Method for synthesizing high-value product by utilizing refinery furnace gas

Abstract

The invention relates to a method for synthesizing a high-value product by using refinery furnace gas, which comprises the following steps: purifying refinery crude furnace gas, feeding the purified refinery crude furnace gas into a chemical looping three-stage normal-pressure reactor, respectively obtaining near-pure carbon dioxide, nitrogen and hydrogen products in each stage of flow, and adjusting a gas framework by using the near-pure hydrogen product obtained by reforming coke oven gas as a supplementary hydrogen source, after reaching the standard of the mixed raw material, pressurizing and feeding into a synthesizer, and carrying out gas-liquid separation to obtain a methanol or ammonia product. The method solves the problem that carbon dioxide and nitrogen cannot be utilized when the traditional refinery furnace gas replaces coal-based carbon monoxide to synthesize high-value products through chemical carbonylation; part of coke oven process tail end product coke oven gas is consumed, and the defect that a cheap hydrogen source needs to be supplemented due to unmatched raw material structures in the technological process is overcome; and the tail gas and low-grade heat recycling process in each stage of production process is also optimized, and near-zero emission in the life cycle and gradient utilization of chemical energy are realized.

Description

Technical Field

[0001] The invention relates to the technical field of energy conversion and chemical synthesis, and in particular to a method for synthesizing high-value products by utilizing refinery furnace gas. Background Art

[0002] China's steel industry accounts for about 15% of the country's total industrial energy consumption, 26% of its waste gas emissions, and 15% of its carbon emissions. Refineries have long produced blast furnace gas / converter gas, which is mainly composed of carbon monoxide (CO), carbon dioxide (CO2), and nitrogen (N2). In addition to being used by enterprises for heating, most of the remaining refinery gas is mainly used for power generation, with a thermal efficiency of only 30% to 40%. Using refinery gas to generate electricity (mainly carbon monoxide combustion) is high-carbon emission. The carbon emission coefficient of furnace gas combustion power generation is 1940 grams of CO2 equivalent / kWh, which is much higher than China's power grid power supply (590 grams of CO2 equivalent / kWh) and even coal-fired power generation (930 grams of CO2 equivalent / kWh). At present, the furnace gas of relevant domestic refineries has been basically balanced, but whether it is used in the process or for power generation, the carbon monoxide in the furnace gas is converted into carbon dioxide emissions, and it is impossible to achieve the essential reduction of carbon dioxide emissions.

[0003] Using refinery gas as a raw material to replace coal-based carbon monoxide, and producing high value-added products such as methanol, ethanol, natural gas or polymers through the chemical carbonylation process, and avoiding the high carbon emission coefficient of converting carbon elements in refinery gas into electricity, is a key link in reducing greenhouse gas emissions from the steel and chemical industries. Although extracting carbon monoxide from refinery gas as a non-fossil raw material improves the quality of gas utilization and omits the traditional carbon-chemical gasification and air separation process, it also faces the defect that a large amount of carbon dioxide and nitrogen resources in the gas cannot be utilized and thus need to be released.

[0004] In addition, since the synthesis of the above-mentioned typical chemical products basically involves hydrogenation, enterprises with coking processes can separate hydrogen from coke oven gas to achieve hydrogenation, while for enterprises without coking processes, the source of cheap hydrogen is the first problem to be solved. At the same time, the synthesis of typical chemical products requires a matching raw material structure (such as hydrogen-carbon ratio), and usually requires a supplementary gas link to make up for the process, so there are certain restrictions on large-scale promotion and application. Summary of the invention

[0005] The object of the present invention is to provide a method for synthesizing high-value products using refinery gas, so as to solve the above-mentioned problems of low refinery gas utilization and generation of carbon dioxide greenhouse gas.

[0006] This method uses the furnace gas (mainly blast furnace gas or converter gas) produced in refineries over a long period of time as a non-fossil raw material. After optimizing the structure (hydrogen-carbon ratio and hydrogen-nitrogen ratio) of the gas products obtained at each stage of the three-stage chemical chain reforming reactor, it is pressurized and sent into the methanol or ammonia synthesizer. This solves the problem of the inability to utilize carbon dioxide and nitrogen when traditional refinery gas is used as raw material to replace coal-based carbon monoxide to synthesize high-value products through chemical carbonylation. 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 and uses the oxygen-depleted air (mainly nitrogen) product obtained by the air reactor in the chemical chain tertiary reactor during the oxidation process as a high-purity nitrogen source for the ammonia synthesis process, thereby solving the problem of long-term release of the oxygen-depleted air product in the traditional process, which leads to nitrogen source loss.

[0008] This method also uses chemical chain reforming to produce synthesis gas (carbon monoxide and hydrogen) and hydrogen from the coke oven gas produced in the coke oven process. The synthesis gas can be returned to the waste heat boiler to recover heat and then sent to the methanol synthesizer as a product or after adjusting the gas structure (hydrogen-carbon ratio) as needed. The hydrogen can be used alone as the hydrogen source required for the supplementary gas link to make up for the mismatch of the raw material structure in the process, expanding the refinery furnace gas industry route and solving the problem of cheap hydrogen source required for the supplementary gas link (0.868 yuan / Nm 3 ) problem.

[0009] The method optimizes the process flow, purifies the excess unreacted gas in the methanol or ammonia synthesizer through an absorption tower to reach the gas structure required for synthesizing methanol or ammonia, and then reuses it in the mixing and homogenization process to replace part of the fresh gas source, thereby solving the problem of low single-pass conversion rate of synthesis gas resulting in a large amount of unreacted gas circulating for a long time and enriching it, which requires regular emptying or replenishment of fresh gas to maintain normal operation of the process.

[0010] In order to overcome the above problems existing in the prior art, the specific technical solutions provided by the present invention are as follows: A method for synthesizing high-value products using refinery gas, comprising a raw material preparation process and a product preparation process; The raw material preparation process includes the following steps: S1. The raw gas discharged from the refinery units is dedusted and purified of pollutants to obtain clean gas; S2, after the clean furnace gas recovers heat energy through the first waste heat boiler, it is sent to the first fuel reactor. A solid oxygen-carrying material is arranged inside the first fuel reactor. The clean furnace gas and the solid oxygen-carrying material undergo an oxidation reaction to generate carbon dioxide. A mixed tail gas of carbon dioxide and nitrogen is output at the end of the first fuel reactor. Nearly pure carbon dioxide and near pure nitrogen are obtained through adsorption separation. S3, after the solid oxygen-carrying material undergoes step S2, it becomes an oxygen-depleted solid material, the oxygen-depleted solid material is sent to the first steam reactor, and water vapor is simultaneously sent into the first steam reactor, the oxygen-depleted solid material and the water vapor undergo a reforming reaction to generate hydrogen, and the oxygen-depleted solid material realizes partial oxygen recovery, thereby obtaining a solid material with partial oxygen recovery; S4, sending the solid material from which part of the oxygen is recovered to an air reactor, and reacting the air with the solid material from which part of the oxygen is recovered to obtain nearly pure nitrogen; S5. The crude coke oven gas discharged from the refinery unit is subjected to dust removal and pollutant purification to obtain clean coke oven gas; the clean coke oven gas is sent to the second fuel reactor, and a solid oxygen-carrying material is arranged inside the second fuel reactor. The clean coke oven gas and the solid oxygen-carrying material undergo an oxidation reaction to obtain a synthesis gas including carbon monoxide and hydrogen; The solid oxygen-carrying material is transformed into an oxygen-depleted solid material, and the oxygen-depleted solid material is sent to a second steam reactor of the second stage. Meanwhile, water vapor is sent into the second steam reactor, and the oxygen-depleted solid material and the water vapor undergo a reforming reaction to generate hydrogen. The product preparation process includes the following steps: S6, after adjusting the gas structure hydrogen-carbon ratio or hydrogen-nitrogen ratio of nearly pure carbon dioxide, nearly pure nitrogen and nearly pure hydrogen, send them into a mixing homogenizer to be prepared into synthetic methanol or ammonia raw gas; S7, sending the synthetic methanol or ammonia raw gas into the pressurized buffer, and then sending it into the preheater before the tower after being pressurized; S8. The synthetic methanol or ammonia raw gas preheated in front of the tower is sent to the synthesis tower for synthesis reaction, and methanol or ammonia products are obtained after gas-liquid separation.

[0011] Preferably, in step S1, the clean furnace gas is clean blast furnace gas or clean converter gas.

[0012] Preferably, in step S1, the raw furnace gas is sent to a three-stage full-dry purification bag filter for dust removal, and the dust-removed furnace gas is sent to a catalytic purifier and an adsorption purifier in sequence to remove pollutants to obtain clean furnace gas.

[0013] Preferably, in step S2, the temperature of the first fuel reactor is set to 550-650°C, and the solid oxygen carrier material is one of a homemade cerium iron zirconium / Al2O3 honeycomb ceramic integral oxygen carrier and a cerium iron zirconium / MgO honeycomb ceramic integral oxygen carrier, see invention authorization CN101857458B.

[0014] Preferably, in step S3, the reaction temperature is 550-650°C, and the water vapor is generated by driving a steam generator using low-grade heat energy recovered from the first waste heat boiler.

[0015] Preferably, in step S4, the reaction temperature is 550-650°C, and the solid material from which partial oxygen is recovered achieves complete oxygen recovery to obtain a solid oxygen-carrying material, which is returned to the first fuel reactor for recycling; the heat energy carried by the nearly pure nitrogen is recovered by the first waste heat boiler.

[0016] Preferably, in step S5, the temperature of the second fuel reactor is set to 800-850°C, the solid oxygen carrier material is one of a homemade A-site nickel-doped perovskite oxygen carrier and an A-site strontium-doped perovskite oxygen carrier, see invention authorization CN111232920B; the water vapor is generated by driving a steam generator using low-grade heat energy recovered from the first waste heat boiler.

[0017] Preferably, in the product preparation process, the methanol synthesis catalyst adopts a self-made ordered hierarchical pore copper-based catalyst, as disclosed in the invention application CN117101665A, and the ammonia synthesis catalyst adopts an iron-based catalyst.

[0018] Preferably, the product preparation process includes an in-situ methanol preparation process and an ammonia preparation process arranged in parallel.

[0019] Preferably, the methanol preparation process comprises the following steps: S61, adjusting the carbon dioxide in step S2, the hydrogen in step S3, and the hydrogen in step S5 to have a hydrogen-to-carbon ratio of 3.0 and then feeding them into a first mixing homogenizer to prepare synthetic methanol raw gas; S71, sending the synthetic methanol raw gas into the first pressurizing buffer, after being pressurized to 3-5 MPa, sending it into the first preheater before the tower, and the temperature of the first preheater before the tower is set to 130-150° C.; S81. The synthetic methanol raw gas preheated before the tower is sent to the first synthesis tower for synthesis reaction. The temperature of the first synthesis tower is set at 200-250°C. The reaction product is obtained by gas-liquid separation to obtain methanol at the end of the first synthesis tower. The unreacted gas analyzed from the top of the first synthesis tower enters the first absorption tower, and is returned to the first mixing homogenizer after purification in the first absorption tower to replace part of the fresh methanol raw gas. The low-grade heat energy in the reduced pressure 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.

[0020] Preferably, the ammonia preparation process comprises the following steps: S62, adjusting the nitrogen in step S2 or step S4, the hydrogen in step S3 and the hydrogen in step S5 to have a hydrogen-nitrogen ratio of 2.7-3.0, and then sending the mixture into a second mixing homogenizer to prepare ammonia synthesis feed gas; S72, sending the synthetic ammonia raw gas into the second pressurized buffer, and after being pressurized to 7-8 MPa, sending it into the second preheater before the tower, and the temperature of the second preheater before the tower is set to 150-200° C.; S82. The synthetic ammonia raw gas preheated in front of the tower is sent to the second synthesis tower for synthesis reaction. The temperature of the second synthesis tower is set at 280-320°C. The reaction product is separated into liquid ammonia after gas-liquid separation at the end of the second synthesis tower. The unreacted gas analyzed from the top of the second synthesis tower enters the second absorption tower, and is returned to the second mixing homogenizer after purification in the second absorption tower to replace part of the fresh ammonia raw gas. The low-grade heat energy in the decompressed 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.

[0021] Compared with the prior art, the method of synthesizing high-value products by using refinery gas of the present invention has the following beneficial effects: 1. The method of the present invention comprehensively and efficiently utilizes the resources at all levels in the refinery gas to maximize their development and application. By complementary use of the carbon, hydrogen and nitrogen elements contained in the furnace gas discharged by the refinery for a long time, the method effectively solves the problem of the large amount of carbon dioxide and nitrogen being difficult to be effectively utilized when using traditional refinery gas as a raw material to replace coal-based carbon monoxide. It not only promotes the deep integration and utilization of resources, but also achieves the goal of near-zero carbon dioxide emissions.

[0022] 2. The production process of the method described in the present invention is based on the chemical chain reforming of refinery gas. The inherent high purity of the end product avoids the interference of the contact layer temperature by other inert gases, and the quality improvement compared with the traditional refinery gas component extraction process can be achieved without high investment.

[0023] 3. The method of the present invention uses the gas product obtained from the coking process for self-supplementation within the system according to demand, avoiding additional investment in hydrogen production and energy consumption. When renewable energy develops rapidly in the future, renewable energy can be incorporated into the network described in the invention without large-scale changes in the original technology.

[0024] 4. The method of the present invention optimizes the gas recycling process in the production process, recycles low-grade nitrogen-based tail gas or unreacted gas into the system for internal use, can independently operate the local process shutdown, greatly reduce the long-term operation loss of equipment, and retains most of the original production equipment and facilities. Only appropriate changes can achieve qualitative changes in comprehensive efficiency and improve benefits, and it is easy to promote industrialization in a short time.

[0025] 5. The method of the present invention optimizes the intermittent fluctuation defect of workload in the production process, and realizes high-level production of product gas through gas buffer linkage process between various production links. The low-grade heat energy recovered by the waste heat boiler replaces part of the high-grade fuel combustion heating, alleviates the heat energy consumption in the combustion process, and realizes the cascade utilization of chemical energy.

[0026] 6. The method described in the present invention solves the problem that the current thermal catalytic hydrogenation reaction system and the photocatalytic / electrocatalytic reduction reaction system rely on purchased standard gases as raw materials, which is not conducive to the transition of catalytic reactions from laboratory scale to industrial scale, and provides a feasible solution for the emission and reuse of complex gas sources throughout the life cycle. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 A schematic diagram of the entire process of a method for synthesizing high-value products using refinery furnace gas; Figure 2 Schematic diagram of the process of raw material preparation; Figure 3 A schematic diagram of the product preparation process; Explanation of the marks in the figure: 1. Refinery unit 1; 2. Refinery unit 2; 3. First three-way valve; 4. Bag filter; 5. Catalytic purifier; 6. First adsorption purifier; 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. The second electromagnetic flowmeter; 19, the first steam reactor; 20, the first heat exchanger; 21, the fifth three-way valve; 22, the third saturated storage tank; 23, the air reactor; 24, the second adsorption purifier; 25, the sixth three-way valve; 26, the third electromagnetic flowmeter; 27, the second pressure reducing valve; 28, the fourth electromagnetic flowmeter; 29, the second fuel reactor; 30, the second heat exchanger; 31, the fifth electromagnetic flowmeter; 32, the second steam reactor; 33, the third heat exchanger; 34, the fourth saturated and 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 pressurizing buffer; 45, first pressure indicator; 46, ninth electromagnetic flowmeter; 47, first preheater before tower; 48, first synthesis tower; 49, fourth heat exchanger; 50, first gas-liquid separation device; 51, the first absorption tower; 52, the second waste heat boiler; 53, the tenth electromagnetic flowmeter; 54, the sixth pressure reducing valve; 55, the eleventh electromagnetic flowmeter; 56, the ninth three-way valve; 57, the second mixing homogenizer; 58, the second pressurizing buffer; 59, the second pressure indicator; 60, the twelfth electromagnetic flowmeter; 61, the second preheater before the tower; 62, the second synthesis tower; 63, the fifth heat exchanger; 64, the second gas-liquid separator; 65, the second absorption tower; 66, the third waste heat boiler. DETAILED DESCRIPTION

[0028] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation method, structure, characteristics and effects of the present invention are described in detail below in combination with the preferred embodiments.

[0029] The present invention provides a method for synthesizing high-value products using refinery gas, combined with Figure 1 , the specific implementation methods of the present invention are as follows: The crude furnace gas generated by the refinery units, including crude blast furnace gas and converter gas, is obtained 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 to the first fuel reactor 12 of the chemical chain three-stage reactor as gas fuel. The fuel combustion produces tail gas mixed with carbon dioxide and nitrogen. After passing through the molecular sieve adsorption separator 13, nearly pure carbon dioxide and nearly pure nitrogen products are obtained respectively, and are sent to the first saturated storage tank 14 and the second saturated storage tank 15 respectively.

[0030] 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 nearly pure hydrogen. The hydrogen is sent to the third saturated storage tank 22 through the fifth three-way valve 21. The clean air is sent to the air reactor 23 for oxidation reaction, and the oxygen-depleted air, i.e., the nearly pure nitrogen product, is recycled to 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.

[0031] The raw coke oven gas produced by the coke oven unit is subjected to dust removal and purification to obtain clean coke oven gas. The low-grade heat energy in the coke oven gas is recovered by the first waste heat boiler 7. The clean coke oven gas is sent to the second fuel reactor 29 as a gas fuel. The fuel combustion produces tail gas mixed with carbon monoxide and hydrogen, which is heat exchanged in the second heat exchanger 30 to obtain a synthesis gas product.

[0032] The low-grade heat energy recovered by the first waste heat boiler 7 is sent to the steam generator 16 , and the steam generated by the steam generator 16 is sent to the second steam reactor 32 for reforming reaction. The product is heat exchanged in the third heat exchanger 33 to obtain nearly pure hydrogen, which is sent to the fourth saturated storage tank 34 .

[0033] The carbon dioxide in the first saturated storage tank 14 and the hydrogen in the third saturated storage tank 22 are adjusted for a hydrogen-to-carbon ratio, and the insufficient hydrogen is supplemented by the hydrogen in the fourth saturated storage tank 34; the gas flow after the structure adjustment is sent to the first mixing homogenizer 43, and is prepared into a synthetic methanol raw gas in the first mixing homogenizer 43; the methanol raw gas reaches the standard pressure after passing through the first pressurizing buffer 44 and is sent to the first preheater 47 before the tower, and the preheated high-pressure methanol raw gas is sent to the first synthesis tower 48, and the top analysis product of the first synthesis tower 48 is sent to the first gas-liquid separator 50, and the methanol product is obtained after gas-liquid separation; the reduced pressure unreacted gas analyzed at the top of the first synthesis tower 48 is sent to the first absorption tower 51, and after absorption and purification, it is returned to the first mixing homogenizer 43 to replace part of the fresh methanol raw gas; the low-grade heat energy in the reduced pressure unreacted gas is recovered by the second waste heat boiler 52 and sent to the first preheater 47 before the tower to replace part of the heat energy.

[0034] The nitrogen in the second saturated storage tank 15 and the hydrogen in the third saturated storage tank 22 are adjusted in hydrogen-nitrogen ratio, and the insufficient hydrogen is supplemented by the hydrogen in the fourth saturated storage tank 34; the gas flow after the adjustment structure is sent to the second mixing homogenizer 57, and is prepared into ammonia raw gas in the second mixing homogenizer 57; the ammonia raw gas reaches the standard pressure through the second pressure buffer 58 and is sent to the second preheater 61 before the tower, and the preheated ammonia raw gas is sent to the second synthesis tower 62, and the top analysis product of the second synthesis tower 62 is sent to the second gas-liquid separator 64, Liquid ammonia product is obtained through gas-liquid separation; the decompressed unreacted gas analyzed at 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 mixer homogenizer 57 to replace part of the fresh synthesis ammonia raw gas; the low-grade heat energy in the decompressed 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; by optimizing the 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.

[0035] A method for synthesizing high-value products using refinery gas of the present invention is implemented by a device for synthesizing high-value products using refinery gas, such as Figure 1 shown.

[0036] The refinery unit includes unit 1 and unit 2, wherein 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 purifier 5, the outlet of the catalytic purifier 5 is connected to the inlet of the first adsorption purifier 6, the outlet of the first adsorption purifier 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 of the first fuel reactor 12 of the chemical chain system for the furnace gas of the refinery, and the second three-way valve 8, the first pressure reducing valve 9, the first electromagnetic flowmeter 10 and the third three-way valve 11 are arranged on the connecting pipeline between the first waste heat boiler 7 and the first fuel reactor 12 along the gas flow direction; 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.

[0037] The gas outlet of the chemical chain first steam reactor 19 is connected to the gas inlet of the first heat exchanger 20, and the hydrogen is stored in the third saturated storage tank 22 after heat exchange.

[0038] The heat energy outlet of the chemical chain air reactor 23 is connected to the inlet of the first waste heat boiler 7; the gas outlet of the air reactor 23 passes through the sixth three-way valve 25 and is connected to the first fuel reactor 12 and the second saturated storage tank 15 respectively, and a third electromagnetic flowmeter 26 is installed on the connecting pipeline between the sixth three-way valve 25 and the first fuel reactor 12.

[0039] 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. A second pressure reducing valve 27 and a fourth electromagnetic flowmeter 28 are installed on the connecting pipeline. The second fuel reactor 29 generates a synthesis gas product.

[0040] The water vapor generated by the steam generator 16 passes through the fourth three-way valve 17 and enters the first steam reactor 19 and the second steam reactor 32 respectively. A second electromagnetic flowmeter 18 is installed on the connecting pipeline between the fourth three-way valve 17 and the first steam reactor 19, and a fifth electromagnetic flowmeter 31 is installed on the connecting pipeline 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, and the hydrogen is stored in the fourth saturated storage tank 34 after heat exchange. The third saturated storage tank 22 and the fourth saturated storage tank 34 are connected to each other, and a third pressure reducing valve 35 and a sixth electromagnetic flowmeter 36 are installed on the connecting pipeline.

[0041] 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. The 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. The seventh electromagnetic flowmeter 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. The fifth pressure reducing valve 40, the eighth electromagnetic flowmeter 41 and the 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 pressurizing buffer 44. The gas outlet of the first pressurizing buffer 44 is connected to the gas outlet of the first preheater 47 before the tower. The inlet is connected, and a first pressure indicator 45 and a ninth electromagnetic flowmeter 46 are installed on the connecting pipeline. The gas outlet of the first preheater 47 before the first tower is connected to the gas inlet of the first synthesis tower 48. The first synthesis tower 48 synthesizes methanol products. 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 before the first tower. The gas outlet of the second waste heat boiler 52 is connected to the inlet of the first mixing homogenizer 43. The first gas-liquid separator 50 outlet product is used as the final product of the present invention.

[0042] The tenth electromagnetic flowmeter 53 is installed on the connecting pipeline 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. The sixth pressure reducing valve 54, the eleventh electromagnetic flowmeter 55 and the ninth three-way valve 56 are installed on the connecting pipeline; the gas outlet of the second mixing homogenizer 57 is connected to the gas inlet of the second pressurizing buffer 58, and the gas outlet of the second pressurizing buffer 58 is connected to the gas inlet of the second preheater 61 before the tower. The second pressure indicator 59 and the twelfth electromagnetic flowmeter 60 are installed on the connecting pipeline. The gas outlet of the reactor 61 is connected to the gas inlet of the second synthesis tower 62, the second synthesis tower 62 synthesizes ammonia products, 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 second preheater 61 before the tower, the gas outlet of the third waste heat boiler 66 is connected to the inlet of the second mixing homogenizer 57, and the product of the second gas-liquid separator 64 outlet is used as the final product of the present invention.

[0043] In order to better understand the present invention, the present invention is further specifically described through the following examples, but it should not be understood as limiting the present invention. Some non-essential improvements and adjustments made by technicians in this field according to the above invention content are also considered to fall within the protection scope of the present invention.

[0044] Example 1 This embodiment provides a method for synthesizing high-value products using refinery gas, comprising the following steps: S1. The raw furnace gas discharged from the refinery unit 1 is sent to a three-stage full-dry purification bag dust collector 4 for dust removal to avoid the influence of dust on the quality of the furnace gas; the dust-removed furnace gas is successively sent 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 to obtain clean blast furnace gas. The specific process can be referred to the existing dust removal and purification process, and Example 1 of the present invention will not be explained in detail.

[0045] S2. The clean blast furnace gas that has been dusted and purified and meets the standards is sent to the first fuel reactor 12 of the first stage of the chemical chain three-stage reactor after recovering heat energy through the first waste heat boiler 7. The first waste heat boiler 7 is arranged downstream of the purification process to recover the waste heat of the furnace gas as low-grade heat energy to supply the subsequent process stage; the temperature of the first fuel reactor 12 is set to 550°C, and a solid oxygen-carrying material is arranged inside the first fuel reactor 12. The solid oxygen-carrying material is a self-made cerium iron zirconium / MgO honeycomb ceramic integral oxygen carrier. The solid oxygen-carrying material loses oxygen in a high-temperature environment and undergoes an oxidation reaction with carbon monoxide in the blast furnace gas to generate carbon dioxide. A mixed tail gas of carbon dioxide and nitrogen is output at the end of the first fuel reactor 12, wherein the purity of the carbon dioxide is 45%, and the purity of the nitrogen is 55%; the mixed tail gas of carbon dioxide and nitrogen is passed into the adsorption separator 13, and the two are separated by the existing adsorption separation process to obtain nearly pure carbon dioxide and nearly pure nitrogen, respectively, and the nearly pure carbon dioxide is sent to the first saturated storage tank 14, and the nearly 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 the invention authorization CN101857458B.

[0046] S3. After the solid oxygen-carrying material undergoes step S2, it becomes an oxygen-depleted solid material, and the oxygen-depleted solid material is sent to the first steam reactor 19 of the second stage of the chemical chain three-stage 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 water vapor generated by the steam generator 16 to be sent to the first steam reactor 19. The oxygen-depleted solid material and the water vapor undergo a reforming reaction in a high-temperature environment to generate hydrogen. After condensation at the first heat exchanger 20 at the end of the first steam reactor 19, nearly pure hydrogen is output and sent to the third saturated storage tank 22, wherein the purity of the hydrogen is 99.9%. The oxygen-depleted solid material realizes partial oxygen recovery in the first steam reactor 19, and a solid material with partial oxygen recovery is obtained.

[0047] S4. The solid material from which part of the oxygen is recovered 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 tail gas mixed with oxygen and nitrogen is output at the end of the air reactor 23 and passed into the second adsorption purifier 24. After the existing adsorption purification process, nearly pure nitrogen is enriched and sent to the second saturated storage tank 15, in which the purity of nitrogen is 99.9%. The solid material from which part of the oxygen is recovered 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.

[0048] S5. The crude coke oven gas discharged from the refinery unit 2 is dedusted and purified to obtain clean coke oven gas. The dedusted and purified coke oven gas that meets the standards is sent to the second fuel reactor 29 of the first stage of the chemical chain secondary reactor. The temperature of the second fuel reactor 29 is set to 850°C. A solid oxygen carrier material is arranged inside the second fuel reactor 29. The solid oxygen carrier material is a self-made A-site strontium-doped perovskite oxygen carrier. After condensation at the second heat exchanger 30 at the end of the second fuel reactor 29, a synthesis gas product mixed with 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 it can be sent to the methanol synthesis process after adjusting the structure of carbon monoxide and hydrogen as needed; The solid oxygen-carrying material is changed into an oxygen-depleted solid material, and the oxygen-depleted solid material is sent to the second steam reactor 32 of the second stage of the chemical chain secondary reactor. At the same time, the water vapor generated by the steam generator 16 is sent to the second steam reactor 32. The oxygen-depleted solid material and the water vapor are reformed in a high-temperature environment to generate hydrogen. After condensation at the third heat exchanger 33 at the end of the second steam reactor 32, nearly pure hydrogen is output and sent to the fourth saturated storage tank 34, wherein the purity of the hydrogen is 99.9%. Similarly, the heat energy of the second steam reactor 32 comes from the water vapor generated by the steam generator 16 driven by the low-grade heat energy recovered by the first waste heat boiler 7. The solid oxygen-carrying material used in the second fuel reactor 29 is a self-made A-site doped perovskite oxygen carrier, see the invention authorization CN111232920B publication.

[0049] 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 sent to the first mixing homogenizer 43 after adjusting the hydrogen-to-carbon ratio to 3.0 to prepare synthetic methanol raw gas, wherein the volume ratio of hydrogen in step S3 is 30%, and the volume ratio of hydrogen in step S5 is 70%; wherein the volume ratios of hydrogen in step S3 and step S5 are affected by their respective production capacities.

[0050] S7. The synthetic methanol raw gas is sent to the first pressurizing buffer 44, and after being pressurized to 4 MPa by the compressor, it is sent to the first preheater 47 before the tower. The temperature of the first preheater 47 is set to 140°C. Among them, the gas buffer is linked to the pressurizing process to prevent intermittent fluctuations in the workload in the compression pipeline, providing an excellent working environment for the subsequent synthetic methanol link.

[0051] S8. The synthetic methanol raw gas preheated before the tower is sent to the first synthesis tower 48 to react with the catalyst, wherein the catalyst is a self-made 240 nm ordered hierarchical pore copper-based oxide material, the temperature of the first synthesis tower 48 is set to 220°C, and the reaction product is condensed by the fourth heat exchanger 49 at the end of the first synthesis tower 48, and then enters the first gas-liquid separator 50, and crude methanol is obtained after gas-liquid separation, achieving a carbon dioxide conversion rate of 14.6% and a methanol selectivity of 71.3%; and the unreacted gas analyzed from the top of the first synthesis tower 48 enters the first absorption tower 51, and is purified by the first absorption tower 51 and then returned to the first mixing homogenizer 43 to replace part of the fresh methanol raw gas, wherein the unreacted gas replaces part of the fresh methanol raw gas The available volume accounts for 30%; the second waste heat boiler 52 is set downstream of the first absorption tower 51, and the low-grade heat energy in the decompressed unreacted gas is recovered by the second waste heat boiler 52 and sent to the first preheater 47 before the first tower to replace part of the heat energy. The methanol synthesis catalyst adopts a self-made ordered hierarchical pore copper-based catalyst, as disclosed in the invention application CN 117101665 A.

[0052] Example 2 This embodiment provides a method for synthesizing high-value products using refinery gas, comprising the following steps: S1. The raw gas discharged from refinery unit 1 is subjected to dust removal and purification of pollutants to obtain clean gas. The specific process can be referred to the existing dust removal and purification process, and Example 2 of the present invention will not be explained in detail.

[0053] S2. The clean converter gas that has been dusted and purified and meets the standards is sent to the first fuel reactor 12 of the first stage of the chemical chain three-stage reactor after recovering heat energy through the first waste heat boiler 7. The temperature of the first fuel reactor 12 is set to 650°C. A solid oxygen-carrying material is arranged inside the first fuel reactor 12. The solid oxygen-carrying material is a self-made cerium iron zirconium / Al2O3 honeycomb ceramic integral oxygen carrier. The solid oxygen-carrying material loses oxygen in a high-temperature environment and undergoes an oxidation reaction with carbon monoxide in the converter gas to generate carbon dioxide. A mixed exhaust gas of carbon dioxide and nitrogen is output at the end of the first fuel reactor 12, wherein the purity of the carbon dioxide is 80%, and the purity of the nitrogen is 20%. The two are separated by an existing adsorption separation process to obtain nearly pure carbon dioxide and nearly pure nitrogen, respectively. The nearly pure carbon dioxide is sent to a first saturated storage tank 14, and the nearly pure nitrogen is sent to a second saturated storage tank 15.

[0054] S3. After the solid oxygen-carrying material undergoes step S2, it becomes an oxygen-depleted solid material, and the oxygen-depleted solid material is sent to the first steam reactor 19 of the second stage of the chemical chain three-stage 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 water vapor generated by the steam generator 16 to be sent to the first steam reactor 19. The oxygen-depleted solid material and the water vapor undergo a reforming reaction in a high-temperature environment to generate hydrogen. After condensation at the end of the first steam reactor 19, nearly pure hydrogen is output and sent to the third saturated storage tank 22, wherein the purity of the hydrogen is 99.9%. The oxygen-depleted solid material achieves partial oxygen recovery in the first steam reactor 19, and a solid material with partial oxygen recovery is obtained.

[0055] S4. The solid material from which part of the oxygen is recovered is sent to the air reactor 23 of the third stage of the three-stage chemical chain 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 tail gas mixed with oxygen and nitrogen is output at the end of the air reactor 23. After the existing adsorption purification process, nearly pure nitrogen is enriched and sent to the second saturated storage tank 15, where the purity of nitrogen is 99.9%. The solid material from which part of the oxygen is recovered achieves complete oxygen recovery in the air reactor 23 and is returned to the first fuel reactor 12 of the first stage of the three-stage chemical chain reactor for recycling. The heat energy generated in the high-temperature oxygen-depleted air is recovered by the first waste heat boiler 7.

[0056] S5. The crude coke oven gas discharged from the refinery unit 2 is subjected to dust removal and pollutant purification to obtain clean coke oven gas, and the dust-removed and purified coke oven gas that meets the standards is sent to the second fuel reactor 29 of the first stage of the chemical chain secondary reactor. The temperature of the second fuel reactor 29 is set to 800° C. A solid oxygen-carrying material is arranged inside the second fuel reactor 29. The solid oxygen-carrying material is a self-made A-site nickel-doped perovskite oxygen carrier. A synthesis gas product mixed with carbon monoxide and hydrogen is output at the end of the second fuel reactor 29. The synthesis gas product includes carbon monoxide and hydrogen; The solid oxygen-carrying material is converted into an oxygen-depleted solid material, which is then sent to the second steam reactor 32 of the second stage of the chemical chain secondary reactor. At the same time, the water vapor generated by the steam generator 16 is sent to the second steam reactor 32. The oxygen-depleted solid material and the water vapor are reformed in a high-temperature environment to generate hydrogen. Nearly pure hydrogen is output after condensation at the end of the second steam reactor 32 and is sent to the fourth saturated storage tank 34, wherein the purity of the hydrogen is 99.9%. Similarly, the heat energy of the second steam reactor 32 comes from the water vapor generated by the steam generator 16 driven by the low-grade heat energy recovered by the first waste heat boiler 7.

[0057] 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 sent to the first mixing homogenizer 43 after adjusting the hydrogen-to-carbon ratio to 3.0 to prepare synthetic methanol raw gas, wherein the volume ratio of hydrogen in step S3 is 40%, and the volume ratio of hydrogen in step S5 is 60%; wherein the volume ratios of hydrogen in step S3 and step S5 are affected by their respective production capacities.

[0058] S7. The synthetic methanol raw gas is sent to the first pressurizing buffer 44, and after being pressurized to 4 MPa by the compressor, it is sent to the first preheater 47 before the tower. The temperature of the first preheater 47 is set to 140°C. The buffer prevents intermittent fluctuations in the workload in the compression pipeline, providing an excellent working environment for the subsequent synthetic methanol link.

[0059] S8. The synthetic methanol raw gas preheated before the tower is sent to the first synthesis tower 48 to react with the catalyst, wherein the catalyst is a self-made 55 nm ordered hierarchical pore copper-based oxide material, the temperature of the first synthesis tower 48 is set to 220°C, and the reaction product is separated by gas and liquid at the end of the first synthesis tower 48 to obtain crude methanol, achieving a carbon dioxide conversion rate of 14.9% and a methanol selectivity of 81.0%; and the unreacted gas analyzed from the top of the first synthesis tower 48 enters the first absorption tower 51, and is returned to the first mixing homogenizer 43 after purification by the first absorption tower 51 to replace part of the fresh methanol raw gas, wherein the unreacted gas replaces part of the fresh methanol raw gas with an available volume ratio of 27%, and the low-grade heat energy in the reduced pressure unreacted gas is recovered by the second waste heat boiler 52 and sent to the first preheater 47 before the first tower to replace part of the heat energy.

[0060] Example 3 This embodiment provides a method for synthesizing high-value products using refinery gas, comprising the following steps: S1. The raw furnace gas discharged from refinery unit 1 is subjected to dust removal and purification of pollutants to obtain clean blast furnace gas. The specific process can be referred to the existing dust removal and purification process, and Example 3 of the present invention will not be explained in detail.

[0061] S2. The clean converter gas that has been dusted and purified and meets the standards is sent to the first fuel reactor 12 of the first stage of the chemical chain three-stage reactor after recovering heat energy through the first waste heat boiler 7. The temperature of the first fuel reactor 12 is set to 650°C. A solid oxygen-carrying material is arranged inside the first fuel reactor 12. The solid oxygen-carrying material is a self-made cerium iron zirconium / Al2O3 honeycomb ceramic integral oxygen carrier. The solid oxygen-carrying material loses oxygen in a high-temperature environment and undergoes an oxidation reaction with carbon monoxide in the converter gas to generate carbon dioxide. A mixed exhaust gas of carbon dioxide and nitrogen is output at the end of the first fuel reactor 12, wherein the purity of the carbon dioxide is 80%, and the purity of the nitrogen is 20%. The two are separated by an existing adsorption separation process to obtain nearly pure carbon dioxide and nearly pure nitrogen, respectively. The nearly pure carbon dioxide is sent to a first saturated storage tank 14, and the nearly pure nitrogen is sent to a second saturated storage tank 15.

[0062] S3. After the solid oxygen-carrying material undergoes step S2, it becomes an oxygen-depleted solid material, and the oxygen-depleted solid material is sent to the first steam reactor 19 of the second stage of the chemical chain three-stage 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 water vapor generated by the steam generator 16 to be sent to the first steam reactor 19. The oxygen-depleted solid material and the water vapor undergo a reforming reaction in a high-temperature environment to generate hydrogen. After condensation at the end of the first steam reactor 19, nearly pure hydrogen is output and sent to the third saturated storage tank 22, wherein the purity of the hydrogen is 99.9%. The oxygen-depleted solid material achieves partial oxygen recovery in the first steam reactor 19, and a solid material with partial oxygen recovery is obtained.

[0063] S4. The solid material from which part of the oxygen is recovered is sent to the air reactor 23 of the third stage of the three-stage chemical chain 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 tail gas mixed with oxygen and nitrogen is output at the end of the air reactor 23. After the existing adsorption purification process, nearly pure nitrogen is enriched and sent to the second saturated storage tank 15, where the purity of nitrogen is 99.9%. The solid material from which part of the oxygen is recovered achieves complete oxygen recovery in the air reactor 23 and is returned to the first fuel reactor 12 of the first stage of the three-stage chemical chain reactor for recycling. The heat energy generated in the high-temperature oxygen-depleted air is recovered by the first waste heat boiler 7.

[0064] S5. The crude coke oven gas discharged from the refinery unit 2 is subjected to dust removal and pollutant purification to obtain clean coke oven gas, and the dust-removed and purified coke oven gas that meets the standards is sent to the second fuel reactor 29 of the first stage of the chemical chain secondary reactor. The temperature of the second fuel reactor 29 is set to 800° C. A solid oxygen-carrying material is arranged inside the second fuel reactor 29. The solid oxygen-carrying material is a self-made A-site nickel-doped perovskite oxygen carrier. A synthesis gas product mixed with carbon monoxide and hydrogen is output at the end of the second fuel reactor 29. The synthesis gas product includes carbon monoxide and hydrogen; The solid oxygen-carrying material is converted into an oxygen-depleted solid material, which is then sent to the second steam reactor 32 of the second stage of the chemical chain secondary reactor. At the same time, the water vapor generated by the steam generator 16 is sent to the second steam reactor 32. The oxygen-depleted solid material and the water vapor are reformed in a high-temperature environment to generate hydrogen. Nearly pure hydrogen is output after condensation at the end of the second steam reactor 32 and is sent to the fourth saturated storage tank 34, wherein the purity of the hydrogen is 99.9%. Similarly, the heat energy of the second steam reactor 32 comes from the water vapor generated by the steam generator 16 driven by the low-grade heat energy recovered by the first waste heat boiler 7.

[0065] 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 sent to the second mixing homogenizer 57 after adjusting the hydrogen-nitrogen ratio to 2.8 to prepare synthetic ammonia raw gas, wherein the volume ratio of hydrogen in step S3 is 40%, and the volume ratio of hydrogen in step S5 is 60%; wherein the volume ratios of hydrogen in step S3 and step S5 are affected by their respective production capacities.

[0066] S7. The synthetic ammonia raw gas is sent to the second pressurized buffer 58, and after being pressurized to 7.5 MPa by the compressor, it is sent to the second preheater 61 before the tower. The temperature of the second preheater 61 is set to 180°C. The buffer prevents intermittent fluctuations in the workload in the compression pipeline, providing an excellent working environment for the subsequent synthetic ammonia link.

[0067] S8. The synthetic ammonia raw gas preheated in front of the tower is sent to the second synthesis tower 62 to react with the catalyst, wherein the catalyst is a commercial iron-cobalt material catalyst, and the temperature of the second synthesis tower 62 is set to 300°C. The reaction product is condensed by the fifth heat exchanger 63 at the end of the second synthesis tower 62, and then enters the second gas-liquid separator 64. After gas-liquid separation, crude liquid ammonia is obtained, and the ammonia volume fraction of 25% in the equilibrium mixture is achieved; and the unreacted gas analyzed from the top of the second synthesis tower 62 enters the second absorption tower 65, and is returned to the second mixing homogenizer 57 after purification in the second absorption tower 65 to replace part of the fresh ammonia raw gas for use, wherein the unreacted gas replaces part of the fresh ammonia raw gas The available volume accounts for 20%, and the low-grade heat energy in the reduced pressure unreacted gas is recovered by the third waste heat boiler 66 and sent to the second preheater 61 before the tower to replace part of the heat energy.

[0068] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for synthesizing high-value products using refinery gas, characterized in that: Including raw material preparation process and product preparation process; The raw material preparation process includes the following steps: S1. The raw gas discharged from the refinery units is dedusted and purified of pollutants to obtain clean gas; S2, after the clean furnace gas recovers heat energy through the first waste heat boiler, it is sent to the first fuel reactor. A solid oxygen-carrying material is arranged inside the first fuel reactor. The clean furnace gas and the solid oxygen-carrying material undergo an oxidation reaction to generate carbon dioxide. A mixed tail gas of carbon dioxide and nitrogen is output at the end of the first fuel reactor. Nearly pure carbon dioxide and near pure nitrogen are obtained through adsorption separation. S3, after the solid oxygen-carrying material undergoes step S2, it becomes an oxygen-depleted solid material, the oxygen-depleted solid material is sent to the first steam reactor, and water vapor is simultaneously sent into the first steam reactor, the oxygen-depleted solid material and the water vapor undergo a reforming reaction to generate hydrogen, and the oxygen-depleted solid material realizes partial oxygen recovery, thereby obtaining a solid material with partial oxygen recovery; S4, sending the solid material from which part of the oxygen is recovered to an air reactor, and reacting the air with the solid material from which part of the oxygen is recovered to obtain nearly pure nitrogen; S5. The crude coke oven gas discharged from the refinery unit is subjected to dust removal and pollutant purification to obtain clean coke oven gas; the clean coke oven gas is sent to the second fuel reactor, and a solid oxygen-carrying material is arranged inside the second fuel reactor. The clean coke oven gas and the solid oxygen-carrying material undergo an oxidation reaction to obtain a synthesis gas including carbon monoxide and hydrogen; The solid oxygen-carrying material is transformed into an oxygen-depleted solid material, and the oxygen-depleted solid material is sent to a second steam reactor of the second stage. Meanwhile, water vapor is sent into the second steam reactor, and the oxygen-depleted solid material and the water vapor undergo a reforming reaction to generate hydrogen. The product preparation process includes the following steps: S6, after adjusting the gas structure hydrogen-carbon ratio or hydrogen-nitrogen ratio of nearly pure carbon dioxide, nearly pure nitrogen and nearly pure hydrogen, send them into a mixing homogenizer to be prepared into synthetic methanol or ammonia raw gas; S7, sending the synthetic methanol or ammonia raw gas into the pressurized buffer, and then sending it into the preheater before the tower after being pressurized; S8. The synthetic methanol or ammonia raw gas preheated in front of the tower is sent to the synthesis tower for synthesis reaction, and methanol or ammonia products are obtained after gas-liquid separation.

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

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

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

5. The method for synthesizing high-value products using refinery gas according to claim 1, characterized in that: In step S4, the reaction temperature is 550-650°C, and the solid material from which part of the oxygen is recovered achieves complete oxygen recovery to obtain a solid oxygen-carrying material, which is returned to the first fuel reactor for recycling; the heat energy carried by the nearly pure nitrogen is recovered by the first waste heat boiler.

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

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

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

9. A method for synthesizing high-value products using refinery gas according to claim 8, characterized in that: The methanol preparation process comprises the following steps: S61, adjusting the carbon dioxide in step S2, the hydrogen in step S3, and the hydrogen in step S5 to have a hydrogen-to-carbon ratio of 3.0 and then feeding them into a first mixing homogenizer to prepare synthetic methanol raw gas; S71, sending the synthetic methanol raw gas into the first pressurizing buffer, after being pressurized to 3-5 MPa, sending it into the first preheater before the tower, and the temperature of the first preheater before the tower is set to 130-150° C.; S81. The synthetic methanol raw gas preheated before the tower is sent to the first synthesis tower for synthesis reaction. The temperature of the first synthesis tower is set at 200-250°C. The reaction product is obtained by gas-liquid separation to obtain methanol at the end of the first synthesis tower. The unreacted gas analyzed from the top of the first synthesis tower enters the first absorption tower, and is returned to the first mixing homogenizer after purification in the first absorption tower to replace part of the fresh methanol raw gas. The low-grade heat energy in the reduced pressure 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. The method for synthesizing high-value products using refinery gas according to claim 8, characterized in that: The ammonia preparation process comprises the following steps: S62, adjusting the nitrogen in step S2 or step S4, the hydrogen in step S3 and the hydrogen in step S5 to have a hydrogen-nitrogen ratio of 2.7-3.0, and then sending the mixture into a second mixing homogenizer to prepare ammonia synthesis feed gas; S72, sending the synthetic ammonia raw gas into the second pressurized buffer, and after being pressurized to 7-8 MPa, sending it into the second preheater before the tower, and the temperature of the second preheater before the tower is set to 150-200° C.; S82. The synthetic ammonia raw gas preheated in front of the tower is sent to the second synthesis tower for synthesis reaction. The temperature of the second synthesis tower is set at 280-320°C. The reaction product is separated into liquid ammonia after gas-liquid separation at the end of the second synthesis tower. The unreacted gas analyzed from the top of the second synthesis tower enters the second absorption tower, and is returned to the second mixing homogenizer after purification in the second absorption tower to replace part of the fresh ammonia raw gas. The low-grade heat energy in the decompressed 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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