Supercritical water gasification hydrogen production device and method with high-temperature and high-pressure fluid external circulation

Abstract

A supercritical water gasification hydrogen production device and method for high-temperature and high-pressure fluid external circulation, comprising a gasification reactor, an oxidation reactor, a supercritical water module, a feeding module, a circulation pipeline, an oxygen supply module and a heat exchange module; the circulation pipeline and the oxidation reactor are arranged outside the gasification reactor, the feeding module is in communication with the inside of the gasification reactor, the supercritical water module is connected to the gasification reactor through a supercritical water pipeline, one end of the circulation pipeline is connected to the gasification reactor, and the other end is connected to the oxidation reactor; the oxygen supply module is in communication with the oxidation reactor, and the bottom of the oxidation reactor is connected to the circulation pipeline and an oxidation reactor outlet pipeline; one end of the heat exchange module is in communication with the gasification reactor, and the other end is in communication with the oxidation reactor. The system utilizes the excellent physical and chemical properties of supercritical water, and can realize efficient and clean conversion of organic materials at a lower temperature. This process and method have outstanding economic advantages when processing materials with high water content.

Description

Technical Field

[0001] This invention belongs to the fields of clean energy conversion and coal chemical industry, and specifically relates to a supercritical water gasification hydrogen production device and method with high temperature and high pressure fluid external circulation. Background Technology

[0002] Supercritical gasification technology is a clean and efficient energy conversion technology characterized by high hydrogen content in the produced gas, low conversion temperature, and the absence of nitrogen oxides and sulfur dioxide. It offers significant advantages in producing hydrogen from organic matter and generating electricity. This is primarily due to the unique physicochemical properties of supercritical water, such as weak hydrogen bonds, low polarity, high diffusion coefficient, and the ability to dissolve most organic matter and gases. These properties allow reactions in supercritical water to proceed in a homogeneous phase, greatly accelerating the reaction rate. The high pressure conditions under which supercritical water does not readily evaporate increase the reaction residence time, and the absence of latent heat of vaporization and isothermal evaporation facilitates heat transfer, accelerating heating and heat recovery. Furthermore, the high pressure of supercritical water dissolves carbon dioxide, facilitating carbon recovery from the gasification products of organic matter and reducing atmospheric carbon emissions.

[0003] Many scholars at home and abroad have conducted extensive research on supercritical water gasification technology and have made many progresses and achievements. However, there are still technical difficulties such as optimizing gas production at high concentrations, achieving high energy recovery and self-heating in engineering, corrosion, blockage, stability control, and material transportation. In particular, supercritical water has a large specific heat capacity, and maintaining the heat balance of the reactor requires overcoming the current shortcomings in heat transfer and mass transfer.

[0004] Currently, most of the heat required by gasification reactors is recovered through regenerators. However, according to system thermodynamic calculations, energy loss and effective energy loss also mainly originate from the heat exchange process. Furthermore, the large heat exchange area required and the high operating temperature lead to high material costs and overall equipment costs, especially with larger-scale deployments. Therefore, there is an urgent need for an innovative technology that can achieve efficient heat transfer and system energy balance. Summary of the Invention

[0005] The purpose of this invention is to provide a supercritical water gasification hydrogen production device and method with high temperature and high pressure fluid external circulation, so as to solve the problems of high material cost and construction cost of the current equipment due to large heat exchange area requirements and high operating temperature.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A high-temperature, high-pressure fluid external circulation supercritical water gasification hydrogen production device includes a gasification reactor, an oxidation reactor, a supercritical water module, a feeding module, a circulation pipeline, an oxygen supply module, and a heat exchange module. The circulation pipeline and the oxidation reactor are located inside the gasification reactor. The feeding module is connected to the gasification reactor. The supercritical water module is connected to the gasification reactor through the supercritical water pipeline. One end of the circulation pipeline is connected to the gasification reactor, and the other end is connected to the oxidation reactor. The oxygen supply module is connected to the oxidation reactor, and the bottom of the oxidation reactor is connected to the circulation pipeline. One end of the heat exchange module is connected to the gasification reactor, and the other end is connected to the oxidation reactor.

[0008] Furthermore, the bottom of the oxidation reactor is connected to a supercritical water module via an oxidation reactor outlet pipe.

[0009] Furthermore, the outlet of the circulation pipe is connected to a circulation nozzle, which is located in the central area at the bottom of the gasification reactor.

[0010] Furthermore, the oxygen supply module includes an oxygen pipeline, a third mass flow meter, and a third high-pressure plunger pump; the third high-pressure plunger pump is connected to the oxygen pipeline, the oxygen pipeline is connected to the oxidation reactor, and the third mass flow meter is installed on the oxygen pipeline.

[0011] Furthermore, the feeding module includes a material inlet pipe, a second high-pressure plunger pump, a second mass flow meter, and a feeder; the second high-pressure plunger pump is connected to the feeder, the feeder is connected to the material inlet pipe, and the material inlet pipe is connected to the gasification reactor; the second mass flow meter is located between the second high-pressure plunger pump and the feeder.

[0012] Furthermore, the heat exchange module includes an intermediate heat exchanger, a high-temperature and high-pressure shielded pump, a high-temperature and high-pressure flow meter, an inlet pipe for the oxidation reactor, and an outlet pipe for the gasification reactor. One end of the outlet pipe for the gasification reactor is connected to the gasification reactor, and the other end of the gasification reactor is connected to the intermediate heat exchanger. The intermediate heat exchanger is connected to the oxidation reactor through the inlet pipe for the oxidation reactor. The high-temperature and high-pressure shielded pump and the high-temperature and high-pressure flow meter are both installed on the inlet pipe for the oxidation reactor.

[0013] Furthermore, cooling pipes are installed on the intermediate heat exchanger.

[0014] Furthermore, the supercritical water module includes a first high-pressure plunger pump, a first mass flow meter, and a regenerator; the first high-pressure plunger pump is connected to the regenerator, and the regenerator is connected to the gasification reactor and the oxidation reactor; the first mass flow meter is located between the first high-pressure plunger pump and the regenerator.

[0015] Furthermore, the regenerator is connected to the gasification reactor via a supercritical water pipeline, and the regenerator is connected to the oxidation reactor via the oxidation reactor outlet pipe.

[0016] Furthermore, a method for producing hydrogen by supercritical water gasification with external fluid circulation at high temperature and high pressure includes the following steps:

[0017] Preparation of materials: Add materials, additives and catalysts to a container, stir evenly, add water, let stand for a certain period of time to form a uniform and stable slurry, and then add it to the feeder;

[0018] Coal gasification reaction: Before startup, there is no flow at any inlet or outlet. First, the first plunger pump and the high-temperature and high-pressure shielded pump are turned on, so that water flows sequentially through the first mass flow meter and the regenerator, and is injected into the gasification reactor from the supercritical water pipeline. It exits from the gasification reactor outlet pipeline, enters the oxidation reactor through the heat exchange module, and then exits the system through the oxidation reactor outlet pipe and the regenerator. The heating device outside the gasification reactor raises the temperature of the entire reaction system. After the outlet temperature of the oxidation reactor reaches a stable temperature, the second plunger pump is turned on, so that water flows sequentially through the second mass flow meter, and cold material enters the gasification reactor from the bottom of the feeder through the material inlet pipeline, thus starting the supercritical water gasification reaction of coal.

[0019] Oxidation reaction of coal gasification products: The products of the gasification reactor enter the oxidation reactor from the gasification reactor outlet channel and heat exchange module. The third plunger pump is turned on, so that oxygen flows through the third mass flow meter and enters the oxidation reactor from the oxygen pipeline in sequence, and the exothermic oxidation reaction begins.

[0020] Supercritical fluid external circulation process: The high-temperature and high-pressure shielded pump is turned on to pressurize the fluid, so that the supercritical high-temperature fluid in the oxidation reactor is guided to the circulation pipeline through the internal conduit, and injected into the gasification reactor from the circulation nozzle to form an external circulation. The flow rate of the circulating fluid is controlled by the precise feedback adjustment of the high-temperature and high-pressure shielded pump on the external circulation channel.

[0021] End of reaction process: After the gasification reaction is completed, first turn off the second and third high-pressure plunger pumps. After the device has been running continuously for one hour, turn off the heating device of the gasification reactor. After the system has cooled down slowly, turn off the first high-pressure plunger pump and the high-temperature and high-pressure shielded pump. There is no flow at any inlet or outlet.

[0022] Compared with the prior art, the present invention has the following technical effects:

[0023] This invention incorporates a heat exchange module and circulation pipeline between the oxidation reactor and the gasification reactor, enabling external circulation. The gasification products from the gasification reactor, after reacting exothermically with oxygen in the oxidation reactor, are pressurized and returned to the gasification reactor via external circulation for further gasification. This not only solves the problem of heat transfer within the reactor but also, through the injection of high-temperature fluid into the gasification reactor, creates a high-temperature gasification zone at the center of the reactor, which is beneficial for the gasification reaction.

[0024] This system utilizes the excellent physicochemical properties of supercritical water to achieve efficient and clean conversion of organic materials at relatively low temperatures. This process and method offer significant economic advantages when processing materials with high water content.

[0025] The high-temperature fluid in the oxidation reactor can be returned to the gasification reactor for reuse through an external circulation system, achieving both efficient heat and mass transfer. Simultaneously, the multi-component components in the circulating high-temperature fluid can promote the gasification process of the material in the gasification reactor.

[0026] Using a pump for external circulation not only directly and efficiently utilizes the high-temperature fluid in the oxidation reactor, increasing the reactants and heat source for the material reaction in the gasification reactor, but also accelerates the flow and mixing of materials through the jet impact of the high-temperature fluid, avoiding the formation of flow dead zones and coking, which is beneficial to improving the material conversion rate. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of a high-temperature, high-pressure fluid external circulation supercritical water gasification hydrogen production device and method according to the present invention.

[0028] Among them, 1-gasification reactor, 2-oxidation reactor, 3-oxidation reactor outlet pipe, 4-supercritical water inlet pipe, 5-circulation pipe, 6-material inlet pipe, 7-circulation nozzle, 8-oxidation reactor inlet pipe, 9-oxygen pipe, 10-regenerator, 11-first high-pressure plunger pump, 12-second high-pressure plunger pump, 13-third high-pressure plunger pump, 14-first mass flow meter, 15-second mass flow meter, 16-third mass flow meter, 17-feeder, 18-internal conduit, 19-gasification reactor outlet pipe, 20-intermediate heat exchanger, 21-high temperature and high pressure shielded pump, 22-pressure sensor, 23-high temperature and high pressure flow meter, 24-cooling pipe. Detailed Implementation

[0029] This invention relates to a supercritical water gasification hydrogen production device and method with high-temperature and high-pressure fluid external circulation. It utilizes a pump to circulate the high-temperature fluid externally to achieve fluid reuse, thereby improving efficiency, reducing heat exchange requirements, and providing good benefits.

[0030] Please see Figure 1As shown, the present invention is a supercritical water gasification hydrogen production device with high temperature and high pressure fluid external circulation, including a first high pressure plunger pump 11, a second high pressure plunger pump 12, a third high pressure plunger pump 13, a first mass flow meter 14, a second mass flow meter 15, a third mass flow meter 16, a gasification reactor 1, an oxidation reactor 2, a regenerator 10, a material inlet pipe 6, a supercritical water inlet pipe 4, an oxidation reactor outlet pipe 3, an oxygen pipe 9, an oxidation reactor inlet pipe 8, a circulation pipe 5, a circulation nozzle 7, a feeder 17, a gasification reactor outlet pipe 19, an intermediate heat exchanger 20, a high temperature and high pressure shielded pump 21, a high temperature and high pressure flow meter 23, and multiple pressure and temperature measuring devices, control valves, and systems.

[0031] The outlet of the first high-pressure plunger pump 11 is connected to the inlet of the first mass flow meter 14, and the outlet of the first mass flow meter 14 is connected to the low-temperature side inlet of the regenerator 10. The high-temperature side outlet of the regenerator 10 can be used to supply power to a steam turbine or a waste heat boiler, etc. The outlet of the second high-pressure plunger pump 12 is connected to the inlet of the second mass flow meter 15, and the outlet of the second mass flow meter 15 is connected to the upper side of the feeder 17. The lower side of the feeder 17 is connected to the material inlet pipe 6 of the gasification reactor 1. The outlet of the third high-pressure plunger pump 13 is connected to the inlet of the third mass flow meter 16, and the outlet of the third mass flow meter 16 is connected to the oxygen pipe 9 of the oxidation reactor 2.

[0032] The upper end of the gasification reactor 1 is connected to the tube side of the intermediate heat exchanger on the heat exchange module via the gasification reactor outlet pipe 19. The low-temperature side of the intermediate heat exchanger can be circulated with low-temperature fluid for waste heat utilization, while the high-temperature side outlet is connected to a high-temperature and high-pressure shielded pump. After being pressurized by the pump, the fluid passes through a pressure gauge and a flow meter and enters the oxidation reactor. Then, it is injected into the gasification reactor through the circulation pipe and the circulation nozzle, forming an external circulation closed loop. The oxygen pipe 9 is located between one end of the oxidation reactor and the inlet of the external circulation channel, and the outlet channel 3 of the oxidation reactor is located at the other end of the oxidation reactor. The circulation nozzle 7 is located in the central area at the bottom of the gasification reactor.

[0033] The operating steps of a supercritical water gasification hydrogen production unit with external fluid circulation are as follows:

[0034] (1) Preparation of materials: Add materials, additives and catalysts to a container, stir evenly, add water, let stand for a certain period of time to form a uniform and stable slurry, and add it to the lower end of feeder 17.

[0035] (2) Coal gasification reaction: Before startup, there is no flow at any inlet or outlet. First, turn on the first plunger pump 11 and the high-temperature and high-pressure shielded pump 21, so that water flows through the first mass flow meter 14 and the regenerator 10 in sequence, and is injected into the gasification reactor 1 from the supercritical water pipe 4. It enters the oxidation reactor 2 through the heat exchange module from the gasification reactor outlet pipe 19, and then through the oxidation reactor outlet pipe 3 and is discharged from the system through the regenerator. The heating device outside the gasification reactor 1 raises the temperature of the entire reaction system. After the outlet temperature of the oxidation reactor reaches a stable temperature, turn on the second plunger pump 12, so that water flows through the second mass flow meter 15 in sequence, and cold material enters the gasification reactor 1 from the lower side of the feeder 17 through the material inlet pipe 6, thus starting the supercritical water gasification reaction of coal.

[0036] (3) Oxidation reaction of coal gasification products: The products of gasification reactor 1 enter oxidation reactor 2 from gasification reactor outlet pipe 19 and heat exchange module. The third plunger pump 13 is turned on, so that oxygen flows through the third mass flow meter 16 and enters oxidation reactor 2 from oxygen pipe 9 in sequence, and the exothermic oxidation reaction begins.

[0037] (4) Supercritical fluid external circulation process: The high temperature and high pressure shielded pump is turned on to pressurize the fluid, so that the supercritical high temperature fluid in the oxidation reactor 2 is guided to the circulation pipe 5 through the internal conduit 18 and injected into the gasification reactor from the circulation nozzle 7 to form an external circulation. The flow rate of the circulating fluid can be controlled by the precise feedback adjustment of the high temperature and high pressure shielded pump 21 on the external circulation channel so that the flow rate, pressure and temperature meet the system requirements.

[0038] (5) End of reaction process: After the gasification reaction is completed, first turn off the second high pressure plunger pump 12 and the third high pressure plunger pump 13. After the device has been running continuously for one hour, turn off the heating device of the gasification reactor 1. After the system cools down slowly, turn off the first high pressure plunger pump 11 and the high temperature and high pressure shielded pump 21. There is no flow at all inlets and outlets.

[0039] Cycle principle:

[0040] The system comprises a gasification reactor, a gasification reactor outlet pipe, an intermediate heat exchanger, a high-temperature, high-pressure shielded pump, a pressure sensor, a high-temperature, high-pressure flow meter, an oxidation reactor inlet pipe, an oxidation reactor, a circulation pipeline, and circulation nozzles, forming a closed loop. Supercritical fluid from the gasification reactor flows through the gasification reactor outlet pipe into the intermediate heat exchanger. After cooling in the cooling pipeline, the fluid is cooled to the operating parameters of the high-temperature, high-pressure shielded pump. The pump then pressurizes the fluid, which enters the oxidation reactor and reacts exothermically with oxygen from the oxygen pipeline. A portion of the gasified fluid exits the system through the oxidation reactor outlet channel, while the remaining portion flows through the circulation pipeline and is injected into the gasification reactor through the circulation nozzles to participate in the gasification reaction. The circulation nozzles are located at the bottom center of the gasification reactor, forming a high-temperature gasification zone, which is beneficial for achieving complete gasification.

[0041] The high-temperature and high-pressure shielded pump in the external circulation channel, based on the signal from the high-temperature and high-pressure flow meter, and through a precise feedback adjustment system, can control the flow rate of the circulating fluid so that the flow rate, pressure, and temperature meet the system requirements.

[0042] Water enters the regenerator through the first high-pressure plunger pump, and then the generated supercritical water is injected into the gasification reactor through the supercritical water pipeline.

[0043] This system utilizes the excellent physicochemical properties of supercritical water to achieve efficient and clean conversion of organic materials at relatively low temperatures. This process and method offer significant economic advantages when processing materials with high water content.

[0044] The high-temperature fluid in the oxidation reactor can be returned to the gasification reactor for reuse through an external circulation system, achieving both efficient heat and mass transfer. Simultaneously, the multi-component components in the circulating high-temperature fluid can promote the gasification process of the material in the gasification reactor.

[0045] Using a pump for external circulation not only directly and efficiently utilizes the high-temperature fluid in the oxidation reactor, increasing the reactants and heat source for the material reaction in the gasification reactor, but also accelerates the flow and mixing of materials through the jet impact of the high-temperature fluid, avoiding the formation of flow dead zones and coking, which is beneficial to improving the material conversion rate.

[0046] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A supercritical water gasification hydrogen production device with high temperature and high pressure fluid external circulation, characterized in that, It includes a gasification reactor (1), an oxidation reactor (2), a supercritical water module, a feeding module, a circulation pipeline (5), an oxygen supply module, and a heat exchange module; the circulation pipeline (5) and the oxidation reactor (2) are located outside the gasification reactor (1), the feeding module is connected to the inside of the gasification reactor (1), the supercritical water module is connected to the gasification reactor (1) through the supercritical water pipeline (4), one end of the circulation pipeline (5) is connected to the gasification reactor (1), and the other end is connected to the oxidation reactor (2); the oxygen supply module is connected to the oxidation reactor (2), and the bottom of the oxidation reactor (2) is connected to the circulation pipeline (5); one end of the heat exchange module is connected to the gasification reactor (1), and the other end is connected to the oxidation reactor (2).

2. The supercritical water gasification hydrogen production device with high temperature and high pressure fluid external circulation according to claim 1, characterized in that, The bottom of the oxidation reactor (2) is also connected to the supercritical water module through the oxidation reactor outlet pipe (3).

3. The supercritical water gasification hydrogen production device with high temperature and high pressure fluid external circulation according to claim 2, characterized in that, The circulating nozzle (7) is located in the central area at the bottom of the gasification reactor (1), and the outlet of the circulating pipe (5) is connected to the circulating nozzle (7).

4. The supercritical water gasification hydrogen production device with high temperature and high pressure fluid external circulation according to claim 3, characterized in that, The oxygen supply module includes an oxygen pipeline (9), a third mass flow meter (16), and a third high-pressure plunger pump (13); the third high-pressure plunger pump (13) is connected to the oxygen pipeline (9), the oxygen pipeline (9) is connected to the oxidation reactor (2), and the third mass flow meter (16) is installed on the oxygen pipeline (9).

5. The supercritical water gasification hydrogen production device with high temperature and high pressure fluid external circulation according to claim 4, characterized in that, The feeding module includes a material inlet pipe (6), a second high-pressure plunger pump (12), a second mass flow meter (15), and a feeder (17); the second high-pressure plunger pump (12) is connected to the feeder (17), the feeder (17) is connected to the material inlet pipe (6), and the material inlet pipe (6) is connected to the gasification reactor (1); the second mass flow meter (15) is located between the second high-pressure plunger pump (12) and the feeder (17).

6. The supercritical water gasification hydrogen production device with high temperature and high pressure fluid external circulation according to claim 5, characterized in that, The heat exchange module includes an intermediate heat exchanger (20), a high-temperature and high-pressure shielded pump (21), a high-temperature and high-pressure flow meter (23), an oxidation reactor inlet pipe (8), and a gasification reactor outlet pipe (19). One end of the gasification reactor outlet pipe (19) is connected to the gasification reactor (1), and the other end of the gasification reactor (1) is connected to the intermediate heat exchanger (20). The intermediate heat exchanger (20) is connected to the oxidation reactor (2) through the oxidation reactor inlet pipe (8). The high-temperature and high-pressure shielded pump (21) and the high-temperature and high-pressure flow meter (23) are both installed on the oxidation reactor inlet pipe (8).

7. A supercritical water gasification hydrogen production device with high-temperature and high-pressure fluid external circulation according to claim 6, characterized in that, Cooling pipes (24) are provided on the intermediate heat exchanger (20).

8. A supercritical water gasification hydrogen production device with high-temperature and high-pressure fluid external circulation according to claim 6, characterized in that, The supercritical water module includes a first high-pressure plunger pump (11), a first mass flow meter (14), and a regenerator (10); the first high-pressure plunger pump (11) is connected to the regenerator (10), and the regenerator (10) is connected to the gasification reactor (1) and the oxidation reactor (2); the first mass flow meter (14) is located between the first high-pressure plunger pump (11) and the regenerator (10).

9. A supercritical water gasification hydrogen production device with external fluid circulation according to claim 8, characterized in that, The regenerator (10) is connected to the gasification reactor (1) through the supercritical water pipe (4), and the regenerator (10) is connected to the oxidation reactor (2) through the oxidation reactor outlet pipe (3).

10. A method for producing hydrogen by supercritical water gasification with external fluid circulation at high temperature and high pressure, characterized in that, The supercritical water gasification hydrogen production device based on the high-temperature and high-pressure fluid external circulation according to claim 9 includes the following steps: Preparation of materials: Add materials, additives and catalysts to a container, stir evenly, add water, let stand, form a uniform and stable slurry, and add it to the feeder (17). Coal gasification reaction: Before startup, there is no flow at any inlet or outlet. First, turn on the first high-pressure plunger pump (11) and the high-temperature high-pressure shielded pump (21) so that water flows through the first mass flow meter (14) and the regenerator (10) in sequence. Water is injected into the gasification reactor (1) from the supercritical water pipe (4), exits from the gasification reactor outlet pipe (19), enters the oxidation reactor (2) through the heat exchange module, and then exits through the oxidation reactor outlet pipe (3) and is discharged from the system through the regenerator (10). The heating device outside the gasification reactor (1) raises the temperature of the entire reaction system. After the outlet temperature of the oxidation reactor reaches a stable level, turn on the second high-pressure plunger pump (12) so that water flows through the second mass flow meter (15) in sequence. Cold material is fed from the bottom of the feeder (17) through the material inlet pipe (6) into the gasification reactor (1) to start the supercritical water gasification reaction of coal. Oxidation reaction of coal gasification products: The products of gasification reactor (1) enter oxidation reactor (2) from gasification reactor outlet pipe (19) and heat exchange module. The third high-pressure plunger pump (13) is turned on, so that oxygen flows through the third mass flow meter (16) and enters oxidation reactor (2) from oxygen pipe (9) in sequence, and the exothermic oxidation reaction begins. Supercritical fluid external circulation process: The high temperature and high pressure shielded pump (21) is turned on to pressurize the fluid, so that the supercritical high temperature fluid in the oxidation reactor (2) is guided to the circulation pipe (5) through the internal conduit (18), and injected into the gasification reactor from the circulation nozzle (7) to form an external circulation. The flow rate of the circulating fluid is controlled by the precise feedback adjustment of the high temperature and high pressure shielded pump (21) on the external circulation channel. End of reaction process: After the gasification reaction is completed, first turn off the second high-pressure plunger pump (12) and the third high-pressure plunger pump (13). After the device has been running continuously for one hour, turn off the heating device of the gasification reactor (1). After the system cools down slowly, turn off the first high-pressure plunger pump (11) and the high-temperature high-pressure shielded pump (21). There is no flow at all inlets and outlets.

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