System and method for preparing methanol by coupling high-sulfur petroleum coke with green hydrogen
By using a high-sulfur petroleum coke coupled with a green hydrogen-to-methanol system, and through multiple desulfurization and hydrocarbon reforming processes, the problems of hydrogen-carbon imbalance, sulfur corrosion, and catalyst poisoning in the high-sulfur petroleum coke gasification to methanol production process have been solved, achieving low-carbon integration and reduced energy consumption in methanol production.
Patent Information
- Application Number
- CN202511003389.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-21
- Publication Date
- 2025-12-09
AI Technical Summary
High-sulfur petroleum coke faces challenges in the traditional gasification process for methanol production, including an imbalance in the hydrogen-to-carbon ratio of syngas, sulfur corrosion and catalyst poisoning, and a lack of green hydrogen coupling technology. These issues lead to increased energy consumption and carbon emissions.
A high-sulfur petroleum coke coupled with green hydrogen to methanol system is adopted, including petroleum coke pretreatment, gasification, hydrocarbon reforming and methanol synthesis unit, combined with electrolytic hydrogen production unit, to generate and purify methanol through multiple desulfurization and hydrocarbon reforming processes.
It achieves precise control of the hydrogen-to-carbon ratio in syngas, reduces energy consumption and carbon emissions, prevents sulfur corrosion and catalyst poisoning, and forms a low-carbon integration of efficient synergistic conversion and full-process sulfur closed loop.
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Figure CN121082205A_ABST
Abstract
Description
Technical Field
[0001] The embodiments of the present invention belong to the field of methanol preparation technology, specifically relating to a high-sulfur petroleum coke coupled with green hydrogen methanol production system and method. Background Technology
[0002] High-sulfur petroleum coke (sulfur content > 3%) is a major byproduct of the oil refining industry. Its high carbon-to-hydrogen ratio (H / C ≈ 0.8-1.5) and high sulfur content lead to the following challenges in traditional gasification for methanol production:
[0003] 1) The hydrogen-to-carbon ratio of the syngas is unbalanced, and the H2 content needs to be increased through water-gas shift, which leads to increased energy consumption and carbon emissions;
[0004] 2) Sulfur corrosion and catalyst poisoning: Traditional copper-based methanol synthesis catalysts are sensitive to sulfur (sulfur content must be <0.1ppm);
[0005] 3) There is a lack of green hydrogen coupling technology, and the application of green hydrogen in the production of methanol from petroleum coke lacks systematic process integration.
[0006] Therefore, there is an urgent need for a high-sulfur petroleum coke methanol production system that reduces carbon emissions and prevents corrosion. Summary of the Invention
[0007] The embodiments of the present invention aim to at least solve one of the technical problems existing in the prior art, and provide a high-sulfur petroleum coke coupled green hydrogen to methanol system and method.
[0008] The embodiments of this disclosure provide a high-sulfur petroleum coke coupled with green hydrogen to methanol system. The system includes: a petroleum coke pretreatment unit, a petroleum coke gasification unit, a hydrocarbon reforming unit, and a methanol synthesis unit connected in sequence. The petroleum coke pretreatment unit is used to crush, desulfurize, and activate the petroleum coke. The petroleum coke gasification unit is used to gasify the pretreated petroleum coke. The hydrocarbon reforming unit is used to desulfurize and perform two hydrocarbon reforming processes on the gasified gas. The methanol synthesis unit is used to synthesize methanol from the gas output from the hydrocarbon reforming unit.
[0009] The system further includes an electrolytic hydrogen production device, which is connected to the petroleum coke gasification device and the hydrocarbon reforming device respectively. The electrolytic hydrogen production device is used to provide oxygen to the petroleum coke gasification device and to provide hydrogen to the hydrocarbon reforming device.
[0010] In some embodiments of this disclosure, the petroleum coke pretreatment device includes a jaw crusher, a vibrating screen, a microwave desulfurization reactor, and an alkali metal impregnation tank connected in sequence. The alkali metal impregnation tank is connected to the petroleum coke gasification device and is used to activate the desulfurized petroleum coke.
[0011] In some embodiments of this disclosure, the hydrocarbon reforming unit includes a low-temperature gas scrubbing tower, a sulfur-resistant shift reactor, and an activated carbon desulfurizer. The syngas output of the petroleum coke gasification unit and the hydrogen output of the electrolytic hydrogen production unit are respectively connected to the input of the low-temperature gas scrubbing tower. The output of the low-temperature gas scrubbing tower and the hydrogen output of the electrolytic hydrogen production unit are respectively connected to the input of the sulfur-resistant shift reactor. The output of the sulfur-resistant shift reactor is connected to the input of the activated carbon desulfurizer. The output of the activated carbon desulfurizer is connected to the input of the methanol synthesis unit. The low-temperature gas scrubbing tower is used for primary hydrocarbon reforming and desulfurization, and the sulfur-resistant shift reactor is used for secondary hydrocarbon reforming.
[0012] In some embodiments of this disclosure, the methanol synthesis apparatus includes a microchannel reactor that integrates a plasma generator.
[0013] In some embodiments of this disclosure, the system further includes a three-tower distillation unit connected to the output of the methanol synthesis unit, the three-tower distillation unit being used to purify methanol.
[0014] A second aspect of this disclosure provides a method for producing methanol from high-sulfur petroleum coke coupled with green hydrogen, the method comprising:
[0015] The petroleum coke is subjected to crushing, vibration, desulfurization and activation treatment in sequence;
[0016] The activated petroleum coke is then subjected to high-temperature oxidation to generate syngas.
[0017] Syngas is mixed with hydrogen produced by water electrolysis and then subjected to a primary hydrocarbon reforming process, while simultaneously undergoing desulfurization.
[0018] The gas obtained from the first hydrocarbon reforming is mixed with hydrogen produced by water electrolysis for a second hydrocarbon reforming process.
[0019] The gas after secondary hydrocarbon reforming is desulfurized and then subjected to methanol synthesis to produce methanol.
[0020] The generated methanol is then purified.
[0021] In some embodiments disclosed herein, the oxygen-to-coal ratio of the high-temperature oxidation treatment is 0.8–1.0 Nm³ / kg, the temperature of the high-temperature oxidation treatment is 1400°C–1600°C, the pressure of the high-temperature oxidation treatment is 4–6 MPa, and the syngas obtained from the high-temperature oxidation treatment comprises 45%–50% CO, 35%–40% H₂, and 2%–4% H₂S.
[0022] In some embodiments disclosed herein, the temperature of the primary reforming C-H ratio treatment is 800–1000°C, the catalyst for the primary reforming C-H ratio treatment is Ni-Mg-Al-O, and the H2 to CO ratio after the first reforming C-H ratio treatment is 2.0–2.1.
[0023] In some embodiments disclosed herein, the temperature of the secondary reforming C-H ratio treatment is 300–400°C, the catalyst for the secondary reforming C-H ratio treatment is Co-Mo, and the H2 to CO ratio after the secondary reforming C-H ratio treatment is 2.05.
[0024] In some embodiments disclosed herein, the temperature of the methanol synthesis treatment is 230–260°C, the catalyst for the methanol synthesis treatment is Cu-Zn-Al-Mn, the pressure for the methanol synthesis treatment is 5–8 MPa, and the methanol synthesis treatment employs plasma technology.
[0025] According to an embodiment of this disclosure, a high-sulfur petroleum coke coupled with green hydrogen to methanol production system and method firstly involves crushing, vibrating, desulfurizing, and activating the high-sulfur petroleum coke in a petroleum coke pretreatment device to ensure sufficient reaction between the petroleum coke and oxygen. Then, the activated petroleum coke and oxygen produced by an electrolytic hydrogen production device are respectively transported to a petroleum gasification device for high-temperature oxidation treatment to generate syngas composed of CO, H2, and H2S. Next, the syngas is transported to a hydrocarbon reforming system and undergoes two hydrocarbon reforming treatments to adjust the hydrocarbon ratio of the syngas. Simultaneously, the syngas undergoes two desulfurization treatments within the hydrocarbon reforming system. Finally, the syngas with adjusted hydrocarbon ratios is subjected to methanol synthesis treatment to generate methanol, which is then purified. By performing the first desulfurization treatment in the petroleum coke pretreatment process and the second and third desulfurization treatments in the two hydrocarbon reforming processes, the sulfur content in the gas output from the hydrocarbon reforming unit can be made extremely low, ensuring that methanol synthesis takes place in a low-sulfur environment. This prevents sulfur corrosion from high-sulfur petroleum coke gasification and catalyst poisoning. The methanol production system in this embodiment, based on the characteristics of petroleum coke and combined with green hydrogen energy from water electrolysis to produce hydrogen, forms a systematic methanol production process integration, achieving precise control of the hydrogen-carbon ratio of the synthesis gas, reducing energy consumption and carbon emissions, and achieving breakthroughs in efficient synergistic conversion, closed-loop sulfur production throughout the entire process, and low-carbon integration. Attached Figure Description
[0026] Figure 1 This is a schematic diagram of a high-sulfur petroleum coke coupled with green hydrogen to methanol system according to an embodiment of the present invention;
[0027] Figure 2 This is a logic flowchart of a method for producing methanol from high-sulfur petroleum coke coupled with green hydrogen, according to an embodiment of the present invention.
[0028] The labels in the attached diagram are as follows:
[0029] 100. A high-sulfur petroleum coke coupled with green hydrogen to methanol system;
[0030] 10. Petroleum coke pretreatment unit; 11. Jaw crusher; 12. Vibrating screen; 13. Microwave desulfurization reactor; 14. Alkali metal immersion tank; 20. Petroleum coke gasification unit; 30. Carbon-hydrogen reforming unit; 31. Low temperature gas scrubbing tower; 32. Sulfur-resistant shift reactor; 33. Activated carbon remover; 40. Methanol synthesis unit; 50. Electrolytic hydrogen production unit; 60. Renewable energy power generation unit; 70. Three-tower distillation unit. Detailed Implementation
[0031] Exemplary embodiments of the invention will now be described in more detail with reference to the accompanying drawings. While exemplary embodiments of the invention are shown in the drawings, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of the invention and to fully convey the scope of the invention to those skilled in the art.
[0032] It should be understood that the terminology used herein is for the purpose of describing particular exemplary embodiments only and is not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “described” as used herein may also include the plural forms. The terms “comprising,” “including,” “containing,” and “having” are inclusive and therefore indicate the presence of the stated features, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, elements, components, and / or combinations thereof. The method steps, processes, and operations described herein are not construed as requiring them to be performed in a particular order described or illustrated unless the order of performance is explicitly indicated. It should also be understood that additional or alternative steps may be used.
[0033] Although terms such as first, second, third, etc., may be used in this document to describe multiple elements, components, regions, layers, and / or segments, these elements, components, regions, layers, and / or segments should not be limited by these terms. These terms may be used only to distinguish one element, component, region, layer, or segment from another. Unless the context clearly indicates otherwise, terms such as "first," "second," and their numerical terms, when used in this document, do not imply order or sequence. Therefore, the first element, component, region, layer, or segment discussed below may be referred to as the second element, component, region, layer, or segment without departing from the teachings of the exemplary embodiments.
[0034] For ease of description, spatial relative terms may be used in the text to describe the relationship of one element or feature relative to another element or feature, as shown in the figure. These relative terms include, for example, "inside," "outside," "middle," "outer," "below," "below," "above," "over," etc. Such spatial relative terms are intended to include different orientations of the device in use or operation, other than those depicted in the figure. For example, if the device in the figure is flipped, an element described as "below other elements or features" or "below other elements or features" would subsequently be oriented as "above other elements or features" or "above other elements or features." Therefore, the example term "below" can include both upper and lower orientations. The device may be otherwise oriented (rotated 90 degrees or in other directions), and the spatial relative descriptors used in the text will be interpreted accordingly.
[0035] like Figure 1 As shown, an embodiment of this disclosure provides a high-sulfur petroleum coke coupled with green hydrogen to methanol system 100. The system includes: a petroleum coke pretreatment unit 10, a petroleum coke gasification unit 20, a hydrocarbon reforming unit 30, and a methanol synthesis unit 40 connected in sequence. The petroleum coke pretreatment unit 10 is used to crush, desulfurize, and activate the petroleum coke. The petroleum coke gasification unit 20 is used to gasify the pretreated petroleum coke. The hydrocarbon reforming unit is used to desulfurize and perform two hydrocarbon reforming processes on the gasified gas. The methanol synthesis unit 40 is used to synthesize methanol from the gas output from the hydrocarbon reforming unit 30.
[0036] The system also includes an electrolytic hydrogen production unit 50, which is connected to the petroleum coke gasification unit 20 and the hydrocarbon reforming unit 30 respectively. The electrolytic hydrogen production unit 50 is used to provide oxygen to the petroleum coke gasification unit 20 and to provide hydrogen to the hydrocarbon reforming unit 30.
[0037] According to an embodiment of this disclosure, a high-sulfur petroleum coke coupled with green hydrogen to methanol system 100 firstly crushes, vibrates, desulfurizes, and activates the high-sulfur petroleum coke through a petroleum coke pretreatment device 10 to ensure that the petroleum coke can fully react with oxygen. Then, the activated petroleum coke and oxygen produced by the electrolytic hydrogen production device 50 are respectively transported to a petroleum gasification device for high-temperature oxidation treatment to generate syngas composed of CO, H2, and H2S. Next, the syngas is transported to a hydrocarbon reforming system and undergoes two hydrocarbon reforming treatments to adjust the hydrocarbon ratio of the syngas. Simultaneously, the syngas undergoes two desulfurization treatments within the hydrocarbon reforming system. Finally, the syngas with adjusted hydrocarbon ratios is subjected to methanol synthesis treatment to generate methanol, which is then purified. Through the first desulfurization treatment in the petroleum coke pretreatment process and the second and third desulfurization treatments in the two hydrocarbon reforming processes, the sulfur content in the gas output from the hydrocarbon reforming unit 30 can be made extremely low, ensuring that methanol synthesis takes place in a low-sulfur environment. This prevents sulfur corrosion from high-sulfur petroleum coke gasification and catalyst poisoning. The methanol production system in this embodiment, based on the characteristics of petroleum coke and combined with green hydrogen energy from water electrolysis to produce hydrogen, forms a systematic methanol production process integration, achieving precise control of the hydrogen-carbon ratio of the synthesis gas, reducing energy consumption and carbon emissions, and achieving breakthroughs in efficient synergistic conversion, closed-loop sulfur production throughout the process, and low-carbon integration.
[0038] In some embodiments of this disclosure, the petroleum coke pretreatment device 10 includes a jaw crusher 11, a vibrating screen 12, a microwave desulfurization reactor 13, and an alkali metal immersion tank 14 connected in sequence. The alkali metal immersion tank 14 is connected to the petroleum coke gasification device 20 and is used to activate the desulfurized petroleum coke.
[0039] Specifically, high-sulfur petroleum coke enters the jaw crusher 11 of the petroleum coke pretreatment unit 10, where it is crushed into smaller pieces. The crushed petroleum coke pieces then enter a vibrating screen 12, which separates the petroleum coke particles to smaller than 5 mm. These smaller particles then enter a microwave desulfurization reactor 13, where they are mixed with Na2CO3. The reaction temperature of the microwave desulfurization reactor 13 is 300–400°C, and its operating frequency is 2.45 GHz. After desulfurization in the microwave desulfurization reactor 13, the desulfurization rate of the petroleum coke pieces is greater than 50%. Finally, the desulfurized petroleum coke pieces enter an alkali metal immersion tank 14, where they are activated by a K2CO3 solution to enhance their reactivity and ensure a more complete reaction with oxygen.
[0040] The petroleum coke gasification unit 20 is a high-temperature gasifier. The input end of the high-temperature gasifier is connected to the output end of the alkali metal impregnation tank 14 and the oxygen output end of the electrolytic hydrogen production unit 50, respectively, so that the activated petroleum coke particles and the oxygen produced by the electrolytic hydrogen production unit 50 enter the high-temperature gasifier and undergo a high-temperature gasification reaction in the high-temperature gasifier. The reaction temperature is 1400℃~1600℃, the reaction pressure is 4~6MPa, the oxygen-to-coal ratio is 0.8~1.0Nm3 / kg, and a synthesis gas of 45%-50% CO, 35%-40% H2 and 2%-4% H2S is produced.
[0041] In some embodiments of this disclosure, the hydrocarbon reforming unit 30 includes a low-temperature gas scrubbing tower 31, a sulfur-resistant shift reactor 32, and an activated carbon desulfurizer 33. The syngas output of the petroleum coke gasification unit 20 and the hydrogen output of the electrolytic hydrogen production unit 50 are respectively connected to the input of the low-temperature gas scrubbing tower 31. The output of the low-temperature gas scrubbing tower 31 and the hydrogen output of the electrolytic hydrogen production unit 50 are respectively connected to the input of the sulfur-resistant shift reactor 32. The output of the sulfur-resistant shift reactor 32 is connected to the input of the activated carbon desulfurizer. The output of the activated carbon desulfurizer is connected to the input of the methanol synthesis unit 40. The low-temperature gas scrubbing tower 31 is used for primary hydrocarbon reforming and desulfurization, and the sulfur-resistant shift reactor 32 is used for secondary hydrocarbon reforming.
[0042] Specifically, the syngas formed in the high-temperature gasifier is transported to the low-temperature gas scrubbing tower 31. At the same time, hydrogen formed by the electrolysis of water in the electrolysis hydrogen production unit 50 is transported into the low-temperature gas scrubbing tower 31. Desulfurization and hydrocarbon reforming are carried out in the low-temperature gas scrubbing tower 31, so that the H2S in the gas output from the low-temperature gas scrubbing tower 31 is less than 0.1 ppm and the CO2 in the gas output from the low-temperature gas scrubbing tower 31 is less than 1%. That is, the syngas output from the low-temperature gas scrubbing tower 31 mainly contains H2 and CO, and the H2 / CO ratio ranges from 2.0 to 2.1.
[0043] The gas output from the low-temperature gas scrubbing tower 31 is transported to the sulfur-resistant shift reactor 32. Simultaneously, a certain amount of hydrogen is supplied to the sulfur-resistant shift reactor 32 for secondary hydrocarbon reforming. The H2 / CO ratio output from the low-temperature gas scrubbing tower 31, with a ratio of 2.0 to 2.1, undergoes secondary hydrocarbon reforming with the hydrogen output from the electrolyzer, resulting in an H2 / CO ratio of 2.05.
[0044] The H2 / CO ratio of 2.05 obtained after the secondary hydrocarbon reforming is fed to an activated carbon desulfurizer to desulfurize the gas obtained after the secondary hydrocarbon reforming. The sulfur in the gas is removed again to ensure that the H2S in the gas after the secondary reforming is <0.1ppm. This ensures that the gas after the secondary hydrocarbon reforming is in a low-sulfur state when it is used for methanol synthesis, and prevents sulfur corrosion and catalyst poisoning.
[0045] In some embodiments of this disclosure, the methanol synthesis apparatus 40 includes a microchannel reactor that integrates a plasma generator.
[0046] Specifically, the H2 / CO ratio of 2.05, obtained after desulfurization by an activated carbon desulfurizer, is conveyed to a microchannel reactor. The hydraulic diameter or width of the microchannel reactor ranges from 0.5 to 2 mm. The catalyst within the microchannel reactor is Cu-Zn-Al-Mn. The methanol synthesis reaction temperature within the microchannel reactor is 230–260 °C, and the pressure for methanol synthesis is 5–8 MPa. Under these reaction conditions in the microchannel reactor, combined with the synergistic effect of a plasma generator, low-purity methanol is synthesized from the 2.05 H2 / CO ratio. With the synergistic effect of the microchannel reactor and the plasma generator, the single-pass conversion rate of methanol is >18%.
[0047] In some embodiments of this disclosure, the system further includes a three-tower distillation unit 70, which is connected to the output of the methanol synthesis unit 40. The three-tower distillation unit 70 is used to purify methanol. Low-purity methanol synthesized in the microchannel reactor is fed to the three-tower distillation unit 70, where it is purified to obtain high-purity methanol with a purity greater than or equal to 99.9%.
[0048] The high-sulfur petroleum coke coupled green hydrogen to methanol system of this disclosure embodiment also includes a renewable energy power generation device 60, which is connected to the electrolytic hydrogen production device 50. The renewable energy power generation device 60 is used to provide electrical energy to the electrolytic hydrogen production device 50. The renewable energy power generation device 60 can generate electricity using renewable energy sources such as wind energy and solar energy. The setting of the renewable energy power generation device 60 can improve energy utilization efficiency.
[0049] In this embodiment, the electrolytic hydrogen production device 50 is an electrolytic cell, which produces hydrogen and oxygen by electrolyzing water.
[0050] like Figure 2 As shown, the second aspect of this disclosure proposes a method for producing methanol from high-sulfur petroleum coke coupled with green hydrogen, the method comprising:
[0051] S100: Petroleum coke is subjected to crushing, vibration, desulfurization and activation treatment in sequence;
[0052] S200: High-temperature oxidation treatment of activated petroleum coke to generate syngas;
[0053] S300: Purifies the hydrogen produced by syngas and water electrolysis and performs a primary hydrocarbon reforming process.
[0054] S400: The gas obtained from the first hydrocarbon reforming is mixed with hydrogen produced by water electrolysis for a second hydrocarbon reforming process.
[0055] S500: The gas after secondary hydrocarbon reforming is desulfurized and then subjected to methanol synthesis to produce methanol.
[0056] S600: Purifies the generated methanol.
[0057] According to the method for producing methanol from high-sulfur petroleum coke coupled with green hydrogen according to the embodiments of this disclosure, the high-sulfur petroleum coke is first crushed, vibrated, desulfurized and activated in a petroleum coke pretreatment device so that the petroleum coke can react fully with oxygen; then the activated petroleum coke is subjected to high-temperature oxidation treatment to generate syngas composed of CO, H2 and H2S; then the syngas is subjected to two carbon-hydrogen ratio reforming treatments to adjust the carbon-hydrogen ratio of the syngas; finally, the syngas with adjusted carbon-hydrogen ratio is subjected to methanol synthesis treatment to generate methanol and then subjected to methanol purification treatment. The methanol production method using high-sulfur petroleum coke coupled with green hydrogen in this embodiment involves reacting petroleum coke particles with oxygen obtained through water electrolysis to generate syngas. By mixing the syngas with hydrogen produced from water electrolysis and reforming the carbon-hydrogen ratio, the hydrogen content is increased compared to the water-gas shift conversion technology. Electrolysis of water to produce hydrogen can reduce energy consumption and carbon emissions. Through primary desulfurization treatment in the petroleum coke pretreatment process, secondary desulfurization treatment in the primary carbon-hydrogen ratio reforming process, and tertiary desulfurization treatment after the secondary carbon-hydrogen ratio reforming, methanol synthesis can be carried out in a low-sulfur environment, thereby preventing sulfur corrosion from high-sulfur petroleum coke gasification and preventing catalyst poisoning. The methanol production method in this embodiment, based on the characteristics of petroleum coke and combined with green hydrogen energy from water electrolysis to form a systematic methanol production process integration, achieves precise control of the hydrogen-carbon ratio of syngas, reduces energy consumption and carbon emissions, and has breakthroughs in efficient synergistic conversion, closed-loop sulfur production throughout the entire process, and low-carbon integration.
[0058] S100: Petroleum coke is subjected to crushing, vibration, desulfurization and activation treatment in sequence.
[0059] First, high-sulfur petroleum coke enters the jaw crusher of the petroleum coke pretreatment unit, where it is crushed into smaller pieces. Then, the crushed petroleum coke pieces are screened to separate particles smaller than 5 mm. These smaller particles then enter a microwave desulfurization reactor, where they are mixed with 10%–15% Na₂CO₃ at a reaction temperature of 300–400°C and an operating frequency of 2.45 GHz. After desulfurization in the microwave desulfurization reactor, the desulfurization rate of the petroleum coke pieces is greater than 50%. Finally, the desulfurized petroleum coke pieces enter an alkali metal immersion tank, where they are activated by a 5%–8% K₂CO₃ solution to enhance their reactivity and ensure a more complete reaction with oxygen.
[0060] S200: High-temperature oxidation treatment of activated petroleum coke to generate syngas.
[0061] Specifically, the activated petroleum coke particles and oxygen produced by electrolysis of water in an electrolytic cell are fed into a high-temperature vaporization furnace, where they are heated to a temperature range of 1400℃~1600℃, a pressure range of 4~6MPa, and a flow rate of 0.8~1.0Nm. 3 Within the oxygen-to-coal ratio range of / kg, petroleum coke particles undergo high-temperature oxidation gasification with oxygen to produce syngas containing 45%-50% CO, 35%-40% H2, and 2%-4% H2S.
[0062] In some embodiments of this disclosure, the oxygen-to-coal ratio in the high-temperature oxidation treatment within the high-temperature gasification furnace is 0.8–1.0 Nm³. 3 Within this oxygen-to-coal ratio range, a good gasification effect can be achieved. Preferably, the oxygen-to-coal ratio for high-temperature oxidation treatment is 0.8 Nm³ / kg. 3 / kg, 0.9Nm 3 / kg, 1.0Nm 3 / kg; most preferably, the oxygen-to-coal ratio for high-temperature oxidation treatment is 0.9 Nm³. 3 / kg.
[0063] In some embodiments of this disclosure, the high-temperature oxidation treatment temperature is 1400℃ to 1600℃, within which a good gasification effect can be achieved. Preferably, the high-temperature oxidation treatment temperature is 1400℃, 1500℃, or 1600℃; most preferably, the high-temperature oxidation treatment temperature is 1500℃.
[0064] In some embodiments of this disclosure, the pressure of the high-temperature oxidation treatment is 4–6 MPa. Within this pressure range, a good gasification effect can be achieved. Preferably, the pressure of the high-temperature oxidation treatment is 4 MPa, 5 MPa, or 6 MPa, and most preferably, the pressure of the high-temperature oxidation treatment is 5 MPa.
[0065] S300: Syngas is mixed with hydrogen produced by water electrolysis and then subjected to a primary hydrocarbon reforming process, while simultaneously undergoing desulfurization.
[0066] Specifically, the syngas formed in the high-temperature gasifier is transported to a low-temperature scrubbing tower. Simultaneously, hydrogen formed from water electrolysis in an electrolyzer is introduced into the low-temperature scrubbing tower for desulfurization and hydrocarbon reforming. The low-temperature scrubbing tower contains a Ni-Mg-Al-O catalyst. Within a temperature range of 800–1000°C, the hydrocarbon ratio of the syngas and hydrogen changes, increasing the H2 / CO ratio to 2.0–2.1. Simultaneously, under the action of the Ni-Mg-Al-O catalyst, most of the H2S and CO2 in the syngas are removed. The H2S output from the low-temperature scrubbing tower is <0.1 ppm, and the CO2 output is <1%. This means that the syngas output from the low-temperature scrubbing tower mainly contains H2 and CO, with an H2 / CO ratio ranging from 2.0 to 2.1.
[0067] In some embodiments of this disclosure, the reaction temperature range within the low-temperature gas scrubbing tower is 800–1000°C. Within this temperature range, the reforming effect of the C-H ratio is better, and the removal of H2S and CO2 is also better. Preferably, the reaction temperature within the low-temperature gas scrubbing tower is 800°C, 900°C, or 1000°C; most preferably, the temperature of the high-temperature oxidation treatment is 90°C.
[0068] S400: The gas obtained from the first hydrocarbon reforming is mixed with hydrogen produced by water electrolysis for a second hydrocarbon reforming process.
[0069] Specifically, the gas output from the low-temperature gas scrubbing tower is transported to a sulfur-resistant shift reactor, and simultaneously, a certain amount of hydrogen is supplied to the sulfur-resistant shift reactor for secondary hydrocarbon reforming. The catalyst in the sulfur-resistant shift reactor is Co-Mo, and the reaction temperature is 300–400°C. Within this catalyst and temperature range, the H2 / CO ratio of 2.0–2.1 output from the low-temperature gas scrubbing tower undergoes secondary hydrocarbon reforming with the hydrogen output from the electrolyzer, resulting in an H2 / CO ratio of 2.05.
[0070] In some embodiments of this disclosure, the reaction temperature range within the sulfur-resistant shift reactor is 300–400°C, within which the reforming effect of the C-H ratio is better. Preferably, the reaction temperature within the sulfur-resistant shift reactor is 300°C, 350°C, or 400°C; most preferably, the reaction temperature within the sulfur-resistant shift reactor is 350°C.
[0071] S500: The gas after secondary hydrocarbon reforming is desulfurized and then subjected to methanol synthesis to produce methanol.
[0072] Specifically, the H2 / CO ratio of 2.05 obtained after the secondary hydrocarbon reforming is fed to an activated carbon desulfurizer to desulfurize the gas obtained after the secondary hydrocarbon reforming, and remove sulfur from the gas again to ensure that the H2S in the gas after the secondary reforming is <0.1ppm. This ensures that the gas after the secondary hydrocarbon reforming is in a low-sulfur state when it is used for methanol synthesis, and prevents sulfur corrosion and catalyst poisoning.
[0073] The H2 / CO ratio of 2.05, obtained after desulfurization by an activated carbon desulfurizer, is fed into a microchannel reactor. The hydraulic diameter or width of the channels in the microchannel reactor ranges from 0.5 to 2 mm. The catalyst in the microchannel reactor is Cu-Zn-Al-Mn. The methanol synthesis reaction temperature in the microchannel reactor is 230–260 °C, and the pressure of the methanol synthesis process is 5–8 MPa. Under the reaction conditions of the microchannel reactor, combined with the synergistic effect of a plasma generator, low-purity methanol is synthesized from the 2.05 H2 / CO ratio. With the synergistic effect of the microchannel reactor and the plasma generator, the single-pass conversion rate of methanol is >18%.
[0074] S600: Purifies the generated methanol.
[0075] The low-purity methanol synthesized by the microchannel reactor is transported to a three-tower distillation unit, where it is purified to obtain high-purity methanol with a purity of ≥99.9%.
[0076] It is understood that the above embodiments are merely exemplary implementations used to illustrate the principles of the present invention, and the present invention is not limited thereto. For those skilled in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also considered to be within the scope of protection of the present invention.
Claims
1. A high-sulfur petroleum coke coupled with green hydrogen to methanol system, characterized in that, The system includes: a petroleum coke pretreatment unit, a petroleum coke gasification unit, a hydrocarbon reforming unit, and a methanol synthesis unit connected in sequence. The petroleum coke pretreatment unit is used to crush, desulfurize, and activate the petroleum coke. The petroleum coke gasification unit is used to gasify the pretreated petroleum coke. The hydrocarbon reforming unit is used to desulfurize and perform two hydrocarbon reforming processes on the gasified gas. The methanol synthesis unit is used to synthesize methanol from the gas output by the hydrocarbon reforming unit. The system further includes an electrolytic hydrogen production device, which is connected to the petroleum coke gasification device and the hydrocarbon reforming device respectively. The electrolytic hydrogen production device is used to provide oxygen to the petroleum coke gasification device and to provide hydrogen to the hydrocarbon reforming device.
2. The high-sulfur petroleum coke coupled green hydrogen to methanol system according to claim 1, characterized in that, The petroleum coke pretreatment device includes a jaw crusher, a vibrating screen, a microwave desulfurization reactor, and an alkali metal impregnation tank connected in sequence. The alkali metal impregnation tank is connected to the petroleum coke gasification device and is used to activate the desulfurized petroleum coke.
3. The high-sulfur petroleum coke coupled green hydrogen to methanol system according to claim 1, characterized in that, The hydrocarbon reforming unit includes a low-temperature gas scrubbing tower, a sulfur-resistant shift reactor, and an activated carbon desulfurizer. The syngas output of the petroleum coke gasification unit and the hydrogen output of the electrolytic hydrogen production unit are respectively connected to the input of the low-temperature gas scrubbing tower. The output of the low-temperature gas scrubbing tower and the hydrogen output of the electrolytic hydrogen production unit are respectively connected to the input of the sulfur-resistant shift reactor. The output of the sulfur-resistant shift reactor is connected to the input of the activated carbon desulfurizer. The output of the activated carbon desulfurizer is connected to the input of the methanol synthesis unit. The low-temperature gas scrubbing tower is used for primary hydrocarbon reforming and desulfurization, and the sulfur-resistant shift reactor is used for secondary hydrocarbon reforming.
4. The high-sulfur petroleum coke coupled green hydrogen to methanol system according to claim 1, characterized in that, The methanol synthesis apparatus includes a microchannel reactor, which integrates a plasma generator.
5. The high-sulfur petroleum coke coupled green hydrogen to methanol system according to claim 1, characterized in that, The system also includes a three-tower distillation unit, which is connected to the output of the methanol synthesis unit and is used to purify methanol.
6. A method for producing methanol from high-sulfur petroleum coke coupled with green hydrogen, characterized in that, The method includes: The petroleum coke is subjected to crushing, vibration, desulfurization and activation treatment in sequence; The activated petroleum coke is then subjected to high-temperature oxidation to generate syngas. Syngas is mixed with hydrogen produced by water electrolysis and then subjected to a primary hydrocarbon reforming process, while simultaneously undergoing desulfurization. The gas obtained from the first hydrocarbon reforming is mixed with hydrogen produced by water electrolysis for a second hydrocarbon reforming process. The gas after secondary hydrocarbon reforming is desulfurized and then subjected to methanol synthesis to produce methanol. The generated methanol is then purified.
7. The method for producing methanol from high-sulfur petroleum coke coupled with green hydrogen according to claim 6, characterized in that, The oxygen-to-coal ratio in the high-temperature oxidation treatment is 0.8–1.0 Nm³. 3 / kg, the temperature of the high-temperature oxidation treatment is 1400℃~1600℃, the pressure of the high-temperature oxidation treatment is 4~6MPa, and the synthesis gas obtained by the high-temperature oxidation treatment includes 45%-50% CO, 35%-40% H2 and 2%-4% H2S.
8. The method for producing methanol from high-sulfur petroleum coke coupled with green hydrogen according to claim 6, characterized in that, The temperature of the primary reforming C-H ratio treatment is 800-1000℃, the catalyst for the primary reforming C-H ratio treatment is Ni-Mg-Al-O, and the H2 to CO ratio after the first reforming C-H ratio treatment is 2.0-2.
1.
9. The method for producing methanol from high-sulfur petroleum coke coupled with green hydrogen according to claim 6, characterized in that, The temperature for the secondary reforming C-H ratio treatment is 300–400°C, the catalyst for the secondary reforming C-H ratio treatment is Co-Mo, and the H2 to CO ratio after the secondary reforming C-H ratio treatment is 2.
05.
10. The method for producing methanol from high-sulfur petroleum coke coupled with green hydrogen according to claim 6, characterized in that, The methanol synthesis treatment is carried out at a temperature of 230–260°C, the catalyst is Cu-Zn-Al-Mn, the pressure is 5–8 MPa, and plasma technology is used in the methanol synthesis treatment.