A method for synthesis of high value products using refinery furnace gas

Abstract

The present application relates to a method for synthesizing high-value products by using refinery furnace gas, which is purified and then sent to a chemical chain three-stage atmospheric reactor, near-pure carbon dioxide, nitrogen and hydrogen products are obtained in each stage, the near-pure hydrogen product after reforming of coke oven gas is used as a supplement hydrogen source to adjust the gas structure, after being pressurized, the mixed raw material is sent to a synthesizer, and then methanol or ammonia products are obtained after gas-liquid separation. The present application solves the problem that carbon dioxide and nitrogen cannot be utilized when traditional refinery furnace gas replaces coal-based carbon monoxide to synthesize high-value products by chemical carbonylation; absorbs part of the coke oven gas at the tail end of the coke oven process, and makes up for the defect that the raw material structure needs cheap hydrogen source supplement in the process; and optimizes the tail gas and low-grade heat recycling process in each production process, realizes near-zero emission in the life cycle and chemical energy cascade utilization.

Description

Technical Field

[0001] This invention relates to the fields of energy conversion and chemical synthesis technology, and in particular to a method for synthesizing high-value products using refinery furnace gas. Background Technology

[0002] China's steel industry consumes approximately 15% of the nation's total industrial energy consumption, accounts for 26% of total industrial emissions, and contributes about 15% of the nation's total carbon emissions. Refineries have long produced blast furnace gas / converter gas, primarily composed of carbon monoxide (CO), carbon dioxide (CO2), and nitrogen (N2). Aside from its use for heating, most of this refinery gas is used for power generation, with a thermal efficiency of only 30%–40%. Power generation using refinery gas (mainly through carbon monoxide combustion) is highly carbon-emitting, with a carbon emission coefficient of 1940 g CO2 equivalent / kWh, far exceeding that of grid power (590 g CO2 equivalent / kWh) and even coal-fired power generation (930 g CO2 equivalent / kWh). Currently, domestic refineries have largely balanced the use of their blast furnace gas, but whether used in processes or for power generation, the carbon monoxide in the gas is converted into carbon dioxide emissions, failing to achieve a fundamental reduction in carbon dioxide emissions.

[0003] Replacing coal-based carbon monoxide with refinery furnace gas as a feedstock, and producing high-value-added products such as methanol, ethanol, natural gas, or polymers through chemical carbonylation processes, avoids the high-carbon-emission method of converting carbon in refinery furnace gas into electricity. This is a key step in reducing greenhouse gas emissions from the steel and chemical industries. While extracting carbon monoxide from refinery furnace gas as a non-fossil feedstock improves the quality of furnace gas utilization and eliminates traditional C1 chemical gasification and air separation processes, it also faces the drawback of not being able to utilize the large amounts of carbon dioxide and nitrogen resources in the furnace gas and thus having to be released.

[0004] Furthermore, since the synthesis of these typical chemical products generally involves a hydrogenation process, companies with coking facilities can achieve this by separating hydrogen from coke oven gas. However, for companies without coking facilities, securing a cheap hydrogen source is the primary challenge. Additionally, the matching raw material structure (such as the hydrogen-to-carbon ratio) required for synthesizing these typical chemical products typically necessitates supplementary gas processes to compensate for the process variations, thus limiting their large-scale application. Summary of the Invention

[0005] The purpose of this invention is to provide a method for synthesizing high-value products using refinery furnace gas, in order to solve the problems of low utilization rate of refinery furnace gas and generation of carbon dioxide greenhouse gas.

[0006] This method uses furnace gas (mainly blast furnace gas or converter gas) generated by refineries over a long period of time as a non-fossil feedstock. After optimizing the structure (hydrogen-to-carbon ratio and hydrogen-to-nitrogen ratio) of the gas products obtained from each stage of the three-stage chemical loop reforming reactor, the gas is pressurized and sent to a methanol or ammonia synthesizer. This solves the problem that carbon dioxide and nitrogen cannot be utilized when using refinery furnace gas as a feedstock to replace coal-based carbon monoxide for chemical carbonylation synthesis of high-value products. At the same time, it solves the problem of additional costs and carbon emissions faced by other methods of hydrogen production.

[0007] This method optimizes the process flow by using the oxygen-depleted air (mainly nitrogen) product obtained from the oxidation process in the air reactor of the three-stage chemical loop reactor as a high-purity nitrogen source for the ammonia synthesis process. This solves the problem of nitrogen source loss caused by the long-term release and treatment of oxygen-depleted air products in the traditional process.

[0008] This method also uses coke oven gas produced in the coke oven process to produce syngas (carbon monoxide and hydrogen) and hydrogen through chemical loop reforming. The syngas can be returned to the waste heat boiler to recover heat and then used as a product, or fed into the methanol synthesizer after adjusting the gas structure (hydrogen-to-carbon ratio) as needed. The hydrogen can be used independently as a supplementary gas source to compensate for the mismatch in raw material structure during the process, expanding the refinery's flue gas industrial route and solving the problem of obtaining a cheap hydrogen source (0.868 yuan / Nm³) for the supplementary gas stage. 3 The problem is...

[0009] This method optimizes the process flow by purifying excess unreacted gas in the methanol or ammonia synthesizer through an absorption tower to achieve the gas structure required for methanol or ammonia synthesis, and then reusing it in the mixing and homogenization process to replace part of the fresh gas source. This solves the problem of low single-pass conversion rate of synthesis gas leading to long-term circulation and enrichment of large amounts of unreacted gas, requiring periodic venting or replenishment of fresh gas to maintain normal operation of the process.

[0010] To overcome the aforementioned problems in the existing technology, the present invention provides the following specific technical solution:

[0011] A method for synthesizing high-value products using refinery furnace gas includes a raw material preparation process and a product preparation process;

[0012] The raw material preparation process includes the following steps:

[0013] S1. The crude furnace gas emitted by the refinery unit is purified by dust removal and pollutant removal to obtain clean furnace gas.

[0014] S2. After recovering heat energy from the first waste heat boiler, the clean furnace gas is sent to the first fuel reactor. The first fuel reactor is equipped with a solid oxygen carrier material. The clean furnace gas reacts with the solid oxygen carrier material to produce carbon dioxide. At the end of the first fuel reactor, a mixture of carbon dioxide and nitrogen is output as tail gas. After adsorption and separation, nearly pure carbon dioxide and nearly pure nitrogen are obtained respectively.

[0015] S3. After step S2, the solid oxygen-carrying material becomes an oxygen-depleted solid material. The oxygen-depleted solid material is sent to the first steam reactor, and water vapor is sent into the first steam reactor at the same time. The oxygen-depleted solid material and water vapor undergo a reforming reaction to generate hydrogen. The oxygen-depleted solid material achieves partial oxygen recovery, resulting in a partially oxygen-recovered solid material.

[0016] S4. The partially oxygen-recovered solid material is sent to the air reactor, where air reacts with the partially oxygen-recovered solid material to obtain near-pure nitrogen.

[0017] S5. The crude coke oven gas emitted by the refinery unit is purified by dust removal and pollutant removal to obtain clean coke oven gas. The clean coke oven gas is sent to the second fuel reactor, which is equipped with solid oxygen carrier material. The clean coke oven gas reacts with the solid oxygen carrier material to produce syngas including carbon monoxide and hydrogen.

[0018] The solid oxygen-carrying material is transformed into an oxygen-depleted solid material, which is then sent to the second stage steam reactor. Simultaneously, water vapor is introduced into the second steam reactor, where the oxygen-depleted solid material and water vapor undergo a reforming reaction to generate hydrogen.

[0019] The product preparation process includes the following steps:

[0020] S6. After adjusting the hydrogen-carbon ratio or hydrogen-nitrogen ratio of the gas structure, near-pure carbon dioxide, near-pure nitrogen and near-pure hydrogen are sent to the mixer and homogenizer to prepare the raw material gas for the synthesis of methanol or ammonia.

[0021] S7. The raw material gas for synthesizing methanol or ammonia is sent into a pressurizing buffer and then sent to the tower preheater after being pressurized.

[0022] S8. The preheated raw material gas for the synthesis of methanol or ammonia is sent into the synthesis tower for synthesis reaction, and methanol or ammonia products are obtained after gas-liquid separation.

[0023] Preferably, in step S1, the clean furnace gas is clean blast furnace gas or clean converter gas.

[0024] Preferably, in step S1, the raw furnace gas is sent to a three-stage dry bag filter for dust removal, and the dust-removed furnace gas is sequentially sent to a catalytic purifier and an adsorption purifier to remove pollutants, thus obtaining clean furnace gas.

[0025] Preferably, in step S2, the temperature of the first fuel reactor is set to 550-650℃, and the solid oxygen carrier material is one of the self-made cerium iron zirconium / Al2O3 honeycomb ceramic integral oxygen carrier and cerium iron zirconium / MgO honeycomb ceramic integral oxygen carrier, as disclosed in invention patent CN101857458B.

[0026] Preferably, in step S3, the reaction temperature is 550-650℃, and the steam is generated by a steam generator driven by low-grade heat energy recovered from the first waste heat boiler.

[0027] Preferably, in step S4, the reaction temperature is 550-650℃, and the partially oxygen-recovered solid material achieves complete oxygen recovery, resulting in a solid oxygen-carrying material, which is then returned to the first fuel reactor for recycling; the thermal energy carried by the near-pure nitrogen gas is recovered by the first waste heat boiler.

[0028] Preferably, in step S5, the temperature of the second fuel reactor is set to 800-850℃, and the solid oxygen carrier material is one of a self-made A-site nickel-doped perovskite oxygen carrier and an A-site strontium-doped perovskite oxygen carrier, as disclosed in invention patent CN111232920B; the steam is generated by a steam generator driven by low-grade heat energy recovered from the first waste heat boiler.

[0029] Preferably, in the product preparation process, the methanol synthesis catalyst is a self-made ordered hierarchical porous copper-based catalyst, as disclosed in invention application CN117101665A, and the ammonia synthesis catalyst is an iron-based catalyst.

[0030] Preferably, the product preparation process includes an in-situ methanol preparation process and an ammonia preparation process arranged in parallel.

[0031] Preferably, the methanol preparation process includes the following steps:

[0032] S61. The carbon dioxide from step S2, the hydrogen from step S3, and the hydrogen from step S5 are adjusted to a hydrogen-to-carbon ratio of 3.0 and then fed into the first mixing and homogenizing unit to prepare the raw material gas for methanol synthesis.

[0033] S71. The raw material gas for methanol synthesis is sent into the first pressurization buffer and pressurized to 3-5 MPa before being sent to the first tower preheater. The temperature of the first tower preheater is set to 130-150℃.

[0034] S81. The preheated methanol feed gas is fed into the first synthesis tower for synthesis reaction. The temperature of the first synthesis tower is set to 200-250℃. The reaction product is separated into methanol at the end of the first synthesis tower. The unreacted gas desorbed from the top of the first synthesis tower enters the first absorption tower. After purification by the first absorption tower, it is sent back to the first mixing homogenizer to replace part of the fresh methanol feed gas. The low-grade heat energy in the depressurized unreacted gas is recovered by the second waste heat boiler and sent to the preheater before the first tower to replace part of the heat energy.

[0035] Preferably, the ammonia preparation process includes the following steps:

[0036] S62. After adjusting the nitrogen gas from step S2 or step S4, the hydrogen gas from step S3, and the hydrogen gas from step S5 to a hydrogen-nitrogen ratio of 2.7-3.0, the mixture is sent to the second mixing and homogenizing unit to prepare ammonia synthesis feed gas.

[0037] S72. The ammonia synthesis feed gas is sent into the second pressurizing buffer and pressurized to 7-8 MPa before being sent into the second tower preheater. The temperature of the second tower preheater is set to 150-200℃.

[0038] S82. The preheated ammonia feed gas is sent to the second synthesis tower for synthesis reaction. The temperature of the second synthesis tower is set to 280-320℃. The reaction product is separated into liquid ammonia at the end of the second synthesis tower. The unreacted gas desorbed from the top of the second synthesis tower enters the second absorption tower. After being purified by the second absorption tower, it is sent back to the second mixing and homogenizing unit to replace part of the fresh ammonia feed gas. The low-grade heat energy in the depressurized unreacted gas is recovered by the third waste heat boiler and sent to the preheater before the second tower to replace part of the heat energy.

[0039] The present invention provides a method for synthesizing high-value products using refinery furnace gas, which has the following advantages compared with the prior art:

[0040] 1. This invention comprehensively and efficiently utilizes resources at all levels within refinery furnace gas, maximizing their development and application. By complementarily utilizing the carbon, hydrogen, and nitrogen elements contained in the furnace gas emitted by refineries over long periods, this method effectively solves the problem of the ineffective utilization of large amounts of carbon dioxide and nitrogen when using traditional refinery furnace gas as a feedstock to replace coal-based carbon monoxide. This not only promotes the deep integration and utilization of resources but also achieves the goal of near-zero carbon dioxide emissions.

[0041] 2. The production process of the method described in this invention takes the chemical reforming of refinery furnace gas as the starting point. The inherent high purity of the end product avoids the interference of other inert gases on the contact layer temperature. It can achieve a qualitative improvement compared to the traditional refinery furnace gas component extraction process without high investment.

[0042] 3. The method described in this invention utilizes the gaseous products obtained from the coking process for internal self-supplementation within the system as needed, avoiding additional investment in hydrogen production and energy consumption. When renewable energy develops rapidly in the future, it can be integrated into the network described in this invention without large-scale modifications to existing technology.

[0043] 4. The method described in this invention optimizes the gas recycling process in the production process, recycling low-grade tail gas, mainly nitrogen, or unreacted gas into the system for use. It allows for the independent operation of local process shutdowns, significantly reducing long-term equipment operation losses, while retaining most of the original production equipment and facilities. Only appropriate modifications are needed to achieve a qualitative change in overall efficiency and improve benefits, making it easy to promote industrialization in a short period of time.

[0044] 5. The method described in this invention optimizes the intermittent fluctuation defect of the working load in the production process, and achieves high-level production of product gas by linking various production stages through gas buffering. Furthermore, it replaces part of the high-grade fuel combustion heating with low-grade heat energy recovered from the waste heat boiler, alleviating heat energy consumption during combustion and realizing the cascade utilization of chemical energy.

[0045] 6. The method described in this invention solves the problem that current thermocatalytic hydrogenation reaction systems and photocatalytic / electrocatalytic reduction reaction systems rely on purchased standard gases as raw materials, which is not conducive to the transition of catalytic reactions from laboratory scale to industrial scale. It provides a feasible solution for the emission and reuse of complex gas sources throughout the entire life cycle. Attached Figure Description

[0046] Figure 1 This is a schematic diagram of the entire process of synthesizing high-value products using refinery furnace gas.

[0047] Figure 2 This is a flowchart illustrating the raw material preparation process.

[0048] Figure 3 A flowchart illustrating the product preparation process;

[0049] Diagram markings: 1. Refinery Unit 1; 2. Refinery Unit 2; 3. First three-way valve; 4. Bag filter; 5. Catalytic converter; 6. First adsorption converter; 7. First waste heat boiler; 8. Second three-way valve; 9. First pressure reducing valve; 10. First electromagnetic flowmeter; 11. Third three-way valve; 12. First fuel reactor; 13. Adsorption separator; 14. First saturated storage tank; 15. Second saturated storage tank; 16. Steam generator; 17. Fourth three-way valve; 18. 19. Second electromagnetic flowmeter; 20. First steam reactor; 21. First heat exchanger; 22. Fifth three-way valve; 23. Third saturated storage tank; 24. Air reactor; 25. Second adsorption purifier; 26. Sixth three-way valve; 27. Third electromagnetic flowmeter; 28. Second pressure reducing valve; 29. ​​Fourth electromagnetic flowmeter; 30. Second fuel reactor; 31. Second heat exchanger; 32. Fifth electromagnetic flowmeter; 33. Second steam reactor; 34. Third heat exchanger; 35. Fourth saturated storage tank; 26. Air reactor; 27. Second adsorption purifier; 28. Sixth three-way valve; 29. ​​Third electromagnetic flowmeter; 20. Second three-way valve; 20. Third three-way valve; 21. Fifth three-way valve; 22. Third three-way valve; 23. Fourth three-way valve; 24. Third three-way valve; 25. Third three-way valve; 26. Fourth electromagnetic flowmeter; 27. Second pressure reducing valve; 28. Fourth electromagnetic flowmeter; 29. ​​Second fuel reactor; 30. Second heat exchanger; 31. Fifth electromagnetic flowmeter; 32. Second steam reactor; 33. Third heat exchanger; 34. Fourth three-way valve; 25. Third three-way valve; 26. Third three-way valve ... three-way valve; 28. Third three-way valve; 29. ​​Second fuel reactor; 30. Second heat exchanger; 31. Fifth electromagnetic flowmeter; 22. Second three- Storage tank; 35. Third pressure reducing valve; 36. Sixth electromagnetic flowmeter; 37. Fourth pressure reducing valve; 38. Seventh three-way valve; 39. Seventh electromagnetic flowmeter; 40. Fifth pressure reducing valve; 41. Eighth electromagnetic flowmeter; 42. Eighth three-way valve; 43. First mixing homogenizer; 44. First pressurization buffer; 45. First pressure gauge; 46. Ninth electromagnetic flowmeter; 47. First tower preheater; 48. First synthesis tower; 49. Fourth heat exchanger; 50. First gas-liquid separator. 51. First absorption tower; 52. Second waste heat boiler; 53. Tenth electromagnetic flowmeter; 54. Sixth pressure reducing valve; 55. Eleventh electromagnetic flowmeter; 56. Ninth three-way valve; 57. Second mixing homogenizer; 58. Second pressure buffer; 59. Second pressure gauge; 60. Twelfth electromagnetic flowmeter; 61. Second tower preheater; 62. Second synthesis tower; 63. Fifth heat exchanger; 64. Second gas-liquid separator; 65. Second absorption tower; 66. Third waste heat boiler. Detailed Implementation

[0050] To further illustrate the technical means and effects of the present invention in achieving the intended purpose, the following detailed description of the specific implementation methods, structures, features and effects of the present invention, in conjunction with preferred embodiments, is provided below.

[0051] This invention provides a method for synthesizing high-value products using refinery furnace gas, combined with Figure 1 The specific embodiments of the present invention are as follows:

[0052] The crude furnace gas produced by the refinery units, including crude blast furnace gas and converter gas, is purified by dust removal and purification units to obtain clean blast furnace gas or converter gas. The low-grade heat energy in the furnace gas is recovered by the first waste heat boiler 7. The clean blast furnace gas or converter gas is sent as gaseous fuel to the first fuel reactor 12 of the three-stage chemical loop reactor. The combustion of fuel produces a mixture of carbon dioxide and nitrogen in the tail gas. After passing through the molecular sieve adsorption separator 13, near-pure carbon dioxide and near-pure nitrogen products are obtained respectively and sent to the first saturated storage tank 14 and the second saturated storage tank 15.

[0053] The low-grade heat energy recovered by the first waste heat boiler 7 is sent to the steam generator 16. The steam generated by the steam generator 16 is sent to the first steam reactor 19 for reforming reaction. The product is heat exchanged by the first heat exchanger 20 to obtain near-pure hydrogen. The hydrogen is sent to the third saturated storage tank 22 through the fifth three-way valve 21.

[0054] Clean air is sent into air reactor 23 for oxidation reaction, and the resulting oxygen-depleted air, i.e. near-pure nitrogen product, is recycled into the chemical chain system or sent to the second saturated storage tank 15; the heat energy generated in the high-temperature oxygen-depleted air is recovered by the first waste heat boiler 7.

[0055] The crude coke oven gas produced by the coke oven unit is purified by dust removal and purification units to obtain clean coke oven gas. The low-grade heat energy in the gas is recovered by the first waste heat boiler 7. The clean coke oven gas is sent to the second fuel reactor 29 as gaseous fuel. The fuel combustion produces a tail gas that is a mixture of carbon monoxide and hydrogen. After heat exchange in the second heat exchanger 30, syngas product is obtained.

[0056] The low-grade heat energy recovered by the first waste heat boiler 7 is sent to the steam generator 16. The steam generated by the steam generator 16 is sent to the second steam reactor 32 for reforming reaction. The product is then heat-exchanged by the third heat exchanger 33 to obtain near-pure hydrogen, which is then sent to the fourth saturated storage tank 34.

[0057] The carbon dioxide in the first saturated storage tank 14 and the hydrogen in the third saturated storage tank 22 are adjusted to a hydrogen-carbon ratio. The insufficient hydrogen is supplemented by hydrogen in the fourth saturated storage tank 34. The adjusted gas stream is sent to the first mixing and homogenizing unit 43, where it is formulated into methanol synthesis feed gas. After the methanol feed gas reaches the standard pressure through the first pressurization buffer 44, it is sent to the first tower preheater 47. The preheated high-pressure methanol feed gas is sent to the first synthesis tower 48. The top product of the first synthesis tower 48 is sent to the first gas-liquid separator 50, where methanol product is obtained through gas-liquid separation. The depressurized unreacted gas at the top of the first synthesis tower 48 is sent to the first absorption tower 51. After absorption and purification, it is returned to the first mixing and homogenizing unit 43 to replace part of the fresh methanol feed gas. The low-grade heat energy in the depressurized unreacted gas is recovered by the second waste heat boiler 52 and sent to the first tower preheater 47 to replace part of the heat energy.

[0058] The nitrogen in the second saturated storage tank 15 and the hydrogen in the third saturated storage tank 22 are adjusted to a hydrogen-nitrogen ratio. Any insufficient hydrogen is supplemented by hydrogen from the fourth saturated storage tank 34. The adjusted gas stream is then fed into the second mixing and homogenizing unit 57, where it is formulated into ammonia synthesis feed gas. After reaching the standard pressure via the second pressurization buffer 58, the ammonia synthesis feed gas is fed into the second preheater 61. The preheated ammonia synthesis feed gas is then fed into the second synthesis tower 62. The top desorption product from the second synthesis tower 62 is fed into the second gas-liquid separator 64. Liquid ammonia is obtained through gas-liquid separation; the unreacted gas from the top of the second synthesis tower 62 is sent to the second absorption tower 65, and after absorption and purification, it is returned to the second mixing and homogenizing unit 57 to replace part of the fresh ammonia raw material gas; the low-grade heat energy in the unreacted gas is recovered by the third waste heat boiler 66 and sent to the preheater 61 before the second tower to replace part of the heat energy; through optimized process design, the third waste heat boiler 66 can be completely replaced by the second waste heat boiler 52, that is, the second waste heat boiler 52 and the third waste heat boiler can be integrated into one waste heat boiler.

[0059] The present invention discloses a method for synthesizing high-value products using refinery furnace gas, which is implemented by an apparatus for synthesizing high-value products using refinery furnace gas, such as... Figure 1 As shown.

[0060] The refinery unit includes Unit 1 and Unit 2. The furnace gas outlet of the refinery unit is connected to the inlet of the first three-way valve 3. The outlet of the first three-way valve 3 is connected to the inlet of the bag filter 4. The outlet of the bag filter 4 is connected to the inlet of the catalytic converter 5. The outlet of the catalytic converter 5 is connected to the inlet of the first adsorption converter 6. The outlet of the first adsorption converter 6 is connected to the inlet of the first waste heat boiler 7. The heat energy outlet of the first waste heat boiler 7 is connected to the heat energy inlet of the steam generator 16. The gas outlet of the first waste heat boiler 7 serves as the inlet for the refinery furnace gas to enter the first fuel reactor 12 of the chemical loop system. A second three-way valve 8, a first pressure reducing valve 9, a first electromagnetic flowmeter 10, and a third three-way valve 11 are installed in the direction of gas flow on the connecting pipeline between the first waste heat boiler 7 and the first fuel reactor 12.

[0061] The gas outlet of the chemical chain first fuel reactor 12 is connected to the gas inlet of the adsorption separator 13. The adsorption separator 13 separates carbon dioxide and nitrogen and stores them in the first saturated storage tank 14 and the second saturated storage tank 15, respectively.

[0062] The gas outlet of the first steam reactor 19 in the chemical chain is connected to the gas inlet of the first heat exchanger 20. After heat exchange, hydrogen is stored in the third saturated storage tank 22.

[0063] The thermal outlet of the chemical loop air reactor 23 is connected to the inlet of the first waste heat boiler 7; the gas outlet of the air reactor 23 is connected to the first fuel reactor 12 and the second saturated storage tank 15 via the sixth three-way valve 25, and a third electromagnetic flow meter 26 is installed on the connecting pipe between the sixth three-way valve 25 and the first fuel reactor 12.

[0064] The gas outlet of the first waste heat boiler 7 is also connected to the gas inlet of the second fuel reactor 29 through the second three-way valve 8. The connecting pipeline is equipped with a second pressure reducing valve 27 and a fourth electromagnetic flow meter 28. The second fuel reactor 29 generates syngas products.

[0065] The steam generated by the steam generator 16 enters the first steam reactor 19 and the second steam reactor 32 through the fourth three-way valve 17. A second electromagnetic flow meter 18 is installed on the connecting pipe between the fourth three-way valve 17 and the first steam reactor 19. A fifth electromagnetic flow meter 31 is installed on the connecting pipe between the fourth three-way valve 17 and the second steam reactor 32. The gas outlet of the second steam reactor 32 is connected to the gas inlet of the third heat exchanger 33. After heat exchange, the hydrogen is stored in the fourth saturated storage tank 34.

[0066] The third saturated storage tank 22 and the fourth saturated storage tank 34 are interconnected, and a third pressure reducing valve 35 and a sixth electromagnetic flow meter 36 are installed on the connecting pipeline.

[0067] The third saturated storage tank 22 enters the first mixing homogenizer 43 and the second mixing homogenizer 57 of the synthesis system through the seventh three-way valve 38. A fourth pressure reducing valve 37 is installed on the connecting pipe between the third saturated storage tank 22 and the seventh three-way valve 38. A seventh electromagnetic flow meter 39 is installed on the connecting pipe between the seventh three-way valve 38 and the first mixing homogenizer 43. The gas inlet of the first mixing homogenizer 43 is also connected to the first saturated storage tank 14. A fifth pressure reducing valve 40, an eighth electromagnetic flow meter 41, and an eighth three-way valve 42 are installed on the connecting pipe. The gas outlet of the first mixing homogenizer 43 is connected to the gas inlet of the first pressure buffer 44. The gas outlet of the first pressure buffer 44 is connected to the gas inlet of the first tower preheater 47. The inlet is connected, and a first pressure gauge 45 and a ninth electromagnetic flowmeter 46 are installed on the connecting pipeline. The gas outlet of the first preheater 47 is connected to the gas inlet of the first synthesis tower 48. The first synthesis tower 48 synthesizes methanol. The gas outlet of the first synthesis tower 48 is connected to the inlet of the first gas-liquid separator 50 after passing through the fourth heat exchanger 49. The unreacted top gas outlet of the first synthesis tower 48 is connected to the inlet of the first absorption tower 51. The outlet of the first absorption tower 51 is connected to the inlet of the second waste heat boiler 52. The heat energy outlet of the second waste heat boiler 52 is connected to the inlet of the first preheater 47. The gas outlet of the second waste heat boiler 52 is connected to the inlet of the first mixing homogenizer 43. The product from the outlet of the first gas-liquid separator 50 is the final product of this invention.

[0068] A tenth electromagnetic flowmeter 53 is installed on the connecting pipe between the seventh three-way valve 38 and the second mixing homogenizer 57. The gas inlet of the second mixing homogenizer 57 is also connected to the second saturated storage tank 15. A sixth pressure reducing valve 54, an eleventh electromagnetic flowmeter 55, and a ninth three-way valve 56 are installed on the connecting pipe. The gas outlet of the second mixing homogenizer 57 is connected to the gas inlet of the second pressure buffer 58. The gas outlet of the second pressure buffer 58 is connected to the gas inlet of the second tower preheater 61. A second pressure gauge 59 and a twelfth electromagnetic flowmeter 60 are installed on the connecting pipe. The second tower preheater... The gas outlet of unit 61 is connected to the gas inlet of the second synthesis tower 62. The second synthesis tower 62 synthesizes ammonia. The gas outlet of the second synthesis tower 62 is connected to the inlet of the second gas-liquid separator 64 after passing through the fifth heat exchanger 63. The unreacted top gas outlet of the second synthesis tower 62 is connected to the inlet of the second absorption tower 65. The outlet of the second absorption tower 65 is connected to the inlet of the third waste heat boiler 66. The heat energy outlet of the third waste heat boiler 66 is connected to the inlet of the preheater 61 before the second tower. The gas outlet of the third waste heat boiler 66 is connected to the inlet of the second mixing and homogenizing device 57. The product from the outlet of the second gas-liquid separator 64 is the final product of this invention.

[0069] To better understand the present invention, the following embodiments are provided for further detailed description of the invention, but they should not be construed as limiting the invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description are also considered to fall within the protection scope of the present invention.

[0070] Example 1

[0071] This embodiment provides a method for synthesizing high-value products using refinery furnace gas, including the following steps:

[0072] S1. The raw furnace gas emitted from refinery unit 1 is sent to a three-stage dry bag filter 4 for dust removal to avoid the impact of dust on the quality of the furnace gas. The dust-removed furnace gas is then sent sequentially to a catalytic purifier 5 containing a specific catalyst and a first adsorption purifier 6 containing a specific adsorbent to remove most of the pollutants and obtain clean blast furnace gas. The specific process can be referred to in existing dust removal and purification processes. This embodiment of the present invention will not explain it in detail.

[0073] S2. The cleaned blast furnace gas, after dust removal and purification, is fed into the first fuel reactor 12 of the first stage of the three-stage chemical loop reactor after heat energy recovery via the first waste heat boiler 7. The first waste heat boiler 7 is located downstream of the purification process to recover the waste heat of the furnace gas as low-grade heat energy to supply subsequent processes. The temperature of the first fuel reactor 12 is set at 550℃. The first fuel reactor 12 is equipped with a solid oxygen-carrying material, which is a self-made cerium-iron-zirconium / MgO honeycomb ceramic integral oxygen carrier. The solid oxygen-carrying material loses oxygen in the high-temperature environment and reacts with carbon monoxide in the blast furnace gas to generate carbon dioxide. At the end of the first fuel reactor 12, a mixture of carbon dioxide and nitrogen is output as tail gas, in which the purity of carbon dioxide is 45% and the purity of nitrogen is 55%. The mixture of carbon dioxide and nitrogen is fed into an adsorption separator 13, where the two are separated by the existing adsorption separation process to obtain near-pure carbon dioxide and near-pure nitrogen. The near-pure carbon dioxide is sent to the first saturated storage tank 14, and the near-pure nitrogen is sent to the second saturated storage tank 15. The solid oxygen-carrying material used in the first fuel reactor 12 is a self-made cerium-iron-zirconium honeycomb ceramic integral oxygen carrier, as disclosed in invention patent CN101857458B.

[0074] S3. After step S2, the solid oxygen-carrying material becomes an oxygen-depleted solid material. The oxygen-depleted solid material is sent to the first steam reactor 19 of the second stage of the three-stage chemical loop reactor. The temperature of the first steam reactor 19 is set to 550°C. At the same time, the low-grade heat energy recovered by the first waste heat boiler 7 drives the steam generated by the steam generator 16 and sends it into the first steam reactor 19. The oxygen-depleted solid material and the steam undergo a reforming reaction in a high-temperature environment to generate hydrogen. After being condensed by the first heat exchanger 20 at the end of the first steam reactor 19, near-pure hydrogen is output and sent to the third saturated storage tank 22. The purity of the hydrogen is 99.9%. The oxygen-depleted solid material achieves partial oxygen recovery in the first steam reactor 19, resulting in a partially oxygen-recovered solid material.

[0075] S4. The partially oxygen-recovered solid material is sent to the air reactor 23 of the third stage of the chemical chain three-stage reactor. The temperature of the air reactor 23 is set to 550°C. The pure air loses oxygen in the high-temperature environment. A small amount of unreacted oxygen and nitrogen mixture is output at the end of the air reactor 23 and passed into the second adsorption purifier 24. After the existing adsorption purification process, near-pure nitrogen is enriched and sent to the second saturated storage tank 15. The purity of the nitrogen is 99.9%. The partially oxygen-recovered solid material achieves complete oxygen recovery in the air reactor 23 and is returned to the first fuel reactor 12 of the first stage of the chemical chain three-stage reactor for recycling. The heat energy generated in the high-temperature oxygen-depleted air is recovered by the first waste heat boiler 7.

[0076] S5. The crude coke oven gas emitted from Refinery Unit 2 is purified by dust removal and pollutant removal to obtain clean coke oven gas. The purified coke oven gas is then fed into the second fuel reactor 29, the first stage of the chemical loop reactor. The temperature of the second fuel reactor 29 is set at 850℃. The second fuel reactor 29 is equipped with a solid oxygen carrier material, which is a self-made A-site strontium-doped perovskite oxygen carrier. After condensation by the second heat exchanger 30 at the end of the second fuel reactor 29, a synthesis gas product consisting of carbon monoxide and hydrogen is output. The synthesis gas product includes carbon monoxide and hydrogen. The synthesis gas can be returned to the first waste heat boiler 7 to recover heat and then sold as a product, or the structure of carbon monoxide and hydrogen can be adjusted as needed and then sent to the methanol synthesis process.

[0077] The solid oxygen-carrying material is transformed into an oxygen-depleted solid material, which is then sent to the second steam reactor 32 of the second stage of the chemical loop reactor. Simultaneously, steam generated by the steam generator 16 is fed into the second steam reactor 32. The oxygen-depleted solid material and steam undergo a reforming reaction at high temperature to generate hydrogen. After condensation by the third heat exchanger 33 at the end of the second steam reactor 32, near-pure hydrogen is output and sent to the fourth saturated storage tank 34. The purity of the hydrogen is 99.9%. Similarly, the heat energy of the second steam reactor 32 comes from the low-grade heat energy recovered from the first waste heat boiler 7 to drive the steam generated by the steam generator 16. The solid oxygen-carrying material used in the second fuel reactor 29 is a self-made A-site doped perovskite oxygen carrier, as disclosed in invention patent CN111232920B.

[0078] S6. The carbon dioxide in the first saturated storage tank 14 of step S2, the hydrogen in the third saturated storage tank 22 of step S3, and the hydrogen in the fourth saturated storage tank 34 of step S5 are adjusted to a hydrogen-to-carbon ratio of 3.0 and then fed into the first mixing and homogenizing unit 43 to prepare the raw material gas for methanol synthesis. In step S3, the volume ratio of hydrogen is 30%, and in step S5, the volume ratio of hydrogen is 70%. The volume ratio of hydrogen in steps S3 and S5 is affected by their respective production capacities.

[0079] S7. The raw material gas for methanol synthesis is sent into the first pressurization buffer 44, and after being pressurized to 4 MPa by the compressor, it is sent into the first tower preheater 47. The temperature of the first tower preheater 47 is set to 140℃. The gas buffer is linked to the pressurization process to prevent intermittent fluctuations in the working load in the compression pipeline and to provide an excellent working environment for the subsequent methanol synthesis process.

[0080] S8. The preheated methanol feed gas is fed into the first synthesis tower 48 to react with the catalyst, which is a self-made 240 nm ordered hierarchical porous copper-based oxide material. The temperature of the first synthesis tower 48 is set to 220℃. The reaction product is condensed at the end of the first synthesis tower 48 by the fourth heat exchanger 49 and then enters the first gas-liquid separator 50. After gas-liquid separation, crude methanol is obtained, achieving a carbon dioxide conversion rate of 14.6% and a methanol selectivity of 71.3%. The unreacted gas desorbed from the top of the first synthesis tower 48 enters the first absorption tower 51. After purification by the first absorption tower 51, it is returned to the first mixing and homogenizing unit 43 to replace part of the fresh methanol feed gas. The usable volume of the unreacted gas replacing the fresh methanol feed gas is 30%. The second waste heat boiler 52 is set downstream of the first absorption tower 51. The low-grade heat energy in the depressurized unreacted gas is recovered by the second waste heat boiler 52 and sent to the first tower preheater 47 to replace part of the heat energy. The methanol synthesis catalyst is a self-made ordered hierarchical porous copper-based catalyst, as published in invention application CN 117101665 A.

[0081] Example 2

[0082] This embodiment provides a method for synthesizing high-value products using refinery furnace gas, including the following steps:

[0083] S1. The crude furnace gas emitted from refinery unit 1 is purified by dust removal and pollutant purification to obtain clean furnace gas. The specific process can be found in existing dust removal and purification processes. This embodiment of the present invention will not provide a detailed explanation of this process.

[0084] S2. The purified converter gas, after dust removal and purification, is fed into the first fuel reactor 12 of the first stage of the three-stage chemical loop reactor after heat energy recovery via the first waste heat boiler 7. The temperature of the first fuel reactor 12 is set at 650℃. The first fuel reactor 12 is equipped with a solid oxygen carrier material, which is a self-made cerium iron zirconium / Al2O3 honeycomb ceramic integral oxygen carrier. The solid oxygen carrier material loses oxygen in the high-temperature environment and reacts with carbon monoxide in the converter gas to generate carbon dioxide. At the end of the first fuel reactor 12, a mixture of carbon dioxide and nitrogen is output as tail gas, in which the purity of carbon dioxide is 80% and the purity of nitrogen is 20%. The two are separated by the existing adsorption separation process to obtain near-pure carbon dioxide and near-pure nitrogen. The near-pure carbon dioxide is sent to the first saturated storage tank 14 and the near-pure nitrogen is sent to the second saturated storage tank 15.

[0085] S3. After step S2, the solid oxygen-carrying material becomes an oxygen-depleted solid material. The oxygen-depleted solid material is sent to the first steam reactor 19 of the second stage of the three-stage chemical loop reactor. The temperature of the first steam reactor 19 is set to 650°C. At the same time, the low-grade heat energy recovered by the first waste heat boiler 7 drives the steam generated by the steam generator 16 and sends it into the first steam reactor 19. The oxygen-depleted solid material and the steam undergo a reforming reaction in a high-temperature environment to generate hydrogen. After condensation at the end of the first steam reactor 19, near-pure hydrogen is output and sent to the third saturated storage tank 22. The purity of the hydrogen is 99.9%. The oxygen-depleted solid material achieves partial oxygen recovery in the first steam reactor 19, resulting in a partially oxygen-recovered solid material.

[0086] S4. The partially oxygen-recovered solid material is sent to the air reactor 23 of the third stage of the chemical chain three-stage reactor. The temperature of the air reactor 23 is set to 650°C. The pure air loses oxygen in the high-temperature environment. A small amount of unreacted oxygen and nitrogen mixture is output at the end of the air reactor 23. The near-pure nitrogen is enriched through the existing adsorption purification process and sent to the second saturated storage tank 15. The purity of the nitrogen is 99.9%. The partially oxygen-recovered solid material achieves complete oxygen recovery in the air reactor 23 and is returned to the first fuel reactor 12 of the first stage of the chemical chain three-stage reactor for recycling. The heat energy generated in the high-temperature oxygen-depleted air is recovered by the first waste heat boiler 7.

[0087] S5. The crude coke oven gas emitted from Refinery Unit 2 is purified by dust removal and pollutant purification to obtain clean coke oven gas. The purified coke oven gas is sent to the second fuel reactor 29 of the first stage of the chemical loop secondary reactor. The temperature of the second fuel reactor 29 is set at 800℃. The second fuel reactor 29 is equipped with a solid oxygen carrier material, which is a self-made A-site nickel-doped perovskite oxygen carrier. At the end of the second fuel reactor 29, a syngas product of carbon monoxide and hydrogen is output. The syngas product includes carbon monoxide and hydrogen.

[0088] The solid oxygen-carrying material is transformed into an oxygen-depleted solid material, which is then sent to the second steam reactor 32 of the second stage of the chemical loop secondary reactor. Simultaneously, the water vapor generated by the steam generator 16 is sent to the second steam reactor 32. The oxygen-depleted solid material and water vapor undergo a reforming reaction in a high-temperature environment to generate hydrogen. After condensation at the end of the second steam reactor 32, near-pure hydrogen is output and sent to the fourth saturated storage tank 34. The purity of the hydrogen is 99.9%. Similarly, the heat energy of the second steam reactor 32 comes from the low-grade heat energy recovered by the first waste heat boiler 7 to drive the water vapor generated by the steam generator 16.

[0089] S6. The carbon dioxide in the first saturated storage tank 14 of step S2, the hydrogen in the third saturated storage tank 22 of step S3, and the hydrogen in the fourth saturated storage tank 34 of step S5 are adjusted to a hydrogen-to-carbon ratio of 3.0 and then fed into the first mixing and homogenizing unit 43 to prepare the raw material gas for methanol synthesis. In step S3, the volume ratio of hydrogen is 40%, and in step S5, the volume ratio of hydrogen is 60%. The volume ratio of hydrogen in steps S3 and S5 is affected by their respective production capacities.

[0090] S7. The raw material gas for methanol synthesis is sent into the first pressurization buffer 44, and after being pressurized to 4 MPa by the compressor, it is sent into the first tower preheater 47. The temperature of the first tower preheater 47 is set to 140℃. The buffer prevents intermittent fluctuations in the working load in the compression pipeline and provides an excellent working environment for the subsequent methanol synthesis process.

[0091] S8. The preheated methanol feed gas is fed into the first synthesis tower 48 to react with the catalyst, which is a self-made 55 nm ordered hierarchical porous copper-based oxide material. The temperature of the first synthesis tower 48 is set to 220℃. The reaction product is separated into crude methanol at the end of the first synthesis tower 48, achieving a carbon dioxide conversion rate of 14.9% and a methanol selectivity of 81.0%. The unreacted gas desorbed from the top of the first synthesis tower 48 enters the first absorption tower 51. After purification by the first absorption tower 51, it is returned to the first mixing homogenizer 43 to replace part of the fresh methanol feed gas. The usable volume of the unreacted gas replacing the fresh methanol feed gas is 27%. The low-grade heat energy in the depressurized unreacted gas is recovered by the second waste heat boiler 52 and sent to the first tower preheater 47 to replace part of the heat energy.

[0092] Example 3

[0093] This embodiment provides a method for synthesizing high-value products using refinery furnace gas, including the following steps:

[0094] S1. The crude furnace gas emitted from refinery unit 1 is purified into clean blast furnace gas after dust removal and pollutant purification. The specific process can be found in existing dust removal and purification processes. This embodiment of the present invention will not provide a detailed explanation of this process.

[0095] S2. The purified converter gas, after dust removal and purification, is fed into the first fuel reactor 12 of the first stage of the three-stage chemical loop reactor after heat energy recovery via the first waste heat boiler 7. The temperature of the first fuel reactor 12 is set at 650℃. The first fuel reactor 12 is equipped with a solid oxygen carrier material, which is a self-made cerium iron zirconium / Al2O3 honeycomb ceramic integral oxygen carrier. The solid oxygen carrier material loses oxygen in the high-temperature environment and reacts with carbon monoxide in the converter gas to generate carbon dioxide. At the end of the first fuel reactor 12, a mixture of carbon dioxide and nitrogen is output as tail gas, in which the purity of carbon dioxide is 80% and the purity of nitrogen is 20%. The two are separated by the existing adsorption separation process to obtain near-pure carbon dioxide and near-pure nitrogen. The near-pure carbon dioxide is sent to the first saturated storage tank 14 and the near-pure nitrogen is sent to the second saturated storage tank 15.

[0096] S3. After step S2, the solid oxygen-carrying material becomes an oxygen-depleted solid material. The oxygen-depleted solid material is sent to the first steam reactor 19 of the second stage of the three-stage chemical loop reactor. The temperature of the first steam reactor 19 is set to 650°C. At the same time, the low-grade heat energy recovered by the first waste heat boiler 7 drives the steam generated by the steam generator 16 and sends it into the first steam reactor 19. The oxygen-depleted solid material and the steam undergo a reforming reaction in a high-temperature environment to generate hydrogen. After condensation at the end of the first steam reactor 19, near-pure hydrogen is output and sent to the third saturated storage tank 22. The purity of the hydrogen is 99.9%. The oxygen-depleted solid material achieves partial oxygen recovery in the first steam reactor 19, resulting in a partially oxygen-recovered solid material.

[0097] S4. The partially oxygen-recovered solid material is sent to the air reactor 23 of the third stage of the chemical chain three-stage reactor. The temperature of the air reactor 23 is set to 650°C. The pure air loses oxygen in the high-temperature environment. A small amount of unreacted oxygen and nitrogen mixture is output at the end of the air reactor 23. The near-pure nitrogen is enriched through the existing adsorption purification process and sent to the second saturated storage tank 15. The purity of the nitrogen is 99.9%. The partially oxygen-recovered solid material achieves complete oxygen recovery in the air reactor 23 and is returned to the first fuel reactor 12 of the first stage of the chemical chain three-stage reactor for recycling. The heat energy generated in the high-temperature oxygen-depleted air is recovered by the first waste heat boiler 7.

[0098] S5. The crude coke oven gas emitted from Refinery Unit 2 is purified by dust removal and pollutant purification to obtain clean coke oven gas. The purified coke oven gas is sent to the second fuel reactor 29 of the first stage of the chemical loop secondary reactor. The temperature of the second fuel reactor 29 is set at 800℃. The second fuel reactor 29 is equipped with a solid oxygen carrier material, which is a self-made A-site nickel-doped perovskite oxygen carrier. At the end of the second fuel reactor 29, a syngas product of carbon monoxide and hydrogen is output. The syngas product includes carbon monoxide and hydrogen.

[0099] The solid oxygen-carrying material is transformed into an oxygen-depleted solid material, which is then sent to the second steam reactor 32 of the second stage of the chemical loop secondary reactor. Simultaneously, the water vapor generated by the steam generator 16 is sent to the second steam reactor 32. The oxygen-depleted solid material and water vapor undergo a reforming reaction in a high-temperature environment to generate hydrogen. After condensation at the end of the second steam reactor 32, near-pure hydrogen is output and sent to the fourth saturated storage tank 34. The purity of the hydrogen is 99.9%. Similarly, the heat energy of the second steam reactor 32 comes from the low-grade heat energy recovered by the first waste heat boiler 7 to drive the water vapor generated by the steam generator 16.

[0100] S6. The nitrogen in the second saturated storage tank 15 in step S2 or step S4, the hydrogen in the third saturated storage tank 22 in step S3, and the hydrogen in the fourth saturated storage tank 34 in step S5 are adjusted to a hydrogen-nitrogen ratio of 2.8 and then fed into the second mixing and homogenizing unit 57 to prepare ammonia synthesis feed gas. In step S3, the hydrogen volume ratio is 40%, and in step S5, the hydrogen volume ratio is 60%. The volume ratio of hydrogen in steps S3 and S5 is affected by their respective production capacities.

[0101] S7. The ammonia synthesis feed gas is sent into the second pressurization buffer 58, and after being pressurized to 7.5 MPa by the compressor, it is sent into the second tower preheater 61. The temperature of the second tower preheater 61 is set to 180℃. The buffer prevents intermittent fluctuations in the working load in the compression pipeline and provides an excellent working environment for the subsequent ammonia synthesis process.

[0102] S8. The preheated ammonia feed gas is fed into the second synthesis tower 62 to react with the catalyst, which is a commercial iron-cobalt catalyst. The temperature of the second synthesis tower 62 is set to 300℃. The reaction product is condensed at the end of the second synthesis tower 62 by the fifth heat exchanger 63 and then enters the second gas-liquid separator 64. After gas-liquid separation, crude liquid ammonia is obtained, achieving a balanced ammonia volume fraction of 25% in the mixture. The unreacted gas desorbed from the top of the second synthesis tower 62 enters the second absorption tower 65. After purification by the second absorption tower 65, it is returned to the second mixing homogenizer 57 to replace part of the fresh ammonia feed gas. The usable volume ratio of the unreacted gas replacing the fresh ammonia feed gas is 20%. The low-grade heat energy in the depressurized unreacted gas is recovered by the third waste heat boiler 66 and sent to the second tower preheater 61 to replace part of the heat energy.

[0103] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for synthesizing high-value products using refinery furnace gas, characterized in that, This includes raw material preparation processes and product preparation processes; The raw material preparation process includes the following steps: S1. The crude furnace gas emitted by the refinery unit is purified by dust removal and pollutant removal to obtain clean furnace gas. S2. After recovering heat energy from the first waste heat boiler, the clean furnace gas is sent to the first fuel reactor. The first fuel reactor is equipped with a solid oxygen carrier material. The clean furnace gas reacts with the solid oxygen carrier material to produce carbon dioxide. At the end of the first fuel reactor, a mixture of carbon dioxide and nitrogen is output as tail gas. After adsorption and separation, nearly pure carbon dioxide and nearly pure nitrogen are obtained respectively. S3. After step S2, the solid oxygen-carrying material becomes an oxygen-depleted solid material. The oxygen-depleted solid material is sent to the first steam reactor, and water vapor is sent into the first steam reactor at the same time. The oxygen-depleted solid material and water vapor undergo a reforming reaction to generate hydrogen. The oxygen-depleted solid material achieves partial oxygen recovery, resulting in a partially oxygen-recovered solid material. S4. The partially oxygen-recovered solid material is sent to the air reactor, where air reacts with the partially oxygen-recovered solid material to obtain near-pure nitrogen. S5. The crude coke oven gas emitted by the refinery unit is purified by dust removal and pollutant removal to obtain clean coke oven gas. The clean coke oven gas is sent to the second fuel reactor, which is equipped with solid oxygen carrier material. The clean coke oven gas reacts with the solid oxygen carrier material to produce syngas including carbon monoxide and hydrogen. The solid oxygen-carrying material is transformed into an oxygen-depleted solid material, which is then sent to the second stage steam reactor. Simultaneously, water vapor is introduced into the second steam reactor, where the oxygen-depleted solid material and water vapor undergo a reforming reaction to generate hydrogen. The product preparation process includes the following steps: S6. After adjusting the hydrogen-carbon ratio or hydrogen-nitrogen ratio of the gas structure, near-pure carbon dioxide, near-pure nitrogen and near-pure hydrogen are sent to the mixer and homogenizer to prepare the raw material gas for the synthesis of methanol or ammonia. S7. The raw material gas for synthesizing methanol or ammonia is sent into a pressurizing buffer and then sent to the tower preheater after being pressurized. S8. The preheated raw material gas for the synthesis of methanol or ammonia is sent into the synthesis tower for synthesis reaction, and methanol or ammonia products are obtained after gas-liquid separation.

2. The method for synthesizing high-value products using refinery furnace gas according to claim 1, characterized in that, In step S1, the raw furnace gas is sent to a three-stage dry bag filter for dust removal. The dust-removed furnace gas is then sent to a catalytic purifier and an adsorption purifier to remove pollutants, resulting in clean furnace gas.

3. The method for synthesizing high-value products using refinery furnace gas according to claim 1, characterized in that, In step S2, the temperature of the first fuel reactor is set to 550-650℃, and the solid oxygen carrier is one of the following: a self-made cerium-iron-zirconium / Al2O3 honeycomb ceramic integral oxygen carrier and a cerium-iron-zirconium / MgO honeycomb ceramic integral oxygen carrier.

4. The method for synthesizing high-value products using refinery furnace gas according to claim 1, characterized in that, In step S3, the reaction temperature is 550-650℃, and the steam is generated by a steam generator driven by low-grade heat energy recovered from the first waste heat boiler.

5. The method for synthesizing high-value products using refinery furnace gas according to claim 1, characterized in that, In step S4, the reaction temperature is 550-650℃. The partially oxygen-recovered solid material achieves complete oxygen recovery, resulting in a solid oxygen-carrying material, which is then recycled back to the first fuel reactor. The thermal energy carried by the near-pure nitrogen gas is recovered by the first waste heat boiler.

6. The method for synthesizing high-value products using refinery furnace gas according to claim 1, characterized in that, In step S5, the temperature of the second fuel reactor is set to 800-850℃, and the solid oxygen carrier material is one of the self-made A-site nickel-doped perovskite oxygen carrier and A-site strontium-doped perovskite oxygen carrier; the steam is generated by a steam generator driven by low-grade heat energy recovered from the first waste heat boiler.

7. The method for synthesizing high-value products using refinery furnace gas according to claim 1, characterized in that, In the product preparation process, the methanol synthesis catalyst uses a self-made ordered hierarchical porous copper-based catalyst, and the ammonia synthesis catalyst uses an iron-based catalyst.

8. The method for synthesizing high-value products using refinery furnace gas according to claim 1, characterized in that, The product preparation process includes an in-situ methanol preparation process and an ammonia preparation process that are set up in parallel.

9. A method for synthesizing high-value products using refinery furnace gas according to claim 8, characterized in that, The methanol preparation process includes the following steps: S61. The carbon dioxide from step S2, the hydrogen from step S3, and the hydrogen from step S5 are adjusted to a hydrogen-to-carbon ratio of 3.0 and then fed into the first mixing and homogenizing unit to prepare the raw material gas for methanol synthesis. S71. The raw material gas for methanol synthesis is sent into the first pressurization buffer and pressurized to 3-5 MPa before being sent to the first tower preheater. The temperature of the first tower preheater is set to 130-150℃. S81. The preheated methanol feed gas is fed into the first synthesis tower for synthesis reaction. The temperature of the first synthesis tower is set to 200-250℃. The reaction product is separated into methanol at the end of the first synthesis tower. The unreacted gas desorbed from the top of the first synthesis tower enters the first absorption tower. After purification by the first absorption tower, it is sent back to the first mixing homogenizer to replace part of the fresh methanol feed gas. The low-grade heat energy in the depressurized unreacted gas is recovered by the second waste heat boiler and sent to the preheater before the first tower to replace part of the heat energy.

10. A method for synthesizing high-value products using refinery furnace gas according to claim 8, characterized in that, The ammonia preparation process includes the following steps: S62. After adjusting the nitrogen gas from step S2 or step S4, the hydrogen gas from step S3, and the hydrogen gas from step S5 to a hydrogen-nitrogen ratio of 2.7-3.0, the mixture is sent to the second mixing and homogenizing unit to prepare ammonia synthesis feed gas. S72. The ammonia synthesis feed gas is sent into the second pressurizing buffer and pressurized to 7-8 MPa before being sent into the second tower preheater. The temperature of the second tower preheater is set to 150-200℃. S82. The preheated ammonia feed gas is sent to the second synthesis tower for synthesis reaction. The temperature of the second synthesis tower is set to 280-320℃. The reaction product is separated into liquid ammonia at the end of the second synthesis tower. The unreacted gas desorbed from the top of the second synthesis tower enters the second absorption tower. After being purified by the second absorption tower, it is sent back to the second mixing and homogenizing unit to replace part of the fresh ammonia feed gas. The low-grade heat energy in the depressurized unreacted gas is recovered by the third waste heat boiler and sent to the preheater before the second tower to replace part of the heat energy.

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