WO2020177753A1 - 一种超重力纳微气泡产生装置及反应系统 - Google Patents

一种超重力纳微气泡产生装置及反应系统 Download PDF

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Publication number
WO2020177753A1
WO2020177753A1 PCT/CN2020/078083 CN2020078083W WO2020177753A1 WO 2020177753 A1 WO2020177753 A1 WO 2020177753A1 CN 2020078083 W CN2020078083 W CN 2020078083W WO 2020177753 A1 WO2020177753 A1 WO 2020177753A1
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gas
nano
liquid
gravity
hollow shaft
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English (en)
French (fr)
Inventor
罗勇
王迪
初广文
刘亚朝
李志浩
蔡勇
邹海魁
孙宝昌
陈建峰
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Priority to US17/418,578 priority Critical patent/US12053746B2/en
Priority to MYPI2021003685A priority patent/MY207450A/en
Priority to DE112020000173.3T priority patent/DE112020000173T5/de
Publication of WO2020177753A1 publication Critical patent/WO2020177753A1/zh
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Definitions

  • the invention relates to the technical field of reactors, and more specifically, to a supergravity nano-micro bubble generating device and a reaction system.
  • the methods for generating nano-micro bubbles mainly include the dissolved gas outgas method and the dispersed gas method.
  • the representative device of the dissolved gas outgas method is usually composed of a pump, a dissolved gas tank and a nozzle.
  • the gas is forcibly dissolved in a pressurized method. In the liquid, a supersaturated state is formed, and then the reduced pressure gas is released again to generate a large number of microbubbles.
  • this method has the disadvantage of cumbersome and discontinuous process of generating microbubbles, and it is difficult to apply to actual industrial production.
  • the gas dispersion law is a method of dispersing gas into the liquid by means of high-speed swirling, tapering and sudden expansion of the flow section, and microporous dispersion, so as to quickly and massively form nano-micro bubbles.
  • microporous dispersion methods are the most common in industrial production. They are mainly used in micromixers or some microporous media (metallurgical powder, ceramics or plastics as materials, and then mixed with appropriate binders.
  • microporous structure formed by sintering forms nano-micro bubbles, but the nano-micro bubbles produced by this method are usually prone to agglomerate and form large bubbles on the surface of the microporous medium, which reduces the gas-liquid contact area between the bubbles and the liquid and restricts This shows the excellent functions of nano-microbubbles in many fields.
  • a first aspect of the present invention provides a supergravity nanobubble generating device, including:
  • a housing on which a liquid inlet and a liquid outlet are arranged;
  • the super-gravity bubble generating unit includes:
  • the rotor arranged in the casing can form a supergravity field through rotation, and the centrifugal force acceleration generated by the supergravity field is greater than 10g;
  • the hollow shaft divides the housing into a communicating inner cavity and an outer cavity, and a number of micrometer-scale pores are provided on the side wall of the hollow shaft.
  • it further includes:
  • the gap between the housing and the hollow shaft is 0.1-10 mm.
  • the distance between the hole centers of two adjacent channels is set at a pitch.
  • the channel includes a first channel located in the upper half of the side wall of the hollow shaft and a second channel located in the lower half of the side wall of the hollow shaft;
  • the aperture of the first channel is greater than, smaller than or equal to the aperture of the second channel.
  • the pore diameter of the pores increases or decreases along the direction of gas flow; or,
  • the aperture of the pore channel increases or decreases along the direction of liquid flow in the outer cavity.
  • the holes are distributed symmetrically around the axis of the hollow shaft.
  • the hollow shaft is made of stainless steel or titanium-based materials, and the diameter of the pores is preferably in the range of 0.01-0.1 mm.
  • the hollow shaft is made of a ceramic membrane.
  • the pore diameter of the inner wall membrane pores of the ceramic membrane is in the range of 2-48 nm, and the outer wall membrane pore diameter is in the range of 5-48 nm.
  • the second aspect of the present invention provides a reaction system, which is used for a gas-liquid two-phase reaction, and the reaction system includes a supergravity nanobubble generating device.
  • the third aspect of the present invention provides a reaction system, the reaction system is used for gas-liquid-solid three-phase reaction, or for pseudo-homogeneous gas-liquid-solid reaction, the reaction system includes a connected reactor and A high-gravity nano-micro bubble generating device that mixes a gas reactant and a liquid reactant to form a gas-liquid mixture with nano-micro bubbles, and solid reactant or solid catalyst can be passed into the reactor .
  • the present invention provides a device and system for generating high-gravity nano-microbubbles.
  • the liquid phase is the continuous phase and the gas phase is the dispersed phase.
  • the gas enters the interior from the hollow shaft, and the gas is subjected to the shearing action of the aeration micropores.
  • the bubble is formed by the first shear, and the bubble is then quickly separated from the surface of the shaft under the action of the high-speed rotating shaft, and is subjected to secondary shearing under the strong shear force of the supergravity environment formed by the shaft to form nano-micro bubbles, which is fast, stable, and
  • the advantage of small average particle size is that the average particle size of the formed nano-micro bubbles is between 800 nanometers and 50 microns, and the average particle size of the bubbles can be range controlled by adjusting the rotation speed of the rotating shaft.
  • the device overcomes the discontinuity of the liquid phase and the inability to form a liquid phase containing nano-microbubbles in the traditional high-gravity device, and on the other hand, it overcomes the problem of aggregation of nano-microbubbles on the surface of a static microporous medium.
  • the ultra-gravity nano-micro bubble generator is applied to the field of hydrogenation/oxidation and other reactions. Due to the existence of nano-micro bubbles, the gas-liquid contact area of the hydrogenation/oxidation reaction process is increased, and the gas of the solution to be reacted is increased. It has important industrial application significance in the fields of petrochemical industry, fine chemical industry, coal chemical industry, biochemical industry, etc., thereby enhancing the gas-liquid mass transfer, achieving the purpose of increasing the macroscopic reaction rate and shortening the reaction time.
  • Fig. 1 shows a schematic diagram of the structure of a supergravity nanobubble generating device in an embodiment of the present invention.
  • Fig. 2a shows a schematic diagram of the distribution of holes on the hollow shaft in Fig. 1 in an embodiment of the present invention.
  • Figure 2b shows a top view of the hollow shaft of Figure 1 in an embodiment of the present invention.
  • Figure 3a shows one of the structural schematic diagrams of the reaction system in an embodiment of the present invention.
  • Figure 3b shows the second structural diagram of the reaction system in the embodiment of the present invention.
  • Figure 3c shows the third structural diagram of the reaction system in the embodiment of the present invention.
  • microporous dispersion methods are the most common in industrial production. They are mainly used in micromixers or some microporous media (metallurgical powder, ceramics or plastics as materials, mixed with appropriate binders, and sintered at high temperatures.
  • the micro-porous structure formed by this method forms nano-micro bubbles, but the nano-micro bubbles produced by this method are usually prone to aggregate on the surface of the microporous medium and form large bubbles, which reduces the gas-liquid contact area between the bubbles and the liquid and restricts Nano-microbubbles perform excellent functions in many fields.
  • the first aspect of the present invention provides a high-gravity nano-microbubble generating device.
  • the hollow shaft is fixed on the rotor of the high-gravity reactor, and the hollow shaft is driven by the rotor.
  • the gas enters the interior from the hollow shaft, and the gas is sheared once by the shearing action of the aeration micropores to form bubbles.
  • the bubbles are then quickly separated from the surface of the shaft under the action of the high-speed rotating shaft, and in the supergravity environment formed by the shaft
  • the secondary shearing is performed under strong shearing force to form nano-micro bubbles.
  • centrifugal force acceleration generated by the supergravity field should be greater than 10g (that is, more than 10 times the acceleration of gravity), which will not be repeated here.
  • nanomicro in this application refers to the nano-micro scale, that is, the size is in the range of nanometers and micrometers, that is, between 1nm-100um.
  • the super-gravity nano-microbubble generating device in this application can be a vertical or horizontal type, such as a vertical tubular or a vertical cylindrical shape, which is not limited in this application, but it is understood that the vertical type can be
  • the gas inlet is set below, which utilizes the driving force of gas diffusion, and is more suitable for gas that is "lighter" than air.
  • the super-gravity nano-microbubble generating device includes: a housing 3 on which a liquid inlet 9 and a liquid outlet 6 are arranged; A gravity bubble generating unit; wherein the supergravity bubble generating unit includes: a rotor arranged in the housing, which can form a supergravity field by rotating, and the centrifugal force acceleration generated by the supergravity field is greater than 10g; one end is connected to the rotor Combined with the fixed hollow shaft 7, the other end of the hollow shaft 7 communicates with the gas inlet 5; wherein, the hollow shaft divides the housing into a communicating inner cavity and an outer cavity, and the side of the hollow shaft Several micrometer-scale holes 8 are arranged on the wall.
  • the high-gravity nano-microbubble generating device in which the liquid phase is the continuous phase, the gas phase is the dispersed phase, the gas enters the interior from the hollow shaft, and the gas is sheared once by the shearing action of the aeration micropores. Cut to form bubbles, the bubbles are then quickly separated from the surface of the shaft under the action of the high-speed rotating shaft, and are subjected to secondary shearing under the strong shear force of the supergravity environment formed by the shaft to form nano-micro bubbles, which have a fast, stable, and average particle size.
  • the advantage of small diameter is that the average particle size of the formed nano-micro bubbles is between 800 nanometers and 50 microns, and the average particle size of the bubbles can be adjusted in a range by adjusting the rotation speed of the rotating shaft.
  • the device overcomes the discontinuity of the liquid phase and the inability to form a liquid phase containing nano-microbubbles in the traditional high-gravity device, and on the other hand, it overcomes the problem of aggregation of nano-microbubbles on the surface of static microporous media.
  • the device also includes a seal 2 to prevent gas and liquid leakage; a flange 10 for fixing the device; the hollow shaft is cylindrical, the upper end is connected to the motor drive, and the lower end is connected to the inner bottom bearing 4 of the housing, and The lower end is open and connected to the gas inlet 5.
  • the gas discharged from the hollow shaft is cut once under the action of micron-scale aeration micropores (i.e. pores) to produce micron-scale small bubbles, which are then rapidly driven by the centrifugal force of the high-speed shaft Leaving the wall surface avoids the problem of bubbles gathering and becoming bigger.
  • the high-speed rotating shaft will form a strong shear force and turbulence with the liquid, and form a local vortex.
  • the generated micro-sized bubbles are continuously cut under the action of the shearing force, forming a large number of stable nano-micro bubbles.
  • the functions of the liquid inlet and the liquid outlet can be exchanged, depending on specific requirements. For example, when the liquid is required to flow from top to bottom in the figure, the number 6 in the figure is the liquid inlet and the number 9 is the liquid outlet. This application is not limited to this.
  • the rotor includes a rotating shaft (not shown in the figure), and the rotating shaft is driven by the motor 1 to rotate at a high speed.
  • the power of the motor 1 can be adjusted as needed, thereby adjusting the rotation speed of the rotor.
  • the rotation speed of the rotor may be 100-10000 rpm, for example, the rotation speed of the rotor may be 4000 rpm, 5000 rpm, 6000 rpm, 7000 rpm, 8000 rpm, 9000 rpm, 10000 rpm.
  • the high-gravity nano-microbubble generator is characterized in that the gas enters the hollow shaft from the air inlet, and the gas is cut once under the action of the micro holes on the hollow shaft wall to form small bubbles, which are quickly separated from the shaft wall under the action of the high-speed rotating shaft And dispersed in the liquid phase, and then further cut under the strong shear force and vortex generated by the high-speed rotating shaft, forming a large number of stable nano-micro bubbles.
  • the size of the nano-micro bubbles can be controlled by the rotation speed of the rotor, for example, the higher the rotation speed of the rotor, the smaller the bubbles.
  • the height-to-diameter ratio of the shell is 5-30, which can make the gas flow path longer and expand the range of bubble generation.
  • a gas flow control valve is provided at the gas inlet of the housing, so that the gas flow rate can be controlled to control the gas-liquid mixing ratio.
  • the application does not limit the gas flow control valve Whether it is installed on the shell, for example, the gas flow control valve can be installed on the gas source (generally, each gas cylinder has a gas flow control valve), but for systems with long pipelines, the gas is controlled from the gas source The error of flow is large, and the error of direct control at the gas inlet is small, which can eliminate the influence of the pressure difference of the pipeline itself.
  • the material of the hollow shaft can be one of stainless steel, titanium-based material or ceramic membrane material.
  • the material of the hollow shaft is not limited to the materials shown above, and this application will not exhaustively list.
  • the hollow shaft is made of stainless steel or titanium-based material, and the diameter of the pores is in the range of 0.01-0.1 mm.
  • the hollow shaft is made of a ceramic membrane
  • the inner wall membrane pores of the ceramic membrane have a pore diameter range of 2-48 nm
  • the outer wall membrane pores have a pore diameter range of 5-48 nm, such as the inner wall membrane.
  • the pore size can be 2nm, 5nm, 10nm, 20nm, 48nm
  • the outer wall membrane pore size can be 5nm, 10nm, 20nm, 48nm
  • the above inner wall membrane pore size and outer wall membrane pore size can be combined in any combination, preferably, the inner wall membrane pore size is 20nm ,
  • the outer wall membrane pore size is 5nm.
  • the wall thickness of the hollow shaft is 2-10 mm, preferably, the wall thickness is 3 mm.
  • Figure 2b shows a top view of the hollow shaft.
  • the holes are distributed symmetrically around the axis of the hollow shaft.
  • any two holes The distance between the center of the hole (that is, the center of the channel) is the same.
  • each channel can be the same or different, and can be adjusted according to the situation.
  • the channel includes a first channel located on the upper half of the side wall of the hollow shaft and a hole located on the lower half of the side wall of the hollow shaft.
  • the aperture of the first channel is greater than, smaller than or equal to the aperture of the second channel.
  • the high-gravity nano-microbubble generating device is a vertical cylindrical shape
  • the liquid inlet is arranged below the housing
  • the liquid outlet is arranged above the housing
  • the gas inlet is arranged at the bottom of the housing.
  • the aperture of the first channel is set to be larger than the aperture of the second channel to balance the overflow of the two and avoid the phenomenon of inconsistent bubble density in the upper and lower parts.
  • the liquid outlet is arranged above the shell, and the gas inlet is arranged at the bottom of the shell. Since the gas inlet is arranged below the shell, for a mixed system with a faster liquid flow rate, the liquid in the liquid inlet area It will produce an impact on the hollow shaft and hinder the ejection of bubbles. In the liquid outlet area, the liquid flow will have a driving effect on the bubbles and accelerate the ejection of the bubbles.
  • the diameter of the second channel can be slightly larger than that of the first channel. Aperture, to balance the influence of incoming and outgoing liquid flow.
  • the pore size of the first channel is the same as the pore size of the second channel.
  • the pore diameter of the pores decreases continuously from the bottom to the top in Figure 2a.
  • the pore diameters of two adjacent pores differ by 0.1mm, 0.2mm, etc., which can balance the gas up and down.
  • concentration difference, or the balance liquid flow rate difference there is resistance and gravity in the flow process, resulting in a slight difference in flow rate
  • the pore size is increasing.
  • the hole center spacing of two adjacent holes is the same, which is a set spacing (ie a given spacing value, such as 10mm, 20mm, etc.).
  • the average particle size of the formed nano-microbubbles is between 800 nanometers and 50 microns, which can be specifically achieved by visualization, X-ray imaging techniques, and fiber probes or conductivity probes, and the application is not limited thereto.
  • the average particle size of the bubbles can be controlled by adjusting the rotation speed of the rotating shaft.
  • the device overcomes the discontinuity of the liquid phase and the inability to form a liquid phase containing nano-microbubbles in the traditional high-gravity device, and on the other hand, it overcomes the problem of aggregation of nano-microbubbles on the surface of a static microporous medium.
  • the second aspect of the present invention provides a reaction system for a gas-liquid two-phase reaction, the reaction system including supergravity Nano-micro bubble generating device.
  • this system uses a high-gravity nano-micro bubble generator as a reactor for the steps of gas-liquid two-phase oxidation reaction:
  • the reaction process includes the following steps: open the nitrogen cylinder and purge the entire pipeline to discharge the air; turn on the heating device, open the hydrogen cylinder after the heating device reaches a predetermined temperature, and use a gas mass flowmeter to adjust the gas flow , Use the back pressure valve to adjust to the preset pressure; turn on the super-gravity nano-micro bubble generating device, adjust the speed; turn on the plunger pump, and make the reaction solution fill the entire super-gravity nano-micro bubble generating device, and then use the plunger pump to adjust the liquid flow , Control the time for the reaction solution to pass through the fixed bed reactor, and take samples from the sampling port for analysis after the system is stable.
  • a fixed bed reactor is filled with a Pd/Al 2 O 3 catalyst with an equivalent diameter of 1.6 mm, and hydrogen is passed through at 90°C for pre-reduction before use, and then sealed with nitrogen;
  • the volume ratio of mesitylene and trioctyl phosphate is 3:1 as a mixed solvent, and a 2-ethylanthraquinone working solution with a concentration of 120 (g/L) is prepared.
  • the temperature is 50°C and the pressure is 0.3MPa, super-gravity nanobubbles
  • the mixed fluid containing nano-micro bubbles (the average bubble diameter is 10 microns) is passed into the fixed bed reactor, and the anthraquinone conversion rate is 35%, the selectivity is 92%, and the hydrogenation efficiency is reached in 35s.
  • the high-gravity nano-micro bubble generator has a good catalytic hydrogenation effect on the fixed-bed anthraquinone hydrogenation reaction; at the same time, within a certain range, as the rotating shaft speed of the high-gravity nano-micro bubble generator increases, The average particle size of the nano-micron bubbles produced by the device tends to decrease, and the decrease of the average particle size of the bubbles increases the gas-liquid contact area and the gas holdup, which is beneficial to the improvement of the effect of the fixed bed anthraquinone hydrogenation reaction.
  • the volume ratio of mesitylene and trioctyl phosphate is 3:1 as a mixed solvent to prepare a 2-ethylanthraquinone working solution with a concentration of 120 (g/L). It is 50°C and the pressure is 0.3MPa.
  • the supergravity nano-micro bubble generator Under the condition that the supergravity nano-micro bubble generator does not rotate, it only relies on the aeration micropores on the hollow shaft wall to cut the gas to form a gas-liquid mixed flow, which will contain microbubbles (bubble average).
  • the gas-liquid mixed fluid with a diameter of 550 microns is passed into the fixed bed reactor, and the anthraquinone conversion rate is 12%, the selectivity is 96%, and the hydrogenation efficiency is 1.8 (g/L) in 35s.
  • the supergravity nano-microbubble generator can further reduce the average diameter of the bubbles formed under the shear force generated by the high-speed rotating shaft. It can effectively overcome the problem of the accumulation and enlargement of bubbles on the surface of the static microporous medium, and at the same time, the effect of using the device of the invention to carry out the fixed-bed anthraquinone hydrogenation reaction is better than that of using the static microporous medium alone.
  • the device shown in Figure 1 is used as a reactor for gas-liquid two-phase hydroanthraquinone oxidation reaction.
  • the operation steps are as follows: Add 2-ethylhydroanthraquinone, the hydrogenation product of 2-ethylanthraquinone, into a stirred tank -22, the concentration is 0.43mol/L, turn on the plunger pump to circulate the pseudo-homogeneous solution. After the system is stable, turn on the gas cylinder and the super-gravity nano-microbubble generator, and circulate at 50°C and normal pressure. Oxidation, 2-ethylhydroanthraquinone can be completely oxidized within 5 minutes (and the conversion rate is 100%).
  • the reaction system provided in this application applies the high-gravity nano-bubble generating device to the field of gas-liquid hydrogenation/oxidation reaction.
  • the presence of nano-microbubbles makes the gas-liquid contact area of the hydrogenation/oxidation reaction process Increase and increase the gas content of the solution to be reacted at the same time, thereby enhancing the gas-liquid mass transfer, achieving the purpose of increasing the macro-reaction rate and shortening the reaction time. It is important in petrochemical, fine chemical, coal chemical, biochemical and other fields Significance of industrial applications.
  • the third aspect of the present invention is a reaction system, which is used for gas-liquid-solid three-phase reaction, or for pseudo homogenization Phase gas-liquid-solid reaction.
  • the reaction system includes a connected reactor and a super-gravity nano-micro bubble generating device that mixes the gas reactant with the liquid reactant to form a nano-micro bubble
  • solid reactants or solid catalysts can be passed into the reactor.
  • this system uses a high-gravity nano-microbubble generator for the gas-liquid-solid three-phase hydrogenation/oxidation steps of a fixed bed reactor:
  • step 2) Pass the gas-liquid mixture with nano-microbubbles produced in step 1) into a fixed bed reactor containing catalyst particles for hydrogenation/oxidation reaction.
  • the pressure of the reaction system is controlled by the back pressure valve-17, and the temperature is controlled by Temperature control system control;
  • step 2) The gas-liquid mixture with reaction products produced in step 2) is separated through the gas-liquid separation tank-19, the gas is discharged from the vent valve, the liquid flows into the sample storage tank-20, and the sample is separated for further testing.
  • this system uses a super-gravity nano-micro bubble generator for the pseudo-homogeneous gas-liquid-solid hydrogenation/oxidation reaction steps of a stirred tank reactor:
  • step 2) Turn on the stirred tank reactor, and pass the gas-liquid mixture with nano-micro bubbles produced in step 1) into the stirred tank reactor equipped with nano- or micro-finish powdered catalyst particles for hydrogenation/oxidation reaction.
  • the system pressure is controlled by the back pressure valve-17, and the temperature is controlled by the temperature control system;
  • step 2) The gas-liquid mixture with reaction products produced in step 2) is separated by gas-liquid separation tank-19, the gas is discharged from the vent valve, the liquid flows into the sample storage tank-20, and the sample is filtered or centrifuged and separated. Further testing.
  • the noble metal catalyst used in step 2) is a catalyst supported by solid particles such as alumina, silica or molecular sieve, and loaded with precious metals such as palladium and platinum or mixed metals by high-temperature calcination.
  • the particle size of the catalyst ranges from 10nm to 800um. The best diameter is 50nm-200um.
  • this system uses a supergravity nano-microbubble generator as a reactor for pseudo-homogeneous gas-liquid-solid hydrogenation/oxidation reaction, which is characterized in that it includes the following steps:
  • step 2) The gas-liquid mixture with reaction products produced in step 2) is separated by gas-liquid separation tank-19, the gas is discharged from the vent valve, and the liquid flows into the middle stirred tank-21; in addition, it can be controlled by the switch of the ball valve-22
  • the control system is a single-pass hydrogenation/oxidation reaction or a cyclic hydrogenation/oxidation reaction.
  • the ball valve-22 When the ball valve-22 is opened, the system is a cyclic hydrogenation/oxidation reaction.
  • the ball valve is closed, the system is a single-pass hydrogenation/oxidation reaction; After filtration or centrifugation, and separation for further testing.
  • the catalyst may be micro-nano-scale particles.
  • noble metal catalyst particles can be used.
  • the noble metal catalyst particles are supported by solid particles such as alumina, silica or molecular sieve and supported by high-temperature calcination.
  • the catalyst particle size ranges from 10nm-800um, and the above-mentioned particle size is 50nm-200um.
  • the device shown in Figure 1 is used in the pseudo-homogeneous gas-liquid solid anthraquinone hydrogenation reaction of a stirred tank reactor.
  • the experimental device is different from the above-mentioned gas-liquid two-phase reaction except for the stirred tank reactor-21.
  • the system is the same, and the operation steps are the same.
  • the volume ratio of mesitylene and trioctyl phosphate is 1:1 as a mixed solvent to prepare a 2-ethylanthraquinone working solution with a concentration of 100 (g/L).
  • the hydrogenation rate is 0.3MPa and the Pd/ ⁇ -Al 2 O 3 catalyst concentration is 2%wt for hydrogenation.
  • the anthraquinone conversion rate is 76%, the selectivity is 90.5%, and the hydrogenation efficiency is 9.5 (g/L ).
  • Figure 3c can also be used as a pseudo-homogeneous gas-liquid-solid 1-nitroanthraquinone hydrogenation reaction system, using the device shown in Figure 1 as a reactor for pseudo-homogeneous gas-liquid-solid 1-nitroanthraquinone addition Hydrogen reaction, the operation steps are as follows: prepare 1-nitroanthraquinone and N,N-2 methylformamide into a reaction solution in a mass ratio of 3:20, and have the same particle size as Pd/ ⁇ -Al 2 O 3 of 80 microns Add the catalyst to the stirred tank-22 together, turn on the stirred tank to completely mix the catalyst and the solution and maintain a suspended state; turn on the plunger pump to circulate the pseudo-homogeneous solution.
  • the device After the system is stable, turn on the gas cylinder and generate supergravity nano-micro bubbles
  • the device carries out cyclic hydrogenation under the conditions of 100°C, 1.2MPa and 4%wt of catalyst concentration, and the product 1-aminoanthraquinone can reach a purity of more than 95% within 40 minutes.
  • the reaction system provided in this aspect can be used for gas-liquid-solid three-phase reactions, or for pseudo-homogeneous gas-liquid-solid reactions. Due to the presence of nano-micro bubbles, the hydrogenation/oxidation reaction process gas The liquid contact area increases, and at the same time the gas content of the solution to be reacted is increased, thereby enhancing the gas-liquid mass transfer, achieving the purpose of increasing the macro reaction rate and shortening the reaction time. It is used in petrochemical, fine chemical, coal chemical, biochemical, etc. The field has important industrial application significance.

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Abstract

一种超重力纳微气泡产生装置及反应系统，在该装置中液相为连续相，气相为分散相，气体由中空轴（7）进入内部，经曝气微孔的剪切作用对气体进行一次剪切形成气泡，气泡随后在高速旋转的转轴作用下快速脱离转轴表面，并在转轴所形成的超重力环境强大的剪切力下进行二次剪切形成纳微气泡，所形成的纳微气泡平均粒径处于800纳米-50微米之间，并可通过调节旋转轴的转速对气泡平均粒径进行范围调控。

Description

一种超重力纳微气泡产生装置及反应系统 技术领域
本发明涉及反应器技术领域，更具体的，涉及一种超重力纳微气泡产生装置及反应系统。
背景技术
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目前，纳微气泡产生方法主要包括溶气释气法和分散气体法，溶气释气法的代表性装置通常由泵、溶气罐和喷嘴组成，是通过加压的方法将气体强制溶解于液体中，形成过饱和状态，然后减压气体重新释放出来从而产生大量的微气泡，但该方法存在产生微气泡的过程繁琐且不连续的缺点，很难应用于实际的工业生产中。分散气体法则是通过高速旋流、过流断面渐缩突扩、微多孔分散等手段将气体分散到液体中去，从而快速、大量形成纳微气泡的方法。以上，在工业生产中尤以微多孔分散手段最为常见，其主要通过微混合器或利用某些微孔介质(冶金粉末、陶瓷或塑料做材料，再掺以适当的粘合剂，在高温下烧结而成)的微多孔结构形成纳微米气泡，但该种方法所产生的纳微气泡通常在微孔介质表面易发生聚并形成大气泡，减小了气泡与液体的气液接触面积，制约了纳微气泡在诸多领域优异功能的发挥。
发明内容
为了解决上述问题的至少一个，本发明第一方面提供一种超重力纳微气泡产生装置，包括：
壳体，其上设置有液体进口和液体出口；以及
设置与所述壳体内的超重力气泡产生单元；其中，
所述超重力气泡产生单元包括：
设于所述壳体内的转子，可通过旋转形成超重力场，所述超重力场产生的离心力加速度大于10g；
一端与所述转子结合固定的中空轴，所述中空轴的另一端与气体进口连通；
其中，所述中空轴将所述壳体分为连通的内腔体和外腔体，所述中空轴的侧壁上设置若干微米尺度的孔道。
在某些实施例中，还包括：
设置在所述壳体与中空轴之间的间隙为0.1-10mm。
在某些实施例中，相邻两个孔道的孔心之间距离设定间距。
在某些实施例中，所述孔道包括位于所述中空轴侧壁上半部分的第一孔道和位于所述中空轴侧壁下半部分的第二孔道；
所述第一孔道的孔径大于、小于或等于所述第二孔道的孔径。
在某些实施例中，所述孔道的孔径沿气体流动的方向递增或递减；或，
所述孔道的孔径沿所述外腔体液体流动的方向递增或递减。
在某些实施例中，所述孔道围绕所述中空轴的轴心对称分布。
在某些实施例中，所述中空轴的材料为不锈钢或者钛基材料，优选孔道直径的范围为0.01-0.1mm。
在某些实施例中，所述中空轴由陶瓷膜制成，优选所述陶瓷膜的内壁膜孔道的孔径范围为2-48nm，外壁膜孔道的孔径范围为5-48nm。
本发明第二方面提供一种反应系统，所述反应系统用于气液两相反应，所述反应系统包括超重力纳微气泡产生装置。
本发明第三方面提供一种反应系统，所述反应系统用于气-液-固三相反应，或者用于拟均相的气-液-固反应，所述反应系统包括连通的反应器以及超重力纳微气泡产生装置，所述超重力纳微气泡产生装置将气体反应物与液体反应物混合形成具有纳微气泡的气液混合物，所述反应器中可通入固体反应物或者固体催化剂。
本发明的有益效果：
本发明提供的一种超重力纳微气泡产生装置及系统，在该装置中液相为连续相，气相为分散相，气体由中空轴进入内部，经曝气微孔的剪切作用对气体进行一次剪切形成气泡，气泡随后在高速旋转的转轴作用下快速脱离转轴表面，并在转轴所形成的超重力环境强大的剪切力下进行二次剪切形成纳微气泡，具有快速、稳定、平均粒径小的优点，所形成的纳微气泡平均粒径处于800纳米-50微米之间，并可通过调节旋转轴的转速对气泡平均粒径进行范围调控。该装置一方面克服了传统超重力装置中液相不连续，无法形成含纳微气泡液相的问题，另一方面克服了静态微孔介质表面纳微气泡聚并的问题。此外，将超重力纳微气泡产生装置应用于加氢/氧化等反应领域中，由于纳微气泡的存在使得加氢/氧化等反应过程气液接触面积增大，同时提升了待反应溶液的气含率，从而强化气液传质，达到了提高宏观反应速率，缩短反应时间的目的，在石油化工、精细化工、煤化工、生物化工等领域具有重要的工业应用意义。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1示出本发明实施例中超重力纳微气泡产生装置的结构示意图。
图2a示出本发明实施例中图1中的中空轴上孔道分布示意图。
图2b示出本发明实施例中图1中空轴的俯视图。
图3a示出本发明实施例中反应系统的结构示意图之一。
图3b示出本发明实施例中反应系统的结构示意图之二。
图3c示出本发明实施例中反应系统的结构示意图之三。
具体实施方式
为了更清楚地说明本发明，下面结合优选实施例和附图对本发明做进一步的说明。附图中相似的部件以相同的附图标记进行表示。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。
在附图中示出了根据本发明公开实施例的各种截面图。这些图并非是按比例绘制的，其中为了清楚表达的目的，放大了某些细节，并且可能省略了某些细节。图中所示出的各种区域、层的形状以及他们之间的相对大小、位置关系仅是示例性的，实际中可能由于制造公差或技术限制而有所偏差，并且本领域人员根据实际所需可以另外设计具有不同形状、大小、相对位置的区域/层。
目前在工业生产中尤以微多孔分散手段最为常见，其主要通过微混合器或利用某些微孔介质(冶金粉末、陶瓷或塑料做材料，再掺以适当的粘合剂，在高温下烧结而成)的微多孔结构形成纳微米气泡，但该种方法所产生的纳微气泡通常在微孔介质表面易发生聚并形成大气泡，减小了气泡与液体的气液接触面积，制约了纳微气泡在诸多领域优异功能的发挥。
为此，本发明第一方面提供一种超重力纳微气泡产生装置，通过对常规超重力反应器进行改装，将中空轴固定在超重力反应器的转子上，进而中空轴在转子的带动下旋转，气体由中空轴进入内部，经曝气微孔的剪切作用对气体进行一次剪切形成气泡，气泡随后在高速旋转的转轴作用下快速脱离转轴表面，并在转轴所形成的超重力环境强大的剪切力下进行二次剪切形成纳微气泡。
本领域技术人员公知的是，超重力场所产生的离心力加速度应当大于10g(即10倍以上重力加速度)，在此不予赘述。
本领域技术人员应当知晓的是，本申请中的“纳微”指的是纳微尺度，即大小处于纳米和微米的范围，即1nm-100um之间。
需要说明的是，本申请中的超重力纳微气泡产生装置，可以是立式或者卧式，例如立式管状或者立式筒状，本申请对此不做限制，但可以理解，立式可以将气体进口设置在下方，这样利用了气体扩散的推动力，更适用于比空气“轻”的气体。
以立式为例，如图1所示，该超重力纳微气泡产生装置，包括：壳体3，其上设置有液体进口9和液体出口6；以及设置与所述壳体3内的超重力气泡产生单元；其中，所述超重力气泡产生单元包括：设于所述壳体内的转子，可通过旋转形成超重力场，所述超重力场产生的离心力加速度大于10g；一端与所述转子结合固定的中空轴7，所述中空轴7的另一端与气体进口5连通；其中，所述中空轴将所述壳体分为连通的内腔体和外腔体，所述中空轴的侧壁上设置若干微米尺度的孔道8。
本发明第一方面的超重力纳微气泡产生装置，在该装置中液相为连续相，气相为分散相，气体由中空轴进入内部，经曝气微孔的剪切作用对气体进行一次剪切形成气泡，气泡随后在高速旋转的转轴作用下快速脱离转轴表面，并在转轴所形成的超重力环境强大的剪切力下进行二次剪切形成纳微气泡，具有快速、稳定、平均粒径小的优点，所形成的纳微气泡平均粒径处于800纳米-50微米之间，并可通过调节旋转轴的转速对气泡平均粒径进行范围调控。该装置一方面克服了传统超重力装置中液相不连续，无法形成含纳微气泡液相的问题，另一方面克服了静态微孔介质表面纳微气泡聚并的问题。
在具体实施时，该装置还包括密封2，防止气体和液体泄漏；法兰10，用于固定装置；中空轴为圆柱状，上端与电机传动连接，下端与外壳内底部轴承4连接，并在下端开口，连通气体进口5。
当超重力纳微气泡产生装置工作时，从中空轴内排出的气体在微米级曝气微孔(即孔道)的作用下进行一次切割产生微米级小气泡，随后在高速转轴离心力的作用下迅速脱离壁面，避免了气泡的聚并变大问题。同时，高速旋转的转轴会与液体间形成强大的剪切力和湍动，并形成局部的旋涡，产生的微米级气泡在剪切力作用下不断被切割，形成大量、稳定的纳微气泡。
在一些实施例中，液体进口和液体出口的作用可以调换，取决于具体的需求，例如需要液体由图示中的上至下流动时，图中标号6为液体进口，标号9为液体出口，本申请不限于此。
在一些实施例中，转子包括转动轴(图中未示出)，转动轴通过电机1带动高速旋转，可以根据需要调节电机1的功率，进而调节转子的转速。
在一些具体实施例中，转子的转速可以在100-10000rpm，例如转子的转速可以为4000rpm、5000rpm、6000rpm、7000rpm、8000rpm、9000rpm、10000rpm。
超重力纳微气泡产生装置特点在于气体由进气口进入中空轴，在中空轴壁上微孔的作用下对气体进行一次切割形成小气泡，小气泡在高速旋转的转轴作用下快速脱离转轴壁并分散于液相中，随后在高速旋转转轴所产生强大的剪切力和涡流下进一步切割，形成大量、稳定的纳微气泡。
在一些具体实施例中，可以通过转子的转速控制纳微气泡的大小，例如转子转速越高，气泡越小。
优选的，壳体的高径比为5-30，这样可以使得气体的流动路程变长，扩大了气泡产生的范围。
在一些优选的实施例中，在所述壳体的气体进口处设置有气体流量控制阀，这样可以通过控制气体的流速进而控制气液混合的比例，当然，本申请并不限制气体流量控制阀是否设置于壳体上，例如气体流量控制阀可以设置在气源上(一般地，每个气体钢瓶上都有气体流量控制阀)，但是对于管路较长的系统，从气源处控制气体流量的误差较大，在气体进口处直接控制误差小，可以消除管路本身压差带来的影响。
一般地，中空轴的材质可以为不锈钢、钛基材料或者陶瓷膜材料的一种，当然，实际上，中空轴的材料不限制于上述示出的材料，本申请不做穷举。
在一些具体的优选实施例中，所述中空轴的材料为不锈钢或者钛基材料，孔道直径的范围为0.01-0.1mm。
在另一些具体的优选实施例中，所述中空轴由陶瓷膜制成，所述陶瓷膜的内壁膜孔道的孔径范围为2-48nm，外壁膜孔道的孔径范围为5-48nm，例如内壁膜孔径可为2nm，5nm，10nm，20nm，48nm，外壁膜孔径可为5nm，10nm，20nm，48nm，，以上内壁膜孔径和外壁膜孔径可两两任意组合搭配，优选地，内壁膜孔径为20nm，外壁膜孔径为5nm。
一般地，中空轴壁厚2-10mm，优选地，壁厚3mm。
下面结合图2a和图2b对中空轴进行详细说明。
图2b示出了中空轴的俯视图，在图2b中可以看出，一方面所述孔道围绕所述中空轴的轴心对称分布，另一方面，在中空轴的水平截面上，任意两个孔道的孔心(即孔道的中心)之间距离的间距相同。
每个孔道的孔径可以相同，也可以不同，具体可以根据情况调节，一般地所述孔道包括位于所述中空轴侧壁上半部分的第一孔道和位于所述中空轴侧壁下半部分的第二孔道，所述第一孔道的孔径大于、小于或等于所述第二孔道的孔径。
例如，在一个实施例中，超重力纳微气泡产生装置为立式筒状，液体进口设置在壳体下方，液体出口设置在壳体上方，气体进口设置在壳体下方的底部，由于气体进口设置在壳体下方，则在整个内腔体中，下方的气体密度较大，溢出的推动力较大，相同孔径下更容易溢出，上方的气体密度较小，溢出推动力小，相同孔径下更难溢出，此时设置第一孔道的孔径大于第二孔道的孔径，均衡两者的溢出量，避免上下部分气泡密度不一致的现象。
再例如，在一个实施例中，液体出口设置在壳体上方，气体进口设置在壳体下方的底部，由于气体进口设置在壳体下方，对于液体流速较快的混合体系，进液区域的液体会对中空轴产生冲击力，阻碍气泡甩出，而在液体出口区域，液体流动会对气泡产生带动作用，加快气泡的甩出，该体系中，第二孔道的孔径可以稍大于第一孔道的孔径，以平衡进液和出液流动带来的影响。
当然，在一些可选实施例中，不考虑体系的影响，第一孔道的孔径与第二孔道的孔径相同。
亦或者，在优选的实施例中，由于整个流动体系具有梯度式的规律(例如液体进口处-液体出口处的流速是不断递减的，靠近气体进口处-远离气体进口处的气体密度是不断递减的)，因此，所述孔道的孔径沿气体流动的方向递增或递减；或，所述孔道的孔径沿所述外腔体液体流动的方向递增或递减。这样可以根据整个流动体系调节，使得孔道的尺寸与具体体系更加匹配。
例如，孔道的孔径由图2a中的下至上的方向上，孔径不断递减，通过递减的孔径数值的设置，例如上下相邻的两个孔道的孔径相差0.1mm，0.2mm等，可以平衡气体上下浓度差带来的影响，或者平衡液体流速差(流动过程中具有阻力和重力，导致流速具有微小差别)，孔径不断递增。
此外，从图2a中可以看出，在中空轴的轴向上，相邻两个孔道的孔心间距相同，均为设定间距(即给定的一个间距数值，例如10mm，20mm等)。
在一些实施例中，形成的纳微气泡平均粒径处于800纳米-50微米之间， 具体可以通过可视化、X射线成像技术以及光纤探针或者电导探针的方法，本申请不限于此。
通过上述实施例可以知晓，本发明提供的一种超重力纳微气泡产生装置，在该装置中液相为连续相，气相为分散相，气体由中空轴进入内部，经曝气微孔的剪切作用对气体进行一次剪切形成气泡，气泡随后在高速旋转的转轴作用下快速脱离转轴表面，并在转轴所形成的超重力环境强大的剪切力下进行二次剪切形成纳微气泡，具有快速、稳定、平均粒径小的优点，所形成的纳微气泡平均粒径处于800纳米-50微米之间，并可通过调节旋转轴的转速对气泡平均粒径进行范围调控。该装置一方面克服了传统超重力装置中液相不连续，无法形成含纳微气泡液相的问题，另一方面克服了静态微孔介质表面纳微气泡聚并的问题。
基于与本发明第一方面中的超重力纳微气泡产生装置的发明构思，本发明第二方面提供一种反应系统，所述反应系统用于气液两相反应，所述反应系统包括超重力纳微气泡产生装置。
在一个具体实施例中，本系统将超重力纳微气泡产生装置作为反应器用于用于气-液两相氧化反应的步骤：
1)在超重力纳微气泡产生装置-13进液口连接搅拌釜-22，在超重力纳微气泡产生装置-13出液口处连接气液分离罐-19(如图3c所示)；
2)开启柱塞泵，待反应溶液进入超重力纳微气泡产生装置-13并形成液相循环，待系统稳定后开启气体钢瓶通入氧气进行气-液两相氧化反应，反应体系压力由背压阀-17控制，温度由温控系统控制；
3)由步骤2)产生的带有反应产物的气液混合物经气液分离罐-19进行分离，气体由放空阀排出，液体流入中搅拌釜-21中；另通过控制球阀-22的开关可以控制系统为单程氧化反应或循环氧化反应，当球阀-22开启时系统为循环氧化反应，当球阀关闭时系统为单程氧化反应；反应后的样品经分离后进行进一步检测。
下面结合具体场景对本方面提供的气-液-固三相反应系统进行详细说明。
应用本方面的气液两相反应系统进行加氢反应
参照图3a所示，采用图1所示装置应用于固定床反应器加氢反应，包括 氮气钢瓶-11，氢气钢瓶-12，超重力纳微气泡产生装置-13，气体质量流量计-14，柱塞泵-15，固定床反应器-16，原料罐-17，背压阀-18，气液分离罐-19，样品储罐-20，其中超重力微气泡装置、原料罐和固定床反应器均设有电加热套，反应过程包括如下步骤：打开氮气钢瓶，吹扫整个管路用于排出空气；打开加热装置，加热装置至预定温度后打开氢气钢瓶，利用气体质量流量计调节气体流量，利用背压阀调节至预设压力；开启超重力纳微气泡产生装置，调节转速；开启柱塞泵，并使反应溶液充满整个超重力纳微气泡产生装置，随后利用柱塞泵调节液体流量，控制反应溶液通过固定床反应器的时间，待系统稳定后从取样口取样分析。
以蒽醌加氢反应为例：将固定床反应器内填装好当量直径为1.6mm的Pd/Al 2O 3催化剂，使用前在90℃温度下通氢气进行预还原后用氮气封存；以均三甲苯和磷酸三辛酯体积比3:1做混合溶剂，配制浓度120(g/L)的2-乙基蒽醌工作液，在温度为50℃压力为0.3MPa，超重力纳微气泡产生装置转速2000rpm条件下，将含有纳微气泡(气泡平均直径10微米)的混合流体通入固定床反应器，在35s时间下可达蒽醌转化率35％，选择性92％，加氢效率5.8(g/L)；在相同温度、压力条件下，只改变超重力纳微气泡产生装置转速为2700rpm，将含有纳微气泡(气泡平均直径900纳米)的混合流体通入固定床反应器，在35s时间下可达蒽醌转化率48％，选择性93.5％，加氢效率6.5(g/L)。
由上述结果可知，超重力纳微气泡产生装置对固定床蒽醌加氢反应具有较好的催化加氢效果；同时在一定范围内，随着超重力纳微气泡产生装置内转轴转速的提升，装置产生的纳微米气泡平均粒径成减小趋势，气泡平均粒径的减小增大了气液接触面积和气含率，有利于固定床蒽醌加氢反应效果的提升。
超重力纳微气泡装置不旋转时的气液两相反应系统进行加氢反应
采用与上述场景相同的实验装置和实验流程，以均三甲苯和磷酸三辛酯体积比3:1做混合溶剂，配制浓度120(g/L)的2-乙基蒽醌工作液，在温度为50℃压力为0.3MPa，超重力纳微气泡产生装置不旋转的条件下，只依靠中空转轴壁上的曝气微孔作用对气体进行切割形成气液混合流，将含有微气泡(气泡平均直径550微米)的气液混合流体通入固定床反应器，在35s时间下可达蒽醌转化率12％，选择性96％，加氢效率1.8(g/L)。
由两个场景的对照结果可知，与单独静止微孔介质切割气体相比较，超 重力纳微气泡产生装置在高速旋转转轴产生的剪切力作用下能够使形成的气泡平均直径进一步减小，能有效克服静止微孔介质表面气泡聚并变大问题，同时使用本发明装置进行固定床蒽醌加氢反应效果相较于单独使用静止微孔介质亦更优。
应用本方面的气液两相反应系统进行氧化反应
参见图3c，采用图1所示装置作为反应器应用于气-液两相氢蒽醌氧化反应，操作步骤如下：将2-乙基蒽醌加氢产物2-乙基氢蒽醌加入搅拌釜-22中，浓度为0.43mol/L，开启柱塞泵使拟均相态溶液循环，待系统稳定后，开启气瓶和超重力纳微气泡产生装置，在50℃、常压条件下进行循环氧化，5min内2-乙基氢蒽醌可完全氧化(及转化率为100％)。
通过上述场景可以知晓，本申请提供的反应系统，将超重力纳微气泡产生装置应用于气液加氢/氧化反应领域中，由于纳微气泡的存在使得加氢/氧化反应过程气液接触面积增大，同时提升了待反应溶液的气含率，从而强化气液传质，达到了提高宏观反应速率，缩短反应时间的目的，在石油化工、精细化工、煤化工、生物化工等领域具有重要的工业应用意义。
基于与本发明第一方面中的超重力纳微气泡产生装置的发明构思，本发明第三方面一种反应系统，所述反应系统用于气-液-固三相反应，或者用于拟均相的气-液-固反应，所述反应系统包括连通的反应器以及超重力纳微气泡产生装置，所述超重力纳微气泡产生装置将气体反应物与液体反应物混合形成具有纳微气泡的气液混合物，所述反应器中可通入固体反应物或者固体催化剂。
在一个具体实施例中，本系统将超重力纳微气泡产生装置用于固定床反应器气-液-固三相加氢/氧化反应的步骤：
1)在固定床反应器-16进口连接超重力纳微气泡产生装置-13，在固定床反应器-16出口处连接气液分离罐-19(如图3a所示)；随后开启超重力纳微气泡产生装置，形成气液混合物；
2)将步骤1)产生的携带有纳微气泡的气液混合物通入装有催化剂颗粒的固定床反应器中，进行加氢/氧化反应，反应体系压力由背压阀-17控制，温度由温控系统控制；
3)由步骤2)产生的带有反应产物的气液混合物经气液分离罐-19进行分 离，气体由放空阀排出，液体流入样品储罐-20中，样品经分离后进行进一步检测。
在一个具体实施例中，本系统将超重力纳微气泡产生装置用于搅拌釜反应器拟均相气-液-固加氢/氧化反应的步骤：
1)在搅拌釜反应器-22进口连接超重力纳微气泡产生装置-13，拌釜反应器-21出口处连接气液分离罐-19(如图3b所示)；随后开启超重力纳微气泡产生装置，形成气液混合物；
2)开启搅拌釜反应器，将步骤1)产生的携带有纳微气泡的气液混合物通入装有纳米或微末级粉末状催化剂颗粒的搅拌釜反应器中，进行加氢/氧化反应，反应体系压力由背压阀-17控制，温度由温控系统控制；
3)由步骤2)产生的带有反应产物的气液混合物经气液分离罐-19进行分离，气体由放空阀排出，液体流入样品储罐-20中，样品经过滤或离心、分离后进行进一步检测。
步骤2)中使用的贵金属催化剂为以氧化铝、二氧化硅或分子筛等固体颗粒为载体，通过高温煅烧负载钯、铂等贵金属或混合金属的催化剂，催化剂粒径范围10nm-800um，以上以粒径50nm-200um为最优。
在一个具体实施例中，本系统将超重力纳微气泡产生装置作为反应器用于拟均相气-液-固加氢/氧化反应，其特征在于，包括如下步骤：
1)在超重力纳微气泡产生装置-13进液口连接搅拌釜-22，在超重力纳微气泡产生装置-13出液口处连接气液分离罐-19(如图3c所示)；
2)在搅拌釜-21内加入待反应溶液和纳米或微米级粉状催化剂；随后开启柱塞泵，形成液相循环，待系统稳定后开启气体钢瓶进行拟均相气-液-固三相加氢/氧化反应；反应体系压力由背压阀-17控制，温度由温控系统控制；
3)由步骤2)产生的带有反应产物的气液混合物经气液分离罐-19进行分离，气体由放空阀排出，液体流入中搅拌釜-21中；另通过控制球阀-22的开关可以控制系统为单程加氢/氧化反应或循环加氢/氧化反应，当球阀-22开启时系统为循环加氢/氧化反应，当球阀关闭时系统为单程加氢/氧化反应；反应后的样品经过滤或离心、分离后进行进一步检测。
上述具体实施例中，催化剂可以为微纳尺度的颗粒，对于加氢反应，可以使用贵金属催化剂颗粒，该贵金属催化剂颗粒为以氧化铝、二氧化硅或分子筛等固体颗粒为载体，通过高温煅烧负载钯、铂等贵金属或混合金属的催化剂，催化剂粒径范围10nm-800um，以上以粒径50nm-200um为最优。
下面结合具体场景对本方面提供的拟均相气液固反应体系进行详细说明。
应用本方面的拟均相气液固反应系统进行加氢反应
参照图3b所示，采用图1所示装置应用于搅拌釜反应器拟均相气液固蒽醌加氢反应，实验装置除搅拌釜反应器-21不同外其余装置与上述气液两相反应系统相同，操作步骤亦相同，以均三甲苯和磷酸三辛酯体积比1:1做混合溶剂，配制浓度100(g/L)的2-乙基蒽醌工作液，在温度为60℃压力为0.3MPa，选用Pd/γ-Al 2O 3催化剂浓度为2％wt条件下进行加氢，11min时间下可达蒽醌转化率76％，选择性90.5％，加氢效率9.5(g/L)。
图3c也可以作为拟均相气-液-固1-硝基蒽醌加氢反应系统，采用图1所示装置作为反应器应用于拟均相气-液-固1-硝基蒽醌加氢反应，操作步骤如下：将1-硝基蒽醌与N,N-2甲基甲酰胺以3:20质量比配置成反应溶液，同粒径为80微米的Pd/γ-Al 2O 3催化剂一同加入搅拌釜-22中，开启搅拌釜使催化剂和溶液完全混合并保持悬浮状态；开启柱塞泵使拟均相态溶液循环，待系统稳定后，开启气瓶和超重力纳微气泡产生装置，在100℃、1.2MPa、催化剂浓度4％wt条件下进行循环加氢，产物1-氨基蒽醌可在40min内达纯度95％以上。
由此可知，本方面提供的反应系统能够用于气-液-固三相反应，或者用于拟均相的气-液-固反应，由于纳微气泡的存在使得加氢/氧化反应过程气液接触面积增大，同时提升了待反应溶液的气含率，从而强化气液传质，达到了提高宏观反应速率，缩短反应时间的目的，在石油化工、精细化工、煤化工、生物化工等领域具有重要的工业应用意义。
当然，上述场景仅仅作为示例性说明，本装置可应用于各类加氢/氧化反应，亦或是其他混合反应，在此不做穷举，但可以理解，基于本发明的构思所做的反应体系的替换，虽然不一定是加氢或者氧化的其中一种，但仍然属于本申请所限定的范围。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定，对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动，这里无法对所有的实施方式予以穷举，凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (10)

  1. 一种超重力纳微气泡产生装置，其特征在于，包括：
    壳体，其上设置有液体进口和液体出口；以及
    设置与所述壳体内的超重力气泡产生单元；其中，
    所述超重力气泡产生单元包括：
    设于所述壳体内的转子，可通过旋转形成超重力场，所述超重力场产生的离心力加速度大于10g；
    一端与所述转子结合固定的中空轴，所述中空轴的另一端与气体进口连通；
    其中，所述中空轴将所述壳体分为连通的内腔体和外腔体，所述中空轴的侧壁上设置若干纳微米尺度的孔道。
  2. 根据权利要求1所述的超重力纳微气泡产生装置，其特征在于，还包括：
    设置在所述壳体与中空轴之间的间隙为0.1-10mm。
  3. 根据权利要求1所述的超重力纳微气泡产生装置，其特征在于，相邻两个孔道的孔心之间距离设定间距。
  4. 根据权利要求1所述的超重力纳微气泡产生装置，其特征在于，所述孔道包括位于所述中空轴侧壁上半部分的第一孔道和位于所述中空轴侧壁下半部分的第二孔道；
    所述第一孔道的孔径大于、小于或等于所述第二孔道的孔径。
  5. 根据权利要求1所述的超重力纳微气泡产生装置，其特征在于，所述孔道的孔径沿气体流动的方向递增或递减；或，
    所述孔道的孔径沿所述外腔体液体流动的方向递增或递减。
  6. 根据权利要求1所述的超重力纳微气泡产生装置，其特征在于，所述孔道围绕所述中空轴的轴心对称分布。
  7. 根据权利要求1所述的超重力纳微气泡产生装置，其特征在于，所述中空轴的材料为不锈钢或者钛基材料，优选孔道直径的范围为0.01-0.1mm。
  8. 根据权利要求1所述的超重力纳微气泡产生装置，其特征在于，所述中空轴由陶瓷膜制成，优选所述陶瓷膜的内壁膜孔道的孔径范围为2-48nm，外壁膜孔道的孔径范围为5-48nm。
  9. 一种反应系统，其特征在于，所述反应系统用于气液两相反应，所述反应系统包括超重力纳微气泡产生装置。
  10. 一种反应系统，其特征在于，所述反应系统用于气-液-固三相反应，或者用于拟均相的气-液-固反应，所述反应系统包括连通的反应器以及超重力纳微气泡产生装置，所述超重力纳微气泡产生装置将气体反应物与液体反应物混合形成具有纳微气泡的气液混合物，所述反应器中可通入固体反应物或者固体催化剂。
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