A device for producing chemical raw materials by coupling oil-rich coal graded gas phase catalytic cracking and gasification regeneration

Abstract

The present invention provides a combined device for maximizing the preparation of chemical raw materials by coupling graded gas-phase catalytic cracking and gasification regeneration of oil-rich coal. The bottom of the descending pyrolysis reactor is connected with a primary riser gasification regenerator through a pyrolysis oil-gas gas-solid separator and a semi-coke returner, and the top is connected with a semi-coke gas-solid separator and a heated semi-coke returner / cracking dry gas activator 1 to form an oil-rich coal pyrolysis circulation reaction system; the top of the descending catalytic cracking reactor is connected with a secondary riser regenerator through a regenerated cracking catalyst gas-solid separator and a cracking dry gas activator 2, and the bottom is connected with a cracking oil-gas gas-solid separator and a returner of a to-be-regenerated cracking catalyst to form a pyrolysis oil-gas catalytic cracking circulation reaction system; the oil-rich coal pyrolysis circulation reaction system is connected with the top of the descending catalytic cracking reactor through the oil and gas outlet of the pyrolysis oil-gas gas-solid separator to form a circulation system for maximizing the preparation of chemical raw materials by coupling graded gas-phase catalytic cracking and gasification regeneration of oil-rich coal.

Description

Technical Field

[0001] The invention provides a device for producing chemical raw materials by coupling oil-rich coal graded gas-phase catalytic cracking and gasification regeneration, belonging to the field of coal chemical industry. Background Art

[0002] As a coal-based oil and gas resource that combines the properties of coal, oil, and gas, oil-rich coal (lignite and long flame coal, also known as low-rank coal) with an oil content of 7%-20% is abundant in my country. The pyrolysis volatiles contain hundreds of billions of tons of oil and gas, which is far higher than the existing recoverable reserves of oil and natural gas in my country. It is a potential oil and gas resource that is cheap and easily available. Pyrolysis upgrading with oil and gas as the main products is a recognized technical route for the clean, efficient and high-value utilization of oil-rich coal in the industry. However, due to bottlenecks such as low tar yield, high ash content, coking and clogging of the device, difficulty in treating phenol-containing wastewater, spontaneous combustion of highly active semi-coke powder, and difficulty in large-scale utilization, there is currently no single million-ton demonstration device that can be commercially operated at home and abroad.

[0003] In addition, the tar produced by pyrolysis and upgrading of oil-rich coal is mainly used for hydrogenation to produce gasoline and diesel. However, with the rapid iteration of power battery technology and stricter automobile emission standards, new energy vehicles are showing a rapid development trend, which will inevitably lead to a rapid decline in gasoline and diesel consumption. The current coal tar utilization technology route aimed at automotive fuel is difficult to meet the needs of future changes in the transportation energy system. It is urgent to develop new technologies for directly, cleanly and efficiently preparing bulk chemical raw materials from oil-rich coal and building a high-value utilization industry chain to provide guarantees for the sustainable and high-quality development of the oil-rich coal utilization industry. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the existing coal pyrolysis and upgrading technology and propose a device for producing chemical raw materials by coupling graded gas-phase catalytic cracking and gasification regeneration of oil-rich coal. The device utilizes the pyrolysis of the oil-rich coal in a descending pipe under the activation and enhancement of cracking dry gas to maximize the production of oil and gas. The high-temperature oil and gas are directly catalytically cracked through the descending pipe to produce triolefins and triphenyls and 2-4-ring condensed aromatic hydrocarbons without condensation separation, thereby fully utilizing the heat of the pyrolysis oil and gas, greatly improving the yield and selectivity of low-carbon olefins, overcoming the "cage effect" of liquid phase reactions, reducing the influence of heat and mass transfer on catalytic cracking, and greatly reducing the amount of coke, low-value methane and energy consumption in the cracking process; the pyrolysis semi-coke is heated by gasification and regeneration in the riser to solve the problem of pyrolysis cycle heating of the oil-rich coal, and the problem of spontaneous combustion and large-scale utilization of semi-coke powder, while obtaining high-value-added chemical raw materials and fuel gas such as triolefins and triphenyls, 2-4-ring condensed aromatic hydrocarbons and synthesis gas.

[0005] The technical solution of the present invention:

[0006] The device for producing chemical raw materials by coupling graded gas-phase catalytic cracking and gasification regeneration of oil-rich coal is composed of an oil-rich coal feeding port, a descending pyrolysis reactor, a pyrolysis oil gas-solid separator, a semi-coke returner, a first-stage riser gasification regenerator, a gasifying agent inlet, a semi-coke gas-solid separator, a cracking oil gas-solid separator, a returner for a regenerated cracking catalyst, a heated semi-coke returner, a synthesis gas outlet, a cracking dry gas activator A, a fractionating tower, a second-stage riser regenerator, a regenerated cracking catalyst gas-solid separator, a flue gas outlet, a cracking dry gas outlet, a triene outlet, a triphenylene outlet, a 2-4-ring polycyclic aromatic hydrocarbon outlet, a descending catalytic cracking reactor, a cracking dry gas activator B, etc. The bottom of the descending pyrolysis reactor is connected to the first-stage riser gasification regenerator through a pyrolysis oil gas gas-solid separator and a semi-coke returner, and the top is connected to the first-stage riser gasification regenerator through a semi-coke gas-solid separator and a heated semi-coke returner / cracking dry gas activator A to form an oil-rich coal pyrolysis cycle reaction system. The reaction temperature of the descending pyrolysis reactor is 480°C-580°C, and the reaction temperature of the first-stage riser gasification regenerator is 780°C-1200°C; the top of the descending catalytic cracking reactor is connected to the regenerated cracking catalyst gas-solid separator and the cracking dry gas activator B, and the bottom is connected to the cracking oil gas gas-solid separator and the waiting The raw cracking catalyst return device is connected with the secondary riser regenerator to form a pyrolysis oil and gas gas-phase catalytic cracking circulation reaction system. The reaction temperature of the descending catalytic cracking reactor is 580℃-650℃, and the reaction temperature of the secondary riser regenerator is 650℃-750℃; the oil-rich coal pyrolysis circulation reaction system is connected with the top of the descending catalytic cracking reactor of the pyrolysis oil and gas gas-phase catalytic cracking circulation reaction system through the oil and gas outlet of the pyrolysis oil and gas gas-solid separator to form a circulation system for coupling the graded gas-phase catalytic cracking of oil-rich coal with gasification regeneration to maximize the production of chemical raw materials.

[0007] The first-stage riser gasification regenerator is a combination of one or more of a riser regenerator, a turbulent fluidized bed regenerator, and a bubbling fluidized bed regenerator. The regenerator is a mixture of an oxidant and water vapor or an oxidant. The oxidant is one of oxygen, air, or oxygen-enriched air.

[0008] The cracking catalyst used in the descending catalytic cracking reactor is a mixture of one or more of a ZSM-5 molecular sieve catalyst, an FCC molecular sieve catalyst, an acid-base composite cracking catalyst, and an alkaline solid porous catalyst.

[0009] The secondary riser gasification regenerator is a combination of one or more of a riser regenerator, a turbulent fluidized bed regenerator, and a bubbling fluidized bed regenerator.

[0010] The present invention will be described in detail by way of embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 It is a structural schematic diagram of the present invention.

[0012] Figure 1 The drawing settings are as follows:

[0013] 1. Oil-rich coal charging port 2. Downward pyrolysis reactor 3. Pyrolysis oil gas solid separator 4. Semi-coke return device 5. Primary riser gasification regenerator 6. Gasifying agent inlet 7. Semi-coke gas solid separator 8. Cracking oil gas solid separator 9. Return device for to-be-generated cracking catalyst 10. Heated semi-coke return device 11. Synthesis gas outlet 12. Cracking dry gas activator A 13. Fractionation tower 14. Secondary riser regenerator 15. Regenerated cracking catalyst gas solid separator 16. Flue gas outlet 17. Cracking dry gas outlet 18. Triene outlet 19. Triphenyl outlet 20. 2-4 ring condensed aromatic hydrocarbon outlet 21. Downward catalytic cracking reactor 22. Cracking dry gas activator B.

[0014] The features of the present invention are described in detail below with reference to the accompanying drawings and embodiments. DETAILED DESCRIPTION

[0015] Embodiment: A device for producing chemical raw materials by coupling graded gas-phase catalytic cracking and gasification regeneration of oil-rich coal comprises an oil-rich coal feeding port (1), a descending pyrolysis reactor (2), a pyrolysis oil gas gas-solid separator (3), a semi-coke returner (4), a primary riser gasification regenerator (5), a gasifying agent inlet (6), a semi-coke gas-solid separator (7), a cracking oil gas gas-solid separator (8), a returner for a regenerated cracking catalyst (9), a heated semi-coke returner (10), a synthesis gas outlet (11), a cracking dry gas activator A (12), a fractionating tower (13), a secondary riser regenerator (14), a regenerated cracking catalyst gas-solid separator (15), a flue gas outlet (16), a cracking dry gas outlet (17), a triene outlet (18), a triphenylene outlet (19), a 2-4 ring condensed aromatic hydrocarbon outlet (20), a descending catalytic cracking reactor (21), a cracking dry gas activator B (22), etc. The bottom of the descending pyrolysis reactor (2) is connected to the primary riser gasification regenerator (5) through a pyrolysis oil gas gas-solid separator (3) and a semi-coke returner (4), and the top is connected to the primary riser gasification regenerator (5) through a semi-coke gas-solid separator (7) and a heated semi-coke returner (10) / cracking dry gas activator A (22) to form an oil-rich coal pyrolysis cycle reaction system. The reaction temperature of the descending pyrolysis reactor (2) is 480°C-580°C, and the reaction temperature of the primary riser gasification regenerator (5) is 780°C-1200°C. The top of the descending catalytic cracking reactor (21) is connected to the regenerated cracking catalyst gas-solid separator (15) and the cracking dry gas activator B (22), and the bottom is connected to the cracking oil gas-solid separator (7) and the heated semi-coke returner (10) / cracking dry gas activator A (22). The gas-solid separator (8) and the return device for the cracking catalyst to be generated (9) are connected to the secondary riser regenerator (14) to form a pyrolysis oil and gas gas-phase catalytic cracking circulation reaction system. The reaction temperature of the descending catalytic cracking reactor (21) is 580°C-650°C, and the reaction temperature of the secondary riser regenerator (14) is 650°C-750°C. The oil-rich coal pyrolysis circulation reaction system is connected to the top of the descending catalytic cracking reactor (21) of the pyrolysis oil and gas gas-phase catalytic cracking circulation reaction system through the oil and gas outlet of the pyrolysis oil and gas-solid separator (3) to form a circulation system for coupling the graded gas-phase catalytic cracking of oil-rich coal with gasification regeneration to maximize the production of chemical raw materials.

[0016] The first-stage riser gasification regenerator (5) is a combination of one or more of a riser regenerator, a turbulent fluidized bed regenerator, and a bubbling fluidized bed regenerator; the regenerating agent is a mixture of an oxidant and water vapor or an oxidant; the oxidant is one of oxygen, air, or oxygen-enriched air; and the regenerated gas is synthesis gas.

[0017] The cracking catalyst used in the descending catalytic cracking reactor (21) is a mixture of one or more of a ZSM-5 molecular sieve catalyst, an FCC molecular sieve catalyst, an acid-base composite cracking catalyst, and an alkaline solid porous catalyst.

[0018] The secondary riser gasification regenerator (14) is a combination of one or more of a riser regenerator, a turbulent fluidized bed regenerator, and a bubbling fluidized bed regenerator.

[0019] In specific operation, dry oil-rich coal powder with a size less than 6 mm is added to the top of the descending pyrolysis reactor (2) through the oil-rich coal feeding port (1), and is quickly mixed and heated with the 780-1200°C circulating semi-coke carrier added through the heated semi-coke return device (10). The circulating cracked dry gas is rapidly pyrolyzed at 480-580°C under the enhanced effect of hydrogen and small molecular hydrocarbon free radicals generated by the circulating semi-coke carrier activated by the cracked dry gas activator A (12), thereby maximizing the generation of pyrolysis oil and gas. The pyrolysis oil is separated from the pyrolysis oil and gas by the pyrolysis oil gas-solid separator (3) at the lower part of the descending pyrolysis reactor (2). The pyrolysis semi-coke is separated from the pyrolysis semi-coke, and the pyrolysis semi-coke is returned to the first-stage riser gasification regenerator (5) through the semi-coke return device (4), and is gasified and heated at 780-1200°C with the gasifying agent fed from the gasifying agent inlet (6), and the gas and solid are separated at the top of the first-stage riser gasification regenerator (5). The synthesis gas is sent to the sulfur-resistant conversion and purification section after the waste heat is recovered. The semi-coke powder at 780-1200°C is used as a circulating semi-coke carrier to flow into the top of the descending pyrolysis reactor (2) to react with the dry oil-rich coal powder; the pyrolysis oil gas at 480-580°C directly enters the descending catalytic cracking reactor (21) and reacts with the regenerator. The 650-750°C regenerated cracking catalyst separated by the catalytic cracking catalyst gas-solid separator (15) and the hydrogen and small molecular hydrocarbon free radicals activated by the cracking dry gas activator B (22) are quickly mixed and heated, and catalytically cracked at 580-650°C. The cracking oil and gas are separated from the regenerated cracking catalyst by the cracking oil-gas gas-solid separator (8) at the lower part of the descending catalytic cracking reactor (21). The cracking oil and gas are passed through the fractionation tower (13) to obtain triolefin triphenyl from the triolefin outlet (18) and the triphenyl outlet (19), and 2-4-ring condensed aromatic hydrocarbons from the outlet (20). Basic chemical raw materials such as condensed-ring aromatic hydrocarbons are used to obtain cracking dry gas from the cracking dry gas outlet (17), and part of the cracking dry gas is returned to the cracking dry gas activator (12) as circulating cracking dry gas; the regenerated cracking catalyst separated from the cracking oil gas gas-solid separator (8) is returned to the secondary riser (14) through the regenerated cracking catalyst return device (9), and is burned and regenerated at 650-850°C. The gas and solid are separated at the top of the secondary riser (14), and the regenerated flue gas is discharged after the waste heat is recovered. The regenerated catalytic cracking catalyst is returned to the top of the descending catalytic cracking reactor (21) to mix with the pyrolysis oil gas and react.

[0020] The device for producing chemical raw materials by coupling the graded gas-phase catalytic cracking and gasification regeneration of oil-rich coal provided by the present invention utilizes the rapid pyrolysis of oil-rich coal to maximize the production of oil and gas. The high-temperature oil and gas are directly subjected to high-temperature catalytic cracking to produce chemical raw materials such as triolefins and 2-4-ring condensed aromatics without condensation separation, thereby making full use of the heat of the pyrolysis oil and gas, overcoming the "cage effect" of the liquid phase reaction, reducing the influence of heat and mass transfer on catalytic cracking, and greatly reducing the amount of coke and energy consumption in the cracking process; the reaction temperature and time are easy to control, and the characteristics of the rich olefin production of acid-base composite catalytic cracking can be used for targeted catalytic conversion, greatly improving the yield and selectivity of low-carbon olefins. By coupling the rapid pyrolysis of oil-rich coal strengthened by cracking dry gas activation and the direct gas-phase catalytic cracking of pyrolysis oil and gas to produce triolefins and 2-4-ring condensed aromatics and the process of semi-coke gasification regeneration, the relative yield of tar is more than 130% of the theoretical tar yield, the impurity content in the oil is less than 0.1%, and it is maximized to convert it into the production of triolefins, 2-4-ring condensed aromatics and synthesis gas chemical raw materials. Using Xinjiang Zhundong oil-rich coal with an oil content of 13.4% as raw material, the graded gas-phase catalytic cracking and gasification regeneration combination are used to maximize the production of chemical raw materials, and the relative yield of tar is increased to 140%; based on tar, the total yield of ethylene, propylene and butene is 19.5%, the olefin ratio is 15, crude benzene is 15%, the two to four ring aromatic hydrocarbon fraction is 50.5%, and all coke powder is converted into synthesis gas; the tar deoxygenation rate is 45%, the desulfurization rate is 60%, and the denitrification rate is 40%. In addition, the technical process is short, the equipment steel consumption is low, and the fixed investment is greatly reduced; it is simple to operate at normal pressure, easy to start and stop, has good continuity, and strong adaptability to coal types.

Claims

1. A device for producing chemical raw materials by coupling gas phase catalytic cracking and gasification regeneration of oil-rich coal, characterized in that The bottom of the descending pyrolysis reactor is connected to the first-stage riser gasification regenerator through a pyrolysis oil gas gas-solid separator and a semi-coke returner, and the top is connected to the first-stage riser gasification regenerator through a semi-coke gas-solid separator and a heated semi-coke returner / cracking dry gas activator A to form an oil-rich coal pyrolysis cycle reaction system. The reaction temperature of the descending pyrolysis reactor is 480°C-580°C, and the reaction temperature of the first-stage riser gasification regenerator is 780°C-1200°C; the top of the descending catalytic cracking reactor is connected to the regenerated cracking catalyst gas-solid separator and the cracking dry gas activator B, and the bottom is connected to the cracking oil gas gas-solid separator and the waiting The raw cracking catalyst return device is connected with the secondary riser regenerator to form a pyrolysis oil and gas gas-phase catalytic cracking circulation reaction system. The reaction temperature of the descending catalytic cracking reactor is 580℃-650℃, and the reaction temperature of the secondary riser regenerator is 650℃-750℃; the oil-rich coal pyrolysis circulation reaction system is connected with the top of the descending catalytic cracking reactor of the pyrolysis oil and gas gas-phase catalytic cracking circulation reaction system through the oil and gas outlet of the pyrolysis oil and gas gas-solid separator to form a circulation system for coupling the graded gas-phase catalytic cracking of oil-rich coal with gasification regeneration to maximize the production of chemical raw materials.

2. The device for producing chemical raw materials by coupling the graded gas-phase catalytic cracking and gasification regeneration of oil-rich coal according to claim 1, characterized in that The first-stage riser gasification regenerator is a combination of one or more of a riser regenerator, a turbulent fluidized bed regenerator, and a bubbling fluidized bed regenerator. The regenerator is a mixture of an oxidant and water vapor or an oxidant. The oxidant is one of oxygen or air.

3. The combined riser gasification reactor according to claim 2, characterized in that The cracking catalyst used in the descending catalytic cracking reactor is a mixture of one or more of an FCC molecular sieve catalyst, an acid-base composite cracking catalyst, and an alkaline solid porous catalyst.

4. The device for producing chemical raw materials by coupling the graded gas-phase catalytic cracking and gasification regeneration of oil-rich coal according to claim 1, characterized in that The secondary riser gasification regenerator is a combination of one or more of a riser regenerator, a turbulent fluidized bed regenerator, and a bubbling fluidized bed regenerator.

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