A methanol reforming hydrogen production system and method based on catalytic combustion

Abstract

The application provides a methanol reforming hydrogen production system and method based on catalytic combustion, which integrates a preheater, a vaporizer and a reformer into an integrated reforming device, integrates a hydrogen-rich heater, a purification device and a methanation device into an integrated purification device, greatly simplifies the equipment volume and the system process flow, adds a combustion raw material supply unit for providing combustion raw materials for starting and running of the vaporizer and the reformer, uses high-temperature combustion tail gas generated by combustion of the combustion raw materials to preheat the integrated purification device and provide heat for the preheater, and simultaneously introduces purified tail gas into the vaporizer to replace combustion of methanol and an oxidant, provides heat for methanol water vaporization, and uses the methanol reforming hydrogen production system to achieve a methanol conversion rate of > 98%, a purification efficiency of 60% to 90% that can be adjusted, a hydrogen flow of 1 Nm 3 / h to 100 Nm 3 / h, a purity of the purified hydrogen of > 99.999%, and a CO content of < 0.1 ppm.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of methanol reforming hydrogen production, and further relates to a methanol reforming hydrogen production system and method based on catalytic combustion. BACKGROUND

[0002] Hydrogen energy is a new type of energy with wide sources, clean and low carbon, flexibility and high efficiency, and rich application scenarios, and has unique advantages of storage and power generation, and is one of the best solutions for large-scale and cross-seasonal storage and transportation of renewable energy.

[0003] Methanol has the highest hydrogen-carbon ratio, and its liquid storage and filling process is very convenient, so it is an important high-density hydrogen storage carrier. The methanol reforming hydrogen production reaction has low temperature and mature technology. The traditional methanol reforming hydrogen production reaction temperature is 200-300℃, and a pressure swing adsorption device is often connected to purify hydrogen. However, most of the preheating, evaporation, reforming and heating modules are isolated, and the equipment used in each module is large in size, long in pipeline process and complex in system.

[0004] Moreover, the traditional methanol reforming hydrogen production heating often uses an intermediate heat transfer carrier such as heat conducting oil to provide heat for the reaction, but the heat conducting oil is prone to cracking and deterioration during long-term use, which poses a safety hazard. The use of heat conducting oil requires the provision of high-temperature oil pumps, expansion tanks, heat conducting oil furnaces and other equipment, which further causes the system to be complex and large in size, and is not conducive to integration. At the same time, the pressure swing adsorption device is arranged in a complex manner, and a large amount of adsorbent is required for purifying hydrogen, which limits the miniaturization of methanol reforming hydrogen production and the use of limited space scenarios.

[0005] Chinese patent document CN105152133A discloses an online high-purity hydrogen production system for a fuel cell and a control method thereof, which uses methanol catalytic combustion to heat the entire system, but separates the reforming reactor, vaporizer and heat exchanger, resulting in more system components, complex equipment pipelines, large heat loss, low heat and mass transfer performance of the heat exchanger, slow heat response speed, and no integration of reforming and combustion and no integration of the purification unit.

[0006] Chinese patent document CN112142004A discloses a methanol water reforming reaction hydrogen production and purification method, in which the methanol water heat exchange, vaporization, superheating and reforming equipment are independently separated, and most of them adopt a shell-and-tube mode, which is large in size. At the same time, the heat source is in the form of an electric heater, and in order to meet the pressure swing adsorption purification mode, the heat is mostly cooled, resulting in a complex system, large heat loss and low energy consumption. SUMMARY

[0007] In view of the problems of complex methanol reforming hydrogen production system, large space occupation and high operation cost in the prior art, the present application aims to provide a methanol reforming hydrogen production system and method based on catalytic combustion, which integrates a preheater, a vaporizer and a reformer into an integrated reforming device, and integrates a hydrogen-rich heater, a purification device and a methanation device into an integrated purification device, thereby greatly simplifying the equipment volume and system process; a combustion raw material supply unit is additionally provided to provide combustion raw materials for starting and running of the vaporizer and the reformer, high-temperature combustion tail gas generated by combustion of the combustion raw materials is used to preheat the integrated purification device and provide heat for the preheater, and the purified tail gas is introduced into the vaporizer to replace combustion of methanol and oxidant, thereby greatly improving the energy utilization rate.

[0008] In order to achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0009] A methanol reforming hydrogen production system based on catalytic combustion, comprising an integrated reforming device, an integrated purification device, a methanol water raw material supply unit and a cooler; the integrated reforming device comprises a preheater, a vaporizer and a reformer arranged in sequence along the material flow direction; the reformer is provided with a methanol gas reforming area, and the methanol gas reforming area is provided with a reforming gas outlet; the vaporizer is provided with a methanol water vaporization area; the preheater is provided with a methanol water preheating area, the methanol water preheating area is communicated with the methanol water raw material supply unit, and the methanol water raw material supply unit is used to provide methanol water raw materials for the preheater; the methanol water preheating area, the methanol water vaporization area and the methanol gas reforming area are communicated in sequence; the integrated purification device comprises a hydrogen-rich gas heater, a purification device and a methanation device arranged in sequence along the material flow direction; the hydrogen-rich gas heater is provided with a first hydrogen-rich gas inlet and a hydrogen-rich gas outlet, and the first hydrogen-rich gas inlet is communicated with the reforming gas outlet; the purification device is provided with a second hydrogen-rich gas inlet and a purified hydrogen gas outlet, the second hydrogen-rich gas inlet is connected with the hydrogen-rich gas outlet, and the purified hydrogen gas outlet is communicated with the inlet of the methanation device; and the cooler is provided with a purified hydrogen gas inlet, and the purified hydrogen gas inlet is communicated with the outlet of the methanation device.

[0010] In some technical solutions, the methanol reforming hydrogen production system further comprises a combustion raw material supply unit, the combustion raw material supply unit comprising a methanol storage tank and an oxidant storage tank; the cooler is further provided with a third combustion tail gas inlet; the vaporizer is further provided with a vaporization heating area, the vaporization heating area being provided with a first combustion raw material inlet and a first combustion tail gas outlet, the first combustion raw material inlet being connected with the methanol storage tank and the oxidant storage tank respectively; the reformer is further provided with a reforming heating area, the reforming heating area being provided with a second combustion raw material inlet and a second combustion tail gas outlet, the second combustion raw material inlet being connected with the methanol storage tank and the oxidant storage tank respectively; the hydrogen-rich gas heater is further provided with a first preheating tail gas inlet and a first preheating tail gas outlet, the first preheating tail gas inlet being in communication with the first combustion tail gas outlet and the second combustion tail gas outlet respectively; the purification device is further provided with a second preheating tail gas inlet and a second preheating tail gas outlet, the second preheating tail gas inlet being in communication with the first preheating tail gas outlet, and the second preheating tail gas outlet being in communication with the third combustion tail gas inlet; the preheater is further provided with a heating area, the heating area being provided with a third preheating tail gas inlet and a third preheating tail gas outlet; the third preheating tail gas inlet is in communication with the second preheating tail gas outlet, for preheating the methanol water raw material by using high-temperature combustion tail gas; and the third preheating tail gas outlet is in communication with the third combustion tail gas inlet.

[0011] In some technical solutions, the purification device is further provided with a purification tail gas outlet, and the vaporization heating area is provided with a purification tail gas inlet; the purification tail gas outlet is in communication with the purification tail gas inlet, for providing the purification tail gas combusted with the oxidant to the vaporization heating area; and a high-temperature adjusting valve is arranged on a pipeline between the purification tail gas outlet and the purification tail gas inlet.

[0012] In some technical solutions, the methanol gas reforming area is provided with a methanol gas reforming flow channel, and the methanol gas reforming flow channel is provided with a reforming catalyst; and the methanol water vaporization area is provided with a methanol water vaporization flow channel.

[0013] In some technical solutions, the reforming heating area and the vaporization heating area are both provided with a combustion catalyst flow channel, the combustion catalyst flow channel being provided with a combustion catalyst, and the combustion catalyst being used for catalyzing the combustion of the methanol and the oxidant.

[0014] In some technical solutions, the hydrogen-rich gas heater further comprises a preheating tail gas heating coil, the preheating tail gas heating coil being arranged around an outer wall of the purification device, an inlet of the preheating tail gas heating coil being connected with the first preheating tail gas outlet, an outlet of the preheating tail gas heating coil being connected with the third combustion tail gas inlet, and the preheating tail gas heating coil being used for preheating the purification device by using the heat of the combustion tail gas.

[0015] In some technical solutions, the cooler is further provided with a purified hydrogen outlet and a third combustion tail gas outlet; and the methanol reforming hydrogen production system further comprises a hydrogen back pressure valve and a tail gas back pressure valve, the hydrogen back pressure valve being communicated with the purified hydrogen outlet, and the tail gas back pressure valve being communicated with the third combustion tail gas outlet.

[0016] In some technical solutions, the integrated reforming device and the integrated purification device are an integrated structure, and an outer wall of the integrated structure is coated with thermal insulation material.

[0017] The application further provides a methanol reforming hydrogen production method based on catalytic combustion, which is applied to the methanol reforming hydrogen production system and has the characteristics that the method comprises the following steps:

[0018] S1, the methanol water supply unit supplies methanol water raw materials into the preheater, the preheated methanol water raw materials are vaporized in the vaporizer, and then are reformed in the reformer to obtain hydrogen-rich gas;

[0019] S2, the hydrogen-rich gas is heated by the hydrogen-rich gas heater, and then is purified in the purification equipment to obtain purified hydrogen, and the methanation equipment removes impurities in the purified hydrogen and sends the purified hydrogen into the cooler, and the purified hydrogen is cooled by the cooler and then is discharged into a downstream gas utilization device.

[0020] In some technical solutions, the methanol reforming hydrogen production method further comprises the following step S3: the purification tail gas enters the vaporization heating area to burn and provide heat, and the combustion tail gas generated in the vaporization heating area and the reforming heating area successively enters the hydrogen-rich gas heater, the purification equipment and the preheater to provide heat.

[0021] Compared with the prior art, the methanol reforming hydrogen production system based on catalytic combustion has the following beneficial effects:

[0022] 1, the methanol reforming hydrogen production system integrates the preheater, the vaporizer and the reformer into an integrated reforming device, and integrates the hydrogen-rich heater, the purification equipment and the methanation equipment into an integrated purification device, so that the equipment volume and the system process flow are greatly simplified;

[0023] 2, the methanol reforming hydrogen production system is provided with a combustion raw material supply unit for providing combustion raw materials for starting and running of the vaporizer and the reformer, high-temperature tail gas generated by combustion of the combustion raw materials enters the integrated purification device, the hydrogen-rich heater and the purification equipment are preheated before the methanol reforming hydrogen production process starts, and at the same time, the combustion tail gas of the integrated purification device after preheating enters the preheater to provide heat for the preheater, so that the heat energy utilization rate of the combustion tail gas is greatly improved;

[0024] 3、The purification tail gas purified by the purification equipment in the application enters the vaporizer, replaces the combustion of methanol and oxidant to release heat, provides heat for the vaporization of methanol and water, and further improves the heat energy utilization rate of the whole system;

[0025] 4、The application sets the hydrogen back pressure valve and the tail gas back pressure valve, the purified hydrogen is discharged into the downstream gas device after being adjusted in pressure by the hydrogen back pressure valve, the pressure adjusting range of the hydrogen back pressure valve is normal pressure-2MPa, the combustion tail gas is discharged out of the system after being adjusted in pressure by the tail gas back pressure valve, the pressure adjusting range of the tail gas back pressure valve is normal pressure-6MPa, which can effectively maintain the stability of the internal pressure of the system when discharging the combustion tail gas and the purified hydrogen;

[0026] 5、The integrated reforming device and the integrated purification device are integrated in the application, and the outer wall of the integrated structure is coated with thermal insulation material, which solves the problems of large heat leakage and heat loss, and also reduces the amount of thermal insulation material.

[0027] 6、The methanol reforming hydrogen production system provided by the application can realize a methanol conversion rate of >98%, a purification efficiency of 60%-90% adjustable, a hydrogen flow of between 1Nm 3 / h and 100Nm 3 / h, a purity of the purified hydrogen of >99.999%, and a CO content of <0.1ppm. Meanwhile, the system has the advantages of high system energy efficiency, high volume energy density, short start-up time and easy amplification, and is suitable for market promotion and use. BRIEF DESCRIPTION OF DRAWINGS

[0028] The above-mentioned characteristics, technical features, advantages and implementation modes of the application will be further described in the following in a clear and understandable manner in combination with the preferred embodiments and the accompanying drawings.

[0029] Figure 1 The overall structure schematic diagram of the methanol reforming hydrogen production system based on catalytic combustion provided by the application is shown in the figure.

[0030] Figure 2 The front view of the integrated reforming device provided by the application is shown in the figure.

[0031] Figure 3 The left view of the integrated reforming device provided by the application is shown in the figure.

[0032] Figure 4 The top view of the integrated reforming device provided by the application is shown in the figure.

[0033] Figure 5 The structure schematic diagram of the cross flow channel provided by the application is shown in the figure.

[0034] Figure 6 The structure schematic diagram of the integrated purification unit provided by the application is shown in the figure.

[0035] BRIEF DESCRIPTION OF DRAWINGS

[0036] 1 - Preheater; 101 - Methanol water inlet; 102 - Third preheated tail gas inlet; 103 - Third preheated tail gas outlet;

[0037] 2 - Vaporizer; 201 - First oxidant supply inlet; 202 - First methanol supply inlet; 203 - First combustion tail gas outlet; 204 - Purified tail gas inlet;

[0038] 3 - Reformer; 301 - Second oxidant supply inlet; 302 - Second methanol supply inlet; 303 - Reformed gas outlet; 304 - Second combustion tail gas outlet;

[0039] 4 - Hydrogen-rich gas heater; 401 - First hydrogen-rich gas inlet; 402 - First preheated tail gas inlet; 403 - Hydrogen-rich gas outlet; 404 - First preheated tail gas outlet; 405 - Preheated tail gas heating coil; 406 - Combustion tail gas coil inlet; 407 - Combustion tail gas coil outlet;

[0040] 5 - Purification device; 501 - Purified tail gas outlet; 502 - Second preheated tail gas outlet; 503 - Second hydrogen-rich gas inlet; 504 - Purified hydrogen gas outlet;

[0041] 6 - Methanation device;

[0042] 7 - Cooler; 701 - Purified hydrogen gas inlet; 702 - Purified hydrogen gas outlet; 703 - Third combustion tail gas inlet; 704 - Third combustion tail gas outlet; 705 - Hydrogen back pressure valve; 706 - Tail gas back pressure valve;

[0043] 8 - Methanol water storage tank; 9 - Methanol water pump;

[0044] 10 - Methanol storage tank; 11 - Methanol pump; 12 - First methanol supply valve; 13 - Second methanol supply valve;

[0045] 14 - Oxidant storage tank; 15 - Oxidant pump; 16 - First oxidant supply valve; 17 - Second oxidant supply valve;

[0046] 18 - High temperature regulating valve;

[0047] 19 - Combustion catalytic flow passage; 20 - Heating flow passage; 21 - Methanol gas reforming flow passage; 22 - Partition; 23 - Cross flow passage. DETAILED DESCRIPTION

[0048] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, specific embodiments of the present application will be described below with reference to the drawings. Obviously, the drawings in the following description only represent some of the embodiments of the present application, and for those skilled in the art, other drawings can be obtained from these drawings without creative labor, and other embodiments can also be obtained.

[0049] For the sake of simplicity of the drawings, only the parts related to the present application are shown in each drawing, and they do not represent the actual structure of the product. In addition, in order to make the drawings simple and easy to understand, in some drawings, only one of the components with the same structure or function is shown schematically, or only one of them is marked. In this document, "one" not only means "only one", but also means "more than one" situation.

[0050] It should be further understood that the term "and / or" used in the present application and the appended claims means any combination of one or more of the associated listed items and all possible combinations, and includes these combinations.

[0051] In this document, it should be noted that unless otherwise specified and limited, the terms "mounting", "connecting", "connecting" should be understood broadly, for example, it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected, or it can be electrically connected; it can be directly connected, or it can be indirectly connected through an intermediate medium, or it can be the communication inside two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0052] In addition, in the description of the present application, the terms "first", "second" and the like are only used to distinguish the description, and cannot be understood as indicating or implying relative importance.

[0053] Embodiment 1

[0054] As shown in Figure 1 The present embodiment provides a methanol reforming hydrogen production system based on catalytic combustion, which comprises an integrated reforming device, an integrated purification device, a methanol water raw material supply unit and a cooler 7.

[0055] The methanol water raw material supply unit comprises a methanol water storage tank 8 and a methanol water pump 9.

[0056] The integrated reforming device comprises a preheater 1, a vaporizer 2 and a reformer 3 arranged in sequence along the material flow direction.

[0057] The preheater 1 is internally provided with a methanol water preheating area and a heating area. The methanol water preheating area is in communication with a methanol water raw material supply unit. More specifically, the methanol water preheating area is provided with a methanol water inlet 101. A methanol water storage tank 8, a methanol water pump and the methanol water inlet 101 are sequentially connected to supply methanol water raw material into the methanol water preheating area, and the methanol water raw material is preheated by using the heat of the heating area.

[0058] The vaporizer 2 is internally provided with a methanol water vaporizing area and a vaporizing heating area, and the vaporizing heating area is used to provide heat energy for the methanol water vaporizing area.

[0059] The reformer 3 is internally provided with a methanol gas reforming area and a reforming heating area. The methanol gas reforming area is provided with a reforming gas outlet 303, and the reforming heating area is used to provide heat energy for the methanol gas reforming area.

[0060] The above-mentioned methanol water preheating area, methanol water vaporizing area and methanol gas reforming area are sequentially connected to form a methanol water reforming process. Specifically, the methanol water raw material in the methanol water storage tank 8 is pumped into the methanol water preheating area by the methanol water pump 9, preheated and then vaporized in the methanol water vaporizing area to form gaseous methanol (for convenience of description, hereinafter referred to as methanol gas), and then enters the methanol gas reforming area for reforming to obtain reforming gas, which is hydrogen-rich gas. Finally, the reforming gas is discharged from the reforming gas outlet 303 of the integrated reforming device.

[0061] The integrated purification device comprises a hydrogen-rich gas heater 4, a purification device 5 and a methanation device 6 which are sequentially arranged along the material flow direction.

[0062] The hydrogen-rich gas heater 4 is provided with a first hydrogen-rich gas inlet 401 and a hydrogen-rich gas outlet 403. The first hydrogen-rich gas inlet 401 is in communication with the reforming gas outlet 303. The reforming gas (hydrogen-rich gas) discharged from the integrated reforming device enters the hydrogen-rich gas heater 4 from the first hydrogen-rich gas inlet 401 for heating.

[0063] The purification device 5 is provided with a second hydrogen-rich gas inlet 503 and a purified hydrogen gas outlet 504. The second hydrogen-rich gas inlet 503 is connected with the hydrogen-rich gas outlet 403. The hydrogen-rich gas heated by the hydrogen-rich gas heater 4 to a purification working temperature enters the purification device 5 for purification to generate purified tail gas and purified hydrogen gas. The purified hydrogen gas outlet is in communication with the inlet of the methanation device 6. The purified hydrogen gas enters the methanation device 6. The methanation device 6 is used to remove impurities such as CO in the purified hydrogen gas.

[0064] The cooler 7 is provided with a purified hydrogen gas inlet 701 and a purified hydrogen gas outlet 702. The purified hydrogen gas inlet 701 is in communication with the outlet of the methanation device 6. The purified hydrogen gas treated by the methanation device 6 enters the cooler 7 from the purified hydrogen gas inlet 701 for cooling, and then is transmitted to the downstream gas using device through the purified hydrogen gas outlet 702.

[0065] More preferably, a hydrogen back pressure valve 705 is further provided, the purified hydrogen outlet 702 is connected with the hydrogen back pressure valve 705 in sequence, the hydrogen back pressure valve 705 is used to adjust the pressure of the purified hydrogen delivered to the downstream gas using device, and the hydrogen back pressure valve 705 is controlled by an electromagnetic valve switch.

[0066] In summary, the above-mentioned integrated reforming device, integrated purification device, methanol water raw material supply unit and cooler 7 constitute a methanol reforming hydrogen production process, and the specific process is as follows:

[0067] The methanol water raw material in the methanol water storage tank 8 is pumped into the methanol water preheating area of the preheater 1 by the methanol water pump 9, enters the methanol water vaporization area of the vaporizer 2 after preheating, is vaporized into methanol gas at high temperature, and then enters the methanol gas reforming area of the reformer 3 to be reformed. The hydrogen-rich gas obtained by reforming flows from the reforming gas outlet 303 into the first hydrogen-rich gas inlet 401 of the hydrogen-rich gas heater 4, i.e. into the hydrogen-rich gas heater 4 for heating, and then flows from the hydrogen-rich gas outlet 403 of the hydrogen-rich gas heater 4 into the second hydrogen-rich gas inlet 503 of the purification device 5, and is purified in the purification device 5 to generate purified hydrogen gas which enters the inlet of the methanation device 6 from the purified hydrogen gas outlet 504. After removing impurities such as CO in the methanation device 6, the purified hydrogen gas enters the purified hydrogen gas inlet 701 of the cooler 7 from the outlet of the methanation device 6, is cooled by the cooler 7, and is discharged from the purified hydrogen gas outlet 702 after being adjusted in pressure by the hydrogen back pressure valve 705 and is discharged into the downstream gas using device.

[0068] The reformer 3, vaporizer 2 and preheater 1 in the above-mentioned integrated reforming unit are integrated, the hydrogen-rich gas heater 4, purification device 5 and methanation device 6 in the integrated purification unit are integrated, and the integrated reforming unit and the integrated purification unit are both composed of plate type or plate-fin type structure, and more preferably composed of cross type plate-fin heat exchange unit.

[0069] In some embodiments, the above-mentioned integrated reforming device and integrated purification device are integrated into an integrated structure, and the outer wall of the integrated structure is coated with thermal insulation material to form a hot box structure, thereby reducing heat loss and saving the amount of thermal insulation material.

[0070] The alcohol reforming hydrogen production system can achieve a methanol conversion rate of >98%, a purification efficiency of 60%-90% which can be adjusted, a hydrogen flow rate of 1 Nm 3 / h-100 Nm 3 / h, a purity of the purified hydrogen of >99.999%, a CO content of <0.1 ppm, an exhaust pressure of the combustion tail gas which can be adjusted between normal pressure and 6 MPa (tail gas back pressure valve 706), and a hydrogen supply pressure which can be adjusted between normal pressure and 2 MPa (hydrogen back pressure valve 705).

[0071] Example 2

[0072] On the basis of Embodiment 1, as shown in Figure 1 The methanol reforming hydrogen production system further comprises a combustion raw material supply unit, the combustion raw material supply unit comprises a methanol storage tank 10 and an oxidant storage tank 14, and the oxidant stored in the oxidant storage tank 14 is preferably air or pure oxygen.

[0073] The vaporization heating area of the vaporizer 2 is further provided with a first combustion raw material inlet and a first combustion tail gas outlet 203, the first combustion raw material inlet is connected with the methanol storage tank 10 and the oxidant storage tank 14 respectively, and more preferably, the first combustion raw material inlet can be a first oxidant supply inlet 201 and a first methanol supply inlet 202 arranged in the vaporization heating area, the first oxidant supply inlet 201 is connected with the oxidant storage tank 14, and the first methanol supply inlet 202 is connected with the methanol storage tank 10.

[0074] The reforming heating area of the reformer 3 is further provided with a second combustion raw material inlet and a second combustion tail gas outlet 304, the second combustion raw material inlet is connected with the methanol storage tank 10 and the oxidant storage tank 14 respectively, and more preferably, the second combustion raw material inlet can be a second oxidant supply inlet 301 and a second methanol supply inlet 302 arranged in the reforming heating area, the second oxidant supply inlet 301 is connected with the oxidant storage tank 14, and the second methanol supply inlet 302 is connected with the methanol storage tank 10.

[0075] Specifically, the methanol storage tank 10 introduces methanol into the vaporization heating area through the first methanol supply inlet 202, the oxidant storage tank 14 introduces oxidant into the vaporization heating area through the first oxidant supply inlet 201, and the methanol and the oxidant combust and release heat in the vaporization heating area to provide the heat energy required for the methanol water vaporization area.

[0076] The methanol storage tank 10 introduces methanol into the reforming heating area through the second methanol supply inlet 302, the oxidant storage tank 14 introduces oxidant into the reforming heating area through the second oxidant supply inlet 301, and the methanol and the oxidant combust and release heat in the reforming heating area to provide the heat energy required for the methanol gas reforming area.

[0077] In some embodiments, the combustion raw material supply unit is further provided with a methanol pump 11 and an oxidant pump 15, the methanol pump 11 is used to provide power for the methanol sent into the vaporization heating area and the reforming heating area, and the oxidant pump 15 is used to provide power for the oxidant sent into the vaporization heating area and the reforming heating area.

[0078] In some embodiments, the combustion raw material supply unit further comprises a first methanol supply valve 12, a second methanol supply valve 13, a first oxidant supply valve 16, and a second oxidant supply valve 17.

[0079] Specifically, the first methanol feed valve 12 is arranged on the pipeline between the methanol storage tank 10 and the second methanol feed inlet 302, for controlling the amount of methanol sent into the reforming heating area; the second methanol feed valve 13 is arranged on the pipeline between the methanol storage tank 10 and the first methanol feed inlet 202, for controlling the amount of methanol sent into the vaporization heating area.

[0080] The first oxidant feed valve 16 is arranged on the pipeline between the oxidant storage tank 14 and the second oxidant feed inlet 301, for controlling the amount of oxidant sent into the reforming heating area; the second oxidant feed valve 17 is arranged on the pipeline between the oxidant storage tank 14 and the first oxidant feed inlet 201, for controlling the amount of oxidant sent into the vaporization heating area.

[0081] In some embodiments, the cooler 7 is further provided with a third combustion tail gas inlet 703 and a third combustion tail gas outlet 704.

[0082] The hydrogen-rich gas heater 4 is further provided with a first preheating tail gas inlet 402 and a first preheating tail gas outlet 404, and the first preheating tail gas inlet 402 is in communication with the first combustion tail gas outlet 203 of the vaporization heating area and the second combustion tail gas outlet 304 of the reforming heating area, respectively. The combustion tail gas generated by the combustion of methanol and oxidant in the vaporization heating area enters the hydrogen-rich gas heater 4 through the first combustion tail gas outlet 203 and the first preheating tail gas inlet 402 in sequence, and at the same time, the combustion tail gas generated by the combustion of methanol and oxidant in the reforming heating area enters the hydrogen-rich gas heater 4 through the second combustion tail gas outlet 304 and the first preheating tail gas inlet 402 in sequence, and the combustion tail gas is used to preheat the hydrogen-rich gas heater 4.

[0083] The purification device 5 is further provided with a second preheating tail gas inlet and a second preheating tail gas outlet 502, and the second preheating tail gas inlet is in communication with the first preheating tail gas outlet 404 of the hydrogen-rich gas heater 4. After the combustion tail gas preheats the hydrogen-rich gas heater 4, it enters the purification device 5 through the first preheating tail gas outlet 404 and the second preheating tail gas inlet in sequence, and the combustion tail gas preheats the purification device 5.

[0084] The second preheating tail gas outlet 502 of the purification device 5 is in communication with the third combustion tail gas inlet 703 of the cooler 7, the preheated purification device 5 discharges the combustion tail gas from the second preheating tail gas outlet 502, enters the cooler 7 through the third combustion tail gas inlet 703, and is discharged from the third combustion tail gas outlet 704 of the cooler 7 after being cooled.

[0085] In some embodiments, the methanol reforming hydrogen production system is further provided with a tail gas back pressure valve 706, and the third combustion tail gas outlet 704 is connected to the tail gas back pressure valve 706 in sequence, for adjusting the pressure of the combustion tail gas discharged from the third combustion tail gas outlet 704, and the tail gas back pressure valve 706 is controlled by an electromagnetic valve switch.

[0086] In some embodiments, the cooler 7 can adopt a three-stream heat exchanger such as a plate type, plate-fin type, etc., two streams of gas being the purified tail gas entering from the third combustion tail gas inlet 703 and the high-purity hydrogen gas entering from the purified hydrogen gas inlet, and the cooling medium can adopt cooling water, ethylene glycol water, etc.

[0087] The system also has a preheating process. Specifically, before formally starting the methanol reforming hydrogen production process, the methanol pump 11 and the oxidant pump 15 are first started, and the methanol storage tank 10 and the oxidant storage tank 14 respectively introduce methanol and oxidant into the vaporization heating area of the vaporizer 2 and the reforming heating area of the reformer 3. Methanol and oxidant combustion processes occur in the vaporization heating area and the reforming heating area, respectively, and combustion tail gas is generated and a large amount of heat energy is released to preheat the methanol water vaporization area of the vaporizer 2 and the methanol gas reforming area of the reformer 3, respectively.

[0088] Subsequently, the combustion tail gas generated in the vaporization heating area and the reforming heating area enters the first preheating tail gas inlet 402 through the first combustion tail gas outlet 203 and the second combustion tail gas outlet 304, respectively, and the high-temperature combustion tail gas preheats the hydrogen-rich gas heater 4.

[0089] After the hydrogen-rich gas heater 4 is preheated, the combustion tail gas enters the purification equipment 5 through the first preheating tail gas outlet and the second preheating tail gas inlet to preheat the purification equipment 5, and then is discharged from the second preheating tail gas outlet 502 and enters the cooler 7 through the third combustion tail gas inlet 703. The cooled combustion tail gas is discharged from the system through the third combustion tail gas outlet 704 and the tail gas back pressure valve 18.

[0090] After the preheating process is completed, the formal methanol reforming hydrogen production process can be started.

[0091] Example 3

[0092] On the basis of Example 1 and Example 2, the heating area of the preheater 1 is provided with a third preheating tail gas inlet 102 and a third preheating tail gas outlet 103.

[0093] Specifically, the third preheating tail gas inlet 102 communicates with the second preheating tail gas outlet 502 of the purification equipment 5, and the preheated combustion tail gas of the purification equipment 5 enters the third preheating tail gas inlet 102 through the second preheating tail gas outlet 502 to preheat the heating area of the preheater 1 using the heat of the combustion tail gas.

[0094] The third preheating tail gas outlet 103 communicates with the third combustion tail gas inlet 703 of the cooler 7, and the combustion tail gas is discharged into the cooler 7 after preheating the heating area, and is sequentially discharged from the system through the third combustion tail gas outlet 704 and the tail gas back pressure valve 706 after being cooled.

[0095] Example 4

[0096] On the basis of the above-mentioned embodiments 1-3, the purification device 5 is further provided with a purification tail gas outlet 501, and the vaporization heating area of the vaporizer 2 is provided with a purification tail gas inlet 204, the purification tail gas outlet 501 is in communication with the purification tail gas inlet 204, during the hydrogen production process by methanol reforming, the hydrogen-rich gas is purified by the purification device 5 to generate purified hydrogen and purification tail gas, the purified hydrogen enters the methanation device 6, and the purification tail gas is discharged from the purification tail gas outlet 501 and enters the vaporization heating area through the purification tail gas inlet 204 to burn with the oxidant and release heat.

[0097] In some embodiments, a high-temperature regulating valve 18 is arranged on the pipeline between the purification tail gas outlet 501 and the purification tail gas inlet 204.

[0098] During the preheating process, the amount of methanol and the amount of oxidant entering the vaporization heating area are adjusted by adjusting the second methanol supply valve 13 and the second oxidant supply valve 17 to carry out combustion and release heat to preheat the methanol water vaporization area to the reaction temperature of vaporization.

[0099] During the hydrogen production process by methanol reforming, the high-temperature regulating valve 18 is used to adjust the purification tail gas entering the vaporization heating area, at this time the second methanol supply valve 13 can be closed and the second oxidant supply valve 17 remains open to continuously supply oxidant, and the combustion of the purification tail gas and the oxidant releases heat to supply heat energy for the methanol water vaporization of the methanol water vaporization area.

[0100] The pipeline of the first combustion tail gas outlet 203 and the pipeline of the second combustion tail gas outlet 304 are combined into one, that is, the combustion tail gas generated by the combustion of the purification tail gas and the oxidant in the vaporization heating area and the combustion tail gas in the reforming heating area are combined into one, and then enter the hydrogen-rich gas heater 4 together through the first preheating tail gas inlet 402 to be preheated.

[0101] Further, the high-temperature regulating valve 18 adopts a high-temperature and high-pressure sealing form and selects an electric actuator structure, which can realize a reverse flow coefficient / forward flow coefficient < 0.05%, and can also adjust the pressure difference of the purification tail gas before and after the valve to realize the pressure difference adjustment between the methanol water vaporization area and the vaporization heating area in the vaporizer 2.

[0102] Embodiment 5

[0103] On the basis of embodiments 1-4, as shown in Figures 2 to 5 In the reformer 3, the methanol gas reforming area is provided with a methanol gas reforming flow channel 21, and a reforming catalyst is arranged in the methanol gas reforming flow channel 21, preferably, the reforming catalyst is arranged in the methanol gas reforming flow channel 21 in a coating or bulk filling form.

[0104] The reforming catalyst can be in the form of copper-based, nickel-based and noble metal Pt or Pd, and is mainly used to catalyze the reforming reaction of methanol gas. In a high temperature environment, the methanol gas is reformed into hydrogen-rich gas under the action of the reforming catalyst.

[0105] The reforming heating area is provided with a combustion catalytic flow channel 19, and the combustion catalytic flow channel 19 is provided with a combustion catalyst. Preferably, the combustion catalyst is arranged in the combustion catalytic flow channel 19, which can be in the form of coating or integral filling.

[0106] The combustion catalyst can be in the form of nickel-based and noble metal, and is mainly used to catalyze the combustion of methanol and oxidant to release heat.

[0107] The methanol gas reforming flow channel 21 and the combustion catalytic flow channel 19 are separated by a partition plate 22.

[0108] In the vaporizer 2, the methanol water vaporization area is provided with a methanol water vaporization flow channel, which is mainly used for vaporizing the methanol water raw material.

[0109] The vaporization heating area is provided with a combustion catalytic flow channel 19, and the combustion catalytic flow channel 19 is provided with a combustion catalyst. The combustion catalytic flow channel 19 and the combustion catalyst described above are the same as those in the combustion catalytic flow channel 19 and the combustion catalytic flow channel in the reforming heating area, which will not be described here.

[0110] The methanol water vaporization flow channel and the combustion catalytic flow channel 19 are separated by a partition plate 22.

[0111] In the preheater 1, the methanol water preheating area is provided with a methanol water flow channel, and the methanol water flow channel 504 is mainly used to preheat the methanol water raw material pressurized by the methanol water pump 9.

[0112] The heating area is provided with a heating flow channel 20, which is mainly used to preheat the methanol water flow channel with the combustion tail gas discharged from the integrated purification device.

[0113] The methanol water flow channel and the heating flow channel 20 described above are not filled with catalyst, and the two flow channels are separated by a partition plate 22.

[0114] The methanol gas reforming flow channel 21, the combustion catalytic flow channel 19, the methanol water vaporization flow channel, the methanol water flow channel and the heating flow channel 20 described above preferably adopt a cross-type flow channel 23, which can adopt a straight type, a zigzag type, a porous type and a corrugated type flow channel.

[0115] Example 6

[0116] Based on examples 1-5, as Figure 6As shown, the embodiment provides a combination of the hydrogen-rich heater 4 and the purification device 5, specifically: the hydrogen-rich heater 4 further comprises a preheating tail gas heating coil 405, which is arranged around the outer wall of the purification device 5, and the preheating tail gas heating coil 405 has a combustion tail gas coil inlet 406 and a combustion tail gas coil outlet 407, for preheating the purification device 6 by using the heat of the combustion tail gas.

[0117] In the above-mentioned embodiment, the hydrogen-rich heater 4 retains the first preheating tail gas outlet 404, but cancels the second preheating tail gas inlet and the second preheating tail gas outlet 502 of the purification device 5, that is, the combustion tail gas does not enter the purification device 5 for preheating.

[0118] The inlet 406 of the preheating tail gas heating coil is connected with the first preheating tail gas outlet 404 of the hydrogen-rich heater 4, and the outlet 407 of the preheating tail gas heating coil is directly connected with the third combustion tail gas inlet 703 of the cooler 7, or is directly connected with the third preheating tail gas inlet 102 of the heating area in the preheater 1, and the combustion tail gas enters the heating area.

[0119] In summary, in the embodiment, by arranging the surrounding preheating tail gas heating coil 405 on the outer wall of the purification device 5, the combustion tail gas directly enters the preheating tail gas heating coil 405 after preheating the hydrogen-rich heater 4 to preheat the purification device.

[0120] During the process of the methanol reforming hydrogen production process, the reforming gas enters the hydrogen-rich heater 4 from the first hydrogen-rich gas inlet 401, is heated to the purification working temperature, and is sent to the second hydrogen-rich gas inlet 503 from the hydrogen-rich gas outlet 403. The high-temperature hydrogen-rich gas is purified in the purification device 5, the purified hydrogen gas is discharged from the purified hydrogen gas outlet 504 to the methanation device 6, and the purification tail gas is discharged from the purification tail gas outlet 501.

[0121] Embodiment 7

[0122] The embodiment provides a methanol reforming hydrogen production method using the methanol reforming hydrogen production system described in embodiments 1-6, and the specific steps include:

[0123] S1, the methanol water supply unit supplies the methanol water raw material to the methanol water preheating area, the preheated methanol water raw material enters the methanol water vaporization area for vaporization, and then enters the methanol gas reforming area for reforming to obtain hydrogen-rich gas.

[0124] S2, the hydrogen-rich gas is heated by the hydrogen-rich gas heater 4, enters the purification device 5 for purification to obtain purified hydrogen gas and purification tail gas, and the methanation device 6 removes impurities in the purified hydrogen gas and sends it to the cooler 7. After being cooled by the cooler 7, it is discharged to the downstream gas using device.

[0125] It should be noted that the cooled purified hydrogen is discharged into the downstream gas-using device after being regulated by the hydrogen back pressure valve 705.

[0126] S3. The purified exhaust gas enters the vaporization heating zone for combustion and heating. The combustion exhaust gas generated in the vaporization heating zone and the reforming heating zone enters the hydrogen-rich heater 4, the purification equipment 5 and the preheater 1 for heating in sequence.

[0127] Preferably, the combustion exhaust gases generated in the vaporization heating zone and the reforming heating zone are combined into one stream and then fed into the hydrogen-rich heater 4 for heating.

[0128] More preferably, the combustion exhaust gas enters the preheating exhaust gas heating coil 405 after being preheated in the rich gas heater 4 to preheat the purification equipment 5.

[0129] In summary, the purified exhaust gas enters the vaporization heating zone and burns with the oxidant. The resulting high-temperature exhaust gas can preheat the hydrogen-rich heater 4 and the purification equipment 5, and also provide heat to the preheater 1, thereby improving the overall thermal energy utilization rate and reducing the amount of methanol used as the combustion raw material.

[0130] The methanol reforming hydrogen production system provided by the present invention will be described below with reference to specific embodiments:

[0131] Based on Examples 1-7, Example 8 provides a methanol reforming hydrogen production system in which the oxidant is supplied as high-pressure pure oxygen and is used for high-pressure emissions.

[0132] like Figure 1 As shown, the preheating process begins: methanol is pressurized to 2.5 MPa by methanol pump 11, and then the flow rate is regulated by the first methanol supply valve 12 and the second methanol supply valve 13 before entering the reforming heating zone of reformer 3 and the vaporization heating zone of vaporizer 2, respectively. High-pressure pure oxygen (pressure > 2.5 MPa) is regulated by the first oxidant supply valve 16 and the second oxidant supply valve 17 before entering the reforming heating zone (pressure approximately 2.5 MPa). The combustion of methanol and high-pressure pure oxygen releases heat to heat the integrated reforming unit to the reaction temperature, while the combustion exhaust gas flows sequentially through the hydrogen-rich heater 601 and the purification device 602 to preheat the entire integrated purification device. Then, the combustion exhaust gas flows sequentially through the heating zone of preheater 1 and cooler 7, and is finally discharged after being regulated by the exhaust gas back pressure valve 706 (approximately 2.5 MPa).

[0133] Secondly, when the integrated reformer and the integrated purification device reach the reaction temperature, the methanol reforming process is started, the methanol water is pressurized by the methanol water pump 9 to reach the working pressure (2.6 MPa-6 MPa), enters the methanol water preheating area of the preheater 1 to be preheated, then enters the methanol water vaporization area of the vaporizer 2 to be vaporized into methanol gas, reaches the working temperature 210℃-280℃, then enters the methanol gas reforming area of the reformer 3 to react, generates the reforming gas, i.e. the hydrogen-rich gas. Then, the hydrogen-rich gas enters the hydrogen-rich heater 4 to be heated to reach the purification working temperature (350℃-450℃), then enters the purification device 5 to be purified, is divided into two paths, one path obtains the purified hydrogen gas, enters the methanation device 6 to remove impurities, then is cooled by the cooler 7, is regulated by the hydrogen back pressure valve 705, and is discharged; the other path of the purified tail gas is regulated by the high temperature regulating valve 18 (to reach the pressure of the high pressure pure oxygen, about 2.5 MPa), enters the vaporization heating area of the vaporizer 2, mixes the oxidant to burn and release heat to provide heat for the methanol water vaporization, at this time, the second methanol feeding valve 13 is closed to stop the methanol from being fed into the vaporization heating area. The reformer 3 is still heated by the methanol and the oxidant.

[0134] Then, the combustion tail gas generated by the vaporizer 2 and the reformer 3 enters the hydrogen-rich heater 4 through the first preheated tail gas inlet 402 to heat the hydrogen-rich gas, then enters the preheated tail gas heating coil 405 to continue to preheat the purification device 5, enters the heating area of the preheater 1 to preheat the methanol water. The preheating process at this place can be regarded as the further use of the heat energy of the fuel tail gas in the methanol reforming process. Finally, the combustion tail gas is cooled by the cooler 7, is regulated by the tail gas back pressure valve 9, and is discharged.

[0135] When the oxidant supply is high pressure pure oxygen and is applied to high pressure discharge, the pressure of the pressurized methanol needs to be consistent with the pressure of the high pressure pure oxygen (normal pressure-6 MPa).

[0136] At the same time, the pressure of the pressurized methanol water needs to be slightly higher than the pressure in the vaporization heating area and the pressure in the reforming heating area.

[0137] Example 9

[0138] On the basis of the above examples, in the methanol reforming hydrogen production system provided by the present example, the oxidant supply is normal pressure air, and is applied to normal pressure discharge.

[0139] The difference between the present example and example 8 is that when the oxidant supply is normal pressure air, the oxidant pump 15 is preferably an air compressor. The normal pressure air is pressurized by the air compressor to enter the reformer 3 and the vaporizer 2. The methanol is pressurized by the methanol pump 11 to reach the outlet pressure of the air compressor, i.e. the pressure of the pressurized air is consistent with the pressure of the pressurized methanol.

[0140] The pressure of the methanol water after pressurization is the same as that of Example 8, and the high pressure described in Example 8 is still used, but the purification efficiency of the purification device 5 can be greatly improved, and the purified tail gas after pressure reduction enters the vaporizer 2 and is mixed and burned with air. The pressure of the purified tail gas after pressure reduction is consistent with the pressure of the air after pressurization.

[0141] The other operation steps are the same as described in Example 8.

[0142] The above is only a preferred embodiment of the present application, and it should be noted that for ordinary skilled persons in the art, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered within the scope of protection of the present application.

Claims

1. A methanol reforming hydrogen production system based on catalytic combustion, characterized in that, It includes an integrated reforming unit, an integrated purification unit, a methanol-water feedstock supply unit, and a cooler; The integrated reforming unit includes a preheater, a vaporizer, and a reformer arranged sequentially along the material flow direction. The reformer has a methanol gas reforming area with a reformed gas outlet. The vaporizer has a methanol-water vaporization area. The preheater has a methanol-water preheating area connected to a methanol-water feedstock supply unit. The methanol-water feedstock supply unit provides methanol-water feedstock to the preheater. The methanol-water preheating area, the methanol-water vaporization area, and the methanol gas reforming area are connected sequentially. The integrated purification device includes a hydrogen-rich heater, a purification device, and a methanation device arranged sequentially along the material flow direction. The hydrogen-rich heater has a first hydrogen-rich inlet and a hydrogen-rich outlet, and the first hydrogen-rich inlet is connected to the reformed gas outlet. The purification device has a second hydrogen-rich inlet and a purified hydrogen outlet, and the second hydrogen-rich inlet is connected to the hydrogen-rich outlet. The purified hydrogen outlet is connected to the inlet of the methanation device. The cooler has a purified hydrogen inlet, and the purified hydrogen inlet is connected to the outlet of the methanation device. The system also includes a fuel supply unit, which comprises a methanol storage tank and an oxidant storage tank; the vaporizer further includes a vaporization heating zone, which has a first fuel inlet and a first combustion exhaust gas outlet, the first fuel inlet being connected to the methanol storage tank and the oxidant storage tank respectively; the reformer further includes a reforming heating zone, which has a second fuel inlet and a second combustion exhaust gas outlet, the second fuel inlet being connected to the methanol storage tank and the oxidant storage tank respectively; the hydrogen-rich heater further includes a first preheating exhaust gas inlet and a first... The purification equipment includes a preheated exhaust gas outlet and a first preheated exhaust gas inlet connected to both the first and second combustion exhaust gas outlets. The purification equipment also includes a second preheated exhaust gas inlet and a second preheated exhaust gas outlet, with the second preheated exhaust gas inlet connected to the first preheated exhaust gas outlet. The preheater also includes a heating zone with a third preheated exhaust gas inlet and a third preheated exhaust gas outlet, the third preheated exhaust gas inlet connected to the second preheated exhaust gas outlet. The cooler also includes a third combustion exhaust gas inlet and a third combustion exhaust gas outlet, with the third preheated exhaust gas outlet connected to the third combustion exhaust gas inlet.

2. The methanol reforming hydrogen production system according to claim 1, characterized in that, The purification equipment is also provided with a purification tail gas outlet, and the vaporization heating zone is provided with a purification tail gas inlet. The purified exhaust gas outlet is connected to the purified exhaust gas inlet and is used to provide purified exhaust gas that reacts with the oxidant to generate heat in the vaporization heating zone. A high-temperature regulating valve is installed on the pipeline between the purified exhaust gas outlet and the purified exhaust gas inlet.

3. The methanol reforming hydrogen production system according to claim 1, characterized in that, The methanol reforming area is provided with a methanol reforming channel, and a reforming catalyst is provided in the methanol reforming channel; The methanol-water vaporization area is equipped with a methanol-water vaporization channel.

4. The methanol reforming hydrogen production system according to claim 1, characterized in that, Both the reforming heating zone and the vaporization heating zone are provided with combustion catalytic channels, and combustion catalysts are provided in the combustion catalytic channels. The combustion catalysts are used to catalyze the combustion of methanol and oxidants.

5. The methanol reforming hydrogen production system according to claim 1, characterized in that, The hydrogen-rich heater further includes a preheating exhaust gas heating coil, which is arranged around the outer wall of the purification equipment. The inlet of the preheating exhaust gas heating coil is connected to the first preheating exhaust gas outlet, and the outlet of the preheating exhaust gas heating coil is connected to the third combustion exhaust gas inlet. The preheating exhaust gas heating coil is used to preheat the purification equipment using the heat of the combustion exhaust gas.

6. The methanol reforming hydrogen production system according to claim 1, characterized in that, The cooler is also equipped with a purified hydrogen outlet; The methanol reforming hydrogen production system further includes: a hydrogen back pressure valve and a tail gas back pressure valve, wherein the hydrogen back pressure valve is connected to the purified hydrogen outlet; and the tail gas back pressure valve is connected to the third combustion tail gas outlet.

7. The methanol reforming hydrogen production system according to claim 1, characterized in that, The integrated reforming device and the integrated purification device are a single structure, and the outer wall of the single structure is covered with thermal insulation material.

8. A methanol reforming hydrogen production method based on catalytic combustion, applied to the methanol reforming hydrogen production system according to any one of claims 1-7, characterized in that, include: S1. The methanol-water supply unit feeds methanol-water raw material into the methanol-water preheating area. The preheated methanol-water raw material enters the methanol-water vaporization area for vaporization, and then enters the methanol-gas reforming area for reforming to obtain hydrogen-rich gas. S2. After being heated by the hydrogen-rich gas heater, the hydrogen-rich gas enters the purification equipment for purification to obtain purified hydrogen and purified tail gas. After the methanation equipment removes impurities from the purified hydrogen, it is sent to the cooler and then discharged into the downstream gas-using device after being cooled by the cooler.

9. The method for producing hydrogen from methanol reforming according to claim 8, characterized in that, Also includes: S3. The purified exhaust gas enters the vaporization heating zone for combustion and heating. The combustion exhaust gas generated in the vaporization heating zone and the reforming heating zone enters the hydrogen-rich heater, the purification equipment and the preheater in sequence for heating.

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