CN102068880B - Method for recycling ammonia gas in industrial waste gas - Google Patents
Method for recycling ammonia gas in industrial waste gas Download PDFInfo
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- CN102068880B CN102068880B CN2010105735468A CN201010573546A CN102068880B CN 102068880 B CN102068880 B CN 102068880B CN 2010105735468 A CN2010105735468 A CN 2010105735468A CN 201010573546 A CN201010573546 A CN 201010573546A CN 102068880 B CN102068880 B CN 102068880B
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- Prior art keywords
- ammonia
- absorption liquid
- waste gas
- absorption
- film
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000007789 gas Substances 0.000 title claims abstract description 53
- 239000002440 industrial waste Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000004064 recycling Methods 0.000 title abstract 4
- 238000010521 absorption reaction Methods 0.000 claims abstract description 85
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 65
- 239000007788 liquid Substances 0.000 claims abstract description 65
- 238000005057 refrigeration Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001868 water Inorganic materials 0.000 claims abstract description 18
- 239000002912 waste gas Substances 0.000 claims abstract description 10
- 239000002250 absorbent Substances 0.000 claims description 64
- 230000002745 absorbent Effects 0.000 claims description 64
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 24
- 239000012510 hollow fiber Substances 0.000 claims description 4
- 239000012982 microporous membrane Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 5
- 239000002253 acid Substances 0.000 abstract 3
- 230000001131 transforming effect Effects 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000005518 chemical engineering design Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a method for recycling ammonia gas in industrial waste gas, which relates to treatment of industrial waste gas. A recycling device is provided with an absorption liquid tank, a water pump, refrigeration equipment, a film absorption component, a draft fan and a tail gas absorption acid pool. The method comprises the following steps of: injecting an absorption agent into the absorption liquid tank; leading the absorption agent in the absorption liquid tank out through the water pump and making the absorption agent pass through the refrigeration equipment and enter the film absorption component from an absorption liquid inlet of the film absorption component; introducing ammonia-containing industrial waste gas into the film absorption component through the draft fan; making the absorption agent change into absorption liquid by absorbing ammonia in the ammonia-containing industrial waste gas and making the absorption liquid flow back to the absorption liquid tank through absorption liquid outlet of the film absorption component and reenter an absorption liquid recycling process; transforming the ammonia-containing industrial waste gas into ultralow-ammonia-content waste gas through absorption, exhausting the ultralow-ammonia-content waste gas from the under part of the film absorption component and introducing the exhausted ultralow-ammonia-content waste gas into the tail gas absorption acid pool; transforming the ultralow-ammonia-content waste gas into ammonia-free waste gas by making the ultralow-ammonia-content waste gas pass through the absorption acid pool directly exhausting the ammonia-free waste gas; circularly absorbing the absorption liquid and leading out a finished product; and re-injecting the absorption agent into the absorption liquid tank, and repeating the steps above.
Description
Technical field
The present invention relates to a kind of processing of industrial waste gas, especially relate to ammonia recoverying and utilizing method in a kind of industrial waste gas.
Background technology
Chemical industry is in the production process of using liquefied ammonia, because the effumability of ammonia, a large amount of gaseous ammonias is discharged in the air through the equipment exhausting pipeline, has both caused serious air pollution, causes raw-material waste again.For addressing this problem, the absorption pattern that adopts single cycle water to spray usually reclaims ([1] Shu Shiping etc., the exploitation and the application of useless ammonia (water) recovery and purification techniques, Chemical Engineering Design, 2001,11:34-35; [2] Du Wen, the improvement and the utilization process research of tungsten metallurgical process ammonia tail gas, Chinese tungsten industry, 2008,6:43-46).But there is following defective in this absorption pattern: absorption efficiency is low, can only reach the assimilation effect of total amount 30%; The absorption tower is limited by equipment blow-down pipe distance and potential difference, very easily forms gas and stops up, and influences the normal use of emptying device; The equipment input cost is high, and water loss is big, and the weak aqua ammonia concentration that obtains is low, must absorb perhaps through secondary to carry out just obtaining high-load ammoniacal liquor after the rectifying; Nearly 70% ammonia that can't absorb gets into atmosphere, causes environmental pollution.
Summary of the invention
The objective of the invention is to existing industrial waste gas Main Ingredients and Appearance is ammonia, nitrogen, hydrogen and water vapour, uses the existing shortcoming of ammonia recovery method that is adopted in the production process of liquefied ammonia, and ammonia recycle device in a kind of industrial waste gas is provided.
Another object of the present invention is to provide ammonia recoverying and utilizing method in a kind of industrial waste gas.
The ammonia recycle device is provided with absorption liquid case, water pump, refrigeration plant, film absorbent assembly, air-introduced machine and tail gas and absorbs sour pond in a kind of industrial waste gas according to the invention; The absorbent outlet of absorption liquid case connects the refrigeration plant inlet through water pump; The refrigeration plant outlet connects film absorbent assembly absorption liquid inlet; The external ammonia industrial waste gas that contains of air-introduced machine inlet exports; The air-introduced machine outlet connects film absorbent assembly inlet, and the ultralow ammonia-contaminated gas outlet of film absorbent assembly connects and absorbs sour pond, absorbs sour pond and exports external emptying pipe.
Film in the said film absorbent assembly can adopt hollow fiber microporous membrane etc.; The blast of said film absorbent assembly inlet can be 35～40kPa.
Ammonia recoverying and utilizing method in a kind of industrial waste gas of the present invention uses ammonia recycle device in said a kind of industrial waste gas, said method comprising the steps of:
1) in the absorption liquid case, injects absorbent;
2) absorbent in the absorption liquid case is drawn through behind the refrigeration plant through water pump, get into the film absorbent assembly from film absorbent assembly absorption liquid inlet;
3) will contain the ammonia industrial waste gas and squeeze into the film absorbent assembly through air-introduced machine;
4) absorbent becomes absorption liquid after drawing and containing the ammonia in the ammonia industrial waste gas, and absorption liquid is back to the absorption liquid case through the outlet of film absorbent assembly absorption liquid, gets into the absorption liquid cyclic process once more;
5) contain the ammonia industrial waste gas and after absorbing, change ultralow ammonia-contaminated gas into, insert tail gas and absorb sour pond from the discharge of film absorbent assembly below;
6) ultralow ammonia-contaminated gas changes no ammonia waste gas into after absorbing sour pond, directly emptying;
7) absorption liquid absorbs through circulation, and ammonia content raises after concentration reaches 25%～30% ammoniacal liquor in the absorption liquid, promptly can be used as finished product and draws through valve pipeline;
8) refill absorbent to absorption liquid case, repeating step 2)～step 8).
In step 1), said absorbent can adopt water.
In step 2) in, the film parameter in the said film absorbent assembly is following: the membranous wall aperture is 0.0001～20 μ m, and the film withstand temperature is 0～60 ℃; Film in the said film absorbent assembly can adopt hollow fiber microporous membrane etc.; The blast of said film absorbent assembly inlet can be 35～40kPa.
In step 4), the temperature of said absorption liquid can be 0～10 ℃.
In step 7), the temperature of said ammoniacal liquor can be 0～20 ℃; The proportion of said ammoniacal liquor can be 0.85～1.0.
In above-mentioned technical process; Contain ammonia industrial waste gas and absorbent respectively in the both sides of film, the film absorbent assembly carries out the selectivity absorption to the gases such as ammonia that contain in the ammonia industrial waste gas, and ammonia sees through fenestra and absorbed the entering liquid phase by the absorbent of opposite side; Ammonia content progressively raises after concentration reaches 25%～30% ammoniacal liquor in the absorption liquid; Promptly can be used as finished product and draw, refill absorption liquid then and repeat to absorb, reached the purpose that ammonia is recycled.
This shows that compare with ammonia recoverying and utilizing method in the existing industrial waste gas, the present invention has following advantage:
Ammonia sees through the film absorbent assembly and gets in the recirculated water, forms ammoniacal liquor, through 0～10 ℃ of control absorption liquid temperature; Film absorbent assembly inlet blast 35～40kPa; Make ammonia concn reach the standard of commodity ammoniacal liquor, can sell or personal, practiced thrift processing cost; Make the ammonia in the industrial waste gas get utilization, turn waste into wealth.
In addition, the ultralow ammonia-containing water after ammonia absorbs absorbs sour pond through tail gas, and no ammonia toxic emission atmosphere has reduced atmosphere pollution.
Simultaneously, the single unit system absorptivity is high, and pipeline is not easy to stop up, and the equipment input cost is lower, and energy consumption is less, and water consumption is less, the commodity ammoniacal liquor that can be reused.
Description of drawings
Fig. 1 is the process flow diagram of the embodiment of the invention.
The specific embodiment
Below in conjunction with embodiment the present invention is further described.
The process flow diagram of embodiment is referring to Fig. 1, and concrete technological process is following:
1) in absorption liquid case 1, inject absorbent, said absorbent can adopt water.
2) absorbent in the absorption liquid case 1 is drawn through behind the refrigeration plant 3 through water pump 2 by the outlet 11 of absorption liquid case absorbent, get into film absorbent assembly 4 from film absorbent assembly absorption liquid inlet 41; Film parameter in the said film absorbent assembly is following: the membranous wall aperture is 0.0001～20 μ m, and the film withstand temperature is 0～60 ℃; Film in the said film absorbent assembly can adopt hollow fiber microporous membrane etc.; The blast of said film absorbent assembly inlet can be 35～40kPa.
3) will contain ammonia industrial waste gas P and squeeze into film absorbent assembly 4 through air-introduced machine 5.
4) absorbent becomes absorption liquid after drawing and containing the ammonia in the ammonia industrial waste gas, and absorption liquid is back to absorption liquid case 1 through film absorbent assembly absorption liquid outlet 42, gets into the absorption liquid cyclic process once more; The temperature of said absorption liquid can be 0～10 ℃.
5) contain the ammonia industrial waste gas and after absorbing, change the discharge of ultralow ammonia-contaminated gas into, insert tail gas and absorb sour pond 6 from film absorbent assembly 4 belows.
6) ultralow ammonia-contaminated gas changes no ammonia waste gas into after absorbing sour pond 6, directly exports 61 emptyings from absorbing sour pond.
7) absorption liquid absorbs through circulation, and ammonia content raises after concentration reaches 25%～30% ammoniacal liquor in the absorption liquid, promptly can be used as finished product and draws through pipeline behind valve 7 from absorption liquid case ammoniacal liquor outlet 12; The temperature of said ammoniacal liquor can be 0～20 ℃; The proportion of said ammoniacal liquor can be 0.85～1.0.
8) refill absorbent to absorption liquid case 1, repeating step 2)～step 8).
Press processing step 1)～8) operation, the control parameter is following: the refrigeration plant 3 step 2) makes the absorption liquid temperature remain on 0 ℃, and the film absorbent assembly 4 inlet end air pressure in the step 3) are 40kPa, and obtaining ammoniacal liquor density is 0.891g/cm
3, amount to ammonia concn 30.23%, referring to table 1.
Embodiment 2
Press the processing step 1 of embodiment 1)～8) operation, the control parameter is following: step 2) refrigeration plant 3 makes the absorption liquid temperature remain on 5 ℃, the film absorbent assembly 4 inlet end air pressure 40kPa in the step 3), and obtaining ammoniacal liquor density is 0.901g/cm
3, amount to ammonia concn 27.93%, referring to table 1.
Press the processing step 1 of embodiment 1)～8) operation, the control parameter is following:: step 2) refrigeration plant 3 makes the absorption liquid temperature remain on 5 ℃, the film absorbent assembly 4 inlet end air pressure 40kPa in the step 3), obtaining ammoniacal liquor density is 0.910g/cm
3, amount to ammonia concn 24.98%, referring to table 1.
Embodiment 4
Press the processing step 1 of embodiment 1)～8) operation, the control parameter is following:: step 2) refrigeration plant 3 makes the absorption liquid temperature remain on 5 ℃, the film absorbent assembly 4 inlet end air pressure 40kPa in the step 3), obtaining ammoniacal liquor density is 0.919g/cm
3, amount to ammonia concn 22.08%, referring to table 1.
Embodiment 5
Press the processing step 1 of embodiment 1)～8) operation, the control parameter is following:: step 2) refrigeration plant 3 makes the absorption liquid temperature remain on 10 ℃, the film absorbent assembly 4 inlet end air pressure 30kPa in the step 3), obtaining ammoniacal liquor density is 0.93lg/cm
3, amount to ammonia concn 18.24%, referring to table 1.
Press the processing step 1 of embodiment 1)～8) operation, the control parameter is following:: step 2) refrigeration plant 3 makes the absorption liquid temperature remain on 15 ℃, the film absorbent assembly 4 inlet end air pressure 30kPa in the step 3), obtaining ammoniacal liquor density is 0.936g/cm
3, amount to ammonia concn 16.80%, referring to table 1.
Embodiment 7
Press the processing step 1 of embodiment 1)～8) operation, the control parameter is following:: step 2) refrigeration plant 3 makes the absorption liquid temperature remain on 20 ℃, the film absorbent assembly 4 inlet end air pressure 30kPa in the step 3), obtaining ammoniacal liquor density is 0.942g/cm
3, amount to ammonia concn 14.90%, referring to table 1.
Table 1 ammonia spirit change in concentration
| Embodiment | Ammonia temperature (℃) | Ammoniacal liquor proportion | Ammonia spirit concentration (%) |
| 1 | 0 | 0.891 | 30.23 |
| 2 | 5 | 0.901 | 27.93 |
| 3 | 5 | 0.910 | 24.98 |
| 4 | 5 | 0.919 | 22.08 |
| 5 | 10 | 0.931 | 18.24 |
| 6 | 15 | 0.936 | 16.80 |
| 7 | 20 | 0.942 | 14.90 |
Claims (2)
1. ammonia recoverying and utilizing method in the industrial waste gas; It is characterized in that using ammonia recycle device in a kind of industrial waste gas, the ammonia recycle device is provided with absorption liquid case, water pump, refrigeration plant, film absorbent assembly, air-introduced machine and tail gas and absorbs sour pond in the said industrial waste gas; The absorbent outlet of absorption liquid case connects the refrigeration plant inlet through water pump; The refrigeration plant outlet connects film absorbent assembly absorption liquid inlet; The external ammonia industrial waste gas that contains of air-introduced machine inlet exports; The air-introduced machine outlet connects film absorbent assembly inlet, and the ultralow ammonia-contaminated gas outlet of film absorbent assembly connects and absorbs sour pond, absorbs sour pond and exports external emptying pipe; Film in the said film absorbent assembly is a hollow fiber microporous membrane; The blast of said film absorbent assembly inlet is 35～40KPa;
Said method comprising the steps of:
1) in the absorption liquid case, injects absorbent;
2) absorbent in the absorption liquid case is drawn through behind the refrigeration plant through water pump, get into the film absorbent assembly from film absorbent assembly absorption liquid inlet;
3) will contain the ammonia industrial waste gas and squeeze into the film absorbent assembly through air-introduced machine;
4) absorbent becomes absorption liquid after drawing and containing the ammonia in the ammonia industrial waste gas, and absorption liquid is back to the absorption liquid case through the outlet of film absorbent assembly absorption liquid, gets into the absorption liquid cyclic process once more; The temperature of said absorption liquid is 0～10 ℃;
5) contain the ammonia industrial waste gas and after absorbing, change ultralow ammonia-contaminated gas into, insert tail gas and absorb sour pond from the discharge of film absorbent assembly below;
6) ultralow ammonia-contaminated gas changes no ammonia waste gas into after absorbing sour pond, directly emptying;
7) absorption liquid absorbs through circulation, and ammonia content raises after concentration reaches 25%～30% ammoniacal liquor in the absorption liquid, promptly can be used as finished product and draws through valve pipeline; The temperature of said ammoniacal liquor is 0～20 ℃; The proportion of said ammoniacal liquor is 0.85～1.0;
8) refill absorbent to absorption liquid case, repeating step 2)～step 8); Said absorbent is a water.
2. ammonia recoverying and utilizing method in a kind of industrial waste gas as claimed in claim 1 is characterized in that in step 2) in, the film parameter in the said film absorbent assembly is following: the membranous wall aperture is 0.0001～20 μ m, and the film bearing temperature is 0～60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105735468A CN102068880B (en) | 2010-12-03 | 2010-12-03 | Method for recycling ammonia gas in industrial waste gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105735468A CN102068880B (en) | 2010-12-03 | 2010-12-03 | Method for recycling ammonia gas in industrial waste gas |
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| CN102068880A CN102068880A (en) | 2011-05-25 |
| CN102068880B true CN102068880B (en) | 2012-11-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2010105735468A Ceased CN102068880B (en) | 2010-12-03 | 2010-12-03 | Method for recycling ammonia gas in industrial waste gas |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107875812A (en) * | 2017-11-16 | 2018-04-06 | 达州瓮福蓝剑化工有限责任公司 | A kind of device and method of ammonia washing |
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| CN102380302A (en) * | 2011-09-02 | 2012-03-21 | 黄再新 | Method for collecting, purifying and processing ammonia exhaust gas |
| CN103466656B (en) * | 2012-06-06 | 2015-09-02 | 华东理工大学 | A kind of membrane absorption method prepares the method for ultra-clean high-purity ammonium hydroxide |
| CN103331079B (en) * | 2013-07-10 | 2016-05-04 | 威士邦（厦门）环境科技有限公司 | A kind of membrane method ammonia is processed retracting device and technique |
| CN103466655B (en) * | 2013-09-29 | 2016-06-22 | 浙江建业化工股份有限公司 | The method of ammonia absorption plant and preparation ultra-clean high-purity ammonium hydroxide |
| CN107340319A (en) * | 2017-06-20 | 2017-11-10 | 中国石油化工股份有限公司 | A kind of method that non-contact gas membrane diffusion conductance directly detects ammonia nitrogen in waste water |
| CN107890761A (en) * | 2017-11-14 | 2018-04-10 | 合肥创想能源环境科技有限公司 | A kind of method that the industrial waste gas containing ammonia is handled using membrane separation technique |
| CN108332458A (en) * | 2018-03-26 | 2018-07-27 | 河南开祥精细化工有限公司 | The ammonia recycling device of ammonia refrigeration system |
| CN112106731A (en) * | 2019-06-20 | 2020-12-22 | 中国科学院分子植物科学卓越创新中心 | Integrated device for breeding hermetia illucens in large scale |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4180552A (en) * | 1978-03-20 | 1979-12-25 | Monsanto Company | Process for hydrogen recovery from ammonia purge gases |
| CN2388997Y (en) * | 1999-09-03 | 2000-07-26 | 华北工学院 | Mixed gas absorption deamination device |
| CN101053731A (en) * | 2006-08-31 | 2007-10-17 | 上海交通大学 | Membrane method ammonia leakage adsorption method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52155183A (en) * | 1976-06-18 | 1977-12-23 | Kansai Kagaku Kikai Seisaku Kk | Method of recovering valuable substances by continuous absorption distillation |
-
2010
- 2010-12-03 CN CN2010105735468A patent/CN102068880B/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4180552A (en) * | 1978-03-20 | 1979-12-25 | Monsanto Company | Process for hydrogen recovery from ammonia purge gases |
| CN2388997Y (en) * | 1999-09-03 | 2000-07-26 | 华北工学院 | Mixed gas absorption deamination device |
| CN101053731A (en) * | 2006-08-31 | 2007-10-17 | 上海交通大学 | Membrane method ammonia leakage adsorption method |
Non-Patent Citations (1)
| Title |
|---|
| JP昭52-155183A 1977.12.23 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107875812A (en) * | 2017-11-16 | 2018-04-06 | 达州瓮福蓝剑化工有限责任公司 | A kind of device and method of ammonia washing |
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