CN218654385U - High-efficient dehydrogenation reaction pipe - Google Patents
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- CN218654385U CN218654385U CN202223247234.5U CN202223247234U CN218654385U CN 218654385 U CN218654385 U CN 218654385U CN 202223247234 U CN202223247234 U CN 202223247234U CN 218654385 U CN218654385 U CN 218654385U
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Abstract
The utility model discloses a high-efficient dehydrogenation reaction pipe, high-efficient dehydrogenation reaction pipe includes stainless steel reaction tube and molecular sieve membrane pipe, and the packing has supported catalyst in the stainless steel reaction tube, and the aperture of molecular sieve membrane pipe is between hydrogen and organic hydrogen storage carrier molecule size, only allows the hydrogen micromolecule to pass through. One end of the stainless steel reaction tube is coaxially and hermetically connected with one end of the molecular sieve membrane tube in series. The utility model discloses accomplish catalytic reaction in stainless steel reaction tube, isolate hydrogen in the molecular sieve membrane pipe, break reaction balance, improve dehydrogenation rate. The reactor is small and light, and is suitable for on-line hydrogen supply in a small vehicle or a hydrogen charging station.
Description
Technical Field
The utility model relates to a dehydrogenation hydrogen technical field, concretely relates to a high-efficient dehydrogenation reaction pipe that is used for multistage fixed bed reaction tube coupling multistage molecular sieve membrane separation module of organic liquid phase dehydrogenation reaction.
Background
Hydrogen can be considered as one of the most likely alternatives to fossil fuels, and the only product of the combustion of hydrogen in a fuel cell or combustor is water, which does not contribute to environmental pollution. At present, hydrogen energy is widely applied to the fields of distributed power generation, hydrogen energy traffic, energy storage, electronic industry, metallurgical industry and the like. However, hydrogen storage and transportation and hydrogen supply technologies are still a bottleneck restricting the hydrogen energy fuel cell technology, and the hydrogen storage technology has the disadvantages of low hydrogen storage capacity, high cost, low safety and the like.
The State Federal for improvement and the State energy agency jointly issued "Long-term planning in the development of Hydrogen energy industry (2021-2035)". With regard to hydrogen storage and transportation, the document mentions: on the premise of safety and controllability, technical material process innovation is actively promoted, and exploration and practice of various storage and transportation modes are supported. The efficiency of high-pressure gaseous storage and transportation is improved, the cost of storage and transportation is accelerated and reduced, and the commercialization level of high-pressure gaseous storage and transportation is effectively improved. Promotes the industrial application of low-temperature liquid hydrogen storage and transportation, and explores the application of storage and transportation modes such as solid state, deep cooling, high pressure, organic liquid and the like. And testing demonstration of the hydrogen-doped natural gas pipeline, the pure hydrogen pipeline and the like is carried out. Gradually constructing a high-density, light-weight, low-cost and diversified hydrogen energy storage and transportation system.
Common hydrogen storage techniques include pressurized hydrogen storage, low temperature hydrogen storage, alloy hydrogen storage, activated carbon or other carbon materials hydrogen storage, MOFs hydrogen storage, liquid organic matter hydrogen storage, and the like. The research on the hydrogen storage under pressure is the earliest and the application is the most extensive, but the hydrogen storage quality density is low, and the hydrogen embrittlement phenomenon is generated by the hydrogen storage under pressure, so that the potential danger exists; the low-temperature liquid hydrogen storage volume energy density is high, but the consumption energy in the liquefaction process is high, a liquefaction tank with good heat insulation performance is needed, and the requirement on materials is strict; the advantage of hydrogen storage by using the hydrogen storage alloy is that the volume hydrogen storage amount is large, but hydrogen per se can cause the hydrogen storage alloy material to deteriorate, such as hydrogen damage, hydrogen corrosion, hydrogen brittleness and the like, and the recyclability is poor; when the carbon material stores hydrogen, the adsorption temperature is low (active carbon) or the volume hydrogen storage capacity is small (carbon nano tube), so that the application range is limited; the metal organic framework material hydrogen storage is greatly influenced by preparation conditions and is still in a research stage at present.
The advantages of liquid organic hydrogen storage are many, including large density of hydrogen storage, safe storage and remote transportation, easy maintenance of equipment and pipelines, convenient use of existing conveying pipelines and equipment, and simultaneously, the technical cost is low, and the hydrogen storage material can be recycled for multiple times, thus becoming the most feasible method in the process of hydrogen energy storage and transportation. Numerous industrial and academic research institutions in the world are actively invested in developing a practical liquid organic hydrogen storage technology. Major industrial countries such as germany, switzerland, japan and the uk are actively engaged in this research.
The process of storing hydrogen and releasing hydrogen of the liquid organic matter hydrogen storage technology is a circular process, and specifically comprises 3 stages of hydrogenation reaction of a hydrogen storage agent, storage and transportation of a hydrogen storage medium, dehydrogenation process of hydrogenated liquid organic matter and the like, and the specific process comprises the following steps: firstly, the hydrogen storage agent realizes the storage of hydrogen energy through catalytic hydrogenation reaction; then, storing and transporting the hydrogenated liquid organic matters by utilizing the existing equipment; finally, the hydrogen stored in the hydrogen storage medium is released through dehydrogenation reaction, and the hydrogen is supplied to the end user.
At present, the selection of a proper hydrogen storage medium for liquid organic liquid hydrogen storage is relatively mature, and the main difficulty lies in the dehydrogenation technology of liquid organic liquid hydride. The prior dehydrogenation technology mostly has the problems of low dehydrogenation catalyst activity, higher dehydrogenation temperature, slow dehydrogenation rate and the like. Dehydrogenation of the organic hydrogen storage carrier is a strong endothermic reaction and has a slow reaction speed. The conventional full mixed flow stirring kettle type reactor has the defects of overlong reaction time, discontinuous reaction, unstable dehydrogenation flow rate, difficult product removal and the like when used for dehydrogenation; the continuous fixed bed reactor has the problems of low heat transfer efficiency, slow reaction rate, incomplete dehydrogenation of products, the highest dehydrogenation rate of only 80 percent and the like.
Disclosure of Invention
In order to solve the above-mentioned problems, the reaction conversion rate is improved, and the dehydrogenation facility is made compact and lightweight so that it can be mounted on a mobile vehicle or supplied with hydrogen on-line to a hydrogen station. Therefore, the utility model provides a high-efficiency reactor and a process of a multi-section fixed bed reaction tube coupled with a multi-section molecular sieve membrane separation module.
The adopted technical scheme is as follows:
on the one hand, the utility model provides a high-efficient dehydrogenation reaction pipe, high-efficient dehydrogenation reaction pipe includes stainless steel reaction tube and molecular sieve membrane tube, the loaded catalyst is equipped with in the stainless steel reaction tube, the aperture of molecular sieve membrane tube is between hydrogen and organic hydrogen storage carrier molecule size, the one end of stainless steel reaction tube with the one end of molecular sieve membrane tube is coaxial sealed concatenating.
Preferably, the molecular sieve membrane tube is a DDR all-silicon molecular sieve membrane tube with the aperture of 0.36 multiplied by 0.44 nm.
Furthermore, the inner side surface of the molecular sieve membrane tube is provided with a plurality of annular support frames for enhancing the overall strength of the molecular sieve membrane tube.
Furthermore, an electrothermal tube is surrounded on the outer side of the stainless steel reaction tube.
Preferably, the active component in the supported catalyst is one or more of ruthenium, platinum, palladium and nickel metal.
Furthermore, the high-efficiency dehydrogenation reaction tube comprises a plurality of groups of stainless steel reaction tubes and molecular sieve membrane tubes, and the stainless steel reaction tubes and the molecular sieve membrane tubes are alternately connected in series.
On the other hand, the utility model also provides a high-efficiency reactor of a multi-section fixed bed reaction tube coupling multi-section molecular sieve membrane separation module for organic liquid phase dehydrogenation, the high-efficiency reactor comprises a shell with a hollow cavity, the two ends of the shell are respectively provided with a feed pipe and a discharge pipe which are communicated, the feed pipe and the discharge pipe which are close to the shell are respectively provided with a tube plate which is hermetically connected with the inner side surface of the shell, a plurality of high-efficiency dehydrogenation reaction tubes which are hermetically connected with the tube plates are arranged between the tube plates, a hydrogen collecting tube is arranged on the shell between the two tube plates, the hydrogen collecting tube is communicated with the hollow cavity of the shell,
preferably, the high-efficiency dehydrogenation reaction tube comprises 3-6 groups of the stainless steel reaction tube and the molecular sieve membrane tube.
Furthermore, the high-efficiency dehydrogenation reaction tube comprises 3-6 groups of stainless steel reaction tubes and molecular sieve membrane tubes, electric heating tubes are arranged between the stainless steel reaction tubes in a surrounding manner, the front end and the rear end of each group of molecular sieve membrane tubes are respectively provided with a tube plate which is hermetically connected with the inner side surface of the shell, the front tube plate and the rear tube plate of each molecular sieve membrane tube form a hydrogen collecting cavity, the shell corresponding to the hydrogen collecting cavity is provided with a corresponding hydrogen collecting tube, and the hydrogen collecting tubes are communicated with the corresponding hydrogen collecting cavity.
Furthermore, 25-400 high-efficiency dehydrogenation reaction tubes are arranged in the shell.
Furthermore, a feeding cavity is arranged between the feeding pipe and the adjacent pipe plate, and ceramic balls for uniform distribution are filled in the feeding cavity; and a reaction product collecting cavity is arranged between the discharge pipe and the adjacent pipe plate.
Furthermore, the hydrogen collecting pipe is connected with a compressor with pressure of-0.1 to-0.04 MPa, and the outside of the shell is provided with a heat-insulating layer.
The utility model also provides a multi-section fixed bed reaction tube coupling multi-section molecular sieve membrane separation process, organic hydrogen storage liquid is heated to reach the reaction inlet temperature of 150-300 ℃ and enters a high-efficiency reactor; the organic hydrogen storage liquid fully reacts with a catalyst in a stainless steel reaction tube and enters a molecular sieve membrane tube together with the generated hydrogen; the molecular sieve membrane tube separates the generated hydrogen and then discharges the hydrogen from the hydrogen collecting tube; the residual organic hydrogen storage liquid enters a next-stage reaction tube for catalytic dehydrogenation reaction, and then enters a next-stage molecular sieve membrane separation unit for hydrogen separation, the processes of catalytic dehydrogenation in the reaction tube, hydrogen separation in the molecular sieve membrane, reaction balance breaking and reaction kinetic dehydrogenation rate pushing are alternately carried out in multiple stages, and finally the organic hydrogen storage liquid is discharged from a discharge tube of the shell.
Further, when the organic hydrogen storage liquid passes through the stainless steel reaction tube, the electric heating tube on the organic hydrogen storage liquid is controlled to heat; after the organic hydrogen storage liquid is subjected to alternate stainless steel reaction tube catalyst reaction and molecular sieve membrane tube dehydrogenation, the generated hydrogen is sucked by a corresponding hydrogen collecting tube under negative pressure by a compressor and then discharged, and the residual organic hydrogen storage liquid is discharged from a discharge tube of the shell.
The organic hydrogen storage liquid is 18H-dibenzyl toluene, 12H-benzyl toluene, methylcyclohexane and 12H-N-ethyl carbazole organic hydrogen storage media.
Utility model technical scheme has following advantage:
A. the utility model designs the multi-channel multi-section reactor structure, so that the organic hydrogen storage medium can perform catalytic reaction when passing through the stainless steel reaction tube, the hydrogen adsorbed on the surface of the catalyst can be separated from the catalyst in time under the negative pressure of-0.1 to-0.04 MPa, and the hydrogen can be separated out from the organic hydrogen storage medium through the molecular sieve membrane tube, thereby breaking the balance of reaction kinetics, leading the reaction to be carried out towards the dehydrogenation direction continuously, and improving the dehydrogenation conversion rate;
B. utility model sets dehydrogenation reaction pipe to multiunit stainless steel reaction tube and molecular sieve membrane pipe of establishing ties, and organic hydrogen storage medium reacts step by step through dehydrogenation reaction pipe's multistage in high-efficient reactor, strengthens the mass transfer, makes the reaction more abundant, improves dehydrogenation efficiency.
C. Utility model has still set up the efficient electrothermal tube in high-efficient reactor, encircle the electrothermal tube heating in the stainless steel reaction tube outside through control, and accurate heat that provides has removed a large amount of reaction sections and firing equipment from, realizes that dehydrogenation equipment is miniaturized, lightweight, makes it carry on to in the mobile device.
D. The utility model discloses a high-efficient dehydrogenation reaction pipe includes stainless steel reaction tube and molecular sieve membrane tube, and the loading type catalyst is filled in the stainless steel reaction tube, and the aperture of molecular sieve membrane tube is between hydrogen and organic hydrogen storage carrier molecule size, only allows the hydrogen micromolecule to pass through. One end of the stainless steel reaction tube is coaxially and hermetically connected with one end of the molecular sieve membrane tube in series; the high-efficiency reactor comprises a shell with a hollow cavity, wherein the two ends of the shell are respectively provided with a feeding pipe and a discharging pipe which are communicated, the feeding pipe and the discharging pipe which are close to the shell are respectively provided with a pipe plate which is hermetically connected with the inner side surface of the shell, a plurality of dehydrogenation reaction pipes which are hermetically connected with the pipe plates are arranged between the pipe plates, a hydrogen collecting pipe is arranged on the shell between the two pipe plates, and the hydrogen collecting pipe is communicated with the hollow cavity of the shell. The utility model discloses accomplish catalytic reaction in stainless steel reaction tube, isolate hydrogen in the molecular sieve membrane pipe, break reaction balance, improve dehydrogenation rate. The reactor is small and light, and is suitable for on-line hydrogen supply in a small vehicle or a hydrogen charging station.
Drawings
In order to illustrate the embodiments of the invention more clearly, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the invention, and that other drawings can be obtained by those skilled in the art without inventive effort.
FIG. 1 is a schematic diagram of a multiple reaction-dehydrogenation unit reactor tube provided by the utility model;
figure 2 is a high efficiency reactor block diagram provided by the utility model.
The designations in the figures are as follows:
1-high efficiency dehydrogenation reaction tube
11-stainless steel reaction tube, 12-molecular sieve membrane tube and 13-electrothermal tube
2-shell
21-feeding pipe, 22-discharging pipe, 23-pipe plate and 24-hydrogen gas collecting pipe
a-a feeding cavity, b-a reaction product collecting cavity and c-a hydrogen collecting cavity.
Detailed Description
The technical solutions of the present invention will be described more clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only some, but not all embodiments of the present invention. Based on the embodiments of the utility model, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the utility model.
As shown in fig. 1, the utility model provides a high-efficient dehydrogenation reaction pipe 1, including stainless steel reaction tube 11 and molecular sieve membrane tube 12, the loading type catalyst is filled in stainless steel reaction tube 11, and the aperture of molecular sieve membrane tube 12 is between hydrogen and organic hydrogen storage carrier molecule size, and the one end of stainless steel reaction tube 11 is coaxial sealed concatenating with the one end of molecular sieve membrane tube 12, and the two passes through graphite ring extrusion seal at the series connection section, forms a high-efficient dehydrogenation reaction pipe. In order to improve the hydrogen conversion rate, utility model can set up a plurality of stainless steel reaction tubes 11 and molecular sieve membrane tube 12 and establish ties and constitute in a high-efficient dehydrogenation reaction tube, and utility model well preferred stainless steel reaction tube 11 quantity and molecular sieve membrane tube 12 quantity are preferred respectively to be 3 ~ 6, and stainless steel reaction tube 11 and molecular sieve membrane tube 12 are the sealed setting of alternative series connection. The active component in the supported catalyst is one or more of ruthenium, platinum, palladium and nickel.
Utility model prefers DDR all-silicon type molecular sieve membrane tube, which has higher hydrogen permeability and chemical stability, and the kinetic diameter of each molecule of the organic hydrogen storage carrier dehydrogenation reaction system is shown in table 1. As can be seen from the table, the hydrogen gas has the smallest molecular kinetic diameter (0.289 nm), while the organic hydrogen storage carrier has larger molecular kinetic diameters before and after the reaction. The DDR molecular sieve membrane tube has the aperture of 0.36nm multiplied by 0.44nm which is between the molecular size of hydrogen and the organic hydrogen storage carrier, so the DDR molecular sieve membrane tube is suitable for being used as a high-efficiency dehydrogenation reaction tube.
TABLE 1 molecular kinetic diameters of different methylcyclohexane-toluene systems
Further for preventing to cause the damage because of the negative pressure to equipment, the inside of molecular sieve membrane pipe additionally increases many rings of annular support frame, plays fine reinforcement supporting role.
As shown in fig. 2, the utility model also provides a high-efficiency reactor, including casing 2 that has well cavity, inlet pipe 21 and discharging pipe 22 that are equipped with the intercommunication respectively at casing 2's both ends, inlet pipe 21 department and discharging pipe 22 punishment that are close to casing 2 are equipped with respectively with casing 2 medial surface sealing connection's tube sheet 23, be equipped with a plurality of high-efficient dehydrogenation reaction pipe 1 rather than sealing connection between the tube sheet 23, be equipped with hydrogen collecting pipe 24 on the casing 2 that is located between two tube sheets 23, hydrogen collecting pipe 24 communicates with the well cavity of casing 2, hydrogen collecting pipe 24 here can be connected with the compressor, the compressor provides the negative pressure of-0.1 ~ 0.04MPa for the hydrogen that will adsorb on the catalyst surface is sucked out in by the molecular sieve membrane tube.
The high-efficiency dehydrogenation reaction tube 1 preferably comprises 3-6 groups of stainless steel reaction tubes 11 and molecular sieve membrane tubes 12 which are connected in series, an electric heating tube 13 is arranged around the stainless steel reaction tubes 11, a heat insulation layer is arranged between the electric heating tubes 13, and the heating temperature of the electric heating tube 13 can be controlled by an external controller. Meanwhile, tube plates 23 which are hermetically connected with the inner side surface of the shell 2 are respectively arranged at the front end and the rear end of each group of molecular sieve membrane tubes 12, a hydrogen collecting cavity c is formed by the front tube plate and the rear tube plate of each molecular sieve membrane tube 12, a corresponding hydrogen collecting tube 24 is arranged on the shell 2 corresponding to the hydrogen collecting cavity c, the hydrogen collecting tube 24 is communicated with the corresponding hydrogen collecting cavity c, a feeding cavity a is arranged between the feeding tube 21 and the adjacent tube plate 23, and ceramic balls for uniform distribution are filled in the feeding cavity a; reaction product collecting cavities b are arranged between the discharge pipe 22 and the adjacent pipe plate 23, the feeding cavity a is connected with a raw material pump, and the high-efficiency dehydrogenation reaction pipes 1 are fixed on the pipe plate 23 in the feeding cavity a and are uniformly distributed.
The number of the high-efficiency dehydrogenation reaction tubes contained in the inner cavity of one high-efficiency reactor is preferably 25-400, hydrogen storage carriers entering the high-efficiency reactor are subjected to catalytic dehydrogenation reaction through a first stainless steel reaction tube at 150-300 ℃, then enter a DDR full-silicon type molecular sieve membrane tube, hydrogen in organic hydrogen storage liquid is removed under negative pressure of-0.1-0.04 MPa, the dehydrogenated hydrogen storage carriers enter a next stainless steel reaction tube for continuous catalytic dehydrogenation, and the hydrogen is removed in time through step-by-step reaction, so that reaction balance is broken, the hydrogen removal efficiency is higher, the dehydrogenation is more thorough, the product separation is simple and convenient, the miniaturization and light weight of dehydrogenation equipment can be realized, and the dehydrogenation equipment can be carried into a mobile device.
Taking 18H-dibenzyltoluene reaction dehydrogenation as an example, 18H-dibenzyltoluene reaction dehydrogenation is a reversible strong endothermic reaction, needs to consume a large amount of heat, has low equilibrium conversion rate in low-temperature reaction, removes hydrogen in a product after each stage of catalytic reaction through a molecular sieve membrane tube, is favorable for promoting the reaction equilibrium to move forward, and improves the reaction conversion rate. The following is a series of 18H-DBT dehydrogenation steps with complete removal of hydrogen by a series of catalytic reactions.
The utility model provides a high-efficient reactor is applicable to organic hydrogen storage media such as 18H-dibenzyltoluene, 12H-benzyltoluene, methylcyclohexane, 12H-N-ethylcarbazole, through designing multichannel multistage formula reactor structure, make organic hydrogen storage media pass through the stainless steel reaction tube and the molecular sieve membrane tube that have the catalyst repeatedly, under-0.1-0.04 MPa negative pressure that the compressor provided, the hydrogen that adsorbs on the catalyst surface can in time separate with the catalyst, and separate out from organic hydrogen storage media through the molecular sieve membrane tube, break reaction kinetics balance, make the reaction constantly improve the dehydrogenation conversion rate towards the dehydrogenation direction; through multistage step-by-step catalytic reaction in the high-efficiency reactor, mass transfer is enhanced, the reaction is more sufficient, and the dehydrogenation efficiency is improved. A modularized high-efficiency heat exchange system is arranged in the high-efficiency reactor, so that a large number of reaction sections and heating equipment are omitted, and the miniaturization and light weight of dehydrogenation equipment are realized, so that the dehydrogenation equipment can be carried into a mobile device.
For the heating efficiency who improves stainless steel reaction tube in the casing to because the negative pressure state that molecular sieve membrane tube and compressor link to each other, be unfavorable for utilizing heat transfer medium such as heat conduction oil to heat, utility model discloses stainless steel reaction tube outside installation electrothermal tube in high-efficient dehydrogenation reaction tube carries out temperature regulation through control panel, keeps reaction temperature to maintain 150 ~ 300 ℃. Because the dehydrogenation reaction of the organic hydrogen storage liquid is an endothermic reaction, the transverse and longitudinal reaction temperatures of a reactor bed layer are required to be uniform, the temperature difference is less than 5 ℃, the multistage structure of the coupled multistage reactor can control the reaction to be carried out smoothly, the phenomena of violent reaction and sudden temperature reduction are prevented, the occupied volume is small, and the temperature control capability is strong.
Further, utility model discloses still pack porcelain ball in the feeding intracavity of high-efficient reactor for inside the even reactor that gets into of distribution material.
The utility model provides a multichannel fixed bed coupling multistage molecular sieve membrane separation technology, its process steps as follows:
heating the organic hydrogen storage liquid to the reaction inlet temperature of 150-300 ℃, and feeding the organic hydrogen storage liquid into a high-efficiency reactor; the organic hydrogen storage liquid fully reacts with a catalyst in a stainless steel reaction tube and enters a molecular sieve membrane tube together with the generated hydrogen; the molecular sieve membrane tube separates the generated hydrogen and then discharges the hydrogen from the hydrogen collecting tube; and discharging the residual organic hydrogen storage liquid from a discharge pipe of the shell.
When the organic hydrogen storage liquid passes through the stainless steel reaction tube, the electric heating tube on the organic hydrogen storage liquid is controlled to heat; after the organic hydrogen storage liquid is subjected to alternate stainless steel reaction tube catalyst reaction and molecular sieve membrane tube dehydrogenation, the generated hydrogen is sucked by a corresponding hydrogen collecting tube under negative pressure of a compressor and then discharged, and the residual organic hydrogen storage liquid is discharged from a discharging tube of the shell.
The process flow is described as follows: raw material organic hydrogen storage liquid (18H-DBT, 12H-MBT and the like) is heated to reach the reaction inlet temperature of 150-300 ℃, enters a high-efficiency reactor of a fixed bed coupled multi-section molecular sieve membrane tube, the organic hydrogen storage liquid after dehydrogenation is discharged from a discharge tube of the high-efficiency reactor, and hydrogen separated from the molecular sieve membrane tube is discharged from a hydrogen gas collecting tube.
The reaction raw materials enter a plurality of stainless steel reaction tubes which are arranged in a multi-beam mode after being uniformly distributed through a feeding cavity, fully react with a ruthenium-based or nickel-based catalyst at the reaction temperature of 150-300 ℃, and enter a molecular sieve membrane tube together with generated hydrogen for separation, after the generated hydrogen is separated, the residual organic hydrogen storage liquid continuously enters the next-stage stainless steel reaction tube for catalytic reaction, and the generated hydrogen is separated out through the next-stage molecular sieve membrane tube.
Under the negative pressure of-0.1 to-0.04 MPa generated by the compressor, hydrogen is sucked out by the hydrogen collecting pipe and enters the hydrogen storage unit, and dehydrogenation is completed.
Example 1
2.0% of 60 mesh supported Pt/gamma-Al 2 O 3 The catalyst pellets are filled into a stainless steel reaction tube, and the specification of a single stainless steel reaction tube is 8mm in inner diameter, 10mm in outer diameter and 80mm in length. The single molecular sieve membrane tube is connected with the single molecular sieve membrane tube through a screw pipe fitting, the specification of the single molecular sieve membrane tube is 8mm in inner diameter, 10mm in outer diameter and 80mm in length. Three stainless steel reaction tubes are connected with three molecular sieve membrane tubes to assemble a high-efficiency dehydrogenation reaction tube with coupled multi-section molecular sieve membrane separation. The method is characterized in that 36 efficient dehydrogenation reaction tubes are adopted and arranged to form an efficient reactor core, the efficient reactor core is placed in an efficient reactor shell, the volume of the efficient reactor core is 2.5L, and the loading amount of a catalyst is 0.45L.
The reaction dehydrogenation raw material is methylcyclohexane, the temperature is preheated to 240 ℃, the inlet pressure is 1.7bar, the vacuum degree in the hydrogen collecting cavity is-0.08 MPa, and the methylcyclohexane feeding rate is 20ml/min.
Under the process condition, the yield of the hydrogen at the outlet of the compressor is 11.81L/min, the dehydrogenation rate reaches 92.6 percent, the content of CO in the hydrogen is less than 1ppm 4 The content is less than 50ppm. High-purity hydrogen (more than 99.99%) is produced in 600-800L/hr.
Example 2
2.0% of 60 mesh supported Pt/gamma-Al 2 O 3 The catalyst pellets are filled into a stainless steel reaction tube, and the specification of a single stainless steel reaction tube is 8mm in inner diameter, 10mm in outer diameter and 80mm in length. The single molecular sieve membrane tube is connected with the single molecular sieve membrane tube through a screw pipe fitting, the specification of the single molecular sieve membrane tube is 8mm in inner diameter, 10mm in outer diameter and 80mm in length. 5 stainless steel reaction tubes are connected with 5 molecular sieve membrane tubes to assemble a coupled multi-section molecular sieve membrane tubeA high-efficiency dehydrogenation reaction tube for sieve membrane separation. 64 high-efficiency dehydrogenation reaction tubes are adopted in total and arranged into a high-efficiency reactor core, the high-efficiency reactor core is placed in a high-efficiency reactor shell, the volume of the core reactor is 5.9L, and the loading amount of a catalyst is 1.3L.
The reaction dehydrogenation raw material is 12H-MBT, the temperature is preheated to 250 ℃, the inlet pressure is 1.5bar, the vacuum degree of a hydrogen collecting cavity is-0.08MPa, and the feeding rate of 12H-MBT is 50ml/min.
Under the process condition, the yield of the hydrogen at the outlet of the compressor is 31.09L/min, the dehydrogenation rate reaches 96.4 percent, the content of CO in the hydrogen is less than 1ppm 4 The content is less than 50ppm. 1500-2000L of high-purity hydrogen with the yield of more than 99.99 percent per hour.
Example 3
2.0% of 60-mesh kneading type Pt/γ -Al 2 O 3 The catalyst pellets are filled into a stainless steel reaction tube, and the specification of a single stainless steel reaction tube is 8mm in inner diameter, 10mm in outer diameter and 80mm in length. The single molecular sieve membrane tube is connected with the single molecular sieve membrane tube through a screw pipe fitting, the specification of the single molecular sieve membrane tube is 8mm in inner diameter, 10mm in outer diameter and 80mm in length. 5 stainless steel reaction tubes are connected with 5 molecular sieve membrane tubes to assemble a high-efficiency dehydrogenation reaction tube with coupled multi-section molecular sieve membrane separation. 64 high-efficiency dehydrogenation reaction tubes are adopted in total and arranged into a high-efficiency reactor core, the high-efficiency reactor core is placed in a high-efficiency reactor shell, the volume of the core reactor is 5.9L, and the loading amount of a catalyst is 1.3L.
The reaction dehydrogenation raw material is 12H-N-ethyl carbazole, the temperature is preheated to 150 ℃, the inlet pressure is 1.9bar, the vacuum degree of a hydrogen collecting cavity is-0.08MPa, and the feeding rate of 12H-N-ethyl carbazole is 70ml/min.
Under the process condition, the yield of the hydrogen at the outlet of the compressor is 42.95L/min, the dehydrogenation rate reaches 94.83 percent, the content of CO in the hydrogen is lower than 1ppm 4 Less than 50ppm. 2200-2700 liters of high-purity hydrogen with the yield of over 99.99 percent per hour.
Example 4
2.0% of 60-mesh kneading type 2 O 3 The catalyst pellets are filled into a stainless steel reaction tube, and the specification of a single stainless steel reaction tube is 8mm in inner diameter, 10mm in outer diameter and 80mm in length. Is connected with a single molecular sieve membrane pipe through a screw pipe fittingThe specification of a single molecular sieve membrane tube is 8mm of inner diameter, 10mm of outer diameter and 80mm of length. 3 stainless steel reaction tubes are connected with 3 molecular sieve membrane tubes to assemble a high-efficiency dehydrogenation reaction tube with coupled multi-section molecular sieve membrane separation. 64 high-efficiency dehydrogenation reaction tubes are adopted in total and arranged into a high-efficiency reactor core which is arranged in a reactor shell, the volume of the core reactor is 3.54L, and the loading amount of the catalyst is 0.78L.
The reaction dehydrogenation raw material is 18H-DBT, the temperature is preheated to 250 ℃, the inlet pressure is 1.6bar, the vacuum degree of a hydrogen collecting cavity is-0.08MPa, and the feeding rate of 18H-DBT is 50ml/min.
Under the process condition, the yield of the hydrogen at the outlet of the compressor is 29.22L/min, the dehydrogenation rate reaches 89.34 percent, the content of CO in the hydrogen is less than 1ppm 4 Less than 50ppm. 1500-2000L of high-purity hydrogen with the yield of more than 99.99 percent per hour.
Example 5
2.0% of 60-mesh kneading type 2 O 3 The catalyst pellets are filled into a stainless steel reaction tube, and the specification of a single stainless steel reaction tube is 8mm in inner diameter, 10mm in outer diameter and 80mm in length. The single molecular sieve membrane tube is connected with the single molecular sieve membrane tube through a screw pipe fitting, the specification of the single molecular sieve membrane tube is 8mm in inner diameter, 10mm in outer diameter and 80mm in length. 5 stainless steel reaction tubes are connected with 5 molecular sieve membrane tubes to assemble a high-efficiency dehydrogenation reaction tube with coupled multi-section molecular sieve membrane separation. 64 high-efficiency dehydrogenation reaction tubes are adopted in total and arranged into a high-efficiency reactor core, the high-efficiency reactor core is placed in a high-efficiency reactor shell, the volume of the core reactor is 5.9L, and the loading amount of a catalyst is 1.3L.
The reaction dehydrogenation raw material is 18H-DBT, the temperature is preheated to 300 ℃, the inlet pressure is 1.6bar, the vacuum degree of a hydrogen collecting cavity is-0.08MPa, and the feeding rate of 18H-DBT is 50ml/min.
Under the process condition, the yield of the hydrogen at the outlet of the compressor is 32.14L/min, the dehydrogenation rate reaches 98.27 percent, the content of CO in the hydrogen is less than 1ppm 4 Less than 50ppm. 1500-2000L of high-purity hydrogen with the yield of more than 99.99 percent per hour.
The utility model does not describe the part and all is applicable to prior art.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications can be made without departing from the scope of the invention.
Claims (6)
1. The utility model provides a high-efficient dehydrogenation reaction pipe, its characterized in that, high-efficient dehydrogenation reaction pipe (1) includes stainless steel reaction pipe (11) and molecular sieve membrane tube (12), it has supported catalyst to pack in stainless steel reaction pipe (11), the aperture of molecular sieve membrane tube (12) is between hydrogen and organic hydrogen storage carrier molecule size, the one end of stainless steel reaction pipe (11) with the one end of molecular sieve membrane tube (12) is coaxial sealed concatenating.
2. The high efficiency dehydrogenation reaction tube of claim 1, wherein the molecular sieve membrane tube (12) is a DDR all-silicon molecular sieve membrane tube with a pore size of 0.36 x 0.44 nm.
3. The high-efficiency dehydrogenation reaction tube according to claim 2, wherein the inner side surface of the molecular sieve membrane tube (12) is provided with a plurality of annular supporting frames for enhancing the overall strength of the molecular sieve membrane tube.
4. The high efficiency dehydrogenation reactor tube according to claim 1, wherein the stainless steel reactor tube (11) is surrounded by electrical heating tubes (13).
5. The high-efficiency dehydrogenation reaction tube according to any one of claims 1-4, wherein the high-efficiency dehydrogenation reaction tube (1) comprises a plurality of sets of the stainless steel reaction tubes (11) and the molecular sieve membrane tubes (12), and the stainless steel reaction tubes (11) and the molecular sieve membrane tubes (12) are arranged in an alternating series.
6. The high efficiency dehydrogenation reaction tube according to claim 5, wherein the high efficiency dehydrogenation reaction tube (1) comprises 3-6 groups of the stainless steel reaction tubes (11) and the molecular sieve membrane tubes (12).
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| Application Number | Priority Date | Filing Date | Title |
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| CN202223247234.5U CN218654385U (en) | 2022-12-05 | 2022-12-05 | High-efficient dehydrogenation reaction pipe |
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| CN202223247234.5U CN218654385U (en) | 2022-12-05 | 2022-12-05 | High-efficient dehydrogenation reaction pipe |
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