CN216472231U - Efficient temperature control membrane reformer - Google Patents

Abstract

The embodiment of the application provides a membrane type reformer capable of efficiently controlling temperature, and belongs to the technical field of hydrogen production through reforming. The efficient temperature control membrane reformer comprises a tank body and a reaction tube, wherein the tank body is provided with a first inlet and a second inlet, the first inlet is used for inputting steam, and the second inlet is used for inputting methanol-water mixed gas into the tank body; the reaction tube is internally provided with an annular hydrogen separation part which extends along the axial direction of the reaction tube so as to divide the inner space of the reaction tube into a first reaction area and a second reaction area, the first reaction area is communicated with the second inlet and is used for reforming and cracking reaction, the first reaction area is partially communicated with the second reaction area and is used for carrying out water gas reaction, and the hydrogen separation part is used for separating and guiding out the hydrogen generated by the first reaction area and the second reaction area. The efficient temperature control membrane reformer can stably produce hydrogen, separates to obtain a high-purity hydrogen product, accurately controls the temperature, and saves complex control sensing equipment.

Description

Efficient temperature control membrane reformer

Technical Field

The application relates to the technical field of hydrogen production by reforming, in particular to a membrane reformer with efficient temperature control.

Background

In order to be matched with the popularization and application of power generation of a hydrogen fuel cell stack system, portable, simple and highly controllable hydrogen production equipment needs to be carried to provide stable and reliable hydrogen raw materials for the stack, so that the total cost is reduced, and the suitability of the stack is improved. The conditions to be met by hydrogen production equipment matched with the fuel cell include high-purity hydrogen to prevent a catalyst in a galvanic pile from being damaged, and the lifting and the carrying response are quick, namely the hydrogen supply response is quick. In addition, the method has the requirements of high hydrogen yield, loose reaction conditions, cheap catalyst selection and stable and reliable equipment in the aspect of cost. The most serious problems of the conventional reformer are the contradiction between the purity and the yield of hydrogen, and the problems of catalyst damage or by-product increase caused by poor reaction temperature control at high temperature.

SUMMERY OF THE UTILITY MODEL

The embodiment of the application provides a membrane reformer of high-efficient accuse temperature, can stably produce hydrogen, and separation purity is high, and temperature control is accurate, has saved the complicated facility of control sensor.

The embodiment of the application provides a film reformer with high-efficiency temperature control, which comprises a tank body and a reaction tube, wherein the tank body is provided with a first inlet and a second inlet which are oppositely arranged, the first inlet is used for inputting water vapor into the tank body, and the second inlet is used for inputting methanol-water mixed gas into the tank body; the reaction tube is arranged in the tank body and used for supplying methanol-water mixed gas to carry out reforming reaction so as to produce hydrogen, and the high-pressure steam is used for improving the environmental temperature in the tank body; the reaction tube is internally provided with an annular hydrogen separation part, the hydrogen separation part extends along the axial direction of the reaction tube so as to divide the inner space of the reaction tube into a first reaction area and a second reaction area, and the first reaction area is closer to the outer wall of the reaction tube than the second reaction area; the first reaction area is communicated with the second inlet and is used for reforming and cracking reaction, the first reaction area is partially communicated with the second reaction area so that reaction gas generated in the first reaction area after reforming and cracking reaction can enter the second reaction area, the second reaction area is used for carrying out water gas reaction, the hydrogen separation part is used for separating and guiding out hydrogen generated in the first reaction area and the second reaction area, and the bottom of the second reaction area is communicated with a reaction gas outlet.

In this scheme, the steam of high pressure high temperature that fills into in the jar body comes the demand temperature of control reaction in the reaction tube, because the fixed easy accuse of steam thermodynamic characteristics, the temperature is controlled to the pressure of accessible steam, on the one hand, because the heat capacity of water is big, reduce the steam quantity through this kind of mode, reduced the volume demand in heat transfer space, and reduce the volume of reforming equipment, on the other hand is under the prerequisite of the heat exchange wall thickness and the material of setting for the reaction tube, the heat transfer coefficient of reaction tube is fixed, therefore the temperature of the catalyst coating on the reaction tube also is fixed by thermodynamic characteristics, the reaction is even stable. Because the water vapor in the tank body is uniformly distributed outside the reaction tube, the heat transfer and the contact of the water vapor to the reaction tube are uniform. Meanwhile, the reaction tube is internally divided into a first reaction area and a second reaction area by the hydrogen separation part, the first reaction area is a reforming cracking reaction, the required temperature is higher, and therefore the reaction tube is positioned at one side close to the outer wall of the reaction tube, the temperature of the first reaction area is improved by steam more, the second reaction area positioned at the inner side is a water gas reaction, the required temperature is relatively low, and therefore the reaction gas in the reaction tube is converged into the second reaction area after the reaction of the first reaction area to perform the water gas reaction, the hydrogen separation part is positioned between the first reaction area and the second reaction area, and the generated hydrogen source is continuously separated to enter the hydrogen separation part. Therefore, the reaction tube structure is matched with water vapor to control the temperature, so that the separation selectivity of hydrogen and impurities can reach 1000:1, the hydrogen yield is high, and the structure is simple.

In some embodiments, a preheating pipe is further arranged between the second inlet and the reaction pipe, the preheating pipe is located in the area enclosed by the plurality of reaction pipes, and the outer wall of the preheating pipe is in contact with the steam of the tank body so as to preheat the methanol-water mixed gas in the preheating pipe.

According to the technical scheme, the preheating temperature of the preheating pipe can be determined by the heat exchange wall area of the preheating pipe and the steam pressure at the periphery of the preheating pipe, the temperature of the steam distributed in the tank body is the highest, the preheating pipe is arranged between the second inlet and the reaction pipe, and the outer wall of the preheating pipe is contacted with the steam to preheat the methanol-water mixed gas before entering the reaction pipe, so that the temperature in the subsequent reaction pipe can be smoothly raised to the required temperature, and the reforming reaction can be smoothly carried out.

In some embodiments, the first inlet is located at the top of the tank body, the second inlet is located at the bottom of the tank body, the extending direction of the reaction tube is arranged in the same direction as the height direction of the tank body, and a water vapor collecting pipe is arranged on one side of the bottom in the tank body and used for recovering water vapor on the side.

Among the above-mentioned technical scheme, because vapor is at the internal from top to bottom flow of jar, consequently be provided with the vapor collecting pipe in the bottom of the jar body, the vapor collecting pipe can be retrieved the vapor after the heat transfer, avoids the heat waste of vapor to do benefit to the follow-up temperature control to the water gas reaction through the heating pipe in the second reaction zone.

In some embodiments, a heating pipe is further arranged in the reaction pipe, the heating pipe is communicated with the water vapor collecting pipe, the heating pipe is arranged in the second reaction zone in a penetrating mode and used for heating the reaction gas in the second reaction zone, and the second reaction zone is formed between the outer wall of the heating pipe and the inner wall of the hydrogen separation part.

Among the above-mentioned technical scheme, through be provided with the heating pipe in the reaction tube, because the temperature that first reaction zone and second reaction zone required is different, the demand temperature of first reaction zone is higher than the second reaction zone, consequently, through be provided with the heating pipe in the second reaction zone, and this heating pipe and vapor collecting pipe intercommunication, just can retrieve the vapor after the first reaction zone heat transfer, then the vapor temperature is because the heat exchange can reduce, through suitable pipeline length design, the temperature that gets into the heating pipe just can heat the temperature of the relatively low water gas reaction of demand, the vapor of temperature accords with the heat transfer temperature in the second reaction zone more this moment, and then improved the utilization ratio to vapor, and improve the formation rate of hydrogen through the two-stage reaction. Meanwhile, the heating pipe penetrates through the second reaction zone, so that the temperature of the second reaction zone can reach the preset temperature, the reaction efficiency of the second reaction zone is accelerated, and the efficiency of hydrogen production is further ensured.

In some embodiments, the inner wall of the reaction tube is provided with a first catalyst coating for catalyzing the reforming cracking reaction in the first reaction zone; and the outer wall of the heating pipe is provided with a second catalyst coating for catalyzing the water gas reaction in the second reaction zone.

Among the above-mentioned technical scheme, because first catalyst coating and second catalyst coating are thin, the use amount of catalyst has been reduced on the one hand, the cost is reduced, need not increase unnecessary catalyst bed quantity greatly with the mode of packing, and need not the packed bed and reduced the pressure drop loss of intraductal gas circulation, improve the circulation, on the other hand thin evenly distributed between the catalyst can not cause local hot spot or coking because of being heated unevenly, and also improve reaction contact area, the rate of utilization of catalyst coating has been improved.

In some embodiments, the hydrogen separation part has one side abutting against the bottom of the reaction tube and the other side having a gap with the top of the reaction tube so that the first reaction zone communicates with the second reaction zone, the bottom of the first reaction zone communicates with the second inlet, and the bottom of the second reaction zone has a reaction gas exhaust port.

Among the above-mentioned technical scheme, because the entering of methanol-water gas mixture in the first reaction zone is by supreme down, consequently through hydrogen separation portion and reaction tube bottom butt, make first reaction zone and second reaction zone below isolated completely, ensure the independence of the methanol-water gas mixture that gets into in the first reaction zone, can not get into the second reaction zone, and have the clearance with the top of hydrogen separation portion and reaction tube, make the reaction gas after the reforming and cracking reaction reentrant to carry out the water gas reaction in the second reaction zone, make first reaction zone and second reaction zone be the runner of falling U-shaped, ensure mutual independence and the intercommunication after the reaction of twice reactions.

In some embodiments, the hydrogen separation part is of a tubular structure, the tube cavity in the hydrogen separation part is used for hydrogen circulation and export, the inner side and the outer side of the hydrogen separation part are respectively provided with a separation membrane, and the separation membranes are used for allowing hydrogen on the corresponding sides of the first reaction zone and the second reaction zone to pass through the separation membranes and enter the tube cavity.

The outer wall of the hydrogen separation part is a stainless steel pipe with a gap of about 0.2 mu m, a palladium alloy coating of about 70 mu m is coated on the stainless steel pipe, the palladium alloy coating forms the separation membrane, and a nickel alloy and the like are adopted between the palladium alloy coating and the stainless steel pipe to adjust the gap to prevent hydrogen leakage, so that the hydrogen is continuously separated from one side close to the inner wall of the reaction pipe and enters a pipe cavity of the hydrogen separation part due to concentration and pressure difference, and the separation rate of the hydrogen is improved.

In some embodiments, the reaction tube is provided in a plurality, and the plurality of reaction tubes are uniformly distributed in the tank body along the circumferential direction thereof.

Among the above-mentioned technical scheme, establish to a plurality ofly through the quantity with jar internal reaction tube, a plurality of reaction tubes can carry out hydrogen production reaction simultaneously to let in jar internal vapor also can carry out the heat transfer to a plurality of reaction tubes simultaneously, improved the utilization ratio of heat energy, and also improved the productivity of hydrogen energy. Simultaneously, with a plurality of reaction tubes at jar internal peripheral evenly distributed for the heat energy that a plurality of reaction tubes received is more even, thereby is more accurate to the temperature control of reaction tube.

In some embodiments, the preheating pipe is located in the region enclosed by the plurality of reaction pipes, and one end of the preheating pipe, which is far away from the second inlet, enters the first reaction zone in each reaction pipe through the distribution pipe.

Among the above-mentioned technical scheme, the preheating pipe passes through the distribution pipe at the bottom of the jar body and distributes the methanol-water mist after preheating, lets the bottom that the methanol-water mist after preheating can evenly get into each reaction tube to carry out the reforming reaction.

In some embodiments, the preheat tube is in a U-shaped or S-shaped flow path arrangement.

Among the above-mentioned technical scheme, the heat transfer area between preheating pipe and the vapor can be increased to the S-shaped runner to improve the preheating effect of vapor to the preheating pipe.

Additional features and advantages of the present application will be described in detail in the detailed description which follows.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.

FIG. 1 is a schematic diagram of the configuration of an efficient temperature controlled membrane reformer provided in some embodiments herein;

fig. 2 is a top view of the efficient temperature controlled membrane reformer of fig. 1.

Icon: 1-tank body; 2-a reaction tube; 3-a hydrogen separation section; 4-a first reaction zone; 5-a second reaction zone; 7-heating a tube; 8-a water vapor collection pipe; 9-a steam inlet pipe; 10-preheating tube; 11-a reaction gas distribution pipe; 12-a hydrogen gas collection pipe; 13-reaction tail gas collecting pipe; 14-water vapor distribution tubes; a-a first inlet; b-a second inlet; c-a hydrogen outlet; d-a reaction gas outlet; e-a water vapor outlet.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. The components of the embodiments of the present application, generally described and illustrated in the figures herein, can be arranged and designed in a wide variety of different configurations.

Thus, the following detailed description of the embodiments of the present application, presented in the accompanying drawings, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.

In the description of the embodiments of the present application, it should be noted that the indication of the orientation or positional relationship is based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship which is usually placed when the product of the application is used, and is only for the convenience of describing the application and simplifying the description, and does not indicate or imply that the indicated device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the application. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.

In the description of the present application, it is further noted that, unless otherwise explicitly stated or limited, the terms "disposed" and "connected" are to be interpreted broadly, e.g., as being either fixedly connected, detachably connected, or integrally connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art.

Examples

The embodiment of the application provides a membrane reformer with high-efficiency temperature control, please refer to fig. 1 and fig. 2, the membrane reformer with high-efficiency temperature control comprises a tank 1 and a reaction tube 2, the tank 1 is provided with a first inlet a and a second inlet b which are oppositely arranged, the first inlet a is used for inputting high-pressure steam into the tank 1, and the second inlet b is used for inputting methanol-water mixed gas into the tank 1; the reaction tube 2 is arranged in the tank body 1, the reaction tube 2 is used for supplying methanol-water mixed gas to carry out reforming reaction so as to produce hydrogen, and high-pressure steam is used for increasing the environmental temperature in the tank body 1; wherein, the reaction tube 2 is internally provided with an annular hydrogen separation part 3, the hydrogen separation part 3 extends along the axial direction of the reaction tube 2 so as to divide the space in the reaction tube 2 into a first reaction zone 4 and a second reaction zone 5, and the first reaction zone 4 is closer to the outer wall of the reaction tube 2 than the second reaction zone 5; the first reaction zone 4 is communicated with the second inlet b, the first reaction zone 4 is used for reforming and cracking reaction, the first reaction zone 4 is partially communicated with the second reaction zone 5, so that the reaction gas after the reforming and cracking reaction in the first reaction zone 4 can enter the second reaction zone 5, the second reaction zone 5 is used for water gas reaction, the hydrogen separation part 3 is used for separating and guiding out the hydrogen generated by the first reaction zone 4 and the second reaction zone 5, and the bottom of the second reaction zone 5 is communicated with a reaction gas outlet d.

In the scheme, the required temperature of the reforming reaction in the reaction tube 2 is controlled by the high-pressure and high-temperature steam filled into the tank body 1, the thermodynamic property of the steam is fixed and easy to control, and the temperature can be controlled by the pressure of the steam, on one hand, the heat capacity of water is large, the using amount of the steam is reduced in such a way, the volume requirement of a heat transfer space is reduced, the volume of reforming equipment is reduced, on the other hand, the heat transfer coefficient of the reaction tube 2 is fixed on the premise of setting the heat exchange wall thickness and the material of the reaction tube 2, so that the temperature of the catalyst coating on the reaction tube 2 is also fixed by the thermodynamic property, and the reaction is uniform and stable. Because the water vapor in the tank body 1 is uniformly distributed outside the reaction tubes 2, the heat transfer and the contact of the water vapor to the reaction tubes 2 are uniform. Meanwhile, the inside of the reaction tube 2 is divided into a first reaction area 4 and a second reaction area 5 by the hydrogen separation part 3, and the first reaction area 4 is a reforming cracking reaction, which has a high demand for temperature, and is located at one side close to the outer wall of the reaction tube 2, so that the temperature of the water vapor in the first reaction area 4 is raised higher, and the second reaction area 5 located at the inner side is a water gas reaction, which has a low demand for temperature, so that the reaction gas in the reaction tube 2 is converged into the second reaction area 5 after reacting in the first reaction area 4, and is subjected to the water gas reaction, and the hydrogen separation part 3 is located between the first reaction area 4 and the second reaction area 5, and the generated hydrogen source is continuously separated and enters the hydrogen separation part 3. Therefore, the reaction tube 2 structure is matched with high-pressure high-temperature steam for temperature control, so that the separation selectivity of hydrogen and impurities can reach 1000:1, the hydrogen yield is high, the structure is simple, the size of the reformer can be small due to continuous separation of the hydrogen, the reaction progress can be carried out in the direction of hydrogen production all the time, and the yield is improved.

Wherein, the outer wall of the tank body 1 is isolated by heat insulating materials, so as to prevent heat loss, in order to increase the heat exchange area and the reaction time, the diameter of the reaction tube 2 needs to be designed as small as possible, the number of the reaction tubes 2 can be one, two or even more, and the number of the reaction tubes 2 is as dense as possible and is uniformly distributed in the tank body 1.

It should be noted that the reforming reaction is composed of two parts, a methanol cracking reaction which is endothermic reaction and a water gas reaction which is exothermic reaction, and the reaction is endothermic as a whole, and heat is required to be supplied from the outside, so that the hydrogen yield is finally improved by adjusting the reaction region in which the reaction temperature is lowered step by step in the reformer. The first reaction zone 4 in the reaction tube 2 is mainly reforming cracking reaction, the required temperature is high and is about 250 ℃, the second reaction zone 5 is mainly water gas reaction, and the required temperature is relatively low and is about 200 ℃.

In some embodiments, a preheating pipe 10 is further disposed between the second inlet b and the reaction tubes 2, the preheating pipe 10 is located in the region enclosed by the plurality of reaction tubes 2, and the outer wall of the preheating pipe 10 contacts with the steam of the tank 1 to preheat the methanol-water mixture in the preheating pipe 10.

In the above technical solution, the preheating temperature of the preheating pipe 10 can be determined by the heat exchange wall area of the preheating pipe 10 and the steam pressure at the periphery, the temperature of the steam distributed in the tank body 1 is the highest, and the preheating pipe 10 is further arranged between the second inlet b and the reaction pipe 2, and the outer wall of the preheating pipe 10 is contacted with the steam to preheat the methanol-water mixed gas before entering the reaction pipe 2, so that the temperature in the subsequent reaction pipe 2 can be smoothly raised to the required temperature, and the reforming reaction can be smoothly performed.

In some embodiments, the first inlet is located at the top of the tank 1, the second inlet b is located at the bottom of the tank 1, the extending direction of the reaction tube 2 is arranged in the same direction as the height direction of the tank 1, and a water vapor collecting tube 8 is arranged at one side of the bottom in the tank 1, and the water vapor collecting tube 8 is used for recovering water vapor at the side.

Among the above-mentioned technical scheme, because vapor flows from top to bottom in jar body 1, consequently be provided with vapor collecting pipe 8 in the bottom of jar body 1, vapor collecting pipe 8 can retrieve the vapor after the heat transfer, avoids the heat waste of vapor to do benefit to the follow-up temperature control to the water gas reaction through heating pipe 7 in the second reaction zone 5.

In some embodiments, a heating pipe 7 is further disposed in the reaction pipe 2, the heating pipe 7 is communicated with a water vapor collecting pipe 8, the heating pipe 7 is disposed through the second reaction zone 5 for heating the reaction gas in the second reaction zone 5, and the second reaction zone 5 is formed between an outer wall of the heating pipe 7 and an inner wall of the hydrogen separation part 3.

Among the above-mentioned technical scheme, through be provided with heating pipe 7 in reaction tube 2, because the temperature that first reaction zone 4 and second reaction zone 5 demand is different, the demand temperature of first reaction zone 4 is higher than second reaction zone 5, consequently through be provided with heating pipe 7 in second reaction zone 5, and this heating pipe 7 and vapor collecting pipe 8 intercommunication, just can retrieve the vapor behind the first reaction zone 4 heat transfer, then the vapor temperature is because the heat exchange can reduce, the temperature that gets into heating pipe 7 just can heat the temperature of the relatively low water gas reaction of demand, the vapor of temperature accords with the heat transfer temperature in the second reaction zone 5 more this moment, and then improved the utilization ratio to the vapor, and improve the formation rate of hydrogen through the two-stage reaction. Meanwhile, the heating pipe 7 penetrates through the second reaction zone 5, so that the temperature of the second reaction zone 5 can reach a preset temperature, the reaction efficiency of the second reaction zone 5 is accelerated, and the efficiency of hydrogen production is further ensured.

Wherein, the heating pipe 7 is arranged coaxially with the reaction pipe 2, so that the heating pipe 7 heats the water gas in the second reaction area 5 more uniformly, and the hydrogen production rate is further ensured.

In some embodiments, the inner wall of the reaction tube 2 is provided with a first catalyst coating layer for catalyzing the reforming cracking reaction in the first reaction zone 4; the outer wall of the heating pipe 7 is provided with a second catalyst coating for catalyzing the water gas reaction in the second reaction zone 5.

Because the first catalyst coating and the second catalyst coating are thin, on one hand, the use amount of the catalyst can be reduced, the cost is reduced, the unnecessary use amount of the catalyst bed is greatly increased without a filling mode, the pressure drop loss of gas circulation in the pipe is reduced without a filling bed, the circulation is improved, on the other hand, the catalysts are uniformly distributed, local hot spots or coking caused by uneven heating can be avoided, the reaction contact area is also improved, and the use rate of the catalyst coating is improved.

Wherein the first catalyst coating layer may be a Cu alloy, etc., and when the methanol-water mixture gas flows through the first reaction zone 4 in the reaction tube 2, on one hand, the reaction temperature is reached at the side of the reaction tube 2 having the catalyst layer due to heat exchange with the outer wall of the reaction tube 2, the hydrogen concentration is high at the first catalyst coating layer, and the second reaction zone 5 is close to the side of the hydrogen separation part 3, i.e., the outer wall of the hydrogen separation part 3 is a stainless steel tube having a gap of about 0.2 μm, on which a palladium alloy coating layer of about 70 μm is coated, and the gap between the palladium alloy coating layer and the stainless steel tube is adjusted by a nickel alloy, etc. to prevent hydrogen leakage, so that the hydrogen concentration is higher at the side of the first reaction zone 4 close to the inner wall of the reaction tube 2 than at the side of the second reaction zone 5 close to the hydrogen separation part 3 due to concentration and pressure difference, therefore, the hydrogen in the first reaction zone 4 can also diffuse towards the hydrogen separation part 3 due to the concentration difference, so that the hydrogen enters the hydrogen separation part 3, and the separation rate of the hydrogen entering the hydrogen separation part 3 from the first reaction zone 4 is improved. Similarly, the second reaction zone 5 is also suitable, since the second catalyst coating is located on the outer wall of the heating tube 7, and the process is not described in detail here.

In some embodiments, the hydrogen separation part 3 has one side abutting against the bottom of the reaction tube 2 and the other side having a gap with the top of the reaction tube 2 so that the first reaction zone 4 communicates with the second reaction zone 5, the bottom of the first reaction zone 4 communicates with the second inlet b, and the bottom of the second reaction zone 5 has the reaction gas exhaust port d.

Among the above-mentioned technical scheme, because the entering of the methanol-water mist in first reaction zone 4 is by supreme down, consequently, through hydrogen separation portion 3 and 2 bottom butts of reaction tube, make first reaction zone 4 completely isolated with second reaction zone 5 below, ensure the independence of the methanol-water mist that gets into in first reaction zone 4, can not get into second reaction zone 5, and have the clearance between the top of hydrogen separation portion 3 and reaction tube 2, make the reaction gas after reforming and cracking reaction reentrant to carry out the water gas reaction in second reaction zone 5, make first reaction zone 4 and second reaction zone 5 be the U-shaped runner, ensure mutual independence and the intercommunication after the reaction of twice reactions.

In some embodiments, the hydrogen separation part 3 is a tubular structure, a tube cavity in the hydrogen separation part 3 is used for hydrogen circulation and export, and the inside and outside of the hydrogen separation part 3 are both provided with separation membranes, and the separation membranes are used for hydrogen on the corresponding sides of the first reaction zone 4 and the second reaction zone 5 to pass through the separation membranes and enter the tube cavity.

Wherein, the outer wall of the hydrogen separation part 3 is a palladium alloy coating with about 70 μm coated on a stainless steel pipe with about 0.2 μm gap, the palladium alloy coating forms the separation membrane, and the gap between the palladium alloy coating and the stainless steel pipe is adjusted by nickel alloy and the like to prevent hydrogen leakage, so that the hydrogen is continuously separated from one side close to the inner wall of the reaction pipe 2 and enters the pipe cavity of the hydrogen separation part 3 due to concentration and pressure difference, thereby improving the separation rate of the hydrogen.

In some embodiments, the reaction tube 2 is provided in plural, and the plural reaction tubes 2 are uniformly distributed in the tank 1 along the circumferential direction thereof.

Among the above-mentioned technical scheme, establish to a plurality ofly through the quantity with the internal reaction tube 2 of jar, a plurality of reaction tubes 2 can carry out hydrogen production reaction simultaneously to let in jar vapor in 1 and also can carry out the heat transfer to a plurality of reaction tubes 2 simultaneously, improved the utilization ratio of heat energy, and also improved the productivity of hydrogen energy. Simultaneously, with a plurality of reaction tubes 2 at jar body 1 internal peripheral evenly distributed for the heat energy that a plurality of reaction tubes 2 received is more even, thereby is more accurate to the temperature control of reaction tubes 2.

In some embodiments, the preheating pipe 10 is located in the region enclosed by the plurality of reaction tubes 2, and one end of the preheating pipe 10 away from the second inlet b enters the first reaction zone 4 in each reaction tube 2 through a distribution pipe.

In the above technical solution, the preheating pipe 10 distributes the preheated methanol-water mixture at the bottom of the tank body 1 through a distribution pipe, so that the preheated methanol-water mixture can uniformly enter the bottom of each reaction pipe 2, thereby performing the reforming reaction.

In some embodiments, the preheater tubes 10 are in a U-shaped or S-shaped flow path arrangement.

In the above technical scheme, the S-shaped flow channel can increase the heat exchange area between the preheating pipe 10 and the steam, thereby improving the preheating effect of the steam on the preheating pipe 10.

It should be noted that, in operation, if the utilization rate of the unused reaction gas in the reaction off-gas needs to be increased, the reaction off-gas at the reaction gas exhaust port d and the new reaction gas can be mixed in a certain proportion and introduced from the second inlet b for further reaction, and the reduced-temperature steam exhausted from the steam exhaust port can be re-introduced from the first inlet for heating operation after being pressurized by the thermal cycle. If the reaction speed of the hydrogen needs to be accelerated, namely the hydrogen response is fast, namely the response to the load driven by the fuel cell is fast, the flow rate of the reaction gas can be increased, meanwhile, the tail gas at the reaction gas exhaust port d is much unused, the tail gas circulation proportion can also be increased, and as the purity of the separated hydrogen of the separation membrane is close to 100%, the reaction speed in the reaction tube 2 can not cause any influence on the purity of the hydrogen product.

The temperature in the equipment of the reformer can be controlled by only controlling the flow of the steam pressure of the inlet air at the first inlet, and the temperature of the reaction wall of the corresponding reaction tube 2, the temperature of the reaction wall of the heating tube 7 and the temperature of the outer wall of the preheating tube 10 can be automatically determined according to the thermodynamic characteristics of all components through the theory of thermodynamic exchange without the need of regulating by an external control temperature measuring device. On one hand, the test control has the problem of low precision and inaccurate response, on the other hand, the additional introduction of the devices also increases the structural complexity and the cost of the equipment, and for a regulating loop for controlling the temperature, the regulating loop has the fluctuation depending on a feedback mechanism and has the fluctuation instability of the temperature, and the design utilizes the inherent physical property of thermodynamics and achieves the requirement of self-stabilizing temperature control through a flow channel design.

In summary, the efficient temperature control membrane reformer has the following advantages:

1. the temperature control is stable, the fluctuation is small, the heat transfer is uniform by utilizing the mode that water vapor exchanges heat with the wall in the tank body, and the temperature is not easy to fluctuate due to the large specific heat capacity of water. Because the heat exchange is temperature difference multiplied by component heat capacity multiplied by component flow, and the heat transfer is temperature gradient/heat resistance, for the corresponding reaction gas flow, the corresponding reaction wall temperature can be fixed only by designing the corresponding heat exchange wall thickness and the steam pressure.

2. The temperature control is accurate, the temperature in the tank body 1 of the equipment is controlled, the pressure flow of the steam which is fed in is controlled correspondingly to the flow of the corresponding reaction gas, and the temperature of the reaction wall of the corresponding reaction tube 2, the temperature of the reaction wall of the heating tube 7 and the temperature of the preheating tube 10 can be automatically determined according to the thermodynamic characteristics of all components through the theory of thermodynamic exchange without the adjustment of an external control temperature measuring device.

3. The temperature control mode is simple. The reaction temperature which is reduced step by step is controlled without using a plurality of groups of heat sources, the characteristic that the reaction temperature is reduced by two steps is utilized, the water vapor which is transferred with the first step (namely the preheating pipe 10 and the reaction pipe 2) and is cooled is introduced into the heating pipe 7 to be transferred with the second step, and because the heat is the temperature difference multiplied by the component heat capacity multiplied by the component flow, the first-class three-heat effect can be realized only by calculating according to the heat transfer coefficient and the flow, so the design is simple. And the two-stage reaction is designed in the interlayer in the middle of the reaction tube 2, so that the reaction process is simplified and designed, the heat loss is minimized, and the heat energy is utilized to the maximum extent.

4. The equipment volume is small, and the cost efficiency is improved. The required volume of the tank body is small, and the reformer equipment can be made simply because the steam heat capacity is large and the required volume of the same heat transfer quantity is small. The structure is simple: the temperature control mode is simple, and the complicated temperature control and devices are reduced, so the structural design of the reformer is simple. The cost is low: because the volume is small, the structural design is simple, the required complex devices are few, the catalyst consumption is small, and the service life of the catalyst in the reaction is prolonged by stable temperature control, the cost brought by the method is reduced. Weight: the catalyst is coated without filling, and an additional temperature adjusting device is omitted, so that the overall weight is reduced. The heat loss is small: the precise temperature control design does not cause additional heat loss due to fluctuation, and the design of utilizing the temperature difference among the multilayer tubes also minimizes the heat loss.

5. The operation is convenient and flexible, in use, if the reaction speed is high, namely the hydrogen response is high, namely the response to the load driven by the fuel cell is high, the flow rate of the reaction gas can be increased, meanwhile, the unused reaction gas in the tail gas is more, and the tail gas circulation proportion can be increased to meet the hydrogen demand, so that the flow channel temperature control design utilizing the water vapor to transfer heat can flexibly operate and respond, a complex element device sensing temperature control system is not needed, and the demands of different hydrogen flows are met.

6. The suitability for PEM is high. The fuel cell has high matching performance, if the hydrogen demand is suddenly increased, the temperature of the common reformer is not reached, so that the hydrogen production is small and the reverse pole of the pile is caused. If the hydrogen demand is suddenly reduced, the temperature reduction process of the common reformer can cause a local hot area, and the design can achieve the effect by only reducing the flow of the steam.

7. The reaction progress is high. By using the membrane separation method of coating a catalyst on the reaction wall side of the reaction tube 2, hydrogen is generated by the reaction, and the hydrogen concentration is reduced by separation, so that the hydrogen concentration difference is increased, the hydrogen separation diffusivity is increased, and the reaction conversion rate is also improved. The reformer size can be reduced due to the continuous separation of hydrogen.

8. High hydrogen production purity, low pressure drop and low catalyst requirement. The hydrogen production purity is high by the way of membrane separation while controlling the temperature, the complicated subsequent purification operation equipment is saved, and the hydrogen fuel cell can be matched with the hydrogen fuel cell to realize closed operation in one step. The method has the advantages of no influence on the purity of hydrogen caused by the selection of the reaction rate and the catalyst, low requirement on the catalyst and cost reduction. A significant problem with membrane reformers is pressure drop, where the flow-through pressure drop is reduced by coating the catalyst in the reaction layer. And the coating has small dosage, reduces the overall cost of the system and the weight, and on the other hand, the catalysts are uniformly distributed, so that local hot spots or coking caused by uneven heating can be avoided, the reaction contact area is also increased, and the utilization rate of the catalysts is increased.

The overall process of the reforming reaction is: after reaching the steam inlet pipe 9 from the first inlet a at the top of the tank 1, the high-temperature and high-pressure steam uniformly enters the tank 1 of the reformer through the steam distribution pipe 14, the mixed gas exchanges heat with the mixed gas of methanol and water from bottom to top through the pipe wall of a preheating pipe 10 to preheat the mixed gas of methanol and water, the preheating pipe 10 is distributed at the bottom of a tank body 1 through a reaction gas distribution pipe 11 to ensure that the mixed gas of methanol and water uniformly enters a first reaction zone 4 in the bottom of each reaction pipe 2, the mixed gas of methanol and water carries out reforming reaction in the first reaction zone 4, the mixed gas of methanol and water after the reforming reaction is converged in a top zone and then enters a second reaction zone 5, and performing water gas reaction, further reacting the reaction gas, and then improving the hydrogen conversion rate, collecting the reaction gas of each reaction tube under the collecting action of the reaction tail gas collecting tube 13, and then merging the reaction gas from the reaction gas outlet d and discharging the merged reaction gas. Meanwhile, the water vapor distributed in the tank body 1 exchanges heat with the outer wall of the reaction tube 2 through the tube wall to provide stable heat for the reaction tube 2, so that the first reaction zone 4 is at a corresponding reaction temperature. The water vapor entering the bottom enters the water vapor collecting pipe 8 and then is redistributed, and enters the heating pipe 7 of each reaction pipe 2, the heating pipe 7 can heat the reaction gas in the second reaction zone 5, the water vapor is converged at the top of the heating pipe 7 and then leaves from the water vapor outlet e at the top of the tank body 1, and the hydrogen generated in the first reaction zone 4 and the second reaction zone 5 is separated and guided by the hydrogen separating part 3 and then is discharged from the hydrogen outlet c of the hydrogen collecting pipe 12 at the bottom.

It should be noted that the features of the embodiments in the present application may be combined with each other without conflict.

The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. An efficient temperature control membrane reformer, comprising:

the tank body is provided with a first inlet and a second inlet which are oppositely arranged, the first inlet is used for inputting water vapor into the tank body, and the second inlet is used for inputting methanol-water mixed gas into the tank body;

the reaction tube is arranged in the tank body and used for reforming the methanol-water mixed gas to produce hydrogen, and the steam is used for increasing the environmental temperature in the tank body;

the reaction tube is internally provided with an annular hydrogen separation part, the hydrogen separation part extends along the axial direction of the reaction tube so as to divide the inner space of the reaction tube into a first reaction area and a second reaction area, and the first reaction area is closer to the outer wall of the reaction tube than the second reaction area; the first reaction zone is communicated with the second inlet, the first reaction zone is used for carrying out reforming cracking reaction, the first reaction zone is partially communicated with the second reaction zone so that reaction gas after the reforming cracking reaction in the first reaction zone can enter the second reaction zone, the second reaction zone is used for carrying out water gas reaction, the hydrogen separation part is used for separating and leading out hydrogen generated by the first reaction zone and the second reaction zone, and the bottom of the second reaction zone is communicated with a reaction gas outlet.

2. The efficient temperature controlled membrane reformer according to claim 1, wherein a preheating pipe is further disposed between the second inlet and the first reaction zone of the reaction pipe, the preheating pipe is located in the tank body, and an outer wall of the preheating pipe contacts with the steam in the tank body to preheat the methanol-water mixed gas flowing through the preheating pipe.

3. A high efficiency temperature controlled membrane reformer as claimed in claim 2, wherein said first inlet is located at the top of said tank, said second inlet is located at the bottom of said tank, said reaction tubes are arranged in the same direction as the height of said tank, and a steam collecting tube is provided at one side of the bottom of said tank for collecting the steam at the side.

4. The efficient temperature-controlled membrane reformer according to claim 3, wherein a heating pipe is further disposed in the reaction pipe, the heating pipe is communicated with the steam collecting pipe, the heating pipe is penetratingly disposed in the second reaction zone for heating the reaction gas in the second reaction zone, and the second reaction zone is formed between an outer wall of the heating pipe and an inner wall of the hydrogen separation part.

5. The efficient temperature controlled membrane reformer according to claim 4, wherein the inner walls of said reaction tubes are provided with a first catalyst coating for catalyzing the reforming cracking reaction in said first reaction zone; and the outer wall of the heating pipe is provided with a second catalyst coating for catalyzing the water gas reaction in the second reaction zone.

6. The temperature-efficient membrane reformer according to claim 5, wherein one side of the hydrogen separation part abuts against a bottom of the reaction tube, and the other side of the hydrogen separation part has a gap from a top of the reaction tube, so that the first reaction region communicates with the second reaction region, the bottom of the first reaction region communicates with the second inlet, and the bottom of the second reaction region has the reactant gas exhaust port.

7. The efficient temperature control membrane reformer according to claim 6, wherein the hydrogen separation part is a tubular structure, a tubular cavity in the hydrogen separation part is used for hydrogen circulation and discharge, and separation membranes are arranged on the inner side and the outer side of the hydrogen separation part and are used for allowing hydrogen on the corresponding sides of the first reaction zone and the second reaction zone to pass through the separation membranes and enter the tubular cavity.

8. An efficient temperature controlled membrane reformer as claimed in any of claims 2 to 7 wherein said reaction tubes are provided in plurality and said plurality of reaction tubes are uniformly distributed along the circumference of said tank body.

9. A high efficiency temperature controlled membrane reformer as claimed in claim 8, wherein said preheat tubes are located in the region enclosed by said plurality of reaction tubes, and the ends of said preheat tubes remote from said second inlet are passed through distribution tubes into said first reaction zone in each reaction tube.

10. The efficient temperature controlled membrane reformer according to claim 9, wherein the preheat tubes are in a U-shaped or S-shaped flow path arrangement.

Images