CN115888313B - Energy production regulating process for preparing fuel cell hydrogen and pipeline natural gas from coke oven gas - Google Patents
Energy production regulating process for preparing fuel cell hydrogen and pipeline natural gas from coke oven gas Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 368
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 136
- 239000001257 hydrogen Substances 0.000 title claims abstract description 136
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000000446 fuel Substances 0.000 title claims abstract description 102
- 239000000571 coke Substances 0.000 title claims abstract description 92
- 239000003345 natural gas Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 230000007363 regulatory process Effects 0.000 title claims description 3
- 238000001179 sorption measurement Methods 0.000 claims abstract description 125
- 238000003795 desorption Methods 0.000 claims abstract description 73
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 53
- 230000023556 desulfurization Effects 0.000 claims abstract description 53
- 238000007906 compression Methods 0.000 claims abstract description 40
- 230000008929 regeneration Effects 0.000 claims abstract description 40
- 238000011069 regeneration method Methods 0.000 claims abstract description 40
- 230000006835 compression Effects 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 125000001741 organic sulfur group Chemical group 0.000 claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 56
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 31
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 31
- 238000000746 purification Methods 0.000 claims description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 28
- 239000001569 carbon dioxide Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- 150000002431 hydrogen Chemical class 0.000 claims description 24
- 239000002737 fuel gas Substances 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 230000008901 benefit Effects 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
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- 238000011161 development Methods 0.000 description 3
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- 239000002803 fossil fuel Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- -1 halogen ions Chemical class 0.000 description 2
- 238000004891 communication Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Fuel Cell (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The invention discloses a production capacity adjusting process for preparing fuel cell hydrogen and pipeline natural gas from coke oven gas, which comprises a temperature swing adsorption unit (X3) which is connected with a compression and pretreatment unit (X1) or a conversion unit (X2) to remove heavy component impurities in the coke oven gas, a fine desulfurization unit (X4) which is connected with the temperature swing adsorption unit (X3) to remove inorganic sulfur and organic sulfur in the coke oven gas, and the like. According to the invention, after bypass conversion, temperature swing adsorption and fine desulfurization are carried out on the coke oven gas subjected to compression and pretreatment, a part of the coke oven gas is subjected to pressure swing adsorption and separation to obtain fuel hydrogen meeting requirements of the proton exchange membrane fuel cell automobile, the other part of the coke oven gas is mixed with the pressurized pressure swing adsorption desorption gas, and the pipeline natural gas is obtained through methanation synthesis, and hydrogen and carbon effective components in the coke oven gas are fully utilized by arranging a conversion bypass pipeline, changing the temperature swing adsorption regeneration gas source and adjusting the de-methanation desorption gas flow, so that flexible adjustment of the hydrogen capacity and the pipeline natural gas productivity of the fuel cell is realized.
Description
Technical Field
The invention belongs to the technical field of new energy preparation, and particularly relates to a capacity adjusting process for preparing fuel cell hydrogen and pipeline natural gas from coke oven gas.
Background
In recent years, with increasing importance placed on environmental protection in the world, energy systems mainly using fossil fuels are gradually changed into diversified structures such as fossil fuels, renewable energy sources, nuclear energy, and the global energy structures are being developed in the direction of lower and lower carbon content. Hydrogen does not contain carbon, and is a clean energy source. The hydrogen fuel cell industry is one of the current new energy development directions, and is gradually accepted by the market due to the advantages of environmental protection, good low-temperature performance, long endurance mileage, short filling time and the like.
The data show that the device for producing hydrogen by taking fossil energy sources such as coal, natural gas, petroleum and the like as raw materials in China is more than 70 percent, the hydrogen production carbon emission of the industrial raw materials is higher, and the hydrogen production cost is 10-20 yuan/kg; and the industrial byproduct gas is used for hydrogen production, and the large-scale hydrogen production cost is only 8-14 yuan/kg. Therefore, the hydrogen production by utilizing the industrial byproduct gas has great advantages in energy conservation, carbon reduction and economic benefit.
The coke oven gas is gas containing hydrogen, carbon monoxide, carbon dioxide and other effective components and benzene, ammonia, sulfur and other impurities as by-products in the process of producing coke by using coal as a raw material. The main components of the coke oven gas are hydrogen (55% -60%), methane (23% -27%), small amount of carbon monoxide (5% -8%), C 2 and unsaturated hydrocarbon (2%), carbon dioxide (1.5% -3%), oxygen (0.3% -0.8%), and nitrogen (3% -7%). From the above composition, coke oven gas is a high-quality hydrogen production raw material gas, carbon monoxide and carbon dioxide in the coke oven gas can be converted into methane through hydrogenation, and natural gas products are obtained through separation. Therefore, the hydrogen of the fuel cell is prepared from the coke oven gas, and meanwhile, the pipeline natural gas is obtained through separation, so that the effective components in the coke oven gas can be utilized to the maximum extent.
Another problem with the production of fuel cell hydrogen from coke oven gas is the uncertainty of market demand. At present, the hydrogen industry of the fuel cell can be highly aggregated, the application and popularization are large-scale, and the low-cost collaborative development is realized in fresh cities. While the hydrogen of the fuel cell manufactured in the industrial developed area takes up certain development advantages, the embarrassment of smaller number of hydrogen fuel cell vehicles is faced, so that the hydrogen energy cannot be completely consumed, and the hydrogen productivity of the fuel cell needs to be reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a production capacity adjusting process for preparing fuel cell hydrogen and pipeline natural gas from coke oven gas. In the device, by arranging a conversion bypass pipeline, changing the source of the temperature swing adsorption regenerated gas and adjusting the flow of the methanation stripping gas, the hydrogen and carbon effective components in the coke oven gas are fully utilized, when the hydrogen demand of the fuel cell is insufficient, the natural gas productivity of the pipeline is improved, and the economic benefit is ensured.
In order to achieve the aim of the invention, the specific technical scheme of the invention is as follows:
The production capacity adjusting process for preparing fuel cell hydrogen and pipeline natural gas from coke oven gas comprises the following steps:
The compression unit and the pretreatment unit are connected or disconnected with the conversion unit and then enter the temperature swing adsorption unit; the device comprises a temperature swing adsorption unit which is connected with a compression unit, a pretreatment unit or a conversion unit to remove heavy component impurities in coke oven gas, a fine desulfurization unit which is connected with the temperature swing adsorption unit to remove inorganic sulfur and organic sulfur in the coke oven gas, a pressure swing adsorption unit which is connected with the fine desulfurization unit to prepare hydrogen of a fuel cell, a desorption gas compression unit which is connected with the pressure swing adsorption unit to pressurize desorption gas, and a methanation and drying unit which is connected with the gas mixture of a second fine purified gas transmission pipe from the desorption gas compression unit to convert carbon monoxide and carbon dioxide into methane. The coke oven gas conveying pipe is connected to the compression and pretreatment unit, the third desorption gas conveying pipe is connected with a fuel gas outer conveying pipe, the pressure swing adsorption unit is connected with a fuel cell hydrogen outer conveying pipe, and the methanation and drying unit is connected with a pipeline natural gas outer conveying pipe.
Further, whether a conversion unit is arranged between the compression unit, the pretreatment unit and the temperature swing adsorption unit is selected according to the situation; when the conversion unit is arranged, the air inlet and the air outlet of the conversion unit are both connected with a pre-purified gas bypass pipe, and the conversion unit converts carbon monoxide into hydrogen and carbon dioxide.
Further, a pre-purified gas conveying pipe is connected between the compression unit, the pre-treatment unit and the temperature swing adsorption unit, a first pre-purified gas bypass pipe starting point is connected to a pre-purified gas conveying pipe air flow starting point, and a second pre-purified gas bypass pipe ending point is connected to a pre-purified gas conveying pipe air flow end point.
Preferably, in the air flow direction, the inlet valves are arranged on the rear pre-purified gas conveying pipe and the initial end of the first pre-purified gas bypass pipe at the three-way joint. When the hydrogen productivity of the fuel cell is pursued to be greater, closing an air inlet valve of the pre-purified gas conveying pipe, and opening an air inlet valve of the first pre-purified gas bypass pipe; and otherwise, closing the air inlet valve of the first pre-purified gas bypass pipe, and opening the air inlet valve of the pre-purified gas conveying pipe.
Further, a purified gas conveying pipe is connected between the temperature swing adsorption unit and the fine desulfurization unit, the temperature swing adsorption unit is provided with a regenerated gas conveying pipe and a regenerated gas output pipe, and the regenerated gas output pipe is connected to the fuel gas output pipe.
Preferably, a self-purification gas conveying pipe is led out from the purification gas conveying pipe, the self-purification gas conveying pipe is connected to the regeneration gas conveying pipe, and whether the self-purification gas is used as the temperature swing adsorption regeneration gas is selected according to the capacity adjustment requirement.
Further, the fine desulfurization unit is connected with a fine purified gas conveying pipe, a first fine purified gas conveying pipe of the pressure swing adsorption unit and a second fine purified gas conveying pipe of the methanation removal and drying unit are connected to the fine purified gas conveying pipe, and the gas amounts of the second desorption gas conveying pipe, the first fine purified gas conveying pipe and the second fine purified gas conveying pipe are adjusted according to the capacity adjustment requirement.
Preferably, the purified gas in the fine desulfurization unit is sequentially subjected to pre-hydrogenation, primary adsorption desulfurization, secondary hydrogenation, secondary adsorption desulfurization and copper-based fine desulfurization, so that the total sulfur in the purified gas after the fine desulfurization unit is not more than 0.02ppmv.
Further, the pressure swing adsorption unit is connected with the fuel cell hydrogen gas output pipe and the first desorption gas output pipe.
Preferably, a hydrogen regeneration conveying pipe is led out from the hydrogen external conveying pipe of the fuel cell, the hydrogen regeneration conveying pipe is connected to the regeneration gas conveying pipe and led out of the hydrogen fuel conveying pipe, the hydrogen fuel conveying pipe is connected to the fuel gas external conveying pipe, and the hydrogen of the fuel cell is selected as product gas or fuel gas or temperature swing adsorption regeneration gas according to the capacity adjustment and the hydrogen product filling requirement.
Preferably, a second desorption gas conveying pipe and a third desorption gas conveying pipe are led out of the first desorption gas conveying pipe, the second desorption gas conveying pipe is connected to the desorption gas compression unit, the third desorption gas conveying pipe is led out of the fuel gas outer conveying pipe and the regeneration desorption gas conveying pipe, the regeneration desorption gas conveying pipe is connected to the regeneration gas conveying pipe, the desorption gas flow of the desorption gas compression unit in the second desorption gas conveying pipe is adjusted according to the productivity adjustment requirement, and meanwhile, desorption gas is selected as fuel gas or temperature swing adsorption regeneration gas.
Further, the desorption gas compression unit is connected with a desorption gas conveying pipe, the desorption gas conveying pipe and the second fine purification gas conveying pipe are connected to a third fine purification gas conveying pipe, and the third fine purification gas conveying pipe is connected to the methanation and drying unit.
Preferably, the stripping gas compressor unit outlet pressure or methanation unit operating pressure is determined based on the pressure required by the pipeline natural gas export pipeline.
Preferably, the third fine purified gas conveying pipe is provided with analysis points for the contents of hydrogen, carbon monoxide, carbon dioxide and low-carbon hydrocarbons, and the hydrogen-carbon ratio of the gas in the third fine purified gas conveying pipe is obtained according to the analysis result.
Preferably, the hydrogen-carbon ratio of the gas in the third refined purified gas conveying pipe is 3.0-3.3.
According to the invention, after bypass conversion, temperature swing adsorption and fine desulfurization are carried out on the coke oven gas subjected to compression and pretreatment, a part of the coke oven gas is subjected to pressure swing adsorption and separation to obtain fuel hydrogen meeting requirements of the proton exchange membrane fuel cell automobile, the other part of the coke oven gas is mixed with the pressurized pressure swing adsorption desorption gas, and the pipeline natural gas is obtained through methanation synthesis, and hydrogen and carbon effective components in the coke oven gas are fully utilized by arranging a conversion bypass pipeline, changing the temperature swing adsorption regeneration gas source and adjusting the de-methanation desorption gas flow, so that flexible adjustment of the hydrogen capacity and the pipeline natural gas productivity of the fuel cell is realized.
Compared with the prior art, the invention has the following positive effects:
The invention is provided with a temperature swing adsorption unit to adsorb heavy component impurities of coke oven gas, and the total sulfur of the purified coke oven gas is not more than 0.02ppmv through serial copper-based fine desulfurization after hydrodesulfurization, which is the key for successfully preparing fuel cell hydrogen (the total sulfur requirement of the fuel cell hydrogen is not more than 0.004 ppmv); the adoption of a plurality of strands of temperature swing adsorption regenerated gas sources is a key for regulating the hydrogen capacity of the fuel cell and the natural gas capacity of the pipeline.
And secondly, the invention is provided with a conversion bypass pipeline. When the hydrogen market demand of the fuel cell is smaller, the fuel cell does not pass through the conversion unit; otherwise, the hydrogen product of the fuel cell is obtained by entering the bypass conversion unit.
And thirdly, the temperature swing adsorption regenerated gas source of the invention is self-purifying gas, fuel cell hydrogen and pressure swing adsorption desorption gas, and flexible adjustment of productivity can be realized. When the hydrogen market demand of the fuel cell is particularly small or no hydrogen product of the fuel cell is filled, the hydrogen of the fuel cell is used as the temperature swing adsorption regenerated gas, and only the pipeline natural gas product is produced at the moment; when the requirements of the hydrogen market of the fuel cell and the natural gas market of the pipeline are smaller, self-purifying gas is adopted as temperature swing adsorption regenerated gas, and at the moment, the natural gas of the pipeline has high yield and the hydrogen of the fuel cell has low yield; when the markets of the fuel cell hydrogen and the pipeline natural gas are good, the pressure swing adsorption desorption gas is used as the temperature swing adsorption regeneration gas, and the pipeline natural gas and the fuel cell hydrogen can reach high productivity.
Drawings
FIG. 1 is a block diagram of the process according to example 1 of the present invention.
Fig. 2 is a block diagram of the process according to embodiment 2 of the present invention.
Fig. 3 is a block diagram of the process according to embodiment 3 of the present invention.
Fig. 4 is a block diagram of the process according to embodiment 4 of the present invention.
Wherein, the names corresponding to the reference numerals are:
1-coke oven gas conveying pipe, 2-pre-purified gas conveying pipe, 3-first pre-purified gas bypass pipe, 4-second pre-purified gas bypass pipe, 5-purified gas conveying pipe, 6-self-purified gas conveying pipe, 7-refined purified gas conveying pipe, 8-first refined purified gas conveying pipe, 9-second refined purified gas conveying pipe, 10-fuel cell hydrogen gas outer conveying pipe, 11-hydrogen regeneration conveying pipe, 12-first desorption gas conveying pipe, 13-second desorption gas conveying pipe, 14-third desorption gas conveying pipe, 15-desorption gas conveying pipe, 16-third refined purified gas conveying pipe, 17-pipeline natural gas outer conveying pipe, 18-hydrogen gas fuel conveying pipe, 20-fuel gas outer conveying pipe, 21-regenerated gas conveying pipe, X1-compression, pretreatment unit, X2-conversion unit, X3-temperature-adsorption unit, X4-refined desulfurization unit, X5-pressure swing adsorption unit, X6-desorption gas compression unit, X7-methanation and drying unit.
Detailed Description
The device comprises a temperature-variable adsorption unit X3 which is connected with a compression and pretreatment unit X1 or a conversion unit X2 (a first pre-purified gas bypass pipe 3 and a second pre-purified gas bypass pipe 4 are respectively connected with an air inlet and an air outlet of the conversion unit X2, the conversion unit X2 can convert carbon monoxide into hydrogen and carbon dioxide, the conversion unit X2 is arranged between the compression and pretreatment unit X1 and the temperature-variable adsorption unit X3 according to the situation, the temperature-variable adsorption unit X3 is connected with the temperature-variable adsorption unit X3 to remove heavy component impurities in the coke oven gas, a fine desulfurization unit X4 which is connected with the temperature-variable adsorption unit X3 to remove inorganic sulfur and organic sulfur in the coke oven gas, a pressure-variable adsorption unit X5 which is connected with the fine desulfurization unit X4 to prepare the fuel cell hydrogen, a desorption gas compression unit X6 which is connected with the pressure-variable adsorption unit X5 to pressurize the desorption gas, and a gas transmission unit X7 which is connected with the second fine purified gas pipe 9 to convert the carbon monoxide and the carbon dioxide into methane after being mixed according to the situation. The coke oven gas conveying pipe 1 is connected with a compression and pretreatment unit X1, a fuel gas outer conveying pipe 20 is connected to the third desorption gas conveying pipe 14, a fuel cell hydrogen outer conveying pipe 10 is connected to the pressure swing adsorption unit X5, and a pipeline natural gas outer conveying pipe 17 is connected to the methanation and drying unit X7. A pre-purified gas conveying pipe 2 is connected between the compression and pretreatment unit X1 and the temperature swing adsorption unit X3, the starting point of a first pre-purified gas bypass pipe 3 is connected to the air flow starting end of the pre-purified gas conveying pipe 2, and the end point of a second pre-purified gas bypass pipe 4 is connected to the air flow end of the pre-purified gas conveying pipe 2. Preferably, in the air flow direction, the rear pre-purified gas delivery pipe 2 and the initial end of the first pre-purified gas bypass pipe 3 at the three-way joint are both provided with air inlet valves. When the hydrogen productivity of the fuel cell is pursued to be greater, closing the air inlet valve of the pre-purified gas conveying pipe 2 and opening the air inlet valve of the first pre-purified gas bypass pipe 3; otherwise, the air inlet valve of the first pre-purified gas bypass pipe 3 is closed, and the air inlet valve of the pre-purified gas conveying pipe 2 is opened. A purified gas conveying pipe 5 is connected between the temperature swing adsorption unit X3 and the fine desulfurization unit X4, the temperature swing adsorption unit X3 is provided with a regenerated gas conveying pipe 21 and a regenerated gas output pipe 22, and the regenerated gas output pipe 22 is connected to the fuel gas output pipe 20. The self-purification gas conveying pipe 6 is led out from the purification gas conveying pipe 5, the self-purification gas conveying pipe 6 is connected to the regenerated gas conveying pipe 21, and whether the self-purification gas is used as the temperature swing adsorption regenerated gas or not is selected according to the production capacity adjustment requirement. The fine desulfurization unit X4 is connected with a fine purified gas conveying pipe 7, a first fine purified gas conveying pipe 8 for removing the pressure swing adsorption unit X5 and a second fine purified gas conveying pipe 9 for removing methanation and drying the unit X7 are connected to the fine purified gas conveying pipe 7, and the gas amounts of the second desorption gas conveying pipe 13, the first fine purified gas conveying pipe 8 and the second fine purified gas conveying pipe 9 are adjusted according to the capacity adjustment requirement. Preferably, the purified gas in the fine desulfurization unit X4 is sequentially subjected to pre-hydrogenation, primary adsorption desulfurization, secondary hydrogenation, secondary adsorption desulfurization and copper-based fine desulfurization, so that the total sulfur in the purified gas after the fine desulfurization unit X4 is not more than 0.02ppmv.
The hydrogen regeneration conveying pipe 11 is led out from the hydrogen outer conveying pipe 10 of the fuel cell, the hydrogen regeneration conveying pipe 11 is connected to the regenerated gas conveying pipe 21, the hydrogen fuel conveying pipe 18 is led out, the hydrogen fuel conveying pipe 18 is connected to the fuel gas outer conveying pipe 20, and the hydrogen of the fuel cell is selected as product gas or fuel gas or temperature swing adsorption regeneration gas according to the capacity adjustment and the hydrogen product filling requirement. Preferably, a second desorption gas delivery pipe 13 and a third desorption gas delivery pipe 14 are led out of the first desorption gas delivery pipe 12, the second desorption gas delivery pipe 13 is connected to the desorption gas compression unit X6, the third desorption gas delivery pipe 14 leads out a fuel gas external delivery pipe 20 and a regeneration desorption gas delivery pipe, the regeneration desorption gas delivery pipe is connected to the regeneration gas delivery pipe 21, and the desorption gas flow rate of the desorption gas compression unit X6 in the second desorption gas delivery pipe 13 is adjusted according to the capacity adjustment requirement, and simultaneously, the desorption gas is selected as fuel gas or temperature swing adsorption regeneration gas.
The desorption gas compression unit X6 is connected with a desorption gas conveying pipe 15, the desorption gas conveying pipe 15 and the second fine purification gas conveying pipe 9 are connected to a third fine purification gas conveying pipe 16, and the third fine purification gas conveying pipe 16 is connected to the methanation and drying unit X7. Preferably, the pressure at the outlet of the stripping compressor unit X6 or the operating pressure of the methanation unit X7 is determined on the basis of the pressure required for the pipeline natural gas export pipeline 17. Preferably, the third fine purified gas conveying pipe 16 is provided with analysis points for the contents of hydrogen, carbon monoxide, carbon dioxide and low-carbon hydrocarbons, and the hydrogen-carbon ratio of the gas in the third fine purified gas conveying pipe 16 is obtained according to the analysis result. Preferably, the hydrogen-carbon ratio of the gas in the third fine purification gas delivery pipe 16 is 3.0 to 3.3.
The process method provided by the invention is used for adjusting the production capacity of hydrogen and pipeline natural gas of a fuel cell prepared from coke oven gas, a temperature swing adsorption unit is arranged to adsorb heavy component impurities of the coke oven gas, the total sulfur of the purified coke oven gas is not more than 0.02ppmv through serial copper-based fine desulfurization after hydrodesulfurization, and a plurality of strands of temperature swing adsorption regenerated gas sources are adopted, which is the key for successfully preparing the hydrogen of the fuel cell and adjusting the production capacity of the hydrogen of the fuel cell and the pipeline natural gas.
The invention sets up and changes the bypass pipeline. When the hydrogen market demand of the fuel cell is smaller, the fuel cell does not pass through the conversion unit; otherwise, the hydrogen product of the fuel cell is obtained by entering the bypass conversion unit.
The temperature swing adsorption regenerated gas sources of the invention are self-purifying gas, fuel cell hydrogen and pressure swing adsorption desorption gas, and flexible adjustment of productivity can be realized. When the hydrogen market demand of the fuel cell is particularly small or the hydrogen product of the fuel cell is not filled, the hydrogen of the fuel cell is used as the temperature swing adsorption regenerated gas, and only the pipeline natural gas product is produced at the moment; when the requirements of the hydrogen market of the fuel cell and the natural gas market of the pipeline are smaller, self-purifying gas is adopted as temperature swing adsorption regenerated gas, and at the moment, the natural gas of the pipeline has high yield and the hydrogen of the fuel cell has low yield; when the market demand of the fuel cell hydrogen is large, the pressure swing adsorption desorption gas is used as the temperature swing adsorption regeneration gas, and the pipeline natural gas and the fuel cell hydrogen can reach high productivity at the moment.
The present invention will be described in further detail with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation or be constructed and operated in a specific orientation, and thus they should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; of course, it may be mechanically or electrically connected; in addition, the connection may be direct, indirect via an intermediate medium, or communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
According to the capacity adjusting process for preparing the hydrogen and the pipeline natural gas of the fuel cell from the coke oven gas as shown in the abstract drawing, by arranging a conversion bypass pipeline, changing the source of the temperature swing adsorption regenerated gas and adjusting the flow of the methanation stripping gas, the hydrogen and carbon effective components in the coke oven gas are fully utilized, and when the hydrogen demand of the fuel cell is insufficient, the capacity of the pipeline natural gas is improved, and the economic benefit is ensured.
Example 1:
The fuel cell hydrogen of this example is not on the market, is not filled, and is used as a temperature swing adsorption regeneration gas, as shown in fig. 1.
The coke oven gas after compression and pretreatment has the temperature of 40 ℃, the pressure of 1.6MPaG, the flow rate of 20029Nm 3/h, and the molar composition of 60.69 percent of hydrogen, 10.46 percent of carbon monoxide, 2.82 percent of carbon dioxide, 19.40 percent of methane, 0.94 percent of ethylene, 0.94 percent of ethane, 3.86 percent of nitrogen, 0.42 percent of water and 0.46 percent of oxygen. Wherein each standard coke oven gas contains 6mg of tar and naphthalene, 20mg of hydrogen sulfide, 200mg of organic sulfur, 44mg of ammonia and 1200mg of benzene. The coke oven gas after pre-purification firstly enters a temperature swing adsorption unit X3, tar and naphthalene are removed to be not more than 1mg/Nm 3, and meanwhile heavy component impurities in the coke oven gas are removed. The regenerated gas of the temperature swing adsorption unit X3 is all fuel cell hydrogen prepared by the subsequent pressure swing adsorption unit X5, and is sent to a fuel pipe network after regeneration.
The purified coke oven gas from the temperature swing adsorption unit X3 enters a fine desulfurization unit X4, and is subjected to pre-hydrogenation, primary adsorption desulfurization, secondary hydrogenation and secondary adsorption desulfurization in sequence, so that the total sulfur in the coke oven gas is removed to be not more than 0.1ppmv, and then enters copper-based fine desulfurization to remove the total sulfur in the coke oven gas to be not more than 0.02ppmv, thereby meeting the purification requirement of hydrogen in a fuel cell prepared by pressure swing adsorption.
The fuel cell hydrogen of this example 1 is not on the market, but depending on the requirements of methanation pipeline natural gas on the hydrogen-carbon ratio, part of the coke oven gas is still required to remove the excess hydrogen.
The refined coke oven gas volume 19717Nm 3/h from the refined desulfurization unit X4 is divided into two streams, namely a pressure swing adsorption unit X5 and a methanation and drying unit X7. According to the requirement of subsequent methanation on the hydrogen-carbon ratio, the refined purified coke oven gas of the de-methanation and drying unit X7 is 14717Nm 3/h, and the cooled water diversion of the coke oven gas entering the pressure swing adsorption unit X5 is performed, and then the refined purified coke oven gas is 4955Nm 3/h. 2300Nm 3/h of fuel cell hydrogen obtained by pressure swing adsorption unit X5 has a molar purity of not less than 99.97%, total hydrocarbons (calculated as methane) of not more than 2ppmv, carbon monoxide of not more than 0.2ppmv, total sulfur of not more than 0.004ppmv, formaldehyde of not more than 0.01ppmv, total halogen compounds (calculated as halide) of not more than 0.05ppmv, all being used as regeneration gas for pressure swing adsorption X3. The natural gas of the pipeline requires 0.7MPaG, the desorption gas 2655Nm 3/h of the pressure swing adsorption unit X5 has the molar composition of 25.88 percent of hydrogen, 20.02 percent of carbon monoxide, 5.39 percent of carbon dioxide, 37.12 percent of methane, 3.59 percent of ethane, 7.39 percent of nitrogen and 0.6 percent of water, the pressure is increased to 1.2MPaG through the desorption gas compression unit X6, and the molar composition of the mixture with the refined coke oven gas 14717Nm 3/h is hydrogen 54.57 percent, 12.07 percent of carbon monoxide, 3.25 percent of carbon dioxide, 22.37 percent of methane, 2.16 percent of ethane, 4.46 percent of nitrogen and 1.12 percent of water, and the hydrogen-carbon ratio is 3.21, thereby meeting the condition of preparing the natural gas of the pipeline by methanation.
The natural gas 8632Nm 3/h from the methanation and drying unit X7 has the molar composition of 6.49 percent of hydrogen, 84.54 percent of methane and 8.97 percent of nitrogen, and the high-order heat value of 32.09MJ/m 3, thereby meeting the requirements of the second-class natural gas in GB17820-2018 natural gas.
Example 2
The hydrogen market of the fuel cell of this example is very small, and the pipeline natural gas market is also general, and self-purifying gas is adopted as the temperature swing adsorption regenerated gas, as shown in fig. 2.
The coke oven gas after compression and pretreatment has the temperature of 40 ℃, the pressure of 1.6MPaG, the flow rate of 20029Nm 3/h, and the molar composition of 60.69 percent of hydrogen, 10.46 percent of carbon monoxide, 2.82 percent of carbon dioxide, 19.40 percent of methane, 0.94 percent of ethylene, 0.94 percent of ethane, 3.86 percent of nitrogen, 0.42 percent of water and 0.46 percent of oxygen. Wherein each standard coke oven gas contains 6mg of tar and naphthalene, 20mg of hydrogen sulfide, 200mg of organic sulfur, 44mg of ammonia and 1200mg of benzene. The coke oven gas after pre-purification firstly enters a temperature swing adsorption unit X3, tar and naphthalene are removed to be not more than 1mg/Nm 3, and meanwhile heavy component impurities in the coke oven gas are removed. The regenerated gas of the temperature swing adsorption unit X3 adopts purified coke oven gas after the temperature swing adsorption unit X3, the gas quantity is 2000Nm 3/h, and the regenerated gas is sent to a fuel pipe network.
The purified coke oven gas from the temperature swing adsorption unit X3 enters a fine desulfurization unit X4, and is subjected to pre-hydrogenation, primary adsorption desulfurization, secondary hydrogenation and secondary adsorption desulfurization in sequence, so that the total sulfur in the coke oven gas is removed to be not more than 0.1ppmv, and then enters copper-based fine desulfurization to remove the total sulfur in the coke oven gas to be not more than 0.02ppmv, thereby meeting the purification requirement of hydrogen in a fuel cell prepared by pressure swing adsorption.
The refined purified coke oven gas quantity 17745Nm 3/h from the refined desulfurization unit X4 is divided into two streams, namely a pressure swing adsorption unit X5 and a methanation and drying unit X7. The fuel cell hydrogen market of this example 2 is very small, designed to be 2000Nm 3/h of filling, and simultaneously considers the requirement of subsequent methanation on the hydrogen-carbon ratio, the refined purified coke oven gas 13397Nm 3/h of the de-methanation and drying unit X7, and the refined purified coke oven gas 4309Nm 3/h after cooling and water diversion of the pressure swing adsorption unit X5. 2026Nm 3/h of fuel cell hydrogen obtained by pressure swing adsorption unit X5 has a molar purity of not less than 99.97%, total hydrocarbons (calculated as methane) not greater than 2ppmv, carbon monoxide not greater than 0.2ppmv, total sulfur not greater than 0.004ppmv, formaldehyde not greater than 0.01ppmv, total halogen compounds (calculated as halogen ions) not greater than 0.05ppmv, is sold after filling, and is sent to a fuel pipe network when not filled. The natural gas of the pipeline requires 0.5MPaG, the desorption gas 2283Nm 3/h of the pressure swing adsorption unit X5 has the molar composition of 25.04 percent of hydrogen, 20.25 percent of carbon monoxide, 5.45 percent of carbon dioxide, 37.54 percent of methane, 3.63 percent of ethane, 7.48 percent of nitrogen and 0.61 percent of water, the pressure is increased to 1.0MPaG through the desorption gas compression unit X6, and the molar composition of 54.70 percent of hydrogen, 12.03 percent of carbon monoxide, 3.24 percent of carbon dioxide, 22.31 percent of methane, 2.16 percent of ethane, 4.44 percent of nitrogen and 1.13 percent of water after being mixed with the refined coke oven gas 13397Nm 3/h meets the condition of preparing the natural gas of the pipeline by methanation.
The natural gas 7813Nm 3/h from the methanation and drying unit X7 has the molar composition of 7.01 percent of hydrogen, 84.07 percent of methane and 8.92 percent of nitrogen, and the high-position heat value of 31.97MJ/m 3, thereby meeting the requirements of the second-class natural gas in GB17820-2018 natural gas.
Example 3
The hydrogen market of the fuel cell of this example is good, and the pipeline natural gas market generally adopts pressure swing adsorption desorption gas as temperature swing adsorption regeneration gas, as shown in fig. 3.
The coke oven gas after compression and pretreatment has the temperature of 40 ℃, the pressure of 2.0MPaG, the flow rate of 20014Nm 3/h, and the molar composition of 60.74 percent of hydrogen, 10.47 percent of carbon monoxide, 2.82 percent of carbon dioxide, 19.42 percent of methane, 0.94 percent of ethylene, 0.94 percent of ethane, 3.87 percent of nitrogen, 0.35 percent of water and 0.46 percent of oxygen. Wherein each standard coke oven gas contains 6mg of tar and naphthalene, 20mg of hydrogen sulfide, 200mg of organic sulfur, 44mg of ammonia and 1200mg of benzene. The coke oven gas after pre-purification firstly enters a temperature swing adsorption unit X3, tar and naphthalene are removed to be not more than 1mg/Nm 3, and meanwhile heavy component impurities in the coke oven gas are removed. The regenerated gas of the temperature swing adsorption unit X3 is desorbed by the pressure swing adsorption unit X5, the gas quantity is 2000Nm 3/h, and the regenerated gas is sent to a fuel pipe network.
The purified coke oven gas from the temperature swing adsorption unit X3 enters a fine desulfurization unit X4, and is subjected to pre-hydrogenation, primary adsorption desulfurization, secondary hydrogenation and secondary adsorption desulfurization in sequence, so that the total sulfur in the coke oven gas is removed to be not more than 0.1ppmv, and then enters copper-based fine desulfurization to remove the total sulfur in the coke oven gas to be not more than 0.02ppmv, thereby meeting the purification requirement of hydrogen in a fuel cell prepared by pressure swing adsorption.
The refined coke oven gas volume 19731Nm 3/h from the refined desulfurization unit X4 is divided into two streams, namely a pressure swing adsorption unit X5 and a methanation and drying unit X7. The hydrogen yield of the fuel cell of this example 3 was designed to be about 6000Nm 3/h, while taking into account the requirements of the subsequent methanation on the hydrogen-carbon ratio, the refined coke oven gas 6689Nm 3/h of the de-methanation, drying unit X7, and the refined coke oven gas 12915Nm 3/h after cooling and water separation of the pressure swing adsorption unit X5. 6074Nm 3/h fuel cell hydrogen obtained by pressure swing adsorption unit X5 has a molar purity of not less than 99.97%, total hydrocarbons (calculated as methane) of not more than 2ppmv, carbon monoxide of not more than 0.2ppmv, total sulfur of not more than 0.004ppmv, formaldehyde of not more than 0.01ppmv, total halogen compounds (calculated as halogen ions) of not more than 0.05ppmv, is sold for filling and is sent to a fuel pipe network when not filled. The natural gas in the pipeline of the example requires a pressure of 1.0MPaG, the desorption gas 6846Nm 3/h of the pressure swing adsorption unit X5 has a molar composition of 25.04 percent of hydrogen, 20.25 percent of carbon monoxide, 5.45 percent of carbon dioxide, 37.54 percent of methane, 3.63 percent of ethane, 7.48 percent of nitrogen and 0.61 percent of water, wherein 2000Nm 3/h is used as the regeneration gas of the pressure swing adsorption unit X4, 1841Nm 3/h is used as a fuel removing pipe network, the rest 1500Nm 3/h is pressurized to 1.5MPaG through the desorption gas compression unit X6, the molar composition of the mixture after being mixed with refined coke oven gas 6689Nm 3/h is hydrogen 53.51%, carbon monoxide 12.34%, carbon dioxide 3.32%, methane 22.89%, ethane 2.21%, nitrogen 4.56%, water 1.16% and hydrogen-carbon ratio 3.06, and the conditions of preparing pipeline natural gas by methanation are satisfied.
The natural gas 4082Nm 3/h from the methanation and drying unit X7 has the molar composition of 4.62 percent of hydrogen, 85.56 percent of methane, 0.67 percent of carbon dioxide and 9.15 percent of nitrogen, and the high-position heat value of 32.24MJ/m 3, thereby meeting the requirements of the second-class natural gas in GB17820-2018 natural gas.
Example 4
In the hydrogen market of the fuel cell of this example, the pipeline natural gas market is general, a conversion unit X2 is arranged to convert carbon monoxide into hydrogen, and pressure swing adsorption desorption gas is used as temperature swing adsorption regeneration gas, as shown in fig. 3.
The coke oven gas after compression and pretreatment has the temperature of 40 ℃, the pressure of 2.0MPaG, the flow rate of 20014Nm 3/h, and the molar composition of 60.74 percent of hydrogen, 10.47 percent of carbon monoxide, 2.82 percent of carbon dioxide, 19.42 percent of methane, 0.94 percent of ethylene, 0.94 percent of ethane, 3.87 percent of nitrogen, 0.35 percent of water and 0.46 percent of oxygen. Wherein each standard coke oven gas contains 6mg of tar and naphthalene, 20mg of hydrogen sulfide, 200mg of organic sulfur, 44mg of ammonia and 1200mg of benzene. The coke oven gas enters a conversion unit X2, water vapor is supplemented at the same time, carbon monoxide is converted into hydrogen and carbon dioxide, the flow rate of the coke oven gas after conversion cooling water diversion is 21548Nm 3/h, and the molar composition is 63.93% of hydrogen, 0.49% of carbon monoxide, 11.86% of carbon dioxide, 18.03% of methane, 1.74% of ethane, 3.59% of nitrogen and 0.36% of water. The coke oven gas after pre-purification firstly enters a temperature swing adsorption unit X3, tar and naphthalene are removed to be not more than 1mg/Nm 3, and meanwhile heavy component impurities in the coke oven gas are removed. The regenerated gas of the temperature swing adsorption unit X3 is desorbed by the pressure swing adsorption unit X6, the gas quantity is 2000Nm 3/h, and the regenerated gas is sent to a fuel pipe network.
The purified coke oven gas from the temperature swing adsorption unit X3 enters a fine desulfurization unit X4, and is subjected to pre-hydrogenation, primary adsorption desulfurization, secondary hydrogenation and secondary adsorption desulfurization in sequence, so that the total sulfur in the coke oven gas is removed to be not more than 0.1ppmv, and then enters copper-based fine desulfurization to remove the total sulfur in the coke oven gas to be not more than 0.02ppmv, thereby meeting the purification requirement of hydrogen in a fuel cell prepared by pressure swing adsorption.
The refined coke oven gas volume 21545Nm 3/h from the refined desulfurization unit X4 is divided into two streams, namely a pressure swing adsorption unit X5 and a methanation and drying unit X7. The hydrogen yield of the fuel cell of this example 4 was designed to be about 6000Nm 3/h, while taking into account the requirements of the subsequent methanation on the hydrogen-carbon ratio, the refined coke oven gas 8503Nm 3/h of the de-methanation, drying unit X7, and the refined coke oven gas 13058Nm 3/h of the cooled and split water entering the pressure swing adsorption unit X5. 6503Nm 3/h of fuel cell hydrogen obtained by the pressure swing adsorption unit X5 has the molar purity of not less than 99.97%, the total hydrocarbon (calculated as methane) of not more than 2ppmv, the carbon monoxide of not more than 0.2ppmv, the total sulfur of not more than 0.004ppmv, the formaldehyde of not more than 0.01ppmv and the total halide (calculated as halide) of not more than 0.05ppmv, and is filled and sold and sent to a fuel pipe network when not filled. The natural gas in the pipeline of the example requires pressure of 1.0MPaG, the desorption gas 6556Nm 3/h of the pressure swing adsorption unit X5 has the molar composition of 25.04 percent of hydrogen, 20.25 percent of carbon monoxide, 5.45 percent of carbon dioxide, 37.54 percent of methane, 3.63 percent of ethane, 7.48 percent of nitrogen and 0.61 percent of water, wherein 2000Nm 3/h is used as regeneration gas of the pressure swing adsorption unit X4, 2806Nm 3/h is used as a fuel removing pipe network, the rest 1750Nm 3/h is pressurized to 1.5MPaG by the desorption gas compression unit X6, the molar composition of the mixture after being mixed with the refined coke oven gas 8503Nm 3/h is 57.43 percent of hydrogen, 3.82 percent of carbon monoxide, 10.76 percent of carbon dioxide, 21.29 percent of methane, 2.06 percent of ethane, 4.24 percent of nitrogen, 0.4 percent of water and 3.06 percent of hydrogen-carbon ratio, thereby meeting the condition of preparing pipeline natural gas by methanation.
The natural gas 4758Nm 3/h from the methanation and drying unit X7 has the molar composition of 4.69 percent of hydrogen, 85.48 percent of methane, 0.70 percent of carbon dioxide and 9.14 percent of nitrogen, and the high-position heat value of 32.22MJ/m 3, thereby meeting the requirements of the second-class natural gas in GB17820-2018 natural gas.
Finally, it should be noted that: the above embodiments are merely preferred embodiments of the present invention for illustrating the technical solution of the present invention, but not limiting the scope of the present invention; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; that is, even though the main design concept and spirit of the present invention is modified or finished in an insubstantial manner, the technical problem solved by the present invention is still consistent with the present invention, and all the technical problems are included in the protection scope of the present invention; in addition, the technical scheme of the invention is directly or indirectly applied to other related technical fields, and the technical scheme is included in the scope of the invention.
Claims (7)
1. The energy production regulating process for preparing fuel cell hydrogen and pipeline natural gas from coke oven gas is characterized by comprising the following steps: the compression and pretreatment unit (X1) is connected or disconnected with the conversion unit (X2) and then enters the temperature swing adsorption unit (X3);
A temperature swing adsorption unit (X3) connected with the compression and pretreatment unit (X1) or the conversion unit (X2) for removing heavy component impurities in coke oven gas, a fine desulfurization unit (X4) connected with the temperature swing adsorption unit (X3) for removing inorganic sulfur and organic sulfur in the coke oven gas, a pressure swing adsorption unit (X5) connected with the fine desulfurization unit (X4) for preparing fuel cell hydrogen, a desorption gas compression unit (X6) connected with the pressure swing adsorption unit (X5) for pressurizing desorption gas, and a methanation and drying unit (X7) connected with the desorption gas compression unit (X6) and a second fine purified gas conveying pipe (9) after being mixed with gas for converting carbon monoxide and carbon dioxide into methane;
The conversion unit (X2) is a unit which is connected with a first pre-purified gas bypass pipe (3) and a second pre-purified gas bypass pipe (4) to convert carbon monoxide into hydrogen and carbon dioxide;
the coke oven gas conveying pipe (1) is connected to the compression and pretreatment unit (X1), the third desorption gas conveying pipe (14) is connected with a fuel gas outer conveying pipe (20), the pressure swing adsorption unit (X5) is connected with a fuel cell hydrogen outer conveying pipe (10), and the methanation and drying unit (X7) is connected with a pipeline natural gas outer conveying pipe (17);
The fine desulfurization unit (X4) is connected with a fine purified gas conveying pipe (7), a first fine purified gas conveying pipe (8) for removing the pressure swing adsorption unit (X5) and a second fine purified gas conveying pipe (9) for removing the methanation and drying unit (X7) are connected to the fine purified gas conveying pipe (7), and the gas amounts of the second desorption gas conveying pipe (13), the first fine purified gas conveying pipe (8) and the second fine purified gas conveying pipe (9) are adjusted according to the capacity adjustment requirement; the purified gas in the fine desulfurization unit (X4) is sequentially subjected to pre-hydrogenation, primary adsorption desulfurization, secondary hydrogenation, secondary adsorption desulfurization and copper-based fine desulfurization, so that the total sulfur in the purified gas after the fine desulfurization unit (X4) is not more than 0.02ppmv;
The pressure swing adsorption unit (X5) is connected with a fuel cell hydrogen gas output pipe (10) and a first desorption gas output pipe (12); a second desorption gas conveying pipe (13) and a third desorption gas conveying pipe (14) are led out of the first desorption gas conveying pipe (12), the second desorption gas conveying pipe (13) is connected to the desorption gas compression unit (X6), the third desorption gas conveying pipe (14) is led out of the fuel gas outer conveying pipe (20) and the regeneration desorption gas conveying pipe (19), the regeneration desorption gas conveying pipe (19) is connected to the regeneration gas conveying pipe (21), and the desorption gas flow of the desorption gas compression unit (X6) in the second desorption gas conveying pipe (13) is adjusted according to the production capacity adjustment requirement, and meanwhile, desorption gas is selected as fuel gas or temperature swing adsorption regeneration gas.
2. The capacity adjustment process according to claim 1, characterized in that a pre-purge gas transfer pipe (2) is connected between the compression and pre-treatment unit (X1) and the temperature swing adsorption unit (X3), a first pre-purge gas bypass pipe (3) is connected at its start to the start of the flow of the pre-purge gas transfer pipe (2), and a second pre-purge gas bypass pipe (4) is connected at its end to the end of the flow of the pre-purge gas transfer pipe (2).
3. The capacity adjustment process according to claim 2, characterized in that in the direction of the gas flow, inlet valves are provided both on the pre-purge gas feed pipe (2) and at the beginning of the first pre-purge gas bypass pipe (3); when the hydrogen productivity of the fuel cell is pursued to be greater, closing an air inlet valve of the pre-purified gas conveying pipe (2), and opening an air inlet valve of the first pre-purified gas bypass pipe (3); otherwise, closing the air inlet valve of the first pre-purified gas bypass pipe (3), and opening the air inlet valve of the pre-purified gas conveying pipe (2).
4. A capacity modulation process according to claim 2 or 3, characterized in that a purge gas delivery pipe (5) is connected between the temperature swing adsorption unit (X3) and the fine desulfurization unit (X4), the temperature swing adsorption unit (X3) is provided with a regeneration gas delivery pipe (21) and a regeneration gas delivery pipe (22), the regeneration gas delivery pipe (22) being connected to the fuel gas external delivery pipe (20); the self-purification gas conveying pipe (6) is led out from the purification gas conveying pipe (5), the self-purification gas conveying pipe (6) is connected to the regenerated gas conveying pipe (21), and whether the self-purification gas is used as the temperature swing adsorption regenerated gas or not is selected according to the production capacity adjustment requirement.
5. The process according to claim 4, wherein a hydrogen regeneration pipe (11) is led out from the hydrogen outlet pipe (10) of the fuel cell, the hydrogen regeneration pipe (11) is connected to a regeneration gas pipe (21) and a hydrogen fuel pipe (18) is led out, the hydrogen fuel pipe (18) is connected to the fuel gas outlet pipe (20), and the hydrogen of the fuel cell is selected as a product gas or a fuel gas or a temperature swing adsorption regeneration gas according to the capacity adjustment and the hydrogen product filling demand.
6. The capacity adjustment process according to claim 5, characterized in that the stripping gas compression unit (X6) is connected to a stripping gas delivery pipe (15), the stripping gas delivery pipe (15) and the second fine purification gas delivery pipe (9) being connected to the methanation, drying unit (X7) by a third fine purification gas delivery pipe (16) of the methanation, drying unit (X7); the pressure at the outlet of the stripping compressor unit (X6) or the operating pressure of the methanation unit (X7) is determined according to the pressure required by the pipeline natural gas output pipe (17).
7. The capacity adjustment process according to claim 6, characterized in that the third fine purge gas transfer pipe (16) is provided with analysis points for hydrogen, carbon monoxide, carbon dioxide, and low-carbon hydrocarbon content, and the hydrogen-carbon ratio of the gas in the third fine purge gas transfer pipe (16) is obtained according to the analysis result; the hydrogen-carbon ratio of the gas in the third refined purified gas conveying pipe (16) is 3.0-3.3.
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