Oxygen-enriched combustion heater system and method with hydrogen by-product

Abstract

The application discloses a kind of oxygen-enriched combustion heating furnace system and method of by-product hydrogen, and oxygen-enriched combustion heating furnace system includes heating furnace, oxygen release reactor, hydrogen production reactor, oxygen absorption reactor, normal temperature water source, air source, fuel gas source, first heat exchanger, second heat exchanger, third heat exchanger, fourth heat exchanger, first condenser and second condenser.The oxygen-enriched combustion heating furnace system of the application uses chemical chain oxygen production technology to provide oxygen-enriched gas for heating furnace, while passing fuel gas into oxygen release reactor to provide heat for oxygen production and hydrogen production process, promote oxygen release reaction to proceed quickly, at the same time, optimize the heat exchange process of system, improve the temperature of water vapor entering hydrogen production reactor, so as to realize the rapid and efficient operation of oxygen-enriched combustion heating furnace system, and maximize hydrogen production.

Description

Technical Field

[0001] This invention relates to the field of heating furnace technology, and specifically to an oxygen-enriched combustion heating furnace system and method that produces hydrogen as a byproduct. Background Technology

[0002] Currently, conventional heating furnaces heat the process medium through fuel-air contact combustion, with the high-temperature flue gas discharged after passing through a waste heat recovery system. This method suffers from problems such as pollutant emissions, low furnace thermal efficiency, and difficulty in CO2 collection and treatment. To further improve furnace thermal efficiency and reduce pollutant emissions, oxy-fuel combustion technology is considered a very promising technology. However, the high cost of conventional oxygen production technologies such as cryogenic distillation, membrane separation, and pressure swing adsorption (PSA) limits the development of oxy-fuel combustion technology for heating furnaces.

[0003] Chemical looping air separation technology is a novel air separation technology. Its principle involves using an oxygen-enriched oxygen carrier to release oxygen in an oxygen-releasing reactor, while the oxygen-deficient oxygen carrier reacts with air in an oxygen-absorbing reactor for oxidation and regeneration. Compared to conventional oxygen production technologies, it offers advantages such as low energy consumption, rapid start-up, low cost, and convenient operation, providing conditions for the development and application of oxygen-enriched combustion technology in heating furnaces. Under certain conditions, H2O reacts with a reduced oxygen carrier to produce H2, and using the same oxygen carrier to produce hydrogen can further improve the economics of the heating furnace combustion process.

[0004] Reference 1: Chinese patent document with patent publication number CN113669752A.

[0005] Reference 1 describes a method that combines chemical looping oxygen production with aerobic combustion to achieve oxygen-enriched combustion. This approach enables oxygen-enriched combustion without significantly increasing oxygen production costs, while also improving the reaction rate and thermal efficiency of aerobic combustion. However, when used in an oxygen-enriched combustion process in a heater, this method suffers from slow reaction rates, low hydrogen production efficiency, and high system energy consumption. Summary of the Invention

[0006] The purpose of this invention is to solve the problems of slow reaction rate, low hydrogen production efficiency, and high energy consumption in the oxygen-enriched combustion process of existing heating furnaces, and to provide an oxygen-enriched combustion heating furnace system and method that produces hydrogen as a byproduct.

[0007] To address the shortcomings of the aforementioned technical problems, the present invention employs the following technical solution: an oxygen-enriched combustion heating furnace system that produces hydrogen as a byproduct.

[0008] It includes a heating furnace, an oxygen release reactor, a hydrogen production reactor, an oxygen absorption reactor, a normal temperature water source, an air source, a fuel gas source, a first heat exchanger, a second heat exchanger, a third heat exchanger, a fourth heat exchanger, a first condenser, and a second condenser.

[0009] The outlet of the oxygen absorption reactor is connected to the third cyclone separator, the gas phase outlet of the third cyclone separator is connected in sequence to the third heat exchanger and the first heat exchanger, and the solid phase outlet of the third cyclone separator is connected to the solid phase inlet of the oxygen release reactor.

[0010] The outlet of the oxygen release reactor is connected to the first cyclone separator, the gas phase outlet of the first cyclone separator is connected to the heating furnace, and the solid phase outlet of the first cyclone separator is connected to the solid phase inlet of the hydrogen production reactor.

[0011] The outlet of the hydrogen production reactor is connected to the second cyclone separator, the gas phase outlet of the second cyclone separator is connected in sequence to the fourth heat exchanger and the first condenser, and the solid phase outlet of the second cyclone separator is connected to the solid phase inlet of the oxygen absorption reactor.

[0012] The flue gas outlet of the heating furnace is divided into two paths, one of which is connected to the gas phase feed port of the oxygen release reactor, and the other is connected in sequence to the second heat exchanger and the second condenser.

[0013] The ambient temperature water source is connected to the gas phase feed port of the hydrogen production reactor after passing through the first heat exchanger, the second heat exchanger and the third heat exchanger in sequence.

[0014] The air source is connected to the gas phase inlet of the oxygen absorption reactor via a fourth heat exchanger.

[0015] The fuel gas source is divided into two paths, one of which is connected to the burner inlet of the heating furnace, and the other is connected to the gas phase feed port of the oxygen release reactor.

[0016] As a further optimization of the oxygen-enriched combustion heating furnace system for producing hydrogen by-products of the present invention, a gas turbine is also provided between the third cyclone separator and the third heat exchanger.

[0017] As a further optimization of the oxygen-enriched combustion heating furnace system for by-product hydrogen of the present invention: the solid material circulating between the oxygen release reactor, the hydrogen production reactor and the oxygen absorption reactor is an oxygen carrier.

[0018] As a further optimization of the oxygen-enriched combustion heating furnace system for by-product hydrogen of the present invention: the oxygen carrier is a metal oxygen carrier or a non-metal oxygen carrier, the metal oxygen carrier is an iron-aluminum based oxygen carrier or an iron-cobalt based oxygen carrier, and the non-metal oxygen carrier is a perovskite oxygen carrier.

[0019] As a further optimization of the oxygen-enriched combustion heating furnace system for by-product hydrogen of the present invention: the oxygen carrier is an iron-cobalt based composite oxygen carrier, and the elemental mass ratio of Fe / Co in the composite oxygen carrier is 7:3.

[0020] As a further optimization of the oxygen-enriched combustion heating furnace system for producing hydrogen as a byproduct of the present invention: the oxygen release reactor, the hydrogen production reactor, and the oxygen absorption reactor are all fluidized bed reactors, and the working pressure of the reactors is 0.1 to 0.5 MPa.

[0021] As a further optimization of the oxygen-enriched combustion heating furnace system for producing hydrogen as a byproduct of the present invention: the working temperature of the oxygen release reactor is 500-900℃, the working temperature of the hydrogen production reactor is 450-850℃, and the working temperature of the oxygen absorption reactor is 400-950℃.

[0022] An operation method for an oxygen-enriched combustion heater system that produces hydrogen as a byproduct, based on the aforementioned oxygen-enriched combustion heater system that produces hydrogen as a byproduct:

[0023] Normal temperature air enters the fourth heat exchanger and exchanges heat with the hydrogen-rich gas produced by the hydrogen production reactor. After the temperature rises, it enters the oxygen absorption reactor and reacts with the micro-oxygen carrier that enters the oxygen absorption reactor from the hydrogen production reactor. It becomes oxygen-deficient air and enters the third heat exchanger to exchange heat with water vapor to cool down. Alternatively, it becomes oxygen-deficient air and enters the gas turbine to do work before entering the third heat exchanger to exchange heat with water vapor to cool down. After that, it enters the first heat exchanger to exchange heat with normal temperature water. After the temperature drops, it is directly discharged.

[0024] The micro-oxygen carrier absorbs oxygen in the oxygen absorption reactor and becomes an oxygen-rich carrier, then enters the oxygen release reactor. Under the action of the flue gas from the heating furnace and the fuel gas, it releases oxygen and becomes an oxygen-deficient carrier before entering the hydrogen production reactor.

[0025] The oxygen-deficient oxygen carrier enters the hydrogen production reactor and reacts with the high-temperature water vapor entering from the fourth heat exchanger to produce hydrogen. The oxygen-deficient oxygen carrier then becomes a micro-oxygen oxygen carrier and enters the oxygen absorption reactor to complete the oxygen carrier cycle.

[0026] The hydrogen-rich gas produced by the hydrogen production reactor enters the fourth heat exchanger to exchange heat with room temperature air. After the temperature drops, it enters the second condenser for gas-liquid separation, where the hydrogen-rich gas is separated into condensate and hydrogen with a purity of over 99%.

[0027] The oxygen-enriched flue gas generated by the oxygen release reactor oxygen carrier is mixed with fuel gas and enters the heating furnace from the burner for combustion. The high-temperature flue gas generated by combustion heats the feed oil entering the heating furnace. After the feed oil reaches the target temperature, it flows out of the heating furnace and enters the subsequent process.

[0028] After the temperature drops, part of the flue gas and part of the fuel gas enter the oxygen release reactor to participate in the reaction, while another part of the flue gas enters the second heat exchanger to heat the medium-temperature water. After the temperature drops, it enters the first condenser for gas-liquid separation, separating into condensate and carbon dioxide with a purity of over 99%. The carbon dioxide is collected and stored.

[0029] Room temperature water enters the first heat exchanger to exchange heat with oxygen-deficient air. After the temperature rises, it enters the second heat exchanger to exchange heat with the flue gas of the heating furnace and becomes water vapor. Then it enters the third heat exchanger to exchange heat with oxygen-deficient air. After the temperature rises, it enters the hydrogen production reactor as a fluidizing gas to participate in the reaction.

[0030] As a further optimization of the operation method of the oxygen-enriched combustion heating furnace system for producing hydrogen by-products of the present invention: by controlling the amount of fuel gas and flue gas entering the oxygen release reactor, the oxygen concentration of the oxygen-enriched flue gas entering the heating furnace is adjusted to 21-50%.

[0031] As a further optimization of the operation method of the oxygen-enriched combustion heating furnace system for producing hydrogen by-products of the present invention: by controlling the amount of fuel gas and flue gas entering the oxygen release reactor, the oxygen concentration of the oxygen-enriched flue gas entering the heating furnace is adjusted to 25-30%.

[0032] As a further optimization of the operation method of the oxygen-enriched combustion heating furnace system for producing hydrogen by-products of the present invention: the fuel gas entering the oxygen release reactor accounts for 5-30% of the total fuel gas.

[0033] The present invention has the following beneficial effects:

[0034] 1. In the oxygen-enriched combustion heating furnace system of the present invention, the oxygen carrier circulates and reacts between the oxygen release reactor, the hydrogen production reactor and the oxygen absorption reactor, providing oxygen-enriched gas to the heating furnace and producing hydrogen with a purity of more than 99% as a byproduct. All the additional energy consumed in the entire cycle process comes from the heat released by the combustion of fuel gas.

[0035] 2. The oxygen-enriched combustion heater system of the present invention, based on the oxygen release, hydrogen production, and oxygen absorption reactions and the characteristics of the system, optimizes heat exchange. On the one hand, water exchanges heat with flue gas and then with oxygen-deficient air at a higher temperature before entering the hydrogen production reactor. The water vapor temperature can be increased to 400-850°C, significantly increasing the reaction rate of the hydrogen production reactor. Compared with Reference 1, the hydrogen production capacity is increased by 20-50% in the same amount of time. On the other hand, the temperature of the oxygen-deficient air discharged from the heater system can be further reduced, and the heater thermal efficiency can be increased by more than 1 percentage point compared with Reference 1. Through the above two optimizations, the efficient execution of the two reactions is ensured, thereby significantly improving the operating efficiency of the system.

[0036] 3. In the oxygen-enriched combustion heating furnace system of the present invention, a portion of the fuel gas is introduced into the oxygen release reactor. On the one hand, this consumes oxygen, reduces the oxygen partial pressure, and increases the oxygen release rate. On the other hand, the reaction releases heat, which can effectively ensure the reaction temperature of the reactor and promote the rapid progress of the oxygen release reaction. Compared with Reference 1, the oxygen release rate is increased by 20-50% in the same amount of time. Attached Figure Description

[0037] Figure 1This is a schematic diagram of the structure of the oxygen-enriched combustion heating furnace system of the present invention;

[0038] Figure 2 This is a schematic diagram of the operation process of the oxygen-enriched combustion heating furnace system of the present invention;

[0039] Marked in the image:

[0040] 1. Heating furnace;

[0041] 11. Burner;

[0042] 2. Air turbine;

[0043] 3. Oxygen release reactor;

[0044] 33. First cyclone separator;

[0045] 4. Hydrogen production reactor;

[0046] 43. Second cyclone separator;

[0047] 5. Oxygen absorption reactor;

[0048] 53. Third cyclone separator;

[0049] 6. Ambient temperature water source;

[0050] 7. Air source;

[0051] 8. Fuel gas source;

[0052] E1, First heat exchanger;

[0053] E2, Second heat exchanger;

[0054] E3, the third heat exchanger;

[0055] E4, the fourth heat exchanger;

[0056] R1, First condenser;

[0057] R2, the second condenser. Detailed Implementation

[0058] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0059] <Oxygen-enriched combustion heating furnace system with byproduct hydrogen>

[0060] like Figure 1As shown: An oxygen-enriched combustion heating furnace system includes a heating furnace 1, a gas turbine 2, an oxygen release reactor 3, a hydrogen production reactor 4, an oxygen absorption reactor 5, an ambient temperature water source 6, an air source 7, a fuel gas source 8, a first heat exchanger E1, a second heat exchanger E2, a third heat exchanger E3, a fourth heat exchanger E4, a first condenser R1, and a second condenser R2.

[0061] Oxygen release reactor 3, hydrogen production reactor 4, and oxygen absorption reactor 5 all have solid phase inlets located on the lower sidewall of the reactors. Oxygen release reactor 3, hydrogen production reactor 4, and oxygen absorption reactor 5 all have gas phase inlets located at the bottom of the reactors. Oxygen release reactor 3, hydrogen production reactor 4, and oxygen absorption reactor 5 all have outlets located on the upper sidewall of the reactors.

[0062] The outlet of the oxygen absorption reactor 5 is connected to the third cyclone separator 53. The gas phase outlet of the third cyclone separator 53 is connected in sequence to the gas turbine 2, the third heat exchanger E3 and the first heat exchanger E1. The solid phase outlet of the third cyclone separator 53 is connected to the solid phase inlet of the oxygen release reactor 3.

[0063] The gaseous material separated by the third cyclone separator 53 first enters the gas turbine 2 to do work, and then enters the third heat exchanger E3 for heat exchange. After heat exchange, the gaseous material enters the first heat exchanger E1 for heat exchange, and is finally discharged from the first heat exchanger E1.

[0064] The outlet of the oxygen release reactor 3 is connected to the first cyclone separator 33, the gas phase outlet of the first cyclone separator 33 is connected to the burner inlet of the heating furnace 1, and the solid phase outlet of the first cyclone separator 33 is connected to the solid phase inlet of the hydrogen production reactor 4.

[0065] The gaseous material separated by the first cyclone separator 33 is mixed with part of the combustion gas from the fuel gas source 8 and then enters the burner of the heating furnace 1, where it is burned.

[0066] The outlet of the hydrogen production reactor 4 is connected to the second cyclone separator 43. The gas phase outlet of the second cyclone separator 43 is connected in sequence to the fourth heat exchanger E4 and the first condenser R1. The solid phase outlet of the second cyclone separator 43 is connected to the solid phase inlet of the oxygen absorption reactor 5.

[0067] The flue gas outlet of the heating furnace 1 is divided into two paths. One path is connected to the gas phase feed port of the oxygen release reactor 3, and the other path is connected in sequence to the second heat exchanger E2 and the second condenser R2.

[0068] Ambient temperature water source 6 is connected to the gas phase feed port of hydrogen production reactor 4 after passing through the first heat exchanger E1, the second heat exchanger E2 and the third heat exchanger E3 in sequence.

[0069] Air source 7 is connected to the gas phase feed port of oxygen absorption reactor 5 through the fourth heat exchanger E4;

[0070] The fuel gas source 8 is divided into two paths, one of which is connected to the burner inlet of the heating furnace 1, and the other is connected to the gas phase feed port of the oxygen release reactor 3.

[0071] The solid material circulating between the oxygen release reactor 3, the hydrogen production reactor 4, and the oxygen absorption reactor 5 is the oxygen carrier. The oxygen carrier can be a metallic oxygen carrier or a non-metallic oxygen carrier. The metallic oxygen carrier is an iron-aluminum based oxygen carrier or an iron-cobalt based oxygen carrier, and the non-metallic oxygen carrier is a perovskite oxygen carrier.

[0072] Commonly used oxygen carriers include: Co-based oxygen carriers, which have high activity, high reaction rate and high conversion rate, but are relatively expensive; Fe-based oxygen carriers have a lower reaction rate but better stability; Al-based oxygen carriers have a moderate price and moderate reaction rate. Cu-based oxygen carriers have a low melting point, which poses problems for long-term operation; Mn-based oxygen carriers pollute the environment. Therefore, Fe-Co-based oxygen carriers are the most suitable in terms of stability, reaction rate, and economy; Fe-Al-based oxygen carriers have a lower reaction rate than Fe-Co-based oxygen carriers, but can still complete the system reaction well, while non-metallic oxygen carriers have problems for long-term operation.

[0073] In this embodiment, the oxygen carrier is an iron-cobalt based composite oxygen carrier with an elemental mass ratio of Fe / Co of 7:3. Compared with conventional oxygen carriers, this specific composite oxygen carrier has better overall performance in terms of conversion rate, cycle stability, and economy, and can improve the system operating efficiency.

[0074] The oxygen release reactor 3, hydrogen production reactor 4, and oxygen absorption reactor 5 are all fluidized bed reactors, and the working pressure of the reactors is 0.1 to 0.5 MPa.

[0075] The working temperature of oxygen reactor 3 is 500-900℃, the working temperature of hydrogen production reactor 4 is 450-850℃, and the working temperature of oxygen absorption reactor 5 is 400-950℃.

[0076] In this system, the temperature of the water vapor entering the hydrogen production reactor 4 is 500-850℃, the temperature of the flue gas exiting the heating furnace is 150-300℃, and the temperature of the oxygen-deficient air discharged from the first heat exchanger is below 40℃.

[0077] Since both the oxygen release and hydrogen production reactions are endothermic, maintaining the reaction temperature is crucial to ensuring the reaction rate and system efficiency. Conversely, since the oxygen absorption reaction is exothermic, slightly lowering the temperature of the air entering the oxygen absorption reactor has little impact on the system's reaction rate and efficiency. In Reference 1, to achieve the hydrogenation of carbon dioxide, both the oxygen release and hydrogen production reactions are carried out at relatively low temperatures, resulting in slower reaction rates and lower system efficiency.

[0078] Compared with Reference 1 and the prior art, the present invention has at least the following technical advantages:

[0079] First, the oxygen-enriched combustion heating furnace system of this invention can significantly reduce the flue gas temperature of the heating furnace and effectively improve the overall thermal efficiency of the heating furnace. The exhaust temperature of traditional heating furnaces is generally higher than 120°C, and the exhaust gas from the heating furnace in Reference 1 is oxygen-deficient air at 50°C. This invention, through optimized heat exchange processes, achieves cascaded energy utilization, and the exhaust gas from the heating furnace system is only oxygen-deficient air at 30°C. Compared with traditional heating furnaces, this can improve the heating furnace thermal efficiency by more than 3 percentage points, and compared with Reference 1, the thermal efficiency can be improved by more than 1 percentage point.

[0080] Secondly, in the oxygen-enriched combustion heater system of this invention, water exchanges heat with flue gas to become steam, and then exchanges heat with oxygen-deficient air at a higher temperature before entering the hydrogen production reactor. The steam temperature can be raised to 400-850℃, significantly increasing the reaction rate of the hydrogen production reactor. Compared with Reference 1, the hydrogen production per unit time is increased by 20-50%. Simultaneously, this invention uses a portion of the fuel gas to enter the heater for combustion with oxygen-enriched gas, and a portion to enter the oxygen release reactor. This consumes oxygen, reduces oxygen partial pressure, and increases the oxygen release rate. Furthermore, the heat released during the reaction effectively maintains the reactor's reaction temperature, promoting rapid oxygen release. Compared with Reference 1, the oxygen release rate per unit time is increased by 20-50%, the feedstock oil processing capacity of the heater system per unit time can be increased by 20-50%, the system operating efficiency is improved by more than 20%, and the system operation is more stable.

[0081] Compared with traditional heating furnaces, this method can achieve oxygen-enriched combustion in the heating furnace at a low cost and simultaneously produce high-purity hydrogen, significantly improving economic benefits.

[0082] Furthermore, this invention can significantly reduce the spatial dimensions of the heating furnace system. Traditional heating furnaces produce flue gas containing a large amount of N2, whose radiation capacity is almost zero, greatly reducing the flue gas's radiation capacity. However, by using oxygen-enriched combustion, the flue gas composition is CO2 and water vapor, increasing the flue gas radiation capacity by more than 50%. Under the same conditions, the heat exchange area required for the heating process medium can be reduced by more than 50% compared to traditional heating furnaces, significantly reducing the furnace's physical dimensions and lowering construction costs by more than 20%.

[0083] Compared with Reference 1, due to the faster reaction rate, optimized heat exchange process, and tiered energy utilization, the space size of the heating furnace system is significantly reduced under the same processing capacity, which can reduce investment and land occupation by more than 20% to 50%.

[0084] <Operating Methods of Oxygen-Enriched Combustion Heating Furnace System for By-product Hydrogen>, such as Figure 2 As shown.

[0085] 1) 20℃ ambient air enters the fourth heat exchanger E4 and exchanges heat with the 550℃ hydrogen-rich gas produced by the hydrogen production reactor 4. The temperature rises to 450℃ and enters the oxygen absorption reactor 5 through the third inlet. The air exits the fluidized second cyclone separator 43 and enters the 550℃ micro-oxygen carrier (Fe3O4+CO3O4) of the oxygen absorption reactor 5 through the third inlet of the oxygen carrier and reacts with it, becoming a gas-solid mixture of 650℃ oxygen-deficient air and oxygen-rich carrier (Fe3O4+CO3O4). This mixture enters the third cyclone separator 53 for gas-solid separation. The 650℃ oxygen-deficient air enters the gas turbine 2 to do work, and the temperature drops to 600℃. It then enters the third heat exchanger E3 for heat exchange and cooling with residual low-temperature water vapor. After the temperature drops to 170℃, it enters the first heat exchanger E3 and exchanges heat with 20℃ ambient water. After the temperature drops to 30℃, it is directly discharged.

[0086] 2) The oxygen-enriched carrier enters the oxygen release reactor 3 through the first inlet of the oxygen carrier via the feed leg of the third cyclone separator 53. Under the fluidization of the 200°C furnace flue gas and ambient temperature fuel, oxygen is released, transforming into a 650°C oxygen-deficient carrier and an oxygen-enriched gas. The oxygen carrier rises with the oxygen-enriched gas to the first cyclone separator 33 for gas-solid separation. The oxygen-deficient carrier (FeO+COO) enters the hydrogen production reactor 4 through the second inlet of the oxygen carrier via the feed leg of the first cyclone separator 33.

[0087] 3) The 600℃ oxygen-deficient carrier enters the hydrogen production reactor 4 and, under the fluidization of 550℃ high-temperature steam entering from the third heat exchanger E3, reacts with the steam as it rises to produce hydrogen. The oxygen-deficient carrier then becomes a 550℃ micro-oxygen carrier and rises together with the hydrogen-rich gas to the second cyclone separator 43. The micro-oxygen carrier passes through the feed leg of the second cyclone separator 43 and enters the oxygen absorption reactor 5 from the third inlet of the carrier to complete the circulation of the carrier.

[0088] 4) The 550°C hydrogen-rich gas produced by the hydrogen production reactor 4 is separated by the second cyclone separator 43 and then enters the fourth heat exchanger E4 to exchange heat with 20°C air. The temperature drops to 80°C and enters the second condenser R2 for gas-liquid separation. The hydrogen-rich gas is separated into condensate and hydrogen with a purity of over 99%.

[0089] 5) The oxygen-rich flue gas at 600°C generated by the oxygen carrier in the oxygen release reactor 3 is separated by the first cyclone separator 33 and then mixed with 95% ambient temperature fuel gas from the burner 11 into the heating furnace 1 to produce high temperature flue gas.

[0090] 6) After the temperature of the feed oil entering the heating furnace 1 is reduced to 200℃, a portion of the high-temperature flue gas mixes with 5% ambient temperature fuel gas and enters the oxygen release reactor 3 through the first inlet. The fuel gas in the oxygen release reactor reacts with the oxygen released by the oxygen carrier, releasing heat to provide heat for subsequent oxygen release and hydrogen production by the oxygen carrier. Another portion of the flue gas enters the second heat exchanger E2 to heat the medium-temperature water, reducing the temperature to 80℃ before entering the first condenser R1 for gas-liquid separation. The separated gas consists of condensate and CO2 gas with a purity of over 99%, which is then stored.

[0091] 7) The raw oil entering the heating furnace 1 from the raw oil inlet is heated to the target temperature by the high-temperature flue gas and then flows out from the raw oil outlet to enter the subsequent process.

[0092] 8) Room temperature water enters the first heat exchanger E1 to exchange heat with oxygen-deficient air, and after the temperature rises to 70°C, it enters the second heat exchanger E2 to exchange heat with the flue gas of the heating furnace, and becomes 150°C low temperature water vapor. Then it enters the third heat exchanger E3, where the temperature rises to 550°C. As a fluidizing gas, it enters the reactor from the second inlet of the hydrogen production reactor 4 to participate in the reaction.

[0093] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. An oxygen-enriched combustion heating furnace system that produces hydrogen as a byproduct, characterized in that: It includes a heating furnace (1), an oxygen release reactor (3), a hydrogen production reactor (4), an oxygen absorption reactor (5), a normal temperature water source (6), an air source (7), a fuel gas source (8), a first heat exchanger (E1), a second heat exchanger (E2), a third heat exchanger (E3), a fourth heat exchanger (E4), a first condenser (R1), and a second condenser (R2). The outlet of the oxygen absorption reactor (5) is connected to the third cyclone separator (53), the gas phase outlet of the third cyclone separator (53) is connected in sequence to the third heat exchanger (E3) and the first heat exchanger (E1), and the solid phase outlet of the third cyclone separator (53) is connected to the solid phase inlet of the oxygen release reactor (3). The outlet of the oxygen release reactor (3) is connected to the first cyclone separator (33), the gas phase outlet of the first cyclone separator (33) is connected to the burner inlet of the heating furnace (1), and the solid phase outlet of the first cyclone separator (33) is connected to the solid phase inlet of the hydrogen production reactor (4). The outlet of the hydrogen production reactor (4) is connected to the second cyclone separator (43), the gas phase outlet of the second cyclone separator (43) is connected in sequence to the fourth heat exchanger (E4) and the first condenser (R1), and the solid phase outlet of the second cyclone separator (43) is connected to the solid phase inlet of the oxygen absorption reactor (5). The flue gas outlet of the heating furnace (1) is divided into two paths, one of which is connected to the gas phase feed port of the oxygen release reactor (3), and the other path is connected in sequence to the second heat exchanger (E2) and the second condenser (R2). The ambient temperature water source (6) is connected to the gas phase feed port of the hydrogen production reactor (4) after passing through the first heat exchanger (E1), the second heat exchanger (E2) and the third heat exchanger (E3) in sequence. The air source (7) is connected to the gas phase inlet of the oxygen absorption reactor (5) via the fourth heat exchanger (E4); The fuel gas source (8) is divided into two paths, one of which is connected to the burner inlet of the heating furnace (1), and the other is connected to the gas phase feed port of the oxygen release reactor (3).

2. The oxygen-enriched combustion heating furnace system for producing hydrogen as a byproduct as described in claim 1, characterized in that: A gas turbine (2) is also provided between the third cyclone separator (53) and the third heat exchanger (E3).

3. The oxygen-enriched combustion heating furnace system for producing hydrogen as a byproduct as described in claim 1, characterized in that: The solid material circulating between the oxygen release reactor (3), the hydrogen production reactor (4), and the oxygen absorption reactor (5) is an oxygen carrier.

4. The oxygen-enriched combustion heating furnace system for producing hydrogen as a byproduct as described in claim 3, characterized in that: The oxygen carrier can be a metal oxygen carrier or a non-metal oxygen carrier. The metal oxygen carrier can be an iron-aluminum based oxygen carrier or an iron-cobalt based oxygen carrier, and the non-metal oxygen carrier can be a perovskite oxygen carrier.

5. The oxygen-enriched combustion heating furnace system for producing hydrogen as a byproduct as described in claim 4, characterized in that: The oxygen carrier is an iron-cobalt based composite oxygen carrier, and the elemental mass ratio of Fe / Co in the composite oxygen carrier is 7:

3.

6. The oxygen-enriched combustion heating furnace system for producing hydrogen as a byproduct as described in claim 1, characterized in that: The oxygen release reactor (3), hydrogen production reactor (4) and oxygen absorption reactor (5) are all fluidized bed reactors. The working pressure of the reactors is 0.1~0.5MPa. The working temperature of the oxygen release reactor (3) is 500~900℃, the working temperature of the hydrogen production reactor (4) is 450~850℃, and the working temperature of the oxygen absorption reactor (5) is 400~950℃.

7. A method for operating an oxygen-enriched combustion heating furnace system that produces hydrogen as a byproduct, characterized in that: Normal temperature air enters the fourth heat exchanger (E4) to exchange heat with the hydrogen-rich gas produced by the hydrogen production reactor (4). After the temperature rises, it enters the oxygen absorption reactor (5) and reacts with the micro-oxygen carrier that enters the oxygen absorption reactor (5) from the hydrogen production reactor (4). It becomes oxygen-deficient air and enters the third heat exchanger (E3) to exchange heat with water vapor to cool down. Alternatively, it becomes oxygen-deficient air and enters the gas turbine (2) to do work and then enters the third heat exchanger (E3) to exchange heat with water vapor to cool down. After that, it enters the first heat exchanger (E1) to exchange heat with normal temperature water. After the temperature drops, it is directly discharged. The micro-oxygen carrier absorbs oxygen in the oxygen absorption reactor (5) and becomes an oxygen-rich carrier, then enters the oxygen release reactor (3). Under the action of the furnace flue gas and fuel gas, it releases oxygen and becomes an oxygen-deficient carrier, which then enters the hydrogen production reactor (4). The oxygen-deficient oxygen carrier enters the hydrogen production reactor (4) and reacts with the high-temperature water vapor entering from the third heat exchanger (E3) to produce hydrogen. The oxygen-deficient oxygen carrier becomes a micro-oxygen oxygen carrier and enters the oxygen absorption reactor (5) to complete the circulation of the oxygen carrier. The hydrogen-rich gas produced by the hydrogen production reactor (4) enters the fourth heat exchanger (E4) to exchange heat with room temperature air. After the temperature drops, it enters the second condenser (R2) for gas-liquid separation. The hydrogen-rich gas is separated into condensate and hydrogen with a purity of more than 99%. The oxygen-rich flue gas generated by the oxygen carrier in the oxygen release reactor (3) is mixed with the fuel gas and enters the heating furnace (1) from the burner for combustion. The high-temperature flue gas generated by combustion heats the raw oil entering the heating furnace (1). After the raw oil reaches the target temperature, it flows out from the heating furnace (1) and enters the subsequent process. After the temperature drops, part of the flue gas and part of the fuel gas enter the oxygen release reactor (3) to participate in the reaction, and another part of the flue gas enters the second heat exchanger (E2) to heat the medium-temperature water. After the temperature drops, it enters the first condenser (R1) for gas-liquid separation, which separates into condensate and carbon dioxide with a purity of more than 99%. The carbon dioxide is collected and stored. Room temperature water enters the first heat exchanger (E1) to exchange heat with oxygen-deficient air. After the temperature rises, it enters the second heat exchanger (E2) to exchange heat with the flue gas of the heating furnace and becomes water vapor. Then it enters the third heat exchanger (E3) to exchange heat with oxygen-deficient air. After the temperature rises, it enters the hydrogen production reactor (4) as a fluidized gas to participate in the reaction.

8. The method for operating the oxygen-enriched combustion heating furnace system for producing hydrogen as a byproduct as described in claim 7, characterized in that: By controlling the amount of fuel gas and flue gas entering the oxygen release reactor (3), the oxygen concentration of the oxygen-enriched flue gas entering the heating furnace (1) is adjusted to 21~50%.

9. The method for operating the oxygen-enriched combustion heating furnace system for producing hydrogen as a byproduct as described in claim 8, characterized in that: By controlling the amount of fuel gas and flue gas entering the oxygen release reactor (3), the oxygen concentration of the oxygen-enriched flue gas entering the heating furnace (1) is adjusted to 25-30%.

10. The method for operating the oxygen-enriched combustion heating furnace system for producing hydrogen as a byproduct as described in claim 7, characterized in that: The fuel gas entering the oxygen release reactor (3) accounts for 5-30% of the total fuel gas.

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