JP2015085303A - Treatment method of acidic exhaust gas and exhaust gas treatment agent - Google Patents
Treatment method of acidic exhaust gas and exhaust gas treatment agent Download PDFInfo
- Publication number
- JP2015085303A JP2015085303A JP2013228373A JP2013228373A JP2015085303A JP 2015085303 A JP2015085303 A JP 2015085303A JP 2013228373 A JP2013228373 A JP 2013228373A JP 2013228373 A JP2013228373 A JP 2013228373A JP 2015085303 A JP2015085303 A JP 2015085303A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- acidic
- fly ash
- hydroxide
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 89
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 158
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 118
- 239000010881 fly ash Substances 0.000 claims abstract description 83
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 65
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 65
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 65
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 42
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 42
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000000470 constituent Substances 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 172
- 239000010459 dolomite Substances 0.000 claims description 53
- 229910000514 dolomite Inorganic materials 0.000 claims description 53
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 45
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 41
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 29
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000013522 chelant Substances 0.000 claims description 22
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 20
- 230000005484 gravity Effects 0.000 claims description 18
- 230000003472 neutralizing effect Effects 0.000 claims description 18
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- 239000002912 waste gas Substances 0.000 claims description 3
- 239000000834 fixative Substances 0.000 abstract description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 58
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 28
- 238000010828 elution Methods 0.000 description 25
- 230000008569 process Effects 0.000 description 25
- 230000029087 digestion Effects 0.000 description 22
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- 230000000052 comparative effect Effects 0.000 description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
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- 150000001875 compounds Chemical class 0.000 description 16
- -1 phosphoric acid compound Chemical class 0.000 description 16
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
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- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 239000007864 aqueous solution Substances 0.000 description 4
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- AGKZZTAKVYWQLA-UHFFFAOYSA-N carbamodithioic acid;piperazine Chemical compound NC(S)=S.C1CNCCN1 AGKZZTAKVYWQLA-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
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- 239000002440 industrial waste Substances 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003016 phosphoric acids Chemical class 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052815 sulfur oxide Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- ZWHCFDOODAQLLX-UHFFFAOYSA-D bis[(2-oxo-1,3,2lambda5,4lambda2-dioxaphosphaplumbetan-2-yl)oxy]lead chloro-[(2-oxo-1,3,2lambda5,4lambda2-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Cl-].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZWHCFDOODAQLLX-UHFFFAOYSA-D 0.000 description 2
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
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- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical group [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229940116349 dibasic ammonium phosphate Drugs 0.000 description 1
- SZRLKIKBPASKQH-UHFFFAOYSA-M dibutyldithiocarbamate Chemical compound CCCCN(C([S-])=S)CCCC SZRLKIKBPASKQH-UHFFFAOYSA-M 0.000 description 1
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical group [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 150000002013 dioxins Chemical class 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
- 235000011180 diphosphates Nutrition 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical group [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 1
- 229910052630 margarite Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 229940098424 potassium pyrophosphate Drugs 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 229910052820 pyromorphite Inorganic materials 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
本発明は、都市ごみ廃棄物焼却炉、産業廃棄物焼却炉、発電ボイラ、炭化炉、民間工場等の燃焼施設において発生する塩化水素や硫黄酸化物等の有害な酸性ガスを含む排ガスの処理方法に関する。 The present invention relates to a method for treating exhaust gas containing harmful acid gases such as hydrogen chloride and sulfur oxide generated in combustion facilities such as municipal waste waste incinerators, industrial waste incinerators, power generation boilers, carbonization furnaces, and private factories. About.
都市ゴミや産業廃棄物等の廃棄物焼却炉から排出される燃焼排ガスには、炭酸ガスや、水蒸気、酸素、窒素、硫黄酸化物、窒素酸化物、塩化水素、重金属化合物、煤塵などが含まれていることから、大気放出に先立ち、これらの物質を除去する必要がある。 Combustion exhaust gas discharged from waste incinerators such as municipal waste and industrial waste includes carbon dioxide, water vapor, oxygen, nitrogen, sulfur oxides, nitrogen oxides, hydrogen chloride, heavy metal compounds, dust, etc. Therefore, it is necessary to remove these substances prior to release to the atmosphere.
特許文献１のように、一般的に、有害な塩化水素や硫黄酸化物を含む酸性排ガスは、水酸化カルシウム等のアルカリ剤で処理された後、バグフィルター等の集塵機で除塵され、煙突から排出される。一方、集塵機で集塵された飛灰は、有害な鉛、カドミウム等の重金属を含有しており、これら有害重金属を安定化処理した後に埋立処分されている。
集塵機で除塵された飛灰中の重金属の処理方法としては、ピペラジンジチオカルバミン酸塩、ジエチルジチオカルバミン酸塩等のキレート系の重金属固定剤で不溶化処理する方法が一般的である。該方法は、環境庁告示１３号試験等による短期的な重金属の固定効果は高いが、最終処分場において酸性雨によりｐＨが低下した際の影響や、キレートが酸化して自己分解することにより鉛等の重金属が再溶出する問題が懸念されている。
As in Patent Document 1, in general, acidic exhaust gas containing harmful hydrogen chloride and sulfur oxide is treated with an alkaline agent such as calcium hydroxide, and then removed by a dust collector such as a bag filter and discharged from a chimney. Is done. On the other hand, fly ash collected by a dust collector contains harmful heavy metals such as lead and cadmium, and is disposed of in landfill after stabilizing these harmful heavy metals.
As a method for treating heavy metals in fly ash removed by a dust collector, a method of insolubilizing with a chelate heavy metal fixing agent such as piperazine dithiocarbamate or diethyldithiocarbamate is generally used. This method has a high effect of fixing heavy metals in the short term by the Environmental Agency Notification No. 13 test, etc., but lead due to the effect of acid drop at the final disposal site due to acid rain and the chelate oxidation and self-decomposition. There is concern about the problem of heavy metal re-elution.
一方、特許文献２は、重金属固定剤として、リン酸等のリン酸系化合物を用いている。リン酸系化合物は、無機鉱物であるヒドロキシアパタイト形態まで変化させるため最終処分場における鉛等の長期安定性に優れる。このように、リン酸系重金属固定剤は、キレート系重金属固定剤と異なり、長期にわたる重金属固定効果を有しており、酸性雨の影響を加味したアベイラビリティ試験のような厳しい条件下においても、鉛等の重金属を安定的に処理することが可能であり、環境保護の観点から非常に価値の高い重金属の処理方法と考えられている。 On the other hand, Patent Document 2 uses a phosphoric acid compound such as phosphoric acid as a heavy metal fixing agent. The phosphoric acid compound is excellent in long-term stability of lead and the like in the final disposal site because it is changed to the form of hydroxyapatite which is an inorganic mineral. In this way, phosphate-based heavy metal fixing agents, unlike chelate heavy metal fixing agents, have a long-term heavy metal fixing effect, and lead even under severe conditions such as availability tests that take into account the effects of acid rain. In view of environmental protection, it is considered to be a highly valuable heavy metal treatment method.
また、重金属の固定に関して、塩酸、硫酸バンド等の酸性中和剤を添加する方法、ケイ酸ナトリウム水溶液、粉末二酸化ケイ素等の二酸化ケイ素含有化合物を添加する方法が知られている。また、六価クロム、砒素、セレン、水銀等の重金属が溶出する場合には、塩化第一鉄、ポリ硫酸鉄等の鉄含有化合物を添加し、これら重金属の溶出を防止する方法が知られている。 In addition, for fixing heavy metals, a method of adding an acidic neutralizer such as hydrochloric acid or a sulfuric acid band, and a method of adding a silicon dioxide-containing compound such as an aqueous sodium silicate solution or powdered silicon dioxide are known. In addition, when heavy metals such as hexavalent chromium, arsenic, selenium, and mercury are eluted, iron-containing compounds such as ferrous chloride and polyiron sulfate are added to prevent elution of these heavy metals. Yes.
特許文献３には、５〜３０μｍの微粉に加工された重曹（ＮａＨＣＯ3）で酸性排ガスを処理することにより、通常の水酸化カルシウムに比べ酸性排ガスを安定的に処理することができることが記載されている。また、特許文献４には、重曹を添加された飛灰は、残存するアルカリの未反応分が少なくなり、リン酸系の重金属固定剤の使用量を低減できる飛灰の処理方法が記載されている。 Patent Document 3 describes that by treating acidic exhaust gas with baking soda (NaHCO 3 ) processed into a fine powder of 5 to 30 μm, acidic exhaust gas can be treated more stably than ordinary calcium hydroxide. ing. Patent Document 4 describes a fly ash treatment method in which fly ash to which sodium bicarbonate has been added reduces the amount of remaining alkali unreacted and can reduce the amount of phosphoric acid heavy metal fixing agent used. Yes.
特許文献１のように、酸性排ガスを水酸化カルシウムで処理した飛灰は、未反応の水酸化カルシウムを多量に含んでいる。このため、特許文献２のように、重金属固定剤としてリン酸系化合物を用いた場合、リン酸系化合物が未反応水酸化カルシウムに消費され、鉛等の溶出防止に有効な液固比（Ｌ／Ｓ）＝１０における飛灰溶出液のｐＨを低下させるためのリン酸系化合物が大量に必要となる。また、酸性の中和剤、二酸化ケイ素含有化合物についても、未反応水酸化カルシウムの影響により添加量が多大となる。 As in Patent Document 1, fly ash obtained by treating acidic exhaust gas with calcium hydroxide contains a large amount of unreacted calcium hydroxide. For this reason, as in Patent Document 2, when a phosphate compound is used as a heavy metal fixing agent, the phosphate compound is consumed by unreacted calcium hydroxide, and a liquid-solid ratio (L / S) = 10 requires a large amount of a phosphoric acid compound to lower the pH of the fly ash eluate. In addition, the amount of the acidic neutralizing agent and silicon dioxide-containing compound is increased due to the influence of unreacted calcium hydroxide.
特許文献３及び４のように、微粉の重曹で酸性排ガスを処理した飛灰にリン酸系化合物等を添加し重金属を固定する方法は、重金属を長期的に固定するための有効な方法であるが、重曹等のナトリウム系の薬剤は水酸化カルシウム等のカルシウム系の薬剤に比べてコストが高いことに加え、さらに微粉に加工するための粉砕設備等の加工コストがかかり、処理費用が増加するため普及率は低いのが現状である。 As in Patent Documents 3 and 4, a method of fixing a heavy metal by adding a phosphoric acid compound or the like to fly ash obtained by treating acidic exhaust gas with fine powdered sodium bicarbonate is an effective method for fixing a heavy metal for a long period of time. However, sodium-based chemicals such as baking soda are more expensive than calcium-based chemicals such as calcium hydroxide, and in addition, processing costs such as pulverization equipment for processing into fine powder increase, and processing costs increase. Therefore, the penetration rate is low at present.
本発明は、リン酸系化合物等の重金属固定剤の使用量を減らすとともに、低コストで重金属の固定処理を行うことができる酸性排ガスの処理方法、及び排ガス処理剤を提供することを目的とする。 An object of the present invention is to provide an acidic exhaust gas treatment method and an exhaust gas treatment agent capable of reducing the amount of heavy metal fixing agent such as a phosphoric acid compound and performing heavy metal fixing treatment at low cost. .
上記課題を解決すべく、以下の［１］〜［１２］の酸性排ガスの処理方法を提供する。
［１］酸性排ガスに対して、比表面積が２０ｍ2／ｇ以上、メジアン径（ｄ５０）が５〜３０μｍであって、水酸化マグネシウム及び水酸化カルシウムを構成成分として有する粉体を含有してなる排ガス処理剤を添加することにより、ｐＨ８．３を終点とする酸消費量から規定される飛灰のアルカリ度を１５０ｍｇＣａＣＯ3／ｇ以下とする工程を行い、さらに飛灰を集塵する工程を行った後に、無機重金属固定剤及び／又は酸性中和剤を添加する工程を行う酸性排ガスの処理方法。
［２］無機重金属固定剤及び／又は酸性中和剤を添加する工程を行った後の飛灰の液固比１０における溶出液のｐＨが８．０〜１１．５である上記［１］に記載の酸性排ガスの処理方法。
［３］前記粉体中のマグネシウム原子とカルシウム原子とのモルの比が１：０．７９ 〜 １：３．１５である上記［１］又は［２］に記載の酸性排ガスの処理方法。
［４］前記粉体の細孔容積が０．１〜０．７ｃｍ3／ｇ、動的見掛け比重が０．３〜０．７ｇ／ｃｍ3である上記［１］〜［３］の何れかに記載の酸性排ガスの処理方法。
［５］前記水酸化マグネシウム及び水酸化カルシウムとして、水酸化ドロマイトを含有する上記［１］〜［４］の何れかに記載の酸性排ガスの処理方法。
［６］前記酸性排ガスが塩化水素及び硫黄酸化物を含み、該塩化水素及び硫黄酸化物に対して、水酸化マグネシウム及び水酸化カルシウムを合計で０．５〜５．０当量となるように添加する上記［１］〜［５］の何れかに記載の酸性排ガスの処理方法。
［７］酸性排ガスに対して、比表面積２０ｍ2／ｇ以上、メジアン径（ｄ５０）５〜３０μｍであって、水酸化マグネシウム及び水酸化カルシウムを構成成分として有する粉体を含有してなる排ガス処理剤を添加することにより、ｐＨ８．３を終点とする酸消費量から規定される飛灰のアルカリ度を５５ｍｇＣａＣＯ3／ｇ未満とする工程を行い、さらに飛灰を集塵する工程を行った後に、キレート系重金属固定剤を添加する工程を行う酸性排ガスの処理方法。
［８］排ガス処理剤を添加してｐＨ８．３を終点とする酸消費量から規定される飛灰のアルカリ度を５５ｍｇＣａＣＯ3／ｇ未満とする工程において、飛灰の液固比１０における溶出液のｐＨを１１．８以下とする上記［７］に記載の酸性排ガスの処理方法。
［９］前記粉体中のマグネシウム原子とカルシウム原子とのモルの比が１：０．７９ 〜 １：３．１５である上記［７］又は［８］に記載の酸性排ガスの処理方法。
［１０］前記粉体の細孔容積が０．１〜０．７ｃｍ3／ｇ、動的見掛け比重が０．３〜０．７ｇ／ｃｍ3である上記［７］〜［９］の何れかに記載の酸性排ガスの処理方法。
［１１］前記水酸化マグネシウム及び水酸化カルシウムとして、水酸化ドロマイトを含有する上記［７］〜［１０］の何れかに記載の酸性排ガスの処理方法。
［１２］前記酸性排ガスが塩化水素及び硫黄酸化物を含み、該塩化水素及び硫黄酸化物に対して、水酸化マグネシウム及び水酸化カルシウムを合計で０．５〜５．０当量となるように添加する上記［７］〜［１１］の何れかに記載の酸性排ガスの処理方法。
In order to solve the above problems, the following [1] to [12] acidic exhaust gas treatment methods are provided.
[1] A powder having a specific surface area of 20 m 2 / g or more, a median diameter (d50) of 5 to 30 μm and containing magnesium hydroxide and calcium hydroxide as constituents with respect to acidic exhaust gas. By adding an exhaust gas treatment agent, the step of reducing the alkalinity of fly ash specified by the acid consumption with pH 8.3 as the end point to 150 mg CaCO 3 / g or less, and further the step of collecting fly ash After that, the processing method of the acidic exhaust gas which performs the process of adding an inorganic heavy metal fixing agent and / or an acidic neutralizer.
[2] In the above [1], the pH of the eluate at the liquid-solid ratio 10 of fly ash after performing the step of adding the inorganic heavy metal fixing agent and / or the acidic neutralizer is 8.0 to 11.5. The treatment method of the acidic exhaust gas as described.
[3] The method for treating acidic exhaust gas according to the above [1] or [2], wherein a molar ratio of magnesium atom to calcium atom in the powder is 1: 0.79 to 1: 3.15.
[4] pore volume 0.1~0.7cm 3 / g of the powder, either dynamic apparent specific gravity of 0.3 to 0.7 g / cm 3 [1] to [3] The processing method of the acidic waste gas as described in 2.
[5] The method for treating acidic exhaust gas according to any one of the above [1] to [4], which contains dolomite hydroxide as the magnesium hydroxide and calcium hydroxide.
[6] The acidic exhaust gas contains hydrogen chloride and sulfur oxide, and magnesium hydroxide and calcium hydroxide are added to the hydrogen chloride and sulfur oxide so that the total amount is 0.5 to 5.0 equivalents. The method for treating acidic exhaust gas according to any one of [1] to [5] above.
[7] Exhaust gas treatment comprising a powder having a specific surface area of 20 m 2 / g or more and a median diameter (d50) of 5 to 30 μm and containing magnesium hydroxide and calcium hydroxide as constituents with respect to acidic exhaust gas After adding the agent, the step of setting the alkalinity of the fly ash specified from the acid consumption with pH 8.3 as the end point to less than 55 mg CaCO 3 / g, and further the step of collecting the fly ash is performed The processing method of acidic exhaust gas which performs the process of adding a chelate type heavy metal fixing agent.
[8] An eluate at a liquid-solid ratio of 10 in fly ash in the step of adding an exhaust gas treating agent to make the fly ash alkalinity less than 55 mg CaCO 3 / g defined by the acid consumption starting from pH 8.3 The method for treating acidic exhaust gas according to the above [7], wherein the pH of the solution is 11.8 or less.
[9] The method for treating acidic exhaust gas according to the above [7] or [8], wherein a molar ratio of magnesium atom to calcium atom in the powder is 1: 0.79 to 1: 3.15.
[10] pore volume 0.1~0.7cm 3 / g of the powder, either dynamic apparent specific gravity of 0.3 to 0.7 g / cm 3 above [7] to [9] The processing method of the acidic waste gas as described in 2.
[11] The method for treating acidic exhaust gas according to any one of the above [7] to [10], which contains dolomite hydroxide as the magnesium hydroxide and calcium hydroxide.
[12] The acidic exhaust gas contains hydrogen chloride and sulfur oxide, and magnesium hydroxide and calcium hydroxide are added to the hydrogen chloride and sulfur oxide so that the total amount is 0.5 to 5.0 equivalents. The method for treating acidic exhaust gas according to any one of [7] to [11] above.
本発明の酸性排ガスの処理方法によれば、重金属固定剤の使用量を減らすとともに、低コストで重金属の固定処理を行うことができる。 According to the method for treating acidic exhaust gas of the present invention, it is possible to reduce the amount of heavy metal fixing agent used and perform heavy metal fixing treatment at low cost.
［酸性排ガスの処理方法］
本発明の酸性排ガスの処理方法は、酸性排ガスに対して、比表面積２０ｍ2／ｇ以上、メジアン径（ｄ５０）５〜３０μｍであって、水酸化マグネシウム及び水酸化カルシウムを構成成分として有する粉体を含有してなる排ガス処理剤を添加することにより、ｐＨ８．３を終点とする酸消費量から規定される飛灰のアルカリ度を１００ｍｇＣａＣＯ3／ｇ以下とする工程を行い、さらに飛灰を集塵する工程を行った後に、無機重金属固定剤及び／又は酸性中和剤を添加する工程を行うものである（以下、「第一の方法」と称する場合がある。）。
また、本発明の酸性排ガスの処理方法は、酸性排ガスに対して、比表面積２０ｍ2／ｇ以上、メジアン径（ｄ５０）５〜３０μｍであって、水酸化マグネシウム及び水酸化カルシウムを構成成分として有する粉体を含有してなる排ガス処理剤を添加することにより、ｐＨ８．３を終点とする酸消費量から規定される飛灰のアルカリ度を５５ｍｇＣａＣＯ3／ｇ未満とする工程を行い、さらに飛灰を集塵する工程を行った後に、キレート系重金属固定剤を添加する工程を行うものである（以下、「第二の方法」と称する場合がある。）。
[Method of treating acidic exhaust gas]
The method for treating acidic exhaust gas of the present invention is a powder having a specific surface area of 20 m 2 / g or more and a median diameter (d50) of 5 to 30 μm with respect to the acidic exhaust gas, and having magnesium hydroxide and calcium hydroxide as constituent components. By adding an exhaust gas treatment agent containing, the step of setting the alkalinity of fly ash, which is defined from the acid consumption with pH 8.3 as the end point, to 100 mgCaCO 3 / g or less, and further collecting fly ash After performing the dusting step, a step of adding an inorganic heavy metal fixing agent and / or an acidic neutralizing agent is performed (hereinafter sometimes referred to as “first method”).
In addition, the method for treating acidic exhaust gas of the present invention has a specific surface area of 20 m 2 / g or more and a median diameter (d50) of 5 to 30 μm with respect to the acidic exhaust gas, and has magnesium hydroxide and calcium hydroxide as constituent components. By adding an exhaust gas treatment agent containing powder, a step of making the fly ash alkalinity less than 55 mg CaCO 3 / g defined by the acid consumption with pH 8.3 as an end point is carried out, and further fly ash After performing the step of collecting dust, a step of adding a chelate heavy metal fixing agent is performed (hereinafter sometimes referred to as “second method”).
図１は、本発明の第一の方法及び第二の方法における酸性排ガスの処理方法を実施する排ガス処理システムの一実施形態を示す模式図である。図１の酸性排ガス処理システムでは、酸性排ガスは減温塔１で冷却され、煙道２を介して集塵機４に接続されている。また、排ガス処理剤供給装置３から排ガス処理剤が供給され、煙道２の途中において、酸性排ガスと排ガス処理剤とが混合されている。集塵機４からは吸引ファン５により煙が吸い出され、煙突から煙が放出される。また、集塵機４からは飛灰処理装置６に集塵した飛灰が放出され、該装置内で、図示しない薬剤添加手段により、重金属固定剤及び／又は酸性中和剤が添加された後、灰ピット７に放出される。 FIG. 1 is a schematic diagram showing an embodiment of an exhaust gas treatment system for carrying out an acidic exhaust gas treatment method in the first method and the second method of the present invention. In the acidic exhaust gas treatment system of FIG. 1, the acidic exhaust gas is cooled by the temperature reducing tower 1 and connected to the dust collector 4 via the flue 2. Further, the exhaust gas treatment agent is supplied from the exhaust gas treatment agent supply device 3, and the acidic exhaust gas and the exhaust gas treatment agent are mixed in the middle of the flue 2. Smoke is sucked out from the dust collector 4 by the suction fan 5, and smoke is discharged from the chimney. Also, the fly ash collected in the fly ash treatment device 6 is released from the dust collector 4, and after the heavy metal fixing agent and / or the acidic neutralizer is added by the chemical addition means (not shown) in the device, the ash Released to pit 7.
（排ガス処理剤の添加工程）
本発明の第一の方法及び第二の方法における酸性排ガスの処理方法では、まず、酸性排ガスに対して排ガス処理剤を添加する工程を行う。
本発明の酸性排ガスの処理方法が適用できる酸性排ガスは特に制限されない。例えば、都市ごみ廃棄物焼却炉、産業廃棄物焼却炉、発電ボイラ、炭化炉、民間工場等の燃焼施設において発生する、塩化水素や硫黄酸化物等の酸性ガスを含む排ガスが挙げられる。
排ガス処理剤の添加場所は、特に制限はなく、焼却炉内、減温塔手前、バグフィルター等の集塵機の手前で添加することで本発明の効果が見込まれる。ただし、一般的には、排ガス処理剤を、酸性排ガスを減温塔で冷却した後のバグフィルター等の集塵機手前で添加することが好ましい。
(Exhaust gas treatment agent addition process)
In the method for treating acidic exhaust gas in the first method and the second method of the present invention, first, a step of adding an exhaust gas treating agent to the acidic exhaust gas is performed.
The acidic exhaust gas to which the method for treating acidic exhaust gas of the present invention can be applied is not particularly limited. For example, exhaust gas containing acid gases such as hydrogen chloride and sulfur oxides generated in combustion facilities such as municipal waste incinerators, industrial waste incinerators, power generation boilers, carbonization furnaces, and private factories.
The place for adding the exhaust gas treating agent is not particularly limited, and the effect of the present invention can be expected by adding it in the incinerator, before the temperature reducing tower, and before the dust collector such as the bag filter. However, generally, it is preferable to add the exhaust gas treating agent before the dust collector such as a bag filter after the acidic exhaust gas is cooled in the temperature reducing tower.
本発明の酸性排ガスの処理方法では、排ガス処理剤として、比表面積が２０ｍ2／ｇ以上、メジアン径（ｄ５０）が５〜３０μｍであって、水酸化マグネシウム及び水酸化カルシウムを構成成分として有する粉体を含有してなるものを用いる。
従来のように、水酸化カルシウムで酸性排ガスを処理した場合、飛灰に水酸化カルシウムの未反応分が残存し、酸消費量で規定される飛灰中のアルカリ度が高くなる。これにより、リン酸系化合物に代表される重金属固定剤を多量に用いる必要がある。
しかしながら、本発明では、上述の特定の粉体を含有してなる排ガス処理剤を用いることから、酸性排ガスとの反応性に優れるとともに、従来の水酸化カルシウムに比べ、処理剤自身のアルカリ度を大幅に削減できる。具体的には、粉体のアルカリ度を５００〜１０００ ｍｇＣａＣＯ3／ｇにすることができ、好ましくは７００〜９００ ｍｇＣａＣＯ3／ｇにすることができる。これにより、飛灰に残存するアルカリ含有量を大幅に低減でき、重金属固定剤の添加量を大幅に削減することができる。
粉体の比表面積が２０ｍ2／ｇ未満であると、塩化水素や硫黄酸化物等の酸性ガスとの反応性が低下する。また、粉体のメジアン径（ｄ５０）が５μｍ未満であると、集塵機での捕集効率の低下や差圧の上昇が懸念される。また、粉体のメジアン径（ｄ５０）が３０μｍを超えると酸性ガスとの反応性の低下が懸念される。
In the method for treating acidic exhaust gas of the present invention, as an exhaust gas treating agent, a powder having a specific surface area of 20 m 2 / g or more, a median diameter (d50) of 5 to 30 μm, and magnesium hydroxide and calcium hydroxide as constituent components The one containing the body is used.
When the acidic exhaust gas is treated with calcium hydroxide as in the past, the unreacted portion of calcium hydroxide remains in the fly ash, and the alkalinity in the fly ash specified by the acid consumption increases. Thereby, it is necessary to use a heavy metal fixing agent typified by a phosphate compound.
However, in the present invention, since the exhaust gas treatment agent containing the above specific powder is used, the reactivity with acidic exhaust gas is excellent, and the alkalinity of the treatment agent itself is higher than that of conventional calcium hydroxide. It can be greatly reduced. Specifically, the alkalinity of the powder can be 500 to 1000 mgCaCO 3 / g, preferably 700 to 900 mgCaCO 3 / g. Thereby, the alkali content remaining in the fly ash can be greatly reduced, and the amount of heavy metal fixing agent added can be greatly reduced.
When the specific surface area of the powder is less than 20 m 2 / g, the reactivity with acidic gases such as hydrogen chloride and sulfur oxides decreases. Moreover, when the median diameter (d50) of the powder is less than 5 μm, there is a concern that the collection efficiency of the dust collector may be reduced or the differential pressure may be increased. Further, when the median diameter (d50) of the powder exceeds 30 μm, there is a concern that the reactivity with the acid gas is lowered.
なお、本発明において「アルカリ度」は、試料（０．１〜０．５ｇ）と１,０００倍量の純水（１００〜５００ｍｌ）をビーカーに投入し、マグネチックスターラーで、１時間攪拌した試料からマイクロピペットで所定量（ｍｌ）分取し、フェノールフタレイン指示薬を数滴加え混合した後、１／５０Ｎの硫酸を変色する（ｐＨ８．３に至る）まですみやかに滴定し、薬剤１ｇあたりの硫酸の滴定量(ｍｌ)を記録し、以下の換算式により算出した。
（換算式）
アルカリ度(ｍｇＣａＣＯ3/ｇ)
＝０．０２ [滴定硫酸濃度(ｍｏｌ／Ｌ)]×Ａ (ｍｌ)÷Ｂ(ｇ)×Ｃ(ｍｌ)÷Ｄ(ｍｌ)×１００÷２
＝Ａ（ｍｌ）÷Ｂ(ｇ)×Ｃ(ｍｌ)÷Ｄ(ｍｌ)
Ａ：硫酸滴定量（ｍｌ）
Ｂ：試料量（ｇ）
Ｃ：純水添加量（ｍｌ）
Ｄ：攪拌後の分取量（ｍｌ）
In the present invention, “alkalinity” refers to a sample (0.1 to 0.5 g) and 1,000 times the amount of pure water (100 to 500 ml) placed in a beaker and stirred for 1 hour with a magnetic stirrer. Take a predetermined amount (ml) from the sample with a micropipette, mix with a few drops of phenolphthalein indicator, and immediately titrate until 1 / 50N sulfuric acid changes color (to reach pH 8.3). The sulfuric acid titer (ml) was recorded and calculated by the following conversion formula.
(Conversion formula)
Alkalinity (mgCaCO 3 / g)
= 0.02 [Titration sulfuric acid concentration (mol / L)] × A (ml) ÷ B (g) × C (ml) ÷ D (ml) × 100 ÷ 2
= A (ml) / B (g) x C (ml) / D (ml)
A: Sulfuric acid titration (ml)
B: Sample amount (g)
C: Amount of pure water added (ml)
D: Amount taken after stirring (ml)
排ガス処理剤中の粉体は、酸性排ガス処理性能の観点から、比表面積、メジアン径（ｄ５０）、細孔容積及び動的見掛比重が以下の範囲であることが好ましい。
比表面積は２０〜１５０ｍ2／ｇであることが好ましく、２０〜１００ｍ2／ｇであることがより好ましく、２０〜６０ｍ2／ｇであることがさらに好ましい。メジアン径（ｄ５０）は５〜３０μｍであることが好ましく、１０〜２０μｍであることがより好ましい。細孔容積は０．１〜０．７ｃｍ3／ｇであることが好ましく、０．１〜０．６ｃｍ3／ｇであることがより好ましく、０．１〜０．４ｃｍ3／ｇであることがさらに好ましい。動的見掛比重は、０．３〜０．７ｇ／ｃｍ3であることが好ましく、０．４〜０．６ ｇ／ｃｍ3であることがより好ましい。
本発明において「比表面積」とは窒素吸着によるＢＥＴ法により、窒素の吸着量からＢＥＴ１点法により算出される比表面積を意味し、「細孔容積」とはＢＪＨ法により算出される細孔容積を意味し、いずれもQuanta chrome社製の商品名 NOVA 2000等の測定装置により測定できる。また、「メジアン径（ｄ５０）」とは、レーザー回折散乱法によって求めた粒度分布における粒子個数の積算値が５０％となる粒子径（ｄ５０）を意味し、島津製作所社製の商品名SALD-2100等の測定装置により測定できる。また、「動的見掛比重」とは、貯留槽における実際の比重に近い値であり、ホソカワミクロン社製の商品名パウダーテスター等の測定装置により測定される「ゆるみ見掛比重(タップをしない時の見掛比重)」と「固め見掛比重(十分にタップをした際の見掛比重)」の測定値をもとに以下算出式で試算される。
動的見掛比重（ｇ／ｃｍ3）＝Ａ＋｛（Ｂ−Ａ）×（Ｂ−Ａ）÷Ｂ｝
Ａ：ゆるみ見掛比重（ｇ／ｃｍ3）
Ｂ：固め見掛比重（ｇ／ｃｍ3）
The powder in the exhaust gas treating agent preferably has a specific surface area, median diameter (d50), pore volume, and dynamic apparent specific gravity in the following ranges from the viewpoint of acidic exhaust gas treatment performance.
Preferably the specific surface area is 20~150m 2 / g, more preferably 20 to 100 m 2 / g, more preferably from 20~60m 2 / g. The median diameter (d50) is preferably 5 to 30 μm, and more preferably 10 to 20 μm. Preferably the pore volume is 0.1~0.7cm 3 / g, more preferably 0.1~0.6cm 3 / g, it is 0.1~0.4cm 3 / g Is more preferable. Dynamic apparent specific gravity is preferably from 0.3 to 0.7 g / cm 3, more preferably 0.4~0.6 g / cm 3.
In the present invention, the “specific surface area” means a specific surface area calculated by the BET method by nitrogen adsorption and the BET one-point method from the adsorption amount of nitrogen, and the “pore volume” means the pore volume calculated by the BJH method. These can be measured by a measuring device such as the product name NOVA 2000 manufactured by Quanta chrome. The “median diameter (d50)” means a particle diameter (d50) at which the integrated value of the number of particles in the particle size distribution determined by the laser diffraction scattering method is 50%. The trade name SALD- manufactured by Shimadzu Corporation It can be measured with a measuring device such as 2100. The “dynamic apparent specific gravity” is a value close to the actual specific gravity in the storage tank, and is measured by a measuring device such as a product name powder tester manufactured by Hosokawa Micron Co., Ltd. Based on the measured values of “apparent specific gravity” and “solid apparent specific gravity (apparent specific gravity when fully tapped)”, the following calculation formula is used.
Dynamic apparent specific gravity (g / cm 3 ) = A + {(BA) × (BA) ÷ B}
A: Loose apparent specific gravity (g / cm 3 )
B: Solid apparent specific gravity (g / cm 3 )
排ガス処理剤中の粉体は、水酸化マグネシウム及び水酸化カルシウムを構成成分として有する。排ガス処理剤中の粉体に、水酸化マグネシウム及び水酸化カルシウムという２つの成分を構成成分として有することにより、従来の水酸化カルシウムに比べ、処理剤自身のアルカリ度を大幅に削減できる。この理由は、水酸化カルシウムに比べ、水酸化マグネシウムは、水への溶解が非常に遅く、上記アルカリ度において検出しにくいためと考えられる。
さらに、水酸化カルシウムと水酸化マグネシウムの混合物、特に高比表面積の水酸化ドロマイトは、従来の水酸化カルシウムに比べ酸性排ガスとの反応性が優れており、水酸化カルシウムの未反応分が減少し、前記排ガス処理剤を添加し処理した飛灰のアルカリ度を大幅に減少させることができ、無機重金属固定剤、酸性中和剤、キレート系重金属固定剤の必要添加量を大幅に削減することができる。
なお、本発明において、「水酸化マグネシウム及び水酸化カルシウムを構成成分として有する」とは、水酸化マグネシウム及び水酸化カルシウムが独立して存在する構成、並びに、後述する水酸化ドロマイト［Ｃａ（ＯＨ）2・Ｍｇ（ＯＨ）2］のように、水酸化マグネシウム及び水酸化カルシウムが複合化してなる構成等のように、水酸化マグネシウム及び水酸化カルシウムを構成成分中に含むものを意味する。
The powder in the exhaust gas treating agent has magnesium hydroxide and calcium hydroxide as constituent components. By having two components of magnesium hydroxide and calcium hydroxide as constituents in the powder in the exhaust gas treatment agent, the alkalinity of the treatment agent itself can be greatly reduced compared to conventional calcium hydroxide. The reason for this is considered to be that magnesium hydroxide is very slowly dissolved in water as compared with calcium hydroxide and is difficult to detect at the alkalinity.
In addition, a mixture of calcium hydroxide and magnesium hydroxide, especially dolomite hydroxide with a high specific surface area, is more reactive with acidic exhaust gas than conventional calcium hydroxide, reducing the unreacted content of calcium hydroxide. The alkalinity of the fly ash treated by adding the exhaust gas treatment agent can be greatly reduced, and the required amount of inorganic heavy metal fixing agent, acidic neutralizing agent, chelate heavy metal fixing agent can be greatly reduced. it can.
In the present invention, “having magnesium hydroxide and calcium hydroxide as constituent components” means that magnesium hydroxide and calcium hydroxide exist independently, and dolomite hydroxide [Ca (OH) described later] 2 · Mg (OH) 2 ] means that the component contains magnesium hydroxide and calcium hydroxide, such as a structure in which magnesium hydroxide and calcium hydroxide are combined.
粉体である排ガス処理剤に含まれる、水酸化マグネシウム及び水酸化カルシウムは、飛灰アルカリ度の低減効果及び排ガス処理剤の低コスト化の観点から、排ガス処理剤中に含まれるマグネシウム原子とカルシウム原子のモルの比が、１：０．７９〜１：３．１５で含まれることが好ましく、１：０．９６〜１：２．３６で含まれることがより好ましい。
マグネシウム原子とカルシウム原子とのモル比は、EDTA滴定法により算出することができる。例えば、前記排ガス処理剤をＪＩＳ Ｒ９０１１に基づくEDTA滴定法により分析したＣａとＭｇの測定結果から算出することができる。
Magnesium hydroxide and calcium hydroxide contained in the exhaust gas treatment agent that is a powder are magnesium atoms and calcium contained in the exhaust gas treatment agent from the viewpoint of reducing fly ash alkalinity and reducing the cost of the exhaust gas treatment agent. The molar ratio of atoms is preferably included at 1: 0.79 to 1: 3.15, and more preferably 1: 0.96 to 1: 2.36.
The molar ratio of magnesium atom to calcium atom can be calculated by EDTA titration method. For example, it can be calculated from the measurement results of Ca and Mg obtained by analyzing the exhaust gas treating agent by the EDTA titration method based on JIS R9011.
水酸化カルシウムは、以下のように、焼成工程、消化工程を経て製造することができる。
（１）焼成工程 ＣａＣＯ3 → ＣａＯ ＋ＣＯ2 ↑
原料の炭酸カルシウムを主成分とする石灰石は、特に制限されることなく使用できる。石灰石の分解温度は、約９００℃であるが、焼成工程は、一般的には、１１００〜１３００℃程度の熱をかけて焼成される。焼成する時間は、炉の形式にもよるが２〜２４時間程度行うことにより焼成が可能である。
焼成工程により得られた生石灰（酸化カルシウム）を消化原料とする場合には、ロールクラッシャーやインペラブレーカー等の粉砕機を用いて、数ｍｍアンダー程度の粒度に粉砕することが好ましい。
Calcium hydroxide can be produced through a firing step and a digestion step as follows.
(1) Firing process CaCO 3 → CaO + CO 2 ↑
Limestone mainly composed of raw material calcium carbonate can be used without particular limitation. The decomposition temperature of limestone is about 900 ° C., but the firing step is generally performed by applying heat of about 1100 to 1300 ° C. Although the firing time depends on the type of the furnace, firing is possible for about 2 to 24 hours.
When quick lime (calcium oxide) obtained by the baking process is used as a digestion raw material, it is preferably pulverized to a particle size of about several mm under using a pulverizer such as a roll crusher or an impeller breaker.
（２）消化工程 ＣａＯ + Ｈ2Ｏ → Ｃａ（ＯＨ）2
生石灰の消化工程は、一般的には、消化機で生石灰と水を反応させた後、消化反応のムラをなくすため、熟成機で、数十分程度攪拌し、熟成する。消化水の量は、熟成後の消石灰がほぼ乾粉で得られるよう調整される。生石灰の消化工程において必要な理論水量は、生石灰の３割程度であるが、消化に伴う発熱で水分ロスがある為、理論量の倍に相当する６割程度の水を加えて消化するのが一般的である。
前記製造した消石灰には、一部未焼成物や未反応の酸化カルシウムが含まれるため、気流分級機でこれらの不純物を取り除くとともに、ある一定の粒径範囲で消石灰を分級回収する。この際、粗粒のものは、振動ミルやボールミル等の粉砕機により粉砕し、再度分級する場合もある。工業的に使用されるJIS特号消石灰においては、ほぼ１５０μｍアンダーとなるよう粒度調整され、その結果、メジアン径（ｄ５０）が５〜２０μｍ程度になる。また、比表面積は、１０〜２０ｍ2／ｇ、細孔容積が０．０５〜０．１５ｃｍ3／ｇ、動的見掛比重は、０．５〜０．６ｇ／ｃｍ3程度となる。
(2) Digestion process CaO + H 2 O → Ca (OH) 2
In the quick lime digestion process, generally, after reacting quick lime and water with a digester, in order to eliminate the unevenness of the digestion reaction, it is aged by stirring for several tens of minutes with an aging machine. The amount of digested water is adjusted so that the slaked lime after aging is obtained almost as a dry powder. The theoretical amount of water required in the quick lime digestion process is about 30% of that of quick lime, but there is water loss due to the heat generated by digestion, so digesting by adding about 60% of water, equivalent to twice the theoretical amount, is necessary. It is common.
Since the produced slaked lime contains partially unfired products and unreacted calcium oxide, these impurities are removed by an air classifier, and slaked lime is classified and recovered in a certain particle size range. At this time, the coarse particles may be pulverized by a pulverizer such as a vibration mill or a ball mill and classified again. In industrially used JIS special slaked lime, the particle size is adjusted to be under about 150 μm, and as a result, the median diameter (d50) is about 5 to 20 μm. The specific surface area is 10 to 20 m 2 / g, a pore volume of 0.05~0.15cm 3 / g, the dynamic apparent specific gravity becomes 0.5~0.6g / cm 3 order.
また、近年、通常用いられていたＪＩＳ特号消石灰に比べ、酸性ガスとの反応性が高い、高反応性の消石灰が利用されている。この高反応性消石灰の製造においては、前記消化工程において、生石灰と同量の消化水を糖や多価アルコール等の消化遅延剤とともに添加する。この工程により、消石灰の比表面積を高くし、酸性ガスとの反応性を向上させることができる。
消化遅延剤としては、砂糖等の糖類、エタノール、プロパノール、エチレングリコール、ジエチレングリコール、プロピレングリコール等のアルコール類、エタノールアミン、ジエタノールアミン、トリエタノールアミン等のアミノアルコール類が知られている。消化遅延剤は、生石灰１００質量部に対して、０．１〜１．０質量部添加される。
消化後、必要に応じて乾燥、粉砕、分級などの工程を経て、メジアン径（ｄ５０）が５〜２０μｍ程度、比表面積が４０〜５５ｍ2／ｇ、細孔容積が０．１５〜０．３０ｃｍ3／ｇ、動的見掛比重０．３５〜０．５ｇ／ｃｍ3程度の高反応性の消石灰が得られる。
In recent years, highly reactive slaked lime, which has higher reactivity with acidic gas than JIS special slaked lime, which is normally used, has been used. In the production of this highly reactive slaked lime, in the digestion step, the same amount of digested water as quick lime is added along with digestion retarders such as sugar and polyhydric alcohol. By this step, the specific surface area of slaked lime can be increased and the reactivity with acidic gas can be improved.
Known digestion retarders include sugars such as sugar, alcohols such as ethanol, propanol, ethylene glycol, diethylene glycol, and propylene glycol, and amino alcohols such as ethanolamine, diethanolamine, and triethanolamine. The digestion retardant is added in an amount of 0.1 to 1.0 part by mass with respect to 100 parts by mass of quicklime.
After digestion, the median diameter (d50) is about 5 to 20 μm, the specific surface area is 40 to 55 m 2 / g, and the pore volume is 0.15 to 0.30 cm through steps such as drying, pulverization, and classification as necessary. 3 / g, a dynamic apparent specific gravity 0.35~0.5g / cm 3 as high reactivity lime is obtained.
水酸化マグネシウムは、脱炭酸した海水に消石灰や水酸化ナトリウム等のアルカリ剤を添加し、水酸化マグネシウムの製造を行う海水法が一般的である。本方法では、製造する水酸化マグネシウムがコロイド状となり、沈降及び洗浄が困難となるので、循環により種晶を大きくして、沈降性・ろ過性の高い水酸化マグネシウムを得た後、沈降、洗浄、ろ過、乾燥、粉砕の工程を経て製造することができる。
また、酸化マグネシウムに水を接触させ、水酸化マグネシウムを製造する方法も知られている。
水酸化マグネシウムのメジアン径（ｄ５０）は、上記粉砕工程により調整することができる。一般的に市販されている水酸化マグネシウムは、粒子径１〜１０μｍ、比表面積１〜４０ｍ2／ｇのものがある。
本発明では、比表面積の大きい水酸化マグネシウムを用いるのが好ましいことから、神島化学工業社製の商品名「水酸化マグネシウム３００（粒子径７μｍ、ＢＥＴ比表面積３５ｍ2／ｇ）」を適用するのが好適である。また、本発明の効果を得るため特開2005-247604号公報に記載されているようなＢＥＴ比表面積が１００ｍ2／ｇ以上の水酸化マグネシウムを適用することも好適である。
Magnesium hydroxide is generally a seawater method in which an alkali agent such as slaked lime or sodium hydroxide is added to decarboxylated seawater to produce magnesium hydroxide. In this method, the magnesium hydroxide to be produced becomes colloidal, making it difficult to settle and wash. Therefore, the seed crystal is enlarged by circulation to obtain magnesium hydroxide having high sedimentation and filterability, followed by sedimentation and washing. It can be manufactured through the steps of filtration, drying and pulverization.
A method of producing magnesium hydroxide by bringing water into contact with magnesium oxide is also known.
The median diameter (d50) of magnesium hydroxide can be adjusted by the pulverization step. In general, commercially available magnesium hydroxide has a particle diameter of 1 to 10 μm and a specific surface area of 1 to 40 m 2 / g.
In the present invention, it is preferable to use magnesium hydroxide having a large specific surface area. Therefore, the trade name “magnesium hydroxide 300 (particle diameter: 7 μm, BET specific surface area: 35 m 2 / g)” manufactured by Kamishima Chemical Co., Ltd. is applied. Is preferred. In order to obtain the effects of the present invention, it is also preferable to apply magnesium hydroxide having a BET specific surface area of 100 m 2 / g or more as described in JP-A-2005-247604.
水酸化カルシウムと水酸化マグネシウムとを含む粉としては、水酸化ドロマイトが好適である。
水酸化ドロマイトは、ドロマイト（ＣａＣＯ3・ＭｇＣＯ3）を原料として、下記に示すように、焼成工程、消化工程を経て製造される。水酸化ドロマイトは、日本国内に不純物の少ない高品位なドロマイト資源がある点、水酸化カルシウムと水酸化マグネシウムを混合利用する場合や、石灰石や軽焼マグネシウム（ＭｇＯ）を混合して消化製造する場合において原料を混合する工程は不要であり、比較的安価に製造できる点において好適である。
As the powder containing calcium hydroxide and magnesium hydroxide, dolomite hydroxide is suitable.
Hydroxylated dolomite is produced from dolomite (CaCO 3 .MgCO 3 ) as a raw material through a firing step and a digestion step as shown below. Dolomite hydroxide has high-quality dolomite resources with few impurities in Japan, when mixing and using calcium hydroxide and magnesium hydroxide, or when digesting and manufacturing limestone and light calcined magnesium (MgO) The step of mixing the raw materials is not necessary and is preferable in that it can be produced at a relatively low cost.
（１）焼成工程 ＣａＣＯ3・ＭｇＣＯ3 → ＣａＯ・ＭｇＯ
原料のドロマイトは特に制限されることなく使用できる。ドロマイトは、炭酸カルシウムと炭酸マグネシウムの複塩であり、炭酸マグネシウムは、炭酸カルシウムに比べ分解温度が低いため、焼成温度は、１１００〜１２００℃程度と同程度からやや低い温度で焼成できる。焼成する時間は、前記同様、炉の形式にもよるが２〜２４時間程度で十分焼成が可能である。
焼成工程により得られた酸化カルシウムと酸化マグネシウムを含む軽焼ドロマイトを消化原料とする場合には、消化反応を安定させるために、ロールクラッシャーやインペラブレーカー等により、数ｍｍアンダー程度の粒度に粉砕することが好ましい。
(1) Firing process CaCO 3 · MgCO 3 → CaO · MgO
The raw material dolomite can be used without any particular limitation. Dolomite is a double salt of calcium carbonate and magnesium carbonate. Since magnesium carbonate has a lower decomposition temperature than calcium carbonate, the firing temperature can be fired at a temperature as low as about 1100 to 1200 ° C. The firing time depends on the type of the furnace as described above, but it can be sufficiently fired in about 2 to 24 hours.
When lightly burned dolomite containing calcium oxide and magnesium oxide obtained in the baking process is used as a raw material for digestion, it is pulverized to a particle size of about several millimeters under a roll crusher or impeller breaker to stabilize the digestion reaction. It is preferable.
（２）消化工程 ＣａＯ・ＭｇＯ + ２Ｈ2Ｏ → Ｃａ（ＯＨ）2・Ｍｇ（ＯＨ）2
軽焼ドロマイト（ＣａＯ・ＭｇＯ）は、上記生石灰とほぼ同様に消化できる。前記製造した水酸化ドロマイトに含まれる一部未焼成物や未反応物は、前記同様、気流分級機で取り除くとともに、ある一定の粒径範囲で水酸化ドロマイトを分級回収する。この際、粗粒のものは、振動ミルやボールミル等の粉砕機により粉砕し、再度分級しても良い。これらの製造工程を経て、メジアン径（ｄ５０）が５〜３０μｍ程度に調整され、比表面積が２０〜４０ｍ2／ｇ、細孔容積が０．１〜０．２ｃｍ3／ｇ、動的見掛比重０．４５〜０．６５ｇ／ｃｍ3程度の水酸化ドロマイトが得られる。
(2) Digestion process CaO · MgO + 2H 2 O → Ca (OH) 2 · Mg (OH) 2
Lightly burned dolomite (CaO · MgO) can be digested in substantially the same manner as the above-mentioned quicklime. As described above, partially unfired products and unreacted materials contained in the produced hydroxide dolomite are removed by an airflow classifier and classified and recovered in a certain particle size range. At this time, coarse particles may be pulverized by a pulverizer such as a vibration mill or a ball mill and classified again. Through these manufacturing steps, the median diameter (d50) is adjusted to about 5 to 30 μm, the specific surface area is 20 to 40 m 2 / g, the pore volume is 0.1 to 0.2 cm 3 / g, the dynamic appearance Hydroxide dolomite having a specific gravity of about 0.45 to 0.65 g / cm 3 is obtained.
水酸化ドロマイトにおいても、上記の消化工程において、消化水に消化遅延剤を添加することにより比表面積を高くすることができる。比表面積を高くすることにより、本発明における酸性ガス除去性能を向上させるとともに、飛灰に残存するアルカリ度を低減することができ、非常に有効な手段である。
消化遅延剤としては、前記同様、砂糖等の糖類、エタノール、プロパノール、エチレングリコール、ジエチレングリコール、プロピレングリコール等のアルコール類、エタノールアミン、ジエタノールアミン、トリエタノールアミン等のアミノアルコール類が挙げられる。
消化遅延剤は、原料である軽焼ドロマイト１００質量部に対して、０．１〜１．５質量部添加することが好ましく、０．４〜１．２質量部添加することがより好ましい。
消化後、必要に応じて乾燥、粉砕、分級などの工程を経て、メジアン径（ｄ５０）が５〜３０μｍ程度、比表面積が４０〜６０ｍ2／ｇ、細孔容積が０．２〜０．４ｃｍ3／ｇ、動的見掛比重０．４〜０．６ｇ／ｃｍ3程度の高比表面積の水酸化ドロマイトが得られる。
Also in dolomite hydroxide, the specific surface area can be increased by adding a digestion retardant to digestion water in the digestion step. By increasing the specific surface area, the acid gas removal performance in the present invention can be improved and the alkalinity remaining in the fly ash can be reduced, which is a very effective means.
Examples of the digestion retardant include sugars such as sugar, alcohols such as ethanol, propanol, ethylene glycol, diethylene glycol, and propylene glycol, and amino alcohols such as ethanolamine, diethanolamine, and triethanolamine, as described above.
The digestion retardant is preferably added in an amount of 0.1 to 1.5 parts by mass, more preferably 0.4 to 1.2 parts by mass, with respect to 100 parts by mass of the light-burned dolomite as a raw material.
After digestion, the median diameter (d50) is about 5 to 30 μm, the specific surface area is 40 to 60 m 2 / g, and the pore volume is 0.2 to 0.4 cm through steps such as drying, pulverization, and classification as necessary. Hydroxide dolomite having a high specific surface area of about 3 / g and a dynamic apparent specific gravity of about 0.4 to 0.6 g / cm 3 is obtained.
酸性排ガスに対する排ガス処理剤の添加量は、酸性排ガス中の塩化水素及び硫黄酸化物の合計に対して、水酸化マグネシウム及び水酸化カルシウムを合計で０．５〜５．０当量となるように添加することが好ましい。排ガス処理剤をこのような量で添加することにより、飛灰のアルカリ度を後述の範囲としやすくすることができ、重金属固定剤の添加量を大幅に削減しやすくできるとともに、重金属の溶出を安定的に防止しやすくできる。
また、排ガス処理剤の添加量は、第一の方法では、０．７〜４．０当量とすることが好ましく、第二の方法では、０．６〜１．５当量とすることが好ましい。
上述のような適切な量の排ガス処理剤を添加するために、出口の塩化水素や硫黄酸化物濃度を監視する装置を設置し、排ガス処理剤の添加量をフィードバックで制御することにより排出する塩化水素や硫黄酸化物濃度の濃度レベルを調整したり、あるいは、煙道入り口付近の塩化水素や硫黄酸化物の濃度を監視する装置を設置し、入口酸性排ガス濃度に応じて排ガス処理剤の添加量を調整することが好ましい。
Addition amount of exhaust gas treatment agent to acidic exhaust gas is added so that the total amount of magnesium hydroxide and calcium hydroxide is 0.5 to 5.0 equivalents with respect to the total of hydrogen chloride and sulfur oxide in acidic exhaust gas It is preferable to do. By adding the exhaust gas treatment agent in such an amount, the alkalinity of fly ash can be easily adjusted to the range described later, the amount of heavy metal fixing agent added can be greatly reduced, and heavy metal elution is stabilized. Can be easily prevented.
In addition, the amount of the exhaust gas treating agent added is preferably 0.7 to 4.0 equivalents in the first method, and preferably 0.6 to 1.5 equivalents in the second method.
In order to add an appropriate amount of the exhaust gas treatment agent as described above, a device that monitors the concentration of hydrogen chloride and sulfur oxide at the outlet is installed, and the amount of exhaust gas treatment agent added is controlled by feedback. Adjust the concentration level of hydrogen and sulfur oxide concentration, or install a device to monitor the concentration of hydrogen chloride and sulfur oxide near the flue entrance, and add the amount of exhaust gas treatment agent according to the inlet acidic exhaust gas concentration Is preferably adjusted.
排ガス処理剤中の粉体は、本発明の効果を阻害しない範囲で、水酸化マグネシウム及び水酸化カルシウム以外の構成成分を含有していてもよい。例えば、排ガスのダイオキシンを処理する活性炭やバグフィルターのろ過助剤として使用される珪藻土等と配合し排ガス処理剤として添加することは、添加設備を節約できるケースもあり、有用な方法である。また、後述する無機重金属固定剤、酸性中和剤及びキレート剤等の重金属固定剤を配合しても良い。この際、製品の配合上、粉体の重金属固定剤が好ましい。 The powder in the exhaust gas treating agent may contain components other than magnesium hydroxide and calcium hydroxide as long as the effects of the present invention are not impaired. For example, blending with activated carbon for treating dioxins in exhaust gas or diatomaceous earth used as a filter aid for bag filters and adding it as an exhaust gas treatment agent is a useful method because there are cases where the addition equipment can be saved. Moreover, you may mix | blend heavy metal fixing agents, such as the inorganic heavy metal fixing agent mentioned later, an acidic neutralizer, and a chelating agent. In this case, a powdered heavy metal fixing agent is preferable in terms of blending of products.
酸性排ガスに排ガス処理剤を添加する手段は特に制限されない。例えば、図１に示す酸性排ガス処理システム８では、排ガス処理剤供給装置３の薬剤貯留槽に入れられた排ガス処理剤は、ブロアー等により薬注ホースを経由して搬送され、煙道２に設置されたノズルから煙道２の酸性排ガスに吹き付けられる。排ガス処理剤は、粉体の形態で用いてもよいし、粉体を水等に分散して分散液の形態として用いてもよい。また、分散液を煙道２の酸性排ガスに噴霧する際には、一流体もしくは二流体等の分散ノズルを用い、排ガスに噴霧してよいし、減温塔の噴霧水とともに排ガスに噴霧し接触させてもよい。
排ガス処理剤を添加する際の酸性排ガスの温度は、特に制限はない。排ガス処理剤は、集塵機において酸性ガスと反応することから、集塵温度は１００〜３００℃であることが好ましく、１３０〜２３０℃であることがより好ましい。
The means for adding the exhaust gas treating agent to the acidic exhaust gas is not particularly limited. For example, in the acidic exhaust gas treatment system 8 shown in FIG. 1, the exhaust gas treatment agent put in the chemical storage tank of the exhaust gas treatment agent supply device 3 is conveyed via a chemical injection hose by a blower or the like and installed in the flue 2. It is sprayed to the acidic exhaust gas of the flue 2 from the nozzle made. The exhaust gas treating agent may be used in the form of a powder, or may be used in the form of a dispersion by dispersing the powder in water or the like. In addition, when spraying the dispersion liquid on the acidic exhaust gas in the flue 2, it may be sprayed on the exhaust gas using a dispersion nozzle of one fluid or two fluids, or sprayed on the exhaust gas together with the spray water of the temperature-decreasing tower. You may let them.
The temperature of the acidic exhaust gas when adding the exhaust gas treating agent is not particularly limited. Since the exhaust gas treating agent reacts with acid gas in the dust collector, the dust collection temperature is preferably 100 to 300 ° C, and more preferably 130 to 230 ° C.
第一の方法においては、排ガス処理剤を添加した後の飛灰のｐＨ８．３終点における酸消費量から規定されるアルカリ度を１５０ ｍｇＣａＣＯ3／ｇ以下とする。飛灰のアルカリ度を前記範囲とすることにより、無機重金属固定剤及び／又は酸性中和剤の添加量を大幅に削減しやすくできるとともに、重金属の溶出を安定的に防止しやすくできる。同アルカリ度は１２０ ｍｇＣａＣＯ3／ｇ以下であることが好ましく、９０ ｍｇＣａＣＯ3／ｇ以下であることがより好ましい。
また、第二の方法においては、排ガス処理剤を添加した後の飛灰のｐＨ８．３終点における酸消費量から規定されるアルカリ度を５５ｍｇＣａＣＯ3／ｇ未満とする。飛灰のアルカリ度を前記範囲とすることにより、キレート系重金属固定剤の添加量を大幅に削減しやすくできるとともに、重金属の溶出を安定的に防止しやすくできる。同アルカリ度は５２ｍｇＣａＣＯ3／ｇ以下であることがより好ましい。また、アルカリ度を５５ｍｇＣａＣＯ3／ｇ未満とした場合の効果は、排ガス処理剤を添加した後の飛灰の液固比１０における溶出液のｐＨを１１．８以下とすることにより、より顕著なものとすることができる。排ガス処理剤を添加した後の飛灰の液固比１０における溶出液のｐＨは、１１．６以下とすることがより好ましい。
なお、第一及び第二の方法において、排ガス処理剤を添加した後の飛灰のｐＨ８．３終点における酸消費量から規定されるアルカリ度の下限については特に制限はないが、酸性排ガスの処理を確実に行なう観点から、例えば１０ｍｇＣａＣＯ3／ｇ以上、好ましくは２０ｍｇＣａＣＯ3／ｇ以上とすることができる。
In the first method, the alkalinity defined from the acid consumption in pH8.3 end point of fly ash after the addition of the exhaust gas treatment agent and 150 mgCaCO 3 / g or less. By setting the alkalinity of the fly ash in the above range, the amount of inorganic heavy metal fixing agent and / or acidic neutralizing agent can be greatly reduced, and elution of heavy metals can be easily prevented stably. The alkalinity is preferably 120 mgCaCO 3 / g or less, and more preferably 90 mgCaCO 3 / g or less.
In the second method, the alkalinity defined from the acid consumption at the pH 8.3 end point of the fly ash after adding the exhaust gas treating agent is set to less than 55 mg CaCO 3 / g. By making the alkalinity of fly ash within the above range, the amount of chelate heavy metal fixing agent added can be greatly reduced, and elution of heavy metals can be easily prevented stably. The alkalinity is more preferably 52 mgCaCO 3 / g or less. Further, the effect when the alkalinity is less than 55 mg CaCO 3 / g is more remarkable when the pH of the eluate at the liquid-solid ratio of 10 after adding the exhaust gas treatment agent is 11.8 or less. Can be. The pH of the eluate at a liquid-solid ratio of 10 after adding the exhaust gas treating agent is more preferably 11.6 or less.
In the first and second methods, there is no particular limitation on the lower limit of alkalinity defined by the acid consumption at the pH 8.3 end point of the fly ash after the addition of the exhaust gas treatment agent. From the viewpoint of reliably performing the above, for example, it can be 10 mg CaCO 3 / g or more, preferably 20 mg CaCO 3 / g or more.
（飛灰の集塵工程）
酸性排ガスに排ガス処理剤を添加した後は、飛灰の集塵工程を行う。飛灰の集塵はバグフィルター等の公知の集塵機で行うことができる。
(Dust collection process of fly ash)
After the exhaust gas treatment agent is added to the acidic exhaust gas, a fly ash dust collecting step is performed. Fly ash can be collected by a known dust collector such as a bag filter.
（重金属の固定工程）
飛灰を集塵した後は、集塵した飛灰に対して重金属固定剤を添加する工程を行い、重金属の固定を行う。飛灰中の重金属としては、鉛が代表例であり、その他、カドミウム、クロム、砒素、セレン、水銀等が挙げられる。
重金属固定剤としては、第一の方法では、無機重金属固定剤及び／又は酸性中和剤を用いることができる。無機重金属固定剤としては、リン酸系化合物、二酸化ケイ素系化合物、鉄含有化合物及び酸性中和剤が挙げられ、これらから選ばれる少なくとも一種以上を用いることができる。
また、第二の方法で用いる重金属固定剤としては、キレート系重金属固定剤が挙げられる。
なお、本発明の効果を阻害しない範囲で、第一の方法においてキレート系重金属固定剤を用いること、第二の方法において無機重金属固定剤及び／又は酸性中和剤を用いることは差し支えない。
(Heavy metal fixing process)
After collecting the fly ash, a step of adding a heavy metal fixing agent to the collected fly ash is performed to fix the heavy metal. As a heavy metal in fly ash, lead is a typical example, and other examples include cadmium, chromium, arsenic, selenium, mercury and the like.
As the heavy metal fixing agent, in the first method, an inorganic heavy metal fixing agent and / or an acidic neutralizing agent can be used. Examples of the inorganic heavy metal fixing agent include phosphoric acid compounds, silicon dioxide compounds, iron-containing compounds, and acidic neutralizers, and at least one selected from these can be used.
The heavy metal fixing agent used in the second method includes a chelate heavy metal fixing agent.
It should be noted that the chelate heavy metal fixing agent can be used in the first method and the inorganic heavy metal fixing agent and / or the acidic neutralizing agent can be used in the second method as long as the effects of the present invention are not impaired.
リン酸系化合物は、処分場における重金属の長期固定効果を示し、環境保護の観点から有効な材料である。リン酸系化合物は、例えば重金属である鉛と反応し、鉛クロロピロモルファイトや鉛ピロモルファイトを形成し、鉱物の形態で鉛を固定することができる。 Phosphoric acid compounds exhibit a long-term fixing effect of heavy metals at a disposal site, and are effective materials from the viewpoint of environmental protection. A phosphoric acid compound reacts with lead which is a heavy metal, for example, forms lead chloropyromorphite or lead pyromorphite, and can fix lead in the form of a mineral.
リン酸系化合物としては、リン酸を含有していれば特に制限なく用いることができ、リン酸塩であっても鉱物であっても良い。
リン酸系化合物としては、例えば、正リン酸（オルソリン酸）、ポリリン酸、メタリン酸、次リン酸、亜リン酸、次亜リン酸、ピロリン酸、過リン酸、第一リン酸ソーダ、第二リン酸ソーダ、第三リン酸ソーダ、第一リン酸カリウム、第二リン酸カリウム、第三リン酸カリウム、第一リン酸カルシウム、第二リン酸カルシウム、第一リン酸マグネシウム、第二リン酸マグネシウム、第一リン酸アンモニウム、第二リン酸アンモニウム、過燐酸石灰、トリポリリン酸ナトリウム、トリポリリン酸カリウム、ヘキサメタリン酸ナトリウム、ヘキサメタリン酸カリウム、ピロリン酸ナトリウム、ピロリン酸カリウム、亜リン酸ナトリウム、亜リン酸カリウム、次亜リン酸ナトリウム、次亜リン酸カリウム等が挙げられる。
これらの中でも、正リン酸、第一リン酸塩、第二リン酸塩、第三リン酸塩、トリポリリン酸塩、ヘキサメタリン酸塩、ピロリン酸塩、ヒドロキシアパタイトの形態を有する鉱物、特に燐灰石（アパタイト化合物）が良好な重金属固定効果を示す。
リン酸系化合物は、重金属の中でも、鉛の固定化に特に有用である。
The phosphoric acid compound can be used without particular limitation as long as it contains phosphoric acid, and may be a phosphate or a mineral.
Examples of the phosphoric acid compound include orthophosphoric acid (orthophosphoric acid), polyphosphoric acid, metaphosphoric acid, hypophosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, superphosphoric acid, sodium monophosphate, Sodium diphosphate, tribasic sodium phosphate, primary potassium phosphate, secondary potassium phosphate, tertiary potassium phosphate, primary calcium phosphate, secondary calcium phosphate, primary magnesium phosphate, secondary magnesium phosphate, secondary Ammonium monophosphate, dibasic ammonium phosphate, lime superphosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate, potassium hexametaphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium phosphite, potassium phosphite, Examples thereof include sodium phosphite and potassium hypophosphite.
Among these, minerals having the form of orthophosphoric acid, primary phosphate, secondary phosphate, tertiary phosphate, tripolyphosphate, hexametaphosphate, pyrophosphate, hydroxyapatite, especially apatite (apatite Compound) exhibits a good heavy metal fixing effect.
Phosphoric acid compounds are particularly useful for immobilization of lead among heavy metals.
二酸化ケイ素含有化合物は、飛灰中のカルシウム成分と、二酸化ケイ素とが反応してケイ酸カルシウム鉱物（３ＣａＯ・２ＳｉＯ2・３Ｈ2Ｏ）を生成して、該鉱物の中に重金属を封じ込める効果、並びに二酸化ケイ素が直接重金属に作用して、難溶性の重金属ケイ酸塩（ＰｂＳｉＯ3等）を生成することにより重金属を固定する効果が得られると考えられる。二酸化ケイ素含有化合物の重金属固定は、飛灰中のアルカリ含有量の影響を受け、飛灰中のアルカリ含有量が多大な場合、必要添加量が増加する。従って、本発明により、二酸化ケイ素含有化合物においても必要添加量を大幅に削減することができる。 The silicon dioxide-containing compound has the effect of containing calcium metal in fly ash and silicon dioxide to produce calcium silicate mineral (3CaO · 2SiO 2 · 3H 2 O) and encapsulating heavy metals in the mineral, In addition, it is considered that the effect of fixing the heavy metal can be obtained by the silicon dioxide directly acting on the heavy metal to form a hardly soluble heavy metal silicate (PbSiO 3 or the like). The heavy metal fixation of the silicon dioxide-containing compound is affected by the alkali content in the fly ash, and if the alkali content in the fly ash is large, the required addition amount increases. Therefore, according to the present invention, the required addition amount can be greatly reduced even in the silicon dioxide-containing compound.
二酸化ケイ素含有化合物は、ＳｉＯ2成分を有する化合物であれば特に制限なく用いることができ、二酸化ケイ素そのものであってもよいし、塩であっても鉱物であってもよい。
二酸化ケイ素含有化合物は、ケイ酸ナトリウム、ケイ酸カリウム等のアルカリ金属やアルカリ土類金属を含むケイ酸塩、シリカヒューム、シリカゲル、活性白土、ゼオライト、ベントナイト、カオリナイト、ハロイサイト、アンチゴライト、パイオライト、タルク、モンモリロナイト、サボナイト、パーミキュライト、白雲母、バラゴナイト、イライト、金雲母、黒雲母、マーガライト、ザンソフィライト、ドンパサイト、スドウ石、クリノクロア、シャモサイト、セピオライト、パリゴルスカイト、イモゴライト、アロフェン及びヒシンゲライト等のケイ酸塩鉱物などが挙げられる。
二酸化ケイ素含有化合物は、重金属の中でも、鉛の固定化に特に有用である。
The silicon dioxide-containing compound can be used without particular limitation as long as it is a compound having a SiO 2 component, and may be silicon dioxide itself, a salt, or a mineral.
Silicon dioxide-containing compounds include silicates containing alkali metals and alkaline earth metals such as sodium silicate and potassium silicate, silica fume, silica gel, activated clay, zeolite, bentonite, kaolinite, halloysite, antigolite, piolite. Wright, talc, montmorillonite, savonite, permiculite, muscovite, barragonite, illite, phlogopite, biotite, margarite, zansophylite, donpasite, sudite, clinochlore, chamosite, sepiolite, palygorskite, imogolite, allophane, and hychinguerite And silicate minerals.
Silicon dioxide-containing compounds are particularly useful for immobilizing lead among heavy metals.
鉄含有化合物としては、鉄を含有していれば良く、塩化第一鉄、塩化第二鉄、硫酸第一鉄、硫酸第二鉄、ポリ硫酸第二鉄、鉄粉等が挙げられる。
鉄含有化合物は、重金属の中でも、六価クロム、砒素、セレン及び水銀の固定化に特に有用である。
The iron-containing compound only needs to contain iron, and examples thereof include ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, polyferric sulfate, and iron powder.
Iron-containing compounds are particularly useful for immobilization of hexavalent chromium, arsenic, selenium and mercury among heavy metals.
酸性中和剤は、重金属の溶出量を低下させる役割を有する。酸性中和剤も飛灰に残存するアルカリの影響を受け、残存飛灰中のアルカリ含有量が多大な場合、必要添加量が増加する。従って、本発明により、酸性中和剤も必要添加量を大幅に削減することができる。
酸性中和剤としては、塩酸、硫酸、硝酸、塩化アルミニウム、ポリ塩化アルミニウム、硫酸アルミニウム等が例示できる。
酸性中和剤は単独で用いても良いが、重金属の溶出をさらに抑えるという観点からは、上述の無機重金属固定剤と併用して用いることが好ましい。また、無機重金属固定剤と酸性中和剤とを併用した場合、高価である無機重金属固定剤の使用量を低減できる点で好適である。さらに、中和剤とキレート系重金属固定剤を併用しても本発明の効果は得られる。
The acidic neutralizing agent has a role of reducing the elution amount of heavy metals. The acidic neutralizer is also affected by the alkali remaining in the fly ash, and if the alkali content in the remaining fly ash is large, the required addition amount increases. Therefore, according to the present invention, the necessary addition amount of the acidic neutralizer can be greatly reduced.
Examples of the acidic neutralizer include hydrochloric acid, sulfuric acid, nitric acid, aluminum chloride, polyaluminum chloride, aluminum sulfate and the like.
The acidic neutralizer may be used alone, but is preferably used in combination with the above-described inorganic heavy metal fixing agent from the viewpoint of further suppressing elution of heavy metals. Moreover, when an inorganic heavy metal fixing agent and an acidic neutralizing agent are used in combination, it is preferable in that the amount of the expensive inorganic heavy metal fixing agent can be reduced. Furthermore, the effect of the present invention can be obtained even when a neutralizing agent and a chelate heavy metal fixing agent are used in combination.
キレート剤は、飛灰中の重金属と難溶性のキレート化合物を形成して、重金属を固定する作用を有する。本発明においては、飛灰のアルカリ度や溶出液のｐＨを上述の範囲とすることにより、キレート剤においても必要添加量を削減することができる。これは、上述した飛灰性状により、飛灰からの鉛の溶出量を大幅に削減でき、これにより、キレート剤の必要添加量を削減できたものと考えられる。 The chelating agent has an action of fixing a heavy metal by forming a sparingly soluble chelate compound with the heavy metal in the fly ash. In the present invention, the required addition amount of the chelating agent can be reduced by adjusting the alkalinity of the fly ash and the pH of the eluate within the above-mentioned ranges. This is considered to be due to the fact that the amount of lead elution from the fly ash can be greatly reduced due to the above-described fly ash properties, thereby reducing the necessary amount of chelating agent added.
キレート剤としては、キレート化合物の形成により重金属を固定する効果を有すれば良く、特に制限はない。このようなキレート剤としては、ピペラジンジチオカルバミン酸塩、ジエチルジチオカルバミン酸塩、ジメチルジチオカルバミン酸塩、ジブチルジチオカルバミン酸塩等のジチオカルバミン酸塩類、ポリアルキレンポリアミンやポリエチレンイミン等のポリアミン類が挙げられる。
キレート剤は、重金属の中でも、鉛、水銀の固定化に特に有用である。
The chelating agent is not particularly limited as long as it has an effect of fixing heavy metals by forming a chelate compound. Examples of such chelating agents include piperazine dithiocarbamate, diethyldithiocarbamate, dimethyldithiocarbamate, dithiocarbamate such as dibutyldithiocarbamate, and polyamines such as polyalkylenepolyamine and polyethyleneimine.
Chelating agents are particularly useful for immobilizing lead and mercury among heavy metals.
重金属固定剤の添加量は、重金属固定剤の種類、飛灰のアルカリ度や、飛灰中の重金属の量によっても異なるため一概には言えないが、飛灰に対して０．１〜３０質量％であることが好ましく、１〜２５質量％であることがより好ましい。 The amount of heavy metal fixing agent added varies depending on the type of heavy metal fixing agent, the alkalinity of fly ash, and the amount of heavy metal in the fly ash. %, Preferably 1 to 25% by mass.
第一の方法においては、無機重金属固定剤及び／又は酸性中和剤を添加した後の飛灰の液固比（Ｌ／Ｓ）が１０の場合の溶出液のｐＨを８．０〜１１.５とすることが好ましく、特に９．０〜１０．５であることがより好ましい。溶出液のｐＨを前記範囲とすることにより、鉛等重金属の溶出を効果的に防止できるとともに水酸化マグネシウムの溶解を抑え、水酸化マグネシウムの含有量に相当するアルカリ度が低減され、無機重金属固定剤及び／又は酸性中和剤の添加量削減に寄与できる。 In the first method, the pH of the eluate when the liquid solid-solid ratio (L / S) of the fly ash after adding the inorganic heavy metal fixing agent and / or the acidic neutralizer is 10 is 8.0 to 11. 5 is preferable, and 9.0 to 10.5 is particularly preferable. By adjusting the pH of the eluate to the above range, elution of heavy metals such as lead can be effectively prevented, dissolution of magnesium hydroxide is suppressed, alkalinity corresponding to the content of magnesium hydroxide is reduced, and inorganic heavy metal fixation This can contribute to a reduction in the amount of the agent and / or acidic neutralizer.
飛灰に無機重金属固定剤、中和剤、キレート系重金属固定剤を添加する手段は特に制限されない。例えば、図１に示すような酸性排ガス処理システムでは、集塵した飛灰は飛灰処理装置に排出され、該装置内で、薬剤添加手段により、無機重金属固定剤、中和剤、キレート系重金属固定剤を添加することができる。
無機重金属固定剤、中和剤、キレート系重金属固定剤は、粉体の形態で用いてもよいが、粉体を水等に溶解又は分散する等して液状の形態として用いることが好ましい。
The means for adding the inorganic heavy metal fixing agent, neutralizing agent, and chelate heavy metal fixing agent to the fly ash is not particularly limited. For example, in an acidic exhaust gas treatment system as shown in FIG. 1, the collected fly ash is discharged to a fly ash treatment device, and in this device, an inorganic heavy metal fixing agent, a neutralizing agent, a chelate heavy metal is added by a chemical addition means. A fixative can be added.
The inorganic heavy metal fixing agent, neutralizing agent, and chelate heavy metal fixing agent may be used in the form of powder, but it is preferable to use the powder in a liquid form by dissolving or dispersing the powder in water or the like.
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
（Ａ．排ガス処理剤）
［参考例Ａ−１、Ａ−２］
一般的に酸性排ガス処理に使用される水酸化カルシウム（参考例Ａ−１：ＪＩＳ特号水酸化カルシウム、参考例Ａ−２：高反応水酸化カルシウム）のアルカリ度を上述の測定方法に基づいて測定した。結果を表１に示す。
(A. Exhaust gas treatment agent)
[Reference Examples A-1, A-2]
In general, the alkalinity of calcium hydroxide (Reference Example A-1: JIS Special Calcium Hydroxide, Reference Example A-2: Highly Reactive Calcium Hydroxide) used for acidic exhaust gas treatment is based on the above-described measurement method. It was measured. The results are shown in Table 1.
［参考例Ａ−３〜Ａ−５］
ドロマイトを原料として、以下の手法により、参考例Ａ−３〜Ａ−５の排ガス処理剤（水酸化ドロマイト）を得た。参考例Ａ−３〜Ａ−５の水酸化ドロマイトの粉体特性及びアルカリ度を表１に示す。なお、表１の「Ｍｇ：Ｃａ」の値は、ＥＤＴＡ滴定法により算出した。
[Reference Examples A-3 to A-5]
By using dolomite as a raw material, exhaust gas treating agents (hydroxide dolomite) of Reference Examples A-3 to A-5 were obtained by the following method. Table 1 shows the powder characteristics and alkalinity of the dolomite hydroxides of Reference Examples A-3 to A-5. In addition, the value of “Mg: Ca” in Table 1 was calculated by the EDTA titration method.
（参考例Ａ−３の水酸化ドロマイトの製造）
ドロマイトをロータリーキルンで１１００〜１２００℃で加熱、焼成した。本焼成工程の所要時間は約３時間であった。この軽焼ドロマイトをインペラブレーカーで4 mmアンダーに破砕した。
次いで、軽焼ドロマイトに対して、消化水を９５％となるよう添加し、十分熟成消化させた。この後、乾燥、粉砕、分級機能を持った装置で参考例Ａ−３の水酸化ドロマイトを得た。以下、参考例Ａ−３で得られた水酸化ドロマイトを「水酸化ドロマイトａ」という場合がある。
（参考例Ａ−４の水酸化ドロマイトの製造）
軽焼ドロマイトの消化水に、軽焼ドロマイトに対してジエチレングリコールが０．４８％となるように添加した以外は、実施例１と同様にして水酸化ドロマイトを製造した。以下、参考例Ａ−４で得られた水酸化ドロマイトを「水酸化ドロマイトｂ」という場合がある。
（参考例Ａ−５の水酸化ドロマイトの製造）
軽焼ドロマイトの消化水に、軽焼ドロマイトあたりジエチレングリコールが０．９５％となるように溶解させた以外は、実施例１と同様にして水酸化ドロマイトを得た。以下、参考例Ａ−５で得られた水酸化ドロマイトを「水酸化ドロマイトｃ」という場合がある。
(Production of hydroxylated dolomite of Reference Example A-3)
Dolomite was heated and fired at 1100 to 1200 ° C. in a rotary kiln. The time required for the main baking process was about 3 hours. This light-burned dolomite was crushed to 4 mm under by an impeller breaker.
Next, digested water was added to the light-burned dolomite so as to be 95%, and it was fully aged and digested. Thereafter, the dolomite hydroxide of Reference Example A-3 was obtained with an apparatus having drying, pulverization and classification functions. Hereinafter, the hydroxide dolomite obtained in Reference Example A-3 may be referred to as “hydroxy dolomite a”.
(Production of hydroxylated dolomite of Reference Example A-4)
Hydroxide dolomite was produced in the same manner as in Example 1 except that diethylene glycol was added to the digested water of light-burned dolomite so that the amount of diethylene glycol was 0.48% with respect to light-burned dolomite. Hereinafter, the hydroxide dolomite obtained in Reference Example A-4 may be referred to as “hydroxy dolomite b”.
(Production of hydroxylated dolomite of Reference Example A-5)
Hydroxide dolomite was obtained in the same manner as in Example 1 except that diethylene glycol was dissolved in the digested water of lightly burned dolomite so that the amount of diethylene glycol was 0.95%. Hereinafter, the hydroxide dolomite obtained in Reference Example A-5 may be referred to as “hydroxy dolomite c”.
表１から明らかなように、参考例Ａ３〜Ａ５の排ガス処理剤（水酸化ドロマイト）は、参考例Ａ−１及びＡ−２の一般的な水酸化カルシウムに比べて、アルカリ剤自体のアルカリ度を２９〜３４％と大幅に低下できることが分かる。 As is apparent from Table 1, the exhaust gas treatment agent (dolomite hydroxide) of Reference Examples A3 to A5 is more alkaline than the general calcium hydroxide of Reference Examples A-1 and A-2. It can be seen that it can be significantly reduced to 29-34%.
（Ｂ．排ガス処理剤の添加工程）
［参考例Ｂ−１〜Ｂ−５］
カラムに各排ガス処理剤（参考例Ｂ−１：ＪＩＳ特号水酸化カルシウム、参考例Ｂ−２：高反応水酸化カルシウム、参考例Ｂ−３：水酸化ドロマイトａ、参考例Ｂ−４：水酸化ドロマイトｂ、参考例Ｂ−５：水酸化ドロマイトｃ）を０．５ｇ充填し、酸性排ガスを模して作製したガス（ＨＣｌ：１０００ｐｐｍ、ＳＯ2：１００ｐｐｍ、Ｈ2Ｏ：２０％、Ｎ2：残部（Balance））を流速９００ｃｍ3／ｍｉｎの速さで７５分間通過させ、温度１７０℃と１９０℃の２条件で反応させ、酸性成分であるＨＣｌ及びＳＯ2除去率を測定した。
酸性成分の除去率は、ＨＣｌについては未反応ＨＣｌを冷却したトラップに凝縮させ、０．１ＭのＮａＯＨ水溶液を中和滴定して算出した。ＳＯ2については、未反応ＳＯ2をＨ2Ｏ2水溶液で捕集して、０．１ＭのＮａＯＨ水溶液を中和滴定して算出した。結果を表２に示す。
(B. Addition process of exhaust gas treatment agent)
[Reference Examples B-1 to B-5]
Each exhaust gas treating agent (reference example B-1: JIS special calcium hydroxide, reference example B-2: highly reactive calcium hydroxide, reference example B-3: dolomite hydroxide a, reference example B-4: water Gas (HCl: 1000 ppm, SO 2 : 100 ppm, H 2 O: 20%, N 2 ) filled with 0.5 g of oxidized dolomite b, Reference Example B-5: Hydroxide dolomite c) : The balance (Balance) was passed for 75 minutes at a flow rate of 900 cm 3 / min, reacted at two temperatures of 170 ° C. and 190 ° C., and the removal rates of HCl and SO 2 as acidic components were measured.
The removal rate of acidic components was calculated by condensing unreacted HCl in a cooled trap and neutralizing and titrating a 0.1 M NaOH aqueous solution. The SO 2 was calculated by collecting unreacted SO 2 with an aqueous H 2 O 2 solution and neutralizing and titrating a 0.1 M NaOH aqueous solution. The results are shown in Table 2.
参考例Ｂ−３〜Ｂ−５の排ガス処理剤（水酸化ドロマイト）は、１７０℃及び１９０℃において、参考例Ｂ−１のＪＩＳ特号水酸化カルシウムと同等以上の酸性排ガス処理性能を示し、実用に供する酸性排ガス処理性能を有することが分かる。また、参考例Ｂ−３〜Ｂ−５の結果から、ＢＥＴ比表面積の上昇に伴い酸性排ガス処理性能が向上することが分かる。さらに、参考例Ｂ−２と参考例Ｂ−５との排ガス処理剤はＢＥＴ比表面積が同一であるが、参考例Ｂ−５の方が酸性排ガス除去性能に優れている。この結果により、水酸化カルシウム及び水酸化マグネシウムを併用することにより、水酸化カルシウム単体よりも、酸性排ガス除去性能を向上できることが分かる。 The exhaust gas treating agent (hydroxide dolomite) of Reference Examples B-3 to B-5 shows acidic exhaust gas treatment performance equal to or higher than that of JIS special calcium hydroxide of Reference Example B-1 at 170 ° C. and 190 ° C., It can be seen that it has acidic exhaust gas treatment performance for practical use. Moreover, from the results of Reference Examples B-3 to B-5, it is understood that the acidic exhaust gas treatment performance is improved as the BET specific surface area is increased. Further, the exhaust gas treating agents of Reference Example B-2 and Reference Example B-5 have the same BET specific surface area, but Reference Example B-5 is superior in acidic exhaust gas removal performance. From this result, it can be seen that the combined use of calcium hydroxide and magnesium hydroxide can improve the performance of removing acidic exhaust gas as compared with calcium hydroxide alone.
（Ｃ．排ガス処理剤の添加工程、並びに無機重金属固定剤、酸性中和剤、キレート系重金属固定剤の添加工程）
［比較例１］
酸性排ガスの濃度変動が激しい産業廃棄物焼却炉（排ガス量14,000Ｎｍ3／ｈ（乾き）、排ガス水分 １０％）において、高反応水酸化カルシウムを添加する前の煙道に、塩化水素測定機器（京都電子工業社製、ＨＬ−２２）と、硫黄酸化物濃度測定装置（堀場製作所社、ＰＧ−３３７）を設置し、入口塩化水素濃度及び硫黄酸化物濃度を測定した。なお、本試験期間中、ＳＯ2濃度は、１〜７ｐｐｍと低く、影響が軽微であったため、排ガス処理剤の添加当量は、入口塩化水素濃度をもとに試算した。
排ガス処理剤は、粉体切出装置を設置し、バグフィルター前段の煙道に高反応水酸化カルシウム（参考例Ａ−２の排ガス処理剤）を添加した。この際、出口に設置された塩化水素測定機器（京都電子工業社製、ＫＬＡ−１）で測定される信号を元に出口のＨＣｌ濃度を２００ｐｐｍを目標とし、フィードバック制御を実施した。
上記添加条件で安定した後、３〜１０時間かけて飛灰を定期的に採取し、採取した各飛灰中のアルカリ度（ｐＨ８．３終点）を測定するとともに、採取した飛灰のうちの一つの飛灰について重金属の溶出試験（環境庁告示１３号試験）を行い、重金属固定剤及び酸性中和剤の必要添加量を評価した。また、各種重金属固定剤（リン酸系化合物、二酸化ケイ素系化合物、鉄含有化合物及びキレート剤）及び酸性中和剤を添加して、重金属の溶出量を評価した。
酸性排ガスの処理結果を表３、飛灰のアルカリ度を表４に示す。また、重金属溶出試験を行った飛灰の性状（含有量）を表５、各種重金属固定剤の添加による重金属の溶出量及び該溶出量から求めた薬剤の必要添加量の結果を表６に示す。
(C. Addition step of exhaust gas treatment agent and addition step of inorganic heavy metal fixing agent, acidic neutralizing agent, chelate heavy metal fixing agent)
[Comparative Example 1]
In an industrial waste incinerator (exhaust gas volume: 14,000 Nm 3 / h (dry), exhaust gas moisture: 10%), the hydrogen chloride measuring device ( HL-22) manufactured by Kyoto Electronics Industry Co., Ltd. and a sulfur oxide concentration measuring device (Horiba Seisakusho, PG-337) were installed, and the inlet hydrogen chloride concentration and sulfur oxide concentration were measured. During the test period, the SO 2 concentration was as low as 1 to 7 ppm and the influence was slight. Therefore, the addition equivalent of the exhaust gas treating agent was calculated based on the inlet hydrogen chloride concentration.
For the exhaust gas treatment agent, a powder cutting device was installed, and highly reactive calcium hydroxide (exhaust gas treatment agent of Reference Example A-2) was added to the flue before the bag filter. At this time, feedback control was performed with a target HCl concentration of 200 ppm based on a signal measured by a hydrogen chloride measuring device (KLA-1 manufactured by Kyoto Electronics Industry Co., Ltd.) installed at the outlet.
After stabilizing under the above-mentioned addition conditions, fly ash is periodically collected over 3 to 10 hours, and the alkalinity (pH 8.3 end point) in each collected fly ash is measured. One fly ash was subjected to a heavy metal elution test (Environment Agency Notification No. 13 test) to evaluate the necessary addition amounts of heavy metal fixing agent and acidic neutralizer. Various heavy metal fixing agents (phosphoric acid compounds, silicon dioxide compounds, iron-containing compounds and chelating agents) and acidic neutralizers were added to evaluate the elution amount of heavy metals.
Table 3 shows the treatment results of acidic exhaust gas, and Table 4 shows the alkalinity of fly ash. Further, Table 5 shows the properties (contents) of the fly ash subjected to the heavy metal elution test, and Table 6 shows the results of the elution amount of heavy metal by addition of various heavy metal fixing agents and the required addition amount of the drug obtained from the elution amount. .
［実施例１］
排ガス処理剤を水酸化ドロマイトｃに変更した以外は、比較例１と同一の方法で重金属の溶出量等を評価した。結果を表３〜５、７に示す。
[Example 1]
Except for changing the exhaust gas treatment agent to dolomite hydroxide c, the elution amount of heavy metals and the like were evaluated by the same method as in Comparative Example 1. The results are shown in Tables 3-5 and 7.
［比較例２］
出口のＨＣｌ濃度を１００ｐｐｍを目標としてフィードバックした以外は、比較例１と同一の方法で重金属の溶出量等を評価した。結果を表３〜５、８に示す。
[Comparative Example 2]
Except for feeding back the HCl concentration at the outlet with a target of 100 ppm, the elution amount of heavy metals and the like were evaluated by the same method as in Comparative Example 1. The results are shown in Tables 3-5 and 8.
［実施例２］
排ガス処理剤を水酸化ドロマイトｃに変更した以外は、比較例２と同一の方法で重金属の溶出量等を評価した。結果を表３〜５、９に示す。
[Example 2]
Except for changing the exhaust gas treatment agent to dolomite hydroxide c, the elution amount of heavy metals and the like were evaluated by the same method as in Comparative Example 2. The results are shown in Tables 3-5 and 9.
［実施例３］
出口のＨＣｌ濃度を５０ｐｐｍを目標としてフィードバックした以外は、実施例２と同一の方法で重金属の溶出量等を評価した。結果を表３〜５、１０に示す。
[Example 3]
Except for feeding back the HCl concentration at the outlet with a target of 50 ppm, the elution amount of heavy metals and the like were evaluated by the same method as in Example 2. The results are shown in Tables 3-5 and 10.
＜Ｏ2換算値＞
Ｏ2換算値（ｐｐｍ）＝実測値(ｐｐｍ)×(２１％−１２％)÷(２１％−酸素濃度(％))
＜消石灰添加当量；比較例１、２＞
消石灰添加当量＝Ａ ÷ [ ( ( Ｂ ÷０．６１４÷１０００÷３６．５×７４÷２×Ｃ÷１０００) ＋ ( Ｄ ÷０．３５÷１０００÷６４×７４×Ｃ÷１０００)｝
Ａ：消石灰添加量(ｋｇ/ｈ)
Ｂ：入口ＨＣｌ濃度 [実測値] （ｐｐｍ）
Ｃ：排ガス量[乾き] (Ｎｍ3／ｈ)
Ｄ：入口ＳＯ2濃度 [実測値（ｐｐｍ）
＜水酸化ドロマイト添加当量；実施例１〜３＞
水酸化ドロマイト添加当量＝Ｅ÷[ ((Ｂ÷０．６１４÷１０００÷３６．５×（５８＋７４）÷４×Ｃ÷１０００) ＋ ( Ｄ ÷０．３５÷１０００÷６４×（５８＋７４）÷２×Ｃ÷１０００)｝
Ｅ：水酸化ドロマイト添加量(ｋｇ/ｈ)
<O 2 equivalent value>
O 2 conversion value (ppm) = actual value (ppm) × (21% −12%) ÷ (21% −oxygen concentration (%))
<Slaked lime addition equivalent; Comparative Examples 1 and 2>
Slaked lime addition equivalent = A ÷ [((B ÷ 0.614 ÷ 1000 ÷ 36.5 × 74 ÷ 2 × C ÷ 1000) + (D ÷ 0.35 ÷ 1000 ÷ 64 × 74 × C ÷ 1000)}
A: Slaked lime addition amount (kg / h)
B: HCl concentration at the inlet [actual measurement value] (ppm)
C: Exhaust gas amount [dry] (Nm 3 / h)
D: Inlet SO 2 concentration [actual value (ppm)
<Additional equivalent of hydroxide dolomite; Examples 1 to 3>
Hydroxide dolomite addition equivalent = E ÷ [((B ÷ 0.614 ÷ 1000 ÷ 36.5 × (58 + 74) ÷ 4 × C ÷ 1000) + (D ÷ 0.35 ÷ 1000 ÷ 64 × (58 + 74) ÷ 2 × C ÷ 1000)}
E: Hydroxyl dolomite addition amount (kg / h)
比較例１の酸性排ガス処理方法では、入口のＨＣｌ濃度の平均８５６ｐｐｍ（Ｏ2換算）に対し、出口ＨＣｌ濃度の平均は１７５ｐｐｍ（Ｏ2換算）であり、適正に酸性排ガスを処理することができた。この際、排ガス処理剤の添加量は３１ｋｇ／ｈであり、入口の塩化水素及び硫黄酸化物に対する排ガス処理剤の添加当量は１．６当量であった（表３）。
しかし、比較例１における飛灰のアルカリ度は、１５５ｍｇＣａＣＯ3／ｇと高く（表４）、重金属固定剤及び／又は酸性中和剤の必要添加量は、いずれも多量であった（表６）。
Under acidic exhaust gas treatment process of Comparative Example 1, with respect to the average of the inlet of the HCl concentration 856ppm (O 2 equivalent), the average outlet HCl concentration was 175 ppm (O 2 equivalent), it can be properly process the acidic flue gas It was. At this time, the addition amount of the exhaust gas treatment agent was 31 kg / h, and the addition equivalent of the exhaust gas treatment agent to the hydrogen chloride and sulfur oxide at the inlet was 1.6 equivalents (Table 3).
However, the alkalinity of the fly ash in Comparative Example 1 was as high as 155 mg CaCO 3 / g (Table 4), and the necessary addition amounts of heavy metal fixing agent and / or acidic neutralizer were both large (Table 6). .
実施例１の酸性排ガス処理方法では、入口のＨＣｌ濃度１１８６ｐｐｍ（Ｏ2換算）に対し、出口ＨＣｌ濃度は１８１ｐｐｍ（Ｏ2換算）であり、適正に酸性排ガスを処理することができた。この際、排ガス処理剤の添加量は、２３ｋｇ／ｈであり、入口の塩化水素及び硫黄酸化物に対する排ガス処理剤の添加当量は１．０当量であり、比較例１よりも排ガス処理剤の添加量を削減できるものであった（表３）。実施例１における飛灰のアルカリ度は、５２ｍｇＣａＣＯ3／ｇであり、比較例１に比べ、飛灰中のアルカリ度を６６％と大幅に削減できることが分かる（表４）。また、実施例１における無機重金属固定剤及び／又は酸性中和剤の必要添加量は、比較例１に比べて７５〜９５％と大幅に削減できるものであった（表７）。
実施例１では、キレート系重金属固定剤である薬剤ｉ（４０％ピペラジンジチオカルバミン酸カリウム水溶液）においても、比較例１に比べて添加量を２０％削減することができた。実施例１の飛灰は、アルカリ度が５２ｍｇＣａＣＯ3／ｇまで低減され、重金属固定剤を添加しない状態での飛灰からの鉛の溶出が大幅に低減し、キレート系重金属固定剤においても本発明の効果が発揮できたものと考える。
Under acidic exhaust gas treatment process of Example 1, with respect to the inlet of the HCl concentration 1186ppm (O 2 equivalent), the outlet HCl concentration is 181ppm (O 2 equivalent), it was able to properly process the acidic gas. At this time, the addition amount of the exhaust gas treatment agent is 23 kg / h, the addition equivalent of the exhaust gas treatment agent to the hydrogen chloride and sulfur oxide at the inlet is 1.0 equivalent, and the addition of the exhaust gas treatment agent is more than that of Comparative Example 1. The amount could be reduced (Table 3). The alkalinity of the fly ash in Example 1 is 52 mg CaCO 3 / g, and it can be seen that the alkalinity in the fly ash can be greatly reduced to 66% as compared with Comparative Example 1 (Table 4). Moreover, the required addition amount of the inorganic heavy metal fixing agent and / or the acidic neutralizing agent in Example 1 was significantly reduced to 75 to 95% as compared with Comparative Example 1 (Table 7).
In Example 1, the drug i (40% piperazine dithiocarbamate aqueous solution), which is a chelate heavy metal fixing agent, could be reduced by 20% compared to Comparative Example 1. In the fly ash of Example 1, the alkalinity is reduced to 52 mg CaCO 3 / g, the elution of lead from the fly ash without adding a heavy metal fixing agent is greatly reduced, and the present invention is also applied to a chelate heavy metal fixing agent. I think that the effect of was able to be demonstrated.
比較例２の酸性排ガス処理方法では、入口のＨＣｌ濃度１４３２ｐｐｍ（Ｏ2換算）に対し、出口ＨＣｌ濃度は９５ｐｐｍ（Ｏ2換算）であり、適正に酸性排ガスを処理することができた。この際、排ガス処理剤の添加量は４４ｋｇ／ｈであり、入口の塩化水素及び硫黄酸化物に対する排ガス処理剤の添加当量は１．５当量であった（表３）。
しかし、比較例２における飛灰のアルカリ度は、１９５ｍｇＣａＣＯ3／ｇであり（表４）、重金属固定剤及び／又は酸性中和剤の必要添加量は、いずれも多量であった（表８）。
Under acidic exhaust gas treatment process of Comparative Example 2, to the inlet of the HCl concentration 1432ppm (O 2 equivalent), the outlet HCl concentration is 95 ppm (O 2 equivalent), it was able to properly process the acidic gas. At this time, the addition amount of the exhaust gas treatment agent was 44 kg / h, and the addition equivalent of the exhaust gas treatment agent to the hydrogen chloride and sulfur oxide at the inlet was 1.5 equivalents (Table 3).
However, the alkalinity of the fly ash in Comparative Example 2 was 195 mg CaCO 3 / g (Table 4), and the necessary addition amounts of heavy metal fixing agent and / or acidic neutralizer were both large (Table 8). .
実施例２の酸性排ガス処理方法では、入口のＨＣｌ濃度の平均９４６ｐｐｍ（Ｏ2換算）に対し、出口ＨＣｌ濃度の平均は９０ｐｐｍ（Ｏ2換算）であり、適正に酸性排ガスを処理することができた。この際、排ガス処理剤の添加量は、２９ｋｇ／ｈであり、比較例２よりも排ガス処理剤の添加量を削減できるものであったであった（表３）。実施例２における飛灰のアルカリ度は、５６ｍｇＣａＣＯ3／ｇであり、比較例２に比べ、飛灰中のアルカリ度を７１％と大幅に削減できることが分かる（表４）。また、実施例２における無機重金属固定剤及び／又は酸性中和剤の必要添加量は、比較例２に比べて６７〜８８％と大幅に削減できるものであった（表９）。
ただし、キレート系重金属固定剤である薬剤ｉ（４０％ピペラジンジチオカルバミン酸カリウム水溶液）においては、必要添加量が３％であり、比較例２と変わらない結果であった。これは、飛灰のアルカリ度が５９ｍｇＣａＣＯ3／ｇであり、本アルカリ度ではキレート系重金属固定剤を用いても飛灰からの鉛の溶出量が低下せず、効果がなかったものと考えられる。
Under acidic exhaust gas treatment process of Example 2, with respect to the average of the inlet of the HCl concentration 946ppm (O 2 equivalent), the average outlet HCl concentration is 90 ppm (O 2 equivalent), it can be properly process the acidic flue gas It was. At this time, the amount of the exhaust gas treating agent added was 29 kg / h, and the amount of the exhaust gas treating agent added could be reduced as compared with Comparative Example 2 (Table 3). The alkalinity of the fly ash in Example 2 is 56 mg CaCO 3 / g, and it can be seen that the alkalinity in the fly ash can be significantly reduced to 71% as compared with Comparative Example 2 (Table 4). Moreover, the required addition amount of the inorganic heavy metal fixing agent and / or the acid neutralizing agent in Example 2 was able to be greatly reduced to 67 to 88% as compared with Comparative Example 2 (Table 9).
However, in the medicine i (40% piperazine dithiocarbamate aqueous solution) which is a chelate heavy metal fixing agent, the required addition amount is 3%, which is the same result as in Comparative Example 2. This is because fly ash has an alkalinity of 59 mg CaCO 3 / g, and in this alkalinity, even if a chelate heavy metal fixing agent is used, the amount of lead elution from the fly ash is not lowered, and it is considered that there was no effect. .
また、実施例１及び２の処理飛灰を用い、アルカリ度及び液固比１０における溶出液のｐＨと、重金属固定剤無添加の状態でPb溶出量を調査した。結果を表１１に示す。
実施例１の処理飛灰（水酸化ドロマイトｃを添加して出口Ｈｃｌ濃度を２００ｐｐｍで処理した飛灰）は、アルカリ度が４７〜５２ｍｇＣａＣＯ3／ｇの範囲であり、溶出液のｐＨは１１．２〜１１．６の範囲であり、Ｐｂの溶出量は、２．２〜７．９ｍｇ／Ｌであった。
一方、実施例２の処理飛灰（水酸化ドロマイトｃを添加し、出口Ｈｃｌ濃度を１００ｐｐｍで処理した飛灰）は、アルカリ含有量が５５〜７０ｍｇＣａＣＯ3／ｇの範囲であり、溶出液のｐＨは１１．９〜１２．０の範囲であり、Ｐｂの溶出量は、５２．３〜８５．２ｍｇ／Ｌと大量であった。
本結果からアルカリ含有量を５５ｍｇＣａＣＯ3／ｇ未満とすること、好ましくはさらに、液固比10の溶出試験におけるｐＨを１１．８以下に飛灰の性状を改質することにより、キレート系重金属固定剤の添加量を削減できる効果が得られると考えられる。
The treated fly ash of Example 1 (fly ash added with dolomite hydroxide c and treated with an outlet Hcl concentration of 200 ppm) has an alkalinity in the range of 47 to 52 mg CaCO 3 / g, and the pH of the eluate is 11. The elution amount of Pb was 2.2 to 7.9 mg / L.
On the other hand, the treated fly ash of Example 2 (fly ash added with dolomite hydroxide c and treated with an outlet Hcl concentration of 100 ppm) has an alkali content in the range of 55 to 70 mg CaCO 3 / g, and the pH of the eluate Was in the range of 11.9 to 12.0, and the elution amount of Pb was as large as 52.3 to 85.2 mg / L.
From this result, the alkali content is set to less than 55 mg CaCO 3 / g, and further, the chelate heavy metal immobilization is performed by modifying the properties of fly ash to a pH of 11.8 or less in an elution test with a liquid-solid ratio of 10. It is thought that the effect which can reduce the addition amount of an agent is acquired.
実施例３の酸性排ガス処理方法では、入口のＨＣｌ濃度の平均６８２ｐｐｍ（Ｏ2換算）に対し、出口ＨＣｌ濃度の平均は４３ｐｐｍ（Ｏ2換算）であり、適正に酸性排ガスを処理することができた。この際、排ガス処理剤の添加量は、５１ｋｇ／ｈであり、入口の塩化水素及び硫黄酸化物に対する排ガス処理剤の添加当量は３．８当量であった（表３）。実施例３における飛灰のアルカリ度は、８４ｍｇＣａＣＯ3／ｇである（表４）。また、表１０から、実施例３では、重金属の溶出を抑えるための重金属固定剤及び／又は酸性中和剤の添加量が少量で済むことが分かる。 Under acidic exhaust gas treatment process of Example 3, with respect to the average of the inlet of the HCl concentration 682ppm (O 2 equivalent), the average outlet HCl concentration is 43 ppm (O 2 equivalent), can be properly process the acidic flue gas It was. At this time, the addition amount of the exhaust gas treatment agent was 51 kg / h, and the addition equivalent of the exhaust gas treatment agent to the hydrogen chloride and sulfur oxide at the inlet was 3.8 equivalents (Table 3). The alkalinity of the fly ash in Example 3 is 84 mg CaCO 3 / g (Table 4). Table 10 shows that in Example 3, the amount of heavy metal fixing agent and / or acidic neutralizing agent added to suppress elution of heavy metals is small.
１：減温塔
２：煙道
３：排ガス処理剤供給装置
４：集塵機
５：吸引ファン
６：飛灰処理装置
７：灰ピット
８：酸性排ガス処理システム
1: Temperature reduction tower 2: Flue 3: Exhaust gas treatment agent supply device 4: Dust collector 5: Suction fan 6: Fly ash treatment device 7: Ash pit 8: Acidic exhaust gas treatment system
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| JP2016159270A (en) * | 2015-03-04 | 2016-09-05 | 栗田工業株式会社 | Composite treatment agent of acidic gas and heavy metal, and treatment method of acidic gas and heavy metal |
| JP5939328B1 (en) * | 2015-03-04 | 2016-06-22 | 栗田工業株式会社 | Compound treatment agent for acid gas and heavy metal, and method for treating acid gas and heavy metal |
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| JP2020006330A (en) * | 2018-07-10 | 2020-01-16 | エスエヌ環境テクノロジー株式会社 | Soot and dust treatment apparatus, incineration facility, and soot and dust treatment method |
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| CN114471101A (en) * | 2022-03-15 | 2022-05-13 | 金华职业技术学院 | Exhaust gas purification system |
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