An oxygen-enriched coke oven raw gas coupling reforming synthetic gas device and method

Abstract

This invention discloses a device and method for producing syngas from oxygen-enriched coke oven raw gas through coupled reforming, relating to the field of energy-saving and environmental protection technology in coking production. It includes a vertical heat recovery coke oven and an oxygen production unit. The vertical heat recovery coke oven has two combustion zones within its vertical flue, with a reforming zone between them. The reforming zone is separated from the two combustion zones by combustion-supporting gas passages on both sides. A branch flue is located at the lower part of the vertical flue, and a main flue is located at the lower part of the branch flue. The invention also includes a waste heat boiler, a dust removal device, a decarbonization device, a heat exchanger, a desulfurization device, and an induced draft fan, all sequentially connected to the main flue. This invention reconstructs the coking process by modifying the structure of the vertical flue of the vertical heat recovery coke oven. Simultaneously with coking in the coke oven carbonization chamber, incomplete combustion and reforming reactions occur directly within the vertical flue of the combustion chamber, providing heat for coking while yielding clean H2 and CO products, achieving resource utilization and increasing product added value.

Description

Technical Field

[0001] This invention relates to the field of energy-saving and environmental protection technology in coking production, and in particular to a device and method for producing syngas from oxygen-enriched coke oven raw gas through coupled reforming. Background Technology

[0002] In heat recovery coke ovens, the raw coal gas produced during coking is directly burned inside the oven to provide heat for coking. To recover the heat from the high-temperature flue gas after combustion, the current popular method is to use a waste heat boiler to absorb the heat from the flue gas with water to generate steam, which is then used to power a steam turbine. Each conversion process involves energy loss, leading to a decrease in thermal efficiency. Heat recovery coke ovens are classified into horizontal and vertical types based on their structural form.

[0003] As a non-mainstream coking process, heat recovery coke ovens have not seen rapid development due to the complete combustion of all raw coal gas. The coking industry faces immense environmental pressure, and heat recovery coke ovens, with their zero emissions of waste gas, wastewater, and solid waste, are gaining popularity and attention. However, at present, horizontal heat recovery coke ovens are also constrained in their widespread application due to problems such as high heat loss, high energy consumption per ton of coke, resource waste, and high CO2 emissions.

[0004] The patent application with publication number CN109485016A discloses a system and method for directly producing hydrogen or ammonia from coke oven raw gas through steam reforming. The raw gas from the coke oven directly enters a non-catalytic reformer, where it first reacts with oxygen to raise the temperature to 1300℃~1500℃, and then undergoes a reforming reaction with steam to generate syngas mainly composed of H2 and CO. The syngas is then subjected to CO conversion, desulfurization and gas separation to obtain hydrogen or generate ammonia.

[0005] In patent application CN109399564A, coke oven raw gas with a temperature of 550℃~800℃ from the coke oven raw gas collecting pipe enters the steam jet pump through the inlet of the steam jet pump. After being drawn, mixed and pressurized by the superheated steam working fluid of the steam jet pump, it enters the interior of the catalytic reformer through the top side inlet of the reformer. The pressurized superheated steam and high-temperature raw gas are rapidly mixed with oxygen injected from the top of the reformer and undergo a high-temperature combustion reaction, instantly raising the temperature inside the reformer to 1200℃~1500℃. The carbonaceous organic matter in the coke oven raw gas undergoes a reforming reaction with water vapor to generate syngas mainly composed of H2 and CO.

[0006] In the patent application with publication number CN201910045582.8, coke oven gas with a temperature of 600℃~800℃ from the raw gas collection pipe enters the interior of the non-catalytic reformer from the top side. It rapidly mixes with the steam and oxygen or air mixture injected from the top of the non-catalytic reformer and undergoes a high-temperature combustion reaction, instantly raising the temperature inside the non-catalytic reformer to 1300℃~1500℃. The carbonaceous organic matter in the coke oven gas undergoes a reforming reaction with water vapor to generate syngas mainly composed of CO and H2.

[0007] However, the aforementioned patents all rely on the coke oven recovery process, where raw coke oven gas is first introduced into a gas collecting pipe via an ascender pipe and then transported to a dedicated reformer for reforming and conversion. In this process, the raw coke oven gas itself has a low temperature, and it needs to be discharged through an external gas collecting pipe. During this process, large molecules such as tar are easily released, affecting the normal transport of the raw coke oven gas and consequently impacting the normal operation of the reformer. Summary of the Invention

[0008] The purpose of this invention is to provide a device and method for producing syngas from oxygen-enriched coke oven raw gas through coupled reforming, in order to solve the problems existing in the prior art. This invention addresses the challenges of treating the "three wastes" emissions during the production process of chemical product recovery coke ovens, while also solving the problems of low production efficiency and high energy consumption in horizontal heat recovery coke ovens. By modifying the vertical flue structure of the vertical heat recovery coke oven and reconstructing the coking process, incomplete combustion and reforming reactions can be carried out directly in the vertical flue of the combustion chamber while coking occurs in the coke oven carbonization chamber. This provides heat for coking while obtaining clean H2 and CO products, achieving resource utilization and increasing product added value.

[0009] To achieve the above objectives, the present invention provides the following solution:

[0010] This invention provides an oxygen-enriched coke oven raw gas coupled with reforming to produce syngas, comprising a vertical heat recovery coke oven and an oxygen production unit. The vertical heat recovery coke oven is used for coking. Two combustion zones are arranged within the vertical flue of the vertical heat recovery coke oven. One of the combustion zones is located on one side of the carbonization chamber of the vertical heat recovery coke oven. A reforming zone is arranged between the two combustion zones, and the two sides of the reforming zone are separated from the two combustion zones by a combustion-supporting gas passage. Multiple upward distribution ports are arranged on the combustion-supporting gas passage, and the upward distribution ports are connected to the corresponding combustion zone and the reforming zone. The tops of all combustion zones and the top of the reforming zone are connected to the oxygen production unit via connecting channels. The top of the carbonization chamber is connected; a branch flue is provided at the lower part of the vertical flue, and a main flue is provided at the lower part of the branch flue. The oxygen generating device is connected to the upper part of the vertical flue and the side of the branch flue through an oxygen pipeline, so that the raw coal gas coming out of the carbonization chamber and the oxygen-enriched gas coming out of the oxygen generating device can undergo a combustion reaction in the combustion zone and an incomplete oxidation reforming reaction in the reforming zone. The vertical flue is connected to the branch flue through an inclined channel, and the branch flue is connected to the main flue. The gas generated in the combustion zone and the gas generated in the reforming zone can continue to undergo a reforming reaction in the branch flue to generate reducing gas, which then enters the main flue.

[0011] It also includes a waste heat boiler, a dust removal device, a decarbonization device, a heat exchanger, a desulfurization device, and an induced draft fan, all connected in sequence to the main flue. The tube-side inlet of the waste heat boiler is used to introduce the reducing gas for waste heat recovery. The dust removal device is used to remove dust from the reducing gas. The decarbonization device is used to remove carbon dioxide from the reducing gas. The heat exchanger is used to cool the reducing gas. The desulfurization device is used to remove hydrogen sulfide from the reducing gas. The induced draft fan is used to transport the reducing gas to the syngas section. The shell-side outlet of the waste heat boiler is connected to the upper part of the vertical flue and the side of the branch flue to introduce steam into the vertical flue and the branch flue. The carbon dioxide outlet of the decarbonization device is connected to the upper part of the vertical flue and the side of the branch flue to introduce carbon dioxide into the vertical flue and the branch flue.

[0012] Preferably, the device further includes a deaerator, wherein the shell-side inlet of the heat exchanger is used to introduce the reducing gas, the tube-side inlet of the heat exchanger is used to introduce demineralized water, the tube-side outlet of the heat exchanger is connected to the inlet of the deaerator, and the outlet of the deaerator is connected to the shell-side inlet of the waste heat boiler.

[0013] Preferably, the shell-side outlet of the waste heat boiler is provided with two steam pipes, one of which is connected to the upper part of the vertical flue and the side of the branch flue, and the other of which is connected to the power generation section.

[0014] Preferably, the height to diameter ratio of the reforming zone is 8-10.0:1.0.

[0015] Preferably, the oxygen pipeline is equipped with an oxygen regulating valve, which is electrically connected to a controller, and the controller is capable of controlling the opening degree of the oxygen regulating valve.

[0016] Preferably, the oxygen generating device is a VPSA oxygen generating station.

[0017] Preferably, the decarbonization device is a PSA decarbonization device.

[0018] Preferably, the desulfurization device is a PDS desulfurization device.

[0019] Preferably, the dust removal device is a cyclone dust collector or a bag filter dust collector.

[0020] This invention also provides a method for producing syngas from oxygen-enriched coke oven gas through coupled reforming, using the aforementioned oxygen-enriched coke oven gas coupled reforming syngas production apparatus, comprising the following steps:

[0021] Step 1: Allow the raw coal gas escaping from the top of the carbonization chamber to enter the combustion zone and the reforming zone through the connecting channel;

[0022] Step two: Oxygen-enriched gas is introduced into the combustion zone and the reforming zone through the oxygen generator, the oxygen pipeline, and the combustion-supporting pipeline. This causes the oxygen-enriched gas in the combustion zone to react with the raw coal gas, and the oxygen-enriched gas in the reforming zone to undergo an incomplete oxidation reforming reaction with the raw coal gas. This process converts methane, crude benzene, and tar in the raw coal gas into reducing gases. The reducing gases generated in the reforming zone mix with the carbon dioxide and water vapor generated in the combustion zone after entering the flue gas distribution duct. Oxygen-enriched gas is then introduced into the flue gas distribution duct through the oxygen generator. Water vapor is introduced into the vertical flue gas distribution duct through the waste heat boiler. Carbon dioxide is introduced into the vertical flue gas distribution duct through the decarbonization device, allowing the reducing gases to continue undergoing a reforming reaction within the flue gas distribution duct.

[0023] Step 3: The reducing gas in the branch flue enters the tube side of the waste heat boiler through the main flue for waste heat recovery. The boiler feedwater in the shell side of the waste heat boiler exchanges heat with the reducing gas in the tube side of the waste heat boiler to generate steam, which is then introduced into the vertical flue and the branch flue.

[0024] Step four: The reducing gas in the tubes of the waste heat boiler is introduced into the dust removal device for dust removal;

[0025] Step 5: The reducing gas in the dust removal device is introduced into the decarbonization device to remove carbon dioxide, and the carbon dioxide removed by the decarbonization device is introduced into the vertical flue and the distribution flue.

[0026] Step six: Allow the reducing gas in the decarbonization device to enter the heat exchanger for cooling;

[0027] Step 7: Allow the reducing gas in the heat exchanger to enter the desulfurization device to remove hydrogen sulfide;

[0028] Step 8: The reducing gas in the desulfurization unit is transported to the syngas section by the induced draft fan.

[0029] The present invention achieves the following technical effects compared to the prior art:

[0030] The present invention provides an oxygen-enriched coke oven raw gas coupled reforming to syngas production device, comprising a vertical heat recovery coke oven and an oxygen production unit. The vertical heat recovery coke oven is used for coking. Two combustion zones are arranged within the vertical flue of the vertical heat recovery coke oven. One combustion zone is located on one side of the carbonization chamber of the vertical heat recovery coke oven. A reforming zone is arranged between the two combustion zones, and the two sides of the reforming zone are separated from the two combustion zones by a combustion-supporting passage. Multiple upward distribution ports are arranged on the combustion-supporting passage, and the upward distribution ports are connected to the corresponding combustion zone and reforming zone. The tops of all combustion zones and the top of the reforming zone are connected to the top of the carbonization chamber through connecting channels. The system is interconnected; a branch flue is located at the lower part of the vertical flue, and a main flue is located at the lower part of the branch flue. The oxygen generator is connected to the upper part of the vertical flue and the side of the branch flue via oxygen pipelines, so that the raw coal gas from the carbonization chamber and the oxygen-enriched gas from the oxygen generator can undergo a combustion reaction in the combustion zone and an incomplete oxidation reforming reaction in the reforming zone. The vertical flue is connected to the branch flue via an inclined duct, and the branch flue is connected to the main flue. The gas generated in the combustion zone and the gas generated in the reforming zone can continue to undergo a reforming reaction in the branch flue to generate reducing gas, which then enters the main flue. It also includes waste heat systems sequentially connected to the main flue. The waste heat boiler includes a boiler, dust removal unit, decarbonization unit, heat exchanger, desulfurization unit, and induced draft fan. The tube-side inlet of the waste heat boiler is used to introduce reducing gas for waste heat recovery. The dust removal unit removes dust from the reducing gas. The decarbonization unit removes carbon dioxide from the reducing gas. The heat exchanger cools the reducing gas. The desulfurization unit removes hydrogen sulfide from the reducing gas. The induced draft fan transports the reducing gas to the syngas section. The shell-side outlet of the waste heat boiler connects to the upper part of the vertical flue and the side of the branch flue to introduce steam into the vertical flue and branch flue. The carbon dioxide from the decarbonization unit... The carbon outlet is connected to the upper part of the vertical flue and the side part of the branch flue to introduce carbon dioxide into the vertical flue and the branch flue. This invention can solve the problem of "three wastes" emission treatment in the production process of chemical product recovery coke ovens, and at the same time solve the problems of low production efficiency and high energy consumption of horizontal heat recovery coke ovens. By modifying the structure of the vertical flue of the vertical heat recovery coke oven, the coking process is reconstructed. While coking is carried out in the coke oven carbonization chamber, incomplete combustion and reforming reaction are carried out directly in the vertical flue of the combustion chamber. This provides heat for coking and obtains clean H2 and CO products, realizing resource utilization and increasing product added value. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0032] Figure 1This is a schematic diagram of the working process of the oxygen-enriched coke oven raw gas coupled reforming to produce syngas provided in an embodiment of the present invention. Detailed Implementation

[0033] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] The purpose of this invention is to provide a device and method for producing syngas from oxygen-enriched coke oven raw gas through coupled reforming, in order to solve the problems existing in the prior art. This invention can solve the problem of treating the "three wastes" emissions during the production process of chemical product recovery coke ovens, and at the same time solve the problems of low production efficiency and high energy consumption of horizontal heat recovery coke ovens. By modifying the vertical flue structure of the vertical heat recovery coke oven and reconstructing the coking process, incomplete combustion and reforming reactions can be carried out directly in the vertical flue of the combustion chamber while coking is carried out in the coke oven carbonization chamber. This provides heat for coking while obtaining clean H2 and CO products, realizing resource utilization and increasing product added value.

[0035] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0036] Example 1

[0037] like Figure 1As shown, this embodiment provides an oxygen-enriched coke oven raw gas coupled with reforming to produce syngas, including a vertical heat recovery coke oven and an oxygen production unit. The vertical heat recovery coke oven is used for coking. Two combustion zones are arranged within the vertical flue of the vertical heat recovery coke oven. One combustion zone is located on one side of the carbonization chamber of the vertical heat recovery coke oven. A reforming zone is arranged between the two combustion zones, and the two sides of the reforming zone are separated from the two combustion zones by a combustion-supporting passage. Multiple upward distribution ports are arranged on the combustion-supporting passage, and these ports are connected to the corresponding combustion zone and reforming zone. The tops of all combustion zones and the top of the reforming zone are connected to the top of the carbonization chamber through connecting channels. The lower part of the vertical flue is equipped with… The main flue is located at the lower part of the branch flue. The oxygen generator is connected to the upper part of the vertical flue and the side of the branch flue via oxygen pipelines, so that the raw coal gas from the carbonization chamber and the oxygen-enriched gas from the oxygen generator can undergo a combustion reaction in the combustion zone and an incomplete oxidation reforming reaction in the reforming zone. The vertical flue is connected to the branch flue via an inclined duct, and the branch flue is connected to the main flue. The gas generated in the combustion zone and the gas generated in the reforming zone can continue to undergo a reforming reaction in the branch flue to generate reducing gas, which then enters the main flue. The system also includes a waste heat boiler, dust removal device, decarbonization device, heat exchanger, desulfurization device, and induced draft fan, all connected sequentially to the main flue. Specifically… The main flue is located at the bottom of the vertical heat recovery coke oven. Reducing gases from the branch flues converge from both sides and enter the main flue in the center. The main flue is connected to the waste heat boiler. The reducing gases in the main flue enter the tube side of the waste heat boiler for waste heat recovery. A dust removal device removes dust from the reducing gases, a decarbonization device removes carbon dioxide from the reducing gases, a heat exchanger cools the reducing gases, a desulfurization device removes hydrogen sulfide from the reducing gases, and an induced draft fan transports the reducing gases (including H2 and CO) to the syngas section. The shell-side outlet of the waste heat boiler is connected to the upper part of the vertical flue and the side of the branch flues to supply heat to the vertical flue and branch flues. Steam is introduced into the flue, and the carbon dioxide outlet of the decarbonization device is connected to the upper part of the vertical flue and the side of the branch flue to introduce carbon dioxide into the vertical flue and the branch flue. This embodiment can solve the problem of "three wastes" emission treatment in the production process of chemical product recovery coke oven, and at the same time solve the problems of low production efficiency and high energy consumption of horizontal heat recovery coke oven. By modifying the structure of the vertical flue of the vertical heat recovery coke oven, the coking process is reconstructed. While coking is carried out in the coke oven carbonization chamber, incomplete combustion and reforming reaction are carried out directly in the vertical flue of the combustion chamber. This provides heat for coking and obtains clean H2 and CO products, realizing resource utilization and increasing product added value.

[0038] It should be noted that the high-altitude distribution ports are distributed along the vertical flue and are outlets for oxygen-enriched gas. The principle for the arrangement of the high-altitude distribution ports is as follows: after the raw coal gas and the combustion-supporting gas are mixed and burned, they provide heat for coking. In order to ensure more uniform high-altitude heating of the coal in the carbonization chamber and improve heating efficiency, the high-altitude gas temperature in the vertical flue should be kept relatively constant. During the descent of the gas in the vertical flue, some of the gas heat is absorbed by the surroundings and the temperature drops. In order to maintain the gas temperature, a combustion-supporting gas outlet should be set up at this time to provide heat for the combustion of some combustible gas.

[0039] In this embodiment, a deaerator is also included. The shell-side inlet of the heat exchanger is used to introduce reducing gas, the tube-side inlet is used to introduce demineralized water, the tube-side outlet of the heat exchanger is connected to the inlet of the deaerator, and the outlet of the deaerator is connected to the shell-side inlet of the waste heat boiler. It should be noted that since the waste heat boiler heats water to generate high-temperature and high-pressure steam by absorbing heat from flue gas, strict requirements are placed on the water quality (oxygen content, salinity, etc.) entering the waste heat boiler in order to ensure heat exchange efficiency and production safety. Therefore, demineralized water is used and deoxygenated by the deaerator before being used as boiler feedwater for the waste heat boiler to ensure production. The temperature of the reducing gas after waste heat recovery in the waste heat boiler is 160℃~280℃. After passing through the decarbonization device, it enters the shell side of the heat exchanger to preheat the boiler feedwater and reduce the temperature of the reducing gas to 60℃~80℃. The preheated boiler feedwater enters the shell side of the waste heat boiler, where the reducing gas and boiler feedwater exchange heat to generate medium-temperature or high-temperature saturated steam.

[0040] In this embodiment, the shell-side outlet of the waste heat boiler is provided with two steam pipes. One steam pipe is connected to the upper part of the vertical flue and the side of the branch flue, and the other steam pipe is connected to the power generation section for power generation.

[0041] In this embodiment, the height to diameter ratio of the reforming zone is 8-10.0:1.0.

[0042] It should be noted that the vertical flue of the vertical heat recovery coke oven has a relatively large height and diameter, which is suitable for the structural requirement of a "height-to-inner-diameter ratio of 2.0 to 10.0:1.0" for raw coal gas reforming furnaces. This invention, through structural optimization of the vertical flue, enables the reforming of raw coal gas into reducing gas within the flue. Furthermore, by utilizing the structural characteristics of the branch flue and main flue of the vertical heat recovery coke oven, and selecting appropriate nozzles and locations (i.e., combustion gas outlets constructed with refractory materials, the size of which needs to be determined based on theoretical calculations), H2O and CO2 are continuously or intermittently introduced according to the required reducing gas components, adjusting the composition and temperature of the reducing gas to create conditions for subsequent process requirements.

[0043] In this embodiment, an oxygen regulating valve is installed on the oxygen pipeline. The oxygen regulating valve is electrically connected to the controller, which can control the opening degree of the oxygen regulating valve. Specifically, the controller is a computer. The oxygen-enriched gas (O2 > 93%) produced by the oxygen generating device is transmitted through the oxygen pipeline. Under the control of the computer, the oxygen regulating valve is adjusted to control the amount of oxygen input to the combustion zone and reforming zone in the vertical flue.

[0044] In this embodiment, the oxygen generating device is a VPSA oxygen generating station. The oxygen-enriched gas generated by the VPSA oxygen generating station has a concentration of more than 90%, or it can be obtained by mixing pure oxygen with water vapor and carbon dioxide.

[0045] In this embodiment, the decarbonization device is a PSA decarbonization device, but solvent absorption decarbonization can also be used.

[0046] In this embodiment, the desulfurization device is a PDS desulfurization device, but conventional desulfurization methods such as vacuum carbonate desulfurization, alkanolamine desulfurization, or low-temperature methanol washing desulfurization can also be used.

[0047] In this embodiment, the dust removal device is a cyclone dust collector or a bag filter dust collector.

[0048] Example 2

[0049] This embodiment provides a method for producing syngas from oxygen-enriched coke oven gas through coupled reforming, using the aforementioned oxygen-enriched coke oven gas coupled reforming syngas production apparatus, and includes the following steps:

[0050] Step 1: The high-temperature raw coal gas escaping from the top of the carbonization chamber enters the combustion zone and reforming zone through the connecting channel;

[0051] Step 2: Oxygen-enriched gas is introduced into the combustion zone and reforming zone through an oxygen generator, oxygen pipeline, and combustion-supporting pipeline. The oxygen-enriched gas in the combustion zone reacts with the raw coal gas, and the oxygen-enriched gas in the reforming zone undergoes an incomplete oxidation reforming reaction with the raw coal gas, converting methane, crude benzene, and tar in the raw coal gas into reducing gases. The reducing gases generated in the reforming zone mix with the carbon dioxide and water vapor generated in the combustion zone after entering the flue gas distribution channel. Oxygen-enriched gas is then introduced into the flue gas distribution channel through the oxygen generator, water vapor is introduced into the flue gas distribution channel through the waste heat boiler, and carbon dioxide is introduced into the flue gas distribution channel through the decarbonization device, allowing the reducing gases to continue undergoing a reforming reaction in the flue gas distribution channel.

[0052] It should be noted that the high-temperature raw coal gas enters from the top of the combustion chamber, and the oxygen-enriched gas enters the combustion-supporting passage through pipelines from the top of the combustion chamber under the control of a computer program. It then enters each vertical flue of the combustion chamber in sections through the high-altitude distribution port. In the vertical flue, the raw coal gas and the oxygen-enriched gas undergo an incomplete oxidation reaction. By controlling the temperature of the combustion zone and the reforming zone at around 1650℃ and under a slight negative pressure, the methane, crude benzene, and tar in the raw coal gas are converted into reducing gases.

[0053] Step 3: The reducing gas in the branch flue enters the tube side of the waste heat boiler through the main flue for waste heat recovery. The boiler feedwater in the shell side of the waste heat boiler exchanges heat with the reducing gas in the tube side of the waste heat boiler to generate steam, which is then introduced into the vertical flue and the branch flue.

[0054] It should be noted that the upper part of the reforming zone is equipped with high-temperature resistant channel holes, through which H2O / CO2 or H2O is continuously or intermittently introduced by a dedicated pipeline from the furnace top. H2O / CO2 incompletely oxidizes the polyaromatic macromolecules in the tar to form carbon black, which further undergoes a carbon melting reaction to generate H2 / CO. H2O reacts with carbon black and other carbonaceous substances to generate CO and H2 through a water-gas reaction. The reducing gas generated in the reforming zone mixes with the CO2 and H2O generated in the combustion zone after entering the flue. A suitable amount of oxygen-enriched gas or H2O gas is introduced through dedicated pipelines set on both sides of the flue. The reducing gas continues to undergo reforming reactions in the flue.

[0055] Step four: Allow the reducing gas in the tubes of the waste heat boiler to enter the dust removal device for dust removal;

[0056] Step 5: Allow the reducing gas in the dust removal device to enter the decarbonization device to remove carbon dioxide, and then allow the carbon dioxide removed by the decarbonization device to be passed into the vertical flue and the distribution flue.

[0057] Step six: Allow the reducing gas in the decarbonization unit to enter the heat exchanger for cooling;

[0058] Step 7: Allow the reducing gas in the heat exchanger to enter the desulfurization unit to remove hydrogen sulfide;

[0059] Step 8: The reducing gas in the desulfurization unit is transported to the syngas section by an induced draft fan.

[0060] In summary, this invention introduces raw coal gas reforming technology, using oxygen-enriched gas as a combustion aid to incompletely combust high-temperature raw coal gas. The incompletely combusted raw coal gas, combined with H2O and CO2, forms reformed gas, which is quantitatively input into the coke oven vertical flue under computer program control. The vertical heat recovery coke oven vertical flue serves as the reforming site, and by optimizing the flue structure, it simultaneously meets the needs of coke oven heating and raw coal gas reforming. While producing coke, the incompletely combusted raw coal gas is converted into H2 and CO as syngas or metallurgical reducing gas, achieving zero emissions of waste gas, wastewater, and solid waste, as well as zero CO2 emissions. This constructs a completely new near-zero emission coking process, realizing coking-chemical co-production.

[0061] In this invention, the vertical flue structure of the vertical heat recovery coke oven is modified based on the high-ratio, large-structure characteristics of the raw coal gas reformer. During the coking process, raw coal gas at approximately 800°C is released from the carbonization chamber and, under the negative pressure generated by the induced draft fan, directly enters the combustion chamber from the top. Along the optimized combustion and reforming zones within the combustion chamber's vertical flue, it undergoes an incomplete oxidation reaction with the oxygen-rich gas discharged from the combustion-supporting flue. The degree of oxidation is controlled by a computer program to adjust the oxygen supply, maintaining the gas temperature within the combustion chamber's vertical flue at approximately 1650°C to ensure the safety of the coke oven. Under high temperature and slight negative pressure conditions, methane, crude benzene, and tar in the raw coal gas are converted into reducing gases. H2O / CO2 is continuously or intermittently introduced into the combustion chamber's vertical flue. The H2O / CO2 incompletely oxidizes the polyaromatic macromolecules in the tar to form carbon black, which further undergoes a carbon melting reaction to generate H2 / CO. Water vapor is continuously or intermittently introduced into the combustion chamber's vertical flue to adjust the composition ratio of the reducing gases. Under high temperature, impurities such as organic sulfur that were originally difficult to remove in raw coal gas are oxidized into inorganic sulfur that is easier to remove, which greatly reduces the purification cost.

[0062] Compared with existing technologies, this invention couples vertical heat recovery coke oven coking with raw coal gas reforming, allowing high-temperature raw coal gas to undergo incomplete combustion directly within the furnace. The resulting high-temperature gas provides heat for coking while simultaneously creating conditions for the reforming reaction, simplifying the operation process and realizing the resource utilization of heat recovery coke oven flue gas. Specific advantages are as follows:

[0063] First, coking under negative pressure reduces the environmental pollution caused by fugitive emissions during the coking process;

[0064] Second, during the coking process, the raw coal gas directly enters the combustion chamber for combustion and reforming, making full use of the sensible and latent heat of the raw coal gas, thus improving energy utilization efficiency.

[0065] Third, the use of pure oxygen combustion reforming technology in the coking process has high combustion efficiency and high temperature, which is conducive to radiative heat transfer and can shorten the coking time.

[0066] Fourth, the use of pure oxygen combustion reforming during the coking process reduces the amount of nitrogen oxides produced;

[0067] Fifth, coking can also produce reducing gases CO and H2; it can be integrated with hydrogen metallurgical technologies such as direct reduced iron, as well as with synthetic ammonia, methanol synthesis, etc.

[0068] Sixth, the process flow has been optimized, reducing the need for processes such as benzene, ammonia, and tar recovery, thus reducing initial investment and avoiding repeated cooling and heating of the gas during the purification process, thereby further optimizing and reducing the energy consumption of the entire process.

[0069] Seventh, while incompletely oxidizing raw coal gas to generate reducing gas, a large amount of organic sulfur that is difficult to remove is converted into inorganic sulfur, which is beneficial for treatment by desulfurization equipment.

[0070] Specific examples have been used to illustrate the principles and implementation methods of this invention. The descriptions of the above embodiments are only for the purpose of helping to understand the method and core ideas of this invention. Furthermore, those skilled in the art will recognize that, based on the ideas of this invention, there will be changes in the specific implementation methods and application scope. Therefore, the content of this specification should not be construed as a limitation of this invention.

Claims

1. A device for coupled reforming of oxygen-enriched coke oven raw gas to produce syngas, characterized in that: The system includes a vertical heat recovery coke oven and an oxygen production unit. The vertical heat recovery coke oven is used for coking. Two combustion zones are arranged within the vertical flue of the vertical heat recovery coke oven. One of the combustion zones is located on one side of the carbonization chamber of the vertical heat recovery coke oven. A reforming zone is arranged between the two combustion zones, and the two sides of the reforming zone are separated from the two combustion zones by a combustion-supporting duct. Multiple vertical distribution ports are provided on the combustion-supporting duct, and these ports are connected to the corresponding combustion zone and reforming zone. The tops of all combustion zones and the top of the reforming zone are connected to the top of the carbonization chamber through connecting channels. A branch flue is provided at the lower part of the flue, and a main flue is provided at the lower part of the branch flue. The oxygen generating device is connected to the upper part of the vertical flue and the side of the branch flue through an oxygen pipeline, so that the raw coal gas coming out of the carbonization chamber and the oxygen-enriched gas coming out of the oxygen generating device can undergo a combustion reaction in the combustion zone and an incomplete oxidation reforming reaction in the reforming zone. The vertical flue is connected to the branch flue through an inclined channel, and the branch flue is connected to the main flue. The gas generated in the combustion zone and the gas generated in the reforming zone can continue to undergo a reforming reaction in the branch flue to generate reducing gas, which then enters the main flue. It also includes a waste heat boiler, a dust removal device, a decarbonization device, a heat exchanger, a desulfurization device, and an induced draft fan, all connected in sequence to the main flue. The tube-side inlet of the waste heat boiler is used to introduce the reducing gas for waste heat recovery. The dust removal device is used to remove dust from the reducing gas. The decarbonization device is used to remove carbon dioxide from the reducing gas. The heat exchanger is used to cool the reducing gas. The desulfurization device is used to remove hydrogen sulfide from the reducing gas. The induced draft fan is used to transport the reducing gas to the syngas section. The shell-side outlet of the waste heat boiler is connected to the upper part of the vertical flue and the side of the branch flue to introduce steam into the vertical flue and the branch flue. The carbon dioxide outlet of the decarbonization device is connected to the upper part of the vertical flue and the side of the branch flue to introduce carbon dioxide into the vertical flue and the branch flue.

2. The oxygen-enriched coke oven gas coupled reforming to syngas production device according to claim 1, characterized in that: It also includes a deaerator, wherein the shell-side inlet of the heat exchanger is used to introduce the reducing gas, the tube-side inlet of the heat exchanger is used to introduce demineralized water, the tube-side outlet of the heat exchanger is connected to the inlet of the deaerator, and the outlet of the deaerator is connected to the shell-side inlet of the waste heat boiler.

3. The oxygen-enriched coke oven gas coupled with reforming to produce syngas according to claim 1, characterized in that: The waste heat boiler has two steam pipes at the shell outlet. One steam pipe is connected to the upper part of the vertical flue and the side of the branch flue, and the other steam pipe is connected to the power generation section.

4. The oxygen-enriched coke oven gas coupled with reforming to produce syngas according to claim 1, characterized in that: The height to diameter ratio of the reforming zone is 8-10.0:1.

0.

5. The oxygen-enriched coke oven gas coupled with reforming to produce syngas according to claim 1, characterized in that: An oxygen regulating valve is installed on the oxygen pipeline. The oxygen regulating valve is electrically connected to a controller, which can control the opening degree of the oxygen regulating valve.

6. The oxygen-enriched coke oven gas coupled with reforming to produce syngas according to claim 1, characterized in that: The oxygen generating device is a VPSA oxygen generating station.

7. The oxygen-enriched coke oven gas coupled reforming to syngas production device according to claim 1, characterized in that: The decarbonization device is a PSA decarbonization device.

8. The oxygen-enriched coke oven gas coupled reforming to syngas production device according to claim 1, characterized in that: The desulfurization device is a PDS desulfurization device.

9. The oxygen-enriched coke oven gas coupled reforming to produce syngas device according to claim 1, characterized in that: The dust removal device is a cyclone dust collector or a bag filter dust collector.

10. A method for producing syngas from oxygen-enriched coke oven gas through coupled reforming, using the oxygen-enriched coke oven gas coupled reforming syngas production apparatus as described in any one of claims 1-9, characterized in that: Includes the following steps: Step 1: Allow the raw coal gas escaping from the top of the carbonization chamber to enter the combustion zone and the reforming zone through the connecting channel; Step two: Oxygen-enriched gas is introduced into the combustion zone and the reforming zone through the oxygen generator, the oxygen pipeline, and the combustion-supporting pipeline. This causes the oxygen-enriched gas in the combustion zone to react with the raw coal gas, and the oxygen-enriched gas in the reforming zone to undergo an incomplete oxidation reforming reaction with the raw coal gas. This process converts methane, crude benzene, and tar in the raw coal gas into reducing gases. The reducing gases generated in the reforming zone mix with the carbon dioxide and water vapor generated in the combustion zone after entering the flue gas distribution duct. Oxygen-enriched gas is then introduced into the flue gas distribution duct through the oxygen generator. Water vapor is introduced into the vertical flue gas distribution duct through the waste heat boiler. Carbon dioxide is introduced into the vertical flue gas distribution duct through the decarbonization device, allowing the reducing gases to continue undergoing a reforming reaction within the flue gas distribution duct. Step 3: The reducing gas in the branch flue enters the tube side of the waste heat boiler through the main flue for waste heat recovery. The boiler feedwater in the shell side of the waste heat boiler exchanges heat with the reducing gas in the tube side of the waste heat boiler to generate steam, which is then introduced into the vertical flue and the branch flue. Step four: The reducing gas in the tubes of the waste heat boiler is introduced into the dust removal device for dust removal; Step 5: The reducing gas in the dust removal device is introduced into the decarbonization device to remove carbon dioxide, and the carbon dioxide removed by the decarbonization device is introduced into the vertical flue and the distribution flue. Step six: Allow the reducing gas in the decarbonization device to enter the heat exchanger for cooling; Step 7: Allow the reducing gas in the heat exchanger to enter the desulfurization device to remove hydrogen sulfide; Step 8: The reducing gas in the desulfurization unit is transported to the syngas section by the induced draft fan.

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