CA3070255A1 - Sorbent composition for an electrostatic precipitator - Google Patents
Sorbent composition for an electrostatic precipitator Download PDFInfo
- Publication number
- CA3070255A1 CA3070255A1 CA3070255A CA3070255A CA3070255A1 CA 3070255 A1 CA3070255 A1 CA 3070255A1 CA 3070255 A CA3070255 A CA 3070255A CA 3070255 A CA3070255 A CA 3070255A CA 3070255 A1 CA3070255 A1 CA 3070255A1
- Authority
- CA
- Canada
- Prior art keywords
- calcium
- sorbent composition
- weight
- powdery
- magnesium
- 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.)
- Abandoned
Links
- 239000002594 sorbent Substances 0.000 title claims abstract description 169
- 239000000203 mixture Substances 0.000 title claims abstract description 166
- 239000012717 electrostatic precipitator Substances 0.000 title claims abstract description 56
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000003546 flue gas Substances 0.000 claims abstract description 84
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 80
- 230000008569 process Effects 0.000 claims abstract description 69
- 238000009434 installation Methods 0.000 claims abstract description 28
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 74
- 239000000920 calcium hydroxide Substances 0.000 claims description 74
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 72
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 72
- 150000002500 ions Chemical class 0.000 claims description 63
- 239000000654 additive Substances 0.000 claims description 61
- 150000001455 metallic ions Chemical class 0.000 claims description 47
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 44
- 239000011734 sodium Substances 0.000 claims description 44
- 229910052708 sodium Inorganic materials 0.000 claims description 44
- 230000000996 additive effect Effects 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000428 dust Substances 0.000 claims description 25
- 239000010881 fly ash Substances 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 18
- LWNKHILEJJTLCI-UHFFFAOYSA-J calcium;magnesium;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mg+2].[Ca+2] LWNKHILEJJTLCI-UHFFFAOYSA-J 0.000 claims description 14
- -1 clays Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 12
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 12
- 239000004571 lime Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000004568 cement Substances 0.000 claims description 10
- 239000004927 clay Substances 0.000 claims description 10
- 239000000571 coke Substances 0.000 claims description 10
- 239000003077 lignite Substances 0.000 claims description 10
- 150000002823 nitrates Chemical class 0.000 claims description 10
- 150000002826 nitrites Chemical class 0.000 claims description 10
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 10
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 claims description 8
- 229910001848 post-transition metal Inorganic materials 0.000 claims description 8
- 238000003795 desorption Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- AGVJBLHVMNHENQ-UHFFFAOYSA-N Calcium sulfide Chemical compound [S-2].[Ca+2] AGVJBLHVMNHENQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004113 Sepiolite Substances 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 5
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- 235000012216 bentonite Nutrition 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052621 halloysite Inorganic materials 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000010451 perlite Substances 0.000 claims description 5
- 235000019362 perlite Nutrition 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 239000011435 rock Substances 0.000 claims description 5
- 235000019355 sepiolite Nutrition 0.000 claims description 5
- 229910052624 sepiolite Inorganic materials 0.000 claims description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010455 vermiculite Substances 0.000 claims description 5
- 229910052902 vermiculite Inorganic materials 0.000 claims description 5
- 235000019354 vermiculite Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 39
- 238000004519 manufacturing process Methods 0.000 description 31
- 238000002347 injection Methods 0.000 description 27
- 239000007924 injection Substances 0.000 description 27
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 22
- 239000000292 calcium oxide Substances 0.000 description 21
- 235000012255 calcium oxide Nutrition 0.000 description 21
- 239000007789 gas Substances 0.000 description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 description 19
- 235000017550 sodium carbonate Nutrition 0.000 description 19
- 239000002245 particle Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000011144 upstream manufacturing Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 7
- YLUIKWVQCKSMCF-UHFFFAOYSA-N calcium;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Ca+2] YLUIKWVQCKSMCF-UHFFFAOYSA-N 0.000 description 7
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 6
- 239000001095 magnesium carbonate Substances 0.000 description 6
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 6
- 235000014380 magnesium carbonate Nutrition 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000013618 particulate matter Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 235000019738 Limestone Nutrition 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 159000000014 iron salts Chemical class 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 239000011236 particulate material Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000011419 magnesium lime Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010289 potassium nitrite Nutrition 0.000 description 2
- 239000004304 potassium nitrite Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- WVXZIIZKJZXJRX-UHFFFAOYSA-L S([O-])(O)=O.[K+].S([O-])(O)=O.[Mg+2] Chemical compound S([O-])(O)=O.[K+].S([O-])(O)=O.[Mg+2] WVXZIIZKJZXJRX-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241001625808 Trona Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- LVGQIQHJMRUCRM-UHFFFAOYSA-L calcium bisulfite Chemical compound [Ca+2].OS([O-])=O.OS([O-])=O LVGQIQHJMRUCRM-UHFFFAOYSA-L 0.000 description 1
- 235000010260 calcium hydrogen sulphite Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
Powdery calcium-magnesium compound, sorbent composition based on calcium-magnesium for being used in flue gas treatment, compatible with electrostatic precipitators and process for reducing the resistivity of a powdery sorbent composition for flue gas treatment installation comprising an electrostatic precipitator.
Description
SORBENT COMPOSITION FOR AN ELECTROSTATIC PRECIPITATOR
Technical field The present invention relates to a calcium-magnesium compound and to a sorbent composition for use in flue gas installation equipped with an electrostatic precipitator, a method for obtaining such sorbent composition and a process of flue gas treatment using an electrostatic precipitator which comprises a step of injecting such a sorbent composition.
In another aspect, the present invention is related to a flue gas treatment installation using the sorbent composition according to the invention.
State of the art Fuel combustion in industrial processes or energy production generates fly ashes and acid gas for which their release in the atmosphere has to be minimized. The removal of fly ash from flue gas streams can be performed by an electrostatic precipitator (ESP). Some examples of electrostatic precipitators are described in US patent 4,502,872, US patent 8,328,902 or US patent 6,797,035. An electrostatic precipitator generally comprises a shell with a flue gas inlet and a flue gas outlet, the shell enclosing a plurality of collection electrodes, and discharge electrodes spaced from each other and a plurality of hoppers positioned under the collecting plates. A
voltage is applied between the discharge electrodes and the collection electrodes such as to create an electrostatic field charging the particulate material in the flue gas to obtain charged particulate material. The charged particulate material is collected by the collecting electrodes. The electrostatic precipitator further comprises rappers which provide mechanical shocks or vibrations to the collecting electrodes to remove the collected particles from the collecting electrodes. The collected particles fall down into hoppers arranged at the bottom of the shell and which are periodically or continuously emptied. The collecting electrodes can be planar or in a form of tubular or
Technical field The present invention relates to a calcium-magnesium compound and to a sorbent composition for use in flue gas installation equipped with an electrostatic precipitator, a method for obtaining such sorbent composition and a process of flue gas treatment using an electrostatic precipitator which comprises a step of injecting such a sorbent composition.
In another aspect, the present invention is related to a flue gas treatment installation using the sorbent composition according to the invention.
State of the art Fuel combustion in industrial processes or energy production generates fly ashes and acid gas for which their release in the atmosphere has to be minimized. The removal of fly ash from flue gas streams can be performed by an electrostatic precipitator (ESP). Some examples of electrostatic precipitators are described in US patent 4,502,872, US patent 8,328,902 or US patent 6,797,035. An electrostatic precipitator generally comprises a shell with a flue gas inlet and a flue gas outlet, the shell enclosing a plurality of collection electrodes, and discharge electrodes spaced from each other and a plurality of hoppers positioned under the collecting plates. A
voltage is applied between the discharge electrodes and the collection electrodes such as to create an electrostatic field charging the particulate material in the flue gas to obtain charged particulate material. The charged particulate material is collected by the collecting electrodes. The electrostatic precipitator further comprises rappers which provide mechanical shocks or vibrations to the collecting electrodes to remove the collected particles from the collecting electrodes. The collected particles fall down into hoppers arranged at the bottom of the shell and which are periodically or continuously emptied. The collecting electrodes can be planar or in a form of tubular or
2 honeycomb structure and the discharge electrodes, are generally under the form of a wire or a rod.
Generally, the flue gas treatment installations including electrostatic precipitators are provided with an air preheater, which latter being sometimes included in a boiler and/or otherwise provided as an additional element of the flue gas installation. The air preheater comprises a heat exchanger transferring the heat from the flue gas stream produced by the boiler to heat the combustion air to the boiler to increase the thermal efficiency of the boiler. In some embodiments, the flue gas treatment comprises multiple electrostatic precipitators. Cold-side electrostatic precipitators are located downstream the air preheater, thereby operate at lower temperatures generally less than 200 C (392 F). Hot side electrostatic precipitators are located upstream the air preheater and operate at higher temperatures, generally more than 250 C (482 F).
Sometimes for existing plants, the electrostatic precipitator units already operate at the boundary of their design capability due to more stringent particulate matter emission limits that have been introduced over the years and/or changes to plant operating conditions such as fuel switching.
The equation of Deutsch-Anderson describes with some approximations the collection efficiency of an electrostatic precipitator as:
(__vpmpic) -ri = 1 ¨ exp Q ) Wherein n is the fractional collection efficiency, Ac is the area of the collection electrode, Vpm is the particle migration velocity and Q is the volumetric flow rate of gas. The properties of the particles that influence collection efficiency are primarily the particle size distribution and their resistivity. The resistivity of the particles influences the particle migration velocity as described previously in the Deutsch-Anderson equation.
Various attempts have been tried to reduce the resistivity of particles. It is known for example from US patent 4,439,351 that for an
Generally, the flue gas treatment installations including electrostatic precipitators are provided with an air preheater, which latter being sometimes included in a boiler and/or otherwise provided as an additional element of the flue gas installation. The air preheater comprises a heat exchanger transferring the heat from the flue gas stream produced by the boiler to heat the combustion air to the boiler to increase the thermal efficiency of the boiler. In some embodiments, the flue gas treatment comprises multiple electrostatic precipitators. Cold-side electrostatic precipitators are located downstream the air preheater, thereby operate at lower temperatures generally less than 200 C (392 F). Hot side electrostatic precipitators are located upstream the air preheater and operate at higher temperatures, generally more than 250 C (482 F).
Sometimes for existing plants, the electrostatic precipitator units already operate at the boundary of their design capability due to more stringent particulate matter emission limits that have been introduced over the years and/or changes to plant operating conditions such as fuel switching.
The equation of Deutsch-Anderson describes with some approximations the collection efficiency of an electrostatic precipitator as:
(__vpmpic) -ri = 1 ¨ exp Q ) Wherein n is the fractional collection efficiency, Ac is the area of the collection electrode, Vpm is the particle migration velocity and Q is the volumetric flow rate of gas. The properties of the particles that influence collection efficiency are primarily the particle size distribution and their resistivity. The resistivity of the particles influences the particle migration velocity as described previously in the Deutsch-Anderson equation.
Various attempts have been tried to reduce the resistivity of particles. It is known for example from US patent 4,439,351 that for an
3 electrostatic precipitator to work efficiently, the electrical resistivity of the fly ash must be within 1E7 (1x107) to 2E10 (2x101 ) ohms.cm. Another document, Mastropietro, R. A. Impact of Hydrated Lime Injection on Electrostatic Percipitator Performance in ASTM Symposium on Lime Utilization; 2012; pp 2-10, states that the resistivity of fly ash should be within 1E8 (1x108) to (1x1011) ohms.cm. However the electrical resistivity of fly ash is generally higher and chemical additives were used such as SO3, HCI, NH3, Na2CO3, Na2SO4 and NH(CH2CH2OH) to lower the resistivity of fly ash. However, those additives are susceptible to release undesired compounds. The same document discloses the use of polymers for lowering the resistivity of fly ash.
However polymer additives generally degrade at high temperatures and must be injected to the flue gas stream at low temperatures.
Document US patent 6,126,910 discloses the removal of acid gas from a flue gas with an electrostatic precipitator by spraying a solution of sodium bisulfite, calcium bisulfite, magnesium bisulfite potassium bisulfite or ammonium bisulfite or a combination thereof into a stream of gas upstream to the electrostatic precipitator unit. Such bisulfite salts selectively remove the acidic gases such as HCI, HF and SO3 but they don't remove sulfur dioxide.
Sulfur dioxide in the flue gas has to be removed afterwards with a reagent such as hydrated lime. Document US patent 6,803,025 discloses a similar process using a reaction compound selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonium hydroxide, potassium hydroxide, potassium hydroxide, potassium carbonate and potassium bicarbonate to remove acidic gases such as HCI, HF, SO3 and partially SO2 from the flue gas. However, remaining SO2 still has to be removed by using another reagent such as hydrated lime. For the treatment of flue gas released by power plants, the amounts of chloride released by burning fuel or coal are generally very low respect to the SO2, therefore the flue gas treatment process can be simplified by using only hydrated lime as a sorbent.
However polymer additives generally degrade at high temperatures and must be injected to the flue gas stream at low temperatures.
Document US patent 6,126,910 discloses the removal of acid gas from a flue gas with an electrostatic precipitator by spraying a solution of sodium bisulfite, calcium bisulfite, magnesium bisulfite potassium bisulfite or ammonium bisulfite or a combination thereof into a stream of gas upstream to the electrostatic precipitator unit. Such bisulfite salts selectively remove the acidic gases such as HCI, HF and SO3 but they don't remove sulfur dioxide.
Sulfur dioxide in the flue gas has to be removed afterwards with a reagent such as hydrated lime. Document US patent 6,803,025 discloses a similar process using a reaction compound selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonium hydroxide, potassium hydroxide, potassium hydroxide, potassium carbonate and potassium bicarbonate to remove acidic gases such as HCI, HF, SO3 and partially SO2 from the flue gas. However, remaining SO2 still has to be removed by using another reagent such as hydrated lime. For the treatment of flue gas released by power plants, the amounts of chloride released by burning fuel or coal are generally very low respect to the SO2, therefore the flue gas treatment process can be simplified by using only hydrated lime as a sorbent.
4 The document W02015/119880 relates to the drawbacks of trona or hydrated lime as sorbents for flue gas treatment process with electrostatic precipitator units. Sodium based sorbents are known to decrease the resistivity of particulate matter, however a main drawback of the use of sodium sorbents is the leaching of heavy metals from the fly ash is enhanced leading to potential environmental contamination. Calcium hydroxide based sorbents do not present the problem of heavy metal leaching from fly ash, but they are known to increase resistivity of the particulate matter (fly ash) entrained in the flue gas stream so that the efficiency of the electrostatic precipitator unit may be lowered when calcium based sorbents are used. The same document discloses a composition for reducing particulate resistivity in a flue gas and for capturing acid gases, wherein the composition comprises an alkali metal/alkali earth particulate having a formula (Lii_a_p Nac, 1<p)w(Mg1_6 Ca6)x(OH)y(CO3),=nH20, more specifically a formula NawCax(OH)y(CO3)z.r1H20 wherein a ratio of W to x is about 1/3 to about 3/1. Therefore the composition still presents a high amount of sodium which would be likely to not only leach itself, but sodium is also know to increase the leaching of heavy metals contained in the fly ash.
US 6,797,035 discloses a process for reducing the resistivity of fly ash by spraying an aqueous solution of potassium nitrate or potassium nitrite on the stream of flue gas or by injecting powder of potassium nitrate or potassium nitrite into the duct through which the flue gas flows. A drawback of using those powders of nitrate or nitrite salts is that they react with other species than fly ash and results in less reactive chemical reaching the collection plates of the electrostatic precipitator. Therefore, it is suggested to inject those nitrate salts as finely divided powders to reduce the exposed reactive surface area and inhibit reactions with nitrous oxides and sulfur oxides.
US 7,744,678 B2 discloses a method where addition of an alkali metal species, comprising sodium, between 0.2 and 3.5 wt%, to calcium hydroxide sorbents provides an improved reactivity towards SO2 capture.
Addition of the alkaline metal species is carried out in such a way that the BET
specific surface area (SSA) by nitrogen adsorption remains high at 30 < SSA <
40 (m2/g).
The combination of sodium salts and hydrated lime beyond
US 6,797,035 discloses a process for reducing the resistivity of fly ash by spraying an aqueous solution of potassium nitrate or potassium nitrite on the stream of flue gas or by injecting powder of potassium nitrate or potassium nitrite into the duct through which the flue gas flows. A drawback of using those powders of nitrate or nitrite salts is that they react with other species than fly ash and results in less reactive chemical reaching the collection plates of the electrostatic precipitator. Therefore, it is suggested to inject those nitrate salts as finely divided powders to reduce the exposed reactive surface area and inhibit reactions with nitrous oxides and sulfur oxides.
US 7,744,678 B2 discloses a method where addition of an alkali metal species, comprising sodium, between 0.2 and 3.5 wt%, to calcium hydroxide sorbents provides an improved reactivity towards SO2 capture.
Addition of the alkaline metal species is carried out in such a way that the BET
specific surface area (SSA) by nitrogen adsorption remains high at 30 < SSA <
40 (m2/g).
The combination of sodium salts and hydrated lime beyond
5 concentrations mentioned in US 7,744,678 B2 is undesired because of three adverse effects: (1) increase of the sodium content will lead to increased leaching of heavy metals from the fly ash residue, (2) in hydrated lime mixtures of sodium salts yield to a reaction which takes place in the presence of water to form sodium hydroxide thus increasing the pH of said mixture to values above pH = 12.5 thus causing safety issues, (3) addition of sodium in aqueous form to hydrated lime reduces the BET specific surface area of the hydrated lime thus reducing the reactivity towards acidic gases.
In the paper #49 presented at the power plant pollutant control and carbon management "MEGA" symposium, August 16-19, 2016, Baltimore, MD, Foo et al. present a successful industrial application of SO2 removal with an enhanced hydrated lime sorbent used in a cold side electrostatic precipitator. Laboratory resistivity measurements of fly ash mixtures with hydrated lime and enhanced hydrated lime have been performed with CaSO4, wherein CaSO4 was added to simulate typical fly ash residues. Enhanced hydrated lime of this paper has a surface area greater than 40 m2/g, a pore volume greater than 0.2 cm3/g and a median particle size d50 comprised between 6 and 12 micrometers and has been found to present acceptable maximum resistivity of 1E11 (1x1011) Ohms.cm.
However, there is still a need to provide calcium-magnesium compound which can be advantageously used in flue gas treatment installations highly compatible with electrostatic precipitators.
The object of the present invention is to provide calcium-magnesium compound and sorbent composition comprising said calcium-magnesium compound removing the intrinsic drawback of these sorbents in their application in electrostatic precipitator units.
In the paper #49 presented at the power plant pollutant control and carbon management "MEGA" symposium, August 16-19, 2016, Baltimore, MD, Foo et al. present a successful industrial application of SO2 removal with an enhanced hydrated lime sorbent used in a cold side electrostatic precipitator. Laboratory resistivity measurements of fly ash mixtures with hydrated lime and enhanced hydrated lime have been performed with CaSO4, wherein CaSO4 was added to simulate typical fly ash residues. Enhanced hydrated lime of this paper has a surface area greater than 40 m2/g, a pore volume greater than 0.2 cm3/g and a median particle size d50 comprised between 6 and 12 micrometers and has been found to present acceptable maximum resistivity of 1E11 (1x1011) Ohms.cm.
However, there is still a need to provide calcium-magnesium compound which can be advantageously used in flue gas treatment installations highly compatible with electrostatic precipitators.
The object of the present invention is to provide calcium-magnesium compound and sorbent composition comprising said calcium-magnesium compound removing the intrinsic drawback of these sorbents in their application in electrostatic precipitator units.
6 Summary of the invention According to a first aspect, the present invention is related to powdery calcium-magnesium compound comprising at least a calcium-magnesium carbonate content greater or equal to 80 weight % or a calcium-magnesium hydroxide content greater or equal to 80 weight %, with respect to the total weight of the powdery calcium-magnesium compound, further presenting a resistivity at 300 C (372 F) R300 lower than 1E11 (1x1011) Ohms.cm and higher than 1E7 (1x107) Ohms.cm, advantageously lower than 1E10 (1x1019) Ohms.cm and higher than 5E7 (5x107) Ohms.cm, preferably lower than 5E9 (5x109) Ohms.cm, more preferably lower than 1E9 (1x109) Ohms.cm, even more preferably lower than 5E8 (5x108) Ohms.cm.
It was indeed surprisingly observed that a powdery calcium-magnesium compound can be successfully used in flue gas treatment using electrostatic precipitators when the resistivity at 300 C (372 F) is still lower than 1E11 (1x1011) Ohms.cm, preferably lower than 1E10 (1x1019) Ohms.cm, meaning that the powdery calcium-magnesium compound is robust and does not decompose at relatively high temperature. Accordingly, this powdery calcium-magnesium compound is able to positively modify the fly-ash resistivity without impacting negatively the operation of the electrostatic precipitator.
Indeed, if the powdery calcium-magnesium is a calcium-magnesium compound comprising at least a calcium-magnesium carbonate content greater than or equal to 80 weight %, preferably greater than or equal to 82 weight %, more preferably greater than or equal to 85 weight %, advantageously greater or equal to 88 weight %, with respect to the total weight of the powdery calcium-magnesium compound, it will be preferably injected at a location near to the boiler or even in the boiler as in that location of the flue gas flow inside which the calcium-magnesium compound is to be injected, the temperature is favorable for a proper capture of polluting
It was indeed surprisingly observed that a powdery calcium-magnesium compound can be successfully used in flue gas treatment using electrostatic precipitators when the resistivity at 300 C (372 F) is still lower than 1E11 (1x1011) Ohms.cm, preferably lower than 1E10 (1x1019) Ohms.cm, meaning that the powdery calcium-magnesium compound is robust and does not decompose at relatively high temperature. Accordingly, this powdery calcium-magnesium compound is able to positively modify the fly-ash resistivity without impacting negatively the operation of the electrostatic precipitator.
Indeed, if the powdery calcium-magnesium is a calcium-magnesium compound comprising at least a calcium-magnesium carbonate content greater than or equal to 80 weight %, preferably greater than or equal to 82 weight %, more preferably greater than or equal to 85 weight %, advantageously greater or equal to 88 weight %, with respect to the total weight of the powdery calcium-magnesium compound, it will be preferably injected at a location near to the boiler or even in the boiler as in that location of the flue gas flow inside which the calcium-magnesium compound is to be injected, the temperature is favorable for a proper capture of polluting
7 compounds of the flue gases by the high carbonate content. In this case, as the product does not decompose, the resistivity at a temperature of 300 C
(372 F) is still low enough to modify the resistivity of the mixture of the fly ashes present in the flue gas and the calcium-magnesium compound injected.
By the terms calcium-magnesium compound with a calcium-magnesium carbonate content greater than or equal to 80 weight %, preferably greater than or equal to 82 weight %, more preferably greater than or equal to 85 weight %, advantageously greater or equal to 88 weight %, with respect to the total weight of the powdery calcium-magnesium compound, it is meant within the meaning of the present invention natural calcium and/or magnesium carbonate such a dolomite, limestone, or even precipitated carbonate of calcium and/or magnesium.
The molar proportion of calcium to magnesium in dolomite can vary from 0.8 to 1.2. In the calcium-magnesium compound, the proportion of calcium to magnesium can be also higher or lower up to 0.01 to 10 or even 100. Indeed, natural limestone comprises magnesium carbonate at a level which can vary from 1 to 10 weight % with respect to the total weight of the powdery calcium-magnesium compound. If the compound in question is a magnesium carbonate, its content in calcium carbonate can also vary from 1 to 10 weight %.
The calcium-magnesium compound can also contain impurities.
The impurities notably comprise all those which are encountered in natural limestones and dolomites, such as clays of the silico-aluminate type, silica, impurities based on iron or manganese.
Indeed, if the powdery calcium-magnesium compound is a calcium-magnesium compound comprising at least a calcium-magnesium hydroxide content greater than or equal to 80 weight %, preferably greater than or equal to 82 weight %, more preferably greater than or equal to 85 weight %, advantageously greater or equal to 88 weight %, with respect to the total weight of the powdery calcium-magnesium compound, it will be
(372 F) is still low enough to modify the resistivity of the mixture of the fly ashes present in the flue gas and the calcium-magnesium compound injected.
By the terms calcium-magnesium compound with a calcium-magnesium carbonate content greater than or equal to 80 weight %, preferably greater than or equal to 82 weight %, more preferably greater than or equal to 85 weight %, advantageously greater or equal to 88 weight %, with respect to the total weight of the powdery calcium-magnesium compound, it is meant within the meaning of the present invention natural calcium and/or magnesium carbonate such a dolomite, limestone, or even precipitated carbonate of calcium and/or magnesium.
The molar proportion of calcium to magnesium in dolomite can vary from 0.8 to 1.2. In the calcium-magnesium compound, the proportion of calcium to magnesium can be also higher or lower up to 0.01 to 10 or even 100. Indeed, natural limestone comprises magnesium carbonate at a level which can vary from 1 to 10 weight % with respect to the total weight of the powdery calcium-magnesium compound. If the compound in question is a magnesium carbonate, its content in calcium carbonate can also vary from 1 to 10 weight %.
The calcium-magnesium compound can also contain impurities.
The impurities notably comprise all those which are encountered in natural limestones and dolomites, such as clays of the silico-aluminate type, silica, impurities based on iron or manganese.
Indeed, if the powdery calcium-magnesium compound is a calcium-magnesium compound comprising at least a calcium-magnesium hydroxide content greater than or equal to 80 weight %, preferably greater than or equal to 82 weight %, more preferably greater than or equal to 85 weight %, advantageously greater or equal to 88 weight %, with respect to the total weight of the powdery calcium-magnesium compound, it will be
8 preferably injected at a location near upstream the preheater as in that location of the flue gas flow inside which the calcium-magnesium compound is to be injected, the temperature is favorable for a proper capture of polluting compounds of the flue gases by the high hydroxide content. In this case, as the product does not decompose, the resistivity at a temperature of 300 C (372 F) is still low enough to modify the resistivity of the mixture of the fly ashes present in the flue gas and the calcium-magnesium compound injected.
By the terms calcium-magnesium compound with a calcium-magnesium hydroxide content greater than or equal to 80 weight %, preferably greater than or equal to 82 weight %, more preferably greater than or equal to 85 weight %, advantageously greater or equal to 88 weight %, with respect to the total weight of the powdery calcium-magnesium compound, it is meant within the meaning of the present invention Said at least one calcium-magnesium compound according to the present invention is therefore at least formed with (calcitic) slaked lime, slaked dolomitic lime (or dolime), magnesium slaked lime.
The molar proportion of calcium to magnesium in dolomitic lime (also called dolime) can vary from 0.8 to 1.2. In the calcium-magnesium compound, the proportion of calcium to magnesium can be also higher or lower up to 0.01 to 10 or even 100. Indeed, natural limestone which is baked to form quicklime, which latter being further slaked to provide hydrated lime comprises magnesium carbonate at a level which can vary from 1 to 10 weight % with respect to the total weight of the powdery calcium-magnesium compound. If the compound in question is a magnesium carbonate which is baked to form magnesium oxide, which latter being further slaked to provide magnesium hydroxide, its content in calcium carbonate can also vary from 1 to 10 weight %. It has to be noted that a part of the magnesium oxide might remain unslaked.
By the terms calcium-magnesium compound with a calcium-magnesium hydroxide content greater than or equal to 80 weight %, preferably greater than or equal to 82 weight %, more preferably greater than or equal to 85 weight %, advantageously greater or equal to 88 weight %, with respect to the total weight of the powdery calcium-magnesium compound, it is meant within the meaning of the present invention Said at least one calcium-magnesium compound according to the present invention is therefore at least formed with (calcitic) slaked lime, slaked dolomitic lime (or dolime), magnesium slaked lime.
The molar proportion of calcium to magnesium in dolomitic lime (also called dolime) can vary from 0.8 to 1.2. In the calcium-magnesium compound, the proportion of calcium to magnesium can be also higher or lower up to 0.01 to 10 or even 100. Indeed, natural limestone which is baked to form quicklime, which latter being further slaked to provide hydrated lime comprises magnesium carbonate at a level which can vary from 1 to 10 weight % with respect to the total weight of the powdery calcium-magnesium compound. If the compound in question is a magnesium carbonate which is baked to form magnesium oxide, which latter being further slaked to provide magnesium hydroxide, its content in calcium carbonate can also vary from 1 to 10 weight %. It has to be noted that a part of the magnesium oxide might remain unslaked.
9 The calcium-magnesium compound can also contain impurities.
The impurities notably comprise all those which are encountered in natural limestones and dolomites, such as clays of the silico-aluminate type, silica, impurities based on iron or manganese The CaCO3, MgCO3, Ca(OH)2 and Mg(OH)2 contents in calcium-magnesium compounds may easily be determined with conventional methods. For example, they may be determined by X fluorescence analysis, the procedure of which is described in the EN 15309 standard, coupled with a measurement of the loss on ignition and a measurement of the CO2 volume according to the EN 459-2:2010 E standard.
Preferably, the calcium-magnesium compound according to the present invention presents a maximum resitivity Rmax lower than 5E11 (5x1011) Ohms.cm, preferably lower than 1E11 (1x1011) Ohms.cm and more preferably lower than 5E10 (5x10' ) Ohms.cm.
Advantageously, the calcium-magnesium compound is doped with at least one metallic ion M chosen in the group of the metallic ion having an atomic number less than or equal to 74 and belonging to the group consisting of a transition metal ion or a post-transition metal ion at an amount greater than or equal to 0.05 weight % and lower or equal to 5 weight % with respect to the total weight of the powdery calcium-magnesium compound.
In a particular embodiment, the calcium-magnesium compound according to the present invention is further doped with at least one counter ion X chosen in the group consisting of nitrates, nitrites, and their mixture at an amount greater than or equal to 0.05 weight % and lower or equal to 5 .. weight % with respect to the total weight of the powdery calcium-magnesium compound.
In a preferred embodiment of the calcium-magnesium compound according to the present invention, the total weight of said metallic ion and said counter ion is greater than or equal to 0.1 weight % and lower than or equal to 5 weight %, preferably between 0.3 and 3 weight %, with respect to the total weight of the powdery calcium-magnesium compound.
In yet another preferred embodiment, the calcium-magnesium 5 compound of the invention further comprises sodium in an amount up to 3.5 weight % with respect to the total weight of the powdery calcium-magnesium compound, expressed as sodium equivalent. Preferably, sodium is in a minimum amount of 0.2 wt.% with respect to the total weight of the powdery calcium-magnesium compound and expressed as sodium equivalent.
The impurities notably comprise all those which are encountered in natural limestones and dolomites, such as clays of the silico-aluminate type, silica, impurities based on iron or manganese The CaCO3, MgCO3, Ca(OH)2 and Mg(OH)2 contents in calcium-magnesium compounds may easily be determined with conventional methods. For example, they may be determined by X fluorescence analysis, the procedure of which is described in the EN 15309 standard, coupled with a measurement of the loss on ignition and a measurement of the CO2 volume according to the EN 459-2:2010 E standard.
Preferably, the calcium-magnesium compound according to the present invention presents a maximum resitivity Rmax lower than 5E11 (5x1011) Ohms.cm, preferably lower than 1E11 (1x1011) Ohms.cm and more preferably lower than 5E10 (5x10' ) Ohms.cm.
Advantageously, the calcium-magnesium compound is doped with at least one metallic ion M chosen in the group of the metallic ion having an atomic number less than or equal to 74 and belonging to the group consisting of a transition metal ion or a post-transition metal ion at an amount greater than or equal to 0.05 weight % and lower or equal to 5 weight % with respect to the total weight of the powdery calcium-magnesium compound.
In a particular embodiment, the calcium-magnesium compound according to the present invention is further doped with at least one counter ion X chosen in the group consisting of nitrates, nitrites, and their mixture at an amount greater than or equal to 0.05 weight % and lower or equal to 5 .. weight % with respect to the total weight of the powdery calcium-magnesium compound.
In a preferred embodiment of the calcium-magnesium compound according to the present invention, the total weight of said metallic ion and said counter ion is greater than or equal to 0.1 weight % and lower than or equal to 5 weight %, preferably between 0.3 and 3 weight %, with respect to the total weight of the powdery calcium-magnesium compound.
In yet another preferred embodiment, the calcium-magnesium 5 compound of the invention further comprises sodium in an amount up to 3.5 weight % with respect to the total weight of the powdery calcium-magnesium compound, expressed as sodium equivalent. Preferably, sodium is in a minimum amount of 0.2 wt.% with respect to the total weight of the powdery calcium-magnesium compound and expressed as sodium equivalent.
10 Sodium under the form of sodium additive in such amounts is known to have a slight effect on decreasing the resistivity of the sorbent, as presented by Foo et al. (2016) document previously mentioned. The applicant found that sodium additive in such amounts in combination with the presence as described hereunder of at least a metallic ion and/or a counter ion further provides an additional effect on the decreasing of the resistivity of the sorbent composition. The use of sodium additive in combination with the presence as described hereunder of at least a metallic ion and/or a counter ion decreases the resistivity of sorbent composition more than when presence as described hereunder of at least a metallic ion and/or a counter ion is used alone in the calcium-magnesium compound and more than when sodium is used alone in the calcium-magnesium compound.
In an advantageous embodiment of the calcium-magnesium compound, the said metallic ion M is one of the ions among Cu2+, Fe2+, Fe3+, m n2+, co2+, mo2+, Ni2+, zn2+.
Preferably, the said metallic ion M is one of the ions among Cu2+, Fe2+, Fe3+.
Preferably, the said counter ion X is nitrate.
It has been found that the presence of a metallic ion as disclosed hereabove and/or of a counter ion as described before in the
In an advantageous embodiment of the calcium-magnesium compound, the said metallic ion M is one of the ions among Cu2+, Fe2+, Fe3+, m n2+, co2+, mo2+, Ni2+, zn2+.
Preferably, the said metallic ion M is one of the ions among Cu2+, Fe2+, Fe3+.
Preferably, the said counter ion X is nitrate.
It has been found that the presence of a metallic ion as disclosed hereabove and/or of a counter ion as described before in the
11 calcium-magnesium compound,decreases the resistivity of the calcium-magnesium compound.
In a preferred embodiment, the powdery calcium-magnesium comprises particles having a d50 comprised between 5 and 25 um, preferably between 5 and 20um, more preferably between 5 and 16 [im.
The notation dx represents a diameter expressed in um, as measured by laser granulometry in methanol optionally after sonication, relatively to which X % by mass of the measured particles are smaller or equal Preferably, in particular if the powdery calcium-magnesium compound is a calcium-magnesium compound comprising at least a calcium-magnesium hydroxide content greater than or equal to 80 weight %, the calcium-magnesium compound according to the invention has a BET specific surface area of at least 20 m2/g, preferably of at least 25 m2/g, preferably of at least 30 m2/g, more preferably of at least 35 m2/g. The BET surface area is determined by manometry with adsorption of nitrogen after degassing in vacuum at 190 C (374 F) for at least 2 hours and calculated according to the multipoint BET method as described in the ISO 9277/2010E standard.
Preferably, in particular if the powdery calcium-magnesium compound is a calcium-magnesium compound comprising at least a calcium-magnesium hydroxide content greater than or equal to 80 weight %, the sorbent composition according to the invention has a BJH pore volume of at least 0.1 cm3/g, preferably of at least 0.15 cm3/g, preferably of at least 0.17 cm3/g, more preferably of at least 0.2 cm3/g. The BJH pore volume is determined by manometry with desorption of nitrogen after degassing in vacuum at 190 C (374 F) for at least 2 hours and calculated according to the BJH method as described in the ISO 9277/2010E standard.
Other embodiments of the calcium-magnesium compound according to the present invention are mentioned in the appended claims
In a preferred embodiment, the powdery calcium-magnesium comprises particles having a d50 comprised between 5 and 25 um, preferably between 5 and 20um, more preferably between 5 and 16 [im.
The notation dx represents a diameter expressed in um, as measured by laser granulometry in methanol optionally after sonication, relatively to which X % by mass of the measured particles are smaller or equal Preferably, in particular if the powdery calcium-magnesium compound is a calcium-magnesium compound comprising at least a calcium-magnesium hydroxide content greater than or equal to 80 weight %, the calcium-magnesium compound according to the invention has a BET specific surface area of at least 20 m2/g, preferably of at least 25 m2/g, preferably of at least 30 m2/g, more preferably of at least 35 m2/g. The BET surface area is determined by manometry with adsorption of nitrogen after degassing in vacuum at 190 C (374 F) for at least 2 hours and calculated according to the multipoint BET method as described in the ISO 9277/2010E standard.
Preferably, in particular if the powdery calcium-magnesium compound is a calcium-magnesium compound comprising at least a calcium-magnesium hydroxide content greater than or equal to 80 weight %, the sorbent composition according to the invention has a BJH pore volume of at least 0.1 cm3/g, preferably of at least 0.15 cm3/g, preferably of at least 0.17 cm3/g, more preferably of at least 0.2 cm3/g. The BJH pore volume is determined by manometry with desorption of nitrogen after degassing in vacuum at 190 C (374 F) for at least 2 hours and calculated according to the BJH method as described in the ISO 9277/2010E standard.
Other embodiments of the calcium-magnesium compound according to the present invention are mentioned in the appended claims
12 According to a second aspect, the present invention also relates to a sorbent composition for flue gas treatment installation including an electrostatic precipitator comprising said calcium-magnesium compound according to the present invention.
Preferably, the sorbent composition according to the invention further comprises activated charcoal, lignite coke, halloysite, sepiolite, clays such as bentonite, kaolin, vermiculite or any other sorbent such as fire clay, aerated cement dust, perlite, expanded clay, lime sandstone dust, trass dust, Yali rock dust, trass lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulphide, organic sulphide, calcium sulfate, open-hearth coke, lignite dust, fly ash, or water glass.
In a preferred embodiment, the sorbent composition according to the present invention comprises sodium additive comprising sodium in an amount up to 3.5 weight % with respect to the total weight of the powdery calcium-magnesium compound and expressed as sodium equivalent. In particular, the amount of sodium in the composition would be higher than 0.2 weight % with respect to the total weight of the powdery sorbent composition.
In a preferred embodiment, the sorbent composition according to the present invention comprises said metallic ion M and/or said counter ion X being present at an amount greater than or equal to 0.05 weight % and lower or equal to 5 weight % with respect to the total weight of the powdery calcium-magnesium compound and wherein preferably the total weight of said metallic ion and said counter ion is greater than or equal to 0.1 weight %
and lower than or equal to 5 weight %, preferably between 0.3 and 3 weight %, with respect to the total weight of the dry sorbent composition.
In a particular embodiment according to the present invention, the sorbent composition comprises water in such an amount that the sorbent composition is under the form of a suspension. Exemplary amounts can be from 40 to 90 weight % of water wherein the sorbent is comprised in an
Preferably, the sorbent composition according to the invention further comprises activated charcoal, lignite coke, halloysite, sepiolite, clays such as bentonite, kaolin, vermiculite or any other sorbent such as fire clay, aerated cement dust, perlite, expanded clay, lime sandstone dust, trass dust, Yali rock dust, trass lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulphide, organic sulphide, calcium sulfate, open-hearth coke, lignite dust, fly ash, or water glass.
In a preferred embodiment, the sorbent composition according to the present invention comprises sodium additive comprising sodium in an amount up to 3.5 weight % with respect to the total weight of the powdery calcium-magnesium compound and expressed as sodium equivalent. In particular, the amount of sodium in the composition would be higher than 0.2 weight % with respect to the total weight of the powdery sorbent composition.
In a preferred embodiment, the sorbent composition according to the present invention comprises said metallic ion M and/or said counter ion X being present at an amount greater than or equal to 0.05 weight % and lower or equal to 5 weight % with respect to the total weight of the powdery calcium-magnesium compound and wherein preferably the total weight of said metallic ion and said counter ion is greater than or equal to 0.1 weight %
and lower than or equal to 5 weight %, preferably between 0.3 and 3 weight %, with respect to the total weight of the dry sorbent composition.
In a particular embodiment according to the present invention, the sorbent composition comprises water in such an amount that the sorbent composition is under the form of a suspension. Exemplary amounts can be from 40 to 90 weight % of water wherein the sorbent is comprised in an
13 amount of 10 to 60 weight % with respect to the total weight of the sorbent composition under the form of a suspension.
The sorbent composition under the form of a suspension can be used for example in a spray dry absorber, which can be followed by an electrostatic precipitator.
In a particularly preferred embodiment, the said calcium-magnesium compound is hydrated lime. In this case, if the sorbent composition is under the form of a suspension, it will be under the form of a milk of lime where the solid content will be from 10 et 50 weight % with respect to the total weight of the milk of lime.
Other embodiments of the sorbent composition according to the present invention are mentioned in the appended claims According to a third aspect, the present invention is related to a process for manufacturing a sorbent composition for a flue gas treatment installation including an electrostatic precipitator, comprising the step of:
a) Providing a calcium-magnesium compound to a reactor b) adding an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X with M being a metallic ion having an atomic number less than or equal to 74 and is a transition metal ion or a post-transition metal ion, and X being one of the counter ion amongst nitrates, nitrites, oxides (02-), hydroxides (OH-), and their mixture in an amount calculated to obtain between 0.1 weight % and 5 weight %, preferably between 0.3 weight % to 3 weight % of said metallic ion M and /or counter ion X in weight of dry sorbent composition.
Alternatively, the present invention is related to a process for manufacturing a sorbent composition for a flue gas treatment installation including an electrostatic precipitator, comprising the step of :
The sorbent composition under the form of a suspension can be used for example in a spray dry absorber, which can be followed by an electrostatic precipitator.
In a particularly preferred embodiment, the said calcium-magnesium compound is hydrated lime. In this case, if the sorbent composition is under the form of a suspension, it will be under the form of a milk of lime where the solid content will be from 10 et 50 weight % with respect to the total weight of the milk of lime.
Other embodiments of the sorbent composition according to the present invention are mentioned in the appended claims According to a third aspect, the present invention is related to a process for manufacturing a sorbent composition for a flue gas treatment installation including an electrostatic precipitator, comprising the step of:
a) Providing a calcium-magnesium compound to a reactor b) adding an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X with M being a metallic ion having an atomic number less than or equal to 74 and is a transition metal ion or a post-transition metal ion, and X being one of the counter ion amongst nitrates, nitrites, oxides (02-), hydroxides (OH-), and their mixture in an amount calculated to obtain between 0.1 weight % and 5 weight %, preferably between 0.3 weight % to 3 weight % of said metallic ion M and /or counter ion X in weight of dry sorbent composition.
Alternatively, the present invention is related to a process for manufacturing a sorbent composition for a flue gas treatment installation including an electrostatic precipitator, comprising the step of :
14 a) Providing a calcium-magnesium compound to a reactor b) adding an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X with M being a metallic ion having an atomic number less than or equal to 74 and is a transition metal ion or a post-transition metal ion, and X being one of the counter ion amongst nitrates, nitrites, oxides (02-), hydroxides (OH-), and their mixture in an amount calculated to obtain between 0.1 weight % and 5 weight %, preferably between 0.3 weight % to 3 weight % of said metallic ion M and /or counter ion X in weight of calcium-magnesium compound.
In a preferred embodiment, the sorbent composition comprises particles having a d50 comprised between 5 and 25 um, preferably between 5 and 20um, more preferably between 5 and 16 um.
In a preferred embodiment of the process according to the present invention, said calcium-magnesium compound comprises at least a calcium-magnesium carbonate content greater or equal to 80 weight % with respect to the total weight of the dry calcium-magnesium compound.
In another preferred embodiment of the process according to the present invention, said calcium-magnesium compound comprises a calcium-magnesium hydroxide content greater or equal to 80 weight %, with respect to the total weight of the dry calcium-magnesium compound.
Preferably in the process of manufacturing said sorbent composition, the said metallic ion M is one of the ions among Cu2+, Fe2+, Fe3+, me, co2+, mo2+, Ni2+, ze.more preferably in the process of manufacturing said sorbent composition said metallic ion M is one of the ions among Cu 2+, Fe2+, Fe3+.
Preferably in the process of manufacturing said sorbent composition, said counter ion X is nitrate.
Preferably the process of manufacturing said sorbent composition comprises a step of adding another additive comprising sodium expressed as sodium equivalent in an amount calculated to obtain up to 3.5%
of sodium equivalent in weight of the dry sorbent composition.
5 In an embodiment of the process of manufacturing according to the invention, the step of providing a calcium-magnesium compound to a reactor comprises the step of providing a quicklime to said reactor, slaking said quicklime with a predetermined amount of water to obtain said calcium-magnesium compound comprising at least a calcium hydroxide content 10 greater or equal to 80 weight %, with respect to the total weight of the dry calcium-magnesium compound with an predetermined amount of moisture.
More advantageously, said step of slaking is performed in conditions such as to obtain hydrated lime with a BET specific surface area by nitrogen adsorption of at least 20m2/g, preferably of at least 25 m2/g,
In a preferred embodiment, the sorbent composition comprises particles having a d50 comprised between 5 and 25 um, preferably between 5 and 20um, more preferably between 5 and 16 um.
In a preferred embodiment of the process according to the present invention, said calcium-magnesium compound comprises at least a calcium-magnesium carbonate content greater or equal to 80 weight % with respect to the total weight of the dry calcium-magnesium compound.
In another preferred embodiment of the process according to the present invention, said calcium-magnesium compound comprises a calcium-magnesium hydroxide content greater or equal to 80 weight %, with respect to the total weight of the dry calcium-magnesium compound.
Preferably in the process of manufacturing said sorbent composition, the said metallic ion M is one of the ions among Cu2+, Fe2+, Fe3+, me, co2+, mo2+, Ni2+, ze.more preferably in the process of manufacturing said sorbent composition said metallic ion M is one of the ions among Cu 2+, Fe2+, Fe3+.
Preferably in the process of manufacturing said sorbent composition, said counter ion X is nitrate.
Preferably the process of manufacturing said sorbent composition comprises a step of adding another additive comprising sodium expressed as sodium equivalent in an amount calculated to obtain up to 3.5%
of sodium equivalent in weight of the dry sorbent composition.
5 In an embodiment of the process of manufacturing according to the invention, the step of providing a calcium-magnesium compound to a reactor comprises the step of providing a quicklime to said reactor, slaking said quicklime with a predetermined amount of water to obtain said calcium-magnesium compound comprising at least a calcium hydroxide content 10 greater or equal to 80 weight %, with respect to the total weight of the dry calcium-magnesium compound with an predetermined amount of moisture.
More advantageously, said step of slaking is performed in conditions such as to obtain hydrated lime with a BET specific surface area by nitrogen adsorption of at least 20m2/g, preferably of at least 25 m2/g,
15 preferably of at least 30 m2/g, more preferably of at least 35 m2/g.
In further preferred embodiment, said step of slaking is performed in conditions such as to obtain hydrated lime with a BJH pore volume for pores having a diameter lower or equal to 1000 A by nitrogen desorption of at least 0.1 cm3/g, 0.15 cm3/g, preferably of at least 0.17 cm3/g, more preferably of at least 0.2 cm3/g.
Preferably, said step of slaking is performed in the same conditions as the ones described in US patent 6,322,769 of the applicant and incorporated by reference.
In an alternative embodiment of the process of manufacturing according to the invention, the said step of slaking is performed in the same conditions as the ones described in the US patent 7,744,678 of the applicant and incorporated by reference.
In an embodiment of the process of manufacturing said sorbent according to the invention, the step of adding an additive or a mixture of
In further preferred embodiment, said step of slaking is performed in conditions such as to obtain hydrated lime with a BJH pore volume for pores having a diameter lower or equal to 1000 A by nitrogen desorption of at least 0.1 cm3/g, 0.15 cm3/g, preferably of at least 0.17 cm3/g, more preferably of at least 0.2 cm3/g.
Preferably, said step of slaking is performed in the same conditions as the ones described in US patent 6,322,769 of the applicant and incorporated by reference.
In an alternative embodiment of the process of manufacturing according to the invention, the said step of slaking is performed in the same conditions as the ones described in the US patent 7,744,678 of the applicant and incorporated by reference.
In an embodiment of the process of manufacturing said sorbent according to the invention, the step of adding an additive or a mixture of
16 additives, comprising at least one metallic ion M and /or a counter ion X is performed before said step of slaking quicklime.
In another embodiment of the process of manufacturing said sorbent composition, the said step of adding an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X is performed during said step of slaking quicklime.
Alternatively, in the process of manufacturing said sorbent composition, the said step of adding an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X is performed after the said step of slaking quicklime.
It has been found by the applicant that the step of adding an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X is performed during or after the said step of slaking does not substantially change the specific surface area nor the pore volume of the calcium-magnesium compound, for example as sorbent. In particular, the specific surface area and the pore volume of the sorbent composition according to the present invention is substantially the same as for calcium hydroxide sorbent prepared by the known methods such as the one described in US patents 6,322,769 and 7,744,678 incorporated by reference. Therefore, the properties of the sorbent ensuring the efficiency of SO2 removal are preserved.
Preferably, the said process of manufacturing is characterized in that it further comprises a step of adding activated charcoal, lignite coke, halloysite, sepiolite, clays, bentonite, kaolin, vermiculite, fire clay, aerated cement dust, perlite, expanded clay, lime sandstone dust, trass dust, Yali rock dust, trass lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulphide, organic sulphide, calcium sulfate, open-hearth coke, lignite dust, fly ash, or water glass, preferably performed after the said step of slaking.
In another embodiment of the process of manufacturing said sorbent composition, the said step of adding an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X is performed during said step of slaking quicklime.
Alternatively, in the process of manufacturing said sorbent composition, the said step of adding an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X is performed after the said step of slaking quicklime.
It has been found by the applicant that the step of adding an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X is performed during or after the said step of slaking does not substantially change the specific surface area nor the pore volume of the calcium-magnesium compound, for example as sorbent. In particular, the specific surface area and the pore volume of the sorbent composition according to the present invention is substantially the same as for calcium hydroxide sorbent prepared by the known methods such as the one described in US patents 6,322,769 and 7,744,678 incorporated by reference. Therefore, the properties of the sorbent ensuring the efficiency of SO2 removal are preserved.
Preferably, the said process of manufacturing is characterized in that it further comprises a step of adding activated charcoal, lignite coke, halloysite, sepiolite, clays, bentonite, kaolin, vermiculite, fire clay, aerated cement dust, perlite, expanded clay, lime sandstone dust, trass dust, Yali rock dust, trass lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulphide, organic sulphide, calcium sulfate, open-hearth coke, lignite dust, fly ash, or water glass, preferably performed after the said step of slaking.
17 Other embodiments of the process for manufacturing a sorbent composition according to the present invention are mentioned in the appended claims In a fourth aspect, the present invention is related to a flue gas treatment process using an installation comprising an injection zone arranged upstream an electrostatic precipitator, characterized in that it comprises a step of injecting in said injection zone a sorbent composition according to the present invention.
More particularly, the flue gas treatment process using an installation including an electrostatic precipitator, and an injection zone arranged upstream said electrostatic precipitator and through which flue gas is flowing towards said electrostatic precipitator is characterized in that the said process comprises a step of injection of a sorbent composition in said injection zone, said sorbent composition comprising a calcium-magnesium sorbent, at least one metallic ion M having an atomic number less than or equal to 74 and being a transition metal ion or a post-transition metal ion, and optionally at least a counter ion X chosen amongst nitrates, nitrites, and their mixture, the total amount of said at least one metallic ion M and said optionally at least one counter ion X being comprised between 0.1 % and 5 %, preferably 0.3 to 3.5% in weight of the dry composition.
According to the present invention, the said sorbent composition has a lower resistivity compared to calcium-magnesium sorbents of prior art, especially at a temperature of 300 C (372 F). Injection of the sorbent composition according to the invention in an injection zone to mix with flue gas is effective for the removal of SO2 and other gaseous acids and the lower resistivity of such sorbent composition improves the collection of particulate matter on the collecting electrodes of the electrostatic precipitator.
In a preferred embodiment of the process according to the present invention, the sorbent composition comprises as calcium-magnesium
More particularly, the flue gas treatment process using an installation including an electrostatic precipitator, and an injection zone arranged upstream said electrostatic precipitator and through which flue gas is flowing towards said electrostatic precipitator is characterized in that the said process comprises a step of injection of a sorbent composition in said injection zone, said sorbent composition comprising a calcium-magnesium sorbent, at least one metallic ion M having an atomic number less than or equal to 74 and being a transition metal ion or a post-transition metal ion, and optionally at least a counter ion X chosen amongst nitrates, nitrites, and their mixture, the total amount of said at least one metallic ion M and said optionally at least one counter ion X being comprised between 0.1 % and 5 %, preferably 0.3 to 3.5% in weight of the dry composition.
According to the present invention, the said sorbent composition has a lower resistivity compared to calcium-magnesium sorbents of prior art, especially at a temperature of 300 C (372 F). Injection of the sorbent composition according to the invention in an injection zone to mix with flue gas is effective for the removal of SO2 and other gaseous acids and the lower resistivity of such sorbent composition improves the collection of particulate matter on the collecting electrodes of the electrostatic precipitator.
In a preferred embodiment of the process according to the present invention, the sorbent composition comprises as calcium-magnesium
18 compound at least a calcium-magnesium carbonate, and said sorbent composition is injected in said injection zone, wherein said flue gas has a temperature greater than or equal to 850 C ( 1562 F).
In another preferred embodiment of the process according to the present invention, the sorbent composition comprises a calcium-magnesium compound at least a calcium-magnesium hydroxide, and said sorbent composition is injected in said injection zone wherein said flue gas has a temperature greater than or equal to 180 C (356 F), preferably greater than 200 C (392 F), more preferably comprised between 300 C (372 F) and 425 C (797 F).
Preferably, in the flue gas treatment process according to the invention, the said calcium-magnesium compound in the sorbent composition is mixed with an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X before the said step of injection.
Alternatively, in the flue gas treatment process according to the invention, the calcium-magnesium compound and an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X are injected separately and mixed with said flue gas in the said injection zone.
The said sorbent composition can be used in the flue gas treatment process according to the present invention under a broad range of temperatures, for example between 100 C (212 F) and 425 C (797 F) or even higher when the sorbent composition mainly comprises carbonate sorbent (typically temperature higher than 850 C (1562 F) Advantageously, the said additives of the sorbent composition according to the present invention do not encounter degradation at temperatures higher than 180 C (356 F) so that said sorbent composition can be injected in the said injection zone wherein the temperature is greater than or equal to 180 C (356 F), preferably greater than or equal to 300 C (372 F).
As the injection zone is located upstream the air preheater, temperatures at
In another preferred embodiment of the process according to the present invention, the sorbent composition comprises a calcium-magnesium compound at least a calcium-magnesium hydroxide, and said sorbent composition is injected in said injection zone wherein said flue gas has a temperature greater than or equal to 180 C (356 F), preferably greater than 200 C (392 F), more preferably comprised between 300 C (372 F) and 425 C (797 F).
Preferably, in the flue gas treatment process according to the invention, the said calcium-magnesium compound in the sorbent composition is mixed with an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X before the said step of injection.
Alternatively, in the flue gas treatment process according to the invention, the calcium-magnesium compound and an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X are injected separately and mixed with said flue gas in the said injection zone.
The said sorbent composition can be used in the flue gas treatment process according to the present invention under a broad range of temperatures, for example between 100 C (212 F) and 425 C (797 F) or even higher when the sorbent composition mainly comprises carbonate sorbent (typically temperature higher than 850 C (1562 F) Advantageously, the said additives of the sorbent composition according to the present invention do not encounter degradation at temperatures higher than 180 C (356 F) so that said sorbent composition can be injected in the said injection zone wherein the temperature is greater than or equal to 180 C (356 F), preferably greater than or equal to 300 C (372 F).
As the injection zone is located upstream the air preheater, temperatures at
19 the injection zone can range between 300 C (372 F) to 425 C (797 F), preferably 350 C (662 F) to 380 C (716 F).
Preferably, in the flue gas treatment process according to the invention, the said injection zone is located upstream an air preheater itself located upstream said electrostatic precipitator.
Preferably, in the flue gas treatment process according to the invention, the said ion M is one of the ions among Cu2+, Fe2+, Fe3+, M n2+, Co2+, mo2+, Ni2+, zn2+.
More preferably, in the flue gas treatment process of the invention, the said ion M is one of the ions among Cu2+, Fe2+, Fe3+.
Preferably, in the flue gas treatment process of the invention, said counter ion X is nitrate.
Preferably, in the flue gas treatment process of the invention, the said sorbent composition comprises another additive comprising sodium in an amount up to 3.5% in weight of the dry composition and expressed as sodium equivalent.
Preferably, in the flue gas treatment process of the invention, the said sorbent composition has a BET specific surface area of at least 20m2/g.
Preferably, in the flue gas treatment process of the invention, the said sorbent composition has a BJH pore volume obtained from nitrogen desorption of at least 0.1 cm3/g.
Preferably, in the flue gas treatment process of the invention, the said sorbent composition has a BJH pore volume obtained from nitrogen desorption of at least 0.15 cm3/g, preferably of at least 0.17 cm3/g, more preferably of at least 0.2 cm3/g.
Preferably, in the flue gas treatment process of the invention, the said sorbent composition further comprises activated charcoal, lignite coke, halloysite, sepiolite, clays, bentonite, kaolin, vermiculite, fire clay, aerated cement dust, perlite, expanded clay, lime sandstone dust, trass dust, 5 Yali rock dust, trass lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulphide, organic sulphide, calcium sulfate, open-hearth coke, lignite dust, fly ash, or water glass.
Other embodiments of the flue gas treatment process according to the present invention are mentioned in the appended claims.
10 In a fifth aspect, the present invention is related to a flue gas treatment device comprising an electrostatic precipitator downstream of an air preheater, said air preheater being connected to said electrostatic precipitator by a duct, characterized in that it further comprises an injection zone for injecting a sorbent composition according to the present invention 15 .. arranged upstream of said air preheater.
Other embodiments of the flue gas treatment device according to the present invention are mentioned in the appended claims.
Preferably the said flue gas treatment device or installation is used for treating flue gas of a plant, in particular a power plant ,using coal or
Preferably, in the flue gas treatment process according to the invention, the said injection zone is located upstream an air preheater itself located upstream said electrostatic precipitator.
Preferably, in the flue gas treatment process according to the invention, the said ion M is one of the ions among Cu2+, Fe2+, Fe3+, M n2+, Co2+, mo2+, Ni2+, zn2+.
More preferably, in the flue gas treatment process of the invention, the said ion M is one of the ions among Cu2+, Fe2+, Fe3+.
Preferably, in the flue gas treatment process of the invention, said counter ion X is nitrate.
Preferably, in the flue gas treatment process of the invention, the said sorbent composition comprises another additive comprising sodium in an amount up to 3.5% in weight of the dry composition and expressed as sodium equivalent.
Preferably, in the flue gas treatment process of the invention, the said sorbent composition has a BET specific surface area of at least 20m2/g.
Preferably, in the flue gas treatment process of the invention, the said sorbent composition has a BJH pore volume obtained from nitrogen desorption of at least 0.1 cm3/g.
Preferably, in the flue gas treatment process of the invention, the said sorbent composition has a BJH pore volume obtained from nitrogen desorption of at least 0.15 cm3/g, preferably of at least 0.17 cm3/g, more preferably of at least 0.2 cm3/g.
Preferably, in the flue gas treatment process of the invention, the said sorbent composition further comprises activated charcoal, lignite coke, halloysite, sepiolite, clays, bentonite, kaolin, vermiculite, fire clay, aerated cement dust, perlite, expanded clay, lime sandstone dust, trass dust, 5 Yali rock dust, trass lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulphide, organic sulphide, calcium sulfate, open-hearth coke, lignite dust, fly ash, or water glass.
Other embodiments of the flue gas treatment process according to the present invention are mentioned in the appended claims.
10 In a fifth aspect, the present invention is related to a flue gas treatment device comprising an electrostatic precipitator downstream of an air preheater, said air preheater being connected to said electrostatic precipitator by a duct, characterized in that it further comprises an injection zone for injecting a sorbent composition according to the present invention 15 .. arranged upstream of said air preheater.
Other embodiments of the flue gas treatment device according to the present invention are mentioned in the appended claims.
Preferably the said flue gas treatment device or installation is used for treating flue gas of a plant, in particular a power plant ,using coal or
20 fuel containing sulfur species or other acid gas precursors.
Preferably the said flue gas treatment installation further comprises a reservoir comprising said sorbent composition to provide said sorbent composition to the said injection zone through a sorbent inlet.
The present invention can also be described as a process for .. reducing the resistivity a powdery sorbent composition for flue gas treatment installation including an electrostatic precipitator under 1E11 Ohms.cm and over 1E07 Ohms.cm at 300 C, wherein said resistivity of said powdery sorbent composition is measured in a resistivity cell in an oven under a stream of air comprising 10% of humidity, said powdery sorbent composition
Preferably the said flue gas treatment installation further comprises a reservoir comprising said sorbent composition to provide said sorbent composition to the said injection zone through a sorbent inlet.
The present invention can also be described as a process for .. reducing the resistivity a powdery sorbent composition for flue gas treatment installation including an electrostatic precipitator under 1E11 Ohms.cm and over 1E07 Ohms.cm at 300 C, wherein said resistivity of said powdery sorbent composition is measured in a resistivity cell in an oven under a stream of air comprising 10% of humidity, said powdery sorbent composition
21 comprising a powdery calcium-magnesium compound comprising at least a calcium-magnesium carbonate content greater than or equal to 80 weight %
or a calcium-magnesium hydroxide content greater or equal to 80 weight %, with respect to the total weight of the powdery calcium-magnesium content, the process comprising the steps of:
a) providing the said powdery sorbent composition in a reactor and;
b) adding to said powdery sorbent composition an additive or a mixture of additives, comprising at least one metallic ion M and .. /or a counter ion X with M being a metallic ion having an atomic number less than or equal to 74 and is a transition metal ion or a post-transition metal ion, or Mg2+ or Na+ or Li+ and X being one of the counter ion selected from the group consisting of nitrates, nitrites, oxides 02-, and hydroxide OH- and their mixture in an amount calculated to obtain between 0.1 weight % and 5 weight %, preferably between 0.3 weight % to 3 weight % of said metallic ion M and /or counter ion X in weight with respect to the total weight of dry sorbent composition.
Preferably, said metallic ion M is selected from the group consisting of Cu2+, Fe2+, Fe3+, Mn2+, Co2+, Mo2+, Ni2+ and Zn2+.
Preferably, said counter ion X is nitrate.
Preferably, said powdery calcium-magnesium compound presents a BET specific surface area by nitrogen adsorption of at least 20m2/g, preferably of at least 25 m2/g, preferably of at least 30 m2/g, more preferably of at least 35 m2/g.
Preferably, said powdery calcium-magnesium compound presents a BJH pore volume for pores having a diameter lower or equal to 1000 A by nitrogen desorption of at least 0.1 cm3/g, 0.15 cm3/g, preferably of at least 0.17 cm3/g, more preferably of at least 0.2 cm3/g.
or a calcium-magnesium hydroxide content greater or equal to 80 weight %, with respect to the total weight of the powdery calcium-magnesium content, the process comprising the steps of:
a) providing the said powdery sorbent composition in a reactor and;
b) adding to said powdery sorbent composition an additive or a mixture of additives, comprising at least one metallic ion M and .. /or a counter ion X with M being a metallic ion having an atomic number less than or equal to 74 and is a transition metal ion or a post-transition metal ion, or Mg2+ or Na+ or Li+ and X being one of the counter ion selected from the group consisting of nitrates, nitrites, oxides 02-, and hydroxide OH- and their mixture in an amount calculated to obtain between 0.1 weight % and 5 weight %, preferably between 0.3 weight % to 3 weight % of said metallic ion M and /or counter ion X in weight with respect to the total weight of dry sorbent composition.
Preferably, said metallic ion M is selected from the group consisting of Cu2+, Fe2+, Fe3+, Mn2+, Co2+, Mo2+, Ni2+ and Zn2+.
Preferably, said counter ion X is nitrate.
Preferably, said powdery calcium-magnesium compound presents a BET specific surface area by nitrogen adsorption of at least 20m2/g, preferably of at least 25 m2/g, preferably of at least 30 m2/g, more preferably of at least 35 m2/g.
Preferably, said powdery calcium-magnesium compound presents a BJH pore volume for pores having a diameter lower or equal to 1000 A by nitrogen desorption of at least 0.1 cm3/g, 0.15 cm3/g, preferably of at least 0.17 cm3/g, more preferably of at least 0.2 cm3/g.
22 Preferably, said powdery sorbent composition further comprises activated charcoal, lignite coke, halloysite, sepiolite, clays, bentonite, kaolin, vermiculite, fire clay, aerated cement dust, perlite, expanded clay, lime sandstone dust, trass dust, Yali rock dust, trass lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulphide, organic sulphide, calcium sulfate, open-hearth coke, lignite dust, fly ash, or water glass.
Preferably, the said process for reducing the resistivity of said powdery sorbent composition further comprises a step of adding to the said powdery sorbent composition a sodium additive comprising sodium in an amount up to 3.5 weight % with respect to the total weight of the powdery sorbent composition and expressed as sodium equivalent.
Preferably, the said powdery calcium magnesium compound is hydrated lime.
The invention is also related to the use of a powdery sorbent composition as described herein in a flue gas treatment process using an installation comprising an electrostatic precipitator.
Brief description of the drawings Figure 1 presents a schematic embodiment of a flue gas treatment installation carrying out the flue gas treatment process with the sorbent composition according to the present invention.
Detailed description of the invention According to a first aspect, the present invention is related to a sorbent composition for flue gas treatment installation including an electrostatic precipitator, said sorbent composition comprising calcium-magnesium compound, characterized in that it further comprises an additive
Preferably, the said process for reducing the resistivity of said powdery sorbent composition further comprises a step of adding to the said powdery sorbent composition a sodium additive comprising sodium in an amount up to 3.5 weight % with respect to the total weight of the powdery sorbent composition and expressed as sodium equivalent.
Preferably, the said powdery calcium magnesium compound is hydrated lime.
The invention is also related to the use of a powdery sorbent composition as described herein in a flue gas treatment process using an installation comprising an electrostatic precipitator.
Brief description of the drawings Figure 1 presents a schematic embodiment of a flue gas treatment installation carrying out the flue gas treatment process with the sorbent composition according to the present invention.
Detailed description of the invention According to a first aspect, the present invention is related to a sorbent composition for flue gas treatment installation including an electrostatic precipitator, said sorbent composition comprising calcium-magnesium compound, characterized in that it further comprises an additive
23 or a mixture of additives in an amount comprised between 0.1% and 5%, preferably 0.3% to 3% in weight of the dry composition, said additive or additives containing at least one metallic ion M having an atomic number less than or equal to 74 and is a transition metal ion or a post-transition metal ion, and at least one counter ion X chosen amongst nitrates, nitrites, and their mixture.
In a preferred embodiment, the calcium-magnesium compound is based on hydrated lime.
Calcium hydroxide sorbents are manufactured by reacting (or slaking) calcium oxide, CaO or quick lime, with water in a so called hydrator, also called slaking unit. Alternatively, calcium magnesium hydroxide sorbents are manufactured by reacting dolomitic lime (also called dolime) or magnesium lime with water in a hydrator. Alternatively, quick lime and dolomitic lime can be mixed together and slaked with water in a hydrator to .. provide a mixture of calcium hydroxide and calcium magnesium hydroxide. In the following, the process of manufacturing of the sorbent composition will refer to quick lime but the process of manufacturing is not limited to quick lime as a starting material and dolomitic lime or a combination of dolomitic lime and/or magnesium lime and quick lime can also be used as starting materials.
The process of manufacturing of the said sorbent composition according to the invention comprises a step of slaking quicklime with a predetermined amount of water to obtain hydrated lime with an predetermined amount of moisture, and is characterized in that it comprises a step of adding an additive or a mixture of additives in an amount calculated to obtain between 0.1% and 5 %, preferably between 0.3 and 3.5% of said additive or mixture of additives in weight of the dry sorbent composition, said additive or additives containing at least one metallic ion M having an atomic number less than or equal to 74 and is a transition metal ion or a post-
In a preferred embodiment, the calcium-magnesium compound is based on hydrated lime.
Calcium hydroxide sorbents are manufactured by reacting (or slaking) calcium oxide, CaO or quick lime, with water in a so called hydrator, also called slaking unit. Alternatively, calcium magnesium hydroxide sorbents are manufactured by reacting dolomitic lime (also called dolime) or magnesium lime with water in a hydrator. Alternatively, quick lime and dolomitic lime can be mixed together and slaked with water in a hydrator to .. provide a mixture of calcium hydroxide and calcium magnesium hydroxide. In the following, the process of manufacturing of the sorbent composition will refer to quick lime but the process of manufacturing is not limited to quick lime as a starting material and dolomitic lime or a combination of dolomitic lime and/or magnesium lime and quick lime can also be used as starting materials.
The process of manufacturing of the said sorbent composition according to the invention comprises a step of slaking quicklime with a predetermined amount of water to obtain hydrated lime with an predetermined amount of moisture, and is characterized in that it comprises a step of adding an additive or a mixture of additives in an amount calculated to obtain between 0.1% and 5 %, preferably between 0.3 and 3.5% of said additive or mixture of additives in weight of the dry sorbent composition, said additive or additives containing at least one metallic ion M having an atomic number less than or equal to 74 and is a transition metal ion or a post-
24 transition metal ion, and at least one counter ion X chosen amongst nitrates, nitrites, 02-, and OH-and their mixture.
In an embodiment of the process of manufacturing the said sorbent composition, the predetermined amount of water in the said step of slaking is in a water to lime ratio 2:1 by weight or higher.
In an embodiment of the process of manufacturing the said sorbent composition, the amount of water in the slaking step can be adapted to obtain a hydrated lime with a moisture less than or equal to 10 wt.%, preferably less than or equal to 5 wt.%, preferably less than or equal to 2 w%, more preferably less than or equal to 1 w% with respect to the total weight of the sorbent composition at a powdery state.
In another embodiment, the amount of water in the slaking step can be adapted to obtain a hydrated lime with a moisture content comprised between 5 wt.% and 20 wt.%. The amount of water in the slaking step can also be higher such as to obtain a hydrated lime with a moisture content above 20 wt.%, all % being expressed with respect to the total weight of the sorbent composition at a powdery state.
In an embodiment, the hydrated lime obtained after the slaking step is dried in a further step.
In an embodiment of the process of manufacturing of the sorbent composition according to the invention, the said additive containing at least one metallic ion M and at least one counter ion X is added as an aqueous solution or as a suspension or as a powder before or during the said step of slaking of calcium oxide or calcium magnesium oxide or a combination thereof.
In another embodiment of the process of manufacturing of the sorbent composition according to the invention, the said additive or mixture of additives containing at least one metallic ion M and at least one counter ion X is added as aqueous solution or as a suspension or as a powder after the said step of slaking. The said additive or mixture of additives containing at least one metallic ion M and at least one counter ion X is preferably added to calcium hydroxide or calcium magnesium hydroxide before injection in an injection zone of the flue gas treatment installation. Alternatively, the said 5 additive or mixture of additives containing at least one metallic ion M
and at least one counter ion X can be added during injection in an injection zone of the flue gas treatment installation, separately from the calcium hydroxide or calcium magnesium hydroxide and upstream the electrostatic precipitator.
In a preferred embodiment of the process of manufacturing of 10 the sorbent composition, the said step of slaking quicklime is performed in the conditions such as to obtain hydrated lime with a BET specific surface area from nitrogen adsorption of at least 20m2/g and a BJH pore volume obtained from nitrogen desorption of at least 0.1 cm3/g. Various processes are available to the man skilled in the art to obtain an hydrated lime with such properties, 15 and are disclosed for example in documents US patent 6,322,769 and US
patent 7,744,678 of the applicant and incorporated by reference.
In the process of manufacturing the sorbent composition according to the invention, particles of quicklime are advantageously used having a particle size distribution of less than 5 mm, in particular quicklime 20 particles of particle size distribution 0-2 mm.
Other processes for obtaining hydrated lime with high specific area and/or high pore volume can be found for example in US patent 5,492,685 wherein an amount of alcohol such methanol or ethanol is added prior and/or the step of slaking quicklime and is removed after drying, in
In an embodiment of the process of manufacturing the said sorbent composition, the predetermined amount of water in the said step of slaking is in a water to lime ratio 2:1 by weight or higher.
In an embodiment of the process of manufacturing the said sorbent composition, the amount of water in the slaking step can be adapted to obtain a hydrated lime with a moisture less than or equal to 10 wt.%, preferably less than or equal to 5 wt.%, preferably less than or equal to 2 w%, more preferably less than or equal to 1 w% with respect to the total weight of the sorbent composition at a powdery state.
In another embodiment, the amount of water in the slaking step can be adapted to obtain a hydrated lime with a moisture content comprised between 5 wt.% and 20 wt.%. The amount of water in the slaking step can also be higher such as to obtain a hydrated lime with a moisture content above 20 wt.%, all % being expressed with respect to the total weight of the sorbent composition at a powdery state.
In an embodiment, the hydrated lime obtained after the slaking step is dried in a further step.
In an embodiment of the process of manufacturing of the sorbent composition according to the invention, the said additive containing at least one metallic ion M and at least one counter ion X is added as an aqueous solution or as a suspension or as a powder before or during the said step of slaking of calcium oxide or calcium magnesium oxide or a combination thereof.
In another embodiment of the process of manufacturing of the sorbent composition according to the invention, the said additive or mixture of additives containing at least one metallic ion M and at least one counter ion X is added as aqueous solution or as a suspension or as a powder after the said step of slaking. The said additive or mixture of additives containing at least one metallic ion M and at least one counter ion X is preferably added to calcium hydroxide or calcium magnesium hydroxide before injection in an injection zone of the flue gas treatment installation. Alternatively, the said 5 additive or mixture of additives containing at least one metallic ion M
and at least one counter ion X can be added during injection in an injection zone of the flue gas treatment installation, separately from the calcium hydroxide or calcium magnesium hydroxide and upstream the electrostatic precipitator.
In a preferred embodiment of the process of manufacturing of 10 the sorbent composition, the said step of slaking quicklime is performed in the conditions such as to obtain hydrated lime with a BET specific surface area from nitrogen adsorption of at least 20m2/g and a BJH pore volume obtained from nitrogen desorption of at least 0.1 cm3/g. Various processes are available to the man skilled in the art to obtain an hydrated lime with such properties, 15 and are disclosed for example in documents US patent 6,322,769 and US
patent 7,744,678 of the applicant and incorporated by reference.
In the process of manufacturing the sorbent composition according to the invention, particles of quicklime are advantageously used having a particle size distribution of less than 5 mm, in particular quicklime 20 particles of particle size distribution 0-2 mm.
Other processes for obtaining hydrated lime with high specific area and/or high pore volume can be found for example in US patent 5,492,685 wherein an amount of alcohol such methanol or ethanol is added prior and/or the step of slaking quicklime and is removed after drying, in
25 patent DE3620024 wherein sugar is added in the step of slaking for increasing the specific surface area and wherein glycols or amines are added to increase the flowability, in US patent 5,277,837 and US patent 5,705,141 wherein additives such as ethylene glycol, diethylene glycol, tri ethylene glycol, monoethanolamine, diethanolamine, triethanolamine or a combination
26 thereof is added in the step of slaking for increasing the surface area of hydrated lime.
In the process of manufacturing the sorbent composition, the said additive or mixture of additives containing at least one metallic ion M
and at least one counter ion X can be added before the said step of slaking, during the step of slaking or after the step of slaking without substantially changing the BET specific surface area nor the BJH pore volume for pores having a diameter lower than or equal to 1000 A of the sorbent composition. Moreover the BET specific surface area and the BJH pore volume of the sorbent composition according to the present invention is substantially the same as for calcium hydroxide sorbent prepared by the known methods such as the one described in US patents 6,322,769 and 7,744,678 incorporated by reference. Therefore, the properties of the sorbent ensuring the efficiency of SO2 removal are preserved.
In the said process of manufacturing the sorbent composition according to the invention, if a hydrated lime composition is prepared according to the method described in US patent 7,744,678, such method comprises a step of adding a quantity of an alkali metal, preferably sodium in an quantity to the quicklime or to the slaking water or to the hydrated lime, sufficient to obtain in the hydrated lime an alkali metal content that is equal to or greater than 0.2 % and equal or less than 3.5 % by weight based on the total weight of the dry sorbent composition. According to this embodiment, the said additives or mixture of additives containing at least one metallic ion M and at least one counter ion X is further added to the quicklime or to the slaking water or to the hydrated lime with an amount such as to obtain a content in additive or in a mixture of additives containing at least one metallic ion M and at least one counter ion X between 0.1 % and 5%, preferably 0.3%
to 3% in weight of the dry sorbent composition.
Various sorbent compositions have been prepared according to the method of the present invention and measurements of the resistivity of
In the process of manufacturing the sorbent composition, the said additive or mixture of additives containing at least one metallic ion M
and at least one counter ion X can be added before the said step of slaking, during the step of slaking or after the step of slaking without substantially changing the BET specific surface area nor the BJH pore volume for pores having a diameter lower than or equal to 1000 A of the sorbent composition. Moreover the BET specific surface area and the BJH pore volume of the sorbent composition according to the present invention is substantially the same as for calcium hydroxide sorbent prepared by the known methods such as the one described in US patents 6,322,769 and 7,744,678 incorporated by reference. Therefore, the properties of the sorbent ensuring the efficiency of SO2 removal are preserved.
In the said process of manufacturing the sorbent composition according to the invention, if a hydrated lime composition is prepared according to the method described in US patent 7,744,678, such method comprises a step of adding a quantity of an alkali metal, preferably sodium in an quantity to the quicklime or to the slaking water or to the hydrated lime, sufficient to obtain in the hydrated lime an alkali metal content that is equal to or greater than 0.2 % and equal or less than 3.5 % by weight based on the total weight of the dry sorbent composition. According to this embodiment, the said additives or mixture of additives containing at least one metallic ion M and at least one counter ion X is further added to the quicklime or to the slaking water or to the hydrated lime with an amount such as to obtain a content in additive or in a mixture of additives containing at least one metallic ion M and at least one counter ion X between 0.1 % and 5%, preferably 0.3%
to 3% in weight of the dry sorbent composition.
Various sorbent compositions have been prepared according to the method of the present invention and measurements of the resistivity of
27 dry powders of said sorbent compositions have been carried out in following the procedure outlined by IEEE (Esctcourt, 1984). Basically, a resistivity cell of a determined volume is filled by a dry powder of sorbent composition and the powder is then compacted with a weight such as to obtain a flat surface. An electrode with a guard is placed over the surface of the powder and the resistivity of the powder is measured in an oven under a stream of air comprising 10% of humidity at various temperatures comprised between 150 C (302 F) and 300 C (372 F). The resistivity of comparatives examples have been measured in the same conditions. For each measurement, a maximum resistivity Rmax and a resistivity at 300 C (372 F) has been determined. The resistivity measurements are presented herein after:
Example set A
Example 1 is a comparative sample of calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US 6,322,769 B1. No sodium nor additive of general formula MX
have been added.
Example 2 is a comparative sample of a calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US 7,744,678 B2. This sample comprises 1 wt.% of sodium as Na2CO3. No further sodium or additive of general formula MX has been added.
Example 3 is a calcium hydroxide sorbent manufactured according to the present invention using iron nitrate as dopant.
Table 1 shows the measured resistivity parameters Rmax and R300.
Table 1 : Resistivity parameters of calcium hydroxide sorbents doped with sodium and iron salts.
Example set A
Example 1 is a comparative sample of calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US 6,322,769 B1. No sodium nor additive of general formula MX
have been added.
Example 2 is a comparative sample of a calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US 7,744,678 B2. This sample comprises 1 wt.% of sodium as Na2CO3. No further sodium or additive of general formula MX has been added.
Example 3 is a calcium hydroxide sorbent manufactured according to the present invention using iron nitrate as dopant.
Table 1 shows the measured resistivity parameters Rmax and R300.
Table 1 : Resistivity parameters of calcium hydroxide sorbents doped with sodium and iron salts.
28 Example Composition Na2CO3 Fe(NO3)3 Cu(NO3)2 Rmax (0 Crrl) R300 (0 CM) (Wt.%) (Wt.%) (wt.%) Ex. 1 Ca(OH)2 0 0 0 8 E12 3 E12 Ex. 2 Ca(OH)2 + 1 0 0 4 Ell 1 Ell Na2CO3 Ex. 33 Ca(OH)2 + 0 0.5 0 1 E12 2E10 Fe(NO3)3 From Table 1, it is clear that the both the Rmax value and the R300 value of Example 1 are high at and above the preferred range of resistivity values comprised between 10E7 ohms.cm and 2E10 ohms.cm.
Addition of 1 wt.% of sodium in Example 2 reduces the Rmax and R300 values by more than one order of magnitude. Surprisingly the addition of a small amount of iron nitrate at 0.5 wt% reduces the Rmax value by nearly one order of magnitude and by nearly two orders of magnitude for R300.
Surprisingly the addition of iron nitrate is more effective than the addition of sodium.
Example set B
A set of sorbents was prepared by taking the sorbents manufactured according to US 7,744,678 B2 and adding iron and copper salts according to the method of present invention to said sorbents.
Example 4 is a sample of a calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US
7,744,678 B2 wherein an amount of iron nitrate has been added. According to the manufacturing method presented in US 7,744,678 an amount of sodium has been added.
Example 5 is a sample of a calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US
7,744,678 B2 wherein an amount of copper nitrate has been added. According
Addition of 1 wt.% of sodium in Example 2 reduces the Rmax and R300 values by more than one order of magnitude. Surprisingly the addition of a small amount of iron nitrate at 0.5 wt% reduces the Rmax value by nearly one order of magnitude and by nearly two orders of magnitude for R300.
Surprisingly the addition of iron nitrate is more effective than the addition of sodium.
Example set B
A set of sorbents was prepared by taking the sorbents manufactured according to US 7,744,678 B2 and adding iron and copper salts according to the method of present invention to said sorbents.
Example 4 is a sample of a calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US
7,744,678 B2 wherein an amount of iron nitrate has been added. According to the manufacturing method presented in US 7,744,678 an amount of sodium has been added.
Example 5 is a sample of a calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US
7,744,678 B2 wherein an amount of copper nitrate has been added. According
29 to the manufacturing method presented in US 7,744,678 an amount of sodium has been added.
Table 2 : Resistivity parameters of calcium hydroxide sorbents doped with sodium, iron and copper salts.
Example Composition Na2CO3 Fe(NO3)3 Cu(NO3)2 Rmax (CI
R300 (CI
(Wt.%) (Wt.%) (Wt.%) CM) cm) Ex. 1 Ca(OH)2 0 0 0 8 E12 3 E12 Ex. 4 Ca(OH)2 + 1 0.5 0 1 Ell 1 E10 Na2CO3 +
Fe(NO3)3 Ex. 5 Ca(OH)2 + 1 0 0.5 2 E10 2E8 Na2CO3+Cu(NO3)2 Table 2 shows that for these sorbents, the addition of an iron nitrate result in resistivity value Rmax nearly two orders of magnitude lower than that of the comparative Example 1. The addition of copper nitrate results in nearly three orders of magnitude lower resistivity for Rmax and more than three orders of magnitude resistivity drop of R300.
Example set C
A set of sorbent was prepared by taking the sorbents according to US 7,744,678 and various irons salts have been added to measure the influence of the counter ion on the resistivity of the sorbent.
Example 4 is a sample of a calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US
7,744,678 B2 wherein an amount of iron nitrate has been added. According to the manufacturing method presented in US 7,744,678 an amount of sodium has been added.
Example 6 is a comparative sample of a calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US 7,744,678 B2 wherein an amount of iron sulfate has been added. According to the manufacturing method presented in US 7,744,678 an amount of sodium has been added.
Example 7 is a comparative sample of a calcium hydroxide 5 sorbent designed for the removal of acid gas pollutants manufactured according to US 7,744,678 B2 wherein an amount of iron acetate has been added. According to the manufacturing method presented in US 7,744,678 an amount of sodium has been added.
Table 3: Resistivity parameters of calcium hydroxide sorbents 10 using different iron salts.
Example Composition Na2CO3 Fe(NO3)3 Fe2(504)3 Fe(C2H302)2 Rmax R300 (Wt.%) (Wt.%) (Wt.%) (Wt.%) (Q (Q
CM) cm) Ex. 2 Ca(OH)2 + 1 0 0 0 4 1E11 Na2CO3 Ell Ex. 4 Ca(OH)2+ 1 0.5 0 0 1 1 E10 Na2CO3+ Ell Fe(NO3)3 Ex. 6 Ca(OH)2 + 1 0 0.5 0 2E12 2E12 Na2CO3 +
Fe 2(504)3 Ex. 7 Ca(OH)2 + 1 0 0 0.5 3E12 4E11 Na2CO3 + Fe acetate Table 3 shows that the use of iron nitrate results in a resistivity value Rmax four times lower than that of comparative Example 2 and one order of magnitude lower for R300. Surprisingly the use of iron salts of different 15 composition such as sulfate and acetate result in an increase of the resistivity, both for Rmax and for R300 compared to the comparative Example 2. Note that the use of iron sulfate results in a resistivity that does not show lower values for R300 compared to Rmax=
Example Set D
A set of sorbent was prepared by taking the sorbents according to US 7,744,678 and various copper salts have been added to measure the influence of the counter ion on the resistivity of the sorbent.
C
t..) o ,-, o Table 4: Resistivity parameters of calcium hydroxide sorbents using different copper salts 'a t..) o o ,-, Example Composition Na2CO3 (wt.%) Cu(NO3)2 (wt.%) CuSO4 (wt.%) CuCl2 Cu citrate Rmax (0.cm) R300 (0.cm) (wt.%) (w%) Example 2 Ca(OH)2+ Na2CO3 1 0 0 0 0 4 Ell 1 Ell P
Example 5 Ca(OH)2+ Na2CO3+ 1 0.5 0 0 0 2 E10 2 E8 .
_.]
Cu(NO3)2 .
r., u, u, r., ' Example 8 Ca(OH)2+ Na2CO3+ 1 0 0.5 0 0 2E12 3E11 N-).
, , , Cu(SO4) Example 9 Ca(OH)2+ Na2CO3+ 1 0 0 0.5 0 3 E12 6 Ell CuCl2 Example 10 Ca(OH)2+ Na2CO3+ Cu 1 0 0 0 0.5 7E12 2E12 1-d n citrate t=1 1-d o 1¨
cio 'a o o 1¨
t,.) It is clear from Table 4 that surprisingly all salts, except copper nitrate, increase the resistivity of the sorbent respective of the comparative Example 2.
It is to be mentioned that the examples of sorbent compositions presented herein above are not !imitative for the present invention, and other additives in the amounts comprised between 0.1 and 5 %
in weight of the dry sorbent composition can be used to decrease the resistivity of sorbent compositions destined to be used in flue gas treatment processes using an electrostatic precipitator.
It is to be mentioned that improvements of particulate matter collection on collecting electrodes of an electrostatic precipitators can be observed with the use of the sorbent according to the present invention.
According to another aspect, the present invention is related to a flue gas treatment installation. Figure 1 shows a schematic embodiment of a flue gas treatment installation 100 comprising an electrostatic precipitator 101 arranged downstream a first duct portion 102 arranged downstream an air preheater 103, characterized in that an injection zone 104 is arranged upstream said air preheater 103 and comprises a sorbent inlet 105. The said flue gas treatment installation 100 further comprises a reservoir 106 comprising said sorbent composition S to provide said sorbent composition to the said injection zone through the said sorbent inlet. The hot flue gas FG
produced by a boiler 10 is flown through the injection zone wherein the sorbent S according to the invention is injected to react with SO2 and other acidic gases from the flue gas, then the hot flue gas crosses the air preheater through which cold air CA is flown to absorb the heat of the hot flue gas and to be injected as hot air HA in the boiler. Then the flue gas flows through the electrostatic precipitator 101 wherein charged collecting electrodes collects the particulate matter including the sorbent composition according to the invention that has reacted with undesired acidic gases. The flue gas treatment installation described herein is relatively simple and is well adapted for the use of the sorbent composition according to the present invention.
Preferably the said flue gas treatment installation is used for treating flue gas of a power plant using coal or fuel containing sulfur species or other acid gas precursors.
It should be understood that the present invention is not limited to the described embodiments and that variations can be applied without going outside of the scope of the appended claims.
For example, in the preferred embodiment, the installation for flue gas treatment was described with an electrostatic precipitator downstream of an air preheater, said air preheater being connected to said electrostatic precipitator by a duct with an injection zone for injecting a sorbent composition according to the present invention arranged upstream of said air preheater. An alternative within the scope of the present may comprises a particulate collection device upstream of said preheater.
Another alternative of the flue gas treatment device according to the present invention comprises in sequence an electrostatic precipitator, a preheater followed by optionally a particulate collection device, before reaching the chimney.
The particulate collection device can be another electrostatic precipitator or any king of filter, such as a bag house filter.
In all of those embodiments, the sorbent composition according to the present invention is injected in an injection zone located upstream of said electrostatic precipitator, before or after the preheater, depending on the on-site configuration.
Table 2 : Resistivity parameters of calcium hydroxide sorbents doped with sodium, iron and copper salts.
Example Composition Na2CO3 Fe(NO3)3 Cu(NO3)2 Rmax (CI
R300 (CI
(Wt.%) (Wt.%) (Wt.%) CM) cm) Ex. 1 Ca(OH)2 0 0 0 8 E12 3 E12 Ex. 4 Ca(OH)2 + 1 0.5 0 1 Ell 1 E10 Na2CO3 +
Fe(NO3)3 Ex. 5 Ca(OH)2 + 1 0 0.5 2 E10 2E8 Na2CO3+Cu(NO3)2 Table 2 shows that for these sorbents, the addition of an iron nitrate result in resistivity value Rmax nearly two orders of magnitude lower than that of the comparative Example 1. The addition of copper nitrate results in nearly three orders of magnitude lower resistivity for Rmax and more than three orders of magnitude resistivity drop of R300.
Example set C
A set of sorbent was prepared by taking the sorbents according to US 7,744,678 and various irons salts have been added to measure the influence of the counter ion on the resistivity of the sorbent.
Example 4 is a sample of a calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US
7,744,678 B2 wherein an amount of iron nitrate has been added. According to the manufacturing method presented in US 7,744,678 an amount of sodium has been added.
Example 6 is a comparative sample of a calcium hydroxide sorbent designed for the removal of acid gas pollutants manufactured according to US 7,744,678 B2 wherein an amount of iron sulfate has been added. According to the manufacturing method presented in US 7,744,678 an amount of sodium has been added.
Example 7 is a comparative sample of a calcium hydroxide 5 sorbent designed for the removal of acid gas pollutants manufactured according to US 7,744,678 B2 wherein an amount of iron acetate has been added. According to the manufacturing method presented in US 7,744,678 an amount of sodium has been added.
Table 3: Resistivity parameters of calcium hydroxide sorbents 10 using different iron salts.
Example Composition Na2CO3 Fe(NO3)3 Fe2(504)3 Fe(C2H302)2 Rmax R300 (Wt.%) (Wt.%) (Wt.%) (Wt.%) (Q (Q
CM) cm) Ex. 2 Ca(OH)2 + 1 0 0 0 4 1E11 Na2CO3 Ell Ex. 4 Ca(OH)2+ 1 0.5 0 0 1 1 E10 Na2CO3+ Ell Fe(NO3)3 Ex. 6 Ca(OH)2 + 1 0 0.5 0 2E12 2E12 Na2CO3 +
Fe 2(504)3 Ex. 7 Ca(OH)2 + 1 0 0 0.5 3E12 4E11 Na2CO3 + Fe acetate Table 3 shows that the use of iron nitrate results in a resistivity value Rmax four times lower than that of comparative Example 2 and one order of magnitude lower for R300. Surprisingly the use of iron salts of different 15 composition such as sulfate and acetate result in an increase of the resistivity, both for Rmax and for R300 compared to the comparative Example 2. Note that the use of iron sulfate results in a resistivity that does not show lower values for R300 compared to Rmax=
Example Set D
A set of sorbent was prepared by taking the sorbents according to US 7,744,678 and various copper salts have been added to measure the influence of the counter ion on the resistivity of the sorbent.
C
t..) o ,-, o Table 4: Resistivity parameters of calcium hydroxide sorbents using different copper salts 'a t..) o o ,-, Example Composition Na2CO3 (wt.%) Cu(NO3)2 (wt.%) CuSO4 (wt.%) CuCl2 Cu citrate Rmax (0.cm) R300 (0.cm) (wt.%) (w%) Example 2 Ca(OH)2+ Na2CO3 1 0 0 0 0 4 Ell 1 Ell P
Example 5 Ca(OH)2+ Na2CO3+ 1 0.5 0 0 0 2 E10 2 E8 .
_.]
Cu(NO3)2 .
r., u, u, r., ' Example 8 Ca(OH)2+ Na2CO3+ 1 0 0.5 0 0 2E12 3E11 N-).
, , , Cu(SO4) Example 9 Ca(OH)2+ Na2CO3+ 1 0 0 0.5 0 3 E12 6 Ell CuCl2 Example 10 Ca(OH)2+ Na2CO3+ Cu 1 0 0 0 0.5 7E12 2E12 1-d n citrate t=1 1-d o 1¨
cio 'a o o 1¨
t,.) It is clear from Table 4 that surprisingly all salts, except copper nitrate, increase the resistivity of the sorbent respective of the comparative Example 2.
It is to be mentioned that the examples of sorbent compositions presented herein above are not !imitative for the present invention, and other additives in the amounts comprised between 0.1 and 5 %
in weight of the dry sorbent composition can be used to decrease the resistivity of sorbent compositions destined to be used in flue gas treatment processes using an electrostatic precipitator.
It is to be mentioned that improvements of particulate matter collection on collecting electrodes of an electrostatic precipitators can be observed with the use of the sorbent according to the present invention.
According to another aspect, the present invention is related to a flue gas treatment installation. Figure 1 shows a schematic embodiment of a flue gas treatment installation 100 comprising an electrostatic precipitator 101 arranged downstream a first duct portion 102 arranged downstream an air preheater 103, characterized in that an injection zone 104 is arranged upstream said air preheater 103 and comprises a sorbent inlet 105. The said flue gas treatment installation 100 further comprises a reservoir 106 comprising said sorbent composition S to provide said sorbent composition to the said injection zone through the said sorbent inlet. The hot flue gas FG
produced by a boiler 10 is flown through the injection zone wherein the sorbent S according to the invention is injected to react with SO2 and other acidic gases from the flue gas, then the hot flue gas crosses the air preheater through which cold air CA is flown to absorb the heat of the hot flue gas and to be injected as hot air HA in the boiler. Then the flue gas flows through the electrostatic precipitator 101 wherein charged collecting electrodes collects the particulate matter including the sorbent composition according to the invention that has reacted with undesired acidic gases. The flue gas treatment installation described herein is relatively simple and is well adapted for the use of the sorbent composition according to the present invention.
Preferably the said flue gas treatment installation is used for treating flue gas of a power plant using coal or fuel containing sulfur species or other acid gas precursors.
It should be understood that the present invention is not limited to the described embodiments and that variations can be applied without going outside of the scope of the appended claims.
For example, in the preferred embodiment, the installation for flue gas treatment was described with an electrostatic precipitator downstream of an air preheater, said air preheater being connected to said electrostatic precipitator by a duct with an injection zone for injecting a sorbent composition according to the present invention arranged upstream of said air preheater. An alternative within the scope of the present may comprises a particulate collection device upstream of said preheater.
Another alternative of the flue gas treatment device according to the present invention comprises in sequence an electrostatic precipitator, a preheater followed by optionally a particulate collection device, before reaching the chimney.
The particulate collection device can be another electrostatic precipitator or any king of filter, such as a bag house filter.
In all of those embodiments, the sorbent composition according to the present invention is injected in an injection zone located upstream of said electrostatic precipitator, before or after the preheater, depending on the on-site configuration.
Claims (10)
1. Process for reducing the resistivity a powdery sorbent composition for flue gas treatment installation comprising an electrostatic precipitator under 1E11 Ohms.cm and over 1E07 Ohms.cm at 300°C, wherein said resistivity of said powdery sorbent composition is measured in a resistivity cell in an oven under a stream of air comprising 10% of humidity, said powdery sorbent composition comprising a powdery calcium-magnesium compound comprising at least a calcium-magnesium carbonate content greater than or equal to 80 weight % or a calcium-magnesium hydroxide content greater or equal to 80 weight %, with respect to the total weight of the powdery calcium-magnesium content, the process comprising the steps of :
a) providing said powdery sorbent composition in a reactor and;
b) adding to said powdery sorbent composition an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X with M being a metallic ion having an atomic number less than or equal to 74 and is a transition metal ion or a post-transition metal ion, or Mg2+ or Na+ or Li+ and X being one of the counter ion selected from the group consisting of nitrates, nitrites, oxides O2-, and hydroxide OH- and their mixture in an amount calculated to obtain between 0.1 weight % and 5 weight %, of said metallic ion M and /or counter ion X in weight with respect to the total weight of dry sorbent composition.
a) providing said powdery sorbent composition in a reactor and;
b) adding to said powdery sorbent composition an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X with M being a metallic ion having an atomic number less than or equal to 74 and is a transition metal ion or a post-transition metal ion, or Mg2+ or Na+ or Li+ and X being one of the counter ion selected from the group consisting of nitrates, nitrites, oxides O2-, and hydroxide OH- and their mixture in an amount calculated to obtain between 0.1 weight % and 5 weight %, of said metallic ion M and /or counter ion X in weight with respect to the total weight of dry sorbent composition.
2. Process according to claim 1 wherein said metallic ion M is selected from the group consisting of Cu2+, Fe2+, Fe3+, Mn2+, Co2+, Mo2+, Ni2+ and Zn2+.
3. Process according to claim 1 or 2 wherein said counter ion X is nitrate.
4. Process according to any one of the preceding claims wherein said powdery calcium-magnesium compound presents a BET specific surface area by nitrogen adsorption of at least 20m2/g.
5. Process according to any one of the preceding claims wherein said powdery calcium-magnesium compound presents a BJH pore volume for pores having a diameter lower or equal to 1000 .ANG. by nitrogen desorption of at least 0.1 cm3/g, 0.15 cm/g.
6. Process according to any one of the preceding claims wherein said powdery sorbent composition further comprises activated charcoal, lignite coke, halloysite, sepiolite, clays, bentonite, kaolin, vermiculite, fire clay, aerated cement dust, perlite, expanded clay, lime sandstone dust, trass dust, Yali rock dust, trass lime, fuller's earth, cement, calcium aluminate, sodium aluminate, calcium sulphide, organic sulphide, calcium sulfate, open-hearth coke, lignite dust, fly ash, or water glass.
7. Process according to any one of the preceding claims further comprising a step of adding to the said powdery sorbent composition a sodium additive comprising sodium in an amount up to 3.5 weight % with respect to the total weight of the powdery sorbent composition and expressed as sodium equivalent.
8. Process according to any one of the preceding claims wherein the said powdery calcium magnesium compound is hydrated lime.
9. Powdery sorbent composition for flue gas treatment installation including an electrostatic precipitator, said powdery sorbent composition comprising a powdery calcium-magnesium compound comprising at least a calcium-magnesium carbonate content greater than or equal to 80 weight %
or a calcium-magnesium hydroxide content greater or equal to 80 weight %, with respect to the total weight of the powdery calcium-magnesium content, characterized in that said powdery sorbent composition has a reduced resistivity under 1E11 Ohms.cm and over 1E07 Ohms.cm at 300°C, wherein the said resistivity of said powdery sorbent composition is measured in a resistivity cell in an oven under a stream of air comprising 10% of humidity, said reduced resistivity being provided by an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X with M being a metallic ion having an atomic number less than or equal to 74 and is a transition metal ion or a post-transition metal ion, or Mg2+ or Na+ or Li+
and X being one of the counter ion selected from the group consisting of nitrates, nitrites, oxides O2-, and hydroxide OH- and their mixture in an amount calculated to obtain between 0.1 weight % and 5 weight %of said metallic ion M and /or counter ion X in weight with respect to the total weight of dry sorbent composition.
or a calcium-magnesium hydroxide content greater or equal to 80 weight %, with respect to the total weight of the powdery calcium-magnesium content, characterized in that said powdery sorbent composition has a reduced resistivity under 1E11 Ohms.cm and over 1E07 Ohms.cm at 300°C, wherein the said resistivity of said powdery sorbent composition is measured in a resistivity cell in an oven under a stream of air comprising 10% of humidity, said reduced resistivity being provided by an additive or a mixture of additives, comprising at least one metallic ion M and /or a counter ion X with M being a metallic ion having an atomic number less than or equal to 74 and is a transition metal ion or a post-transition metal ion, or Mg2+ or Na+ or Li+
and X being one of the counter ion selected from the group consisting of nitrates, nitrites, oxides O2-, and hydroxide OH- and their mixture in an amount calculated to obtain between 0.1 weight % and 5 weight %of said metallic ion M and /or counter ion X in weight with respect to the total weight of dry sorbent composition.
10. Use of a powdery sorbent composition according to claim 9 or obtainable by a process according to any one of the claims 1 to 8 in a flue gas treatment process using an installation comprising an electrostatic precipitator.
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EPPCT/EP2017/068625 | 2017-07-24 | ||
PCT/EP2018/070012 WO2019020613A1 (en) | 2017-07-24 | 2018-07-24 | Sorbent composition for an electrostatic precipitator |
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DE3620024A1 (en) | 1986-06-13 | 1987-12-17 | Fels Werke Peine Salzgitter | Process for preparing finely divided calcium hydroxide |
US5334564A (en) * | 1990-07-16 | 1994-08-02 | Board Of Trustees Operating Michigan State University | Method for the preparation of highly reactive clay composites for the removal of SOx from flue gas streams |
US5234877A (en) * | 1990-07-16 | 1993-08-10 | Board Of Trustees Operating Michigan State University | Composite clay materials for removal of SOx from gas streams |
US5298473A (en) * | 1990-07-16 | 1994-03-29 | Board Of Trustees Operating Michigan State University | Hydrated lime clay composites for the removal of SOx from flue gas streams |
US5223239A (en) | 1990-07-24 | 1993-06-29 | Research Corporation Technologies, Inc. | Method of preparing hydrated lime |
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US5173279A (en) | 1990-11-21 | 1992-12-22 | Lhoist Recherche Et Developpement S.A. | Method and composition for treating flue or exhaust gases utilizing modified calcium hydroxide |
BE1009692A3 (en) | 1995-10-19 | 1997-07-01 | Lhoist Rech & Dev Sa | PARTICLE Ca (OH) 2. |
US6126910A (en) | 1997-10-14 | 2000-10-03 | Wilhelm; James H. | Method for removing acid gases from flue gas |
US6797035B2 (en) * | 2002-08-30 | 2004-09-28 | Ada Environmental Solutions, Llc | Oxidizing additives for control of particulate emissions |
US6803025B2 (en) | 2002-12-05 | 2004-10-12 | Frank B. Meserole | Process for removing SO3/H2SO4 from flue gases |
JP2005087893A (en) * | 2003-09-18 | 2005-04-07 | Japan Science & Technology Agency | New desulfurization agent for dry desulfurization process |
BE1016661A3 (en) * | 2005-06-28 | 2007-04-03 | Lhoist Rech & Dev Sa | PULVERULENT LIME COMPOSITION, METHOD FOR MANUFACTURING THE SAME, AND USE THEREOF |
DK1967276T3 (en) | 2007-03-05 | 2019-08-12 | General Electric Technology Gmbh | A METHOD OF DETERMINING THE DUST LOAD OF AN ELECTROSTATIC FILTER AND A METHOD AND DEVICE TO CONTROL THE BANKING OF AN ELECTROSTATIC FILTER |
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WO2015009330A1 (en) * | 2013-07-18 | 2015-01-22 | Novinda Corporation | Carbonate modified compositions for reduction of flue gas resistivity |
WO2015119880A1 (en) | 2014-02-04 | 2015-08-13 | Novinda Corporation | Flue-gas treatment aid |
TW201609222A (en) * | 2014-06-04 | 2016-03-16 | 首威公司 | Stabilization of sodic fly ash using a water-soluble source of silicate and a material containing calcium and/or magnesium |
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- 2018-07-24 BE BE2018/5534A patent/BE1025964B1/en not_active IP Right Cessation
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- 2018-07-24 KR KR1020207003628A patent/KR20200035038A/en unknown
- 2018-07-24 CA CA3070255A patent/CA3070255A1/en not_active Abandoned
- 2018-07-24 JP JP2020502988A patent/JP2020528004A/en active Pending
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2020
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BE1025964A1 (en) | 2019-08-23 |
SG11202000483QA (en) | 2020-02-27 |
WO2019020613A1 (en) | 2019-01-31 |
BR112020001082A2 (en) | 2020-07-21 |
CN110997129A (en) | 2020-04-10 |
CL2020000143A1 (en) | 2020-05-29 |
BE1025964B1 (en) | 2019-08-28 |
KR20200035038A (en) | 2020-04-01 |
CO2020000463A2 (en) | 2020-05-05 |
EP3658275A1 (en) | 2020-06-03 |
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