个鼓泡床反应器中更均匀分布在液体进料中，提高了其中进行的反应的转化率和选择性，在优选的实施方式中，所述气体出口A和气体出口B可以位于所述至少一个气体分布管的相同或不同的气体分布管上。
优选地，所述气体出口A位于第一气体分布管上和所述气体出口B位于第二气体分布管上，更优选地，所述第一和第二气体分布管水平设置。气体分布管水平设置意味着，气体分布管的中心轴线与水平面平行。
还更优选地，所述第一和第二气体分布管各自具有规则形状或不规则形状的截面，并各自具有直管、弯管和环管的形状。
在优选的实施方式中，多个所述第一和第二气体分布管联通以形成气体分布器。
优选地，多个所述第一气体分布管联通形成第一气体分布器，多个所述第二气体分布管联通形成第二气体分布器，其中所述第一和第二气体分布器各自水平设置。联通形成气体分布器的多个气体分布管中的一个称为主管，其它称为支管。主管和支管可以采用本领域中的常用方式联通。
更优选地，所述第一和第二气体分布器各自包括水平设置的直管形状的一个主管和与主管联通的直管形状的一个或多个支管，并且第一和第二气体分布器的两个主管彼此平行，所述两个主管在水平面上的投影存在夹角δ，δ的范围为0°-135°，优选20°-70°。第一和第二气体分布器的两个主管存在夹角δ时，所述第一和第二气体分布器交错设置。这能进一步增加气液湍动程度，促进混合，提高了其中进行的反应的转化率和选择性。
根据本发明，所述气体出口可以为任何形式的可流出气体的装置。例如，所述气体出口可以为开孔或喷嘴。
在本文中，术语“开孔”可以具有适合流出气体的任何形状，例如圆形、椭圆形、矩形(包括方形)或多边形，并优选为圆形。所述开孔的大小可以根据其所在的气体分布管的形状和大小以及反应类型等来确定，优选地，所述开孔当量直径和气体分布管当量直径之比为0.01-0.25，更优选地为0.02-0.15。所述“喷嘴”可以为任何形式和具有任何结构，并且其出口与上述“开孔”的定义相同。
还更优选地，所述第一和第二气体分布管各自为圆形截面的直管，并且所述气体出口A为第一气体分布管上的开孔，所述气体出口B为第二气体分布管上的开孔，其中开孔角度αA和αB分别等同于气体喷射角度εA和εB，其中开孔角度为开孔截面中心点与相应气体分布管的截面圆圆心所在直线与竖直方向的夹角，优选所述第一气体分布管上存在多个开孔作为气体出口A，所述第二气体分布管上存在多个开孔作为气体出口B。
再更优选地，所述第一和第二气体分布管各自具有1‰至60‰，优选1‰-45‰，更优选5‰至30‰的开孔率。
在优选的实施方式中，所述气体出口A、气体出口B和至少一个气体出口C位于所述至少一个气体分布管的相同或不同的气体分布管上。
优选地，所述气体出口A位于第一气体分布管上，所述气体出口B位于第二气体分布管上，所述至少一个气体出口C位于第三气体分布管上，更优选，所述第一、第二和第三气体分布管水平设置。
更优选地，所述第一、第二和第三气体分布管各自具有规则形状或不规则形状的截面，并各自具有直管、弯管和环管的形状。
在优选的实施方式中，多个所述第一、第二和第三气体分布管联通以形成气体分布器。
优选地，多个所述第一气体分布管联通形成第一气体分布器，多个所述第二气体分布管联通形成第二气体分布器，多个所述第三气体分布管联通形成第三气体分布器，其中所述第一、第二和第三气体分布器各自水平设置，优选所述第一、第二和第三气体分布器各自包括水平设置的直管形状的一个主管和与主管联通的直管形状的一个或多个支管，更优选所述第一、第二和第三气体分布器的三个的主管彼此平行，所述三个主管在水平面上的投影存在夹角δ，δ的范围为0°-135°，优选20°-70°。所述第一、第二和第三气体分布器的相邻两个的主管存在夹角δ时，所述第一、第二和第三气体分布器的相邻两个交错设置。这能进一步增加气液湍动程度，促进混合，提高了其中进行的反应的转化率和选择性。
更优选地，所述第一、第二和第三气体分布管各自为圆形截面的直管，并且所述气体出口A为第一气体分布管上的开孔，所述气体出口 B为第二气体分布管上的开孔，并且所述至少一个气体出口C为第三气体分布管上的开孔，其中开孔角度αA，αB，αC分别等同于气体喷射角度εA，εB，εC，其中开孔角度为开孔截面中心点与相应气体分布管的截面圆圆心所在直线与竖直方向的夹角，优选所述第一气体分布管上存在多个开孔作为气体出口A，所述第二气体分布管上存在多个开孔作为气体出口B，并且所述第三气体分布管上存在多个开孔作为气体出口C。
还更优选地，所述第一、第二和第三气体分布管各自具有1‰至60‰，优选1‰-45‰，更优选5‰至30‰的开孔率。
在优选的实施方式中，所述气体分布单元进一步包括底部气体分布管，其位于所有所述至少一个气体分布管的下方，并且底部气体分布管具有至少一个气体出口D，从而以喷射角度β向上喷射气体，其中β是指喷射方向与竖直方向的夹角并在0°至80°或10°至80°，优选20°至70°，更优选30°至60°的范围内。
优选地，多个底部气体分布管联通以形成底部气体分布器。
优选地，所述底部气体分布器和所述底部气体分布管与上文所述的气体分布器和气体分布管的结构相同，除了前者是后者被翻转设置，以使气体喷射方向为倾斜向上。
在本文中，术语“倾斜向上”是指具有向上的分量并与竖直方向形成大于0°但小于90°的夹角的方向。
第二方面，本发明提供了一种鼓泡床反应器，其包括根据第一方面所述的气体分布单元。
在优选的实施方式中，所述气体出口A在鼓泡床反应器中的高度为hA，和所述气体出口B在鼓泡床反应器中的高度为hB，其中hA和hB为鼓泡床反应器总高度H的10-90％，优选20-85％。例如，hA和hB各自独立地为鼓泡床反应器总高度H的10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％、85％或90％。
优选地，hA与hB之间的差为鼓泡床反应器总高度H的5-70％，优选10-60％。例如，hA和hB之间的差为鼓泡床反应器总高度H的5％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％或70％。优选，hA与hB之间的差应大于从气体出口A喷 射的气体的喷射长度，从而使从气体出口A喷射的气体不会接触气体出口B所在的水平面。
鼓泡床反应器总高度H可以为2-16米，例如2米、4米、6米、8米、10米、12米、16米。鼓泡床反应器总高度H与反应器直径Dr之比为1.2-10.5，优先为2.5-7。例如，H/Dr为1.2、2、3、4、5、6、7、8、9、10或10.5。
在优选的实施方式中，所述气体出口C在鼓泡床反应器中的高度为hC，其中hC为鼓泡床反应器总高度H的10-90％，优选20-85％。例如，hC为鼓泡床反应器总高度H的10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％、85％或90％。
优选地，hB与hC之间的差为鼓泡床反应器总高度H的5-60％，优选10-50％，其中hB与hC之间的差与hA与hB之间的差相同或不同。例如，hB与hC之间的差与hA和hB之间的差各自独立地为鼓泡床反应器总高度H的5％、10％、15％、20％、25％、30％、35％、40％、45％或50％，但是hB与hC之间的差与hA和hB之间的差两者之和应小于等于反应器总高度H的80％。优选，相邻高度的两个气体出口之间的差应大于从在上的气体出口喷射的气体的喷射长度，从而使从在上的气体出口喷射的气体不会接触在下的气体出口所在的水平面。
在一个实施方式中，hA为鼓泡床反应器总高度H的30-65％，优选30-55％，和hB为鼓泡床反应器总高度H的10-40％，优选20-30％。
在一个实施方式中，hA为鼓泡床反应器总高度H的50-85％，优选60-80％，hB为鼓泡床反应器总高度H的30-65％，优选30-55％，和hC为鼓泡床反应器总高度H的10-40％，优选20-30％。
在优选的实施方式中，鼓泡床反应器中包括至少一个催化剂床层，所述至少一个催化剂床层由催化剂颗粒构成，其中所述气体分布单元包括第一和第二气体分布管，并且它们各自独立地位于所述至少一个催化剂床层中。第一和第二气体分布管在催化剂床层中的高度为10-90％，优选20-85％，更优选25-80％的催化剂床高度。
优选地，鼓泡床反应器中包括两个催化剂床层，并且第一和第二气体分布管分别位于第一和第二催化剂床层中。第一分布管在第一催化剂床层中的高度为10-90％，优选20-85％，更优选25-80％的第一催化 剂床的高度。第二气体分布管在第二催化剂床层中的高度为10-90％，优选20-85％，更优选25-80％的第二催化剂床的高度。
更优选地，第一和第二催化剂床层各自由催化剂颗粒，优选球形催化剂颗粒构成，其中所述第一和第二催化剂床层中的催化剂颗粒的平均粒径分别为P1和P2，并且P1>P2；
还更优选地，鼓泡床反应器还包括底部气体分布器。当鼓泡床反应器中不包括催化剂床层时，所述底部气体分布器位于所有所述至少一个气体分布管下方。当鼓泡床反应器中包括至少一个催化剂床层时，所述鼓泡床反应器包括至少一个底部气体分布器，其分别位于每个催化剂床层下方的鼓泡床反应器空间中。在一个变型中，鼓泡床反应器中包括至少一个催化剂床层，并且一个底部气体分布器位于所有所述至少一个催化剂床层下方的鼓泡床反应器空间中。
在优选的实施方式中，鼓泡床反应器中包括至少一个催化剂床层，所述至少一个催化剂床层由催化剂颗粒构成，其中所述气体分布单元包括第一、第二和第三气体分布管，并且它们各自独立地位于所述至少一个催化剂床层中。第一、第二和第三气体分布管在相应催化剂床层中的高度为10-90％，优选20-85％，更优选25-80％的催化剂床高度。
优选地，所述第一、第二和第三气体分布管分别位于第一、第二和第三催化剂床层中。第一分布管在第一催化剂床层中的高度为10-90％，优选20-85％，更优选25-80％的第一催化剂床的高度。第二气体分布管在第二催化剂床层中的高度为10-90％，优选20-85％，更优选25-80％的第二催化剂床的高度。第三分布管在第三催化剂床层中的高度为10-90％，优选20-85％，更优选25-80％的第三催化剂床的高度。
更优选地，所述第一、第二和第三催化剂床层各自由催化剂颗粒构成，其中所述第一、第二和第三催化剂床层中的催化剂颗粒的平均粒径分别为P1、P2和P3，并且P1>P2>P3。
还更优选地，鼓泡床反应器还包括底部气体分布器。当鼓泡床反应器中不包括催化剂床层时，所述底部气体分布器位于所有所述至少一个气体分布管下方。当鼓泡床反应器中包括至少一个催化剂床层时，所述鼓泡床反应器包括至少一个底部气体分布器，其分别位于每个催化剂床层下方的鼓泡床反应器空间中。在一个变型中，鼓泡床反应器中包括至少一个催化剂床层，并且一个底部气体分布器位于所有所述至少 一个催化剂床层的下方的鼓泡床反应器空间中。
在优选的实施方式中，所述鼓泡床反应器还包括液体分布管。当鼓泡床反应器中不包括催化剂床层时，液体分布管在鼓泡床反应器中的高度大于所有所述至少一个气体分布管在鼓泡床反应器中的高度。当鼓泡床反应器中包括至少一个催化剂床层时，所述液体分布管的高度大于所有至少一个催化剂床层在在鼓泡床反应器中的高度。液体分布管将液体原料输入鼓泡床反应器中，以浸没所有的气体分布管和催化剂床层。
优选地，多个液体分布管联通以形成液体分布器。所述液体分布管和液体分布器可以具有在鼓泡床反应器领域中用于引入液体反应物的任何形状和结构。优选地，所述液体分布器具有多个用于引入液体反应物的开孔并且开孔率为1‰-65‰，优选5‰-60‰，更优选10‰-50‰。优选地，所述开孔当量直径和液体分布管当量直径之比为0.02-0.3，更优选地为0.05-0.2。
在优选的实施方式中，所述鼓泡床反应器包括两个或更多个催化剂床层，优选两个催化剂床层，其由催化剂颗粒构成，其中每个催化剂床层的催化剂颗粒的平均粒径都大于其下方的催化剂床层的催化剂颗粒的平均粒径。
在优选的实施方式中，所述催化剂床层的催化剂颗粒的平均粒径各自独立地为0.01mm至10mm，优选0.1mm至5mm，更优选0.3mm至3mm。
在一个实施方式中，所述气体分布单元包括两个催化剂床层，上方的催化剂床层的催化剂颗粒的平均粒径P1大于下方的催化剂床层的催化剂颗粒的平均粒径P2。优选地，P1为0.1mm至10mm，优选1mm至5mm，更优选1mm至3mm，和P2为0.01mm至5mm，优选0.1mm至2mm，更优选0.3mm至1mm。
在一个实施方式中，本发明在鼓泡床反应器中设置至少一个催化剂床层，并在各催化剂床层内安装至少一个本发明的气体分布器。该构造能增加气体均匀分布程度，增加进料与催化剂的接触，并减少催化剂返混现象，从而提高反应速率、转化率和选择性。
在优选方案中，设置至少两个催化剂床层，并且位于鼓泡床反应器中更高位置的床层包含平均粒径较大的催化剂颗粒，而位于鼓泡床反 应器中更低位置的床层包含平均粒径较小的催化剂颗粒。一方面，由于反应物在平均粒径较小的催化剂颗粒内的扩散路径更短，并且平均粒径较小的催化剂颗粒的比表面积更大，因此反应物在平均粒径较小的催化剂颗粒上的反应效率更高。相应地，在位于鼓泡床反应器中更低位置的催化剂床层包含平均粒径较小的催化剂颗粒，这使更多的气体反应物进行反应，而更少的未反应的气体反应物沿反应器上升并离开反应器。另一方面，平均粒径较大的催化剂颗粒在液体中的沉降速度较大，反应物在其上的反应效率较低。如上所述，在鼓泡床反应器的不同高度设置有多个气体出口，其喷射气体的喷射角度自上到下依次减小，优选自上而下以幅度增加的方式减小喷射角度。该构造可以自下而上地增加进入反应器的气体的水平速度分量，这增加了对液相和催化剂颗粒的湍动程度，进而抵消了较大平均粒度对反应效率的不利影响。催化剂层的构造和气体分布器的构造可以导致协同作用，更进一步提高反应的转化率和选择性。
第三方面，本发明提供一种反应方法，其包括步骤：使用根据第一方面所述的气体分布单元将气体反应物喷射到鼓泡床反应器中，与其中的液体反应物进行反应。
在优选的实施方式中，所述的方法包括如下步骤：
a)将液体反应物供入鼓泡床反应器内并浸没所述气体分布单元，并且当所述鼓泡床反应器不包括固体颗粒催化剂床层时，液体反应物浸没反应器高度90％-95％的空间，或者当所述鼓泡床反应器包括一个或多个催化剂床层时，液体反应物浸没所有催化剂床层；和
b)使气体反应物通过所述气体分布单元供入鼓泡床反应器内。
根据本发明的反应方法可以用于进行任何气体反应物与液体反应物的反应，而不管是否存在催化剂，或者催化剂形态为均相催化剂或者非均相催化剂。在优选的实施方式中，所述反应方法用于合成碳酸乙烯酯、碳酸丙烯酯或碳酸丁烯酯，其中液体反应物环氧乙烷与气体反应物二氧化碳在固体催化剂颗粒作用下生成碳酸乙烯酯，液体反应物环氧丙烷与气体反应物二氧化碳在固体催化剂颗粒作用下生成碳酸丙烯酯，或者液体反应物环氧丁烷与气体反应物二氧化碳在固体催化剂颗粒作用下生成碳酸丁烯酯。
以下参照附图对本申请的鼓泡床反应器的优选实施方案进行具体 说明，但本申请的范围不限于这些优选实施方案。
如图1所示，在一个优选实施方案中，本发明的鼓泡床反应器1为柱状罐体结构。在鼓泡床反应器1外壁包裹冷却夹套15。鼓泡床反应器1包括催化剂床层11，第一气体分布器12A、第二气体分布器12B、第三气体分布器12C、底部气体分布器12D、以及液体分布器13。催化剂床层11由上下支撑筛板14之间的催化剂颗粒构成。液体分布器13设置在催化剂床层11的上方。底部气体分布器12D设置在催化剂床层11的下方。第一气体分布器12A、第二气体分布器12B和第三气体分布器12C从上到下设置在催化剂床层11内。第一气体分布器12A的高度小于等于催化剂床层高度的80％。此外，鼓泡床反应器1还包括在顶端的反应器气体出口16和在底部的反应器液体产物出口17。第一气体分布器12A、第二气体分布器12B、第三气体分布器12C、底部气体分布器12D、液体分布器13、支撑筛板14都是水平放置。
液体分布器13包括水平设置的液体分布管作为主管和支管，其中支管与主管联通并垂直于主管。作为主管和支管的液体分布管上的液体出口为至少一排开孔，开孔率为1‰-65‰。所述至少一排开孔对称分布，并且开孔方向竖直向下或倾斜向下。
底部气体分布器12D包括水平设置的底部气体分布管作为主管和支管，其中支管与主管联通并垂直于主管。作为主管和支管的底部气体分布管上的气体出口为两排开孔，其中所述两排开孔对称分布并且具有倾斜向上的开孔角度αD，其中开孔角度为开孔截面中心点与相应气体分布管的截面圆圆心所在直线与竖直方向的夹角，其中开孔角度αD等于气体喷射角度β，β为10°至80°。在一个变型中，作为主管和支管的底部气体分布管上的气体出口为一排开孔，其开孔角度αD等于气体喷射角度β，β为0°至80°。
如图2所示，第三气体分布器12C包括水平设置的第二气体分布管作为主管121和支管122，其中支管122与主管121联通并垂直于主管121。如图3所示，所述主管121和支管122各自独立地包括两排开孔作为气体出口，它们被设置成对称且具有倾斜向下的开孔角度αC，其中开孔角度为开孔截面中心点与相应气体分布管的截面圆圆心所在直线与竖直方向的夹角。气体出口的开孔角度αC等于气体喷射角度εC。在一个变型中，所述主管121和支管122各自独立地包括一排开 孔作为气体出口，其中开孔具有倾斜向下的开孔角度αC。并且，所述主管121和支管122各自的开孔率为1‰-60‰，优选为1‰-45‰。优选地，第三气体分布器12C与底部气体分布器12D的结构相同，并且第三气体分布器12C的主管121被设置成与底部气体分布器12D的主管的水平面投影存在夹角δ，夹角δ在0°-90°，优选0-45°的范围内。
第一气体分布器12A和第二气体分布器12B具有与第三气体分布器12C相同的结构，不同之处在于，第一气体分布器12A和第二气体分布器12B的气体分布管上的开孔的开孔角度分别为αA和αB，其中αA>αB>αC，优选αA与αB的差小于αB与αC的差。气体出口的开孔角度αA、αB和αC分别等于气体喷射角度εA、εB和εC。优选，所述第一气体分布器12A、第二气体分布器12B和第三气体分布器12C的相邻两个的主管的水平面投影各自独立地存在夹角δ，δ的范围为0°-135°，优选20°-70°。
如图4所示，在另一个优选实施方案中，本发明的鼓泡床反应器1为柱状罐体结构。在鼓泡床反应器1外壁包裹冷却夹套15。鼓泡床反应器1包括上方催化剂床层11A、下方催化剂床层11B、设置在上方催化剂床层11A中的第一气体分布器12A、设置在上方催化剂床层11A和下方催化剂床层11B之间的底部气体分布器12D1、设置在下方催化剂床层11B的第二气体分布器12B、设置在下方催化剂床层11B下方的底部气体分布器12D2、以及液体分布器13。所述上方催化剂床层11A和下方催化剂床层11B各自独立地由上下支撑筛板14之间的催化剂颗粒构成，其中上方的催化剂床层11A的催化剂颗粒的平均粒径大于下方的催化剂床层11B的催化剂颗粒的平均粒径。液体分布器13设置在上方催化剂床层11A之上。此外，鼓泡床反应器1还包括在顶端的反应器气体出口16和在底部的反应器液体产物出口17。
第一气体分布器12A、第二气体分布器12B、底部气体分布器12D1和底部气体分布器12D2、液体分布器13具有在描述图1所示鼓泡床反应器时所提及的结构，在此不再进行赘述。
以下参照附图对本申请的反应方法的优选实施方案进行具体说明，但本申请的范围不限于这些优选实施方案。
在图1所示鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应，由环氧丙烷和二氧化碳合成碳酸丙烯酯的反应或由 环氧丁烷和二氧化碳合成碳酸丁烯酯的反应。液相(环氧乙烷、环氧丙烷、环氧丁烷三者中的任一种液体)由液体分布器13进入鼓泡床反应器1内，使液相浸没催化剂床层11。气相(二氧化碳)由第一气体分布器12A、第二气体分布器12B、第三气体分布器12C和底部气体分布器12D进入反应器1内。液相环氧乙烷与气相二氧化碳在催化剂床层11中进行反应生成碳酸乙烯酯，液相环氧丙烷与气相二氧化碳在催化剂床层11中进行反应生成碳酸丙烯酯，或液相环氧丁烷与气相二氧化碳在催化剂床层11中进行反应生成碳酸丁烯酯。反应产物以液相形式经反应器液体产物出口17流出反应器1，并且未反应的二氧化碳由反应器气体出口16排出反应器1。
本申请可以包括以下的实施方案：
1.一种气体分布单元，其特征在于，应用于气液固三相鼓泡床反应器中，包括：
底部气体分布器，其设置在催化剂床层的下方并向上鼓泡；
第一气体分布器，其设置在催化剂床层的内部，该第一气体分布器向下鼓泡。
2.根据权利要求1所述的气体分布单元，其特征在于，所述催化剂床层中设置颗粒状的、且被限制于床层内的固体催化剂。
3.根据权利要求1所述的气体分布单元，其特征在于，所述第一气体分布器在催化剂床层内的不同高度上分设1至4层，优选为2层。
4.根据权利要求1所述的气体分布单元，其特征在于，所述底部气体分布器上均匀开设向上鼓泡的底部气孔；所述第一气体分布器上均匀开设向下鼓泡的第一气孔。
5.根据权利要求4所述的气体分布单元，其特征在于，所述第一气孔设置两排或两排以上；当第一气孔为两排时，两排气孔对称且倾斜向下设置，气孔朝向与竖直方向的夹角α取值范围为25°-65°。
6.根据权利要求5所述的气体分布单元，其特征在于，当第一气体分布器设置两层时，上层第一气孔的所述夹角α大于等于下层第一气孔的夹角α。
7.根据权利要求6所述的气体分布单元，其特征在于，上、下两层的夹角α的差值为5°-25°。
8.根据权利要求3所述的气体分布单元，其特征在于，当所述第 一气体分布器设置两层或两层以上时，相邻层的第一气体分布器整体在水平方向上具有一倾斜角度δ，δ的角度范围为0°-135°。
9.根据权利要求3所述的气体分布单元，其特征在于，最上一层的所述第一气体分布器的安装高度小于等于催化剂床层高度的80％。
10.根据权利要求1所述的气体分布单元，其特征在于，所述底部气孔设置两排或两排以上；当底部气孔为两排时，两排气孔对称且倾斜向上设置，气孔朝向与竖直方向的夹角β取值范围为30°-60°。
11.根据权利要求1所述的气体分布单元，其特征在于，所述底部气体分布器和第一气体分布器由相互垂直的一根主管和多根支管组成，所述支管的覆盖范围与鼓泡床反应器的横截面相适配；主管和支管的开孔率为1‰-45‰。
12.一种鼓泡床反应器，其特征在于，应用于权利要求1至11中任意一项所述的气体分布单元。
13.根据权利要求12所述的鼓泡床反应器，其特征在于，还包括：
液体分布器，其设置在催化剂床层的上方，用于提供反应的液相进料；该液相进料浸没固体催化剂床层。
14.根据权利要求13所述的鼓泡床反应器，其特征在于，所述液体分布器的开孔率为1‰-65‰。
15.根据权利要求12所述的鼓泡床反应器，其特征在于，还包括：
催化剂床层，其为一层或多层，当催化剂床层为多层时，所述气体分布单元在每个床层独立设置。
16.根据权利要求15所述的鼓泡床反应器，其特征在于，所述催化剂床层上端和下端分别设有支撑筛板。
17.根据权利要求12所述的鼓泡床反应器，其特征在于，所述鼓泡床反应器外壁包裹冷却夹套。
18.一种反应方法，其特征在于，应用如权利要求12至17中任意一项所述的鼓泡床反应器，包括：
液体进料经液体分布器进入反应器内并建立浸没催化剂床层的液位；
气体进料分别通过底部气体分布器和第一气体分布器形成对喷，来自所述第一气体分布器的气泡在催化剂床层处的液相中折返运行；
在所述折返运行的气泡以及来自所述底部气体分布器的上升气泡 的共同作用下，固体催化剂颗粒在床层内处于翻滚运动状态。
19.根据权利要求18所述的反应方法，其特征在于，所述反应方法用于合成碳酸乙烯酯。
20.根据权利要求19所述的反应方法，其特征在于，所述液体进料为环氧乙烷，气体进料为二氧化碳。
实施例
下面的实施例用于对本申请进行进一步的说明，但并不因此而限制本申请。
以下实施例与对比例中所用的催化剂是来自中石化(上海)石油化工研究院有限公司的商用催化剂颗粒，商品牌号为SEC-22。
实施例1
提供鼓泡床反应器1。鼓泡床反应器1的内径为1600mm，反应器高度6000mm。鼓泡床反应器1包括一个催化剂床层11(其由所述商用催化剂颗粒构成)、自上而下设置在所述催化剂床层内的第一气体分布器12A和第二气体分布器12B、设置在催化剂床层11下方的底部气体分布管12D、以及设置在催化剂床层11上方的液体分布器13。所述第一气体分布器12A、第二气体分布器12B和底部气体分布器12D均由水平设置的一根气体分布主管121和五根气体分布支管122组成，其中支管122与主管121联通并垂直于主管121。第一气体分布器12A和第二气体分布器12B的主管与底部气体分布器12D的主管的水平面投影的夹角δ＝0°。第一气体分布器12A和第二气体分布器12B的主管和支管上开设两排对称分布且倾斜向下的开孔。开孔截面中心点与相应气体分布管的截面圆圆心所在直线与竖直方向的夹角，即开孔角度分别为α12A＝55°和α12B＝45°。相应地，从中流出的气体与竖直方向的夹角，即喷射角度分别为ε12A＝55°和ε12B＝45°。底部气体分布器12D的主管和支管上开设两排对称分布且倾斜向上的开孔，从中流出的气体与竖直方向的夹角，即喷射角度β＝30°。第二气体分布器12B的安装高度为催化剂床层11高度的25％，和第一气体分布器12A的安装高度为催化剂床层11高度的50％。第一气体分布器12A、第二气体分布器12B和底部气体分布器12D的开孔率为25‰，液体分布器13的开孔率为45‰。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本实施例实现的转化率为91.8％和选择性为99.1％。
实施例2
提供与实施例1的鼓泡床反应器1相同的鼓泡床反应器1，除了由第一气体分布器12A的气体分布管上的开孔的开孔角度α12A＝65°，第二气体分布器12B的气体分布管上的开孔的开孔角度α12B＝45°。相应地，由第一气体分布器12A和第二气体分布器12B上的开孔流出的气体的喷射角度分别为ε12A＝65°和ε12B＝45°。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本实施例实现的转化率为93.5％和选择性为99.8％。
实施例2与实施例1的差异仅在于喷射角度差值不同：实施例1的喷射角度差值为10°，实施例2的喷射角度差值为20°。随着喷射角度差值增加，转化率和选择性均得到提高。
对比例1
提供与实施例1的鼓泡床反应器1相同的鼓泡床反应器1，除了第一气体分布器12A和第二气体分布器12B的开孔的开孔角度相等，且α12A＝α12B＝45°。相应地，喷射角度ε12A＝ε12B＝45°。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本对比例实现的转化率为87.1％和选择性为96.5％。
相对于实施例1和实施例2，对比例1的喷射角度差值降低为0°，即在上方的气体分布器的开孔的喷射角度与下方的气体分布器的开孔的喷射角度相同。这使得转化率和选择性均明显降低。
实施例3
提供鼓泡床反应器1。鼓泡床反应器1的内径为1600mm，反应器高度6000mm。鼓泡床反应器1包括一个催化剂床层11(其由所述商用催化剂颗粒构成)、自上而下设置在所述催化剂床层内的第一气体分布器12A、第二气体分布器12B和第三气体分布器12C、设置在催化剂床层11下方的底部气体分布管12D、以及设置在催化剂床层11上方的液体分布器13。第一气体分布器12A、第二气体分布器12B、第三气体分布器12C和底部气体分布管12D均由水平设置的一根气体分布主管121和五根气体分布支管122组成，其中支管122与主管121联通并垂直于主管121。第一气体分布器12A、第二气体分布器12B和 第三气体分布器12C的主管与底部气体分布器12D的主管的水平面投影的夹角均为δ＝0°。第一气体分布器12A、第二气体分布器12B和第三气体分布器12C的主管和支管上开设两排对称分布且倾斜向下的开孔。开孔截面中心点与相应气体分布管的截面圆圆心所在直线与竖直方向的夹角，即开孔角度分别为α12A＝75°、α12B＝68°和α12C＝45°。相应地，从中流出的气体与竖直方向的夹角，即喷射角度分别为ε12A＝75°、ε12B＝68°和ε12C＝45°。底部气体分布器12D的主管和支管上开设两排对称分布且倾斜向上的气孔，从中流出的气体与竖直方向的夹角，即喷射角度β＝30°。第三气体分布器12C的安装高度为催化剂床层11高度的25％，第二气体分布器12B的安装高度为催化剂床层11高度的50％，和第一气体分布器12A的安装高度为催化剂床层11高度的70％。第一气体分布器12A、第二气体分布器12B、第三气体分布器12C和底部气体分布器12D的开孔率为25‰，液体分布器13的开孔率为45‰。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本实施例实现的转化率为96.5％和选择性为大于99.9％。
对比例2
提供与实施例3的鼓泡床反应器1相同的鼓泡床反应器1，除了第一气体分布器12A、第二气体分布器12B和第三气体分布器12C的开孔的开孔角度相等，即α12A＝α12B＝α12C＝45°。相应地，喷射角度分别为ε12A＝ε12B＝ε12C＝45°。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本对比例实现转化率为89.2％和选择性为98.0％。
对比例2与实施例3的差异在于三个气体分布器的开孔的喷射角度(及其差值)不同。对比例2的所述喷射角度之间的差值均为0°。实施例3的第一气体分布器12A与第二气体分布器12B的开孔的所述喷射角度之间的差值为7°，和第二气体分布器12B与第三气体分布器12C的开孔的所述喷射角度之间的差值为23°。换言之，自上而下，相邻高度的两个气体分布器的开孔的所述喷射角度之间的差值幅度增大。相应地，相对于实施例3，对比例2实现的转化率和选择性均降低。
对比例3
提供与实施例3的鼓泡床反应器1相同的鼓泡床反应器1，除了由第一气体分布器12A的开孔的开孔角度α12A＝75°，第二气体分布器12B 的开孔的开孔角度α12B＝60°，第三气体分布器12C的开孔的开孔角度α12C＝45°。相应地，喷射角度分别为ε12A＝75°，ε12B＝60°，和ε12C＝45°。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本对比例实现的转化率为94.1％和选择性为大于99.9％。
在对比例3中，自上而下，气体分布器的开孔的所述喷射角度逐渐降低，并且相邻高度的两个气体分布器的开孔的所述喷射角度之间的差值相同，均为15°。与对比例2相比，对比例3的喷射角度自上而下逐渐降低，并实现了转化率和选择性的提高。与实施例3相比，对比例3的喷射角度之间的差值不变，并且导致转化率降低。
对比例4
提供与实施例3的鼓泡床反应器1相同的鼓泡床反应器1，除了由第一气体分布器12A的开孔的开孔角度α12A＝75°，第二气体分布器12B的开孔的开孔角度α12B＝52°，第三气体分布器12C的开孔的开孔角度α12C＝45°。相应地，喷射角度分别为ε12A＝75°，ε12B＝52°，和ε12C＝45°。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本对比例实现转化率为92.2％和选择性为99.3％。
在对比例4中，自上而下，气体分布器的开孔的所述喷射角度逐渐降低，并且所述喷射角度之间的差值也逐渐降低。与对比例2相比，对比例4的喷射角度自上而下逐渐降低，并实现了转化率和选择性的提高。与实施例3相反，对比例4的相邻高度的两个气体分布器的开孔的所述喷射角度之间的差值自上而下逐渐降低，并导致转化率和选择性降低。
实施例4
提供与实施例1的鼓泡床反应器1相同的鼓泡床反应器1，除了第一气体分布器12A的主管与底部气体分布器12D的主管的水平面投影的夹角δ＝55°，第二气体分布器12B的主管与底部气体分布器12D的主管的水平面投影的夹角δ＝30°。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本实施例实现的转化率为92.7％和选择性为99.6％。
实施例4与实施例1的差异仅在于夹角δ不同。可见夹角δ的存在将提高反应转化率和选择性。
对比例5
提供与实施例4的鼓泡床反应器1相同的鼓泡床反应器1，除了在所述催化剂床层内仅设置第一气体分布器12A。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本对比例实现的转化率为82.0％和选择性为93.5％。
对比例6
提供与实施例4的鼓泡床反应器1相同的鼓泡床反应器1，除了由第一气体分布器12A和第二气体分布器12B的开孔的开孔角度分别为α12A＝30°和α12B＝60°。相应地，喷射角度分别为ε12A＝30°和ε12B＝60°。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本对比例实现的转化率为86.1％和选择性为95.1％。
实施例5
提供鼓泡床反应器1。鼓泡床反应器1的内径为1600mm，反应器高度6000mm。鼓泡床反应器1包括一个催化剂床层11(其由所述催化剂颗粒)、自上而下设置在所述催化剂床层内的气体分布器12A和12B、设置在催化剂床层11下方的底部气体分布管12D、以及设置在催化剂床层11上方的液体分布器13。所述第一气体分布器12A、第二气体分布器12B和底部气体分布器12D均由水平设置的一根气体分布主管121和五根气体分布支管122组成，其中支管122与主管121联通并垂直于主管121。第一气体分布器12A的主管与底部气体分布器12D的主管的水平面投影的夹角δ＝45°，第二气体分布器12B的主管与底部气体分布器12D的主管的水平面投影的夹角δ＝0°。第一气体分布器12A和第二气体分布器12B的主管和支管上开设两排对称分布且倾斜向下的开孔。开孔截面中心点与相应气体分布管的截面圆圆心所在直线与竖直方向的夹角，即开孔角度分别为α12A＝70°和α12B＝60°。相应地，从中流出的气体与竖直方向的夹角，即喷射角度分别为ε12A＝70°和ε12B＝60°。底部气体分布器12D的主管和支管上开设两排对称分布且倾斜向上的气孔，从中流出的气体与竖直方向的夹角，即喷射角度β＝45°。第二气体分布器12B的安装高度为催化剂床层11高度的30％，和第一气体分布器12A的安装高度为催化剂床层11高度的60％。第一气体分布器12A、第二气体分布器12B和底部气体分布器12D的开孔率为15‰，液体分布器13的开孔率为40‰。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯 的反应。本实施例实现的转化率为90.8％和选择性为98.6％。
实施例6
提供鼓泡床反应器1。鼓泡床反应器1的内径为1600mm，反应器高度6000mm。鼓泡床反应器1包括上方催化剂床层11A和下方催化剂床层11B(其各自独立地由所述商用催化剂颗粒构成)、设置在上方催化剂床层11A内的第一气体分布器12A、设置在下方催化剂床层11B内的第二气体分布器12B、设置在催化剂床层11A与11B两者区域中间的底部气体分布器12D1、设置在下方催化剂床层11B下方的底部气体分布器12D2以及设置在上方催化剂床层11A上方的液体分布器13。所述第一气体分布器12A、第二气体分布器12B和底部气体分布器12D1、12D2均由水平设置的一根气体分布主管121和五根气体分布支管122组成，其中支管122与主管121联通并垂直于主管121。第一气体分布器12A和第二气体分布器12B的主管与底部气体分布器12D1和12D2的主管的水平面投影的夹角均为δ＝0°。第一气体分布器12A和第二气体分布器12B的主管和支管上开设两排对称分布且倾斜向下的开孔。开孔截面中心点与相应气体分布管的截面圆圆心所在直线与竖直方向的夹角，即开孔角度分别为α12A＝65°和α12B＝45°。相应地，从中流出的气体与竖直方向的夹角，即喷射角度为ε12A＝65°和ε12B＝45°。底部气体分布器12D1与12D2的主管和支管上开设两排对称分布且倾斜向上的气孔，从中流出的气体与竖直方向的夹角，即喷射角度β＝45°。第一气体分布器12A的安装高度为上方催化剂床层11A高度的25％，和第二气体分布器12B的安装高度为下方催化剂床层11B高度的25％。、第一气体分布器12A、第二气体分布器12B和底部气体分布器12D1与12D2的开孔率为25‰，液体分布器13的开孔率为45‰。上方催化剂床层11A的催化剂颗粒的平均直径为1.4mm，和下方催化剂床层11B的催化剂颗粒的平均直径为0.5mm。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本实施例实现的转化率为97.5％，和选择性为大于99.9％。
对比例7
提供与实施例6的鼓泡床反应器1相同的鼓泡床反应器1，除了上方催化剂床层11A和下方催化剂床层11B都由平均直径为0.95mm的催化剂颗粒构成。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本对比例实现的转化率为95.4％，和选择性为大于99.9％。
对比例7与实施例6的差异仅在于由不同平均直径的催化剂颗粒构成上方催化剂层和下方催化剂层。与实施例6相比，对比例7的反应性能降低。
对比例8
提供与实施例6的鼓泡床反应器1相同的鼓泡床反应器1，除了上方的催化剂床层11A由平均直径0.5mm的催化剂颗粒构成，和下方的催化剂床层11B由平均直径1.4mm的催化剂颗粒构成。
在鼓泡床反应器1中进行由环氧乙烷和二氧化碳合成碳酸乙烯酯的反应。本对比例实现的转化率为92.4％和选择性为99.4％。
对比例8与实施例6的差异仅在于由不同平均直径的催化剂颗粒构成上方催化剂层和下方催化剂层。与实施例6相比，对比例8的转化率和选择性降低。
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所发明的内容。

Claims (16)

  1. 一种气体分布单元，其包括至少一个气体分布管，所述至少一个气体分布管自上而下包括至少一个气体出口A和至少一个气体出口B，其中气体出口A以喷射角度εA倾斜向下喷射气体，并且气体出口B以喷射角度εB倾斜向下喷射气体，其中喷射角度为气体喷射方向与竖直方向的夹角，并且εA>εB。
  2. 根据权利要求1所述的气体分布单元，其特征在于，εA和εB分别为10-85°，优选20-65°；
    优选地，εA与εB的差为5-60°，优选5-45°。
  3. 根据权利要求1或2所述的气体分布单元，其特征在于，所述气体出口A和所述气体出口B位于相同或不同的气体分布管上，
    优选，所述气体出口A和所述气体出口B位于不同的气体分布管上，其中所述气体出口A位于第一气体分布管上，所述气体出口B位于第二气体分布管上，更优选，所述第一和第二气体分布管水平设置。
  4. 根据权利要求3所述的气体分布单元，其特征在于，多个所述第一和第二气体分布管联通以形成气体分布器，
    优选多个所述第一气体分布管联通形成第一气体分布器，多个所述第二气体分布管联通形成第二气体分布器，其中所述第一和第二气体分布器各自水平设置，优选所述第一和第二气体分布器各自包括水平设置的直管形状的一个主管和与主管联通的直管形状的一个或多个支管，并且第一和第二气体分布器的两个主管彼此平行，所述两个主管在水平面上的投影存在夹角δ，δ的范围为0°-135°，优选20°-70°；
    更优选，所述第一和第二气体分布管各自为圆形截面的直管，并且所述气体出口A为第一气体分布管上的开孔，所述气体出口B为第二气体分布管上的开孔，其中开孔角度αA和αB分别等同于气体喷射角度εA和εB，其中开孔角度为开孔截面中心点与相应气体分布管的截面圆圆心所在直线与竖直方向的夹角，优选所述第一气体分布管上存在多个开孔作为气体出口A，所述第二气体分布管上存在多个开孔作为气体出口B，并且更优选所述第一和第二气体分布管各自具有1‰至60‰，优选1‰-45‰，更优选5‰至30‰的开孔率。
  5. 根据权利要求1-4任一项所述的气体分布单元，其特征在于， 还包括：
    底部气体分布管，其位于所有所述至少一个气体分布管的下方，并且底部气体分布管具有至少一个气体出口D，从而以喷射角度β向上喷射气体，其中β为0-80°，优选30-60°；
    优选，多个底部气体分布管联通以形成底部气体分布器。
  6. 根据权利要求1或2所述的气体分布单元，其特征在于，所述至少一个气体分布管还包括至少一个气体出口C，其位于所述气体出口A和所述气体出口B的下方，并以喷射角度εC倾斜向下喷射气体，并且εA>εB>εC，优选εA与εB的差小于εB与εC的差；
    更加优选，εC为10-65°，优选20-50°；
    进一步优选，εB与εC的差为5-60°，优选5-45°；
    更进一步优选，εA与εB的差比εB与εC的差小1-30°，优选5-25°。
  7. 根据权利要求6所述的气体分布单元，其特征在于，所述气体出口A、所述气体出口B和所述气体出口C位于相同或不同的气体分布管上，
    优选，所述气体出口A、所述气体出口B和所述气体出口C分别位于不同的气体分布管上，其中所述气体出口A位于第一气体分布管上，所述气体出口B位于第二气体分布管上，所述至少一个气体出口C位于第三气体分布管上，更优选，所述第一、第二和第三气体分布管水平设置。
  8. 根据权利要求6或7所述的气体分布单元，其特征在于，多个所述第一、第二和第三气体分布管联通以形成气体分布器，
    优选多个所述第一气体分布管联通形成第一气体分布器，多个所述第二气体分布管联通形成第二气体分布器，多个所述第三气体分布管联通形成第三气体分布器，其中所述第一、第二和第三气体分布器各自水平设置，优选所述第一、第二和第三气体分布器各自包括水平设置的直管形状的一个主管和与主管联通的直管形状的一个或多个支管，更优选所述第一、第二和第三气体分布器的三个主管彼此平行，所述三个主管在水平面上的投影存在夹角δ，δ的范围为0°-135°，优选20°-70°；
    更优选，所述第一、第二和第三气体分布管各自为圆形截面的直管， 并且所述气体出口A为第一气体分布管上的开孔，所述气体出口B为第二气体分布管上的开孔，并且所述至少一个气体出口C为第三气体分布管上的开孔，其中开孔角度αA，αB，αC分别等同于气体喷射角度εA，εB，εC，其中开孔角度为开孔截面中心点与相应气体分布管的截面圆圆心所在直线与竖直方向的夹角，优选所述第一气体分布管上存在多个开孔作为气体出口A，所述第二气体分布管上存在多个开孔作为气体出口B，并且所述第三气体分布管上存在多个开孔作为气体出口C，更优选所述第一、第二和第三气体分布管各自具有1‰至60‰，优选1‰-45‰，更优选5‰至30‰的开孔率。
  9. 根据权利要求6-8任一项所述的气体分布单元，其特征在于，还包括
    底部气体分布管，其位于所有所述至少一个气体分布管的下方，并以喷射角度β向上喷射气体，其中β为0-80°，优选30-60°；
    优选，多个底部气体分布管联通以形成底部气体分布器。
  10. 一种鼓泡床反应器，其特征在于，包括权利要求1至4中任意一项所述的气体分布单元，
    优选，所述气体出口A在鼓泡床反应器中的高度为hA，和所述气体出口B在鼓泡床反应器中的高度为hB，其中hA和hB为鼓泡床反应器总高度H的10-90％，优选20-85％；
    优选，hA与hB之间的差为鼓泡床反应器总高度H的5-70％，优选10-60％。
  11. 根据权利要求10所述的鼓泡床反应器，其特征在于，所述鼓泡床反应器中还包括至少一个催化剂床层，所述至少一个催化剂床层由催化剂颗粒构成，其中所述第一和第二气体分布管各自独立地位于所述至少一个催化剂床层中，
    优选，第一和第二气体分布管分别位于第一和第二催化剂床层中，优选，第一和第二催化剂床层各自由催化剂颗粒构成，其中所述第一和第二催化剂床层中的催化剂颗粒的平均粒径分别为P1和P2，并且P1>P2；
    更优选，所述鼓泡床反应器还包括至少一个底部气体分布器，其位于每个催化剂床层下方或位于所有催化剂床层下方，所述底部气体分布器由多个底部气体分布管联通形成并且底部气体分布管包括气体出 口以喷射角度β向上喷射气体，其中β为0-80°，优选30-60°。
  12. 一种鼓泡床反应器，其特征在于，包括权利要求6至8中任意一项所述的气体分布单元，
    优选，所述气体出口A在鼓泡床反应器中的高度为hA、所述气体出口B在鼓泡床反应器中的高度为hB、和所述气体出口C在鼓泡床反应器中的高度为hC，优选hA、hB和hC为鼓泡床反应器总高度H的10-90％，优选20-85％；
    更优选，hA与hB之间的差为鼓泡床反应器总高度H的5-70％，优选10-60％，hB与hC之间的差为鼓泡床反应器总高度H的5-60％，优选10-50％，其中hB与hC之间的差与hA与hB之间的差相同或不同。
  13. 根据权利要求12所述的气体分布单元，其特征在于，所述鼓泡床反应器中还包括至少一个催化剂床层，所述至少一个催化剂床层由催化剂颗粒构成，其中所述第一、第二和第三气体分布管各自独立地位于所述至少一个催化剂床层中，
    优选，所述第一、第二和第三气体分布管分别位于第一、第二和第三催化剂床层中，优选，所述第一、第二和第三催化剂床层各自由催化剂颗粒构成，其中所述第一、第二和第三催化剂床层中的催化剂颗粒的平均粒径分别为P1、P2和P3，并且P1>P2>P3；
    更优选，所述鼓泡床反应器还包括至少一个底部气体分布器，其位于每个催化剂床层下方或所有催化剂床层下方，所述底部气体分布器由多个底部气体分布管联通形成并且底部气体分布管包括气体出口以喷射角度β向上喷射气体，其中β为0-80°，优选30-60°。
  14. 根据权利要求10至13任一项所述的鼓泡床反应器，其特征在于，还包括：
    液体分布管，其在鼓泡床反应器中的高度大于所有所述至少一个气体分布管在鼓泡床反应器中的高度，并大于所有所述至少一个催化剂床层在鼓泡床反应器中的高度，并且其将液体原料输入鼓泡床反应器中；
    优选，多个液体分布管联通以形成顶部液体分布器。
  15. 一种反应方法，其特征在于，其包括步骤：使用如权利要求1至9中任意一项所述的气体分布单元将气体反应物喷射到鼓泡床反应 器中，与其中的液体反应物进行反应。
  16. 根据权利要求15所述的反应方法，其特征在于，所述反应方法用于合成碳酸乙烯酯、碳酸丙烯酯或碳酸丁烯酯，所述液体反应物分别为环氧乙烷、环氧丙烷或环氧丁烷，并且所述气体反应物为二氧化碳。
PCT/CN2024/100542 2023-06-28 2024-06-21 气体分布单元、鼓泡床反应器以及使用其的反应方法 Ceased WO2025001983A1 (zh)

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