CN110803680A - Chemical chain reforming hydrogen production device capable of recycling reaction byproducts - Google Patents

Chemical chain reforming hydrogen production device capable of recycling reaction byproducts Download PDF

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CN110803680A
CN110803680A CN201911296263.0A CN201911296263A CN110803680A CN 110803680 A CN110803680 A CN 110803680A CN 201911296263 A CN201911296263 A CN 201911296263A CN 110803680 A CN110803680 A CN 110803680A
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reformer
outlet
inlet
gas
byproduct
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CN110803680B (en
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廖明正
王超
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Guangdong University of Technology
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Abstract

The application relates to the technical field of hydrogen production by reforming, in particular to a chemical-looping reforming hydrogen production device for recycling reaction byproducts. The application includes: a first reformer, a second reformer, a regenerator, a heater, a byproduct recovery tank, and a vaporization tube; the product outlet of the first reformer is connected with the first inlet pipeline of the byproduct recovery tank through a heater; the first outlet of the byproduct recovery tank is connected with the inlet of the vaporization pipe; the outlet of the vaporization pipe is connected with the reactant inlet of the second reformer; the product outlet of the second reformer is connected with the second inlet of the byproduct recovery tank; the catalyst outlets of the first reformer and the second reformer are connected to the catalyst inlet of the regenerator. The device provided by the application can recycle reaction byproducts and make the reaction byproducts reused, so that the utilization rate of fuel in the hydrogen production process by chemical looping reforming is improved, and the energy consumption and the emission of pollutants are reduced.

Description

Chemical chain reforming hydrogen production device capable of recycling reaction byproducts
Technical Field
The application relates to the technical field of hydrogen production by reforming, in particular to a chemical-looping reforming hydrogen production device for recycling reaction byproducts.
Background
Hydrogen energy has become a focus of energy revolution with its characteristics of cleanliness, high efficiency, high calorific value, environmental friendliness, and the like. According to the international Hydrogen energy commission (Hydrogen Council), the percentage of Hydrogen energy in the total energy consumption is increased to 18% by 2050, and the market size of Hydrogen economy reaches $ 2.5 trillion. Among them, the most important field of hydrogen energy utilization is transportation, and in 2050, the proportion of the transportation hydrogen energy in the total consumption of hydrogen energy reaches 28%.
The hydrogen is produced by a steam reforming method, and the method has the characteristics of mature technology and low cost for producing oxygen, so that the method has absolute advantages in industrial hydrogen production, but has the defects of long conversion process flow, large investment, high water-carbon ratio, high energy consumption, easiness in sintering, low anti-poisoning capacity and the like. The process is inevitably accompanied by CO and H2O is generated but can be eliminated by a water-gas shift reaction. Therefore, the invention of this patent needs to be matched with CO2The adsorbent is used, and can play a role in removing main reaction by-products CO in situ in the hydrogen production reaction process2The effect of promoting the water-vapor transformation balance to shift right can improve the conversion rate of raw materials and the purity of hydrogen.
Researches show that the safety and local overheating problems of the air direct contact oxidation process usually adopted by partial oxidation reaction are more prominent, and by reintroducing the byproduct tar and steam generated by the reaction, the heat emitted by the partial oxidation reaction can be used for supplementing the heat absorbed by hydrogen production through tar or steam reforming, so that not only is the energy saved, but also the chemical reaction is accelerated, the fuel consumption is reduced, and the fuel utilization rate is improved.
Based on Le Chartelier's principle, adsorption enhancement is the continuous production of hydrogen gas by an adsorbent while hydrogen gas is being producedIn situ CO removal2This shifts the reaction equilibrium of this reversible reaction towards a favorable hydrogen production. The method has the advantages of being capable of being fixed by in-situ adsorption and greatly improving the purity of the product, thereby reducing the cost of re-separating the gas product. And the method also strengthens the steam shift reaction so as to reduce CO and CO in the product2Concentration, the methanation side reaction is inhibited. On the other hand, CO2The chemisorption of (a) is generally an exothermic reaction, thus partially compensating for the heat required for the reforming reaction to proceed, and making the energy utilization of the whole system more efficient.
The adsorption-enhanced methane (or natural gas) steam reforming hydrogen production (SE-MSR) widely studied at home and abroad has preliminarily confirmed these important effects. Published patents at home and abroad are based on the above principles, such as P.Pimeniou and V.Dupont et al in UK, who published on Bioresource Technology in 2010 (P.Pimeniou, et al, Biorsouree Technology in 2010, 9279-2The oxygen transfer performance of the reduction oxidation of NiO was experimentally determined, but the process was operated batchwise using a fixed bed reactor and did not involve any regeneration problems. The existing reforming hydrogen production technology does not consider the problem that byproducts such as tar and the like are generated in the reaction process, and does not consider the problem of pollutant emission in the reaction process.
Disclosure of Invention
The application provides a device for recycling chemical looping reforming hydrogen production of reaction byproducts, which can recycle the reaction byproducts and make the reaction byproducts reused, so that the utilization rate of fuel in the hydrogen production process by chemical looping reforming is improved, and the energy consumption and the emission of pollutants are reduced.
In view of the above, the present application provides, in a first aspect, an apparatus for recycling chemical looping reforming hydrogen production from reaction byproducts, the apparatus comprising:
a first reformer, a second reformer, a regenerator, a heater, a byproduct recovery tank, and a vaporization tube;
a product outlet of the first reformer is connected to a first inlet conduit of the byproduct recovery tank through the heater;
the first outlet of the byproduct recovery tank is connected with the inlet of the vaporization pipe; the outlet of the vaporization pipe is connected with the reactant inlet of the second reformer; the product outlet of the second reformer is connected to the second inlet of the byproduct recovery tank;
catalyst outlets of the first reformer and the second reformer are connected to a catalyst inlet of the regenerator; the catalyst outlet of the regenerator is connected to the catalyst inlets of the first and second reformers, respectively.
Preferably, the byproduct recovery tank comprises a tank body, a partition plate and a gas conduit;
the separation plate is arranged in the tank body, a byproduct recovery cavity is formed by the separation plate and the bottom wall of the tank body, a first inlet and a second inlet are formed in the side wall of the byproduct recovery cavity, a first outlet is formed in the bottom wall of the tank body, and a hydrogen outlet is formed in the top wall of the tank body;
the baffle is equipped with the through-hole, the gas pipe is fixed to be set up on the baffle, just the one end opening of gas pipe with the through-hole intercommunication, the other end opening of gas pipe to the diapire of the jar body extends, the other end opening of gas pipe with first export aligns, just the other end opening of gas pipe not with the diapire of the jar body is connected.
Preferably, the device further comprises a water tank, a pump, a spray pipe and spray heads, wherein the spray heads are uniformly arranged on the lower surface of the partition plate, the spray heads are connected with the spray pipe, and the spray pipe is connected with the water tank through the pump.
Preferably, the vaporizing tube is disposed inside the first reformer.
Preferably, the apparatus further comprises a pressurizing pump disposed on a pipeline between the first outlet of the byproduct recovery tank and the inlet of the vaporization pipe.
Preferably, the device further comprises a condenser, the hydrogen outlet is connected with an inlet of the condenser, and a first outlet of the condenser is connected with a second inlet of the byproduct recovery tank.
Preferably, the device further comprises a drying pipe, and the second outlet of the condenser is connected with the inlet of the drying pipe.
Preferably, the device further comprises a fuel cell, and the outlet of the drying pipe is connected with the gas inlet of the fuel cell.
Preferably, the device also comprises a propane gas cylinder, a gas flow meter and an air compression pump;
an air outlet of the air compression pump is connected with a gas inlet pipeline of the first reformer through a gas flow meter, and an outlet of the propane gas bottle is connected with a gas inlet pipeline of the first reformer through a gas flow meter.
Preferably, the gas inlet of the regenerator is connected to the air outlet of the air compressor pump by a flow meter pipe.
According to the technical scheme, the method has the following advantages:
in the application, a chemical chain reforming hydrogen production device for recycling reaction byproducts is provided, and hydrogen production of the device is divided into three parts: CO 22In-situ adsorption catalysis of propane partial oxidation chemical chain reforming hydrogen production, cyclic recycling of reaction by-products, hydrogen production catalyst and CO2And (4) regenerating the adsorbent.
1、CO2In-situ adsorption catalysis of partial oxidation of propane and chemical chain reforming for hydrogen production: introducing a mixture of propane and air into the first reformer from a gas inlet of the first reformer, flowing the mixture of propane and air from a lower portion to an upper portion of the first reformer, and introducing CO2The adsorbent and the hydrogen production catalyst move from top to bottom in the first reformer, and are in countercurrent contact reaction with a mixed gas of propane and air, and the generated hydrogen and reaction byproducts (such as tar, acetic acid, propionaldehyde and propionic acid) flow out from an outlet of the first reformer. And the reacted hydrogen production catalyst enters the regenerator from the catalyst outlet at the lower side of the first reformer for regeneration.
2. Recycling and reusing reaction byproducts: the gas generated after the reaction in the first reformer flows into the byproduct recovery tank through a pipeline, the heater heats and preserves the temperature of the gas generated after the reaction in the first reformer 6 to ensure that the generated reaction byproducts can be liquefied in the byproduct recovery tank, and the hydrogen gas flows from a hydrogen outlet of the byproduct recovery tank; meanwhile, the reaction byproduct forming liquid drops flows to the inlet of the vaporization pipe from the first outlet of the byproduct recovery tank, the vaporization pipe 9 vaporizes the liquid reaction byproduct into gas, the gas reaction byproduct is introduced into the reactant inlet of the second reformer, the second reformer carries out catalytic and adsorption reaction on the reaction byproduct to obtain hydrogen and the reaction byproduct of the second reformer, the hydrogen and the reaction byproduct of the second reformer enter the byproduct recovery tank from the product outlet of the second reformer, and the hydrogen of the second reformer flows from the hydrogen outlet of the byproduct recovery tank; in essence, the byproduct recovery tank functions to trap and hold the reaction byproducts, which are sent to the vaporization tube for vaporization. Therefore, the device can catalyze and adsorb reaction byproducts generated in the hydrogen production reforming process for many times, so that the reaction byproducts are not directly discharged to the outside, thereby reducing pollution in the hydrogen production reforming process and improving the hydrogen production efficiency.
3. Hydrogen production catalyst and CO2Regeneration of the adsorbent: CO 22The adsorbent and the hydrogen production catalyst move from top to bottom in the first reformer, and the hydrogen production catalyst and CO are obtained after the adsorbent and the hydrogen production catalyst are in countercurrent contact reaction with the mixed gas of propane and air2The adsorbent mixture enters a regenerator, the byproduct catalyst and the byproduct adsorbent move from top to bottom in the first reformer 6', and the byproduct catalyst and the byproduct adsorbent obtained after the countercurrent contact reaction with the mixed gas of the reaction byproducts enter the regenerator. Air enters the regenerator, heat is supplied to the regenerator from the outside, the temperature is kept at 700 ℃ and 800 ℃, the oxidation and carbon burning regeneration of the catalyst are carried out inside the regenerator, and CO adsorbed by the CaO adsorbent is used2Because of CaCO3Is decomposed by heat and desorbed. CO 22And is discharged from a gas outlet at the upper side of the regenerator. Thus, the device of the present application canThe adsorbent, the hydrogen production catalyst, the byproduct catalyst and the byproduct adsorbent in the reforming hydrogen production process are regenerated to obtain the adsorbent, the hydrogen production catalyst, the byproduct catalyst and the byproduct adsorbent which can be recycled, and harmless CO is discharged from a regenerator2Thereby reducing the pollution in the process of regenerating the adsorbent, the hydrogen production catalyst, the byproduct catalyst and the byproduct adsorbent and reducing the hydrogen production cost.
Aiming at the problem that liquid byproducts can be generated in the partial oxidation reaction of propane, the device with the recycling function is designed, the device can adapt to the operation in a large space velocity state, can collect and recycle the liquid byproducts which are not completely reacted or generated in the reaction, improves the utilization rate and the conversion rate of raw material gas propane, not only improves the hydrogen yield, but also greatly reduces the emission of pollutants, recycles the reaction byproducts and CO2The adsorption enhancement is coupled together, so that the adsorption enhanced catalyst can continuously move, react and regenerate, the catalyst is always in a fresh state, and H is realized2Continuous production, so that the device can continuously run for a long time. The invention ensures continuous and stable hydrogen production at low temperature and normal pressure, and greatly saves the hydrogen production cost.
Drawings
FIG. 1 is a block diagram of an apparatus for hydrogen production by chemical looping reforming with recycling of reaction by-products provided in the examples of the present application;
FIG. 2 is another block diagram of an apparatus for hydrogen production by chemical looping reforming with recycling of reaction by-products provided in the examples of the present application;
FIG. 3 is a block diagram of a byproduct recovery tank of an apparatus for hydrogen production by chemical-looping reforming, which is provided in an embodiment of the present application and which recycles reaction byproducts;
fig. 4 is an internal structure view of the byproduct recovery tank of fig. 3.
Detailed Description
The technical solutions of the embodiments of the present application will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without any creative effort belong to the protection scope of the embodiments in the present application.
In the description of the embodiments of the present application, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience in describing the embodiments of the present application and simplifying the description, but do not indicate or imply that the referred devices or elements must have specific orientations, be configured in specific orientations, and operate, and thus, should not be construed as limiting the embodiments of the present application. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the embodiments of the present application, it should be noted that the terms "mounted," "connected," and "connected" are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally connected unless explicitly stated or limited otherwise; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. Specific meanings of the above terms in the embodiments of the present application can be understood in specific cases by those of ordinary skill in the art.
It should be understood that the present application is applied to the field of hydrogen production by reforming, please refer to fig. 1, fig. 1 is a structural diagram of a chemical-looping hydrogen production by reforming apparatus for recycling reaction byproducts provided in the embodiment of the present application, as shown in fig. 1, and fig. 1 includes a first reformer 6, a second reformer 6', a regenerator 7, a heater 11, a byproduct recycling tank 14 and a vaporization pipe 9; the product outlet 25' of the first reformer is connected to the first inlet pipe of the byproduct recovery tank 14 through the heater 11; a first outlet of the byproduct recovery tank 14 is connected with an inlet of the vaporization pipe 9; the outlet of the vaporization tube 9 is connected to the reactant inlet 26 of the second reformer; the product outlet 26' of the second reformer is connected to a second inlet of the byproduct recovery tank 14; the catalyst outlets 12 'of the first reformer 6 and the second reformer 6' are connected to the catalyst inlet of the regenerator 7; the catalyst outlet of the regenerator 7 is connected to the catalyst inlets of the first reformer 6 and the second reformer 6', respectively.
The application designs a chemical chain reforming hydrogen production device for recycling reaction byproducts, which is suitable for different raw materials for reforming hydrogen production, and uses propane and air as raw materials and CO2The hydrogen production of the device is explained by adopting the adsorbent and the hydrogen production catalyst as additives, and the hydrogen production of the device is divided into three parts: CO 22In-situ adsorption catalysis of propane partial oxidation chemical chain reforming hydrogen production, cyclic recycling of reaction by-products, hydrogen production catalyst and CO2And (4) regenerating the adsorbent.
Further, the embodiment of the present application further includes a pressure pump 10, the pressure pump 10 is disposed on a pipeline between the first outlet 14-6 of the byproduct recovery tank and the inlet of the vaporization pipe 9, and the pressure pump 10 functions to push the liquid reaction byproduct of the byproduct recovery tank 14 into the vaporization pipe 9.
Referring to fig. 1, a flow meter 27 and a stop valve 4 are provided in the piping of the heater 11 and the byproduct recovery tank 14, a flow meter 27 and a stop valve 4 are provided in the hydrogen outlet of the byproduct recovery tank 14, a flow meter 27 and a pressure pump 10 (the pressure pump 10 functions to push the liquid reaction byproduct of the byproduct recovery tank 14 into the vaporization pipe 9) are provided in the piping of the first outlet of the byproduct recovery tank 14 and the vaporization pipe 9, a flow meter 27 and a stop valve 4 are provided in the piping of the vaporization pipe 9 and the first reformer 6 ', a flow meter 27 and a stop valve 4 are provided in the piping of the product outlet 26 ' of the first reformer 6 ' and the second inlet of the byproduct recovery tank 14, a stop valve is provided in the piping of the catalyst outlet of the regenerator 7 and the piping of the first reformer 6, and a stop valve is provided in the piping of the catalyst outlet of the regenerator 7 and the catalyst inlet.
1、CO2In-situ adsorption catalysis of partial oxidation of propane and chemical chain reforming for hydrogen production: the propane and air are fed into the first reformer 6 from the gas inlet 25 of the first reformer in a ratio of 1/7.14 by volume (i.e. 1/1.5 vol.% for C3H 8/O2), propane and airThe air-mixed gas flows from the lower portion to the upper portion of the first reformer 6, and CO flows2The adsorbent and the hydrogen production catalyst move from top to bottom in the first reformer 6, and are in countercurrent contact reaction with a mixed gas of propane and air, the moving speed of the catalyst is kept at 5-20cm/min, and the generated hydrogen and reaction byproducts (such as tar, acetic acid, propionaldehyde and propionic acid) flow out from an outlet 25' of the first reformer 6. And the reacted hydrogen production catalyst enters the regenerator 7 from the catalyst outlet 12' at the lower side of the first reformer 6 for regeneration.
2. Recycling and reusing reaction byproducts: the gas generated after the reaction in the first reformer 6 flows into the byproduct recovery tank 14 through a pipeline, the heater 11 heats and preserves the temperature of the gas generated after the reaction in the first reformer 6 to ensure that the generated reaction byproduct can be liquefied in the byproduct recovery tank 14, the reaction byproduct enters the byproduct recovery cavity from the first inlet of the byproduct recovery tank 14, contacts with the surfaces of the partition plate 14-1 and the gas conduit 14-2 and falls down along the surfaces of the partition plate 14-1 and the gas conduit 14-2 to form liquid drops, and hydrogen gas is introduced into a hydrogen outlet of the byproduct recovery tank 14 from the opening at the other end of the gas conduit 14-2; meanwhile, the reaction byproduct forming liquid drops flows from the first outlet of the byproduct recovery tank 14 to the inlet of the vaporization pipe 9, the vaporization pipe 9 vaporizes the liquid reaction byproduct into gas, the gas reaction byproduct is introduced into the reactant inlet 26 of the second reformer, the second reformer 6 'performs catalytic and adsorption reaction on the reaction byproduct to obtain hydrogen and reaction byproduct of the second reformer, the hydrogen and reaction byproduct of the second reformer enter the second inlet of the byproduct recovery tank 14 from the product outlet 26' of the second reformer, and the hydrogen of the second reformer is introduced into the hydrogen outlet of the byproduct recovery tank 14 from the opening at the other end of the gas conduit 14-2; the reaction by-products of the second reformer come into contact with the surfaces of the partition 14-1 and the gas conduit 14-2 and fall down along the surfaces of the partition 14-1 and the gas conduit 14-2 to form liquid droplets, and the reaction by-products of the second reformer, which form the liquid droplets, flow from the first outlet of the by-product recovery tank 14 to the inlet of the vaporization pipe 9, completing one cycle; in essence, the byproduct recovery tank 14 functions to trap and hold reaction byproducts, which are sent to the vaporization tube 9 for vaporization. Therefore, the device can catalyze and adsorb reaction byproducts generated in the hydrogen production reforming process for many times, so that the reaction byproducts are not directly discharged to the outside, thereby reducing pollution in the hydrogen production reforming process and improving the hydrogen production efficiency.
3. Hydrogen production catalyst and CO2Regeneration of the adsorbent: CO 22The adsorbent and the hydrogen production catalyst move from top to bottom in the first reformer 6, and the hydrogen production catalyst and CO are obtained after the countercurrent contact reaction of the adsorbent and the mixed gas of propane and air2The adsorbent mixture enters a regenerator 7, the byproduct catalyst and the byproduct adsorbent move from top to bottom in the first reformer 6', and the byproduct catalyst and the byproduct adsorbent obtained after the countercurrent contact reaction with the mixed gas of the reaction byproduct enter the regenerator 7. Air enters the regenerator 7, heat is supplied to the regenerator 7 from the outside, the temperature is kept at 700 ℃ and 800 ℃, the oxidation and carbon burning regeneration of the catalyst are carried out inside the regenerator 7, and CO adsorbed by the CaO adsorbent2Because of CaCO3Is decomposed by heat and desorbed. CO 22And is discharged from a gas outlet 23 at the upper side of the regenerator 7. Therefore, the device can regenerate the adsorbent, the hydrogen production catalyst, the byproduct catalyst and the byproduct adsorbent in the hydrogen production reforming process to obtain the recyclable adsorbent, the recyclable hydrogen production catalyst, the recyclable byproduct catalyst and the recyclable byproduct adsorbent, and harmless CO is discharged from the regenerator 72Thereby reducing the pollution in the process of regenerating the adsorbent, the hydrogen production catalyst, the byproduct catalyst and the byproduct adsorbent and reducing the hydrogen production cost.
Specifically, the partial oxidation catalyst in the first reformer 6 is reduced as indicated by (the catalyst is NiO/Al)2O3 for example, CaO for example):
C3H8(g)+3NiO→3CO(g)+4H2(g)+3Ni；
C3H8(g)+10NiO→3CO2(g)+4H2O(g)+10Ni。
the main reactions of partial oxidation hydrogen production in the reformer 6 include:
C3H8(g)+1.5O2(g)→3CO(g)+4H2(g)；
CO(g)+H2O(g)CO2(g)+H2(g)；
CO in reformer2The in-situ adsorption is as follows:
CaO(s)+CO2(g)→CaCO3(s)。
partial oxidation side reaction of propane in reformer 6:
C3H8(g)+1.5O2(g)→CH2CHCHO(l)+2H2O(g)；
C3H8(g)+1.5O2(g)→CH3CH2COOH(l)+H2O(g)；
C3H8(g)→Tar+Char+Gas；
CH2CHCHO、CH3CH2COOH, Tar and H2The O becomes liquid after condensation.
Steam reforming reaction of by-product in the reformer 6':
CH2CHCHO(g)+5H2O(g)→3CO2(g)+7H2(g)；
CH3CH2COOH(g)+4H2O(g)→3CO2(g)+7H2(g)；
Tar+H2O(g)→C(s)+H2(g)+CO(g)+CnHm；
CnHm+H2O→CO2(g)+H2(g)。
the adsorption-enhanced catalyst in the regenerator mainly heats the adsorbed CO2Desorption and regeneration:
CaCO3(s)→CaO(s)+CO2(g)。
the carbon burning regeneration reaction of the carbon deposition of the catalyst in the regenerator comprises the following steps:
C+O2→CO2。
the technical scheme of the invention is as follows: the invention can take the product oil byproduct propane as the raw material to carry out moving bed continuous catalytic adsorption to strengthen the chemical chain partial oxidation reforming hydrogen production, and is provided with a byproduct recovery tank 14 to recover and recycle the reaction byproducts generated in the reactionAnd (4) utilizing. The vaporization heat absorption of the waste liquid in the first reformer 6 and the partial oxidation heat release of the propane complement each other, and the hydrogen production water-vapor shift reaction and the CO are performed2The in situ adsorption reaction is highly coupled, wherein the main chemical reactions in the first reformer 6 include partial oxidation, steam reforming, steam shift reaction and CO2And (5) carrying out adsorption reaction.
Further, the by-product recovery tank 14 of the embodiment of the present application includes a tank body, a partition 14-1, and a gas conduit 14-2; the partition plate 14-1 is arranged in the tank body, the partition plate 14-1 and the bottom wall of the tank body form a byproduct recovery cavity 14-3, the side wall of the byproduct recovery cavity 14-3 is provided with a first inlet 14-4 and a second inlet 14-5, the bottom wall of the tank body is provided with a first outlet 14-6, and the top wall of the tank body is provided with a hydrogen outlet 14-7;
the partition plate 14-1 is provided with a through hole 14-8, the gas conduit 14-2 is fixedly arranged on the partition plate 14-1, one end opening of the gas conduit is communicated with the through hole 14-8, the other end opening 14-9 of the gas conduit extends towards the bottom wall of the tank body, the other end opening 14-9 of the gas conduit is aligned with the first outlet 14-6, and the other end opening 14-9 of the gas conduit is not connected with the bottom wall of the tank body. Hydrogen gas and reaction byproducts of the first reformer 6 enter the byproduct recovery chamber 14-3 from the first inlet 14-4, and the hydrogen gas of the first reformer 6 is introduced into the hydrogen gas outlet 14-7 from the other end opening 14-9 of the gas conduit; hydrogen and reaction byproducts from the second reformer 6 'enter the byproduct recovery chamber 14-3 through a second inlet 14-5, and hydrogen from the second reformer 6' passes through a hydrogen outlet 14-7 from the other end opening 14-9 of the gas conduit; the reaction by-products condensed into liquid droplets by contacting the outer walls of the partition 14-1 and the gas guide 14-2 flow out from the first outlet 14-6.
Furthermore, the water tank, the pump, the spray pipe and the spray head are further included, the spray head is evenly arranged on the lower surface of the partition plate 14-1, the spray head is connected with the spray pipe, and the spray pipe is connected with the water tank through the pump. By arranging the spray head on the partition plate 14-1 and spraying the byproduct recovery cavity 14-3, on one hand, reaction byproducts are washed off from the outer wall of the gas guide pipe 14-2, and are diluted to form waste liquid, and the reaction amount of the waste liquid can be adjusted.
Wherein the partial oxidation reaction has a specific water vaporLess tar is produced in the reforming reaction, and since the gas discharged from the reformer is directly introduced into the byproduct recovery tank, although CH is inevitably produced in the reaction2CHCHO and CH3CH2Liquid byproducts such as COOH and the like are generated, but the concentration of tar can be diluted, so that the pipeline is prevented from being blocked by the tar; and the byproduct recovery cavity 14-3 of the byproduct recovery tank can be added with water, which is beneficial to strengthening the water-vapor transformation reaction, improving the hydrogen yield and adjusting the reaction amount of materials, and the exothermic reaction is beneficial to compensating the heat absorbed in the steam reforming, and reducing the energy consumption.
Referring to fig. 2, the vaporization tube 9 of the embodiment of the present invention is disposed inside the first reformer 6, and the heat of the first reformer 6 can be fully utilized by disposing the vaporization tube 9 inside the first reformer 6.
Further, the embodiment of the application also comprises a condenser 16, the hydrogen outlet 14-7 is connected with an inlet of the condenser 16, a first outlet 17 of the condenser is connected with a second inlet 14-5 of the byproduct recovery tank, on one hand, the condenser 16 can be cooled by hydrogen with high temperature, and on the other hand, a small amount of liquid reaction byproducts which are carried by the hydrogen and are not condensed are further condensed and returned to the byproduct recovery tank 14.
Further, the embodiment of the present application further includes a drying pipe 19, the second outlet of the condenser 16 is connected to the inlet of the drying pipe 16, and the drying pipe 19 is used for drying the hydrogen, thereby facilitating subsequent energy generation.
Further, the embodiment of the present application further includes a fuel cell 21, an outlet of the drying pipe 19 is connected to a gas inlet of the fuel cell 21, and the fuel cell 21 is used for generating hydrogen. Operation of the fuel cell: the hydrogen gas flows out from the condenser 16, is dried by the drier 19 and then enters the fuel cell through the hydrogen inlet 20, and the air enters through the air inlet 24. The generated power is output from the power supply 22. The fuel cell may have a conventional fuel cell.
Further, referring to fig. 2, the embodiment of the present application further includes a propane gas cylinder 1, a flow meter 4, and an air compression pump 2; an air outlet 3 of the air compression pump is connected with a gas inlet pipeline of the first reformer 6 through a flow meter 4, and an outlet of the propane gas bottle 1 is connected with a gas inlet pipeline of the first reformer 6 through the flow meter 4. Propane is stored in a propane gas cylinder 1, and air is directly compressed by an air compressor 2 and then supplied, and a suitable mixed gas of propane and air is formed by designing a flow meter 4.
Referring to fig. 2, a flow meter and a stop valve may be provided at the gas inlet 25 of the first reformer 6, and the gas inlet of the regenerator 7 may be connected to the air outlet 3 of the air compression pump through a flow meter 27 and a stop valve 4, and may be connected to each other through a three-way valve 5.
The embodiment of the application relates to a device for coupling by-product recycling and continuous adsorption enhanced catalytic propane chemical-looping reforming hydrogen production, which comprises a plurality of reformers, an air compressor, a by-product recycling tank, a gasification pipe, a condenser, a drying pipe, a fuel cell and the like. The whole process can be divided into two cycles, which are respectively as follows: recycling and reusing the by-products; and (3) circulating the reaction and regeneration of the adsorbent and the catalyst. The tail gas propane in the petroleum industry is used as a hydrogen production raw material, the outside air is directly used as a carrier gas in a reformer, the mixed gas of the propane and the air flows from bottom to top in the reformer and is in countercurrent contact reaction with adsorption-enhanced catalyst particles, and the air has five functions: the catalyst is used as a raw material to participate in hydrogen production reaction, is used as a carrier gas of a reformer, is used as a raw material gas for burning and regenerating the catalyst in a regenerator, pushes the catalyst to move in a moving bed, and is used as an oxygen source of a fuel cell. And the product hydrogen and the reaction by-products are discharged from the upper side of the reformer and enter a by-product recovery tank for condensation. The by-product recovery tank is internally provided with a clapboard which can lead the by-product to be condensed and then fall down along the board wall. The product hydrogen flows out from the upper part of the byproduct recovery tank, condensed water flows back to the byproduct recovery tank after being condensed again by the condenser, the hydrogen enters the drying pipe and is supplied to the fuel cell after being dried, and the oxygen source is directly supplied by the air compression pump. And the waste liquid flows out from the lower part of the byproduct recovery tank, is conveyed to the vaporizing tube by the pressurizing pump to be heated and vaporized and then enters another reformer to react, and the generated gas is introduced into the byproduct recovery tank to be condensed to complete a cycle. The catalyst and the adsorbent are sent out from the bottom outlet of the reformer and are sent to the regenerator through the moving bed for carbon burning regeneration and CO2After desorption and regeneration, the high-pressure air is pushed to be sent to the reformer for reaction, and continuous circulation operation is carried out.
The fuel propane in the embodiment of the application is a product oil byproduct which is easy to store, easy to compress and liquefy, and the raw material sources of the whole process are only propane and air, so that the hydrogen production process and the equipment complexity are greatly simplified, and the fuel propane is more compact and miniaturized; the steam reforming needs to be provided with a steam generator, liquid water needs to be vaporized firstly, the energy consumption is very large because the steam reforming reaction is a strong endothermic reaction, and the partial oxidation reaction is a strong exothermic reaction, and a large amount of heat is released during the reaction, so that the steam reforming reaction can have the function of self-heating, the external energy consumption is reduced, and compared with the traditional steam reforming reaction, the energy consumption and the production cost are greatly reduced; and because the air can be obtained at any time, unlike the steam reforming which needs to be vaporized firstly, when the device is in a severe cold region such as a temperature below zero, the advantages of the device can be fully expressed, in other words, the raw material only needs propane and a catalyst, the device can be used anywhere, and the application occasions are very wide.
The terms "first," "second," "third," "fourth," and the like in the description of the application and the above-described figures, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
It should be understood that in the present application, "at least one" means one or more, "a plurality" means two or more. "and/or" for describing an association relationship of associated objects, indicating that there may be three relationships, e.g., "a and/or B" may indicate: only A, only B and both A and B are present, wherein A and B may be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single item(s) or plural items. For example, at least one (one) of a, b, or c, may represent: a, b, c, "a and b", "a and c", "b and c", or "a and b and c", wherein a, b, c may be single or plural.
The above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.

Claims (10)

1. An apparatus for recycling chemical looping reforming hydrogen production of reaction by-products, comprising: a first reformer, a second reformer, a regenerator, a heater, a byproduct recovery tank, and a vaporization tube;
a product outlet of the first reformer is connected to a first inlet conduit of the byproduct recovery tank through the heater;
the first outlet of the byproduct recovery tank is connected with the inlet of the vaporization pipe; the outlet of the vaporization pipe is connected with the reactant inlet of the second reformer; the product outlet of the second reformer is connected to the second inlet of the byproduct recovery tank;
catalyst outlets of the first reformer and the second reformer are connected to a catalyst inlet of the regenerator; the catalyst outlet of the regenerator is connected to the catalyst inlets of the first and second reformers, respectively.
2. The apparatus of claim 1, wherein the byproduct recovery tank comprises a tank body, a baffle, and a gas conduit;
the separation plate is arranged in the tank body, a byproduct recovery cavity is formed by the separation plate and the bottom wall of the tank body, a first inlet and a second inlet are formed in the side wall of the byproduct recovery cavity, a first outlet is formed in the bottom wall of the tank body, and a hydrogen outlet is formed in the top wall of the tank body;
the baffle is equipped with the through-hole, the gas pipe is fixed to be set up on the baffle, just the one end opening of gas pipe with the through-hole intercommunication, the other end opening of gas pipe to the diapire of the jar body extends, the other end opening of gas pipe with first export aligns, just the other end opening of gas pipe not with the diapire of the jar body is connected.
3. The device of claim 2, further comprising a water tank, a pump, a spray pipe and a spray head, wherein the spray head is uniformly arranged on the lower surface of the partition plate, the spray head is connected with the spray pipe, and the spray pipe is connected with the water tank through the pump.
4. The apparatus of claim 1 wherein the vaporization tube is disposed internally within the first reformer.
5. The apparatus of claim 1, further comprising a booster pump disposed on a conduit between the first outlet of the byproduct recovery tank and the inlet of the vaporization tube.
6. The apparatus of claim 2, further comprising a condenser, the hydrogen gas outlet being connected to an inlet of the condenser, a first outlet of the condenser being connected to a second inlet of the byproduct recovery tank.
7. The apparatus of claim 6, further comprising a drying tube, wherein the second outlet of the condenser is connected to an inlet of the drying tube.
8. The apparatus of claim 7, further comprising a fuel cell, wherein the outlet of the drying duct is connected to a gas inlet of the fuel cell.
9. The apparatus of claim 1, further comprising a propane cylinder, a gas flow meter, and an air compression pump;
an air outlet of the air compression pump is connected with a gas inlet pipeline of the first reformer through a gas flow meter, and an outlet of the propane gas bottle is connected with a gas inlet pipeline of the first reformer through a gas flow meter.
10. The apparatus of claim 9, wherein the gas inlet of the regenerator is connected to the air outlet of the air compressor pump by a flow meter conduit.
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