CN215404060U - Device for coproduction of liquefied natural gas and synthetic ammonia by methanation of coke oven gas - Google Patents
Device for coproduction of liquefied natural gas and synthetic ammonia by methanation of coke oven gas Download PDFInfo
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- CN215404060U CN215404060U CN202120738511.9U CN202120738511U CN215404060U CN 215404060 U CN215404060 U CN 215404060U CN 202120738511 U CN202120738511 U CN 202120738511U CN 215404060 U CN215404060 U CN 215404060U
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Abstract
The utility model provides a device for coproducing liquefied natural gas and synthetic ammonia by methanation of coke oven gas, belonging to the technical field of comprehensive utilization of coke oven gas; the system comprises a coke-oven gas pretreatment device, a screw compressor, a coke-oven gas purification device, a reciprocating compressor and a primary fine desulfurization device which are sequentially connected, wherein the primary fine desulfurization device is connected with a pressure swing adsorption device through a first pipeline and is connected with a secondary fine desulfurization device through a second pipeline; the pressure swing adsorption device is connected with the ammonia synthesis system through a hydrogen pipeline and is connected with a second pipeline through a desorption gas pipeline; the secondary fine desulfurization device is connected with the methanation reactor and the cryogenic separation device; the utility model fully processes the coke oven gas and realizes the co-production of liquefied natural gas and ammonia, fully utilizes the effective components of the coke oven gas, improves the utilization rate of the coke oven gas and realizes the maximization of resource utilization.
Description
Technical Field
The utility model belongs to the technical field of comprehensive utilization of coke oven gas, and relates to a device for co-producing liquefied natural gas and synthetic ammonia by methanation of coke oven gas.
Background
The Liquefied Natural Gas (LNG) is mainly composed of methane, and a small amount of ethane, propane, nitrogen and the like. Are widely used for: 1) urban resident fuel gas; 2) alternative automotive fuels; 3) the cold source is used for producing quick-cooling food and low-temperature grinding of plastics and rubber; 4) as industrial gas fuel, etc. Along with the popularization of clean energy utilization, the gap of clean energy liquefied natural gas is larger and larger.
Composition of coke oven gas is H2 58-66%，CH4 21-25% ，CO 5-8%，CO2 2-2.3%，N2 2-6% ，O2 0.3-0.8%，CNHM 1.6-2.0% and some impurities such as tar, benzene, naphthalene, etc.
As can be seen from the coke oven gas components, the coke oven gas components contain CH4The content of the active ingredients reaches more than 20 percentThe balance of CO and CO2、H2、N2If the comprehensive utilization of the coke oven gas is realized, the development of energy and environment is combined, and resources such as hydrogen, carbon and the like in the coke oven gas must be fully utilized. At present, the comprehensive utilization ways of coke oven gas mainly comprise the following ways: the coke oven gas is used for producing methanol, power generation, civil fuel and the like. Although the technologies are mature, the methods have the defect of low utilization rate of raw material gas, and the economic benefit cannot reach the optimal effect, so that the continuous extension of the industrial chain is restricted.
SUMMERY OF THE UTILITY MODEL
The utility model overcomes the defects of the prior art, and provides a device for co-producing liquefied natural gas and synthetic ammonia by methanation of coke oven gas, so as to improve the utilization rate of the coke oven gas.
In order to achieve the purpose, the utility model is realized by the following technical scheme:
a device for co-producing liquefied natural gas and synthetic ammonia by methanation of coke oven gas comprises a coke oven gas pretreatment device, a screw compressor, a coke oven gas purification device, a reciprocating compressor and a primary fine desulfurization device which are sequentially connected, wherein the primary fine desulfurization device is connected with a pressure swing adsorption device through a first pipeline and is connected with a secondary fine desulfurization device through a second pipeline; the pressure swing adsorption device is connected with an ammonia synthesis system through a hydrogen pipeline, and is connected with a second pipeline through a desorption gas pipeline; the second-stage fine desulfurization device is connected with the methanation reactor and the cryogenic separation device, the top of the cryogenic separation device is connected with the ammonia synthesis system through a hydrogen-rich tail gas pipeline, and the bottom of the cryogenic separation device is connected with the storage tank through a liquefied natural gas pipeline.
Further, the analysis gas pipeline is connected to the external fuel gas pipeline through a branch pipeline.
Furthermore, the coke oven gas purification device comprises an activated carbon filtration device and a temperature swing adsorption device which are connected with each other.
Further, the coke oven gas pretreatment device is a fiber bed filter.
Further, a drying device is arranged between the methanation reactor and the cryogenic separation device.
Further, the ammonia synthesis system is connected to a rich nitrogen line of an air separation unit.
Compared with the prior art, the utility model has the following beneficial effects:
1. the utility model adopts fiber filtration for pretreatment before the compression of the coke-oven gas, effectively treats the impurities such as tar, dust, naphthalene, benzene and the like in the coke-oven gas, and can improve the efficiency of subsequent treatment and the purity of liquefied natural gas.
2. The excess coke-oven gas is subjected to gas separation by pressure swing adsorption, on one hand, the synthesis of ammonia is facilitated, and simultaneously, the generated analytic gas enters a methanation process to play a positive promoting role in methanation treatment.
3. The coke-oven gas pressure swing adsorption analysis gas is used as a carbon supplement resource for methanation of the coke-oven gas, so that the gas is fully utilized, and the waste of effective gas is reduced.
4. The multistage methanation reaction is combined with the cryogenic technology, so that the yield and the quality of the liquefied natural gas are effectively improved.
5. Cryogenic hydrogen-rich tail gas and coke oven gas pressure swing adsorption H2As the raw material for synthesizing ammonia, the effective components of the gas are fully utilized, the resource utilization is maximized, and the cost advantage is achieved.
Drawings
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the following drawings are taken for illustration:
FIG. 1 is a schematic connection diagram of a device for producing liquefied natural gas and synthetic ammonia by methanation of coke oven gas.
FIG. 2 is a process flow diagram of the methanation of coke oven gas for the co-production of liquefied natural gas and synthetic ammonia in the embodiment.
In the figure, 1 is a fiber filter, 2 is a screw compressor, 3 is an activated carbon filter, 4 is a temperature-changing adsorber, 5 is a reciprocating compressor, 6 is a primary fine desulfurization tower, 7 is a pressure-changing adsorber, 8 is a secondary fine desulfurization tower, 9 is an ammonia synthesis system, 10 is a first pipeline, 11 is a second pipeline, 12 is a hydrogen pipeline, 13 is a desorption gas pipeline, 14 is a methanation reactor, 15 is a cryogenic separation tower, 16 is a hydrogen-rich tail gas pipeline, 17 is a liquefied natural gas pipeline, 18 is a storage tank, and 19 is a branch pipeline.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the utility model and are not intended to limit the utility model. The technical solution of the present invention is described in detail below with reference to the embodiments and the drawings, but the scope of protection is not limited thereto.
As shown in fig. 1, the device adopted in the method for co-producing liquefied natural gas and synthetic ammonia by methanation of coke oven gas comprises a fiber filter 1, a screw compressor 2, an activated carbon filter 3, a temperature-changing adsorber 4, a reciprocating compressor 5 and a primary fine desulfurization tower 6 which are connected in sequence, wherein the primary fine desulfurization tower 6 is connected with a pressure-changing adsorber 7 through a first pipeline 10 and is connected with a secondary fine desulfurization tower 8 through a second pipeline 11; the pressure swing adsorber 7 is connected with an ammonia synthesis system 9 through a hydrogen pipeline 12, and the pressure swing adsorber 7 is connected with a second pipeline 11 through an analysis gas pipeline 13; the desorption gas line 13 is connected to the outgoing fuel gas line via a branch line 19. The second-stage fine desulfurization tower 8 is connected with the methanation reactor 14 and the cryogenic separation tower 15, the top of the cryogenic separation tower 15 is connected with the ammonia synthesis system 9 through a hydrogen-rich tail gas pipeline 16, and the bottom of the cryogenic separation tower 15 is connected with the storage tank 18 through a liquefied natural gas pipeline 17. The working process of the device is shown in the following process method.
The device is used for carrying out methanation on the coke oven gas to coproduce liquefied natural gas and synthetic ammonia, and specifically comprises the following steps as shown in figure 2:
1. pretreating coke oven gas: the coke oven gas is filtered by using a fiber bed technology, and the impurities such as tar, dust, naphthalene, benzene and the like in the coke oven gas are mainly treated.
2. Removing benzene, desulfurizing and compressing coke oven gas: pressurizing the pretreated coke-oven gas to 0.6MPa by using a screw compressor, then purifying the coke-oven gas, specifically, performing fine oil and naphthalene removal and coarse desulfurization by using activated carbon, then performing Temperature Swing Adsorption (TSA) to remove impurities such as benzene, naphthalene, sulfide and the like in the coke-oven gas, then pressurizing the coke-oven gas to 2.3MPa by using a reciprocating machine, and performing heat exchange to 350 ℃ for coke-oven gas pre-hydrogenation and primary fine desulfurization.
Wherein, the operating pressure of the coke-oven gas screw compressor is as follows: 0-0.8MPa, and the optimized pressure range is as follows: 0-0.6MPa, and the outlet temperature is 40 ℃; the refined deoiling, the naphthalene removing and the crude desulfurization all adopt active carbon, the operation temperature is normal temperature, and the operation pressure is as follows: 0-0.8MPa, optimizing: 0-0.6MPa, the content of both naphthalene and tar at the outlet is reduced to less than or equal to 1mg/Nm3。
The temperature swing adsorption adopts a composite bed, at least two different adsorbents (any two or more of inert alumina, activated alumina, coke, silica gel, activated carbon and the like can be preferably selected according to different impurity components) are respectively filled in the same adsorption bed, the adsorption beds in the impurity removal system form a continuous operation system, and each adsorption bed undergoes several processes of adsorption, depressurization, heating, cold blowing and pressurization in one cycle period.
3. Coke oven gas pressure swing adsorption and carbon supplement by desorption gas: the coke-oven gas compressed to 2.3MPa is subjected to pre-hydrogenation, primary fine desulfurization to remove oxygen and most of sulfur in the coke-oven gas, and then a small part of the coke-oven gas enters a pressure swing adsorption device for gas separation, so that hydrogen with the purity of 99.75% and the analyzed gas with the methane content of 41.38% are obtained. Hydrogen is sent to ammonia synthesis to be used as raw material gas, part of the resolved gas is pressurized to 2.3MPa and returns to the original system to be mixed with the coke oven gas of the other part after the primary fine desulfurization to enter a secondary fine desulfurization system, and the rest resolved gas is sent out to be used as fuel.
Pressure swing adsorption separation conditions: adsorption pressure 1.5-2.0MPa, desorption pressure 0.01-0.03MPa, operation temperature: the adsorbent is a combination of a plurality of molecular sieves, active fillers, fine-pore silica gel and active alumina at the temperature of between 0 and 40 ℃; the separated hydrogen has pressure of 2.0MPa, purity of 99.7-99.9%, and is used for producing synthetic ammonia, and a part of the separated gas is returned to the second-stage fine desulfurization for carbon supplement of the system to increase methane yield.
In the first-stage and second-stage fine desulfurization processes, the pre-hydrogenation, the first-stage hydrogenation and the second-stage hydrogenation adopt iron-molybdenum and cobalt-molybdenum catalysts, the operating pressure is 2-2.5MPa, and the operating temperature is as follows: 300 ℃ and 350 ℃, and the total sulfur in the coke-oven gas after the coke-oven gas is subjected to zinc oxide after the secondary hydrogenation is less than 0.1 ppm.
4. Methanation reaction: after a certain amount of water vapor is added into the coke oven gas passing through the secondary fine desulfurization system, methanation reaction is carried out by the first, second and third sections of adiabatic methanation reactors under the action of a catalyst, and a gas mixture mainly containing methane is obtained.
The methanation reaction process conditions are as follows: the reaction pressure is 2-5MPa, the reaction temperature is 300-. Two to three adiabatic fixed bed reactors are adopted for methanation reaction, and heat generated by steam recovery reaction is generated between the reactors through a waste heat boiler; the first reactor regulates the bed temperature by the amount of circulating gas.
5. Cryogenic treatment: and (3) deeply freezing and rectifying the methanated methane-rich gas through a mixed refrigerant refrigeration cycle process after dedusting, demercuration and drying, obtaining liquefied natural gas at the bottom of the tower, and re-heating the hydrogen-rich tail gas at the top of the tower to synthesize ammonia.
The deep cooling process adopts a mixed refrigerant of methane, ethylene, nitrogen, isobutane and isopentane for deep freezing, and the process conditions are as follows: the operation temperature is between 150 ℃ below zero and 180 ℃ below zero, and the separation pressure is 1.6 to 3 MPa.
6. Ammonia synthesis: the low-pressure ammonia synthesis is carried out on the cryogenic hydrogen-rich tail gas, hydrogen from pressure swing adsorption of coke-oven gas and rich nitrogen from an original air separation device of a factory under the action of an ammonia synthesis catalyst by pressurizing 15MPa and heat exchange to 320 ℃.
The ammonia synthesis process conditions are as follows: the reaction pressure is 15-30MPa, the reaction temperature is 300-550 ℃, and the space velocity is 8000-40000h-1。
While the utility model has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the utility model as defined by the appended claims.
Claims (6)
1. The device for coproducing liquefied natural gas and synthetic ammonia by methanation of coke oven gas is characterized by comprising a coke oven gas pretreatment device, a screw compressor, a coke oven gas purification device, a reciprocating compressor and a primary fine desulfurization device which are sequentially connected, wherein the primary fine desulfurization device is connected with a pressure swing adsorption device through a first pipeline and is connected with a secondary fine desulfurization device through a second pipeline; the pressure swing adsorption device is connected with an ammonia synthesis system through a hydrogen pipeline, and is connected with a second pipeline through a desorption gas pipeline; the second-stage fine desulfurization device is connected with the methanation reactor and the cryogenic separation device, the top of the cryogenic separation device is connected with the ammonia synthesis system through a hydrogen-rich tail gas pipeline, and the bottom of the cryogenic separation device is connected with the storage tank through a liquefied natural gas pipeline.
2. The device for co-producing liquefied natural gas and synthetic ammonia through methanation of coke oven gas as claimed in claim 1, wherein the desorption gas pipeline is connected to an external fuel gas pipeline through a branch pipeline.
3. The device for co-producing liquefied natural gas and synthetic ammonia through methanation of coke oven gas as claimed in claim 1, wherein the coke oven gas purification device comprises an activated carbon filtration device and a temperature swing adsorption device which are connected with each other.
4. The device for co-producing liquefied natural gas and synthetic ammonia through methanation of coke oven gas as claimed in claim 1, wherein the pretreatment device of coke oven gas is a fiber bed filter.
5. The device for co-producing liquefied natural gas and synthetic ammonia through methanation of coke oven gas as claimed in claim 1, wherein a drying device is arranged between the methanation reactor and the cryogenic separation device.
6. The device for co-producing liquefied natural gas and synthetic ammonia through methanation of coke oven gas as claimed in claim 1, wherein the ammonia synthesis system is connected with a rich nitrogen pipeline of an air separation device.
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| CN202120738511.9U CN215404060U (en) | 2021-04-13 | 2021-04-13 | Device for coproduction of liquefied natural gas and synthetic ammonia by methanation of coke oven gas |
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| CN202120738511.9U CN215404060U (en) | 2021-04-13 | 2021-04-13 | Device for coproduction of liquefied natural gas and synthetic ammonia by methanation of coke oven gas |
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