CN109929578B - With CO2Coal dry distillation process and system as heat carrier - Google Patents
With CO2Coal dry distillation process and system as heat carrier Download PDFInfo
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- CN109929578B CN109929578B CN201910195154.3A CN201910195154A CN109929578B CN 109929578 B CN109929578 B CN 109929578B CN 201910195154 A CN201910195154 A CN 201910195154A CN 109929578 B CN109929578 B CN 109929578B
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Abstract
The invention discloses a method for preparing a catalyst with CO2The coal dry distillation process using CO as heat carrier2Heating CO by fuel gas as gas heat carrier2Formation of high temperature CO2Entering the coal dry distillation furnace, performing dry distillation on the granular coal in the coal dry distillation furnace, and generating dry distillation gas and high-temperature CO after dry distillation2Leaving the coal gas retort together, purifying, separating, and separating CO2Reheating the fuel gas to form high temperature CO2Returning the coal to the coal dry distillation furnace. The invention also discloses the use of CO2Coal dry distillation system using CO as heat carrier2The composite material is a gas heat carrier, and adopts the combination of multiple technologies such as a direct heating furnace, a granular coal vertical dry distillation furnace, water mist dry quenching, desulfurization and decarburization, selective oxidation sulfur production and the like, so that various targets such as more effective dry distillation gas production, stable operation, reasonable utilization of dry distillation products and the like are realized.
Description
Technical Field
The invention relates to the technical field of low-temperature coal carbonization in low-rank coal upgrading, in particular to a method for preparing granular pulverized coal (6-60mm) by using CO as a raw material2A medium-low temperature coal dry distillation process and a system which are heat carriers.
Background
China is in short supply of petroleum resources, and the external dependence degree is over 50 percent at present. The annual consumption of coal is over 40 hundred million tons, and the specific gravity of coal in primary energy consumption is 2/3. The consumed coal contains 50% of low-rank coal with high volatile matters such as brown coal and long flame coal. If the low-rank coal can be thermally dry distilled before being combusted, the obtained coal tar can reach 2 hundred million tons per year and can become an important supplement of petroleum. Therefore, coal dry distillation technology increasingly draws the attention of the Chinese energy world.
Coal carbonization can obtain coal tar and coal gas with high added value with lower energy consumption, so that a coal grading quality improvement utilization technology taking coal carbonization as a tap becomes one of the most effective ways for realizing efficient and clean utilization of coal. In the existing coal pyrolysis technology, the lump coal dry distillation technology is developed earlier and relatively mature, but is limited by lump coal resources and has limited development space. Accordingly, many enterprises and scientific research institutes have begun to develop pulverized coal pyrolysis technology.
Typical foreign pulverized coal dry distillation technologies include tospore rotary kiln pyrolysis technology of American oil shale company, AOOP pyrolysis technology of western energy company, fluidized bed fast pyrolysis technology of Australian science and industry research institute, and the like. The multi-stage rotary kiln MRF of China coal science research institute, the DG fixed heat carrier dry distillation process of the university of the major company, the BT coal topping process of Shanxi coal chemical institute, the CFP pulverized coal fluidized bed fast pyrolysis process of Shanghai Boshen company and the like exist in China, and the processes are researched and developed for many years, but are still in the experimental research or industrial verification stage at present. Most of the methods have the defects of complex process systems, low reliability, high running cost and the like, and no large-scale industrial experience exists at present.
The patent application publication No. CN107739624A, and has already been a primary commercial operation project, and its core technology is to use all gas fractions of coal dry distillation gas as gas heat carrier, and the dry distillation gas directly used as fuel gas of regenerative heating furnace. The technology has the advantages of simple process and realization of industrialized operation. The defects that coking in the regenerative heating furnace is still unavoidable, the operation period is not long, a part of effective dry distillation gas is consumed in the regenerative heating furnace, and the yield of finished products is not high.
Disclosure of Invention
One of the objectives of the present invention is to provide a method for producing CO with low yield of finished products by using part of the available dry distillation gas consumed in regenerative heating furnace in the prior art of coal dry distillation2A coal dry distillation process of a heat carrier. It is used for dry distillation of granular coal (6-60mm), produces coal tar and high-heat value dry distillation gas to the maximum extent, and fully utilizes H produced by the coal tar2、CH4、CO、C2、C3And the effective components are added, the operation stability of the equipment is improved, the investment is reduced, and the large-scale, large-scale and long-period continuous production of the granular coal dry distillation is realized.
The second purpose of the invention is to provide a method for realizing the above-mentioned reaction with CO2A system of coal dry distillation process as heat carrier.
CO as the first aspect of the present invention2The dry distillation process of coal as heat carrier features use of CO2Heating CO by fuel gas as gas heat carrier2Formation of high temperature CO2Entering the coal dry distillation furnace, performing dry distillation on the granular coal in the coal dry distillation furnace, and generating dry distillation gas and heat carrier CO after dry distillation2Leaving the coal gas retort together, purifying, separating, and separating CO2Reheating the fuel gas to form high temperature CO2Returning the coal to the coal dry distillation furnace.
In a preferred embodiment of the invention, the high temperature CO2The temperature range of (A) is 600-900 ℃.
In a preferred embodiment of the invention, the high temperature CO2The temperature range of the reaction is 700-850 ℃.
In a preferred embodiment of the invention, the high temperature CO2In the temperature range of the heating of CO by the fuel gas2Formation of high temperature CO2The mode of the method adopts a tube furnace heating mode, a regenerative furnace heating mode or a direct mixing heating mode.
In a preferred embodiment of the invention, the high temperature CO2In the temperature range of the heating of CO by the fuel gas2Formation of high temperature CO2Preferably, direct mixing heating is used.
In a preferred embodiment of the invention, the granular coal after dry distillation is quenched by one or a combination of more than two of a wet quenching mode, a gas heat carrier dry quenching mode and a water mist dry quenching mode.
In a preferred embodiment of the invention, the carbonized granular coal is quenched by dry quenching with water mist.
In a preferred embodiment of the invention, the dry distillation gas and the heat carrier CO generated after dry distillation2By said purification is meant the dry distillation gas leaving the coal gas retort and the heat carrier CO2Firstly, gas-liquid separation treatment is carried out, and then CO is formed through desulfurization, decarbonization and sulfur production treatment2Is the main tail gas.
In a preferred embodiment of the invention, the dried product is driedThe dry distillation gas and heat carrier CO generated after distillation2The gas-liquid separation treatment is carried out on the dry distillation gas leaving the coal dry distillation furnace and the heat carrier CO2Separating out particles, water and coal tar.
In a preferred embodiment of the invention, the dry distillation gas and the heat carrier CO generated after dry distillation2One or the combination of more than two of the cyclone separator, the water spray cooler, the horizontal tube cooler and the electrostatic oil catcher adopted by the gas-liquid separation treatment is adopted.
In a preferred embodiment of the invention, the dry distillation gas after gas-liquid separation and the heat carrier CO are subjected to gas-liquid separation2The desulfurization, decarburization and sulfur production treatment is composed of one or the combination of more than two of the modes of low-temperature methanol removal of acid gas, MDEA removal of acid gas, iron complex sulfur production, Claus process sulfur production and selective oxidation sulfur production.
In a preferred embodiment of the invention, the dry distillation gas after gas-liquid separation and the heat carrier CO are subjected to gas-liquid separation2The desulfurization, decarburization and sulfur production treatment is combined by an MDEA acid gas removal mode and a selective oxidation sulfur production mode.
In a preferred embodiment of the invention, the CO is2The gas as the main body directly enters CO as a heat carrier2A storage system.
In a preferred embodiment of the present invention, the separation is a separation of H from a gas mainly composed of a dry distillation gas2、CH4、CO、C2、C3、N2In which H is separated2、CH4For external feeding, the separated CO is used as fuel gas or is further converted into H2Or CH4N is isolated2Directly discharging, separating out C2、C3As a fuel.
In a preferred embodiment of the invention, the heating of the heat carrier CO by means of fuel gas is carried out in said2Formation of high temperature CO2In the process, the oxygen content is controlled to be 0-8%.
In a preferred embodiment of the invention, the separation consists of compression, PSA pressure swing adsorption, cryogenic separation.
CO as the second aspect of the present invention2The coal dry distillation system as heat carrier comprises a heating furnace, a dry distillation furnace, a gas-liquid separation device, a coal tar separation device, a desulfurization and decarbonization device, a sulfur production device and CO2The heat carrier buffer tank, the gas separation device and the fuel gas buffer tank are arranged in the heating furnace, and the heating furnace is provided with a fuel gas inlet and CO2Heat carrier inlet, oxygen inlet and high temperature CO2An outlet, the retort having a particulate coal inlet, high temperature CO2Inlet, dry distillation gas and heat carrier CO generated after dry distillation2An outlet, the gas-liquid separation device is provided with a dry distillation gas and a heat carrier CO which are generated after dry distillation2Inlet, dry distillation gas after gas-liquid separation and heat carrier CO2An outlet, a particulate matter outlet, a water outlet, a coal tar separation device, a desulfurization and decarbonization device, a gas-liquid separation device, a heat carrier CO and a dry distillation gas2Inlet with CO2A heat carrier gas outlet as a main body, a gas outlet taking the dry distillation gas as a main body and a hydrogen sulfide outlet, wherein the sulfur production device is provided with a hydrogen sulfide inlet and a sulfur outlet, and the CO is2The heat carrier buffer tank is filled with CO2Heat carrier inlet and CO as main body2A heat carrier gas outlet mainly, the gas separation device is provided with a gas inlet mainly containing dry distillation gas, and H2Outlet, CH4Outlet, CO outlet, C2And C3Outlet, N2An outlet, the fuel gas buffer tank having C2And C3An inlet and a fuel gas outlet; the fuel gas inlet of the heating furnace is connected with the fuel gas outlet of the fuel gas buffer tank through a fuel gas delivery pipe, and the CO is discharged from the fuel gas outlet of the fuel gas buffer tank2Inlet of heat carrier by CO2The heat carrier delivery pipe is connected with the CO2CO for heat carrier buffer tank2A heat carrier gas outlet as a main body, an oxygen inlet of the heating furnace is connected with an oxygen source through an oxygen transmission pipeline, and high-temperature CO of the heating furnace2Outlet through high temperature CO2The conveying pipe is connected with the high-temperature CO of the gas retort2An inlet; of the retort furnaceThe granular coal inlet is connected with a granular coal conveying device through a granular coal conveying pipe, and the dry distillation gas and the heat carrier CO generated after the dry distillation of the dry distillation furnace2The dry distillation gas and the heat carrier CO generated after the dry distillation are passed through the outlet2The delivery pipe is connected with the dry distillation gas and the heat carrier CO generated after the dry distillation of the gas-liquid separation device2An inlet for the dry distillation gas and the heat carrier CO after the gas-liquid separation of the gas-liquid separation device2The dry distillation gas and the heat carrier CO are subjected to gas-liquid separation at the outlet2The delivery pipe and the induced draft fan are connected with the dry distillation gas and the heat carrier CO after the gas-liquid separation of the desulfurization and decarburization device2The particle, water and coal tar outlets of the gas-liquid separation device are connected with the particle, water and coal tar inlets of the coal tar separation device through a particle, water and coal tar conveying pipe, and the coal tar is sent out from the coal tar outlet of the coal tar separation device; the desulfurization and decarbonization device uses CO2The heat carrier gas outlet of the main body is filled with CO2The heat carrier gas delivery pipe as the main body is connected with the CO2CO for heat carrier buffer tank2A heat carrier gas inlet which is mainly used, a gas outlet which takes the dry distillation gas as the main body of the desulfurization and decarburization device is connected with a gas inlet which takes the dry distillation gas as the main body of the gas separation device through a gas conveying pipe which takes the dry distillation gas as the main body of the gas separation device and a supercharger, a hydrogen sulfide outlet of the desulfurization and decarburization device is connected with a hydrogen sulfide inlet of the sulfur production device through a hydrogen sulfide conveying pipe, and a sulfur outlet of the sulfur production device outputs sulfur; h of the gas separation device2Outlet, CH4Outlet, CO outlet, N2The outlets respectively send out H2、CH4、CO、N2C of said gas separation device2And C3Outlet through C2And C3A delivery pipe connected with the fuel gas buffer tank C2And C3An inlet.
In a preferred embodiment of the present invention, the heating furnace is a tube furnace, a regenerative furnace or a direct heating furnace.
In a preferred embodiment of the invention, the furnace is preferably a direct furnace.
In a preferred embodiment of the invention, the retort is preferably a vertical retort.
In a preferred embodiment of the invention, the vertical retort furnace consists of three parts, namely a granular coal preheating section, a retorting section and a quenching section from top to bottom.
In a preferred embodiment of the invention, the granular coal is preheated in the granular coal preheating section by using the dry distillation gas from the dry distillation section and the quenching gas from the quenching section, and heat is recovered.
In a preferred embodiment of the invention, a bell-shaped refractory brick masonry is arranged at the central part of the dry distillation section, so that an inner channel and an outer channel are formed, wherein the inner channel is a coke quenching gas ascending channel, and the outer channel is a reaction zone for heating coal by a high-temperature heat carrier to perform dry distillation.
In a preferred embodiment of the invention, the quenching section is quenched by one or a combination of any two or more of a wet quenching mode, a gas heat carrier dry quenching mode and a water mist dry quenching mode.
In a preferred embodiment of the invention, the quenching section is quenched by dry quenching with water mist.
In a preferred embodiment of the present invention, the gas-liquid separation device is one or a combination of any two or more of a cyclone separator, a water spray cooler, a horizontal tube cooler and an electrostatic oil trap.
In a preferred embodiment of the invention, the desulfurization and decarbonization device is one or a combination of a low-temperature methanol acid gas removal device and an MDEA acid gas removal device.
In a preferred embodiment of the present invention, the sulfur production device is one or a combination of any two or more of a complex iron sulfur production device, a claus process sulfur production device, and a selective oxidation sulfur production device.
In a preferred embodiment of the invention, the coal tar separating device consists of a slag pool, a water pool and an oil pool.
In a preferred embodiment of the invention, the gas separation device consists of a compression device, a PSA pressure swing adsorption device and a refrigeration separation device.
Due to the adoption of the technical scheme, compared with the prior art, the invention adopts CO2The composite material is a gas heat carrier, and adopts the combination of multiple technologies such as a direct heating furnace, a granular coal vertical dry distillation furnace, water mist dry quenching, desulfurization and decarburization, selective oxidation sulfur production and the like, so that various targets such as more effective dry distillation gas production, stable operation, reasonable utilization of dry distillation products and the like are realized.
Drawings
FIG. 1 shows the present invention using CO2Is a flow schematic diagram of a coal dry distillation process of a heat carrier.
FIG. 2 is a schematic view of the vertical retort according to the present invention.
FIG. 3 is a schematic view showing the construction of a retort section in the vertical retort of the present invention.
Detailed Description
The invention is further described below in conjunction with the appended drawings and detailed description.
Referring to FIG. 1, shown is CO2The coal dry distillation system as a heat carrier comprises a heating furnace 100, a dry distillation furnace 200, a gas-liquid separation device 300, a coal tar separation device 400, a desulfurization and decarburization device 500, a sulfur production device 600 and CO2A heat carrier buffer tank 700, a gas separation device 800, and a fuel gas buffer tank 900.
The heating furnace 100 is a tube-type heating furnace, a regenerative heating furnace, or a direct heating furnace. Preferably a direct fired furnace. Having a fuel gas inlet 110, CO2 Heat carrier inlet 120, oxygen inlet 130 and high temperature CO2An outlet 140.
Retort 200 is a vertical retort with a particulate coal inlet 210, high temperature CO2An inlet 220, dry distillation gas and high temperature CO generated after dry distillation2An outlet 230.
Referring to fig. 2 and 3, the dry distillation furnace 200 is composed of three parts, from top to bottom, a granular coal preheating section 240, a dry distillation section 250 and a quenching section 260. The granular coal is preheated in the granular coal preheating section 240 by using the dry distillation gas from the dry distillation section 250 and the quenching gas from the quenching section 260, and heat is recovered.
A bell-shaped firebrick masonry 251 is arranged at the central part of the dry distillation section 250, thereby forming an inner passage 252 and an outer passage 250, wherein the inner passage 252 is a coke quenching gas rising passage, and the outer passage 250 is a reaction zone for heating coal by a high-temperature heat carrier to perform dry distillation. The quenching section 260 is quenched by one or a combination of more than two of a wet quenching mode, a gas heat carrier dry quenching mode and a water mist dry quenching mode. Preferably, the coke quenching is carried out by a water mist dry coke quenching method.
The gas-liquid separator 300 may be one or a combination of two or more of a cyclone separator, a water spray cooler, a horizontal tube cooler, and an electrostatic oil trap. It has a dry distillation gas and high-temperature CO generated after dry distillation2Inlet 310, dry distillation gas after gas-liquid separation and high temperature CO2An outlet 320 and a particulate, water and coal tar outlet 330.
The coal tar separation device 400 consists of a slag bath 410, a water bath 420 and an oil bath 430, which have a particulate, water and coal tar inlet 440 and a coal tar outlet 450.
The desulfurization and decarbonization device 500 is one or a combination of two of a low-temperature methanol acid gas removal device and an MDEA acid gas removal device, and preferably is an MDEA acid gas removal device. The desulfurization and decarburization device 500 has the dry distillation gas and the heat carrier CO after gas-liquid separation2Inlet 510 with CO2A heat carrier gas outlet 520 mainly, a gas outlet 530 mainly composed of a dry distillation gas, and a hydrogen sulfide outlet 540.
The sulfur production device 600 is one or a combination of any two or more of a complex iron sulfur production device, a claus process sulfur production device, and a selective oxidation sulfur production device. Preferably a selective oxidation sulfur plant. The sulfur plant 600 has a hydrogen sulfide inlet 610 and a sulfur outlet 620.
CO2The heat carrier buffer tank 700 is filled with CO2Heat carrier gas inlet 710 with CO as main body2Heat carrier gas outlet 720 and CO as the main body2Is the main exhaust outlet 730.
The gas separation apparatus 800 is composed of a compression apparatus, a PSA pressure swing adsorption apparatus, and a freezing separation apparatus. It has gas inlet 810, H mainly composed of dry distillation gas2Outlet 820, CH4Outlet 830, CO outlet 840, C2And C3Outlet 850, N2And an outlet 860.
The fuel gas surge tank 900 has C2And C3An inlet 910 and a fuel gas outlet 920.
The fuel gas inlet 110 of the heating furnace 100 is connected to the fuel gas outlet 920 of the fuel gas buffer tank 900 through the fuel gas delivery pipe 111, and CO2 Heat carrier inlet 120 through CO2The heat carrier delivery pipe 121 is connected with CO2CO for heat carrier buffer tank 7002A heat carrier gas outlet 720 of the main body, an oxygen inlet 130 of the heating furnace 100 is connected with an oxygen source through an oxygen conveying pipeline 131, and high-temperature CO of the heating furnace 1002 Outlet 140 for passing high temperature CO2The delivery pipe 141 is connected with the high-temperature CO of the gas retort 2002An inlet 220.
The granular coal inlet 210 of the retort 200 is connected with a granular coal conveying device (not shown in the figure) through a granular coal conveying pipe 211, and the dry distillation gas and the heat carrier CO generated after the dry distillation of the retort 2002The outlet 230 passes the dry distillation gas and the heat carrier CO generated after dry distillation2The delivery pipe 231 is connected with the dry distillation gas and the heat carrier CO generated after the dry distillation of the gas-liquid separation device 3002An inlet 310.
The dry distillation gas and the heat carrier CO after the gas-liquid separation in the gas-liquid separator 3002The dry distillation gas and the heat carrier CO which are subjected to gas-liquid separation at the outlet 3202The delivery pipe 321 and the induced draft fan 322 are connected with the dry distillation gas and the heat carrier CO after gas-liquid separation of the desulfurization and decarburization device 5002And an inlet 510, wherein a particulate matter, water and coal tar outlet 330 of the gas-liquid separation device 300 is connected with a particulate matter, water and coal tar inlet 410 of the coal tar separation device 400 through a particulate matter, water and coal tar conveying pipe 331. The coal tar is discharged from the coal tar outlet 420 of the coal tar separation device 400.
Desulfurization and decarburization device 500 using CO2The heat carrier gas outlet 520 of the main body is filled with CO2The heat carrier gas delivery pipe 521 as the main body is connected with CO2CO for heat carrier buffer tank 7002A heat carrier gas inlet 710 which is mainly used, and a gas outlet 530 which takes the dry distillation gas as the main body of the desulfurization and decarburization device 500 to pass throughThe gas duct 531 and the booster 532 for the main dry distillation gas are connected to the gas inlet 810 for the main dry distillation gas of the gas separation apparatus 800, the hydrogen sulfide outlet 540 of the desulfurization and decarburization apparatus 500 is connected to the hydrogen sulfide inlet 610 of the sulfur production apparatus 600 via the hydrogen sulfide duct 541, and the sulfur is output from the sulfur outlet 620 of the sulfur production apparatus 600.
H of gas separation apparatus 8002 Outlet 820, CH4Outlet 830, CO outlet 840, N2The outlets 860 respectively send out H2、CH4、CO、N2C of gas separation apparatus 8002And C3An outlet 850 through C2And C3Delivery pipe 851 is connected to C of fuel gas buffer tank 9002And C3An inlet 910.
The invention uses CO2The coal dry distillation process as a heat carrier is realized by the following specific method:
in the basic flow diagram shown in FIG. 1, furnace 100 employs a direct furnace for heating CO2A heat carrier. In order to avoid nitrogen mixing into the dry distillation gas, the direct heating furnace adopts pure oxygen to support combustion. To avoid excessive combustion temperature of pure oxygen, a portion of CO is added2The heat carrier needs to be incorporated from the burner into the flame zone.
According to different requirements of coal types and carbonization products, the direct heating furnace can flexibly adjust the heated CO2The temperature of the heat carrier may be generally 600 ℃ to 900 ℃, preferably 700 ℃ to 850 ℃.
The invention can flexibly control the oxygen content in the flue gas at the outlet of the direct heating furnace so as to control the oxidized proportion of coal in the dry distillation furnace and finally control the dry distillation temperature of the coal and the yield of CO. Generally, the oxygen content can be controlled between 0% and 8%.
600-900 ℃ high-temperature CO2The heat carrier smoke enters the dry distillation section 250 through 3-4 smoke tunnels 253, and is uniformly mixed with the granular coal through a plurality of small holes on the side surface of the tunnel wall to generate dry distillation reaction.
The incandescent blue char that descends from the retort section 250 enters the lower quench section 260. The coke quenching can be performed by wet quenching or dry quenching by a heat carrier. The invention preferably adopts water mist dry quenching, namely: spraying water mist into the bottom of the coke quenching area, wherein the sprayed water amount is based on the principle that the water mist can be completely vaporized and free water is not generated, and the generated water vapor and the incandescent blue carbon generate water gas reaction in the rising process to generate water gas.
The generated water gas rises through an inner passage 252 of a bell-shaped refractory brick masonry 251 provided in the dry distillation section 250, and enters the granular coal preheating section 240. The water gas produced by quenching does not enter the dry distillation section 250 to avoid lowering the temperature in the dry distillation zone.
The particle coal preheating section 240 at the top of the gas retort 200 is a waste heat recovery area of the dry distillation gas, and the dry distillation gas and CO are2The heat carried by the gas heat carrier, water gas, etc. is transferred to the granular coal at this stage. The temperature of the mixed gas leaving the retort section can be reduced to around 100 ℃.
The 300-mesh gas-liquid separator is used for separating particle impurities, water and the like from the dry distillation products and separating coal tar, and can be composed of a cyclone separator, a water spray cooler, a horizontal pipe cooler, an electrostatic oil catcher and the like.
The desulfurization and decarbonization device 500 and the sulfur production device 600 adopt solvent absorption (preferably MDEA) to remove acid gas, and regenerated CO2+H2S gas is due to H2The S concentration is low, the sulfur can be prepared by adopting a selective oxidation sulfur preparation method or a complex iron method, and CO is used after the sulfur is prepared2The tail gas as the main body directly enters into CO2A heat carrier surge tank 700, which continues into circulation as a heat carrier. If CO is present2When the heat carrier buffer tank 700 is full, CO can be used2Evacuation of the exhaust gas outlet 730 of the body.
The dry distillation produced gas which is not absorbed by the solvent enters a subsequent gas separation device 800, and H is separated out through compression, PSA pressure swing adsorption, freezing separation and the like2、CH4For external feeding, CO separated can be used as fuel gas or further converted into H2Or CH4N is isolated2Can be directly discharged. The remainder being e.g. C2、C3The components can be used as fuel gas for combustion of a heating furnace.
It should be understood that the above-mentioned examples are only for illustrating the technical idea and features of the present invention, and are intended to provide those skilled in the art with understanding the content of the present invention and deciding the implementation thereof, and are not exhaustive of the specific embodiments, and the scope of the present invention should not be limited thereby. It should be understood that the technical solutions according to the present invention may be partially modified or partially replaced with equivalents without departing from the spirit and scope of the technical solutions of the present invention, and the technical solutions of the present invention are included in the claims of the present invention.
Claims (29)
1. With CO2The coal dry distillation system is a heat carrier and is characterized by comprising a heating furnace, a dry distillation furnace, a gas-liquid separation device, a coal tar separation device, a desulfurization and decarburization device, a sulfur production device and CO2The heat carrier buffer tank, the gas separation device and the fuel gas buffer tank are arranged in the heating furnace, and the heating furnace is provided with a fuel gas inlet and CO2Heat carrier inlet, oxygen inlet and high temperature CO2An outlet, the retort having a particulate coal inlet, high temperature CO2Inlet, dry distillation gas and heat carrier CO generated after dry distillation2An outlet, the gas-liquid separation device is provided with a dry distillation gas and a heat carrier CO which are generated after dry distillation2Inlet, dry distillation gas after gas-liquid separation and heat carrier CO2An outlet, a particulate matter outlet, a water outlet, a coal tar separation device, a desulfurization and decarbonization device, a gas-liquid separation device, a heat carrier CO and a dry distillation gas2Inlet with CO2A heat carrier gas outlet as a main body, a gas outlet taking the dry distillation gas as a main body and a hydrogen sulfide outlet, wherein the sulfur production device is provided with a hydrogen sulfide inlet and a sulfur outlet, and the CO is2The heat carrier buffer tank is filled with CO2Heat carrier inlet and CO as main body2A heat carrier gas outlet mainly, the gas separation device is provided with a gas inlet mainly containing dry distillation gas, and H2Outlet, CH4Outlet, CO outlet, C2And C3Outlet, N2An outlet, the fuel gas buffer tank having C2And C3An inlet and a fuel gas outlet; the fuel gas inlet of the heating furnace is connected with the fuel of the fuel gas buffer tank through a fuel gas delivery pipeA feed gas outlet, the CO2Inlet of heat carrier by CO2The heat carrier delivery pipe is connected with the CO2CO for heat carrier buffer tank2A heat carrier gas outlet as a main body, an oxygen inlet of the heating furnace is connected with an oxygen source through an oxygen transmission pipeline, and high-temperature CO of the heating furnace2Outlet through high temperature CO2The conveying pipe is connected with the high-temperature CO of the gas retort2An inlet; the granular coal inlet of the gas retort is connected with a granular coal conveying device through a granular coal conveying pipe, and the dry distillation gas and the heat carrier CO generated after the dry distillation of the gas retort2The dry distillation gas and the heat carrier CO generated after the dry distillation are passed through the outlet2The delivery pipe is connected with the dry distillation gas and the heat carrier CO generated after the dry distillation of the gas-liquid separation device2An inlet for the dry distillation gas and the heat carrier CO after the gas-liquid separation of the gas-liquid separation device2The dry distillation gas and the heat carrier CO are subjected to gas-liquid separation at the outlet2The delivery pipe and the induced draft fan are connected with the dry distillation gas and the heat carrier CO after the gas-liquid separation of the desulfurization and decarburization device2The particle, water and coal tar outlets of the gas-liquid separation device are connected with the particle, water and coal tar inlets of the coal tar separation device through a particle, water and coal tar conveying pipe, and the coal tar is sent out from the coal tar outlet of the coal tar separation device; the desulfurization and decarbonization device uses CO2The heat carrier gas outlet of the main body is filled with CO2The heat carrier gas delivery pipe as the main body is connected with the CO2CO for heat carrier buffer tank2A heat carrier gas inlet which is mainly used, a gas outlet which takes the dry distillation gas as the main body of the desulfurization and decarburization device is connected with a gas inlet which takes the dry distillation gas as the main body of the gas separation device through a gas conveying pipe which takes the dry distillation gas as the main body of the gas separation device and a supercharger, a hydrogen sulfide outlet of the desulfurization and decarburization device is connected with a hydrogen sulfide inlet of the sulfur production device through a hydrogen sulfide conveying pipe, and a sulfur outlet of the sulfur production device outputs sulfur; h of the gas separation device2Outlet, CH4Outlet, CO outlet, N2The outlets respectively send out H2、CH4、CO、N2C of said gas separation device2And C3Outlet through C2And C3A delivery pipe connected with the fuel gas buffer tank C2And C3An inlet.
2. The catalyst of claim 1 in the presence of CO2The coal dry distillation system is a heat carrier, and is characterized in that the heating furnace is a tubular heating furnace, a heat storage heating furnace or a direct heating furnace.
3. The catalyst of claim 1 in the presence of CO2The coal dry distillation system is a heat carrier, and is characterized in that the heating furnace is a direct heating furnace.
4. The catalyst of claim 1 in the presence of CO2The coal dry distillation system is a heat carrier, and is characterized in that the dry distillation furnace is a vertical dry distillation furnace.
5. The catalyst of claim 4 in the presence of CO2The coal carbonization system is a heat carrier and is characterized in that the vertical carbonization furnace consists of a granular coal preheating section, a carbonization section and a coke quenching section from top to bottom.
6. The catalyst of claim 5 in the presence of CO2The coal dry distillation system is a heat carrier, and is characterized in that dry distillation gas from a dry distillation section and quenching gas from a quenching section are adopted in the granular coal preheating section to preheat granular coal, and heat is recovered.
7. The catalyst of claim 5 in the presence of CO2The coal dry distillation system is a heat carrier, and is characterized in that a bell-shaped refractory brick masonry is arranged at the center of the dry distillation section, so that an inner channel and an outer channel are formed, wherein the inner channel is a coke quenching gas rising channel, and the outer channel is a reaction area for heating coal by a high-temperature heat carrier to perform dry distillation.
8. The catalyst of claim 5 in the presence of CO2The coal dry distillation system is a heat carrier and is characterized in that the coke quenching section adopts one or more of a wet coke quenching mode, a gas heat carrier dry coke quenching mode and a water mist dry coke quenching modeQuenching coke by combining any two or more modes.
9. The catalyst of claim 5 in the presence of CO2The coal dry distillation system is a heat carrier and is characterized in that a coke quenching section adopts a water mist dry coke quenching mode to quench coke.
10. The catalyst of claim 1 in the presence of CO2The coal dry distillation system is a heat carrier, and is characterized in that the gas-liquid separation device is one or the combination of more than two of a cyclone separator, a water spray cooler, a horizontal pipe cooler and an electrostatic oil trap.
11. The catalyst of claim 1 in the presence of CO2The coal dry distillation system is a heat carrier, and is characterized in that the desulfurization and decarburization device is one or the combination of a low-temperature methanol acid gas removal device and an MDEA acid gas removal device.
12. The catalyst of claim 1 in the presence of CO2The coal dry distillation system is a heat carrier, and is characterized in that the sulfur production device is one or the combination of more than two of a complex iron sulfur production device, a Claus process sulfur production device and a selective oxidation sulfur production device.
13. The catalyst of claim 1 in the presence of CO2The coal dry distillation system is a heat carrier and is characterized in that the coal tar separation device consists of a slag pool, a water pool and an oil pool.
14. The catalyst of claim 1 in the presence of CO2The coal dry distillation system is a heat carrier and is characterized in that the gas separation device consists of a compression device, a PSA pressure swing adsorption device and a freezing separation device.
15. CO according to any one of claims 1 to 142CO used as heat carrier for coal dry distillation system2The dry distillation process of coal as heat carrier features use of CO2Is qiHeating CO with a body heat carrier by means of a fuel gas2Formation of high temperature CO2Entering the coal dry distillation furnace, performing dry distillation on the granular coal in the coal dry distillation furnace, and generating dry distillation gas and heat carrier CO after dry distillation2Leaving the coal gas retort together, purifying, separating, and separating CO2Reheating the fuel gas to form high temperature CO2Returning to the coal dry distillation furnace; the high temperature CO2The temperature range of (A) is 600-900 ℃.
16. The catalyst of claim 15 with CO2The coal dry distillation process as a heat carrier is characterized in that the high-temperature CO2The temperature range of the reaction is 700-850 ℃.
17. The catalyst of claim 15 with CO2The coal dry distillation process as a heat carrier is characterized in that the high-temperature CO2In the temperature range of the heating of CO by the fuel gas2Formation of high temperature CO2The mode of the method adopts a tube furnace heating mode, a regenerative furnace heating mode or a direct mixing heating mode.
18. The catalyst of claim 15 with CO2The coal dry distillation process as a heat carrier is characterized in that the high-temperature CO2In the temperature range of the heating of CO by the fuel gas2Formation of high temperature CO2The mode of the method adopts a direct mixing heating mode.
19. The catalyst of claim 15 with CO2The coal dry distillation process is characterized in that the granular coal after dry distillation is quenched by one or the combination of more than two of a wet quenching mode, a gas heat carrier dry quenching mode and a water mist dry quenching mode.
20. The catalyst of claim 15 with CO2The coal dry distillation process as heat carrier features that the coke quenching is performed in water mist dry quenching mode.
21. The catalyst of claim 15 with CO2The coal dry distillation process as heat carrier features that dry distillation gas and heat carrier CO produced through dry distillation2By said purification is meant the dry distillation gas leaving the coal gas retort and the heat carrier CO2Firstly, gas-liquid separation treatment is carried out, and then CO is formed through desulfurization, decarbonization and sulfur production treatment2Is the main tail gas.
22. The method of claim 21 with CO2The coal dry distillation process as heat carrier features that dry distillation gas and heat carrier CO produced through dry distillation2The gas-liquid separation treatment is carried out on the dry distillation gas leaving the coal dry distillation furnace and the heat carrier CO2Separating out particles, water and coal tar.
23. The method of claim 21 with CO2The coal dry distillation process as heat carrier features that dry distillation gas and heat carrier CO produced through dry distillation2The equipment adopted for the gas-liquid separation treatment is one or the combination of more than two of a cyclone separator, a water spray cooler, a horizontal pipe cooler and an electrostatic oil trap.
24. The method of claim 21 with CO2The coal dry distillation process as heat carrier features that the dry distillation gas after gas-liquid separation and heat carrier CO are used2The desulfurization and decarburization treatment is composed of one or two of low-temperature methanol-removed acid gas and MDEA-removed acid gas; the dry distillation gas and the heat carrier CO after gas-liquid separation2The sulfur preparation treatment is one or the combination of more than two of the methods of preparing sulfur by complexing iron, preparing sulfur by a Claus method and preparing sulfur by selective oxidation.
25. The method of claim 21 with CO2The coal dry distillation process as heat carrier features that the dry distillation gas after gas-liquid separation and heat carrier CO are used2The method for removing acid gas by MDEA by adopting the desulfurization, decarbonization and sulfur production treatment and the methodThe selective oxidation sulfur production mode.
26. The catalyst of claim 15 with CO2The coal dry distillation process as a heat carrier is characterized in that CO is used2The gas as the main body directly enters CO as a heat carrier2A storage system.
27. The catalyst of claim 15 with CO2The coal dry distillation process is a heat carrier, and is characterized in that the separation refers to the separation of H from gas mainly containing dry distillation gas2、CH4、CO、C2、C3And N2In which H is separated2And CH4For external feeding, the separated CO is used as fuel gas or is further converted into H2Or CH4N is isolated2Directly discharging, separating out C2And C3As a fuel.
28. The catalyst of claim 15 with CO2The coal dry distillation process is a heat carrier and is characterized in that the heat carrier CO is heated by fuel gas2Formation of high temperature CO2In the process, the oxygen content is controlled to be 0-8%.
29. The catalyst of claim 15 with CO2The coal dry distillation process is a heat carrier and is characterized in that the separation consists of compression, PSA pressure swing adsorption and freezing separation.
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| US3480082A (en) * | 1967-09-25 | 1969-11-25 | Continental Oil Co | In situ retorting of oil shale using co2 as heat carrier |
| DD227594A3 (en) * | 1983-03-23 | 1985-09-18 | Schwermasch Liebknecht Veb K | FAST PYROLYSIS OF BROWN COALS AND ARRANGEMENT FOR IMPLEMENTING THE PROCESS |
| CN102199433A (en) * | 2011-03-05 | 2011-09-28 | 何巨堂 | Coal carbonization technology with treating CO2 as temperature control component in combustion process |
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| WO2004097298A1 (en) * | 2003-04-29 | 2004-11-11 | Gennady Kuznetsov | Method for recycling megalopolis waste |
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