JP2011045827A - Desulfurizing agent and method of manufacturing the same - Google Patents
Desulfurizing agent and method of manufacturing the same Download PDFInfo
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- JP2011045827A JP2011045827A JP2009195897A JP2009195897A JP2011045827A JP 2011045827 A JP2011045827 A JP 2011045827A JP 2009195897 A JP2009195897 A JP 2009195897A JP 2009195897 A JP2009195897 A JP 2009195897A JP 2011045827 A JP2011045827 A JP 2011045827A
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- desulfurization
- volcanic ash
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 239000002689 soil Substances 0.000 claims abstract description 41
- 239000008187 granular material Substances 0.000 claims abstract description 32
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 25
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 23
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 23
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 23
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910000358 iron sulfate Inorganic materials 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000010304 firing Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000001877 deodorizing effect Effects 0.000 claims abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 claims description 66
- 230000023556 desulfurization Effects 0.000 claims description 66
- 238000004332 deodorization Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000014413 iron hydroxide Nutrition 0.000 description 5
- 235000013980 iron oxide Nutrition 0.000 description 5
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 230000002459 sustained effect Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000003864 humus Substances 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 1
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910001583 allophane Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- 229940095100 fulvic acid Drugs 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron hydroxide Chemical compound 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processing Of Solid Wastes (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Description
本発明は、気体中の硫化水素を除去するのに好適に用いられる脱硫剤、及び、その製造方法に関するものである。 The present invention relates to a desulfurizing agent suitably used for removing hydrogen sulfide in a gas, and a method for producing the same.
従来、硫化水素の脱臭に当たっては、下記特許文献1に記載されているように酸化鉄や水酸化鉄を利用したものや、下記特許文献2に記載されているようにゼオライトを利用したものがある。これらの酸化鉄やゼオライトを利用したものは、脱硫効果やその持続効果において不十分な場合があり、改良が求められる。 Conventionally, in the deodorization of hydrogen sulfide, there are those using iron oxide and iron hydroxide as described in Patent Document 1 below, and those using zeolite as described in Patent Document 2 below. . Those using these iron oxides and zeolites may be insufficient in the desulfurization effect and the sustained effect, and improvement is required.
ところで、下記特許文献3には、保形性に優れた脱臭剤として、腐植質を含む火山灰土壌と粘結剤とバインダーを含む造粒物が開示されている。また、下記特許文献4には、硫化水素だけでなく、アンモニア等の塩基性ガスも同時に脱臭できる固形脱臭組成物として、硫酸鉄、消石灰、活性炭及び火山灰土壌を含む脱臭剤としての造粒物が開示されている。 By the way, the following patent document 3 discloses a granulated product containing volcanic ash soil containing humic substances, a binder and a binder as a deodorizing agent having excellent shape retention. Patent Document 4 below discloses a granulated product as a deodorizer containing iron sulfate, slaked lime, activated carbon, and volcanic ash soil as a solid deodorizing composition capable of simultaneously deodorizing not only hydrogen sulfide but also basic gases such as ammonia. It is disclosed.
従来、このような火山灰土壌を含有する造粒物は、悪臭ガスの脱臭処理に使用されて、所定の使用期間を得た後には、廃棄するしかなかった。しかしながら、資源の有効利用の観点からは、使用済みの火山灰造粒物をリサイクルして、再利用することが望まれる。 Conventionally, the granulated material containing such volcanic ash soil has been used for deodorizing treatment of malodorous gas, and after obtaining a predetermined period of use, it has only been discarded. However, from the viewpoint of effective use of resources, it is desirable to recycle and reuse the used volcanic ash granule.
本発明は、上記に鑑みてなされたものであり、使用済みの火山灰造粒物のリサイクルを可能にしながら、脱硫性能の持続効果に優れた脱硫剤を提供することを目的とする。 This invention is made | formed in view of the above, and it aims at providing the desulfurization agent excellent in the sustained effect of desulfurization performance, enabling the recycling of used volcanic ash granule.
本発明者は、脱硫剤としての持続効果と使用済みの火山灰造粒物のリサイクルに着目して鋭意検討していく中で、水酸化鉄などの硫化水素と反応し得る脱硫成分に、火山灰土壌を含有する造粒物を焼成してなる焼成物を配合することにより、優れた脱硫持続効果が奏されることを見い出した。本発明はかかる知見に基づくものである。 The present inventor has been studying earnestly while paying attention to the sustained effect as a desulfurization agent and the recycling of used volcanic ash granulated materials. In the desulfurization component that can react with hydrogen sulfide such as iron hydroxide, It has been found that an excellent desulfurization sustaining effect is achieved by blending a fired product obtained by firing a granulated product containing slag. The present invention is based on such knowledge.
すなわち、本発明に係る脱硫剤は、火山灰土壌の焼成物と、硫化水素と反応し得る脱硫成分とを混合してなるものである。 That is, the desulfurization agent according to the present invention is a mixture of a calcined product of volcanic ash soil and a desulfurization component that can react with hydrogen sulfide.
また、本発明に係る脱硫剤の製造方法は、火山灰土壌を含有する造粒物を焼成し、得られた焼成物に、硫化水素と反応し得る脱硫成分を混合して造粒するものである。 Moreover, the method for producing a desulfurizing agent according to the present invention is to granulate a granulated product containing volcanic ash soil, and mix the resulting calcined product with a desulfurization component capable of reacting with hydrogen sulfide for granulation. .
本発明によれば、硫化水素の除去の持続効果に優れた脱硫剤を提供することができる。また、脱硫成分に配合する焼成物には、脱臭剤として使用済みの造粒物を原料に用いることができるので、当該使用済みの造粒物のリサイクルを可能にして、資源の有効利用を図ることができる。 ADVANTAGE OF THE INVENTION According to this invention, the desulfurization agent excellent in the continuous effect of removal of hydrogen sulfide can be provided. Moreover, since the used granulated material used as a deodorant can be used as a raw material for the fired product to be blended with the desulfurization component, the used granulated material can be recycled to effectively use resources. be able to.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
本発明に係る脱硫剤は、(A)火山灰土壌の焼成物と、(B)硫化水素と反応し得る脱硫成分と、を含有するものである。 The desulfurization agent according to the present invention contains (A) a calcined product of volcanic ash soil and (B) a desulfurization component capable of reacting with hydrogen sulfide.
上記(A)成分において、火山灰土壌の焼成物としては、焼成された火山灰土壌が含まれるものであれば、火山灰土壌を単独で焼成したものであってもよく、あるいはまた、火山灰土壌を含む混合粉体を焼成したものであってもよく、更には、火山灰土壌を含有する造粒物を焼成してなるものであってもよい。該火山灰土壌を含有する造粒物としては、脱臭処理に使用された造粒物を回収した回収物でもよく、また、未使用の造粒物を用いることもできるが、資源の有効利用の点からは、使用済みの造粒物(即ち、回収物)を用いることが好ましい。 In the above component (A), the fired product of the volcanic ash soil may be one obtained by calcining volcanic ash soil alone, or a mixture containing volcanic ash soil, as long as the calcined volcanic ash soil is included. The powder may be fired, and may further be obtained by firing a granulated material containing volcanic ash soil. The granulated product containing the volcanic ash soil may be a recovered product obtained by recovering the granulated product used in the deodorization treatment, and an unused granulated product may be used. It is preferable to use a used granulated product (that is, a recovered product).
上記火山灰土壌としては、種々の火山灰土を用いることができ、特に限定されない。好ましくは、腐植質を含む火山灰土壌(即ち、腐植質土壌)を用いることである。腐植質土壌は、非晶質粘土鉱物であるアロフェン土を主成分とし、フミン酸、ニトロフミン酸、フルボ酸などの有機成分を含む火山灰土壌であり、黒ボク土や黒土、黒暗土と呼称される火山灰土壌である。該腐植質土壌は、有機成分が10重量%以上含有されているものであることが好ましく、15重量%以上含有されているものがさらに好ましい。有機成分は焼成によって消失するが、その消失によって火山灰土壌の粉体に特有の多孔質構造が形成されるものと考えられ、その空隙に付着した上記脱硫成分の作用により、優れた脱硫の持続効果が奏されるものと推測される。 Various volcanic ash soils can be used as the volcanic ash soil, and are not particularly limited. Preferably, volcanic ash soil containing humus (that is, humus soil) is used. Humic soil is a volcanic ash soil that contains allophane soil, an amorphous clay mineral, and contains organic components such as humic acid, nitrohumic acid, and fulvic acid. Volcanic ash soil. The humic soil preferably contains 10% by weight or more of organic components, and more preferably contains 15% by weight or more. The organic component disappears by firing, but the disappearance of the organic component is thought to form a porous structure peculiar to the powder of volcanic ash soil. Is presumed to be played.
火山灰土壌を含有する造粒物は、バインダー等を用いて火山灰土壌を粒状に成形してなるものである。造粒物には、特開2008−272225号公報に開示されているように、硫酸鉄及び消石灰等の脱硫成分を含むものが好ましく用いられる。焼成する造粒物にも脱硫成分が配合されていることにより、使用済みの造粒物をリサイクルするに当たって、該脱硫成分も有効活用することができる。 The granulated material containing volcanic ash soil is formed by forming volcanic ash soil into a granular shape using a binder or the like. As the granulated product, those containing desulfurization components such as iron sulfate and slaked lime are preferably used as disclosed in JP-A-2008-272225. Since the desulfurization component is blended in the granulated product to be fired, the desulfurization component can also be effectively used in recycling the used granulated product.
特開2008−272225号公報に開示された造粒物は、硫酸鉄、消石灰、活性炭および腐植質土壌を含み、該硫酸鉄の配合量が造粒物の全量中、固形分として10〜50重量%であり、pHが6〜8であるものであり、本発明では、これを通常の脱臭処理に使用し、回収した使用済みのものが好ましく用いられる。 The granulated material disclosed in Japanese Patent Application Laid-Open No. 2008-272225 includes iron sulfate, slaked lime, activated carbon, and humic soil, and the blended amount of the iron sulfate is 10 to 50 weight as solid content in the total amount of the granulated material. %, And the pH is 6 to 8. In the present invention, this is used for ordinary deodorization treatment, and the recovered used one is preferably used.
該造粒物に含まれる硫酸鉄及び消石灰としては、後述する(B)成分として配合する脱硫成分としての硫酸鉄及び消石灰と同様のものを用いることができる。硫酸鉄の配合量は、造粒物の全量中、固形分で10〜50重量%であり、好ましくは20〜40重量%である。消石灰の配合量は、造粒物の全量中、5〜25重量%であることが好ましく、より好ましくは10〜20重量%である。 As iron sulfate and slaked lime contained in the granulated product, the same iron sulfate and slaked lime as desulfurization components blended as the component (B) described later can be used. The compounding amount of iron sulfate is 10 to 50% by weight, preferably 20 to 40% by weight, based on the solid content in the total amount of the granulated product. It is preferable that the compounding quantity of slaked lime is 5-25 weight% in the whole quantity of a granulated material, More preferably, it is 10-20 weight%.
上記活性炭としては、オガクズ等の木質材料、果実殻(ヤシガラ等)の植物系材料、石炭等の鉱物系材料を原料とする活性炭が挙げられる。活性炭の配合量は、造粒物の全量中、5〜80重量%であることが好ましく、より好ましくは10〜40重量%である。また、腐植質土壌の配合量は、造粒物の全量中、5〜60重量%であることが好ましく、より好ましくは15〜40重量%である。該造粒物には、ベントナイトやアタパルジャイト等の粘結剤が更に配合されてもよい。 Examples of the activated carbon include activated carbons made from woody materials such as sawdust, plant materials such as fruit shells (coconut shells), and mineral materials such as coal. The blending amount of the activated carbon is preferably 5 to 80% by weight, more preferably 10 to 40% by weight, based on the total amount of the granulated product. Moreover, it is preferable that the compounding quantity of humic soil is 5 to 60 weight% in the whole quantity of a granulated material, More preferably, it is 15 to 40 weight%. The granulated product may further contain a binder such as bentonite or attapulgite.
該造粒物は、例えば、腐植質土壌、消石灰及び活性炭を予め混合し、硫酸鉄溶液を添加混合した後、更にバインダーを添加して、造粒、乾燥することで製造することができる。 The granulated product can be produced, for example, by previously mixing humic soil, slaked lime and activated carbon, adding and mixing an iron sulfate solution, adding a binder, granulating and drying.
以上説明した火山灰土壌やそれを含む造粒物を焼成するに際しては、300〜1000℃で焼成することが好ましい。焼成温度は、より好ましくは500℃以上であり、更に好ましくは700℃以上である。焼成時間は、特に限定されないが、十分な焼成を行うべく、30分〜3時間程度で行うことが好ましい。 When calcining the volcanic ash soil described above and the granulated material containing the volcanic ash soil, it is preferably calcined at 300 to 1000 ° C. The firing temperature is more preferably 500 ° C. or higher, and still more preferably 700 ° C. or higher. Although baking time is not specifically limited, In order to perform sufficient baking, it is preferable to carry out in about 30 minutes-3 hours.
焼成することにより、上記のように火山灰土壌中に含まれる有機成分を消失させることができる。また、特に、使用済みの造粒物を用いた場合に、当該造粒物に捕捉された悪臭成分を脱離・消失させることができる。 By baking, the organic components contained in the volcanic ash soil can be eliminated as described above. In particular, when a used granulated product is used, malodorous components captured by the granulated product can be desorbed and eliminated.
焼成は、大気下で実施してもよく、窒素雰囲気下で実施してもよく、特に限定されない。窒素雰囲気下で焼成することにより、最終的に得られた脱硫剤の脱硫持続効果をより高めることができるが、大気下でも十分な効果が得られ、設備上の点からは大気下で焼成する方が実用的で好ましい。 Firing may be performed in the air or in a nitrogen atmosphere, and is not particularly limited. By firing in a nitrogen atmosphere, the desulfurization lasting effect of the finally obtained desulfurizing agent can be further enhanced, but a sufficient effect can be obtained even in the air, and firing is performed in the air from the viewpoint of equipment. Is more practical and preferred.
上記(B)成分の脱硫成分としては、硫化水素と反応して気体中の硫化水素を除去できるものであれば、特に限定されない。例えば、2価の遷移金属などの金属元素を含む化合物(酸化物、水酸化物、硫酸塩等)は、硫化水素と反応して硫化物を形成するため、(B)成分の脱硫成分として用いることができる。2価の遷移金属としては、例えば、鉄、銅、亜鉛、水銀、銀、ニッケル等が挙げられ、また、その他の2価の金属元素としては、例えば、スズ、鉛などが挙げられる。従って、脱硫成分としては、例えば、酸化鉄、水酸化鉄、酸化銅、水酸化銅、酸化亜鉛、硫酸亜鉛、硫酸銅、硫酸鉛、硫酸銀、硫酸ニッケル、硫酸スズ等が挙げられる。 The desulfurization component (B) is not particularly limited as long as it can react with hydrogen sulfide and remove hydrogen sulfide in the gas. For example, a compound containing a metal element such as a divalent transition metal (oxide, hydroxide, sulfate, etc.) reacts with hydrogen sulfide to form a sulfide, and is therefore used as a desulfurization component of the component (B). be able to. Examples of the divalent transition metal include iron, copper, zinc, mercury, silver, and nickel, and examples of other divalent metal elements include tin and lead. Accordingly, examples of the desulfurization component include iron oxide, iron hydroxide, copper oxide, copper hydroxide, zinc oxide, zinc sulfate, copper sulfate, lead sulfate, silver sulfate, nickel sulfate, and tin sulfate.
脱硫成分として、好ましくは、硫酸鉄と消石灰を組み合わせて用いることである。硫酸鉄と消石灰は、反応により酸化鉄及び/又は水酸化鉄を生成するので、これにより、気体中の硫化水素と反応して硫化鉄にすることで脱硫効果を発揮する。同様に、硫酸亜鉛と消石灰を組み合わせて用い、これにより生成される酸化亜鉛で脱硫効果を発揮するようにしてもよい。 As the desulfurization component, iron sulfate and slaked lime are preferably used in combination. Since iron sulfate and slaked lime produce iron oxide and / or iron hydroxide by reaction, this produces a desulfurization effect by reacting with hydrogen sulfide in the gas to form iron sulfide. Similarly, zinc sulfate and slaked lime may be used in combination, and the desulfurization effect may be exhibited with the zinc oxide produced thereby.
硫酸鉄としては、硫酸第一鉄、硫酸第二鉄およびポリ硫酸第二鉄からなる群から選択される1種以上の化合物であることが好ましく、ポリ硫酸第二鉄がより好ましい。ポリ硫酸第二鉄は、[Fe2(OH)n(SO4)3−n/2]m(但し、0<n≦2、m=f(n)である。)で表される化合物であり、市販されているものを用いることができる。市販品としては、例えば、日鉄鉱業(株)製「ポリテツ」などを挙げることができる。 The iron sulfate is preferably one or more compounds selected from the group consisting of ferrous sulfate, ferric sulfate and polyferric sulfate, and polyferric sulfate is more preferable. Polyferric sulfate is a compound represented by [Fe 2 (OH) n (SO 4 ) 3−n / 2 ] m (where 0 <n ≦ 2, m = f (n)). Yes, commercially available products can be used. Examples of commercially available products include “Politetsu” manufactured by Nippon Steel Mining Co., Ltd.
消石灰は硫酸鉄との反応により脱硫成分としての酸化鉄及び/又は水酸化鉄を生成するために添加される塩基性化合物である。塩基性化合物として消石灰を用いることにより、硫酸カルシウム(石膏)が副生するが、石膏は水に難溶性であるため、脱硫剤の使用時に高湿度の気体が通過しても造粒物から溶出することがないため好ましい。 Slaked lime is a basic compound added to produce iron oxide and / or iron hydroxide as a desulfurization component by reaction with iron sulfate. By using slaked lime as a basic compound, calcium sulfate (gypsum) is produced as a by-product. However, since gypsum is poorly soluble in water, it is eluted from the granulated material even when high-humidity gas passes through when using a desulfurizing agent. This is preferable.
硫酸鉄(特にはポリ硫酸第二鉄)と消石灰との配合比は、重量比で、硫酸鉄/消石灰=2/1〜1/2であることが好ましく、より好ましくは1.5/1〜1/1である。このような配合比に設定することにより、脱硫性能を高くすることができる。 The blending ratio of iron sulfate (particularly polyferric sulfate) and slaked lime is preferably a weight ratio of iron sulfate / slaked lime = 2/1 to 1/2, more preferably 1.5 / 1 to 1. 1/1. By setting to such a compounding ratio, desulfurization performance can be improved.
本発明に係る脱硫剤は、上記(A)成分と(B)成分とを混合してなるものである。両者の混合比は、焼成物の配合割合が、当該焼成物と脱硫成分との合計量に対し20〜60重量%の範囲内で設定されることが好ましい。すなわち、焼成物と脱硫成分の合計量を100重量部としたとき、焼成物の配合量を20〜60重量部とすることが好適である。このような配合割合に設定することで、脱硫性能を高くすることができる。該配合割合は、より好ましくは20〜40重量%である。 The desulfurizing agent according to the present invention is a mixture of the above component (A) and component (B). The mixing ratio of the two is preferably set so that the blended ratio of the fired product is within a range of 20 to 60% by weight with respect to the total amount of the fired product and the desulfurization component. That is, when the total amount of the fired product and the desulfurized component is 100 parts by weight, the blended amount of the fired product is preferably 20 to 60 parts by weight. By setting to such a blending ratio, desulfurization performance can be increased. The blending ratio is more preferably 20 to 40% by weight.
該脱硫剤は、(A)成分と(B)成分を混合し、造粒してなる造粒物であることが好ましく、造粒物とすることにより、気体中の硫化水素を除去する脱硫剤としての利便性を向上することができる。 The desulfurizing agent is preferably a granulated product obtained by mixing and granulating the component (A) and the component (B). By using the granulated product, the desulfurizing agent removes hydrogen sulfide in the gas. As a convenience, it can be improved.
造粒物の保形性を良好に保つため、バインダーを添加してもよい。バインダーとしては、例えば、ウレタン樹脂、アクリル樹脂、ポリエステル系生分解性樹脂、カルボキシメチルセルロース(CMC)、デンプン、アルギン酸ソーダ、キサンタンガム、グアーガム、カラギーナン、ポリビニルアルコールなどが挙げられる。バインダーの添加量としては、脱硫剤の全固形分(バインダー分は除く)を100重量%とし、これに対し、固形分として0.1〜15重量%となるように添加することが好ましく、より好ましくは1〜5重量%となるように添加することである。 In order to keep the shape retention of the granulated material good, a binder may be added. Examples of the binder include urethane resin, acrylic resin, polyester-based biodegradable resin, carboxymethyl cellulose (CMC), starch, sodium alginate, xanthan gum, guar gum, carrageenan, and polyvinyl alcohol. As the addition amount of the binder, the total solid content of the desulfurizing agent (excluding the binder content) is set to 100% by weight, and it is preferably added so that the solid content is 0.1 to 15% by weight. Preferably it is adding so that it may become 1 to 5 weight%.
本発明の脱硫剤には、発明の効果を損なわない程度で種々の添加物を配合することができる。そのような添加物としては、上記の粘結剤や活性炭などが挙げられ、特に限定されない。 Various additives can be blended in the desulfurizing agent of the present invention to the extent that the effects of the invention are not impaired. Examples of such additives include the above binders and activated carbon, and are not particularly limited.
脱硫剤の製造方法としては、火山灰土壌を含有する造粒物を焼成し、得られた焼成物に、硫化水素と反応し得る脱硫成分を混合した後、造粒、乾燥することが好ましい。焼成に際しては、脱臭処理に使用された使用済みの造粒物を回収し、回収した造粒物を焼成することが好ましい。 As a method for producing a desulfurizing agent, it is preferable to calcinate a granulated product containing volcanic ash soil, mix a desulfurization component capable of reacting with hydrogen sulfide, and granulate and dry the resulting calcined product. At the time of firing, it is preferable to collect the used granulated material used in the deodorization treatment and to fire the collected granulated material.
また、焼成物と脱硫成分を混合するに際しては、焼成物と消石灰を予め混合し、硫酸鉄溶液を添加混合することが好ましい。また、硫酸鉄溶液を添加混合した後に、さらに、バインダーを添加混合することが好ましい。 Moreover, when mixing a baked product and a desulfurization component, it is preferable to mix a baked product and slaked lime beforehand, and to add and mix an iron sulfate solution. Moreover, after adding and mixing an iron sulfate solution, it is preferable to add and mix a binder.
造粒方法、乾燥方法としては、通常の方法を用いることができるが、たとえば、圧縮造粒機や押出造粒機により造粒し、振動乾燥機や流動層乾燥機等により乾燥することができる。 As the granulation method and the drying method, usual methods can be used. For example, the granulation method can be granulated by a compression granulator or an extrusion granulator, and dried by a vibration dryer, a fluidized bed dryer or the like. .
本発明に係る脱硫剤は、気体中の硫化水素を除去するのに好適に用いられるものであり、例えば、下水処理場やし尿処理場、農業畜産廃棄物(堆肥)や食品廃棄物を原料としたバイオマスプラント、排水嫌気性処理場などの硫化水素を含む気体が発生する各種施設の乾式吸着脱臭塔の充填剤として好適に用いることができる。 The desulfurization agent according to the present invention is suitably used for removing hydrogen sulfide in a gas. For example, sewage treatment plants, human waste treatment plants, agricultural livestock waste (compost) and food waste are used as raw materials. It can be suitably used as a filler for dry adsorption deodorization towers of various facilities where gas containing hydrogen sulfide is generated, such as a biomass plant and a wastewater anaerobic treatment plant.
以下、本発明を実施例および比較例によりさらに具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples at all.
[脱硫性能の評価方法]
直径34mmのガラスカラムに、評価対象の脱硫剤を、充填高さ150mmまで充填した。このガラスカラムの下部から、硫化水素濃度が約1000ppmの空気を通気させた。通気開始から所定時間ごとにカラム入口と出口の硫化水素濃度を検知管で測定し、次式により硫化水素脱臭率を求めた。
硫化水素脱臭率(%)={(入口濃度−出口濃度)/入口濃度}×100
[Method for evaluating desulfurization performance]
A desulfurization agent to be evaluated was filled in a glass column having a diameter of 34 mm to a filling height of 150 mm. Air having a hydrogen sulfide concentration of about 1000 ppm was vented from the bottom of the glass column. The hydrogen sulfide concentration at the column inlet and outlet was measured with a detector tube every predetermined time from the start of aeration, and the hydrogen sulfide deodorization rate was determined by the following equation.
Hydrogen sulfide deodorization rate (%) = {(inlet concentration−outlet concentration) / inlet concentration} × 100
[第1実施例]
下水処理場の脱臭塔で使用され、回収された火山灰土壌を含有する造粒物を、小型電気炉を用いて、窒素雰囲気下で、表1に示す焼成温度まで2時間で昇温し、その温度で2時間焼成し、その後、冷却した。これを上記(A)成分の焼成物とした。上記造粒物は、特開2008−272225号公報に記載の方法で調製された、ポリ硫酸第二鉄24重量%、消石灰14%、活性炭22重量%、アタパルジャイト12重量%、及び腐植質土壌29重量%を配合してなる造粒物である。
[First embodiment]
The granulated material containing the volcanic ash soil collected and used in the deodorization tower of the sewage treatment plant was heated up to the firing temperature shown in Table 1 in 2 hours using a small electric furnace in a nitrogen atmosphere. It was calcined at temperature for 2 hours and then cooled. This was used as the fired product of the component (A). The above granulated material was prepared by the method described in JP-A-2008-272225, 24% by weight polyferric sulfate, 14% slaked lime, 22% by weight activated carbon, 12% by weight attapulgite, and humic soil 29. It is a granulated product formed by blending weight%.
小型ミキサー(MARUI(株)製)の受け皿に表1に示す量の焼成物と消石灰(特号消石灰、弓橋工業(株)製)を投入し、攪拌しながら、表1に示す量のポリ硫酸第二鉄の水溶液(日鉄鉱業(株)製「ポリテツ」、固形分濃度:40重量%)とバインダー水溶液(ポリビニルアルコール(PVA)、日本合成化学工業(株)製「ゴーゼノールGH17」の7.7重量%水溶液)を投入した。投入後5分間攪拌し、造粒用粉体を得た。バインダー水溶液は、脱硫剤の固形分全量を100重量%とし、これに対し固形分で2重量%を、外数で添加した。なお、表1中のポリ硫酸第二鉄の比率は、固形分としての重量%である。 In a small mixer (made by MARUI Co., Ltd.), the amount of the calcined product and slaked lime (special slaked lime, manufactured by Yumihashi Kogyo Co., Ltd.) shown in Table 1 are put into a tray and stirred while stirring. An aqueous solution of ferric sulfate (“Polits” manufactured by Nittetsu Mining Co., Ltd., solid content concentration: 40% by weight) and an aqueous binder solution (polyvinyl alcohol (PVA), “Gozenol GH17” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 7 .7 wt% aqueous solution). After the addition, the mixture was stirred for 5 minutes to obtain a granulating powder. In the binder aqueous solution, the total solid content of the desulfurizing agent was 100% by weight, and 2% by weight of the solid content was added in an external number. In addition, the ratio of the polyferric sulfate in Table 1 is weight% as solid content.
得られた造粒用粉体をディスクペレッター(不二パウダル(株)製f−5/11型)に全量投入し、5mm径の円柱状造粒物を得た。その後、造粒物を105℃の恒温乾燥機にて2時間乾燥させ、実施例1〜4の脱硫剤を得た。 The entire amount of the obtained granulating powder was put into a disk pelleter (f-5 / 11 type manufactured by Fuji Powder Co., Ltd.) to obtain a cylindrical granulated product having a diameter of 5 mm. Then, the granulated material was dried for 2 hours with a constant temperature drier at 105 ° C. to obtain the desulfurization agents of Examples 1 to 4.
また、(A)成分として上記回収された造粒物を未焼成のままで用い、その他は実施例と同様にして調製した比較例1の脱硫剤を得た。更に、下水処理場で使用していない新品の火山灰土壌造粒物を比較例2とした。 Moreover, the said granulated material collect | recovered as (A) component was used as it was unbaked, and others obtained the desulfurization agent of the comparative example 1 prepared like the Example. Furthermore, a new volcanic ash soil granulated material not used in the sewage treatment plant was used as Comparative Example 2.
実施例1〜4及び比較例1,2の各脱硫剤について、脱硫性能を評価した。結果は、表1及び図1に示す通りであり、実施例の脱硫剤であると、未焼成の回収造粒物を用いて調製した比較例1の脱硫剤に対し、脱硫性能の持続効果が大幅に改善されていた。特に、焼成温度が高くなるほど、脱硫性能の持続効果に優れていた。また、実施例の脱硫剤であると、脱臭剤として使用済みの造粒物を原料に用いたリサイクル品でありながら、新品の脱臭剤である比較例2に対しても、硫化水素の脱硫効果に優れていた。 About each desulfurization agent of Examples 1-4 and Comparative Examples 1 and 2, desulfurization performance was evaluated. The results are as shown in Table 1 and FIG. 1, and the desulfurization agent of the example has a sustained effect on the desulfurization performance with respect to the desulfurization agent of Comparative Example 1 prepared using the unfired recovered granulated product. It was greatly improved. In particular, the higher the firing temperature, the better the desulfurization performance sustaining effect. Moreover, the desulfurization effect of hydrogen sulfide is also a comparative example 2 which is a new deodorant, although it is a recycled product using the granulated material used as a deodorizer as a raw material when it is a desulfurization agent of an Example. It was excellent.
[第2実施例]
焼成条件を窒素雰囲気下に代えて、大気下とした他は、第1実施例と同様にして、表2に示す実施例5〜7の脱硫剤を調製した。得られた実施例5〜7の各脱硫剤について、脱硫性能を評価した。
[Second Embodiment]
The desulfurization agents of Examples 5 to 7 shown in Table 2 were prepared in the same manner as in the first example except that the firing conditions were changed to the atmosphere instead of the nitrogen atmosphere. About each obtained desulfurization agent of Examples 5-7, desulfurization performance was evaluated.
結果は、表2及び図2に示す通りであり、窒素雰囲気下での焼成品を用いた実施例1〜4に比べれば劣るものの、実施例5〜7の脱硫剤でも、未焼成の回収造粒物を用いて調製した比較例1の脱硫剤に対し、脱硫性能の持続効果が大幅に改善されていた。また、脱臭剤として使用済みの造粒物を原料に用いたリサイクル品でありながら、新品の脱臭剤である比較例2に対しても、硫化水素の脱硫効果に優れていた。 The results are as shown in Table 2 and FIG. 2 and are inferior to those of Examples 1 to 4 using a baked product in a nitrogen atmosphere, but even with the desulfurization agent of Examples 5 to 7, the unfired recovery structure was obtained. The sustaining effect of the desulfurization performance was greatly improved with respect to the desulfurization agent of Comparative Example 1 prepared using the granules. Moreover, although it was the recycled product which used the used granulated material as a raw material as a deodorizing agent, it was excellent also in the desulfurization effect of hydrogen sulfide also with respect to the comparative example 2 which is a new deodorizing agent.
[第3実施例]
(A)成分の焼成物の配合割合を表3に示すように変更し、その他は第2実施例と同様にして、実施例8〜13の脱硫剤を調製した。得られた実施例8〜13の各脱硫剤について、脱硫性能を評価した。
[Third embodiment]
The blending ratio of the fired product of the component (A) was changed as shown in Table 3, and the others were the same as in the second example, and desulfurization agents of Examples 8 to 13 were prepared. About each obtained desulfurization agent of Examples 8-13, desulfurization performance was evaluated.
結果は、表3及び図3に示す通りであり、(A)成分の焼成物の配合割合としては、20〜60重量%とすることが脱硫性能の持続効果の点から好ましいことが分かった。 The results are as shown in Table 3 and FIG. 3, and it was found that the blending ratio of the fired product of the component (A) is preferably 20 to 60% by weight from the viewpoint of the sustained effect of desulfurization performance.
[その他の実施例]
(1)第1実施例の実施例3において、ポリ硫酸第二鉄の水溶液を用いる代わりに、硫酸亜鉛の水溶液を固形分換算で46重量%添加し、かつ、消石灰を24重量%添加し、その他は同様にして、脱硫剤を調製してもよい。
[Other Examples]
(1) In Example 3 of the first example, instead of using an aqueous solution of polyferric sulfate, an aqueous solution of zinc sulfate was added in an amount of 46% by weight in terms of solid content, and 24% by weight of slaked lime was added, Otherwise, a desulfurizing agent may be prepared in the same manner.
(2)第1実施例の実施例3において、ポリ硫酸第二鉄の水溶液を用いる代わりに、硫酸第一鉄の水溶液を固形分換算で44重量%添加し、かつ、消石灰を26重量%添加し、その他は同様にして、脱硫剤を調製してもよい。 (2) In Example 3 of the first example, instead of using an aqueous solution of ferric sulfate, 44% by weight of an aqueous solution of ferrous sulfate is added in terms of solid content, and 26% by weight of slaked lime is added. Otherwise, the desulfurizing agent may be prepared in the same manner.
(3)第1実施例の実施例3において、ポリ硫酸第二鉄の水溶液を用いる代わりに、硫酸銅の水溶液を固形分換算で70重量%添加し、かつ、消石灰は配合せず、その他の同様にして、脱硫剤を調製してもよい。 (3) In Example 3 of the first example, instead of using an aqueous solution of polyferric sulfate, an aqueous solution of copper sulfate is added in an amount of 70% by weight in terms of solid content, and slaked lime is not blended. Similarly, a desulfurizing agent may be prepared.
その他、一々列挙しないが、本発明の趣旨を逸脱しない限り、種々の変更が可能である。 Although not enumerated one by one, various modifications can be made without departing from the spirit of the present invention.
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