CN217900304U - Device for recovering argon and methane from synthetic ammonia tail gas - Google Patents
Device for recovering argon and methane from synthetic ammonia tail gas Download PDFInfo
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- CN217900304U CN217900304U CN202122971011.2U CN202122971011U CN217900304U CN 217900304 U CN217900304 U CN 217900304U CN 202122971011 U CN202122971011 U CN 202122971011U CN 217900304 U CN217900304 U CN 217900304U
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- nitrogen
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- 239000007789 gas Substances 0.000 title claims abstract description 414
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 356
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 314
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 title claims abstract description 248
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 178
- 229910052786 argon Inorganic materials 0.000 title claims abstract description 124
- JVFDADFMKQKAHW-UHFFFAOYSA-N C.[N] Chemical compound C.[N] JVFDADFMKQKAHW-UHFFFAOYSA-N 0.000 claims abstract description 216
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 92
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 313
- 229910052757 nitrogen Inorganic materials 0.000 claims description 158
- 239000007788 liquid Substances 0.000 claims description 127
- 239000001257 hydrogen Substances 0.000 claims description 93
- 229910052739 hydrogen Inorganic materials 0.000 claims description 93
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 90
- 230000015572 biosynthetic process Effects 0.000 claims description 68
- 238000003786 synthesis reaction Methods 0.000 claims description 68
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 30
- 238000010992 reflux Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 13
- 239000002826 coolant Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 3
- 230000008676 import Effects 0.000 claims 1
- 238000005057 refrigeration Methods 0.000 abstract description 32
- 238000005265 energy consumption Methods 0.000 abstract description 26
- 238000005516 engineering process Methods 0.000 abstract description 6
- PSWKVGHKABDSRC-UHFFFAOYSA-N $l^{1}-azanylmethane Chemical compound [N]C PSWKVGHKABDSRC-UHFFFAOYSA-N 0.000 description 62
- 238000000034 method Methods 0.000 description 18
- 238000001704 evaporation Methods 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 10
- -1 methyl nitride Chemical class 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000003507 refrigerant Substances 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LRMHVVPPGGOAJQ-UHFFFAOYSA-N methyl nitrate Chemical compound CO[N+]([O-])=O LRMHVVPPGGOAJQ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
- F25J3/0219—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0257—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of nitrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/028—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of noble gases
- F25J3/0285—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of noble gases of argon
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/72—Refluxing the column with at least a part of the totally condensed overhead gas
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/20—H2/N2 mixture, i.e. synthesis gas for or purge gas from ammonia synthesis
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2215/00—Processes characterised by the type or other details of the product stream
- F25J2215/04—Recovery of liquid products
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/12—External refrigeration with liquid vaporising loop
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/66—Closed external refrigeration cycle with multi component refrigerant [MCR], e.g. mixture of hydrocarbons
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The utility model discloses a retrieve device of argon and methane in follow synthetic ammonia tail gas has solved among the prior art energy consumption height, flow, cryogen ratio and the equal comparatively complicated technical problem of control that retrieve argon and methane and exist in the synthetic ammonia tail gas. The device comprises a heat exchanger, a dehydrogenation tower, a demethanizer, a denitrification tower and a precooler; a dehydrogenation tower top condenser is arranged at the upper part of the dehydrogenation tower; the upper part and the lower part of the demethanization are respectively provided with a demethanization tower top condenser and a demethanization tower bottom evaporator; the upper part and the lower part of the denitrification tower are respectively provided with a denitrification tower top condenser and a denitrification tower bottom evaporator. The utility model discloses retrieve argon and methane from synthetic ammonia tail gas by the nitrogen methane refrigeration cycle who takes the precooling and provide cold volume, the energy consumption is low, and nitrogen methane ratio is simple, easy operation, and investment and running cost are lower, and the mature easy control of precooling unit technology is maintained a little.
Description
Technical Field
The utility model relates to an argon extraction technical field in the synthetic ammonia tail gas, in particular to a device for recovering argon and methane from the synthetic ammonia tail gas by using precooled nitrogen methane refrigeration cycle.
Background
The synthesis ammonia tail gas is used as purge gas in the synthesis ammonia industry, and after purification treatment such as deamination, dehydration and the like, the main components are nitrogen, hydrogen, methane and argon, and the components change with the process conditions, wherein the general volume ratio is as follows: 4-12% of argon and 6-35% of methane.
Argon is a rare gas which is widely applied at present, can be used as a main filling gas of an incandescent lamp and a protective gas for welding and cutting metal, can also be used for extinguishing fire and replacing air to provide an argon sealing environment to avoid oxidation of articles and the like, and has higher economic value.
The existing process recovers argon and LNG from the synthesis ammonia tail gas, but when the content of methane in the synthesis ammonia tail gas is low, or the methane does not need to be liquefied into LNG for recovery, the methane can be subjected to gaseous recovery to be used as fuel gas of upstream industry.
The existing refrigeration process for recovering argon and methane from the synthesis ammonia tail gas mainly comprises nitrogen double-expansion refrigeration, mixed refrigerant and nitrogen double-refrigeration.
And (3) nitrogen double-expansion refrigeration: the refrigeration process mobile equipment comprises a low-pressure circulating nitrogen compressor, a medium-pressure circulating nitrogen compressor, a low-temperature supercharging turboexpander and a high-temperature supercharging turboexpander, and has the advantages of more devices, complex control, large maintenance workload, longer period and energy consumption which is only about 5 percent lower than that of single nitrogen expansion refrigeration.
Mixed refrigerant and nitrogen double refrigeration: the refrigeration process flow equipment comprises a mixed refrigerant circulating compressor and a medium-pressure circulating nitrogen compressor, and has less equipment, but the mixed refrigerant is more complex in proportion and control.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide a take nitrogen methane refrigeration cycle of precooling retrieves argon and methane device from synthetic ammonia tail gas to retrieve the energy consumption height that argon and methane exist among the synthetic ammonia tail gas among the solution prior art, flow, cryogen ratio and control all comparatively complicated technical problem.
In order to achieve the above purpose, the utility model provides a following technical scheme:
the utility model provides a device with precooling for recycling argon and methane from synthesis ammonia tail gas by nitrogen methane refrigeration cycle, which comprises a heat exchanger, a subcooler, a dehydrogenation tower, a demethanizer, a denitrogenation tower and a precooler; wherein,
a dehydrogenation tower top condenser is arranged at the upper part of the dehydrogenation tower;
the upper part and the lower part of the demethanizer are respectively provided with a demethanizer top condenser and a demethanizer bottom evaporator;
the upper part and the lower part of the denitrification tower are respectively provided with a denitrification tower top condenser and a denitrification tower bottom evaporator;
a synthetic ammonia tail gas channel I, a synthetic ammonia tail gas channel II, a hydrogen-rich tail gas channel I, a methane-rich gas channel I, a nitrogen-rich tail gas channel I, a azomethane forward flow channel I, an azomethane forward flow channel II, an azomethane forward flow channel III and an azomethane backflow channel I are arranged in the heat exchanger;
a hydrogen-rich tail gas channel II, a nitrogen methane backflow channel II, a nitrogen methane positive flow channel IV, a liquid argon channel and a nitrogen-rich tail gas channel II are arranged in the subcooler;
a hydrogen-rich tail gas channel III and a nitrogen methane channel I are arranged in the dehydrogenation tower top condenser;
a nitrogen-rich gas channel I and a nitrogen methane channel II are arranged in the demethanizer overhead condenser;
a nitrogen-rich gas channel II and a nitrogen methane channel III are arranged in the denitrification tower top condenser;
a synthetic ammonia tail gas channel III, a nitrogen methane positive flow channel V and a precooling medium channel are arranged in the precooler;
the heat exchanger is connected with a synthetic ammonia tail gas inlet pipe, a hydrogen-rich tail gas outlet pipe, a methane outlet pipe, a nitrogen-rich tail gas outlet pipe and a nitrogen methane circulating air inlet device; the subcooler is connected with a liquid argon outlet pipe;
the nitrogen-methane circulating gas inlet device comprises a nitrogen-methane compressor, wherein an inlet of the nitrogen-methane compressor is connected with a nitrogen-methane feeding pipe, the nitrogen-methane feeding pipe is connected with a nitrogen-methane feeding pipe and a methane feeding pipe, an outlet of the nitrogen-methane compressor is connected with a nitrogen-methane outlet pipe, an outlet of the nitrogen-methane outlet pipe is connected with an inlet of a nitrogen-methane positive flow channel I, an outlet of the nitrogen-methane positive flow channel I is connected with an inlet of a nitrogen-methane positive flow channel V, an outlet of the nitrogen-methane positive flow channel V is connected with an inlet of a nitrogen-methane positive flow channel II, and an outlet of the nitrogen-methane positive flow channel II is connected with an inlet pipe of a demethanizer tower bottom evaporator;
the inlet of the synthetic ammonia tail gas channel I is connected with a synthetic ammonia tail gas inlet pipe, the outlet of the synthetic ammonia tail gas channel I is connected with the inlet of a synthetic ammonia tail gas channel III, the outlet of the synthetic ammonia tail gas channel III is connected with the inlet of a synthetic ammonia tail gas channel II, and the outlet of the synthetic ammonia tail gas channel II is connected with the inlet at the lower part of the dehydrogenation tower;
a gas phase outlet at the top of the dehydrogenation tower is connected with an inlet of a hydrogen-rich tail gas channel II, an outlet of the hydrogen-rich tail gas channel II is connected with an inlet of a hydrogen-rich tail gas channel I, and an outlet of the hydrogen-rich tail gas channel I is connected with a hydrogen-rich tail gas outlet pipe; a hydrogen-rich gas outlet at the upper part of the dehydrogenation tower is connected with an inlet of a hydrogen-rich tail gas channel III of a condenser at the top of the dehydrogenation tower, an outlet of the hydrogen-rich tail gas channel III is connected with a reflux liquid inlet at the upper part of the dehydrogenation tower, and a liquid phase outlet at the bottom of the dehydrogenation tower is connected with a feed inlet at the middle part of the demethanizer;
the nitrogen-rich outlet of the demethanizer is connected with the inlet of a nitrogen-rich channel I of a demethanizer overhead condenser, the outlet of the nitrogen-rich channel I is connected with the reflux inlet at the upper part of the demethanizer, the methane-rich liquid outlet at the bottom of the demethanizer is connected with the inlet of the methane-rich channel I, and the outlet of the methane-rich channel I is connected with a methane outlet pipe;
the outlet of the demethanizer bottom evaporator is connected with the inlet pipe of the denitrogenation tower bottom evaporator, the outlet of the denitrogenation tower bottom evaporator is connected with the inlet of a N-methyl alkane forward flow channel III, the outlet of the N-methyl alkane forward flow channel III is respectively connected with a N-methyl alkane return flow channel I and a N-methyl alkane forward flow channel IV, and the outlet of the N-methyl alkane forward flow channel III is connected with the N-methyl alkane forward flow channel IV through a branch pipe A; the outlet of the nitrogen methane backflow channel I is connected with a nitrogen methane feeding pipe of a nitrogen methane circulating air inlet device; the outlet of the nitrogen methane forward flow channel IV is respectively connected with the inlets of a nitrogen methane channel I, a nitrogen methane channel II and a nitrogen methane channel III, the outlets of the nitrogen methane channel I, the nitrogen methane channel II and the nitrogen methane channel III are respectively connected with the inlet of a nitrogen methane return flow channel II, the outlet of the nitrogen methane return flow channel II is connected with the inlet of the nitrogen methane return flow channel I, and the outlet of the nitrogen methane return flow channel I is connected with a nitrogen methane feeding pipe of a nitrogen methane circulating air inlet device;
the nitrogen-rich outlet at the upper part of the denitrification tower is connected with the inlet of a nitrogen-rich channel II, the outlet of the nitrogen-rich channel II is connected with the reflux liquid inlet at the upper part of the denitrification tower, the nitrogen-rich outlet at the top of the denitrification tower is connected with the inlet of a nitrogen-rich tail gas channel II, the outlet of the nitrogen-rich tail gas channel II is connected with the inlet of a nitrogen-rich tail gas channel I, and the outlet of the nitrogen-rich tail gas channel I is connected with a nitrogen-rich tail gas outlet pipe;
the liquid argon outlet of the denitrification tower bottom evaporator is connected with the inlet of the liquid argon channel, and the outlet of the liquid argon channel is connected with the liquid argon outlet pipe.
Furthermore, a methane branch pipe is connected between the methane outlet pipe and the methane feeding pipe.
Furthermore, a precooling medium feeding pipe is connected to the precooling compressor, the precooling compressor is connected to the precooling medium channel through a circulating pipeline, and the precooling medium feeding pipe is connected to the circulating pipeline close to the inlet of the precooling compressor.
Further, the device also comprises a control device; the control device is respectively and electrically connected with the nitrogen methane compressor, the heat exchanger, the precooling compressor, the precooler, the subcooler, the dehydrogenation tower top condenser, the demethanizer tower bottom evaporator, the demethanizer tower top condenser, the denitrogenation tower bottom evaporator, the denitrogenation tower and the denitrogenation tower top condenser.
Furthermore, a throttle valve a for throttling and depressurizing high-pressure methyl nitride is arranged on a pipeline between the outlet of the methyl nitride positive flow channel III and the inlet of the methyl nitride return flow channel I;
an outlet of the azomethane positive flow channel IV is connected with an inlet of the azomethane channel I through a branch pipe B, an outlet of the azomethane positive flow channel IV is connected with an inlet of the azomethane channel II through a branch pipe C, and an outlet of the azomethane positive flow channel IV is connected with an inlet of the azomethane channel III through a branch pipe D; the branch pipe B, the branch pipe C and the branch pipe D are respectively provided with a throttle valve B for throttling and depressurizing the methyl nitrate;
a throttle valve c is arranged on an inlet pipeline of the precooling medium channel;
a throttling valve d is arranged on a pipeline between the outlet of the synthetic ammonia tail gas channel II and the inlet of the dehydrogenation tower;
a throttle valve e for throttling and depressurizing the hydrogen-rich tail gas is arranged between the outlet at the top of the dehydrogenation tower and the inlet of the hydrogen-rich tail gas channel II;
a throttling valve f for throttling and depressurizing the liquid at the bottom of the dehydrogenation tower is arranged on a pipeline between the liquid outlet at the bottom of the dehydrogenation tower and the inlet of the demethanizer;
a throttling valve g for throttling and depressurizing the methane-rich liquid is arranged on an inlet pipeline of the methane-rich gas channel I;
an inlet pipeline of the nitrogen-rich tail gas channel II is provided with a throttle valve h for throttling and depressurizing the nitrogen-rich tail gas;
a throttle valve i for throttling and depressurizing the precooling medium is arranged on the precooling medium feeding pipe;
the nitrogen feeding pipe and the methane feeding pipe are respectively provided with a throttle valve j for throttling and depressurizing nitrogen and methane;
a throttling valve k for throttling and depressurizing methane is arranged on the methane branch pipe;
a throttle valve l for throttling and depressurizing the liquid argon is arranged on the liquid argon outlet pipe;
the throttle valve a; a throttle valve b; a throttle valve c; a throttle valve d; a throttle valve e; a throttle valve f; a throttle valve g; a throttle valve h; and a throttle valve i; a throttle valve j; a throttle valve k; and the throttle valve l is respectively electrically connected with the control device.
Furthermore, connecting pipelines in the device are cold insulation pipelines.
The device for recovering argon and methane from the synthetic ammonia tail gas by applying the precooled nitrogen methane refrigeration cycle to recover argon and methane from the synthetic ammonia tail gas; the method specifically comprises the following steps:
s1, determining a nitrogen-methane ratio according to a synthesis ammonia tail gas component, and introducing nitrogen and methane into a nitrogen-methane feed pipe of a nitrogen-methane compressor through a nitrogen feed pipe and a methane feed pipe respectively according to the ratio;
s2, the high-pressure nitromethane gas compressed by the nitromethane compressor enters a nitromethane positive flow channel I of a heat exchanger to be initially cooled to 0-minus 30 ℃, the high-pressure nitromethane gas is discharged from the heat exchanger from the upper part after being initially cooled to be pre-cooled to-10-minus 40 ℃ and enters a nitromethane positive flow channel V of a pre-cooler, the pre-cooled high-pressure nitromethane gas returns to enter a nitromethane positive flow channel II of the heat exchanger to be continuously cooled to-80-minus 130 ℃, and then the high-pressure nitromethane gas is discharged from the heat exchanger from the middle lower part and enters a demethanizer bottom evaporator;
the high-pressure azomethane after heat exchange is discharged from a tower bottom evaporator of a demethanizer and enters a tower bottom evaporator of a denitrogenation tower, the high-pressure azomethane discharged from the tower bottom evaporator of the denitrogenation tower after heat exchange returns to a azomethane forward flow channel III entering a heat exchanger and is cooled to-140-160 ℃, the high-pressure azomethane discharged from the azomethane forward flow channel III of the heat exchanger is divided into two parts, the first part is throttled and decompressed by a throttle valve a and then enters a azomethane backflow channel I of the heat exchanger, and the second part enters a azomethane forward flow channel IV of a subcooler through a branch pipe A;
high-pressure methyl nitrogen which is subcooled to the temperature of between-170 and-180 ℃ through a methyl nitrogen normal flow channel IV of a subcooler is divided into three parts, throttled and depressurized through a throttle valve b, and then respectively enters a methyl nitrogen channel I, a methyl nitrogen channel II and a methyl nitrogen channel III of a dehydrogenation tower top condenser, a demethanizer tower top condenser and a denitrogenation tower top condenser to provide cooling capacity for the methyl nitrogen, the methyl nitrogen which is heated from the dehydrogenation tower top condenser, the demethanizer tower top condenser and the denitrogenation tower top condenser is converged and then enters a methyl nitrogen return channel II of the subcooler to provide cooling capacity for high-pressure methyl nitrogen in the methyl nitrogen normal flow channel IV of the subcooler, the methyl nitrogen which is from the methyl nitrogen return channel II of the subcooler and the methyl nitrogen which is throttled for the second time enters a methyl nitrogen return channel I of the heat exchanger, low-temperature low-pressure methyl nitrogen in the methyl nitrogen return channel I and a synthetic ammonia tail gas channel I of the heat exchanger, a synthetic ammonia tail gas and a synthetic ammonia tail gas in the synthetic ammonia tail gas channel II of the heat exchanger to repeatedly perform heat exchange from a normal-temperature methane normal-pressure heat exchanger, and a high-pressure methyl nitrogen return channel I of the methyl nitrogen compressor to provide cooling capacity for the synthetic ammonia, and a high-pressure methyl nitrogen return channel III to repeatedly perform heat exchange for the high-methane, and a high-pressure methane in the high-pressure methane compressor;
s3, a precooling medium enters an inlet pipe of a precooling compressor through a precooling medium inlet pipe, the compressed liquid-phase precooling medium is throttled and depressurized by a throttle valve c and then enters a precooler precooling medium channel, the evaporation temperature of the precooling medium is controlled to be-20 ℃ to-43 ℃, the liquid-phase low-temperature low-pressure precooling medium in the precooler precooling medium channel exchanges heat with the synthetic ammonia tail gas in a synthetic ammonia tail gas channel III in the precooler and the methyl azone in a methyl azone normal flow channel V to provide cold energy, and the gas-phase low-temperature low-pressure precooling medium discharged from the precooler enters the precooling compressor again to repeatedly perform compression cycle refrigeration;
s4, synthetic ammonia tail gas enters a synthetic ammonia tail gas channel I of a heat exchanger from a synthetic ammonia tail gas inlet pipe and is primarily cooled to 0-minus 30 ℃, the synthetic ammonia tail gas enters a synthetic ammonia tail gas channel III of a precooler after exiting the heat exchanger from the synthetic ammonia tail gas channel I and is precooled to-10-minus 40 ℃, the precooled synthetic ammonia tail gas returns to a synthetic ammonia tail gas channel II of the heat exchanger to be continuously cooled and condensed to-140-160 ℃, the synthetic ammonia tail gas exiting from the synthetic ammonia tail gas channel II of the heat exchanger enters a dehydrogenation tower after being throttled and depressurized by a throttling valve d, the synthetic ammonia tail gas is rectified and separated, hydrogen-rich gas exiting from the upper part of the dehydrogenation tower enters a hydrogen-rich tail gas channel III of a dehydrogenation tower top condenser, the hydrogen-rich tail gas channel III is cooled and condensed and returns to the top of the dehydrogenation tower, liquid is used as reflux liquid at the top of the dehydrogenation tower to be rectified, the gas exits from the top of the dehydrogenation tower and enters a hydrogen-rich tail gas channel II of a hydrogen-rich tail gas channel I after being throttled and depressurized by a throttling valve e, the hydrogen-rich tail gas from the bottom of the hydrogen-rich tail gas channel II of the subcooler enters a hydrogen-rich tail gas channel I of the heat exchanger, the hydrogen-rich tail gas channel I of the heat exchanger after being heated and reheated;
throttling and depressurizing the liquid at the bottom of the dehydrogenation tower by a throttling valve f, then feeding the liquid into a demethanizer, rectifying and separating the liquid, exchanging heat and evaporating the liquid at the bottom of the demethanizer by a bottom evaporator of the demethanizer to obtain methane-rich liquid, throttling and depressurizing the methane-rich liquid by a throttling valve g, feeding the methane-rich liquid into a methane-rich gas channel I from the bottom of a heat exchanger, and discharging the heated and reheated methane-rich gas from the top of the heat exchanger into a methane outlet pipe;
the nitrogen-rich gas discharged from the upper part of the demethanizer enters a nitrogen-rich gas channel I of a demethanizer overhead condenser, is cooled and condensed and then returns to the top of the demethanizer, the liquid is used as reflux liquid of the demethanizer overhead to participate in rectification, the gas is discharged from the top of the demethanizer to enter a denitrogenator and is rectified and separated, the nitrogen-rich gas discharged from the upper part of the denitrogenator enters a nitrogen-rich gas channel II of a denitrogenator overhead condenser, is cooled and condensed and then returns to the top of the denitrogenator, the liquid is used as reflux liquid of the denitrogenator overhead to participate in rectification, the gas is discharged from the top of the denitrogenator and enters a nitrogen-rich tail gas channel II of a subcooler after throttling and pressure reduction by a throttle valve h, the nitrogen-rich tail gas from the nitrogen-rich tail gas channel II of the subcooler enters a nitrogen-rich tail gas channel I (A5) from the bottom of a heat exchanger, and the heated and reheated nitrogen-rich tail gas enters a nitrogen-rich tail gas outlet pipe from the top of the heat exchanger;
and (3) exchanging heat and evaporating liquid at the bottom of the denitrification tower by using an evaporator at the bottom of the denitrification tower to obtain high-purity liquid argon, enabling the liquid argon to enter a liquid argon channel of the subcooler, enabling the subcooled liquid argon from the liquid argon channel of the subcooler to enter a liquid argon outlet pipe, and controlling the temperature of a liquid argon product to be-170 ℃ to-178 ℃.
Further, the purified synthesis ammonia tail gas comprises: hydrogen, nitrogen, methane and argon, wherein the molar ratio of argon to methane in the synthetic ammonia tail gas is as follows: argon: 4.0 to 12.0%, methane: 6.0 to 35 percent.
Further, the pressure of the synthetic ammonia tail gas entering the synthetic ammonia tail gas channel I of the heat exchanger is controlled to be 4.0-6.0 MPa.G;
the pressure of the low-pressure nitrogen methane gas returned from the nitrogen methane return channel I and entering the nitrogen methane compressor is controlled to be 0.1-0.25MPa.G;
the outlet pressure of the nitrogen methane compressor is controlled to be 2.0-5.0 MPa.G;
the pressure of the dehydrogenation tower is controlled to be 1.5-4.0 MPa.G;
the pressure of the demethanizer is controlled to be 0.5-1.0 MPa.G;
the pressure of the denitrification tower is controlled to be 0.5-1.0 MPa.G.
Further, the precooling medium adopts ammonia, or propane, or Freon.
Based on the technical scheme, the embodiment of the utility model provides a can produce following technological effect at least:
(1) The utility model provides a retrieve argon and methane device from synthetic ammonia tail gas, retrieve argon and methane from synthetic ammonia tail gas by the azomethane refrigeration cycle who takes the precooling and provide cold volume, the energy consumption is low, the azomethane ratio is simple, easy to operate, investment and running cost are lower, the mature easy control of precooling unit technology, the maintenance volume is few;
(2) The utility model provides a retrieve argon and methane device in follow synthetic ammonia tail gas, when retrieving argon and methane in follow synthetic ammonia tail gas, the compressor is changeable efficiently and gets 80%, and the unit energy consumption is compressor shaft power and divides by per hour technology argon product standard output, and argon product unit energy consumption 2.0 ~ 3.0kW Nm 3 And the unit energy consumption of the nitrogen expansion refrigeration process argon product is 3.5-4.7 kW/Nm 3, The energy consumption of a single machine can be reduced by at least 36.5 percent, and the cost is far lower than that of the prior art, which shows that the utility model has wide market prospect.
(3) The utility model provides a retrieve argon and methane device in follow synthetic ammonia tail gas, the precooling unit of the azomethane refrigeration cycle who takes the precooling is ammonia precooling unit, or propane precooling unit, or freon precooling unit, and precooling unit technology is mature easily to be controlled, and the maintenance volume is few; the nitrogen methane refrigeration is only provided with a nitrogen methane compressor, the refrigerant consists of nitrogen and methane, the proportion is adjusted according to the components of the tail gas of the synthetic ammonia, and the operation is simple and rapid.
Drawings
Fig. 1 is a schematic structural diagram of an embodiment of the present invention;
in the figure: 1-synthetic ammonia tail gas inlet pipe, 2-hydrogen-rich tail gas outlet pipe, 3-methane outlet pipe, 4-nitrogen-rich tail gas outlet pipe, 5-nitrogen gas inlet pipe, 6-methane inlet pipe, 7-liquid argon outlet pipe, 8-nitrogen methane compressor, 9-heat exchanger, 10-precooler, 11-precooler, 12-subcooler, 13-dehydrogenation tower, 14-dehydrogenation tower top condenser, 15-demethanizer tower bottom evaporator, 16-demethanizer, 17-demethanizer tower top condenser, 18-denitrogenizer tower bottom evaporator, 19-denitrogenator, 20-denitrogenation tower top condenser, 21-branch pipe A, 22-branch pipe B, 23-branch pipe C, 24-branch pipe D, 25-precooling medium inlet pipe and 26-methane branch pipe; 27. a throttle valve a; 28. A throttle valve b; 29. a throttle valve c; 30. a throttle valve d; 31. a throttle valve e; 32. a throttle valve f; 33. A throttle valve g; 34. a throttle valve h; 35. a throttle valve i; 36. a throttle valve j; 37. a throttle valve k; 38. A throttle valve l;
a1, a synthetic ammonia tail gas channel I; a2, a synthetic ammonia tail gas channel II; a3, a hydrogen-rich tail gas channel I; a4, a methane-rich gas channel I; a5, a nitrogen-rich tail gas channel I; a6, a nitrogen methane normal flow channel I; a7, a nitrogen methane positive flow channel II; a8, a nitrogen methane positive flow channel III; a9, a nitrogen methane backflow channel I;
b1, a hydrogen-rich tail gas channel II; b2, a nitrogen methane backflow channel II; b3, a nitrogen methane positive flow channel IV; b4, a liquid argon channel; b5, a nitrogen-rich tail gas channel II;
c1, a hydrogen-rich tail gas channel III; c2, a nitrogen methane channel I;
d1, a nitrogen-rich gas channel I; d2, a nitrogen methane channel II;
e1, a nitrogen-rich gas channel II; e2, a nitrogen methane channel III;
f1, a synthetic ammonia tail gas channel III; f2, a nitrogen methane positive flow channel V; f3, pre-cooling medium channel.
Detailed Description
Example 1:
a device with precooling for recycling argon and methane from synthesis ammonia tail gas by nitrogen methane refrigeration circulation is characterized in that: comprises a heat exchanger 9, a subcooler 12, a dehydrogenation tower 13, a demethanizer 16, a denitrogenation tower 19 and a precooler 11; wherein,
a dehydrogenation tower top condenser 14 is arranged at the upper part of the dehydrogenation tower 13;
the upper part and the lower part of the demethanizer 16 are respectively provided with a demethanizer overhead condenser 17 and a demethanizer bottom evaporator 15;
the upper part and the lower part of the denitrification tower 19 are respectively provided with a denitrification tower top condenser 20 and a denitrification tower bottom evaporator 18;
a synthesis ammonia tail gas channel IA 1, a synthesis ammonia tail gas channel IIA 2, a hydrogen-rich tail gas channel IA 3, a methane-rich gas channel IA 4, a nitrogen-rich tail gas channel IA 5, a methyl azone normal flow channel IA 6, a methyl azone normal flow channel IIA 7, a methyl azone normal flow channel IIIA 8 and a methyl azone return flow channel IA 9 are arranged in the heat exchanger 9;
a hydrogen-rich tail gas channel IIB 1, a nitrogen methane return channel IIB 2, a nitrogen methane positive flow channel IVB 3, a liquid argon channel B4 and a nitrogen-rich tail gas channel IIB 5 are arranged in the subcooler 12;
a hydrogen-rich tail gas channel IIIC 1 and a nitrogen methane channel IC 2 are arranged in the dehydrogenation tower top condenser 14;
a nitrogen-rich channel ID 1 and a nitrogen methane channel IID 2 are arranged in a condenser at the top of the demethanizer 16;
a nitrogen-rich gas channel II E1 and a nitrogen methane channel III E2 are arranged in the denitrification tower top condenser;
a synthesis ammonia tail gas channel III F1, a nitrogen methane positive flow channel V F2 and a precooling medium channel F3 are arranged in the precooler 11;
the heat exchanger 9 is connected with a synthetic ammonia tail gas inlet pipe 1, a hydrogen-rich tail gas outlet pipe 2, a methane outlet pipe 3, a nitrogen-rich tail gas outlet pipe 4 and a nitrogen methane circulating air inlet device; the subcooler (12) is connected with a liquid argon outlet pipe (7);
the nitrogen-methane circulating gas inlet device comprises a nitrogen-methane compressor 8, wherein a nitrogen-methane inlet pipe is connected to the inlet of the nitrogen-methane compressor 8, a nitrogen inlet pipe 5 and a methane inlet pipe 6 are connected to the nitrogen-methane inlet pipe, a nitrogen-methane outlet pipe is connected to the outlet of the nitrogen-methane compressor 8, the outlet of the nitrogen-methane outlet pipe is connected with the inlet of a nitrogen-methane positive flow channel IA 6, the outlet of the nitrogen-methane positive flow channel IA 6 is connected with the inlet of a nitrogen-methane positive flow channel VF 2, the outlet of the nitrogen-methane positive flow channel VF 2 is connected with the inlet of a nitrogen-methane positive flow channel IIA 7, and the outlet of the nitrogen-methane positive flow channel IIA 7 is connected with the inlet pipe of a demethanizer bottom evaporator 15;
the inlet of the synthetic ammonia tail gas channel IA 1 is connected with a synthetic ammonia tail gas inlet pipe 1, the outlet of the synthetic ammonia tail gas channel IA 1 is connected with the inlet of a synthetic ammonia tail gas channel IIIF 1, the outlet of the synthetic ammonia tail gas channel IIIF 1 is connected with the inlet of a synthetic ammonia tail gas channel IIA 2, and the outlet of the synthetic ammonia tail gas channel IIA 2 is connected with the inlet at the lower part of a dehydrogenation tower 13;
a gas phase outlet at the top of the dehydrogenation tower 13 is connected with an inlet of a hydrogen-rich tail gas channel IIB 1, an outlet of the hydrogen-rich tail gas channel IIB 1 is connected with an inlet of a hydrogen-rich tail gas channel IA 3, and an outlet of the hydrogen-rich tail gas channel IA 3 is connected with a hydrogen-rich tail gas outlet pipe 2; a hydrogen-rich gas outlet at the upper part of the dehydrogenation tower 13 is connected with an inlet of a hydrogen-rich tail gas channel IIIC 1 of a dehydrogenation tower top condenser 14, an outlet of the hydrogen-rich tail gas channel IIIC 1 is connected with a reflux liquid inlet at the upper part of the dehydrogenation tower 13, and a liquid phase outlet at the bottom of the dehydrogenation tower 13 is connected with a feed inlet at the middle part of a demethanizer 16;
the nitrogen-rich outlet of the demethanizer 16 is connected with the inlet of a nitrogen-rich channel ID 1 of a demethanizer overhead condenser 17, the outlet of the nitrogen-rich channel ID 1 is connected with the reflux inlet at the upper part of the demethanizer 16, the methane-rich liquid outlet at the bottom of the demethanizer 16 is connected with the inlet of a methane-rich channel IA 4, and the outlet of the methane-rich channel IA 4 is connected with a methane outlet pipe 3;
an outlet of a demethanizer bottom evaporator 15 is connected with an inlet pipe of a denitrogenation tower bottom evaporator 18, an outlet of the denitrogenation tower bottom evaporator 18 is connected with an inlet of a N-methyl alkane positive flow channel IIIA 8, an outlet of the N-methyl alkane positive flow channel IIIA 8 is respectively connected with a N-methyl alkane return flow channel IA 9 and a N-methyl alkane positive flow channel IVB 3, and an outlet of the N-methyl alkane positive flow channel IIIA 8 is connected with the N-methyl alkane positive flow channel IVB 3 through a branch pipe A21; the outlet of the nitrogen methane backflow channel IA 9 is connected with a nitrogen methane feeding pipe of a nitrogen methane circulating air inlet device; the outlet of the azomethane forward flow channel IVB 3 is respectively connected with the inlets of a azomethane channel IC 2, an azomethane channel IID 2 and an azomethane channel IIIE 2, the outlets of the azomethane channel IC 2, the azomethane channel IID 2 and the azomethane channel IIIE 2 are respectively connected with the inlet of an azomethane return flow channel IIB 2, the outlet of the azomethane return flow channel IIB 2 is connected with the inlet of an azomethane return flow channel IA 9, and the outlet of the azomethane return flow channel IA 9 is connected with a azomethane feeding pipe of an azomethane circulating air inlet device;
a nitrogen-rich gas outlet in the upper part of the denitrification tower 19 is connected with an inlet of a nitrogen-rich gas channel II E1, an outlet of the nitrogen-rich gas channel II E1 is connected with a reflux liquid inlet in the upper part of the denitrification tower, a nitrogen-rich gas outlet in the top part of the denitrification tower 19 is connected with an inlet of a nitrogen-rich tail gas channel II B5, an outlet of the nitrogen-rich tail gas channel II B5 is connected with an inlet of a nitrogen-rich tail gas channel IA 5, and an outlet of the nitrogen-rich tail gas channel IA 5 is connected with a nitrogen-rich tail gas outlet pipe 4;
the liquid argon outlet of the denitrification tower bottom evaporator 18 is connected with the inlet of a liquid argon channel B4, and the outlet of the liquid argon channel B4 is connected with a liquid argon outlet pipe 7.
The utility model provides a take precooling's nitrogen methane refrigeration cycle to retrieve argon and methane device from synthetic ammonia tail gas, the utility model discloses retrieve argon and methane from synthetic ammonia tail gas by taking precooling's nitrogen methane refrigeration cycle and provide cold volume, the energy consumption is low, nitrogen methane ratio is simple, easy operation, investment and running cost are lower, the mature easy control of precooling unit technology, the maintenance volume is few; the utility model provides a take precooling's nitrogen methane refrigeration cycle to retrieve argon and methane device from synthetic ammonia tail gas, when retrieving argon and methane in the synthetic ammonia tail gas, 80% are got to the compressor changeable efficiency, and the unit energy consumption is compressor shaft power and divides by per hour technology argon product standard side output, and argon product unit energy consumption 2.0 ~ 3.0kW Nm 3 And the unit energy consumption of the nitrogen expansion refrigeration process argon product is 3.5-4.7 kW/Nm 3, The energy consumption of the single machine can be reduced by at least 36.5 percent, and the cost is far lower than that of the prior art, which shows that the utility model has wide market prospect.
In an alternative embodiment, a methane branch pipe 26 is connected between the methane outlet pipe 3 and the methane feeding pipe 6.
As an optional embodiment, a pre-cooling medium feeding pipe 25 is connected to the pre-cooling compressor 10, the pre-cooling compressor 10 is connected to the pre-cooling medium channel F3 through a circulation pipe, and the pre-cooling medium feeding pipe 25 is connected to the circulation pipe near an inlet of the pre-cooling compressor 10.
As an optional embodiment, the device further comprises a control device; the control device is respectively electrically connected with a nitrogen methane compressor 8, a heat exchanger 9, a pre-cooling compressor 10, a pre-cooler 11, a subcooler 12, a dehydrogenation tower 13, a dehydrogenation tower top condenser 14, a demethanizer tower bottom evaporator 15, a demethanizer 16, a demethanizer tower top condenser 17, a denitrification tower bottom evaporator 18, a denitrification tower 19 and a denitrification tower top condenser 20.
As an optional embodiment, a throttling valve a27 for throttling and depressurizing the high-pressure nitrogen methane is arranged on a pipeline between the outlet of the nitrogen methane normal flow channel IIIA 8 and the inlet of the nitrogen methane return flow channel IA 9;
the outlet of the azomethane positive flow channel IVB 3 is connected with the inlet of the azomethane channel IC 2 through a branch pipe B22, the outlet of the azomethane positive flow channel IVB 3 is connected with the inlet of the azomethane channel IID 2 through a branch pipe C23, and the outlet of the azomethane positive flow channel IVB 3 is connected with the inlet of the azomethane channel IIIE 2 through a branch pipe D24; the branch pipe B22, the branch pipe C23 and the branch pipe D24 are respectively provided with a throttle valve B28 for reducing the flow and pressure of the nitrogen methane, and the circulating amount of the nitrogen methane is adjusted by adjusting the opening of the throttle valve B28, so that the pressure and the temperature of each point of the nitrogen methane system are in a correct range;
a throttle valve c29 is arranged on an inlet pipeline of the precooling medium channel F3;
a throttle valve d30 is arranged on a pipeline between the outlet of the synthetic ammonia tail gas channel IIA 2 and the inlet of the dehydrogenation tower 13;
a throttle valve e31 for throttling and depressurizing the hydrogen-rich tail gas is arranged between the outlet at the top of the dehydrogenation tower 13 and the inlet of the hydrogen-rich tail gas channel IIB 1;
a throttle valve f32 for throttling and depressurizing the liquid at the bottom of the dehydrogenation tower 13 is arranged on a pipeline between the liquid outlet at the bottom of the dehydrogenation tower 13 and the inlet of the demethanizer 16;
a throttling valve g33 for throttling and depressurizing methane-rich liquid is arranged on an inlet pipeline of the methane-rich gas channel IA 4;
a throttle valve h34 for throttling and depressurizing the nitrogen-rich tail gas is arranged on an inlet pipeline of the nitrogen-rich tail gas channel IIB 5;
a throttle valve i35 for throttling and depressurizing the precooling medium is arranged on the precooling medium feeding pipe 25;
throttle valves j36 for throttling and depressurizing nitrogen and methane are respectively arranged on the nitrogen feeding pipe 5 and the methane feeding pipe 6;
a throttle valve k37 for throttling and depressurizing methane is arranged on the methane branch pipe 26;
a throttle valve l38 for throttling and depressurizing the liquid argon is arranged on the liquid argon outlet pipe 7;
the throttle valve a27; a throttle valve b28; throttle valve c29; throttle valve d30; throttle valve e31; a throttle f32; throttle valve g33; a throttle valve h34; a throttle valve i35; throttle j36; throttle valve k37; the throttle valves l38 are electrically connected to the control device, respectively.
As an alternative embodiment, the connecting pipelines in the device are cold insulation pipelines.
Application example 1:
the device for recovering argon and methane from the synthetic ammonia tail gas by using the pre-cooled nitrogen methane refrigeration cycle in the embodiment 1 is used for recovering argon and methane from the synthetic ammonia tail gas; the method specifically comprises the following steps:
s1, the synthetic ammonia tail gas purified according to the components of the synthetic ammonia tail gas comprises the following components: the molar ratio of the nitrogen to the methane is determined by hydrogen, nitrogen, methane and argon as follows: methane: 30%, nitrogen gas: 70 percent, then respectively introducing nitrogen and methane into a nitrogen methane feed pipe of a nitrogen methane compressor 8 through a nitrogen feed pipe 5 and a methane feed pipe 6 according to the mixture ratio,
when the purified synthesis ammonia tail gas component changes, the nitrogen methane ratio deviates from the design value, the nitrogen methane ratio needs to be determined again according to the changed synthesis ammonia tail gas component, and nitrogen and methane needing to be supplemented are introduced into an inlet pipe of a nitrogen methane compressor 8 through a nitrogen inlet pipe 5, a methane inlet pipe 6 or a methane branch pipe 26;
s2, the high-pressure nitromethane gas compressed by the nitromethane compressor 8 enters a nitromethane positive flow channel IA 6 of a heat exchanger 9 and is primarily cooled to minus 10 ℃, the outlet pressure of the nitromethane compressor 8 is controlled to be 4.0MPa.G, the high-pressure nitromethane gas after primary cooling is discharged from the heat exchanger 9 from the upper part and enters a nitromethane positive flow channel V F2 of a precooler 11 and is precooled to minus 15 ℃, the high-pressure nitromethane gas after precooling returns to enter a nitromethane positive flow channel IIA 7 of the heat exchanger 9 and is continuously cooled to minus 86 ℃, and then the high-pressure nitromethane gas is discharged from the heat exchanger 9 from the middle lower part and enters a demethanizer tower bottom evaporator 15;
the high-pressure azomethane after heat exchange is discharged from a tower bottom evaporator 15 of the de-methanization tower, enters a tower bottom evaporator 18 of the de-nitrification tower, is cooled to minus 131 ℃, then is discharged from the tower bottom evaporator 18 of the de-methanization tower, returns to enter a azomethane positive flow channel IIIA 8 of a heat exchanger 9, is cooled to minus 160 ℃, the high-pressure azomethane discharged from the azomethane positive flow channel IIIA 8 of the heat exchanger 9 is divided into two strands, the first strand is throttled and depressurized by a throttle valve a27 and then enters a azomethane return channel IA 9 of the heat exchanger 9, and the second strand enters a nitrogen methane positive flow channel IVB 3 of a subcooler 12;
high-pressure methyl nitrogen is subcooled to minus 173 ℃ through a methyl nitrogen normal flow channel IVB 3 of a subcooler 12, the methyl nitrogen flows out of a methyl nitrogen normal flow channel IVB 3 and respectively enters a dehydrogenation tower top condenser 14, a demethanizer tower top condenser 17 and a methyl nitrogen channel IC 2, a methyl nitrogen channel IID 2 and a methyl nitrogen channel IIIE 2 of a denitrification tower top condenser 20 after being throttled and depressurized through a throttle valve B28, the methyl nitrogen heated from the dehydrogenation tower top condenser 14, the demethanizer tower top condenser 17 and the denitrification tower top condenser 20 is converged and then enters a methyl nitrogen return channel IIB 2 of the subcooler 12, cold is provided for the high-pressure methyl nitrogen in the methyl nitrogen normal flow channel IVB 3 of the subcooler 12, the methyl nitrogen from the methyl nitrogen return channel IIB 2 of the subcooler 12 and the methyl nitrogen heated by the first throttle flow channel are converged and then enter a methyl nitrogen return channel IA 9 of a heat exchanger, the low-pressure methyl nitrogen I methane in the methyl nitrogen return channel IA 9 and the low-pressure ammonia synthesis tail gas channel I1 of the methyl nitrogen tail gas channel IA heat exchanger I, the methyl nitrogen and the normal-pressure ammonia synthesis gas flow channel III are repeatedly compressed and the high-pressure methane return channel III, the high-pressure ammonia synthesis gas flow channel III, the high-pressure methane return channel III is controlled by a high-pressure ammonia synthesis gas compressor I8A 9, the normal-pressure methane return channel III, the normal-pressure methane-pressure ammonia synthesis gas compressor I8A-pressure methane return channel III, the high-pressure methane-pressure ammonia synthesis gas compressor I8A-pressure ammonia synthesis gas compressor I and the normal-pressure methane return channel III;
s3, adopting ammonia as a precooling medium, enabling the precooling medium to enter an inlet pipe of a precooling compressor 10 through a precooling medium feed pipe 25, throttling and depressurizing the compressed liquid-phase precooling medium through a throttling valve c29, then enabling the liquid-phase precooling medium to enter a precooling medium channel F3 of a precooler 11, controlling the evaporation temperature of the precooling medium to be-20 ℃, enabling the liquid-phase low-temperature low-pressure precooling medium in the precooling medium channel F3 of the precooler 11 to exchange heat with the synthetic ammonia tail gas in a synthetic ammonia tail gas channel III F1 in the precooler 11 and the methyl-amine in a methyl-amine normal flow channel V F2 and providing cold energy, and enabling the gas-phase low-temperature low-pressure precooling medium discharged from the precooler 11 to enter the precooling compressor 10 again to be repeatedly subjected to compression cycle refrigeration;
s4, the pressure of the purified synthesis ammonia tail gas is 6.0MPa.G, the synthesis ammonia tail gas enters a synthesis ammonia tail gas channel IA 1 of a heat exchanger 9 from a synthesis ammonia tail gas inlet pipe 1 and is primarily cooled to-10 ℃, the synthesis ammonia tail gas enters a synthesis ammonia tail gas channel IIIF 1 of a precooler 11 after exiting the heat exchanger 9 from the synthesis ammonia tail gas channel IA 1 and is precooled to-15 ℃, the synthesis ammonia tail gas after precooling returns to a synthesis ammonia tail gas channel IIA 2 of the heat exchanger 9 and is continuously cooled and condensed to-155 ℃, the synthesis ammonia tail gas exiting a synthesis ammonia tail gas channel IIA 2 of the heat exchanger 9 enters a dehydrogenation tower 13 after being throttled and depressurized by a throttle valve d30, the pressure of the dehydrogenation tower 0.0 MPa.G, after rectification separation, hydrogen-rich gas from the upper part of the dehydrogenation tower 13 enters a hydrogen-rich tail gas channel IIIC 1 of a dehydrogenation tower top condenser 14, is cooled and condensed and then returns to the top of the dehydrogenation tower 13, liquid is used as reflux liquid at the top of the dehydrogenation tower 13 to participate in rectification, gas is discharged from the top of the dehydrogenation tower 13, is throttled and depressurized by a throttle valve e 31-2.55MPa G and then enters a hydrogen-rich tail gas channel IIB 1 of a subcooler 12, hydrogen-rich tail gas from the hydrogen-rich tail gas channel IIB 1 of the subcooler 12 enters a hydrogen-rich tail gas channel IA 3 from the bottom of a heat exchanger 9, and the hydrogen-rich tail gas after being heated and reheated is discharged from a hydrogen-rich tail gas channel IA 3 of the heat exchanger 9 and enters a hydrogen-rich tail gas outlet pipe 2;
the liquid at the bottom of the dehydrogenation tower 13 enters a demethanizer 16 after being throttled and depressurized by a throttle valve f32, the pressure of the demethanizer 16 is controlled at 0.8MPa.G, the liquid is rectified and separated, the liquid at the bottom of the demethanizer 16 enters a methane-rich liquid after being subjected to heat exchange and evaporation by a demethanizer bottom evaporator 15, the methane-rich liquid enters a methane-rich gas channel IA 4 from the bottom of a heat exchanger 9 after being throttled and depressurized by a throttle valve g33, and the heated and reheated methane-rich gas flows out of the top of the heat exchanger 9 and enters a methane outlet pipe 3;
the nitrogen-rich gas discharged from the upper part of the demethanizer 16 enters a nitrogen-rich gas channel ID 1 of a demethanizer overhead condenser 17, the cooled and condensed nitrogen-rich gas returns to the top of the demethanizer 16, the liquid is taken as the tower top reflux liquid of the demethanizer 16 to participate in rectification, the gas is discharged from the top of the demethanizer 16 to enter a denitrification tower 19, the pressure of the denitrification tower 19 is controlled to be 0.7MPa.G, the rectification separation is carried out, the nitrogen-rich gas discharged from the top of the denitrification tower 19 enters a nitrogen-rich gas channel II E1 of a denitrification tower overhead condenser 20, the cooled and condensed nitrogen-rich gas returns to the top of the denitrification tower 19, the liquid is taken as the tower top reflux liquid of the denitrification tower 19 to participate in rectification, the gas is discharged from the top of the denitrification tower 19, throttled and reduced pressure to be 0.3MPa.G through a throttle valve h34 and enters a nitrogen-rich tail gas channel II B5 of a subcooler 12, the nitrogen-rich tail gas channel II B5 from the bottom of a heat exchanger 9 enters a nitrogen-rich tail gas channel IA 5, and the heated and the nitrogen-rich tail gas outlet pipe 4 from the top of the heat exchanger 9 after being reheated and reheated;
liquid at the bottom of the denitrification tower 19 is subjected to heat exchange and evaporation through a denitrification tower bottom evaporator 18 to obtain high-purity liquid argon, the liquid argon enters a liquid argon channel B4 of the subcooler 12, the subcooled liquid argon from the liquid argon channel B4 of the subcooler 12 enters a liquid argon outlet pipe 7, and the temperature of a liquid argon product is controlled to be-175 ℃.
In the present application example, the mole percentages of the components in the synthesis ammonia tail gas and the mole percentages of the components in the obtained hydrogen-rich tail gas, methane, nitrogen-rich tail gas and liquid argon are shown in table 1 below:
TABLE 1 component mol percents
| Argon gas | Methane | Nitrogen gas | Hydrogen gas | |
| Synthetic ammonia tail gas | 8.1495％ | 13.2180％ | 56.1022％ | 22.5303％ |
| Hydrogen rich tail gas | 1.5000％ | 0.0019％ | 32.1342％ | 66.3640％ |
| Methane | 1.0000％ | 98.9431％ | 0.0569％ | - |
| Nitrogen rich tail gas | 1.4997％ | - | 87.7719％ | 10.7284％ |
| Liquid argon component | 99.9994％ | 0.0001％ | 0.0005％ | - |
The variable efficiency of the compressor is 80%, and the single-machine energy consumption is the shaft power of the compressor divided by the standard output of the process argon product per hour; in the application example, the single machine energy consumption of the process argon product is 2.524kW/Nm 3 And the single-machine energy consumption of the argon product in the nitrogen expansion refrigeration process is 4.642kW/Nm 3, And the energy consumption of a single machine is reduced by 45.4 percent.
Application example 2:
the device for recovering argon and methane from the synthesis ammonia tail gas by using the pre-cooled nitrogen methane refrigeration cycle in the embodiment 1 is used for recovering argon and methane from the synthesis ammonia tail gas; the method specifically comprises the following steps:
s1, the synthetic ammonia tail gas purified according to the components of the synthetic ammonia tail gas comprises the following components: the molar ratio of the nitrogen to the methane is determined by hydrogen, nitrogen, methane and argon as follows: methane: 33%, nitrogen gas: 67 percent, then respectively introducing nitrogen and methane into a nitrogen methane feeding pipe of a nitrogen methane compressor 8 through a nitrogen feeding pipe 5 and a methane feeding pipe 6 according to the mixture ratio,
when the purified synthesis ammonia tail gas component changes, the nitrogen methane ratio deviates from the design value, the nitrogen methane ratio needs to be determined again according to the changed synthesis ammonia tail gas component, and nitrogen and methane needing to be supplemented are introduced into an inlet pipe of a nitrogen methane compressor 8 through a nitrogen inlet pipe 5, a methane inlet pipe 6 or a methane branch pipe 26;
s2, the high-pressure nitromethane gas compressed by the nitromethane compressor 8 enters a nitromethane positive flow channel IA 6 of a heat exchanger 9 and is primarily cooled to-29 ℃, the outlet pressure of the nitromethane compressor 8 is controlled to be 3.42MPa.G, the high-pressure nitromethane gas after primary cooling is discharged from the heat exchanger 9 from the upper part and enters a nitromethane positive flow channel V F2 of a precooler 11 and is precooled to-38 ℃, the high-pressure nitromethane gas after precooling returns to enter a nitromethane positive flow channel IIA 7 of the heat exchanger 9 and is continuously cooled to-103 ℃, and then the high-pressure nitromethane gas is discharged from the heat exchanger 9 from the middle lower part and enters a demethanizer tower bottom evaporator 15;
the high-pressure nitrogen methane after heat exchange is discharged from a methane removal tower bottom evaporator 15 and enters a nitrogen removal tower bottom evaporator 18, the high-pressure nitrogen methane is discharged from the nitrogen removal tower bottom evaporator 18 after being cooled to-131 ℃, returns to enter a nitrogen methane positive flow channel IIIA 8 of a heat exchanger 9 and is cooled to-160 ℃, the high-pressure nitrogen methane discharged from the nitrogen methane positive flow channel IIIA 8 of the heat exchanger 9 is divided into two strands, the first strand is throttled and depressurized by a throttle valve a27 and then enters a nitrogen methane backflow channel IA 9 of the heat exchanger 9, and the second strand enters a subcooler 12 nitrogen methane positive flow channel IVB 3;
high-pressure methyl nitrogen which is subcooled to minus 175 ℃ through a methyl nitrogen positive flow channel IV B3 of a subcooler 12 is divided into three parts from the methyl nitrogen positive flow channel IV B3, the three parts are throttled and depressurized through a throttle valve B28 and then respectively enter a dehydrogenation tower top condenser 14, a demethanizer tower top condenser 17 and a methyl nitrogen channel IC 2, a methyl nitrogen channel IID 2 and a methyl nitrogen channel III E2 of a denitrification tower top condenser 20 to provide cold energy for the methyl nitrogen, the heated methyl nitrogen from the dehydrogenation tower top condenser 14, the demethanizer tower top condenser 17 and the denitrification tower top condenser 20 is converged and then enters a methyl nitrogen reflux channel II B2 of the subcooler 12 to provide cold energy for the high-pressure methyl nitrogen in the methyl nitrogen positive flow channel IV B3 of the subcooler 12, the nitrogen methane from the nitrogen methane return channel IIB 2 of the subcooler 12 and the first throttled nitrogen methane are converged together and enter a nitrogen methane return channel IA 9 of the heat exchanger 9, the low-temperature low-pressure nitrogen methane in the nitrogen methane return channel IA 9 and the synthesis ammonia tail gas channel IA 1 of the heat exchanger 9, the synthesis ammonia tail gas in the synthesis ammonia tail gas channel IIA 2 and the high-pressure nitrogen methane gas in the nitrogen methane positive flow channel IA 6, the nitrogen methane positive flow channel IIA 7 and the nitrogen methane positive flow channel IIIA 8 exchange heat to provide cold energy for the synthesis ammonia tail gas and the high-pressure nitrogen methane gas, the normal-temperature low-pressure nitrogen methane flowing out of the nitrogen methane return channel IA 9 of the heat exchanger 9 enters the nitrogen methane compressor 8 again to perform compression cycle refrigeration, and the pressure of the low-pressure nitrogen methane gas flowing back from the nitrogen methane return channel IA 9 of the nitrogen methane compressor 8 is controlled to be 0.16MPa.G;
s3, adopting propane as a precooling medium, enabling the precooling medium to enter an inlet pipe of a precooling compressor 10 through a precooling medium feed pipe 25, enabling the compressed liquid-phase precooling medium to be throttled and depressurized through a throttle valve c29 and then enter a precooling medium channel F3 of a precooler 11, controlling the evaporation temperature of the precooling medium to be-42 ℃, enabling the liquid-phase low-temperature low-pressure precooling medium in the precooling medium channel F3 of the precooler 11 to exchange heat with the synthetic ammonia tail gas in a synthetic ammonia tail gas channel III F1 in the precooler 11 and the methyl-nitrogen in a methyl-nitrogen positive flow channel V F2 and providing cold energy, and enabling the gas-phase low-temperature low-pressure precooling medium discharged from the precooler 11 to enter the precooler compressor 10 again to be compressed and cyclically refrigerated in such a way;
s4, the pressure of the purified synthetic ammonia tail gas is 5.0MPa.G, the synthetic ammonia tail gas enters a synthetic ammonia tail gas channel IA 1 of a heat exchanger 9 from a synthetic ammonia tail gas inlet pipe 1 and is primarily cooled to-29 ℃, the synthetic ammonia tail gas enters a synthetic ammonia tail gas channel IIIF 1 of a precooler 11 after exiting the heat exchanger 9 from the synthetic ammonia tail gas channel IA 1 and is precooled to-38 ℃, the precooled synthetic ammonia tail gas returns to a synthetic ammonia tail gas channel IIA 2 of the heat exchanger 9 and is continuously cooled and condensed to-160 ℃, the synthetic ammonia tail gas exiting the synthetic ammonia tail gas channel IIA 2 of the heat exchanger 9 enters a dehydrogenation tower 13 after being throttled and depressurized by a throttle valve d30, the pressure of the dehydrogenation tower 13 is controlled to be 3.4MPa.G, after rectification separation, hydrogen-rich gas from the upper part of the dehydrogenation tower 13 enters a hydrogen-rich tail gas channel IIIC 1 of a dehydrogenation tower top condenser 14, is cooled and condensed and then returns to the top of the dehydrogenation tower 13, liquid is used as reflux liquid at the top of the dehydrogenation tower 13 to participate in rectification, gas is discharged from the top of the dehydrogenation tower 13, is throttled and depressurized by a throttle valve e 31-2.55MPa G and then enters a hydrogen-rich tail gas channel IIB 1 of a subcooler 12, hydrogen-rich tail gas from the hydrogen-rich tail gas channel IIB 1 of the subcooler 12 enters a hydrogen-rich tail gas channel IA 3 from the bottom of a heat exchanger 9, and the hydrogen-rich tail gas after being heated and reheated is discharged from a hydrogen-rich tail gas channel IA 3 of the heat exchanger 9 and enters a hydrogen-rich tail gas outlet pipe 2;
the liquid at the bottom of the dehydrogenation tower 13 enters a demethanizer 16 after being throttled and depressurized by a throttle valve f32, the pressure of the demethanizer 16 is controlled at 0.7MPa.G, the liquid is rectified and separated, the liquid at the bottom of the demethanizer 16 enters a methane-rich liquid after being subjected to heat exchange and evaporation by a demethanizer bottom evaporator 15, the methane-rich liquid enters a methane-rich gas channel IA 4 from the bottom of a heat exchanger 9 after being throttled and depressurized by a throttle valve g33, and the heated and reheated methane-rich gas enters a methane outlet pipe 3 from the top of the heat exchanger 9;
the nitrogen-rich gas from the upper part of the demethanizer 16 enters a nitrogen-rich gas channel ID 1 of a demethanizer overhead condenser 17, is cooled and condensed and then returns to the top of the demethanizer 16, the liquid is used as reflux liquid at the top of the demethanizer 16 to participate in rectification, the gas is discharged from the top of the demethanizer 16 to enter a denitrogenation tower 19, the pressure of the denitrogenation tower 19 is controlled at 0.66MPa.G, after rectification and separation, the nitrogen-rich gas from the upper part of the denitrogenation tower 19 enters a nitrogen-rich gas channel II E1 of a denitrogenation tower overhead condenser 20, is cooled and condensed and then returns to the top of the denitrogenation tower 19, the liquid is used as reflux liquid at the top of the denitrogenation tower 19 to participate in rectification, the gas is discharged from the top of the denitrogenation tower 19, is throttled and reduced to 0.3MPa.G by a throttle valve h34 and then enters a nitrogen-rich tail gas channel II B5 of a subcooler 12, the nitrogen-rich tail gas from the bottom of a nitrogen-rich tail gas channel II B5 of a heat exchanger 9 enters an I A5, and the heated and the warmed and reheated tail gas exits from the top of the heat exchanger 9 and enters a nitrogen-rich tail gas outlet pipe 4;
liquid at the bottom of the denitrification tower 19 is subjected to heat exchange and evaporation through a denitrification tower bottom evaporator 18 to obtain high-purity liquid argon, the liquid argon enters a liquid argon channel B4 of the subcooler 12, the subcooled liquid argon from the liquid argon channel B4 of the subcooler 12 enters a liquid argon outlet pipe 7, and the temperature of a liquid argon product is controlled to be-175 ℃.
In the present application example, the mole percentages of the components in the synthesis ammonia tail gas and the mole percentages of the components in the obtained hydrogen-rich tail gas, methane, nitrogen-rich tail gas and liquid argon are shown in table 2 below:
TABLE 2 component mol percents
| Argon gas | Methane | Nitrogen gas | Hydrogen gas | |
| Synthetic ammonia tail gas | 12.0％ | 8.0％ | 50.0％ | 30.0％ |
| Hydrogen-rich tail gas | 1.5000％ | 0.0002％ | 25.4854％ | 73.0144％ |
| Methane | 1.0000％ | 98.9700％ | 0.0300％ | - |
| Nitrogen rich tail gas | 1.5021％ | - | 88.2579％ | 10.2400％ |
| Liquid argon component | 99.9994％ | 0.0001％ | 0.0005％ | - |
The variable efficiency of the compressor is 80%, and the single-machine energy consumption is the shaft power of the compressor divided by the standard output of the process argon product per hour; in the application example, the single machine energy consumption of the argon product is 2.242kW/Nm 3 The unit energy consumption of the nitrogen expansion refrigeration process argon product is 3.528kW/Nm 3, And the energy consumption of a single machine is reduced by 36.5 percent.
Application example 3:
the device for recovering argon and methane from the synthesis ammonia tail gas by using the pre-cooled nitrogen methane refrigeration cycle in the embodiment 1 is used for recovering argon and methane from the synthesis ammonia tail gas; the method specifically comprises the following steps:
s1, the synthetic ammonia tail gas purified according to the components of the synthetic ammonia tail gas comprises the following components: the molar ratio of the nitrogen to the methane is determined by hydrogen, nitrogen, methane and argon as follows: methane: 35% and nitrogen: 65 percent, then respectively introducing nitrogen and methane into a nitrogen methane feed pipe of a nitrogen methane compressor 8 through a nitrogen feed pipe 5 and a methane feed pipe 6 according to the mixture ratio,
when the purified synthesis ammonia tail gas component changes, the nitrogen methane ratio deviates from the design value, the nitrogen methane ratio needs to be determined again according to the changed synthesis ammonia tail gas component, and nitrogen and methane needing to be supplemented are introduced into an inlet pipe of a nitrogen methane compressor 8 through a nitrogen inlet pipe 5, a methane inlet pipe 6 or a methane branch pipe 26;
s2, the high-pressure nitrogen-methane gas compressed by the nitrogen-methane compressor 8 enters a nitrogen-methane positive flow channel IA 6 of a heat exchanger 9 and is primarily cooled to-30 ℃, the outlet pressure of the nitrogen-methane compressor 8 is controlled to be 2.62MPa.G, the high-pressure nitrogen-methane gas after primary cooling is discharged from the heat exchanger 9 from the upper part and enters a nitrogen-methane positive flow channel V F2 of a precooler 11 and is precooled to-38 ℃, the high-pressure nitrogen-methane gas after precooling returns to enter a nitrogen-methane positive flow channel IIA 7 of the heat exchanger 9 and is continuously cooled to-121 ℃, and then the high-pressure nitrogen-methane gas is discharged from the heat exchanger 9 from the middle lower part and enters a demethanizer tower bottom evaporator 15;
the high-pressure nitrogen methane after heat exchange is discharged from a methane removing tower bottom evaporator 15 and enters a nitrogen removing tower bottom evaporator 18, the high-pressure nitrogen methane is discharged from the nitrogen removing tower bottom evaporator 18 after being cooled to-136 ℃, returns to enter a nitrogen methane positive flow channel IIIA 8 of a heat exchanger 9 and is cooled to-150 ℃, the high-pressure nitrogen methane discharged from the nitrogen methane positive flow channel IIIA 8 of the heat exchanger 9 is divided into two strands, the first strand is throttled and depressurized by a throttle valve a27 and then enters a nitrogen methane backflow channel IA 9 of the heat exchanger 9, and the second strand enters a subcooler 12 nitrogen methane positive flow channel IVB 3;
high-pressure methyl nitrogen which is subcooled to minus 178 ℃ through a methyl nitrogen positive flow channel IV B3 of a subcooler 12 is divided into three parts from the methyl nitrogen positive flow channel IV B3, the three parts are throttled and depressurized by a throttle valve B28 and then respectively enter a dehydrogenation tower top condenser 14, a demethanizer tower top condenser 17, a methyl nitrogen channel IC 2, a methyl nitrogen channel IID 2 and a methyl nitrogen channel III E2 of a denitrification tower top condenser 20 to provide cold energy for the methyl nitrogen, the heated methyl nitrogen from the dehydrogenation tower top condenser 14, the demethanizer tower top condenser 17 and the denitrification tower top condenser 20 is converged and then enters a methyl nitrogen reflux channel II B2 of the subcooler 12 to provide cold energy for the high-pressure methyl nitrogen in the methyl nitrogen positive flow channel IV B3 of the subcooler 12, the nitrogen methane from the nitrogen methane return channel IIB 2 of the subcooler 12 and the first throttled nitrogen methane are converged together and enter a nitrogen methane return channel IA 9 of the heat exchanger 9, the low-temperature low-pressure nitrogen methane in the nitrogen methane return channel IA 9 and the synthesis ammonia tail gas channel IA 1 of the heat exchanger 9, the synthesis ammonia tail gas in the synthesis ammonia tail gas channel IIA 2 and the high-pressure nitrogen methane gas in the nitrogen methane positive flow channel IA 6, the nitrogen methane positive flow channel IIA 7 and the nitrogen methane positive flow channel IIIA 8 exchange heat to provide cold energy for the synthesis ammonia tail gas and the high-pressure nitrogen methane gas, the normal-temperature low-pressure nitrogen methane flowing out of the nitrogen methane return channel IA 9 of the heat exchanger 9 enters the nitrogen methane compressor 8 again to perform compression cycle refrigeration in such a way, and the pressure of the low-pressure nitrogen methane gas flowing back from the nitrogen methane return channel IA 9 of the nitrogen methane compressor 8 is controlled to be 0.1MPa.G;
s3, adopting Freon as a precooling medium, enabling the precooling medium to enter an inlet pipe of a precooling compressor 10 through a precooling medium inlet pipe 25, throttling and depressurizing the compressed liquid-phase precooling medium through a throttling valve c29, then enabling the liquid-phase precooling medium to enter a precooling medium channel F3 of a precooler 11, controlling the evaporation temperature of the precooling medium to be-42 ℃, enabling the liquid-phase low-temperature low-pressure precooling medium in the precooling medium channel F3 of the precooler 11 to exchange heat with the synthetic ammonia tail gas in a synthetic ammonia tail gas channel III F1 in the precooler 11 and the nitrogen methane in a nitrogen methane normal flow channel V F2 and providing cold energy, and enabling the gas-phase low-temperature low-pressure precooling medium discharged from the precooler 11 to enter the precooling compressor 10 again to be compressed and cyclically refrigerated in such a way;
s4, the pressure of the purified synthesis ammonia tail gas is 4.0MPa.G, the synthesis ammonia tail gas enters a synthesis ammonia tail gas channel IA 1 of a heat exchanger 9 from a synthesis ammonia tail gas inlet pipe 1 and is primarily cooled to-30 ℃, the synthesis ammonia tail gas enters a synthesis ammonia tail gas channel IIIF 1 of a precooler 11 after exiting the heat exchanger 9 from the synthesis ammonia tail gas channel IA 1 and is precooled to-38 ℃, the synthesis ammonia tail gas after precooling returns to a synthesis ammonia tail gas channel IIA 2 of the heat exchanger 9 and is continuously cooled and condensed to-150 ℃, the synthesis ammonia tail gas exiting the synthesis ammonia tail gas channel IIA 2 of the heat exchanger 9 enters a dehydrogenation tower 13 after throttling and pressure reduction by a throttle valve d30, the pressure of the dehydrogenation tower 0.0 MPa.G, after rectification separation, hydrogen-rich gas from the upper part of the dehydrogenation tower 13 enters a hydrogen-rich tail gas channel IIIC 1 of a dehydrogenation tower top condenser 14, is cooled and condensed and then returns to the top of the dehydrogenation tower 13, liquid is used as reflux liquid at the top of the dehydrogenation tower 13 to participate in rectification, gas is discharged from the top of the dehydrogenation tower 13, is throttled and depressurized by a throttle valve e 31-1.9MPa.G and then enters a hydrogen-rich tail gas channel IIB 1 of a subcooler 12, hydrogen-rich tail gas from the hydrogen-rich tail gas channel IIB 1 of the subcooler 12 enters a hydrogen-rich tail gas channel IA 3 from the bottom of a heat exchanger 9, and the hydrogen-rich tail gas after being heated and reheated is discharged from a hydrogen-rich tail gas channel IA 3 of the heat exchanger 9 and enters a hydrogen-rich tail gas outlet pipe 2;
the liquid at the bottom of the dehydrogenation tower 13 enters a demethanizer 16 after being throttled and depressurized by a throttle valve f32, the pressure of the demethanizer 16 is controlled at 0.5MPa.G, the liquid at the bottom of the demethanizer 16 is rectified and separated, the liquid at the bottom of the demethanizer 16 is subjected to heat exchange and evaporation by a demethanizer bottom evaporator 15 to obtain methane-rich liquid, the methane-rich liquid is throttled and depressurized by a throttle valve g33 and then enters a methane-rich gas channel IA 4 from the bottom of a heat exchanger 9, and the heated and reheated methane-rich gas flows out of the top of the heat exchanger 9 and enters a methane outlet pipe 3;
the nitrogen-rich gas discharged from the upper part of the demethanizer 16 enters a nitrogen-rich gas channel ID 1 of a demethanizer overhead condenser 17, is cooled and condensed and then returns to the top of the demethanizer 16, the liquid is taken as reflux liquid at the top of the demethanizer 16 to participate in rectification, the gas is discharged from the top of the demethanizer 16 to enter a denitrification tower 19, the pressure of the denitrification tower 19 is controlled to be 0.48MPa.G, the nitrogen-rich gas discharged from the top of the denitrification tower 19 enters a nitrogen-rich gas channel II E1 of a denitrification tower overhead condenser 20 through rectification separation, is cooled and condensed and then returns to the top of the denitrification tower 19, the liquid is taken as reflux liquid at the top of the denitrification tower 19 to participate in rectification, the gas is discharged from the top of the denitrification tower 19, is throttled and reduced to 0.3MPa.G through a throttle valve h34 and then enters a nitrogen-rich tail gas channel II B5 of a subcooler 12, the nitrogen-rich tail gas from the bottom of a nitrogen-rich tail gas channel II B5 of a heat exchanger 9 enters a nitrogen-rich tail gas channel IA 5, and the heated and reheated tail gas enters a nitrogen-rich tail gas outlet pipe 4 from the top of the heat exchanger 9;
liquid at the bottom of the denitrification tower 19 is subjected to heat exchange and evaporation through a denitrification tower bottom evaporator 18 to obtain high-purity liquid argon, the liquid argon enters a liquid argon channel B4 of the subcooler 12, the subcooled liquid argon from the liquid argon channel B4 of the subcooler 12 enters a liquid argon outlet pipe 7, and the temperature of a liquid argon product is controlled to be minus 178 ℃.
In the present application example, the mole percentages of the components in the synthesis ammonia tail gas and the mole percentages of the components in the obtained hydrogen-rich tail gas, methane, nitrogen-rich tail gas and liquid argon are shown in the following table 3:
TABLE 3 component mol percents
| Argon gas | Methane | Nitrogen gas | Hydrogen gas | |
| Synthetic ammonia tail gas | 10.0％ | 30.0％ | 42.0％ | 18.0％ |
| Hydrogen rich tail gas | 1.4983％ | 0.0011％ | 35.8482％ | 62.6525％ |
| Methane | 1.0000％ | 98.9711％ | 0.0288％ | - |
| Nitrogen rich tail gas | 1.5000％ | - | 94.6470％ | 3.8530％ |
| Liquid argon component | 99.9995％ | - | 0.0005％ | - |
The variable efficiency of the compressor is 80%, and the single-machine energy consumption is the shaft power of the compressor divided by the standard output of the process argon product per hour; in the application example, the single machine energy consumption of the argon product is 2.736kW/Nm 3 And the single machine energy consumption of the argon product in the nitrogen expansion refrigeration process is 4.45kW/Nm 3, And the energy consumption of a single machine is reduced by 38.5 percent.
Claims (6)
1. The device for recovering argon and methane from the synthesis ammonia tail gas is characterized in that: comprises a heat exchanger (9), a subcooler (12), a dehydrogenation tower (13), a demethanizer (16), a denitrogenation tower (19) and a precooler (11); wherein,
a dehydrogenation tower top condenser (14) is arranged at the upper part of the dehydrogenation tower (13);
the upper part and the lower part of the demethanizer (16) are respectively provided with a demethanizer overhead condenser (17) and a demethanizer bottom evaporator (15);
the upper part and the lower part of the denitrification tower (19) are respectively provided with a denitrification tower top condenser (20) and a denitrification tower bottom evaporator (18);
a synthetic ammonia tail gas channel I (A1), a synthetic ammonia tail gas channel II (A2), a hydrogen-rich tail gas channel I (A3), a methane-rich gas channel I (A4), a nitrogen-rich tail gas channel I (A5), a nitromethane forward flow channel I (A6), a nitromethane forward flow channel II (A7), a nitromethane forward flow channel III (A8) and a nitromethane return flow channel I (A9) are arranged in the heat exchanger (9);
a hydrogen-rich tail gas channel II (B1), a nitrogen methane backflow channel II (B2), a nitrogen methane forward flow channel IV (B3), a liquid argon channel (B4) and a nitrogen-rich tail gas channel II (B5) are arranged in the subcooler (12);
a hydrogen-rich tail gas channel III (C1) and a nitrogen methane channel I (C2) are arranged in the dehydrogenation tower top condenser (14);
a nitrogen-rich gas channel I (D1) and a nitrogen methane channel II (D2) are arranged in a condenser at the top of the demethanizer (16);
a nitrogen-rich gas channel II (E1) and a nitrogen methane channel III (E2) are arranged in the denitrification tower top condenser;
a synthetic ammonia tail gas channel III (F1), a nitrogen methane positive flow channel V (F2) and a precooling medium channel (F3) are arranged in the precooler (11);
the heat exchanger (9) is connected with a synthetic ammonia tail gas inlet pipe (1), a hydrogen-rich tail gas outlet pipe (2), a methane outlet pipe (3), a nitrogen-rich tail gas outlet pipe (4) and a nitrogen methane circulating air inlet device; the subcooler (12) is connected with a liquid argon outlet pipe (7);
the nitrogen-methane circulating gas inlet device comprises a nitrogen-methane compressor (8), wherein a nitrogen-methane inlet pipe is connected to the inlet of the nitrogen-methane compressor (8), a nitrogen inlet pipe (5) and a methane inlet pipe (6) are connected to the nitrogen-methane inlet pipe, a nitrogen-methane outlet pipe is connected to the outlet of the nitrogen-methane compressor (8), the outlet of the nitrogen-methane outlet pipe is connected with the inlet of a nitrogen-methane positive flow channel I (A6), the outlet of the nitrogen-methane positive flow channel I (A6) is connected with the inlet of a nitrogen-methane positive flow channel V (F2), the outlet of the nitrogen-methane positive flow channel V (F2) is connected with the inlet of a nitrogen-methane positive flow channel II (A7), and the outlet of the nitrogen-methane positive flow channel II (A7) is connected with the inlet pipe of a demethanizer tower bottom evaporator (15);
the inlet of the synthetic ammonia tail gas channel I (A1) is connected with a synthetic ammonia tail gas inlet pipe (1), the outlet of the synthetic ammonia tail gas channel I (A1) is connected with the inlet of a synthetic ammonia tail gas channel III (F1), the outlet of the synthetic ammonia tail gas channel III (F1) is connected with the inlet of a synthetic ammonia tail gas channel II (A2), and the outlet of the synthetic ammonia tail gas channel II (A2) is connected with the inlet at the lower part of a dehydrogenation tower (13);
a gas phase outlet at the top of the dehydrogenation tower (13) is connected with an inlet of a hydrogen-rich tail gas channel II (B1), an outlet of the hydrogen-rich tail gas channel II (B1) is connected with an inlet of a hydrogen-rich tail gas channel I (A3), and an outlet of the hydrogen-rich tail gas channel I (A3) is connected with a hydrogen-rich tail gas outlet pipe (2); a hydrogen-rich gas outlet at the upper part of the dehydrogenation tower (13) is connected with an inlet of a hydrogen-rich tail gas channel III (C1) of a dehydrogenation tower top condenser (14), an outlet of the hydrogen-rich tail gas channel III (C1) is connected with a reflux inlet at the upper part of the dehydrogenation tower (13), and a liquid phase outlet at the bottom of the dehydrogenation tower (13) is connected with a feed inlet at the middle part of a demethanizer (16);
the nitrogen-rich outlet of the demethanizer (16) is connected with the inlet of a nitrogen-rich channel I (D1) of a demethanizer overhead condenser (17), the outlet of the nitrogen-rich channel I (D1) is connected with the reflux liquid inlet at the upper part of the demethanizer (16), the methane-rich liquid outlet at the bottom of the demethanizer (16) is connected with the inlet of a methane-rich channel I (A4), and the outlet of the methane-rich channel I (A4) is connected with the methane outlet pipe (3);
an outlet of a demethanizer tower bottom evaporator (15) is connected with an inlet pipe of a denitrogenation tower bottom evaporator (18), an outlet of the denitrogenation tower bottom evaporator (18) is connected with an inlet of a N-methyl alkane forward flow channel III (A8), an outlet of the N-methyl alkane forward flow channel III (A8) is respectively connected with a N-methyl alkane return flow channel I (A9) and a N-methyl alkane forward flow channel IV (B3), and an outlet of the N-methyl alkane forward flow channel III (A8) is connected with the N-methyl alkane forward flow channel IV (B3) through a branch pipe A (21); the outlet of the nitrogen methane backflow channel I (A9) is connected with a nitrogen methane feeding pipe of a nitrogen methane circulating air inlet device; the outlet of the azomethane forward flow channel IV (B3) is respectively connected with the inlets of an azomethane channel I (C2), an azomethane channel II (D2) and an azomethane channel III (E2), the outlets of the azomethane channel I (C2), the azomethane channel II (D2) and the azomethane channel III (E2) are respectively connected with the inlet of an azomethane return flow channel II (B2), the outlet of the azomethane return flow channel II (B2) is connected with the inlet of an azomethane return flow channel I (A9), and the outlet of the azomethane return flow channel I (A9) is connected with the azomethane feeding pipe of the azomethane circulating air inlet device;
the nitrogen-rich outlet at the upper part of the nitrogen removal tower (19) is connected with the inlet of a nitrogen-rich channel II (E1), the outlet of the nitrogen-rich channel II (E1) is connected with the reflux inlet at the upper part of the nitrogen removal tower, the nitrogen-rich outlet at the top of the nitrogen removal tower (19) is connected with the inlet of a nitrogen-rich tail gas channel II (B5), the outlet of the nitrogen-rich tail gas channel II (B5) is connected with the inlet of a nitrogen-rich tail gas channel I (A5), and the outlet of the nitrogen-rich tail gas channel I (A5) is connected with a nitrogen-rich tail gas outlet pipe (4);
the liquid argon export of denitrogenation tower bottom of the tower evaporimeter (18) meets with the import of liquid argon passageway (B4), the export of liquid argon passageway (B4) meets with liquid argon outlet pipe (7).
2. The apparatus for recovering argon and methane from ammonia synthesis tail gas as set forth in claim 1, wherein: and a methane branch pipe (26) is connected between the methane outlet pipe (3) and the methane feeding pipe (6).
3. The apparatus for recovering argon and methane from ammonia synthesis tail gas as set forth in claim 2, wherein: also comprises a control device; the control device is respectively and electrically connected with a nitrogen methane compressor (8), a heat exchanger (9), a precooling compressor (10), a precooler (11), a subcooler (12), a dehydrogenation tower (13), a dehydrogenation tower top condenser (14), a demethanizer tower bottom evaporator (15), a demethanizer (16), a demethanizer tower top condenser (17), a denitrification tower bottom evaporator (18), a denitrification tower (19) and a denitrification tower top condenser (20).
4. The apparatus for recovering argon and methane from ammonia synthesis tail gas as claimed in claim 3, wherein: the pre-cooling medium feeding device is characterized in that a pre-cooling medium feeding pipe (25) is connected to the pre-cooling compressor (10), the pre-cooling compressor (10) is connected with the pre-cooling medium channel (F3) through a circulating pipeline, and the pre-cooling medium feeding pipe (25) is connected to the circulating pipeline close to the inlet of the pre-cooling compressor (10).
5. The apparatus for recovering argon and methane from ammonia synthesis tail gas as set forth in claim 4, wherein: a throttle valve a (27) for throttling and depressurizing the high-pressure nitrogen methane is arranged on a pipeline between the outlet of the nitrogen methane positive flow channel III (A8) and the inlet of the nitrogen methane backflow channel I (A9);
an outlet of the nitrogen methane positive flow channel IV (B3) is connected with an inlet of the nitrogen methane channel I (C2) through a branch pipe B (22), an outlet of the nitrogen methane positive flow channel IV (B3) is connected with an inlet of the nitrogen methane channel II (D2) through a branch pipe C (23), and an outlet of the nitrogen methane positive flow channel IV (B3) is connected with an inlet of the nitrogen methane channel III (E2) through a branch pipe D (24); a branch pipe B (22), a branch pipe C (23) and a branch pipe D (24) are respectively provided with a throttle valve B (28) for throttling and depressurizing the nitrogen methane;
a throttle valve c (29) is arranged on an inlet pipeline of the precooling medium channel (F3);
a throttle valve d (30) is arranged on a pipeline between the outlet of the synthetic ammonia tail gas channel II (A2) and the inlet of the dehydrogenation tower (13);
a throttle valve e (31) for throttling and depressurizing the hydrogen-rich tail gas is arranged between the outlet at the top of the dehydrogenation tower (13) and the inlet of the hydrogen-rich tail gas channel II (B1);
a throttling valve f (32) for throttling and depressurizing the liquid at the bottom of the dehydrogenation tower (13) is arranged on a pipeline between the liquid outlet at the bottom of the dehydrogenation tower (13) and the inlet of the demethanizer (16);
a throttling valve g (33) for throttling and depressurizing methane-rich liquid is arranged on an inlet pipeline of the methane-rich gas channel I (A4);
an inlet pipeline of the nitrogen-rich tail gas channel II (B5) is provided with a throttle valve h (34) for throttling and depressurizing the nitrogen-rich tail gas;
a throttle valve i (35) for throttling and depressurizing the precooling medium is arranged on the precooling medium feeding pipe (25);
throttle valves j (36) for throttling and depressurizing nitrogen and methane are respectively arranged on the nitrogen feeding pipe (5) and the methane feeding pipe (6);
a throttle valve k (37) for throttling and depressurizing methane is arranged on the methane branch pipe (26);
a throttle valve l (38) for throttling and depressurizing the liquid argon is arranged on the liquid argon outlet pipe (7);
the throttle valve a (27), the throttle valve b (28), the throttle valve c (29), the throttle valve d (30), the throttle valve e (31), the throttle valve f (32), the throttle valve g (33), the throttle valve h (34), the throttle valve i (35), the throttle valve j (36), the throttle valve k (37) and the throttle valve l (38) are respectively electrically connected with the control device.
6. The apparatus for recovering argon and methane from ammonia synthesis tail gas according to any one of claims 1-5, characterized in that: the connecting pipelines in the device are cold insulation pipelines.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202122971011.2U CN217900304U (en) | 2021-11-30 | 2021-11-30 | Device for recovering argon and methane from synthetic ammonia tail gas |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114136055A (en) * | 2021-11-30 | 2022-03-04 | 成都深冷液化设备股份有限公司 | Device and method for recovering argon and methane from synthetic ammonia tail gas |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114136055A (en) * | 2021-11-30 | 2022-03-04 | 成都深冷液化设备股份有限公司 | Device and method for recovering argon and methane from synthetic ammonia tail gas |
| CN114136055B (en) * | 2021-11-30 | 2024-05-14 | 四川蜀道装备科技股份有限公司 | Device and method for recycling argon and methane from tail gas of synthetic ammonia |
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