CN1850586B - Process and equipment for extracting hydrogen from air discharged from synthetic ammonia tank - Google Patents
Process and equipment for extracting hydrogen from air discharged from synthetic ammonia tank Download PDFInfo
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- CN1850586B CN1850586B CN2006100443132A CN200610044313A CN1850586B CN 1850586 B CN1850586 B CN 1850586B CN 2006100443132 A CN2006100443132 A CN 2006100443132A CN 200610044313 A CN200610044313 A CN 200610044313A CN 1850586 B CN1850586 B CN 1850586B
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- ammonia
- gas
- clean
- copper
- hydrogen
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Abstract
The invention discloses a process and the device to recover the hydrogen from the synthetic ammonia storage purge. It uses the technology of the ammonia cleaning, the gas-liquid separating, heating and membrane separation technique. It limits the ammonia content of the limiting membrane separator and the air pressure in the process to recovery the hydrogen. So it can decrease the waste of the material gas and synthetic ammonia cost.
Description
Technical field
The present invention relates to a kind of recovery technology of dropping a hint, specifically a kind of extracting hydrogen from air discharged from synthetic ammonia tank Processes and apparatus.
Background technology
Can produce in fertilizer plant's synthetic ammonia process and drop a hint in a large number, a wherein topmost part produces in building-up process, and its pressure reaches 10-32MPa, and hydrogen content is up to more than 50%.In the prior art, there are many kinds of proven technique schemes the recovery aspect of hydrogen in this section.Particularly membrane sepn is put forward the hydrogen method, with its no materials consumption, take up an area of less, low power consumption and other advantages obtained using widely, the hydrogen purity in dropping a hint can be brought up to more than 90% by about 50%.
Also can produce an other part in the production of synthetic ammonia drops a hint---and synthetic ammonia tank is dropped a hint.Its main component is: H
2About 20%, NH
3About 60%, its pressure is 1.6-3MPa (gauge pressure).Because wherein hydrogen richness is low, the ammonia content height be difficult for handling, and pressure is too little, can not satisfy the requirement of membrane sepn to concentration and pressure reduction, reclaims so can't utilize membrane separating method of the prior art to carry hydrogen.And other carries hydrogen methods, carries hydrogen method, pressure swing adsorption process as deep cooling, and is too high because of dropping into again, and can not get reasonable income.So synthetic ammonia tank is dropped a hint so far or after having carried out the clean ammonia of copper, is sent the burning of gas blowing boiler or other resident families to use.Not only added value of product is low, also can cause the unstripped gas utilization ratio not high, and feed coal consumes high deficiency.
Summary of the invention
Technical assignment of the present invention is at above-mentioned the deficiencies in the prior art, provide a kind of energy-conservation, the volume increase, the consumption reduction extracting hydrogen from air discharged from synthetic ammonia tank technology.
Another technical assignment of the present invention provides the equipment of realizing above-mentioned technology.
Technical assignment of the present invention is realized in the following manner: extracting hydrogen from air discharged from synthetic ammonia tank technology, and the hydrogen recovery in by clean ammonia, gas-liquid separation, heating and membrane sepn ammonia storage tank being dropped a hint,
Recycling step is as follows:
Clean ammonia: with pressure is that the ammonia storage tank of 1.6-3.0MPa is dropped a hint and sent into clean ammonia equipment and remove gas ammonia, requires that the ammonia content of gas is not more than 200PPm behind the clean ammonia;
Gas-liquid separation: dropping a hint behind the clean ammonia carried out gas-liquid separation by entering gas-liquid separator after the clean ammonia equipment discharge;
Heating: send heater heats to 40 ℃-50 ℃ with the gas that obtains after the gas-liquid separation;
Membrane sepn: the gas after will heating is sent into membrane separation apparatus, utilizes hollow-fibre membrane to the hydrogen in the selective recovery gas of hydrogen, and the infiltration atmospheric pressure of membrane separation apparatus is controlled at 0-1.0MPa, and tail gas pressure is 1.0-2.0MPa.
Preferred utilize the clean ammonia of cuprammonia, isobaric clean ammonia and soft water to wash three grades of clean ammonia devices of ammonia successively the ammonia in dropping a hint is absorbed, the ammonia content that requires gas behind the clean ammonia is less than 200PPm.
Employed cuprammonia is the cuprammonia from the low ammonia content of refining copper solution scrubbing process in the clean ammonia process of cuprammonia, absorbs the cuprammonia that generates high ammonia content behind a large amount of ammonias in the clean ammonia process and sends the circulation of refining copper solution scrubbing process back to and wash micro-gas absorption agent as refined matte and use.
Isobaric clean ammonia and soft water are washed in the ammonia process, utilize soft water to absorb ammonia in the gas, and the ammoniacal liquor of generation is sent into the carbonated aqueous ammonia groove, carries dense back through ammonia still process and uses for carbonization production carbon ammonium or as the recovery tower absorption agent.
Be used to realize the above-mentioned production unit of putting forward hydrogen technology, be characterized in comprising that copper washes ammonia-cleaning tower, the copper liquid/gas separator, isobaric clean ammonia device, Ammonic washing tower, gas-liquid separator, double pipe heater and membrane separation apparatus, copper is cleaned the import of ammonia top of tower washing lotion and is connect the outlet of refining ammonia cooler by the copper pump, copper is cleaned the outlet of ammonia tower bottom washing lotion and is connect the import of refining ammonia cooler, bottom air inlet connects ammonia storage tank, the air outlet, top that copper is washed ammonia-cleaning tower is connected in series the copper liquid/gas separator successively by pipeline, isobaric clean ammonia device, Ammonic washing tower, gas-liquid separator, double pipe heater and membrane separation apparatus, the outlet of membrane separation apparatus infiltration gas is bonded into the ammonia system feed gas compressor, and the tail gas outlet connects the tail gas gas holder.
Described copper is washed ammonia-cleaning tower preferred filler tower.
Preferred tray column of the clean ammonia device of described equipressure or bubbling jar or tray column, bubbling jar be used in combination.
The preferred high efficiency structured packing tower of described Ammonic washing tower.
The extracting hydrogen from air discharged route is: from dropping a hint after copper is cleaned ammonia, isobaric clean ammonia of ammonia storage tank, entering Ammonic washing tower is softened water and sponges remaining ammonia, purified gas comes out from the Ammonic washing tower top, enter gas-liquid separator separates and fall droplets entrained, then, after being preheating to certain temperature, double pipe heater enters membrane separation apparatus, after film is selected infiltration, infiltration gas removes the synthesis ammonia system feed gas compressor, and truncate gas gas holder burning of tail gas is used.
The hydrogen technology of carrying of the present invention has compared with prior art realized the drop a hint recycling of mesolow low levels hydrogen of synthetic ammonia tank, both increased this part application added value of dropping a hint, save the energy, material again, can obtain good economic benefits and social benefit:
(1) liquefied ammonia dissolved hydrogen release in the ammonia storage tank is come out, be recycled to compressor and be used for Ammonia Production, reduced available gas waste (hydrogen concentration reaches below 4% in the tail gas), improved the utilization ratio of unstripped gas, reduced synthetic ammonia consumption.
(2) clean ammonia process has adopted the clean ammonia of cuprammonia, isobaric clean ammonia and soft water to wash three grades of clean ammonia such as ammonia, improved assimilation effect, can make the middle ammonia level of dropping a hint be reduced to the level that does not influence the hydrogen membrane infiltration, and also can utilize to the production of carbon ammonium or as the recovery tower absorption agent after cuprammonia behind the absorption ammonia and the ammoniacal liquor recovery, use added value and greatly improve.
Description of drawings
Accompanying drawing 1 is an extracting hydrogen from air discharged from synthetic ammonia tank process frame chart of the present invention;
Accompanying drawing 2 is the equipment flowsheets that are used to realize technology of the present invention.
Embodiment
Explain to extracting hydrogen from air discharged from synthetic ammonia tank technology of the present invention and below the beneficial effect work with reference to specific embodiment.
Embodiment 1:
The ammonia storage tank data of dropping a hint:
Output is 1200Nm
3/ h; Composition is: H
219.5%, N
25%, CH
414%, Ar1.5%, NH
360%; Pressure is 2.2 ± 0.5MPa.
Select equipment for use: copper is washed ammonia-cleaning tower 1, copper liquid/gas separator 2, isobaric clean ammonia device 3, Ammonic washing tower 4, gas-liquid separator 5, double pipe heater 6, membrane separation apparatus 7.
Put forward hydrogen technology:
A, clean ammonia:
1) will contain H from synthetic ammonia tank
2, N
2, NH
3, CH
4Deng drop a hint after line strainer filters, send into copper from the bottom and wash ammonia-cleaning tower 1, with reverse contact of low ammonia cuprammonia that cat head is sent into, carry out the clean ammonia of one-level.(absorb the rich ammonia cuprammonia that obtains behind the ammonia and go out to send into the refining ammonia cooler, wash micro-gas absorption agent as refined matte and use from tower bottom flow.)
2) behind the clean ammonia of one-level, wash ammonia-cleaning tower 1 top effluent air from copper and enter copper liquid/gas separator 2, remove the cuprammonia mist of deentrainment.Copper liquid/gas separator 2 top expellant gas are sent into isobaric clean ammonia device 3 and Ammonic washing tower 4 successively, go into to contact with soft water is contrary, finish two, three grades of clean ammonia operations.The ammonia content of gas is 120 ± 50PPm behind three grades of clean ammonia.(ammoniacal liquor of generation is used for the production of carbon ammonium or uses as the recovery tower absorption agent.)
B, gas-liquid separation:
Gas behind three grades of clean ammonia is sent into gas-liquid separator 5 and is carried out gas-liquid separation, separates entrained drip.
C, heating: gas-liquid separator 5 top expellant gas are sent into double pipe heater 6, with gas heating to 45 ℃.
D, membrane sepn: the gas after will heating is sent into membrane separation apparatus 7, utilizes the low pressure hollow film to the hydrogen in the selective recovery gas of hydrogen.Infiltration gas one wall pressure 0.5 ± 0.2MPa, tail gas one wall pressure is 1.5 ± 0.2MPa.(infiltration pneumatic transmission compressor reclaims, and is used for Ammonia Production; Tail gas truncates the gas gas holder for gas blowing boiler and resident family's burning use.)
After carrying hydrogen, infiltration gas hydrogen concentration is 85%, and the tail gas hydrogen concentration can be reduced to (it is not quick-fried to switch on) below 4%.
Hydrogen recovery rate is 85%.
The hydrogen that this embodiment proposes transforms about 3,000,000 yuan of the synthetic ammonia folding output value, amounts to the output value only about 2,000,000 yuan and send the gas blowing boiler burning to produce steam in the prior art.
In the equipment used, copper is washed ammonia-cleaning tower 1 and is packing tower (Raschig ring filler); The top of isobaric clean ammonia device 3 is the tray column structure, and the bottom is the bubbling jar; Copper liquid/gas separator 2, gas-liquid separator 5 are common gas-liquid separator; Ammonic washing tower 4 is high efficiency structured packing tower (structured packing); Double pipe heater 6 is general double pipe heater, is heating medium with the water vapor; The hollow-fibre membrane that uses in the membrane separation apparatus 7 is the low pressure hollow film.
Embodiment 2:
The ammonia storage tank data of dropping a hint:
Output is 1800Nm
3/ h; Composition is: H
221%, N
24.5%, CH
415%, Ar1.5%, NH
358%; Pressure is 2.3 ± 0.5MPa.
Select equipment for use: copper is washed ammonia-cleaning tower, copper liquid/gas separator, isobaric clean ammonia device, Ammonic washing tower, gas-liquid separator, double pipe heater, membrane separation apparatus.
Put forward hydrogen technology: with among the embodiment 1 to put forward hydrogen technology basic identical, but require that the ammonia content of gas is 130 ± 50PPm behind three grades of clean ammonia.Infiltration gas one wall pressure 0.4 ± 0.2MPa, tail gas one wall pressure is 1.7 ± 0.2MPa.
After carrying hydrogen, infiltration gas hydrogen concentration is 82%, and the tail gas hydrogen concentration can be reduced to (it is not quick-fried to switch on) below 4%.
Hydrogen recovery rate is 80%.
The hydrogen that this embodiment proposes transforms about 5,000,000 yuan of the synthetic ammonia folding output value, amounts to the output value only about 3,000,000 yuan and send the gas blowing boiler burning to produce steam in the prior art.
In the equipment used, substantially with embodiment 1 in identical.Copper washes that filler is the cascade ring filler in the ammonia-cleaning tower; Isobaric clean ammonia device is a tray column; Filler is a ripple twine line filler in the Ammonic washing tower.
If project can be applied in national synthetic ammonia industry,, will produce about 200,000,000 yuan of economic benefit by about 4,500 ten thousand tons of/year calculating of present national synthetic ammonia output.
Claims (7)
1. extracting hydrogen from air discharged from synthetic ammonia tank technology, the hydrogen recovery in it is characterized in that ammonia storage tank being dropped a hint by clean ammonia, gas-liquid separation, heating and membrane sepn,
Recycling step is as follows:
Clean ammonia: with pressure is that the ammonia storage tank of 1.6-3.0MPa is dropped a hint and sent into the clean ammonia of cuprammonia, isobaric clean ammonia and soft water successively and wash three grades of clean ammonia equipment of ammonia and remove gas ammonia, and the ammonia content that requires gas behind the clean ammonia is less than 200PPm;
Gas-liquid separation: dropping a hint behind the clean ammonia carried out gas-liquid separation by entering gas-liquid separator after the clean ammonia equipment discharge;
Heating: send heater heats to 40 ℃-50 ℃ with the gas that obtains after the gas-liquid separation;
Membrane sepn: the gas after will heating is sent into membrane separation apparatus, utilizes hollow-fibre membrane to the hydrogen in the selective recovery gas of hydrogen, and the infiltration atmospheric pressure of membrane separation apparatus is controlled at 1.0MPa, and tail gas pressure is 1.0-2.0MPa.
2. extracting hydrogen from air discharged from synthetic ammonia tank technology according to claim 1, it is characterized in that employed cuprammonia in the clean ammonia process of cuprammonia is the cuprammonia from the low ammonia content of refining copper solution scrubbing process, absorb the cuprammonia that generates high ammonia content behind a large amount of ammonias in the clean ammonia process and send the circulation of refining copper solution scrubbing process back to and wash micro-gas absorption agent as refined matte and use.
3. extracting hydrogen from air discharged from synthetic ammonia tank technology according to claim 1, it is characterized in that isobaric clean ammonia and soft water washes in the ammonia process, utilize soft water to absorb ammonia in the gas, the ammoniacal liquor of generation is sent into the carbonated aqueous ammonia groove, carries dense back through ammonia still process and uses for carbonization production carbon ammonium or as the recovery tower absorption agent.
4. be used to realize the described equipment of putting forward hydrogen technology of claim 1, it is characterized in that comprising that copper washes ammonia-cleaning tower, the copper liquid/gas separator, isobaric clean ammonia device, Ammonic washing tower, gas-liquid separator, double pipe heater and membrane separation apparatus, copper is cleaned the import of ammonia top of tower washing lotion and is connect the outlet of refining ammonia cooler by the copper pump, copper is cleaned the outlet of ammonia tower bottom washing lotion and is connect the import of refining ammonia cooler, bottom air inlet connects ammonia storage tank, the air outlet, top that copper is washed ammonia-cleaning tower is connected in series the copper liquid/gas separator successively by pipeline, isobaric clean ammonia device, Ammonic washing tower, gas-liquid separator, double pipe heater and membrane separation apparatus, the outlet of membrane separation apparatus infiltration gas is bonded into the ammonia system feed gas compressor, and the tail gas outlet connects the tail gas gas holder.
5. equipment according to claim 4 is characterized in that it is packing tower that described copper is washed ammonia-cleaning tower.
6. equipment according to claim 4 is characterized in that the clean ammonia device of described equipressure is tray column, bubbling jar or tray column, bubbling jar be used in combination.
7. equipment according to claim 4 is characterized in that described Ammonic washing tower is a high efficiency structured packing tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100443132A CN1850586B (en) | 2006-05-25 | 2006-05-25 | Process and equipment for extracting hydrogen from air discharged from synthetic ammonia tank |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100443132A CN1850586B (en) | 2006-05-25 | 2006-05-25 | Process and equipment for extracting hydrogen from air discharged from synthetic ammonia tank |
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| Publication Number | Publication Date |
|---|---|
| CN1850586A CN1850586A (en) | 2006-10-25 |
| CN1850586B true CN1850586B (en) | 2010-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100443132A Expired - Fee Related CN1850586B (en) | 2006-05-25 | 2006-05-25 | Process and equipment for extracting hydrogen from air discharged from synthetic ammonia tank |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590364B (en) * | 2009-07-07 | 2012-05-23 | 贵州赤天化股份有限公司 | Method and device for recovering hydrogen on purge gas in synthetic ammonia and gas stored in tank |
| CN103601214B (en) * | 2013-09-22 | 2015-10-07 | 湖北宜化化工股份有限公司 | A kind of technique reclaiming hydrogen in synthetic ammonia periodic off-gases and unpowered ammonia |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0282165A1 (en) * | 1987-03-02 | 1988-09-14 | Air Products And Chemicals, Inc. | Method and plant for recovering hydrogen and argon from ammonia synthesis purge gas |
| CN1063265A (en) * | 1992-01-29 | 1992-08-05 | 浙江大学 | A kind of method of manufacturing-storing and transporting high-purity hydrogen and device |
| CN1066004A (en) * | 1991-12-25 | 1992-11-11 | 化学工业部西南化工研究院 | From methanol-fueled exhaust, gas and synthetic ammonia purge, carry helium and obtain High Purity Hydrogen simultaneously with metallic hydride method |
| US6282880B1 (en) * | 1999-02-03 | 2001-09-04 | Texaco Inc. | Method of utilizing purge gas from ammonia synthesis |
-
2006
- 2006-05-25 CN CN2006100443132A patent/CN1850586B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0282165A1 (en) * | 1987-03-02 | 1988-09-14 | Air Products And Chemicals, Inc. | Method and plant for recovering hydrogen and argon from ammonia synthesis purge gas |
| CN1066004A (en) * | 1991-12-25 | 1992-11-11 | 化学工业部西南化工研究院 | From methanol-fueled exhaust, gas and synthetic ammonia purge, carry helium and obtain High Purity Hydrogen simultaneously with metallic hydride method |
| CN1063265A (en) * | 1992-01-29 | 1992-08-05 | 浙江大学 | A kind of method of manufacturing-storing and transporting high-purity hydrogen and device |
| US6282880B1 (en) * | 1999-02-03 | 2001-09-04 | Texaco Inc. | Method of utilizing purge gas from ammonia synthesis |
Non-Patent Citations (4)
| Title |
|---|
| 周霖.利用中压氨洗设备改造为等压净氨.化工设计通讯22 1.1996,22(1),p39-40. * |
| 张景奇等.膜分离法回收弛放气中氢气的技术应用.氮肥设计33 1.1995,33(1),第30页右栏第3段至第31页右栏第1段. * |
| 贺小伟.用铜液吸收弛放气中的氨.小氮肥1999 9.1999,1999(9),15-16. * |
| 赵曙光等.合成氨放空气氢气提浓系统改造小结.小氮肥2003 3.2003,2003(3),p21-22. * |
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Granted publication date: 20100908 Termination date: 20120525 |