JP2005125146A - Deodorizing method and deodorizing liquid - Google Patents
Deodorizing method and deodorizing liquid Download PDFInfo
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- JP2005125146A JP2005125146A JP2003360668A JP2003360668A JP2005125146A JP 2005125146 A JP2005125146 A JP 2005125146A JP 2003360668 A JP2003360668 A JP 2003360668A JP 2003360668 A JP2003360668 A JP 2003360668A JP 2005125146 A JP2005125146 A JP 2005125146A
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- 230000001877 deodorizing effect Effects 0.000 title claims abstract description 56
- 239000007788 liquid Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims description 9
- 238000004332 deodorization Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 45
- 229910021529 ammonia Inorganic materials 0.000 abstract description 22
- 239000007864 aqueous solution Substances 0.000 abstract description 15
- 239000000243 solution Substances 0.000 abstract description 12
- 235000019645 odor Nutrition 0.000 description 34
- 239000007789 gas Substances 0.000 description 28
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 16
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 12
- JZBWUTVDIDNCMW-UHFFFAOYSA-L dipotassium;oxido sulfate Chemical compound [K+].[K+].[O-]OS([O-])(=O)=O JZBWUTVDIDNCMW-UHFFFAOYSA-L 0.000 description 10
- 238000000855 fermentation Methods 0.000 description 9
- 230000004151 fermentation Effects 0.000 description 9
- 230000000813 microbial effect Effects 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 239000002361 compost Substances 0.000 description 8
- 235000019260 propionic acid Nutrition 0.000 description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 8
- 239000010802 sludge Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- 239000010813 municipal solid waste Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 210000003608 fece Anatomy 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000012476 oxidizable substance Substances 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LPLLVINFLBSFRP-UHFFFAOYSA-N 2-methylamino-1-phenylpropan-1-one Chemical compound CNC(C)C(=O)C1=CC=CC=C1 LPLLVINFLBSFRP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 241000132539 Cosmos Species 0.000 description 2
- 235000005956 Cosmos caudatus Nutrition 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000010871 livestock manure Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000010801 sewage sludge Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- NQGAHEQUJJXMTC-UHFFFAOYSA-N N.CSSC Chemical compound N.CSSC NQGAHEQUJJXMTC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- -1 persulfate ions Chemical class 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Treating Waste Gases (AREA)
- Fertilizers (AREA)
Abstract
Description
本発明は、脱臭方法及び脱臭剤に係り、特に、生ゴミ、汚泥、***物などの微生物発酵に伴って発生するアンモニア類を主体に硫黄化合物や脂肪酸類など微量の臭気成分が混在する悪臭成分を効果的に除去する臭気除去方法及び脱臭剤に関する。 The present invention relates to a deodorizing method and a deodorizing agent, and in particular, malodorous components in which a small amount of odorous components such as sulfur compounds and fatty acids are mixed mainly with ammonia generated by microbial fermentation such as garbage, sludge and excreta. The present invention relates to an odor removing method and a deodorizing agent that effectively remove odor.
従来、微生物発酵に伴う悪臭を無臭化処理する場合、主要な臭気成分がアンモニアやトリメチルアミンなどの水溶性アルカリ臭気成分であるところから、硫酸などの酸成分を含有する酸性脱臭液と悪臭ガスを接触させて、中和反応によりアルカリ性臭気成分を除去し、次いでプロピオン酸、メルカプタン、硫化メチルなど微量に混在する酸性あるいは中性臭気成分を活性炭吸着によって処理を行ったり、あるいは各種の酸化剤、オゾン酸化によって除去、分解処理を行っていた。
例えば、酸化剤として、ペルオキシジサルフェイトを用いた***物の処理方法が提案されている（特許文献１）。
また、過酸化ジ硫酸アンモニウムと硫酸アンモニウム、硫酸ナトリウム、リン酸アンモニウム、リン酸ナトリウムの１種または２種以上を添加する糞尿の脱臭方法が提案されている（特許文献２）。
Conventionally, when the malodor associated with microbial fermentation is treated without bromide, the main odor component is a water-soluble alkaline odor component such as ammonia or trimethylamine, so the acid deodorant containing acid component such as sulfuric acid is contacted with the odor gas. The neutral odor component is removed by neutralization, and then acidic or neutral odor components such as propionic acid, mercaptan and methyl sulfide are treated by activated carbon adsorption, or various oxidizing agents and ozone oxidation. It was removed and decomposed.
For example, a method for treating excreta using peroxydisulfate as an oxidizing agent has been proposed (Patent Document 1).
Further, a method for deodorizing feces and urine has been proposed in which one or more of ammonium persulfate and ammonium sulfate, sodium sulfate, ammonium phosphate, and sodium phosphate are added (Patent Document 2).
これらの方法で用いられている過硫酸塩を用いた脱臭液を吸収液として微生物発酵に伴って発生する悪臭成分を無臭化処理しようとすると、ペルオキソ二硫酸ナトリウム塩等の過硫酸塩は、早期に分解して発生期の酸素を大量に生成するために、余剰の発生期の酸素は悪臭成分の脱臭には有効に利用されないので脱臭剤が分解してしまうという問題点があるのみではなく、微生物発酵に伴って発生する大量のアンモニアの処理には有効ではなかった。 When the deodorizing solution using persulfate used in these methods is used as an absorbing solution and an attempt is made to deodorize malodorous components generated during microbial fermentation, persulfates such as sodium peroxodisulfate are In order to produce a large amount of nascent oxygen by decomposing into, the excess nascent oxygen is not effectively used for deodorizing malodorous components, so there is a problem that the deodorizer decomposes, It was not effective for the treatment of a large amount of ammonia generated by microbial fermentation.
また、活性炭吸着法等では通気ガスの圧力損失が大きく、大容量のガス処理には大容積の吸着塔と大型送風機を要し、オゾン酸化法も機械装置の腐食や、未反応オゾンの無害化処理装置の運転など、脱臭装置の維持管理や運転に多大な設備および費用を要していた。
本発明は、生ゴミ、堆肥、汚泥等の微生物発酵、動物の糞尿等によって発生するアンモニア等のアルカリ性臭気成分からアンモニア、および付随する他の臭気成分を確実に分解除去する脱臭方法および脱臭液を提供することを課題とするものである。 The present invention provides a deodorizing method and a deodorizing liquid for reliably decomposing and removing ammonia and other odorous components accompanying alkaline odorous components such as ammonia generated by microbial fermentation of animal waste, compost, sludge, etc., and animal manure, etc. The issue is to provide.
本発明の課題は、脱臭方法において、臭気成分含有気体を酸濃度０．０５規定以上の硫酸水溶液と過硫酸塩からなる脱臭液とを接触する脱臭方法によって解決することができる。
また、過硫酸塩がペルオキソモノ硫酸塩である前記の脱臭方法である。
酸濃度０．０５規定以上の硫酸水溶液と過硫酸塩からなる前記の脱臭液である。
また、過硫酸塩がペルオキソモノ硫酸塩である前記の脱臭液である。
The object of the present invention can be solved by a deodorizing method in which an odor component-containing gas is brought into contact with a sulfuric acid aqueous solution having an acid concentration of 0.05 N or more and a deodorizing liquid comprising a persulfate.
Further, in the above deodorizing method, the persulfate is peroxomonosulfate.
The deodorizing liquid comprising an aqueous sulfuric acid solution having an acid concentration of 0.05 N or more and a persulfate.
Further, in the above-described deodorizing liquid, the persulfate is peroxomonosulfate.
微生物発酵に伴う悪臭に代表される、アンモニア等のアルカリ性臭気成分を主体に、酸性臭気成分、中性臭気成分が混在する悪臭ガスを、脱臭液との接触によって無臭化処理することができる。 Odorless gas containing mainly acidic odor components such as ammonia and acidic odor components and neutral odor components, represented by malodor caused by microbial fermentation, can be debrominated by contact with a deodorizing liquid.
本発明は、所定の酸濃度以上の硫酸水溶液を用いることによって過硫酸塩の分解を抑制して水溶液中において安定して存在させることができる。被酸化性物質が導入された場合にのみ、過硫酸イオンから発生期の酸素が生成して、被酸化性物質の酸化分解が行われるので、過硫酸塩を有効に利用することが可能となり、しかも、生ゴミ、堆肥、汚泥等の微生物発酵や、動物の糞尿等から大量に発生するアンモニアやアミン類などのアルカリ性臭気成分は、過硫酸塩の安定化剤として作用する硫酸と中和反応し、溶液中に硫酸アンモニウムなどの水溶性成分として取り込まれ除去される。その結果、プロピオン酸、メルカプタン、硫化メチルなどの酸性あるいは中性臭気成分とともにアルカリ性臭気成分を同時に除去することが可能となることを見出したものである。 In the present invention, by using an aqueous sulfuric acid solution having a predetermined acid concentration or more, decomposition of persulfate can be suppressed and the aqueous solution can be stably present in the aqueous solution. Only when an oxidizable substance is introduced, nascent oxygen is generated from persulfate ions and the oxidizable substance is oxidatively decomposed, so that it is possible to effectively use the persulfate. In addition, alkaline odorous components such as ammonia and amines generated in large quantities from microbial fermentation of raw garbage, compost, sludge, etc., and animal manure, etc., neutralize with sulfuric acid that acts as a stabilizer for persulfate. In the solution, it is taken in and removed as a water-soluble component such as ammonium sulfate. As a result, it has been found that it is possible to simultaneously remove an alkaline odor component together with an acidic or neutral odor component such as propionic acid, mercaptan, methyl sulfide and the like.
本発明のペルオキソ硫酸塩の酸化作用をペルオキソモノ硫酸カリウムを例に挙げて説明すると、ペルオキソモノ硫酸カリウムは水溶液中で
ＫＨＳＯ5 → Ｋ+ ＋ ＨＳＯ5 - （１）
ＨＳＯ5 - → Ｈ+ ＋ ＳＯ5 2- （２）
ＨＳＯ5 - → ＨＳＯ4 - ＋ Ｏ（active） （３）
で示すように解離反応をする。そして、生成した発生期の酸素は、被酸化性物質と反応して、
Ｏ(active) ＋２Ｈ+ ＋ ２ｅ- → ＨＳＯ4 - ＋ Ｈ2Ｏ （４）
なる反応によって、水とＨＳＯ4 -イオンを生成する。
The oxidation action of the peroxosulfate of the present invention will be described by taking potassium peroxomonosulfate as an example. Potassium peroxomonosulfate is an aqueous solution of KHSO 5 → K + + HSO 5 −. (1)
HSO 5 − → H + + SO 5 2− (2)
HSO 5 - → HSO 4 - + O (active) (3)
Dissociation reaction as shown in. The generated nascent oxygen reacts with the oxidizable substance,
O (active) + 2H + + 2e − → HSO 4 − + H 2 O (4)
This produces water and HSO 4 − ions.
一方、脱臭液の他の成分として共存する酸濃度０．０５規定以上の硫酸水溶液中の硫酸は、水溶液中において以下のように解離をする。
Ｈ2ＳＯ4 → Ｈ+ ＋ ＨＳＯ4 - （全量）
ＨＳＯ4 - → Ｈ+ ＋ ＳＯ4 2- （２×１０-2）
脱臭液中に臭気成分である被酸化性物質がないときには、大過剰の ＨＳＯ4 - の共通イオン効果で、ペルオキソイオンは極めて安定的に存在するが、被酸化性物質である臭気成分が導入されると、（４）の反応によりこれが分解され、（３）の反応が進行して活性な酸素によって臭気成分が分解消滅することとなる。
On the other hand, sulfuric acid in a sulfuric acid aqueous solution having an acid concentration of 0.05 N or more which coexists as another component of the deodorizing liquid dissociates in the aqueous solution as follows.
H 2 SO 4 → H + + HSO 4 − (Total amount)
HSO 4 − → H + + SO 4 2− (2 × 10 −2 )
When there is no oxidizable material that is odor component in deodorizing liquid, large excess of HSO 4 - a common ion effect, the peroxo ions are present in very stable manner, but introduces odorous component is oxidizable substance Then, this is decomposed by the reaction of (4), and the reaction of (3) proceeds and the odor component is decomposed and extinguished by active oxygen.
以上のようにして、安定的な脱臭作用を長期間進めることが可能となります。また、生ゴミ、堆肥等の有機物の分解においては臭気成分とともに大量のアンモニアが発生するが、アンモニアはペルオキソ硫酸塩と共存している硫酸水溶液中の硫酸と反応してアンモニアを水溶液中に吸収除去して脱臭することが可能となる。 As described above, stable deodorization can be promoted for a long time. In addition, in the decomposition of organic matter such as garbage and compost, a large amount of ammonia is generated along with odor components, but ammonia reacts with sulfuric acid in sulfuric acid aqueous solution coexisting with peroxosulfate to absorb and remove ammonia in the aqueous solution. It becomes possible to deodorize.
本発明で用いることが可能な過硫酸塩としては、ペルオキソモノ硫酸カリウム塩（ＫＨＳＯ5）、ペルオキソ二硫酸カリウム塩（Ｋ2Ｓ2Ｏ8）、ペルオキソ二硫酸ナトリウム塩（Ｎａ2Ｓ2Ｏ8）、ペルオキソ二硫酸アンモニウム塩（（ＮＨ4）2Ｓ2Ｏ8）などを挙げることができる。
これらのなかでも、モノ硫酸塩は二硫酸塩に比べて、発火性、爆発性等が小さく安定であって取り扱いが容易であるという特徴を有しているとともに、分子量に対して活性な酸素の割合が大きく、酸化作用の効率が大きいという特徴を有している。更に先の式（３）で示した分解速度はモノ硫酸塩の方が大きいので、反応速度が二硫酸塩に比べて大きいという特徴も有している。したがって、過硫酸塩としては、モノ硫酸塩を用いることが好ましい。
Examples of persulfates that can be used in the present invention include potassium peroxomonosulfate (KHSO 5 ), potassium peroxodisulfate (K 2 S 2 O 8 ), and sodium peroxodisulfate (Na 2 S 2 O 8). ), Ammonium peroxodisulfate ((NH 4 ) 2 S 2 O 8 ), and the like.
Among these, monosulfate is characterized by being less ignitable, explosive, etc., stable and easy to handle, compared to disulfate, and it also has an active oxygen content with respect to molecular weight. The ratio is large and the efficiency of oxidation action is large. Furthermore, the monosulfate has a higher decomposition rate than that shown in the above formula (3), so that the reaction rate is higher than that of disulfate. Therefore, it is preferable to use a monosulfate as the persulfate.
図１に、ペルオキソモノ硫酸カリウム塩水溶液の安定性とｐＨとの関係を示す。
図１に示すように、ペルオキソモノ硫酸カリウム塩水溶液は、ｐＨ６以下の水溶液とすることによって水溶液中での自己分解を抑制し、酸化剤として長期安定的に機能させることができ、ペルオキソモノ硫酸塩の安定化のためには、共通イオンを有する酸である硫酸が好ましい。
FIG. 1 shows the relationship between the stability of aqueous potassium peroxomonosulfate and pH.
As shown in FIG. 1, a potassium peroxomonosulfate aqueous solution can suppress self-decomposition in an aqueous solution by using an aqueous solution having a pH of 6 or less and can function stably as an oxidizing agent for a long period of time. In order to stabilize, sulfuric acid which is an acid having a common ion is preferable.
脱臭液中の硫酸濃度は、０．０５規定以上とすることが好ましい。０．０５規定以上とすることによって、アンモニア除去率９０％以上を得るとともに、ペルオキソモノ硫酸カリウム塩水溶液を安定なものとすることができる。
また、硫酸の濃度を高くすることによって脱臭処理する処理対象物の量を多くすることができるので一定量の脱臭液によって長期間の脱臭処理が可能となる。
しかしながら、硫酸濃度が２規定よりも高濃度となると、脱臭液の腐食性が高まり、脱臭装置の構造材、ガスケット等として使用可能な部材が制限されるなるので、長期間安定して運転を行うためには、２規定以下とすることが好ましい。
The sulfuric acid concentration in the deodorizing liquid is preferably 0.05 N or more. By making it 0.05 or more, it is possible to obtain an ammonia removal rate of 90% or more and to stabilize the aqueous potassium peroxomonosulfate salt solution.
Further, since the amount of the object to be deodorized can be increased by increasing the concentration of sulfuric acid, a long-term deodorizing process can be performed with a certain amount of deodorizing liquid.
However, when the sulfuric acid concentration is higher than 2N, the corrosiveness of the deodorizing liquid is increased, and the members that can be used as the structural material, gasket, and the like of the deodorizing device are limited. Therefore, it is preferable to set it to 2 regulations or less.
また、本発明の脱臭方法では、過硫酸塩の酸性溶媒を硫酸水溶液としたので、生ゴミ、堆肥、汚泥等の微生物発酵時の臭気性気体の主要な成分であるアンモニアは硫酸水溶液との中和の結果無害な硫酸アンモニウムを生成する。硫酸アンモニウムは肥料成分として有効活用が図られる。更に、ペルオキソ硫酸塩の自己分解に対しても硫酸水溶液が共通イオン効果として抑制的に作用させることができる。 Further, in the deodorization method of the present invention, since the persulfate acidic solvent is an aqueous sulfuric acid solution, ammonia, which is a major component of odorous gas during microbial fermentation, such as garbage, compost, and sludge, is contained in the aqueous sulfuric acid solution. As a result of the sum, harmless ammonium sulfate is produced. Ammonium sulfate can be effectively used as a fertilizer component. Furthermore, the sulfuric acid aqueous solution can act as a common ion effect in a suppressive manner on the self-decomposition of peroxosulfate.
図２は、本発明の脱臭方法の一実施例を説明する図である。
本発明の脱臭装置１には、下部に循環する脱臭液２を蓄えた脱臭液貯槽３を有し、循環ポンプ４によって、充填層５の上部に設けたシャワー部６から脱臭液２を噴霧し、気体入口７から導入された被処理気体８と接触させられる。
アンモニア等のアルカリ性臭気成分は、脱臭液中の硫酸により中和吸収され、二硫化メチルやプロピオン酸などの中性あるいは酸性臭気成分は、硫酸酸性浴中で過硫酸塩から発生する発生期の酸素によって無臭な物質に酸化分解されて排気されて、気液分離部９において被処理気体に伴った液を分離して排出口１０から脱臭処理された気体を排出することができる。
FIG. 2 is a diagram for explaining an embodiment of the deodorizing method of the present invention.
The
Alkaline odor components such as ammonia are neutralized and absorbed by sulfuric acid in the deodorizing solution, and neutral or acidic odor components such as methyl disulfide and propionic acid are nascent oxygen generated from persulfate in a sulfuric acid acidic bath. Thus, the odor-degraded substance is oxidatively decomposed and exhausted, and the gas accompanying the gas to be treated can be separated in the gas-
脱臭装置の運転にしたがって硫酸アンモニウムが蓄積し、硫酸および過硫酸塩が消費されてアンモニアの吸収、あるいはその他の臭気成分の分解能力が低下すると、新規に脱臭液を補充したり、装置内の液を新規な脱臭液に交換して運転することができる。
また、交換後の脱臭液から水分を分離することによって得られた硫酸アンモニウムは、肥料として有効利用することができる。
When ammonium sulfate accumulates as the deodorizer operates, and when sulfuric acid and persulfate are consumed and ammonia is absorbed or the ability to decompose other odorous components decreases, the deodorizer can be replenished or the liquid in the device can be removed. It can be operated by replacing it with a new deodorizing liquid.
Moreover, the ammonium sulfate obtained by isolate | separating a water | moisture content from the deodorizing liquid after replacement | exchange can be effectively utilized as a fertilizer.
図３は、本発明の脱臭方法の他の実施例を説明する図である。
図３に示した脱臭装置２１は、気泡塔式の脱臭装置の一例を説明する図である。脱臭液槽２２の下部には、被処理気体導入管２３が設けられており、分散ノズル２４を通じて脱臭液槽２２の下部から脱臭液槽内に被処理気体が供給されて、脱臭液中を上昇する間にアンモニア等のアルカリ性臭気成分の中和吸収および他の悪臭物質の酸化等が行われた後に、気液分離部９において、被処理気体に伴った液を分離して排出口２５から脱臭処理された気体を排出することができる。
以下に、実施例を示し本発明を説明する。
FIG. 3 is a diagram for explaining another embodiment of the deodorizing method of the present invention.
The deodorizing apparatus 21 shown in FIG. 3 is a diagram for explaining an example of a bubble column type deodorizing apparatus. A to-be-treated gas introduction pipe 23 is provided at the lower part of the deodorizing liquid tank 22, and the to-be-treated gas is supplied from the lower part of the deodorizing liquid tank 22 into the deodorizing liquid tank through the
Hereinafter, the present invention will be described with reference to examples.
過硫酸塩として濃度が異なるペルオキソモノ硫酸カリウムを含有した表１に示した２規定硫酸水溶液を脱臭液として調製し、脱臭液を１００ｍｌ入れた洗気瓶に濃度７００ｐｐｍのアンモニアと濃度０．２９ｐｐｍの二硫化ジメチルを含む混合臭気成分を４０００ｍｌ／ｍｉｎの流量で通気させて脱臭実験を行い、出口気体濃度をガス検知管およびニオイセンサ（新コスモス電機製 ＸＰ−３２９Ｓ）によって測定し、その結果を表１に示す。 A 2N sulfuric acid aqueous solution shown in Table 1 containing potassium peroxomonosulfate having different concentrations as a persulfate was prepared as a deodorizing solution, and a 700 ml ammonia gas and a 0.29 ppm concentration in a washing bottle containing 100 ml of the deodorizing solution. A mixed odor component containing dimethyl disulfide was aerated at a flow rate of 4000 ml / min to conduct a deodorization experiment, and the outlet gas concentration was measured with a gas detector tube and an odor sensor (New Cosmos Electric XP-329S). It is shown in 1.
表１
出口気体濃度(ppm)（ ）内は 除去率（％）
試料 過硫酸塩濃度(g/l) アンモニア 二硫化ジメチル
１−１ ０ ０．５（９９．９） ０．２９ （０）
１−２ １ ０．５（９９．９） ０．０８３（７１．４）
１−３ ２ ０．５（９９．９） ０．０６４（７７．９）
１−４ ５ ０．５（９９．９） ０．０５０（８２．８）
１−５ １０ ０．５（９９．９） ０．０３７（８７．２）
１−６ ２０ ０．５（９９．９） ０．０２８（９０．３）
１−７ ４０ ０．５（９９．９） ０．０２２（９２．４）
１−８ ８０ ０．５（９９．９） ０．０２０（９３．１）
１−９ １６０ ０．５（９９．９） ０．００４（９８．６）
Table 1
Outlet gas concentration (ppm) () indicates removal rate (%)
Sample Persulfate concentration (g / l) Ammonia Dimethyl disulfide
1-1 0 0.5 (99.9) 0.29 (0)
1-2 1 0.5 (99.9) 0.083 (71.4)
1-3 2 0.5 (99.9) 0.064 (77.9)
1-4 5 0.5 (99.9) 0.050 (82.8)
1-5 10 0.5 (99.9) 0.037 (87.2)
1-6 20 0.5 (99.9) 0.028 (90.3)
1-7 40 0.5 (99.9) 0.022 (92.4)
1-8 80 0.5 (99.9) 0.020 (93.1)
1-9 160 0.5 (99.9) 0.004 (98.6)
実施例１において、ペルオキソモノ硫酸カリウムの濃度を表２に記載の濃度に変えるとともに、混合臭気成分として二硫化ジメチルを表２に記載のプロピオン酸とした点を除き、実施例１と同様の条件で、アンモニアとプロピオン酸の脱臭実験を行い、出口気体濃度を測定し、その結果を表１に示す。なお、アンモニアは、いずれの場合も入口濃度７００ｐｐｍであった出口濃度は、実施例１と同様に０．５ｐｐｍとなり、除去率は９９．９％であった。 In Example 1, the same conditions as in Example 1 except that the concentration of potassium peroxomonosulfate was changed to the concentration shown in Table 2 and that dimethyl disulfide was used as the propionic acid shown in Table 2 as the mixed odor component. Then, the deodorization experiment of ammonia and propionic acid was conducted, the outlet gas concentration was measured, and the results are shown in Table 1. In all cases, the concentration of ammonia, which was 700 ppm in each case, was 0.5 ppm as in Example 1, and the removal rate was 99.9%.
表２
プロピオン酸
試料 過硫酸塩濃度（ｇ／ｌ） 入口気体濃度 出口気体濃度 除去率（％）
２−１ ０ ８．５ ppm １．４ ppm ８３
２−２ ２ １１ １ ９０．９
２−３ １０ １１ １ ９０．９
２−４ １００ １１．９ １．１ ９０．８
２−５ ２５０ １２．７ １．３ ８９．８
Table 2
Propionic acid
Sample Persulfate concentration (g / l) Inlet gas concentration Outlet gas concentration Removal rate (%)
2-1 0 8.5 ppm 1.4 ppm 83
2-2 2 11 1 90.9
2-3 10 11 1 90.9
2-4 100 11.9 1.1 90.8
2-5 250 12.7 1.3 89.8
動植物性残渣、食品汚泥、下水汚泥等の有機性廃棄物を日量４トン堆肥化処理をしている総滞留量２４０トンの堆肥舎の排気ガス３００ｍ3／ｍｉｎをペルオキソモノ硫酸カリウム４０ｇ／ｌを溶解させた２規定硫酸水溶液が５００ｋｇ／ｍｉｎで循環する気液接触型充填式脱臭塔で脱臭処理し、アンモニア、二硫化メチル、トリメチルアミン、およびプロピオン酸について入口濃度および出口濃度をガス検知管およびニオイセンサ（新コスモス電機製 ＸＰ−３２９Ｓ）によって測定し、その結果を表３に示す。 Exhaust gas 300m 3 / min from a composting house with a total residence volume of 240 tons, where organic wastes such as animal and vegetable residues, food sludge, sewage sludge etc. are composted daily is 40 g / l of potassium peroxomonosulfate Is deodorized in a gas-liquid contact-type packed deodorization tower in which a 2N aqueous sulfuric acid solution in which the gas is dissolved is circulated at 500 kg / min, and the inlet concentration and outlet concentration of ammonia, methyl disulfide, trimethylamine, and propionic acid are determined with a gas detector tube and Measured with an odor sensor (New Cosmos Electric XP-329S), the results are shown in Table 3.
当該堆肥舎では、Ｃ／Ｎ比８．４、炭素含有量８．６質量％、水分量８０％の食品系汚泥と下水汚泥等の有機性廃棄物を５６日間の発酵で原料嵩高を４０％に減容し、Ｃ／Ｎ比１２、炭素含有量１６．５質量％、水分量３０質量％の堆肥を製造しており、アンモニアの発生速度は、０．０１７１ｋｇ−ＮＨ3／ｈｒ（＝０．０２３ｍ3−ＮＨ3／ｈｒ）である。
また、物質濃度が少なくても強い臭気を放つ二硫化ジメチル等の除去により、臭気指数３４．４の臭気を臭気指数１４．８まで減じることができ、排気口から隣地境界までの敷地内拡散で充分無臭となることが確認できた。
なお、臭気指数は、悪臭防止法に規定する方法によって測定した。
In the compost house, organic waste such as food sludge and sewage sludge with a C / N ratio of 8.4, carbon content of 8.6% by mass, and water content of 80% is fermented for 56 days, and the bulk of the raw material is 40%. To produce compost having a C / N ratio of 12, a carbon content of 16.5% by mass, and a water content of 30% by mass, and the generation rate of ammonia is 0.0171 kg-NH 3 / hr (= 0). 0.023m 3 —NH 3 / hr).
In addition, by removing dimethyl disulfide, which emits strong odors even at low substance concentrations, it is possible to reduce the odor with an odor index of 34.4 to an odor index of 14.8. It was confirmed that it was sufficiently odorless.
The odor index was measured by the method specified in the Odor Control Law.
表３
成分 入口濃度(ppm) 臭気強度 出口濃度(ppm) 臭気強度
アンモニア ８８ ５．６ ０．８８０ ２．３
硫化水素 ０．０１３ ２．３ ０．００１ １．４
二硫化メチル ０．０１９ ２．７ ０．００２ １．９
トリメチルアミン ０．１ ３．７ ０．００１ １．９
プロピオン酸 ０．０１４ ２．３ ０．００１以下 −
Table 3
Component Inlet concentration (ppm) Odor intensity Outlet concentration (ppm) Odor intensity
Ammonia 88 5.6 0.880 2.3
Hydrogen sulfide 0.013 2.3 0.001 1.4
Methyl disulfide 0.019 2.7 0.002 1.9
Trimethylamine 0.1 3.7 0.001 1.9
Propionic acid 0.014 2.3 0.001 or less-
本願の発明によって、生ゴミ、堆肥、汚泥等の微生物発酵、家畜糞尿から大量に発生するアンモニアとともに、アルカリ性臭気成分、酸性臭気成分、中性臭気成分が混在する悪臭気体を、本発明の脱臭液との接触のみによって無臭化処理することができるので、生ゴミ、堆肥、汚泥等の処理施設、家畜飼育施設、動物病院等の臭気成分の除去に適用することができ産業上も極めて有用である。 According to the invention of the present application, odorous gas containing alkaline odor components, acidic odor components, neutral odor components together with ammonia generated in large quantities from microbial fermentation of live garbage, compost, sludge, etc. Because it can be treated without bromide only by contact with it, it can be applied to the removal of odorous components such as garbage, compost, sludge and other treatment facilities, livestock breeding facilities, animal hospitals, etc. .
１…脱臭装置、２…脱臭液、３…脱臭液貯槽、４…循環ポンプ、５…充填層、６…シャワー部、７…気体入口、８…被処理気体、９…気液分離部、１０…排出口、２１…脱臭装置、２２…脱臭液槽、２３…被処理気体導入管、２４…分散ノズル、２５…排出口
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| CN113926307A (en) * | 2021-11-23 | 2022-01-14 | 山鹰国际控股股份公司 | Deodorization adsorption system for energy regeneration workshop |
| CN114425230A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Treatment method of tail gas containing mercaptan and thioether |
| CN114425231A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Device for treating tail gas containing mercaptan and thioether |
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| CN114425231A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Device for treating tail gas containing mercaptan and thioether |
| CN113926307A (en) * | 2021-11-23 | 2022-01-14 | 山鹰国际控股股份公司 | Deodorization adsorption system for energy regeneration workshop |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| EXPY | Cancellation because of completion of term |