CN109289459A - A process for simultaneous removal of ammonia, sulfur and VOCs in waste gas from livestock and poultry breeding - Google Patents
A process for simultaneous removal of ammonia, sulfur and VOCs in waste gas from livestock and poultry breeding Download PDFInfo
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- CN109289459A CN109289459A CN201811174882.8A CN201811174882A CN109289459A CN 109289459 A CN109289459 A CN 109289459A CN 201811174882 A CN201811174882 A CN 201811174882A CN 109289459 A CN109289459 A CN 109289459A
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- ammonia
- vocs
- removal
- exhaust gas
- sulphur
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 77
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 43
- 244000144977 poultry Species 0.000 title claims abstract description 40
- 244000144972 livestock Species 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title claims abstract description 31
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 6
- 239000011593 sulfur Substances 0.000 title abstract description 6
- 239000002912 waste gas Substances 0.000 title abstract description 4
- 238000009395 breeding Methods 0.000 title abstract description 3
- 230000001488 breeding effect Effects 0.000 title abstract description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 73
- 238000010521 absorption reaction Methods 0.000 claims abstract description 61
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000009615 deamination Effects 0.000 claims abstract description 28
- 238000006481 deamination reaction Methods 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 239000005416 organic matter Substances 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 230000007062 hydrolysis Effects 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 82
- 239000005864 Sulphur Substances 0.000 claims description 43
- 239000007921 spray Substances 0.000 claims description 33
- 230000001360 synchronised effect Effects 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000012856 packing Methods 0.000 claims description 11
- 235000015097 nutrients Nutrition 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 244000005700 microbiome Species 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 230000000813 microbial effect Effects 0.000 claims description 4
- 238000006396 nitration reaction Methods 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 4
- 206010002660 Anoxia Diseases 0.000 claims description 3
- 241000976983 Anoxia Species 0.000 claims description 3
- 208000035404 Autolysis Diseases 0.000 claims description 3
- 206010057248 Cell death Diseases 0.000 claims description 3
- 206010021143 Hypoxia Diseases 0.000 claims description 3
- 241001509286 Thiobacillus denitrificans Species 0.000 claims description 3
- 230000007953 anoxia Effects 0.000 claims description 3
- 230000001651 autotrophic effect Effects 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000028043 self proteolysis Effects 0.000 claims description 3
- 230000009935 nitrosation Effects 0.000 claims description 2
- 238000007034 nitrosation reaction Methods 0.000 claims description 2
- 230000008557 oxygen metabolism Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000005507 spraying Methods 0.000 abstract description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- 229910002651 NO3 Inorganic materials 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 206010059410 Faecaluria Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- PDNNQADNLPRFPG-UHFFFAOYSA-N N.[O] Chemical compound N.[O] PDNNQADNLPRFPG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- -1 amino-acid salt Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 238000005261 decarburization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 235000021062 nutrient metabolism Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000012805 post-processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/44—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Treating Waste Gases (AREA)
Abstract
本发明公开了一种同步去除畜禽养殖废气中氨、硫及VOCs的工艺，包括：串联的脱氨模块和脱硫化氢模块；首先，畜禽养殖废气进入脱氨模块，在氨吸收装置中进行氨、VOCs的吸收和氨亚硝化后，得到的液体通过喷淋方式进入氨去除装置，通过厌氧氨去除实现氨的氮气转化，通过短程反硝化实现了液相中有机物的水解；接着进入脱硫化氢模块的硫化氢吸收装置，脱氨液体通过喷淋方式，废气直接导入，进行H2S、VOCs的吸收和有氧条件下H2S转化为硫单质，得到的液体进入硫化氢去除装置，在无氧条件下实现单质S的去除，同时去除VOCs。本发明利用好氧‑厌氧工艺相结合和不同反应模块之间的协同作用，实现氮、硫和VOCs的无害化去除。
The invention discloses a process for synchronously removing ammonia, sulfur and VOCs in waste gas from livestock and poultry breeding, comprising: a deamination module and a dehydrogen sulfide module connected in series; After the absorption of ammonia and VOCs and ammonia nitrification, the obtained liquid enters the ammonia removal device by spraying, realizes the nitrogen conversion of ammonia through anaerobic ammonia removal, and realizes the hydrolysis of organic matter in the liquid phase through short-range denitrification; In the hydrogen sulfide absorption device of the hydrogen sulfide removal module, the deammonia liquid is sprayed, and the waste gas is directly introduced to absorb H 2 S and VOCs and convert H 2 S into sulfur element under aerobic conditions, and the obtained liquid enters the hydrogen sulfide removal. The device realizes the removal of elemental S and VOCs under anaerobic conditions. The invention utilizes the combination of aerobic-anaerobic processes and the synergistic effect between different reaction modules to realize the harmless removal of nitrogen, sulfur and VOCs.
Description
Technical field
The invention belongs to technical field of waste gas treatment, in particular to ammonia in a kind of synchronous removal livestock and poultry cultivation exhaust gas, sulphur and
The technique of VOCs is suitable for the sulphur removal of livestock and poultry cultivation nitrogen emission and deodorization engineering.
Technical background
With the rapidly development of livestock and poultry breeding industry, intensive, modernization is constantly accelerated, and scale livestock farming is to environment
Caused by pollution also result in country attention.Wherein, the foul gas generated during livestock and poultry cultivation not only causes atmosphere dirty
Dye, and cultivated animals growth is impacted, serious person even influences the Health and Living quality of perimeter resident.Cause
This, how the processing livestock and poultry exhaust gas of safe green, to improve atmospheric environment and improve farm's nearby residents quality of life have
Important meaning.
What livestock and poultry cultivation exhaust gas generated be derived from all microorganism is using utilizing fecaluria, sewage and do not digest carbon in feed
The result of the nutrient metabolisms such as hydrate, fat, protein, minerals and vitamins effect.Microorganism is not mainly
Decomposing organic compounds generate foul gas under complete anaerobic condition.Therefore, the main component of livestock and poultry cultivation exhaust gas has ammonia and waves
Hair property amine, sulfur-containing compound (hydrogen sulfide, thioether class, thio-alcohol), volatile fatty acid, aromatic compound.
Livestock and poultry exhaust-gas treatment is exactly to handle its main component ammonia, hydrogen sulfide and volatile fatty acid.Wherein ammonia is de-
Except method has physical method, chemical method, catalytic decomposition, catalysis aerobic breakdown and bioanalysis
1. physical method is the most common technology of ammonia processing, i.e., industrial tail gas is absorbed using soft water or weak aqua ammonia as absorbent
In ammonia, obtained low concentration ammonium hydroxide further distills, liquefied ammonia utilization is made in rectifying, pressurization, condensation.Shortcoming mainly has:
Consume a large amount of water and energy；Recovery ammonia utilization rate is not high, and synthesis ammonia and urea production raw material is caused largely to lose；It generates certain
The NO of amountxCause secondary pollution.
2. chemical method is mainly the alkalinity for utilizing ammonia, so that ammonia and acidic materials is reacted and then generate low value-added nitrogen
Fertilizer, since the usual volatility of recovered solvent is big, corrosivity is strong, the method for ammonia is answered in industry in chemisorbing purifying industrial tail gas
It is gradually eliminated in.
3. catalytic decomposition is that ammonia is thoroughly decomposed into N under the effect of the catalyst2And H2, but there is also very for technique at present
Otherwise more problems will appear loss, catalyst sulfur poisoning or the generation ammonium salt blockage of catalyst if reaction temperature needs strict control
Phenomena such as catalyst, in addition the energy consumption of ammonia catalytic decomposition is high, and operating cost is high, is not suitable for generally using.
4. being catalyzed aerobic breakdown method is that ammonia is catalytically conveted to N under aerobic conditions2And water, decomposition reaction at 300 DEG C just
It can carry out, not generate secondary pollution, but method processing ammonia concentration is lower, is not suitable for the processing of higher concentration ammonia, otherwise wants
Temperature is improved, energy consumption is increased.
5. the Biochemical method of ammonia is to fill out ammonia-containing gas by porous containing fixation of microbe by biofiltration process
Expect that bed, the pollutant in air-flow are absorbed by biomembrane, removal generates CO2, H2O, NO2 -And NO3 -.It is compared with the traditional method, biology
Filtering technique has suitable advantage in terms of handling low concentration pollution gas, and the technology also has efficiently, low Meteorological
And operating cost, safety operation, low energy expenditure do not generate byproduct, can be converted to many inorganic matters and organic matter harmless
Remover the characteristics of.
The common removal methods of hydrogen sulfide mainly have absorption process, absorption method, dry method removal method and wet process removal method.
1. absorption process includes Physical Absorption and chemical absorption method.Physical Absorption method generallys use organic solvent as hydrogen sulfide
Absorbent, process is simple, is not required to the heat source of additional steam and other additional sources.Chemical absorption method is usually that hydrogen sulfide is molten
Yu Shuihou, using the solution of the strong base-weak acid salt with buffer function such as phenates, phosphate, borate, amino-acid salt etc. or one
A little weak base absorption processing.
2. absorption method is the absorption property purification hydrogen sulfide gas using certain porous materials, this method is usually used in handling
The lower gas of concentration of hydrogen sulfide.Usually require that adsorbent resistance is low, high without dust, adsorption capacity height, retention degree, due to absorption
The unsuitable frequent regeneration of deodorization device, it requires that entrance concentration of hydrogen sulfide cannot be too high, otherwise regeneration frequently, cause waste without
Ji.
3. dry method removal is to remove a kind of method of the hydrogen sulfide gas at elemental sulfur or removal of sulphur object, allusion quotation in general
Type has Claus method and selective removal method.It is raw material that Claus method, which is using hydrogen sulfide, interior in Crouse's combustion furnace to make
A part removal in exhaust gas generates SO2, with the H in air inlet2S reaction generates sulphur recovery.Claus method requires temperature in reactor
Degree is necessarily less than 650 DEG C, and the H of exhaust gas2S initial concentration is more than or equal to 15%-20%.Selective removal method is in catalyst
Under the action of with the oxygen in air by H2S directly removes as sulphur, the key of this method be develop selectivity it is good, to H2O and excess
O2Insensitive high activated catalyst is prepared with the different mixtures of iron-based remover at present.Selective removal method sulphur it is total
The rate of recovery can reach 98%-99%.
4. wet process removal is bigger than dry desulfurization processing capacity, operating flexibility is big, and desulfuration efficiency is high.Cardinal principle are as follows:
H2S+Na2CO3—NaHS+NaHCO3
2NaHS+4NaVO3+H2O—Na2V4O9+4NaOH+2S
Na2V4O9+2NaOH+H2O+2ADA—4NaVO3+2HADA
O2+2HADA—2ADA+2H2O
The technological problems are: harmful waste liquid processing is difficult, may cause secondary pollution；Micro-tapping is big；By-product makes
Drug consumption increases；The sulphur simple substance of generation is of poor quality；Suspended particulate recycling is difficult, easily causes plugged filter etc..
Summary of the invention
The present invention provides provide a kind of simultaneous denitrification sulphur removal biological treatment device that aerobic, anaerobism combines, it is therefore an objective to
The harmful components in livestock and poultry exhaust gas are removed, and overcome the shortcomings of existing processing ammonia, hydrogen sulfide and volatile organic matter technology.
Technical solution is as follows:
A kind of synchronous technique for removing ammonia, sulphur and VOCs in livestock and poultry cultivation exhaust gas, comprising: concatenated deamination module and desulfurization
Change hydrogen module；
Firstly, livestock and poultry cultivation exhaust gas enters deamination module, absorption and the ammonia that ammonia and VOCs are carried out in ammonia absorption plant are sub-
After nitrification, the obtained liquid dissolved with ammonia and conversion nitrite nitrogen enters ammonia removal device by spray mode, passes through anaerobism ammonia
The nitrogen conversion of ammonia is realized in removal, and the hydrolysis of the VOCs of dissolution in the liquid phase is realized by short-cut denitrification；
Then, the deamination liquid and exhaust gas that obtain by deamination resume module enter the hydrogen sulfide absorption of depriving hydrogen sulphide module
Device, by way of spray, exhaust gas is introduced directly into deamination liquid, carries out H2S, H under the absorption of VOCs and aerobic conditions2S is converted into
Sulphur simple substance, what is obtained is dissolved with H2S and NO3 -Liquid enters hydrogen sulfide removal device, under anaerobic, by with NO3 -Collaboration
The removal of simple substance S is realized in processing, while realizing the hydrolysis of VOCs in liquid phase.
Preferably, it is provided with spray system and biologic packing material in the gas distribution pipe of the ammonia absorption plant of the deamination module, benefit
The ammonia in exhaust gas is absorbed with spray liquid, and by control spray flow, gas residence time and pH value, is being inoculated with activated sludge
Polyester filler in realize conversion of the ammonia to nitrite nitrogen.
Preferably, the ammonia removal device of the deamination module is internally provided with needle-shaped filler, realize short-cut denitrification and
The synergistic effect of anaerobism ammonia removal forms biomembrane by microorganism and is divided into three regions,
Outermost layer completes NH4 +Removal, primary product NO2 -, a small amount of NO3 -；
NH occurs under anoxia condition for secondary outer layer4 +And NO2 -Reaction directly generates nitrogen；Part NO simultaneously2 -With the VOC in water
Short distance nitration reaction occurs for the organic matter generated with the hydrolysis acidification of organic granular；
The CO that anaerobic organism reaction generates occurs for innermost layer, anoxic organic matter2With the CO contained in exhaust gas2Anaerobism ammonia is provided
Carbon source required for removing.
Preferably, setting spray system and biologic packing material inside the hydrogen sulfide absorption device of the depriving hydrogen sulphide module, lead to
Control liquid spray flow, gas residence time and pH value are crossed, spray liquid autolysis oxygen completes H2The first step is good in aqueous solution by S
Oxygen reaction, forms part simple substance S, completes nutrient solution a part after absorbing and flows back into cyclic absorption exhaust gas in nutrient solution water tank,
Another part enters in hydrogen sulfide removal device；Microorganism in biologic packing material realizes H2S fully absorb and H2S is filled out in biology
To the conversion of sulphur simple substance in material.
Preferably, the hydrogen sulfide removal device of the depriving hydrogen sulphide module utilizes H remaining in spray liquid2S and deamination mould
The a small amount of NO generated in block3 -, generation simultaneous denitrification sulphur removal microorganism under the action of thiobacillus denitrificans is utilized under conditions of anaerobism
Reaction, by NO3 -It is converted into nitrogen, H2S is converted into sulphur simple substance, meanwhile, the part autotrophic microbe in liquid phase utilizes different oxygen metabolism
The VOCs of the remaining dissolution of removal in the liquid phase.
Preferably, polyester sponge filler, hydrogen sulfide removal are provided in the depriving hydrogen sulphide module hydrogen sulfide absorption device
Device is provided with needle-shaped filler.
Preferably, in livestock and poultry cultivation exhaust gas ammonia concentration range 2-20ppm, hydrogen sulfide concentration range in 0.1-
The concentration of 4ppm, VOCs are less than 1ppm.
Preferably, ammonia absorption process gas residence time controls the pH value in ammonia absorption process in 7.5- in 5-20s
Between 9, the spray flow of ammonia absorption process is 0.7-35L/min.
Preferably, the hydrogen sulfide residence time in 25s-30s, controls the pH value of hydrogen sulfide absorption process in 7-8, hydrogen sulfide is inhaled
The spray flow of receipts process is 0.7-35L/min.
The present invention can combine the synergistic effect between differential responses module using Aerobic-anaerobic technique, realize nitrogen, sulphur
With the innoxious removal of volatile organic matter.
Advantage of the present invention compared with the prior art has:
1. livestock and poultry cultivation exhaust-gas treatment synchronization process biological device, structure is simple, easy to process, convenient for future popularization and
Using.
2. the removal of ammonia, hydrogen sulfide and volatile organic matter is combined, treatment effeciency is improved.
3. step by step, stage by stage, subsystem handle livestock and poultry cultivation exhaust gas, by process flow be divided into ammonia abjection and hydrogen sulfide
Deviate from two big modules, while realizing the effect of the collaboration processing between two big modules, not only increases the place of ammonia and hydrogen sulfide
Efficiency is managed, and realizes the removal of volatile organic matter.
4. aerobic combine with anaerobic technique, the harmless treatment of ammonia and hydrogen sulfide is realized, exhaust gas, which uses, first to be absorbed
The mode of post-processing, by controlling operating parameter, during ammonia absorbs, using the oxygen in livestock and poultry exhaust gas by part ammonia
Remove into nitrite.Under anaerobic, by absorbing liquid ammonium ion and nitrite ion be converted into nitrogen, realize ammonia
The harmless treatment of gas；During hydrogen sulfide absorption, partial vulcanization hydrogen is removed as sulphur list using the oxygen in livestock and poultry exhaust gas
Matter.Under anaerobic, using microbial action by hydrogen sulfide absorption liquid sulphur hydrogen radical ion and nitrate ion be converted into
Sulphur simple substance and nitrogen.
5. it is low in cost, it is safe and efficient, it is not necessarily to catalyst and additional carbon, exhaust treatment system need to only supplement a small amount of water.
6. forming elemental sulfur can be with recovery section processing cost.
Detailed description of the invention
Ammonia, sulphur and VOCs process schematic representation in the synchronous removal livestock and poultry cultivation exhaust gas of Fig. 1.
Specific embodiment
To make those skilled in the art more fully understand technical solution of the present invention, below with reference to embodiment to the present invention
Ammonia, sulphur and VOCs technique are described in detail in a kind of synchronous removal livestock and poultry cultivation exhaust gas provided.
In synchronous removal livestock and poultry cultivation exhaust gas provided by the invention the technique of ammonia, sulphur and VOCs be divided into ammonia abjection module and
Hydrogen sulfide deviates from the big module of module two, and realizes the volatile organic matter in livestock and poultry exhaust gas by acting synergistically for two big modules
Removal.In livestock and poultry cultivation exhaust gas the concentration range of ammonia 2-20ppm, hydrogen sulfide concentration range in the dense of 0.1-4ppm, VOCs
Degree is less than 1ppm.
Embodiment 1
A kind of synchronous technique for removing ammonia, sulphur and VOCs in livestock and poultry cultivation exhaust gas, comprising: concatenated deamination module and desulfurization
Change hydrogen module；
Firstly, livestock and poultry cultivation exhaust gas enters deamination module by air-introduced machine, carried out in ammonia absorption plant ammonia absorption and
After nitrosation, what is obtained enters ammonia removal device by spray mode dissolved with ammonia and conversion nitrite nitrogen liquid, passes through anaerobism ammonia
The nitrogen conversion of ammonia is realized in removal, and the hydrolysis of the VOCs of dissolution in the liquid phase is realized by short-cut denitrification；
Then, the deamination liquid and exhaust gas that obtain by deamination resume module enter the hydrogen sulfide absorption of depriving hydrogen sulphide module
Device, by way of spray, exhaust gas is introduced directly into deamination liquid, carries out H2H under the absorption of S and aerobic conditions2S is converted into sulphur list
Matter, what is obtained is dissolved with H2S and NO3 -Liquid enters hydrogen sulfide removal device, under anaerobic, by with NO3 -Collaboration processing
It realizes the removal of simple substance S, while the VOCs of removal dissolution in the liquid phase is acted on by autotrophic microbe.
Finally, treated exhaust gas is discharged into atmosphere, and the solution handled through hydrogen sulphide disposal unit can recycle
It uses in ammonia absorption device.Wherein the removal rate of ammonia can achieve 90% or more in exhaust gas, the treatment effeciency of hydrogen sulfide
The removal efficiency that can achieve 95% or more, VOCs can achieve 70% or more.
It is provided with spray system and biologic packing material in the gas distribution pipe of deamination module ammonia absorption plant, is absorbed using spray liquid useless
Ammonia in gas, and the gas residence time 20s of ammonia absorption device is arranged in 2L-3.5L/min by control spray flow, it controls
PH value processed realizes conversion of the ammonia to nitrite nitrogen between 7-9 in the polyester filler for being inoculated with activated sludge.
Deamination module ammonia removal device is internally provided with needle-shaped filler, realizes the association of short-cut denitrification and the removal of anaerobism ammonia
Same-action forms biomembrane by microorganism and is divided into three regions, and outermost layer completes NH4 +Removal, primary product NO2 -, few
Measure NO3 -；NH occurs under anoxia condition for secondary outer layer4 +And NO2 -Reaction directly generates nitrogen；Part NO simultaneously2 -With in water VOC and
Short distance nitration reaction occurs for the organic matter that the hydrolysis acidification of organic granular generates；Anaerobic organism occurs for innermost layer, anoxic organic matter
React the CO generated2With the CO contained in exhaust gas2Carbon source required for anaerobism ammonia removes is provided.
Setting spray system and biologic packing material inside depriving hydrogen sulphide module hydrogen sulfide absorption device pass through control liquid spray
The gas residence time 30s of hydrogen sulfide absorption device is arranged in 3-3.5L/min in amount, controls pH between 7-8, spray liquid itself
Dissolved oxygen completes H2It is a part of to complete the nutrient solution after absorbing to S by first step aerobic reaction, formation part simple substance S in aqueous solution
Cyclic absorption exhaust gas in nutrient solution water tank is flowed back into, another part enters in hydrogen sulfide removal device；Micro- life in biologic packing material
Object realizes H2S fully absorb and H2S is in biologic packing material to the conversion of sulphur simple substance.
Depriving hydrogen sulphide module hydrogen sulfide removal device, utilizes H remaining in spray liquid2What is generated in S and deamination module lacks
Measure NO3 -, using simultaneous denitrification sulphur removal microbial reaction occurs under the action of thiobacillus denitrificans under conditions of anaerobism, by NO3 -Turn
Nitrogen, H are turned to2S is converted into sulphur simple substance.Polyester sponge filler, sulphur are provided in depriving hydrogen sulphide module hydrogen sulfide absorption device
Change hydrogen removal device and is provided with needle-shaped filler.
The present invention can combine the synergistic effect between differential responses module using Aerobic-anaerobic technique, realize nitrogen, sulphur
With the innoxious removal of volatile organic matter.
Specific process flow is as follows:
(1) process flow
This process flow is divided into gas line and liquid line:
Gas line is livestock and poultry cultivation exhaust gas by air-introduced machine introducing ammonia removing module, de- into hydrogen sulfide after treatment
Except module, atmosphere is discharged into after harmless treatment.
Liquid line is that the absorbing liquid of ammonia is absorbed in ammonia removing module, removes rear portion as repeats itself into ammonia is crossed
Absorbing liquid, another part enter hydrogen sulfide stripping module, after the harmless treatment of hydrogen sulfide stripping module, enter back into ammonia
Module is removed, the circulation of liquid is completed.
(2) course of work of the invention is as follows:
1. ammonia absorption process: livestock and poultry cultivation exhaust gas is entered by air-introduced machine in the gas distribution pipe of deamination module absorption plant,
Subsequently into the polyester filler for being inoculated with activated sludge, the nutrient solution sprayed with screw spraying head is inversely contacted, and is utilized
Ammonia property soluble easily in water fully absorbs ammonia, and passes through the amount of the air inflow of control air-introduced machine and recirculating nutrient solution, control
Time of contact processed, promote NH4 +NO is converted under the action of nitrite bacteria2 -.Standing reservoir after absorption is in absorption plant
Bottom storage at, partial reflux cyclic absorption exhaust gas into nutrient solution water tank, another part enters in ammonia oxygen reaction unit.
2. anaerobism ammonia removal process: the absorbing liquid of previous step enters in deamination module removal device, in this course, living
Property sludge be grown on needle-shaped filler, three regions can be divided by being formed by biomembrane: outermost layer completes NH4 +Removal, lead to
Control is crossed, product is mainly NO2 -, a small amount of NO3 -；In secondary outer layer, since NH can occur for anoxic4 +And NO2 -Reaction, directly produce
Nitrogen；Part NO simultaneously2 -Short distance can also occur with the organic matter (mainly from the hydrolysis acidification of VOC and organic granular) for being dissolved in water
Nitration reaction；CO is generated since anaerobic organism reaction can occur for anoxic organic matter in innermost layer2, the CO of release2In exhaust gas
The CO contained2Carbon source required for anaerobism ammonia removes can be provided.Therefore, denitrogenation can occur simultaneously in this region and decarburization is anti-
It answers, i.e., removes NH simultaneously3, VOCs and organic granular.
3. hydrogen sulfide absorption process: the livestock and poultry exhaust gas by ammonia absorption process goes successively to depriving hydrogen sulphide absorption plant
In, in this process, H is completed using spray liquid autolysis oxygen2S first step aerobic reaction in aqueous solution forms part
Simple substance S.For standing reservoir after absorption at the bottom storage of absorption plant, partial reflux cyclic absorption into nutrient solution water tank is useless
Gas, another part enter in hydrogen sulfide reaction unit.
4. hydrogen sulfide removal process: being dissolved in remaining H in spray liquid2S, into depriving hydrogen sulphide removal device in anaerobism
Under the conditions of with deamination during the NO that is formed3 -Simultaneous denitrification sulphur removal microbial reaction, the following 5HS of key reaction process occurs-+
2NO3 -+7H+→5S+N2+6H2O.Realize completely removing for hydrogen sulfide.
Example of the invention is explained in detail above in conjunction with embodiment, but the present invention is not limited to examples detailed above,
All any improvement and modification made for the present invention belong to the protection scope of the claims in the present invention.
Claims (9)
1. the technique of ammonia, sulphur and VOCs in a kind of synchronous removal livestock and poultry cultivation exhaust gas, comprising: concatenated deamination module and devulcanization
Hydrogen module；It is characterized in that,
Firstly, livestock and poultry cultivation exhaust gas enters deamination module, the absorption and ammonia nitrosation of ammonia and VOCs are carried out in ammonia absorption plant
Afterwards, the liquid dissolved with ammonia and conversion nitrite nitrogen obtained enters ammonia removal device by spray mode, is removed by anaerobism ammonia
The nitrogen conversion for realizing ammonia, the hydrolysis of the VOCs of dissolution in the liquid phase is realized by short-cut denitrification；
Then, the deamination liquid and exhaust gas obtained by deamination resume module enters the hydrogen sulfide absorption dress of depriving hydrogen sulphide module
It sets, by way of spray, exhaust gas is introduced directly into deamination liquid, carries out H2S, H under the absorption of VOCs and aerobic conditions2S is converted into sulphur
Simple substance, what is obtained is dissolved with H2S and NO3 -Liquid enters hydrogen sulfide removal device, under anaerobic, by with NO3 -At collaboration
Reason realizes the removal of simple substance S, while realizing the hydrolysis of VOCs in liquid phase.
2. the synchronous technique for removing ammonia, sulphur and VOCs in livestock and poultry cultivation exhaust gas according to claim 1, which is characterized in that institute
It states in the gas distribution pipe of the ammonia absorption plant of deamination module and is provided with spray system and biologic packing material, absorbed in exhaust gas using spray liquid
Ammonia ammonia is realized in the polyester filler for being inoculated with activated sludge and by control spray flow, gas residence time and pH value
Conversion to nitrite nitrogen.
3. ammonia, sulphur and VOCs technique in synchronous removal livestock and poultry cultivation exhaust gas according to claim 2, which is characterized in that described
The ammonia removal device of deamination module is internally provided with needle-shaped filler, and the collaboration for realizing short-cut denitrification and the removal of anaerobism ammonia is made
With, biomembrane is formed by microorganism and is divided into three regions,
Outermost layer completes NH4 +Removal, primary product NO2 -, a small amount of NO3 -；
NH occurs under anoxia condition for secondary outer layer4 +And NO2 -Reaction directly generates nitrogen；Part NO simultaneously2 -With the VOC in water and have
Short distance nitration reaction occurs for the organic matter that the hydrolysis acidification of machine particle generates；
The CO that anaerobic organism reaction generates occurs for innermost layer, anoxic organic matter2With the CO contained in exhaust gas2The removal of anaerobism ammonia is provided
Required carbon source.
4. the synchronous technique for removing ammonia, sulphur and VOCs in livestock and poultry cultivation exhaust gas according to claim 3, which is characterized in that institute
State setting spray system and biologic packing material inside the hydrogen sulfide absorption device of depriving hydrogen sulphide module, by control liquid spray flow,
Gas residence time and pH value, spray liquid autolysis oxygen complete H2First step aerobic reaction, formation part are single in aqueous solution by S
Matter S, nutrient solution a part after completing absorption flow back into cyclic absorption exhaust gas, another part in nutrient solution water tank and enter hydrogen sulfide
In removal device；Microorganism in biologic packing material realizes H2S fully absorb and H2S is in biologic packing material to the conversion of sulphur simple substance.
5. the synchronous technique for removing ammonia, sulphur and VOCs in livestock and poultry cultivation exhaust gas according to claim 4, which is characterized in that institute
The hydrogen sulfide removal device for stating depriving hydrogen sulphide module utilizes H remaining in spray liquid2It is generated in S and deamination module a small amount of
NO3 -, using simultaneous denitrification sulphur removal microbial reaction occurs under the action of thiobacillus denitrificans under conditions of anaerobism, by NO3 -Conversion
For nitrogen, H2S is converted into sulphur simple substance, meanwhile, the part autotrophic microbe in liquid phase is dissolved in using different oxygen metabolism removal residue
VOCs in liquid phase.
6. the synchronous technique for removing ammonia, sulphur and VOCs in livestock and poultry cultivation exhaust gas according to claim 5, which is characterized in that institute
It states and is provided with polyester sponge filler in the hydrogen sulfide absorption device of depriving hydrogen sulphide module, hydrogen sulfide removal device is provided with needle-shaped fill out
Material.
7. the synchronous technique for removing ammonia, sulphur and VOCs in livestock and poultry cultivation exhaust gas according to claim 6, which is characterized in that poultry
The concentration range of ammonia is less than in concentration of the concentration range in 0-4ppm, VOCs of 2-20ppm, hydrogen sulfide in fowl cultivation exhaust gas
1ppm。
8. the synchronous technique for removing ammonia, sulphur and VOCs in livestock and poultry cultivation exhaust gas according to claim 7, which is characterized in that ammonia
The aspiration process gas residence time in 15-20s, controls the pH value in ammonia absorption process between 7.5-9, ammonia absorbed
The spray flow of journey is 0.7-35L/min.
9. the synchronous technique for removing ammonia, sulphur and VOCs in livestock and poultry cultivation exhaust gas according to claim 8, which is characterized in that sulphur
Change the hydrogen residence time in 25s-30s, controls the pH value of hydrogen sulfide absorption process in 7-8, the spray flow of hydrogen sulfide absorption process is
0.7-35L/min。
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| CN109745851A (en) * | 2019-03-05 | 2019-05-14 | 江苏省农业科学院 | An air purification device in a livestock house |
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