EP2150337A2 - Sorbent bodies comprising activated carbon, processes for making them, and their use - Google Patents
Sorbent bodies comprising activated carbon, processes for making them, and their useInfo
- Publication number
- EP2150337A2 EP2150337A2 EP08754390A EP08754390A EP2150337A2 EP 2150337 A2 EP2150337 A2 EP 2150337A2 EP 08754390 A EP08754390 A EP 08754390A EP 08754390 A EP08754390 A EP 08754390A EP 2150337 A2 EP2150337 A2 EP 2150337A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- sulfur
- sorbent
- metal catalyst
- sorbent body
- mercury
- 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.)
- Withdrawn
Links
- 239000002594 sorbent Substances 0.000 title claims abstract description 288
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 238000000034 method Methods 0.000 title claims abstract description 64
- 230000008569 process Effects 0.000 title claims abstract description 44
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 183
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 157
- 231100000701 toxic element Toxicity 0.000 claims abstract description 55
- 239000012530 fluid Substances 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 39
- 239000003546 flue gas Substances 0.000 claims abstract description 34
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003245 coal Substances 0.000 claims abstract description 14
- 238000002485 combustion reaction Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 216
- 239000002184 metal Substances 0.000 claims description 213
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 186
- 239000003054 catalyst Substances 0.000 claims description 164
- 229910052717 sulfur Inorganic materials 0.000 claims description 156
- 239000011593 sulfur Substances 0.000 claims description 156
- 239000000463 material Substances 0.000 claims description 150
- 239000000203 mixture Substances 0.000 claims description 130
- 239000011159 matrix material Substances 0.000 claims description 66
- 239000011148 porous material Substances 0.000 claims description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 239000011256 inorganic filler Substances 0.000 claims description 30
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 150000004763 sulfides Chemical class 0.000 claims description 23
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 21
- 229910052785 arsenic Inorganic materials 0.000 claims description 21
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 21
- 229910052793 cadmium Inorganic materials 0.000 claims description 21
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- 229910052711 selenium Inorganic materials 0.000 claims description 21
- 239000011669 selenium Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 20
- 229910052725 zinc Inorganic materials 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 19
- 229910052804 chromium Inorganic materials 0.000 claims description 19
- 239000011651 chromium Substances 0.000 claims description 19
- 229910017052 cobalt Inorganic materials 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 229910052788 barium Inorganic materials 0.000 claims description 13
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 13
- 229910010272 inorganic material Inorganic materials 0.000 claims description 13
- 239000011147 inorganic material Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 229910052716 thallium Inorganic materials 0.000 claims description 13
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052787 antimony Inorganic materials 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052790 beryllium Inorganic materials 0.000 claims description 12
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000005011 phenolic resin Substances 0.000 claims description 11
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- 235000013312 flour Nutrition 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 150000002602 lanthanoids Chemical class 0.000 claims description 7
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 229910015451 Mo2S3 Inorganic materials 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 239000011294 coal tar pitch Substances 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 239000011301 petroleum pitch Substances 0.000 claims description 2
- 239000002952 polymeric resin Substances 0.000 claims description 2
- 241000209140 Triticum Species 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000003464 sulfur compounds Chemical class 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 39
- 238000009826 distribution Methods 0.000 description 30
- 238000001179 sorption measurement Methods 0.000 description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 23
- 238000001125 extrusion Methods 0.000 description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 20
- 238000001994 activation Methods 0.000 description 20
- -1 lanthanoids) Chemical class 0.000 description 18
- 239000003921 oil Substances 0.000 description 18
- 235000019198 oils Nutrition 0.000 description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 17
- 238000003763 carbonization Methods 0.000 description 17
- 230000004913 activation Effects 0.000 description 16
- 239000000835 fiber Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 241000264877 Hippospongia communis Species 0.000 description 11
- 229910052878 cordierite Inorganic materials 0.000 description 11
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 11
- 238000011065 in-situ storage Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 210000002421 cell wall Anatomy 0.000 description 9
- 229920003043 Cellulose fiber Polymers 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 230000001737 promoting effect Effects 0.000 description 8
- 229920003091 Methocel™ Polymers 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 241000894007 species Species 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 229920003987 resole Polymers 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 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 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 4
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 229910052863 mullite Inorganic materials 0.000 description 4
- 229910052574 oxide ceramic Inorganic materials 0.000 description 4
- 239000011224 oxide ceramic Substances 0.000 description 4
- 239000000075 oxide glass Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000011819 refractory material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 244000144992 flock Species 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 244000098338 Triticum aestivum Species 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01D53/34—Chemical or biological purification of waste gases
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Definitions
- This disclosure relates to sorbent bodies comprising activated carbon, processes for making them, and methods of using them.
- the sorbent bodies can be used to remove toxic elements from a fluid, such as from a gas stream.
- the sorbent bodies may be used to remove elemental mercury or mercury in an oxidized state from a coal combustion flue gas.
- the ACI process includes injecting activated carbon powder into the flue gas stream and using a fabric fiber or electrostatic precipitator to collect the activated carbon powder that has adsorbed mercury.
- ACI technologies require a high carbon to mercury ratio to achieve the desired mercury removal level (> 90%), which results in a high cost for sorbent material.
- the high carbon to mercury ratio suggests that ACI does not utilize the mercury sorption capacity of carbon powder efficiently.
- the commercial value of fly ash is sacrificed due to its mixing with contaminated activated carbon powder.
- a system with two separate powder collectors and injecting activated carbon sorbent between the first collector for fly ash and the second collector, or a baghouse, for activated carbon powder may be used.
- a baghouse with high collection efficiency may be installed in the power plant facilities. However, these measures are costly and may be impractical, especially for small power plants.
- bituminous coal-fired plants may be able to remove 90% mercury using a wet scrubber combined with NO x and/or SO 2 control technologies.
- Mercury emission control can also be achieved as a co-benefit of particulate emission control.
- Chelating agents may be added to a wet scrubber to sequestrate the mercury from emitting again.
- a chelating agent adds to the cost due to the problems of corrosion of the metal scrubber equipment and treatment of chelating solution.
- Elemental mercury is the dominant mercury species in the flue gas of sub-bituminous coal or lignite coal, and a wet scrubber is not effective for removal of elemental mercury unless additional chemicals are added to the system. It is undesirable, however, to add additional potentially environmentally hazardous material into the flue gas system.
- Certain industrial gases such as syngas and combustion flue gas, may contain toxic elements such as cadmium, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic or selenium, in addition to mercury. Like mercury, these toxic elements may exist in elemental form or in a chemical compound comprising the element. It is highly desired that the presence of one or more of these toxic elements be substantially reduced before a syngas is supplied for industrial and/or residential use or before a gas is emitted to the atmosphere.
- toxic elements such as cadmium, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic or selenium, in addition to mercury. Like mercury, these toxic elements may exist in elemental form or in a chemical compound comprising the element. It is highly desired that the presence of one or more of these toxic
- Embodiments of the invention relate to sorbent bodies comprising activated carbon, processes for making them, and methods of using them.
- the sorbent bodies can be used to remove toxic elements from a fluid, such as from a gas stream.
- the sorbent bodies may be used to remove elemental mercury or mercury in an oxidized state from a coal combustion flue gas.
- Embodiments of the invention have one or more of the following advantages. Sorbent bodies of the invention comprising activated carbon having high specific surface area and a large number of active sites capable of sorbing or promoting sorption of a toxic element can be produced and used effectively for the sorption of toxic elements, including arsenic, cadmium, mercury and selenium.
- the sorbent bodies of certain embodiments of the invention are effective for sorption of not just oxidized mercury, but also elemental mercury. Further, the sorbent bodies according to certain embodiments of the invention are effective in removing mercury from flue gases with high and low concentrations of HCl alike. Sorbent bodies according to certain embodiments of the invention are also effective in removing mercury from flue gases with high concentration of SO 3 .
- FIG. 1 is a diagram comparing the mercury removal capability of a tested sample of a sorbent comprising an in-situ extruded metal catalyst according to the invention and a sorbent which comprises impregnated metal but no in-situ extruded metal catalyst over time.
- FIG. 2 is a diagram showing the inlet mercury concentration (CHgO) and outlet mercury concentration (CHgI) of a sorbent body according to one embodiment of the invention at various inlet mercury concentrations.
- FIG. 3 is an SEM image of part of a cross-section of a sorbent body according to one embodiment of the invention comprising in-situ extruded metal catalyst.
- FIG. 4 is an SEM image of part of a cross-section of a comparative sorbent body comprising post-activation impregnated metal catalyst.
- indefinite article “a” or “an” means “at least one,” and should not be limited to “only one” unless explicitly indicated to the contrary.
- reference to “a metal catalyst” includes embodiments having one, two or more metal catalysts, unless the context clearly indicates otherwise.
- a “wt%” or “weight percent” or “percent by weight” of a component is based on the total weight of the composition or article in which the component is included. As used herein, all percentages are by weight unless indicated otherwise. All ppm with respect to gases are by volume unless indicated otherwise.
- sulfur as used herein includes sulfur element at all oxidation states, including, inter alia, elemental sulfur (0), sulfate (+6), sulfite (+4), and sulfide (-2).
- sulfur thus includes sulfur in any oxidation state, as elemental sulfur or in a chemical compound or moiety comprising sulfur.
- the weight percent of sulfur is calculated on the basis of elemental sulfur, with any sulfur in other states converted to elemental state for the purpose of calculation of the total amount of sulfur in the material.
- metal catalyst includes any metal element in any oxidation state, as elemental metal or in a chemical compound or moiety comprising the metal, which is in a form that promotes the removal of a toxic element (such as cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic or selenium, or such as cadmium, mercury, arsenic or selenium) from a fluid in contact with a sorbent body of the invention.
- a toxic element such as cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic or selenium, or such as cadmium, mercury, arsenic or selenium
- Metal elements can include alkali metals, alkaline earth metals, transition metals, rare earth metals (including lanthanoids), and other metals such as aluminum, gallium, indium, tin, lead, thallium and bismuth.
- the weight percent of metal catalyst is calculated on the basis of elemental metal, with any metal in other states converted to elemental state for the purpose of calculation of the total amount of metal catalyst in the material.
- Metal elements present in an inert from, such as in an inorganic filler compound, are not considered metal catalysts and do not contribute to the weight percent of a metal catalyst.
- the amount of sulfur or metal catalyst may be determined using any appropriate analytical technique, such as mass spectroscopy.
- in-situ extruded is meant that the relevant material, such as sulfur and/or metal catalyst, is introduced into the material by incorporating at least part of the source material thereof into the batch mixture material, such that the formed body comprises the source materials incorporated therein.
- Distribution of sulfur, metal catalyst or other materials across a cross-section of the sorbent body, or an extrusion batch mixture body, or a batch mixture material of the invention can be measured by various techniques, including, but not limited to, microprobe,
- XPS X-ray photoelectron spectroscopy
- laser ablation combined with mass spectroscopy
- Target test areas of the cross-section of at least 500 ⁇ m x 500 ⁇ m size are chosen if the total cross-section is larger than 500 ⁇ m x 500 ⁇ m.
- the total number of target test areas is p (a positive integer).
- Each target test area is divided by a grid into multiple separate 20 ⁇ m x 20 ⁇ m zones. Only zones having an effective area (defined below) not less than 40 ⁇ m 2 are considered and those having an effective area lower than 40 ⁇ m 2 are discarded in the data processing below.
- the total effective area (ATE) of all the square sample zones of the target test area is: where ae(i) is the effective area of zone i, and n is the total number of the square sample zones in the target test area, where ae(i) > 40 ⁇ m 2 .
- Area of individual square zone ae(i) in square micrometers is calculated as follows: where av(i) is the total area in square micrometers of any voids, pores or free space larger than 10 ⁇ m 2 within square zone i.
- CON(max) The arithmetic average concentration of the 5% of all n zones in the target test area having the highest concentrations is CON(max).
- INT(0.05x n) where INT(0.05xn) is the smallest integer larger than or equal to 0.05xn.
- INT(X) yields the smallest integer larger than or equal to X.
- the distribution thereof has the following feature: CON(av)/CON(min) ⁇ 30, and C0N(max)/C0N(av) ⁇ 30. In certain other embodiments, it is desired that CON(av)/CON(min) ⁇ 20, and C0N(max)/C0N(av) ⁇ 20. In certain other embodiments, it is desired that CON(av)/CON(min) ⁇ 15, and CON(max)/CON(av) ⁇ 15.
- CON(av)/CON(min) ⁇ 10 it is desired that CON(max)/CON(av) ⁇ 10. In certain other embodiments, it is desired that CON(av)/CON(min) ⁇ 5, and CON(max)/CON(av) ⁇ 5. In certain other embodiments, it is desired that CON(av)/CON(min) ⁇ 3, and CON(max)/CON(av) ⁇ 3. In certain other embodiments, it is desired that CON(av)/CON(min) ⁇ 2, and CON(max)/CON(av) ⁇ 2.
- the distribution thereof according to the Distribution Characterization Method satisfies the following: in each target test area, for all CON(m) where O.ln ⁇ m ⁇ 0.9n: 0.5 ⁇ CON(m)/CON(av) ⁇ 2.
- the distribution of the relevant material (e.g., sulfur, metal catalyst, and the like) with respect to all p target test areas has the following feature: for all CONA V(k) where O.lp ⁇ k ⁇ 0.9p: 0.5 ⁇ CONAV(k)/CONAV(av) ⁇ 2; in certain embodiments, 0.6 ⁇ CONAV(k)/CONAV(av) ⁇ 1.7. In certain other embodiments, it is desired that 0.7 ⁇ CONAV(k)/CONAV(av) ⁇ 1.4.
- One aspect of the invention is a sorbent body comprising: an activated carbon matrix; sulfur, in any oxidation state, as elemental sulfur or in a chemical compound or moiety comprising sulfur; and a metal catalyst, in any oxidation state, as elemental metal or in a chemical compound or moiety comprising the metal; wherein the metal catalyst is distributed throughout the activated carbon matrix.
- sulfur may be distributed throughout the activated carbon matrix.
- the metal catalyst and/or sulfur is essentially homogeneously distributed throughout the activated carbon matrix, hi some embodiments, at least a portion of the metal catalyst is chemically bound to at least a portion of the sulfur.
- one compound comprising a metal catalyst and sulfur may provide both the sulfur and metal catalyst in the sorbent body.
- sulfur or metal catalyst refers to some or all of the sulfur or metal catalyst content in the sorbent body.
- at least a portion of sulfur is chemically bound to at least a portion of carbon in the activated carbon matrix.
- At least a portion of the sulfur, of the metal catalyst, or of both the sulfur and metal catalyst is in a state capable of chemically bonding with cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic or selenium.
- at least a portion of the sulfur can be in a state capable of chemically bonding with mercury.
- the sorbent bodies of this and other embodiments described herein may, for example, be adapted for removing mercury and other toxic elements from a fluid stream such as a flue gas stream resulting from coal combustion or waste incineration or syngas produced during a coal gasification process.
- a fluid stream such as a flue gas stream resulting from coal combustion or waste incineration or syngas produced during a coal gasification process.
- gas streams can contain various amounts of mercury and/or other toxic elements such as cadmium, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic and selenium.
- any toxic element such as mercury
- the sorbent body comprises a metal catalyst adapted for promoting the removal of arsenic, cadmium, mercury and/or selenium from a fluid stream to be treated.
- the sorbent bodies and material of certain embodiments of the invention are particularly effective for removing mercury at elemental state in a flue gas stream. This is particularly advantageous compared to certain other technology that is usually less effective in removing elemental mercury.
- the sorbent bodies of the invention may take various shapes.
- the sorbent body may be a powder, pellets, and/or extruded monolith.
- the sorbent bodies of the invention may be incorporated in a fixed sorbent bed through which a fluid stream to be treated may flow.
- any fixed bed through which the gas stream passes has a low pressure- drop. To that end, it is desired that sorbent pellets packed in the fixed bed allow for sufficient gas passageways.
- the sorbent body is in the form of a monolith.
- the sorbent body is in the form of a monolithic honeycomb with a plurality of channels through which gas or liquid may pass.
- the sorbent body of the invention is in the form of extruded monolithic honeycomb having multiple channels. Cell density of the honeycomb can be adjusted during the extrusion process to achieve various degree of pressure-drop when in use.
- Cell density of the honeycomb can range from 25 to 500 cells-inch 2 (3.88 to 77.5 cells-cm “2 ) in certain embodiments, from 50 to 200 cells-inch “2 (7.75 to 31.0 cells-cm “2 ) in certain other embodiments, and from 50 to 100 cells-inch "2 (7.75 to 15.5 cells-cm “2 ) in certain other embodiments.
- the thickness of the cell walls ranges from 1 mil to 50 mil, for example from 10 mil to 30 mil. To allow for a more intimate contact between the gas stream and the sorbent body material, it is desired in certain embodiments that part of the channels are plugged at one end of the sorbent body, and part of the channels are plugged at the other end of the sorbent body.
- the plugged and/or unplugged channels form a checkerboard pattern.
- the reference end one end but not the opposite end of the sorbent body
- at least a majority of the channels (preferably all in certain other embodiments) immediately proximate thereto (those sharing at least one wall with the channel of concern) are plugged at the other end of the sorbent body but not on the reference end.
- Multiple honeycombs can be stacked in various manners to form actual sorbent beds having various sizes, service duration, and the like, to meet the needs of differing use conditions.
- the "activated carbon matrix,” as used herein, means a network formed by interconnected carbon atoms and/or particles.
- the activated carbon matrix in the sorbent bodies of the invention is in the form of an uninterrupted and continuous body.
- the matrix comprises wall structure defining a plurality of pores.
- the activated carbon matrix, along with sulfur and the metal catalyst, can provide the backbone structure of the sorbent body.
- the large cumulative areas of the pores in the activated carbon matrix provide a plurality of sites where mercury sorption can occur directly, or where sulfur and the metal catalyst can be distributed, which further promote mercury sorption. It is to be noted that the pores defined by the activated carbon matrix can be different from the pores actually present in the sorbent body.
- the sorbent body comprises from 50% to 97% by weight of activated carbon, in certain embodiments from 60% to 97% or from 85% to 97%. In other embodiments, the sorbent body comprises at least 50% by weight of activated carbon, for example at least 60% by weight, at least 70 % by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, or at least 97% by weight of activated carbon. Higher concentrations of activated carbon usually lead to higher porosity if the same level of carbonization and activation were used during the process of making the sorbent body when made according to the processes described herein.
- the pores defined by the activated carbon matrix can be divided into two categories: nanoscale pores having a diameter of less than or equal to 10 run, and microscale pores having a diameter of higher than 10 nm.
- the activated carbon matrix defines a plurality of nanoscale pores.
- the metal catalyst or sulfur may, for example, be present on the wall surface of at least part of the nanoscale pores.
- the activated carbon matrix further defines a plurality of microscale pores.
- Pore size and distribution thereof in the sorbent bodies can be measured by using techniques available in the art, such as, e.g., nitrogen adsorption. Both the surfaces of the nanoscale pores and the microscale pores together provide the overall high specific area of the sorbent body of the invention. In certain embodiments, the wall surfaces of the nanoscale pores constitute at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% of the specific area of the sorbent body. [0048] The sorbent bodies of the invention may have large specific surface areas.
- the sorbent bodies have specific areas ranging from 50 to 2000 m 2 g ', 200 to 2000 m 2 g ⁇ 400 to 1500 m 2 g ', 100 to 1800 m 2 -g " ', 200 to 1500 m 2 g " ', or 300 to 1200 m -g " .
- Higher specific area of the sorbent body can provide more active sites in the material for the sorption of toxic elements.
- the specific area of the sorbent body is quite high, e.g., higher than 2000 m ⁇ g "1 , the sorbent body becomes quite porous and the mechanical integrity of the sorbent body may suffer. This could be undesirable for certain applications where the strength of the sorbent body may need to meet certain threshold requirements.
- the metal catalyst included within embodiments of the invention may promote the removal of one or more toxic elements such as cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic or selenium from a fluid in contact with the sorbent body, any of which may be in any oxidation state and may be in elemental form or in a chemical compound comprising the element.
- toxic elements such as cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic or selenium
- any such metal catalyst capable of promoting the removal of toxic elements or compounds (also referred to herein as “abatement” of toxic elements or compounds), including mercury, arsenic, cadmium or selenium, from a fluid, such as a fluid stream to be treated upon contacting, can be included in the sorbent body of the invention.
- the terms "removal” and “abatement” in this context are used interchangeably herein. Furthermore, those terms would be understood as covering reducing the presence of the toxic elements by a matter of degree in a fluid, i.e. by a certain percentage, and are not limited to complete removal or abatement of the toxic elements.
- the metal catalyst can function in one or more of the following ways to promote the removal (or abatement) of toxic elements from a fluid in contact with the sorbent body: (i) temporary or permanent chemical sorption (e.g., via covalent and/or ionic bonds) of a toxic element; (ii) temporary or permanent physical sorption of a toxic element; (iii) catalyzing the reaction/sorption of a toxic element with other components of the sorbent body; (iv) catalyzing the reaction of a toxic element with the ambient atmosphere to convert it from one form to another; (v) trapping a toxic element already sorbed by other components of the sorbent body; and (vi) facilitating the transfer of a toxic element to the active sorbing sites.
- the metal catalyst is provided in a form selected from: (i) halides and oxides of alkali and alkaline earth metals; (ii) precious metals and compounds thereof; (iii) oxides, sulfides, and salts of vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, silver, tungsten and lanthanoids; and (iv) combinations and mixtures of two or more of (i), (ii) and (iii).
- the metal catalyst may be provided in a form selected from: (i) oxides, sulfides and salts of manganese; (ii) oxides, sulfides and salts of iron; (iii) combinations of (i) and KI; (iv) combinations of (ii) and KI; and (v) mixtures and combinations of any two or more of (i), (ii), (iii) and (iv).
- the sorbent body comprises an alkaline earth metal hydroxide as a metal for promoting the removal of toxic elements, such as Ca(OH) 2 .
- Precious metals (Ru, Th, Pd, Ag, Re, Os, Ir, Pt and Au) and transition metals and compounds thereof are exemplary metal catalysts.
- Further non-limiting metal catalysts include alkali and alkaline earth halides, hydroxides or oxides; and oxides, sulfides, and salts of vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, silver, tungsten, and lanthanoids.
- the metal catalysts can exist at any valency.
- iron it may be present at +3, +2 or 0 valencies or as mixtures of differing valencies, and can be present as metallic iron (0), FeO, Fe 2 O 3 , Fe 3 O 8 , FeS, FeCl 2 , FeCl 3 , FeSO 4 , and the like.
- manganese it may be present at +4, +2 or 0 valencies or as mixtures of differing valences, and can be present as metallic manganese (0), MnO, MnO 2 , MnS, MnCl 2 , MnCl 4 , MnSO 4 , and the like.
- the metal catalyst is not in the form of an oxide.
- the sorbent body comprises at least one metal catalyst that is not in the form of an oxide.
- the metal catalyst is in a form selected from: alkali halides; and oxides, sulfides and salts of manganese and iron.
- the metal catalyst is in a form selected from: combination of KI and oxides, sulfides and salts of manganese; combination of KI and oxides, sulfides and salts of iron; or a combination of KI, oxides, sulfides and salts of manganese and iron.
- the sorbent body comprises an alkaline earth metal hydroxide as a metal for promoting the removal of toxic elements, such as Ca(OH) 2 .
- the metal catalyst is an alkali metal such as lithium, sodium, or potassium.
- the metal catalyst is an alkaline earth metal such as magnesium, calcium, or barium.
- the metal catalyst is a transition metal, such as palladium, platinum, silver, gold, manganese, or iron. In other embodiments, the metal catalyst is a rare earth metal such as cerium. In some embodiments, the metal catalyst is in elemental form. In other embodiments, the metal catalyst is a metal sulfide. In other embodiments, the metal catalyst is a transition metal sulfide or oxide. In yet other embodiments, the sorbent body comprises at least on catalyst other than an alkali metal, an alkaline earth metal, or transition metal.
- the sorbent body comprises at least one catalyst other than sodium, other than potassium, other than magnesium, other than calcium, other than aluminum, other than titanium, other than zirconium, other than chromium, other than magnesium, other than iron and/or other than zinc.
- the sorbent body comprises at least one metal catalyst other than aluminum, vanadium, iron, cobalt, nickel, copper, or zinc, either in elemental form or as sulfates.
- the amount of the metal catalyst present in the sorbent bodies can be selected, depending on the particular metal catalyst used, and application for which the sorbent bodies are used, and the desired toxic element removing capacity and efficiency of the sorbent body.
- the amount of the metal catalyst ranges from 1% to 20% by weight, in certain other embodiments from 2% to 18%, in certain other embodiments from 5% to 15%, in certain other embodiments from 5% to 10%.
- the sorbent body comprises from 1% to 25% by weight of the metal catalyst (in certain embodiments from 1% to 20%, from 1% to 15%, from 3% to 10%,
- the metal catalyst is distributed throughout the activated carbon matrix. If multiple metal catalysts are present in these embodiments, at least one of them is distributed throughout the activated carbon matrix.
- distributed throughout the activated carbon matrix is meant that the relevant specified material (metal catalyst, sulfur, and the like) is present not just on the external surface of the sorbent body or cell walls, but also deep inside the sorbent body.
- the presence of the specific metal catalyst can be, e.g.: (i) on the wall surfaces of nanoscale pores defined by the activated carbon matrix; (ii) on the wall surfaces of microscale pores defined by the activated carbon matrix; (iii) submerged in the wall structure of the activated carbon matrix; (iv) partly embedded in the wall structure of the activated carbon matrix; (v) partly fill and/or block some pores defined by the activated carbon matrix; and (vi) completely fill and/or block some pores defined by the activated carbon matrix.
- the metal catalyst(s) and/or other components distributed in the activated carbon matrix actually forms part of the wall structure of the pores of the sorbent body.
- multiple metal catalysts are present and all of them are distributed throughout the activated carbon matrix. However, it is not required that all metal catalysts are distributed throughout the activated carbon matrix. Thus, in certain embodiments, multiple metal catalysts are present, with at least one of them distributed throughout the activated carbon matrix, and at least one of them distributed essentially mainly on the external surface area and/or cell wall surface of the sorbent body, and/or within a thin layer beneath the external surface area and/or cell wall surface. In certain embodiments, at least a portion of the metal catalysts may be chemically bonded with other components of the sorbent body, such as carbon or the sulfur. In certain other embodiments, at least a portion of the metal catalysts may be physically bonded with the activated carbon matrix or other components.
- the metal catalyst is present in the sorbent body in the form of particles having nanoscale or microscale size.
- Distribution of a metal catalyst in the sorbent body or other body or material according to the invention can be measured and characterized by the Distribution Characterization Method described supra.
- the distribution of a metal catalyst has the following feature: in each target test area: CON(av)/CON(min) ⁇ 30, and CON(max)/CON(av) ⁇ 30. In certain other embodiments, it is desired that CON(av)/CON(min) ⁇ 20, and CON(max)/CON(av) ⁇ 20.
- At least one metal catalyst is homogeneously distributed throughout the activated carbon matrix according to the Distribution Characterization Method described supra.
- CON(m) where O.ln ⁇ m ⁇ 0.9n: 0.5 ⁇ CON(m)/CON(av) ⁇ 2.
- the distribution of the relevant material (e.g., sulfur, metal catalyst, and the like) with respect to all p target test areas has the following feature: for all CONAV(k) where O.lp ⁇ k ⁇ 0.9p: 0.5 ⁇ CONAV(k)/CONAV(av) ⁇ 2; in certain embodiments, 0.6 ⁇ CONAV(k)/CONAV(av) ⁇ 1.7. In certain other embodiments, it is desired that 0.7 ⁇ CONAV(k)/CONAV(av) ⁇ 1.4.
- the metal catalyst is present on a majority of the wall surfaces of the microscale pores. In certain other embodiments of the invention, the metal catalyst is present on at least 75%, at least 90% or at least 95% of the wall surfaces of the microscale pores.
- the metal catalyst is present on at least 20%, at least 40%, at least 50%, at least 75%, or at least 85% of the wall surfaces of the nanoscale pores, hi certain embodiments, a majority of the specific area of the sorbent body is provided by the wall surfaces of the nanoscale pores, hi these embodiments, it is desired that a higher percentage of the wall surface of the nanoscale pores has the metal catalyst distributed thereon.
- the sorbent bodies of the invention comprise sulfur.
- the amount of sulfur present in the sorbent bodies can be selected depending on the particular metal catalyst used, and application for which the sorbent bodies are used, and the desired toxic element removing capacity and efficiency of sorbent body.
- the sorbent body comprises from 1% to 20% by weight of sulfur (in certain embodiments from 1% to 15%, from 3% to 8%, from 2% to 10%, from 0.1 to 5%, or from 2 to 5%).
- Sulfur may be present in the form of elemental sulfur (0 valency), sulfides (-2 valency, e.g.), sulfite (+4 valency, e.g.), sulfate (+6 valency, e.g.).
- sulfur is not present as a sulfate, or, a sulfate is not the only source of sulfur in the sorbent body. It is desired that at least part of the sulfur is present in a valency capable of chemically bonding with the toxic element to be removed from a fluid stream, such as with mercury. To that end, it is desired that at least part of the sulfur is present at -2 and/or zero valency.
- At least a portion of the sulfur may be chemically or physically bonded to the wall surface of the activated carbon matrix. At least a portion of the sulfur may be chemically or physically bonded to the metal catalyst, as indicated supra, e.g., in the form of a sulfide (FeS, MnS, Mo 2 S 3 , CuS and the like).
- At least a portion of the sulfur is at zero valency.
- at least 10% of the sulfur on the surface of the walls of the pores of the activated carbon matrix may be essentially at zero valency when measured by XPS.
- at least a portion of the sulfur is not at zero valency.
- the sorbent bodies comprise a portion of sulfur at zero valency and a portion of sulfur not at zero valency.
- the sorbent bodies comprise elemental sulfur as well as sulfur present in chemical compound comprising sulfur, such as a metal sulfide.
- At least 40%, at least 50%, at least 60%, or at least 70% by mole of the sulfur in the sorbent body be at zero valency.
- at least 10%, at least 20%, at least 30%, at least 40%, at least 50% or at least 60% of the sulfur on the surface of the walls of the pores is essentially at zero valency, when measured by XPS.
- sorbent bodies of activated carbon, sulfur and metal catalyst can be effective for removing arsenic, cadmium as well as selenium, in addition to mercury, from a gas stream.
- sorbent bodies comprising elemental sulfur tend to have higher mercury removal capability than those without elemental sulfur but with essentially the same total sulfur concentration.
- sulfur is distributed throughout the activated carbon matrix.
- distributed throughout the activated carbon matrix is meant that sulfur is present not just on the external surface of the sorbent body or cell walls, but also deep inside the sorbent body.
- sulfur can be, e.g.: (i) on the wall surfaces of nanoscale pores; (ii) on the wall surfaces of microscale pores; (iii) submerged in the wall structure of the activated carbon matrix; and (iv) partly embedded in the wall structure of the activated carbon matrix.
- sulfur actually forms part of the wall structure of the pores of the sorbent body. Therefore, in certain embodiments, some of sulfur may be chemically bonded (covalently and/or ionically) with other components of the sorbent body, such as carbon or the metal catalyst. In certain other embodiments, some of the sulfur may be physically bonded with the activated carbon matrix or other components. Still in certain other embodiments, some of the sulfur is present in the sorbent body in the form of particles having nanoscale or microscale size.
- Distribution of sulfur in the sorbent body or other body or material according to the present invention can be measured and characterized by the Distribution Characterization Method described supra.
- the distribution of sulfur in any target test area has the following feature: CON(max)/CON(min) > 100. In certain other embodiments: CON(max)/ CON(min) > 200. In certain other embodiments: CON(max) / CON(min) > 300. In certain other embodiments: CON(max) / CON(min) > 400. In certain other embodiments: CON(max) / C0N(min) > 500. In certain other embodiments: C0N(max) / C0N(min) > 1000. In certain other embodiments: CON(max) /CON(av) > 50. In certain other embodiments: CON(max) / CON(av) > 100.
- the distribution thereof has the following feature: CON(av)/CON(min) ⁇ 30. In certain other embodiments: CON(av)/CON(min) ⁇ 20. In certain other embodiments: CON(av)/CON(min) ⁇ 15. In certain other embodiments: CON(av)/CON(min) ⁇ 10. In certain other embodiments: C0N(av)/C0N(min) ⁇ 5. In certain other embodiments: C0N(av)/C0N(min) ⁇ 3. In certain other embodiments: CON(av)/CON(min) ⁇ 2.
- the distribution of sulfur has the following feature: in each target test area, CON(av)/CON(min) ⁇ 30, and CON(max)/CON(av) ⁇ 30. In certain other embodiments, it is desired that CON(av)/CON(min) ⁇ 20, and CON(max)/CON(av) ⁇ 20. In certain other embodiments, it is desired that CON(av)/CON(min) ⁇ 15, and CON(max)/CON(av) ⁇ 15. In certain other embodiments, it is desired that CON(av)/CON(min) ⁇ 10, and CON(max)/CON(av) ⁇ 10.
- sulfur is homogeneously distributed throughout the activated carbon matrix according to the Distribution Characterization Method described supra. Thus: in each target test area, for all CON(m) where O.ln ⁇ m ⁇ 0.9n: 0.5 ⁇ C0N(m)/C0N(av) ⁇ 2.
- CON(m) where 0.05n ⁇ m ⁇ 0.95n 0.5 ⁇ C0N(m)/C0N(av) ⁇ 2; in certain embodiments, 0.6 ⁇ CON(m)/CON(av) ⁇ 1.7. In certain other embodiments, it is desired that 0.7 ⁇ CON(m)/CON(av) ⁇ 1.4. In certain other embodiments, it is desired that 0.8 ⁇ CON(m)/CON(av) ⁇ 1.2. In certain other embodiments, it is desired that 0.9 ⁇ CON(m)/CON(av) ⁇ 1.1.
- the distribution of the relevant material (e.g., sulfur, metal catalyst, and the like) with respect to all p target test areas has the following feature: for all CONA V(k) where O.lp ⁇ k ⁇ 0.9p: 0.5 ⁇ CONAV(k)/CONAV(av) ⁇ 2; in certain embodiments, 0.6 ⁇ CONAV(k)/CONAV(av) ⁇ 1.7. In certain other embodiments, it is desired that 0.7 ⁇ CONAV(k)/CONAV(av) ⁇ 1.4.
- sulfur is present on a majority of the wall surfaces of the microscale pores. In certain other embodiments, sulfur is present on at least 75%, at least 90%, or at least 95% of the wall surfaces of the microscale pores.
- sulfur is present on at least 20%, at least 30%, at least 40%, at least 50%, at least 75%, or at least 85% of the wall surfaces of the nanoscale pores.
- a majority of the specific area of the sorbent body is provided by the wall surfaces of the nanoscale pores.
- it is desired that a high percentage (such as at least 40%, at least 50%, or at least 60%) of the wall surface of the nanoscale pores has sulfur distributed thereon.
- the sorbent body may further comprise inorganic filler material.
- any metal element in the inorganic filler material is chemically and physically inert.
- the metal element included in the inorganic filler does not function in one or more of the following ways to promote the removal of the toxic elements from a fluid in contact with a sorbent body of the invention: (i) temporary or permanent chemical sorption (e.g., via covalent and/or ionic bonds) of a toxic element; (ii) temporary or permanent physical sorption of a toxic element; (iii) catalyzing the reaction/sorption of a toxic element with other components of the sorbent body; (iv) catalyzing the reaction of a toxic element with the ambient atmosphere to convert it from one form to another; (v) trapping a toxic element already sorbed by other components of the sorbent body; and (vi) facilitating the transfer of a toxic element to the active sorbing sites.
- Inorganic fillers may be included for the purpose of, inter alia, reducing cost, and improving physical (coefficient of thermal expansion; modulus of rupture, e.g.); or chemical properties (water resistance; high temperature resistance; corrosion-resistance, e.g.) of the sorbent body.
- Such inorganic filler can be an oxide glass, oxide ceramic, or certain refractory materials.
- Non-limiting examples of inorganic fillers include: silica; alumina; zircon; zirconia; mullite; cordierite; refractory metals; and the like.
- the inorganic fillers are per se porous.
- the inorganic filler may be distributed throughout the sorbent body.
- the inorganic filler may be present in the form of minuscule particles distributed in the sorbent body.
- the sorbent body may comprise, e.g., up to 50% by weight of inorganic filler, in certain other embodiments up to 40%, in certain other embodiments up to 30%, in certain other embodiments up to 20%, in certain other embodiments up to 10%.
- inorganic fillers in and of themselves are porous and contribute partly to the high specific area of the sorbent body.
- Inorganic fillers having specific surface area comparable to that of the activated carbon is usually difficult or costly to be included in the sorbent body. Therefore, along with the typical mechanical reinforcement such inorganic fillers would bring to the final sorbent body, it also tends to compromise the overall specific area of the sorbent body. This can be highly undesirable in some cases.
- a high surface area of the sorbent body usually means more active sites (including carbon sites capable of sorption of the toxic elements, sulfur capable of promoting or direct sorption of the toxic elements, and the metal catalyst capable of promoting sorption of the toxic elements) for the sorption of the toxic elements. It is further believed that close proximity of the three categories of active sorption sites in the sorbent body is conducive to the overall sorption capability.
- the sorbent body has a relative low percentage of inorganic filler (the remainder of the sorbent body being carbon, sulfur and metal catalyst).
- the sorbent body comprises less than 40%, less than 30%, less than 20%, less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, or less than 0.5% by weight of inorganic filler.
- the sorbent body comprises no inorganic filler.
- Sorbent bodies which comprise lesser amounts of inorganic fillers, can lead to a more uniform distribution of mercury capture throughout the cross-section of the walls of the activated carbon matrix.
- the sorbent body comprises at least 90% by weight (in certain embodiments at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, or at least 98%) of activated carbon, sulfur and the metal catalyst in total.
- a further embodiment of the invention is a sorbent body comprising: activated carbon; sulfur, in any oxidation state, as elemental sulfur or in a chemical compound or moiety comprising sulfur; and a metal catalyst, in any oxidation state, as elemental metal or in a chemical compound or moiety comprising the metal; wherein at least a portion of the metal catalyst is chemically bound to at least a portion of the sulfur.
- the sulfur may be chemically bound to at least a portion of carbon in the activated carbon matrix.
- the sulfur and/or metal catalyst may be, in some embodiments, distributed throughout the activated carbon matrix. In other embodiments, the sulfur and/or metal catalyst is not distributed throughout the activated carbon matrix.
- the sorbent body of this and any other embodiment may comprise, for example, a metal sulfide such as manganese sulfide.
- the sorbent body of this embodiment may also have any one or more of the other characteristics mentioned for any other sorbent bodies of the invention, including characteristics of the activated carbon, of sulfur, and of the metal catalyst, that have been described earlier.
- embodiments of the sorbent bodies of the invention are capable of sorbing and removing toxic elements such as cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic and selenium from fluids such as syngas streams and combustion flue gas streams. It has been found that the sorbent bodies are particularly effective in removing mercury from a flue gas stream.
- the removal capabilities of the sorbent materials with respect to a certain toxic element, e.g., mercury are typically characterized by two parameters: initial removal efficiency and long term removal capacity. With respect to mercury, the following procedure is to be used to characterize the initial mercury removal efficiency and long term mercury removal capacity.
- the sorbent body to be tested is loaded into a fixed bed through which a reference flue gas at 160°C having a specific composition is passed at a space velocity of 7500 hr "1 .
- Concentrations of mercury in the gas stream are measured before and after the sorbent bed.
- the instant mercury removal efficiency (Eff(Hg)) is calculated as follows:
- Initial mercury removal efficiency is defined as the average mercury removal efficiency during the first 1 (one) hour of test after the fresh test sorbent material is loaded. Typically, the mercury removal efficiency of a fixed sorbent bed diminishes over time as the sorbent bed is loaded with more and more mercury.
- Mercury removal capacity is defined as the total amount of mercury trapped by the sorbent bed per unit mass of the sorbent body material until the instant mercury removal efficiency diminishes to 90% under the above testing conditions. Mercury removal capacity is typically expressed in terms of mg of mercury trapped per gram of the sorbent material (mg g 1 ).
- An exemplary test reference flue gas (referenced as RFGl herein) has the following composition by volume: O 2 5%; CO 2 14%; SO 2 1500 ppm; NOx 300 ppm; HCl 100 ppm; Hg 20-25 ⁇ g m "3 ; N 2 balance; wherein NO x is a combination of NO 2 , N 2 O and NO; Hg is a combination of elemental mercury (Hg(O), 50-60% by mole) and oxidized mercury (40-50% by mole).
- the sorbent body has an initial mercury removal efficiency with respect to RFGl of at least 90%, at least 91%, at least 92%, at least 95%, at least 97%, at least 98%, at least 99%, or of at least 99.5%.
- the sorbent body advantageously has a high initial mercury removal efficiency of at least 90% for flue gases comprising O 2 5%; CO 2 14%; SO 2 1500 ppm; NO x 300 ppm; Hg 20-25 ⁇ g m "3 , having high concentrations of HCl and low concentrations of HCl alike.
- high concentrations of HCl is meant that HCl concentration in the gas to be treated is at least 20 ppm.
- low concentration of HCl is meant that HCl concentration in the gas to be treated is at most 10 ppm.
- the sorbent body of certain embodiments has a high initial mercury removal efficiency of at least 90%, at least 91%, at least 93%, at least 95%, at least 96%, at least 98%, at least 99%, or at least 99.5% for a flue gas (referred to as RFG2) having the following composition: O 2 5%; CO 2 14%; SO 2 1500 ppm; NO x 300 ppm; HCl 5 ppm; Hg 20-25 ⁇ g m "3 ; N 2 balance.
- RFG2 flue gas having the following composition: O 2 5%; CO 2 14%; SO 2 1500 ppm; NO x 300 ppm; HCl 5 ppm; Hg 20-25 ⁇ g m "3 ; N 2 balance.
- High mercury removal efficiency of these embodiments for low HCl flue gas is particularly advantageous compared to the prior art.
- the sorbent body has a high initial mercury removal efficiency of at least 91% for flue gases comprising O 2 5%; CO 2 14%; SO 2 1500 ppm; NO x 300 ppm; Hg 20-25 ⁇ g-m "3 , having high concentrations of SO 3 (such as 5 ppm, 8 ppm, 10 ppm, 15 ppm, 20 ppm, 30 ppm, 40 ppm) and low concentrations of SO 3 alike (such as 0.01 ppm, 0.1 ppm, 0.5 ppm, 1 ppm, 2 ppm).
- high concentrations of SO 3 is meant that SO 3 concentration in the gas to be treated is at least 3 ppm by volume.
- low concentration of SO 3 is meant that SO 3 concentration in the gas to be treated is less than 3 ppm.
- the sorbent body of certain embodiments advantageously has a high initial mercury removal efficiency of at least 90%, at least 91%, at least 95%, at least 98%, or at least 99% for a flue gas (referred to as RFG3) having the following composition: O 2 5%; CO 2 14%; SO 2 1500 ppm; NO x 300 ppm; SO 3 5 ppm; Hg 20-25 ⁇ g m "3 ; N 2 balance.
- High mercury removal efficiency of certain embodiments for high SO 3 flue gas is particularly advantageous compared to the prior art.
- the sorbent body has a Hg removal capacity of 0.05 mg g "1 with respect to RFGl, in certain embodiments of at least 0.10 mg g "1 , at least 0.15 mg-g "1 , at least 0.20 mg g "1 , at least 0.25 mg-g “1 , at least 0.30 mg g "1 , at least 0.50 mg-g '1 , at least 1.0 mg g "1 , least 2.0 mg g "1 , or at least 3.0 mg g ⁇ or with respect to RFGl.
- the sorbent body has an Hg removal capacity of 0.05 mg g '1 with respect to RFG2, in certain embodiments of at least 0.10 mg g "1 , at least 0.15 mg-g "1 , at least 0.20 mg g “1 , at least 0.25 mg g "1 , at least 0.30 mg-g “1 , at least 0.50 mg-g “1 , at least 1.0 mg g "1 , least 2.0 mg g "1 , or at least 3.0 mg g Wh respect to RFG2.
- the sorbent bodies according to these embodiments have a high mercury removal capacity with respect to low HCl flue gas streams. This is particularly advantageous compared to prior art mercury abatement processes.
- the sorbent body has an Hg removal capacity of 0.05 mg g "1 with respect to RFG3, in certain embodiments of at least 0.10 mg g "1 , at least 0.15 mg-g '1 , at least 0.20 mg-g “1 , at least 0.25 mg g "1 , at least 0.30 mg g "1 , at least 0.50 mg-g “1 , at least 1.0 mg g "1 , least 2.0 mg g "1 , or at least 3.0 mg g "1 with respect to RFG3.
- the sorbent bodies according to these embodiments have a high mercury removal capacity with respect to high SO 3 flue gas streams. This is particularly advantageous compared to the prior art mercury abatement processes.
- a further embodiment of the invention is thus any sorbent body described herein, wherein the sorbent body has an initial mercury removal efficiency of at least 90% with respect to RPGl, RP G2 and/or RPG3, or wherein the sorbent body has a mercury removal capacity of at least 0.05 mg g "1 with respect to RPGl, RFG2 and/or RPG3.
- an embodiment of the invention is a sorbent body comprising: activated carbon; sulfur, in any oxidation state, as elemental sulfur or in a chemical compound or moiety comprising sulfur; and a metal catalyst, in any oxidation state, as elemental metal or in a chemical compound or moiety comprising the metal; wherein the sorbent body has an initial mercury removal efficiency of at least 90% with respect to RFGl, RPG2 and/or RFG3.
- the sorbent body may have an initial mercury removal efficiency of at least 91%, at least 95%, at least 98% or at least 99% with respect to RPGl, RFG2 and/or RPG3.
- the sulfur and/or metal catalyst may be, in some embodiments, distributed throughout the activated carbon matrix. In other embodiments, the sulfur and/or metal catalyst is not distributed throughout the activated carbon matrix.
- the sorbent body of this embodiment may also have any one or more of the other characteristics mentioned for any other sorbent bodies of the invention, including characteristics of the activated carbon, of sulfur, and of the metal catalyst, that have been described earlier.
- a further embodiment of the invention is a sorbent body comprising: activated carbon; sulfur, in any oxidation state, as elemental sulfur or in a chemical compound or moiety comprising sulfur; and a metal catalyst, in any oxidation state, as elemental metal or in a chemical compound or moiety comprising the metal; wherein the sorbent body has a mercury removal capacity of at least 0.05 mg g "1 with respect to RPGl, RPG2 and/or RPG3.
- the sorbent body may have a mercury removal capacity of at least 0.10 mg g "1 , at least 0.15 mg g "1 , at least 0.20 mg g "1 , at least 0.25 mg-g “1 , at least 0.30 mg g "1 , at least 0.50 mg-g “1 , at least 1.0 mg g "1 , least 2.0 mg g "1 , or at least 3.0 mg g "1 with respect to RFGl, RFG2 and/or RFG3.
- the sulfur and/or metal catalyst may be, in some embodiments, distributed throughout the activated carbon matrix. In other embodiments, the sulfur and/or metal catalyst is not distributed throughout the activated carbon matrix.
- the sorbent body of this embodiment may also have any one or more of the other characteristics mentioned for any other sorbent bodies of the invention, including characteristics of the activated carbon, of sulfur, and of the metal catalyst, that have been described earlier.
- Another aspect of the invention is a method for the removal of a toxic element from a fluid, which comprises contacting the fluid containing the toxic element with a sorbent body according to the invention.
- Toxic elements include cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic and selenium, any of which may be in any oxidation state and may be in elemental form or in a chemical compound comprising the element.
- the sorbent bodies may be used, for instance, for treating fluid streams, including gas streams and fluid streams comprising toxic elements, such as arsenic, cadmium, mercury and/or selenium, for abating them.
- Such processes typically comprise a step of placing the sorbent body in the fluid stream.
- Such treatment process is particularly advantageous for abating mercury from the fluid stream.
- a particularly advantageous embodiment of the process comprises placing the sorbent bodies in a gas stream comprising mercury wherein at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60% or at least 70% by mole of the mercury is in elemental state.
- a particularly advantageous embodiment of the process comprises placing the sorbent bodies in a gas stream comprising mercury and HCl at a HCl concentration of lower than 50 ppm by volume, lower than 40 ppm, lower than 30 ppm, lower than 20 ppm, or lower than 10 ppm.
- a particularly advantageous embodiment of the process comprises placing the sorbent bodies in a gas stream comprising mercury and SO 3 at a SO 3 concentration of at least 3 ppm by volume, in certain embodiments higher than 5 ppm, higher than 8 ppm, higher than 10 ppm, or higher than 20 ppm.
- a further aspect of the invention is a process for making a sorbent body, comprising:
- the carbon-source material comprises: synthetic carbon- containing polymeric material; activated carbon powder; charcoal powder; coal tar pitch; petroleum pitch; wood flour; cellulose and derivatives thereof; natural organic materials such as wheat flour; wood flour, corn flour, nut-shell flour; starch; coke; coal; or mixtures or combinations of any two or more of these. All these materials contain certain components comprising carbon atoms in its structure units on a molecular level that can be at least partly retained in the final activated carbon matrix of the sorbent body.
- the carbon-source material comprises a phenolic resin or a resin based on furfuryl alcohol.
- the synthetic polymeric material can be a synthetic resin in the form of a solution or low viscosity liquid at ambient temperatures.
- the synthetic polymeric material can be a solid at ambient temperature and capable of being liquefied by heating or other means.
- useful polymeric carbon-source materials include thermosetting resins and thermoplastic resins (e.g., polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol, and the like).
- relatively low viscosity carbon precursors e.g., thermosetting resins
- any high carbon yield resin can be used.
- the synthetic polymeric material can comprise a phenolic resin or a furfural alcohol based resin such as furan resins.
- Phenolic resins can again be preferred due to their low viscosity, high carbon yield, high degree of cross-linking upon curing relative to other precursors, and low cost.
- Exemplary suitable phenolic resins are resole resin such as plyophen resin.
- An exemplary suitable furan liquid resin is Furcab-LP from QO Chemicals Inc., IN, U.S.A.
- An exemplary solid resin well suited for use as a synthetic carbon precursor is solid phenolic resin or novolak.
- mixtures of novolak and one or more resole resins can also be used as suitable polymeric carbon-source material.
- the phenolic resin may be pre-cured or uncured when mixed with other material to form the batch mixture material. Where the phenolic resin is pre-cured, the pre-cured material may comprise sulfur, metal catalyst or the optional inorganic filler pre-loaded. In certain embodiments, it is desired that a curable, uncured resin is included as part of the carbon-source material in the batch mixture material.
- Curable materials thermoplastic or thermosetting, undergo certain reactions, such as chain propagation, crosslinking, and the like, to form a cured material with higher degree of polymerization when being subjected to cure conditions, such as mild heat treatment, irradiation, chemical activation, and the like.
- organic binders typically used in extrusion and/or injection molding processes can be part of the carbon-source material as well.
- Exemplary binders that can be used are plasticizing organic binders such as cellulose ethers.
- Typical cellulose ethers include methylcellulose, ethylhydroxy ethylcellulose, hydroxybutyl-cellulose, hydroxybutyl methylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, sodium carboxy methylcellulose, and mixtures thereof. Further, cellulose ethers such as methylcellulose and/or methylcellulose derivatives are especially suited as organic binders, with methylcellulose, hydroxypropyl methylcellulose, or combinations of these being preferred.
- An example methylcellulose binder is METHOCEL A, sold by the Dow Chemical Company.
- Example hydroxypropyl methylcellulose binders include METHOCEL E, F, J, K, also sold by the Dow Chemical Company. Binders in the METHCEL 310 Series, also sold by the Dow Chemical Company, can also be used in the context of the invention.
- METHOCEL A4M is an example binder for use with a RAM extruder.
- METHOCEL F240C is an example binder for use with a twin screw extruder.
- Carbonizable organic fillers may be used as part of the carbon-source material in certain embodiments of the process.
- Exemplary carbonizable fillers include both natural and synthetic, hydrophobic and hydrophilic, fibrous and non-fibrous fillers.
- some natural fillers are soft woods, e.g., pine, spruce, redwood, etc.; hardwoods, e.g., ash, beech, birch, maple, oak, etc.; sawdust, shell fibers, e.g., ground almond shell, coconut shell, apricot pit shell, peanut shell, pecan shell, walnut shell, etc.; cotton fibers, e.g., cotton flock, cotton fabric, cellulose fibers, cotton seed fiber; chopped vegetable fibers, for example, hemp, coconut fiber, jute, sisal, and other materials such as corn cobs, citrus pulp (dried), soybean meal, peat moss, wheat flour, wool fibers, corn, potato, rice, tapiocas, etc.
- Some synthetic materials are regenerated cellulose, rayon fabric, cellophane, etc.
- One especially suited carbonizable fiber filler is cellulose fiber as supplied by International Filler Corporation, North Tonawanda, N. Y. This material has the following sieve analysis: 1-2% on 40 mesh (420 micrometers), 90-95% thru 100 mesh (149 micrometers), and 55-60% thru 200 mesh (74 micrometers).
- Some hydrophobic organic synthetic fillers are polyacrylonitrile fibers, polyester fibers (flock), nylon fibers, polypropylene fibers (flock) or powder, acrylic fibers or powder, aramid fibers, polyvinyl alcohol, etc.
- Such organic fiberous fillers may function in part as part of the carbon-source material, in part as mechanical property enhancer to the batch mixture body, and in part as pore-forming agents that would mostly vaporize upon carbonization.
- Non-limiting examples of metal catalyst-source material include: alkali and alkaline earth halides, oxides and hydroxides; oxides, sulfides, and salts of vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, silver, tungsten, and lanthanoids.
- the metallic elements in the metal catalyst-source materials can be at various valencies.
- iron is included in the metal catalyst-source material, it may be present at +3, +2 or 0 valencies or as mixtures of differing valencies, and can be present as metallic iron (0), FeO, Fe 2 O 3 , Fe 3 O 8 , FeS, FeCl 2 , FeCl 3 , FeSO 4 , and the like.
- manganese is present in the metal catalyst source, it may be present at +4, +2 or 0 valencies or mixtures of differing valences, and can be present as metallic manganese (0), MnO, MnO 2 , MnS, MnCl 2 , MnCl 4 , MnSO 4 , and the like.
- the metal catalyst-source material is in a form selected from: (i) halides and oxides of alkali and alkaline earth metals; (ii) precious metals and compounds thereof; (iii) oxides, sulfides, and salts of vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, silver, tungsten and lanthanoids; or (iv) combinations and mixtures of two or more of (i), (ii) and (iii).
- the metal catalyst-source material is in a form selected from: (i) oxides, sulfides, sulfates, acetates and salts of manganese; (ii) oxides, sulfides and salts of iron; (iii) combinations of (i) and KI; (iv) combinations of (ii) and KI; and/or (v) mixtures and combinations of any two or more of (i), (ii), (iii) and (iv).
- Non-limiting examples of sulfur-source material include: sulfur powder; sulfur- containing powdered resin; sulfides; sulfates; and other sulfur-containing compounds; or mixtures or combination of any two or more of these.
- Exemplary sulfur-containing compounds can include hydrogen sulfide and/or its salts, carbon disulfide, sulfur dioxide, thiophene, sulfur anhydride, sulfur halides, sulfuric ester, sulfurous acid, sulfacid, sulfatol, sulfamic acid, sulfan, sulfanes, sulfuric acid and its salts, sulfite, sulfoacid, sulfobenzide, and mixtures thereof.
- Inorganic fillers are not required to be present in the batch mixture material. However, if present, the filler material can be, e.g.: oxide glass; oxide ceramics; or other refractory materials.
- Exemplary inorganic fillers that can be used include oxygen-containing minerals or salts thereof, such as clays, zeolites, talc, etc., carbonates, such as calcium carbonate, alumninosilicates such as kaolin (an aluminosilicate clay), flyash (an aluminosilicate ash obtained after coal firing in power plants), silicates, e.g., wollastonite (calcium metasilicate), titanates, zirconates, zirconia, zirconia spinel, magnesium aluminum silicates, mullite, alumina, alumina trihydrate, boehmite, spinel, feldspar, attapulgites, and aluminosilicate fibers, cordierite powder, mullite; cordierite; silica; alumina; other oxide glass; other oxide ceramics; or other refractory material.
- carbonates such as calcium carbonate
- alumninosilicates such as kaolin (an aluminosilicate clay), fly
- Some examples of especially suited inorganic fillers are cordierite powder, talcs, clays, and aluminosilicate fibers such as provided by Carborundum Co. Niagara Falls, N.Y. under the name of Fiberfax, and combinations of these.
- Fiberfax aluminosilicate fibers measure about 2-6 micrometers in diameter and about 20-50 micrometers in length.
- inorganic fillers are various carbides, such as silicon carbide, titanium carbide, aluminum carbide, zirconium carbide, boron carbide, and aluminum titanium carbide; carbonates or carbonate-bearing minerals such as baking soda, nahcolite, calcite, hanksite and liottite; and nitrides such as silicon nitride.
- carbides such as silicon carbide, titanium carbide, aluminum carbide, zirconium carbide, boron carbide, and aluminum titanium carbide
- carbonates or carbonate-bearing minerals such as baking soda, nahcolite, calcite, hanksite and liottite
- nitrides such as silicon nitride.
- the batch mixture material may also optionally comprise forming aids.
- forming aids can include soaps, fatty acids, such as oleic, linoleic acid, etc., polyoxyethylene stearate, etc. or combinations thereof.
- sodium stearate is a preferred forming aid.
- Optimized amounts of the optional extrusion aid(s) will depend on the composition and binder.
- Other additives that are useful for improving the extrusion and curing characteristics of the batch are phosphoric acid and oil. Phosphoric acid improves the cure rate and increases adsorption capacity. If included, it is typically about 0.1 % to 5 wt% in the batch mixture material.
- an oil addition can aid in extrusion and can result in increases in surface area and porosity.
- an optional oil can be added in an amount in the range from about 0.1 to 5 wt. % of the batch mixture material.
- Exemplary oils that can be used include petroleum oils with molecular weights from about 250 to 1000, containing paraffinic and/or aromatic and/or alicyclic compounds. So called paraffinic oils composed primarily of paraffinic and alicyclic structures are preferred. These can contain additives such as rust inhibitors or oxidation inhibitors such as are commonly present in commercially available oils. Some useful oils are 3 in 1 oil from 3M Co., or 3 in 1 household oil from Reckitt and Coleman Inc., Wayne, NJ.
- oils can include synthetic oils based on poly (alpha olefins), esters, polyalkylene glycols, polybutenes, silicones, polyphenyl ether, CTFE oils, and other commercially available oils.
- Vegetable oils such as sunflower oil, sesame oil, peanut oil, soyabean oil etc. are also useful.
- the batch mixture material may also optionally comprise natural and/or synthetic pore-forming agents.
- the pore- forming agents may then be removed, for example, before or during carbonization and/or activation of the sorbent body. Removal of the pore-forming agents can impart certain characteristics to the pore structure of the sorbent body, such as voids of various sizes and dimensions.
- exemplary pore forming agents can include natural or synthetic pore-forming agents that, upon carbonization of the sorbent body, burn out and leave little or no residue behind in the sorbent body.
- pore- forming agents include polymeric materials, such as polymeric beads.
- Example polymeric materials, such as polymeric beads include polypropylene and polyethylene materials and beads.
- the batch mixture material may comprise, as a pore-forming agent, polypropylene, polyester or acrylic powders or fibers that decompose in inert atmosphere at high temperature (>400°C) to leave little or no residue.
- Additional pore-forming agents include natural and synthetic starches.
- the pore- forming agent when the pore- forming agent is water soluble, such as a starch, the pore- forming agent may be removed after curing the sorbent body via water dissolution before carbonization.
- a suitable pore-forming agent can form macropores due to particle expansion.
- intercalated graphite which contains an acid such as hydrochloric acid, sulfuric acid or nitric acid, will form macropores when heated, due to the resulting expansion of the acid.
- macropores can also be formed by dissolving certain fugitive materials.
- baking soda, calcium carbonate or limestone particles having a particle size corresponding to desired pore size can be extruded with carbonaceous materials to form monolithic sorbents.
- Baking soda, calcium carbonate or limestone forms water soluble oxides during the carbonization and activation processes, which can subsequently be leached to form macropores by soaking the monolithic sorbent in water.
- the carbon-source materials and the metal catalyst-source materials are intimately mixed to form the batch mixture material.
- the various source materials are provided in the form of fine powders, or solutions if possible, and then mixed intimately by using an effective mixing equipment. When powders are used, they are provided in certain embodiments with average size not larger than 100 ⁇ m, in certain other embodiments not larger than 10 ⁇ m, in certain other embodiments not larger than 1 ⁇ m.
- extrusion injection molding (include reactive injection molding), compression molding, casting, pressing, or rapid prototyping may be used to shape the batch mixture body.
- the body may be cured as it is being shaped, for example, when shaped by injection molding or compression molding.
- the body may be cured after it is shaped, for example, when shaped by extrusion, casting, or rapid prototyping.
- the extruded batch mixture or cured batch mixture body takes the shape of a monolithic honeycomb having a plurality of channels
- Extrusion is especially preferred in certain embodiments for forming the batch mixture material into a desired shape of the batch mixture body.
- Extrusion can be done by using standard extruders (ram extruder, single-screw, double-screw, and the like) and custom extrusion dies, to make sorbent bodies with various shapes and geometries, such as honeycombs, pellets, rods, spaghetti, and the like.
- Extrusion is particularly effective for making monolithic honeycomb bodies having a plurality of empty channels that can serve as fluid passageways. Extrusion is advantageous in that it can achieve a highly intimate mixing of all the source materials as well during the extrusion process.
- Rapid prototyping the automatic construction of physical objects using solid freeform fabrication, may also be used to shape the batch material.
- Rapid prototyping comprises obtaining a virtual design, for example a computer aided design, converting the design into virtual thin horizontal cross sections, then creating each cross section of the design in physical space, one after the next, until the shape is completed.
- One embodiment includes obtaining a virtual design of a shaped batch material, converting the design into virtual thin horizontal cross sections, and creating each cross section in physical space from the batch material.
- rapid prototyping is 3D printing.
- the batch mixture material comprises an uncured curable material.
- the sorbent body upon forming of the batch mixture body, is typically subjected to a curing condition, e.g., heat treatment, such that the curable component cures, and a cured batch mixture body forms as a result.
- the cured batch mixture body tends to have better mechanical properties than its non-cured predecessor, and thus handles better in down-stream processing steps.
- the curing step can result in a polymer network having a carbon backbone, which can be conducive to the formation of carbon network during the subsequent carbonization and activation steps.
- the curing is generally performed in air at atmospheric pressures and typically by heating the formed batch mixture body at a temperature of from 70°C to 200°C for about 0.5 to about 5.0 hours.
- the batch mixture body is heated from a low temperature to a higher temperature in stages, for example, from 7O 0 C, to 9O 0 C, to 125 0 C, to 15O 0 C, each temperature being held for a period of time.
- curing additive such as an acid additive at room temperature.
- the curing can, in one embodiment, serve to retain the uniformity of the metal catalyst distribution in the carbon.
- the shaped body is subjected to a carbonization step.
- the batch mixture body (cured or uncured) may be carbonized by subjecting it to an elevated carbonizing temperature in an O 2 -depleted atmosphere.
- the carbonization temperature can range from 600 to 1200°C, in certain embodiments from 700 to 1000°C.
- the carbonizing atmosphere can be inert, comprising mainly a non reactive gas, such as N 2 , Ne, Ar, mixtures thereof, and the like.
- the organic substances contained in the batch mixture body decompose to leave a carbonaceous residue.
- complex chemical reactions take place in this high-temperature step.
- Such reactions can include, inter alia:
- the net effect can include, inter alia: (1) re-distribution of the metal catalyst- source material and/or the metal catalyst; (2) re-distribution of sulfur; (3) formation of elemental sulfur from the sulfur-source material (such as sulfates, sulfites, and the like); (4) formation of sulfur-containing compounds from the sulfur-source material (such as elemental sulfur); (5) formation of metal catalyst in oxide form; (6) formation of metal catalyst in sulfide form; (7) reduction of part of the metal catalyst-source materials.
- Part of the sulfur (especially those in elemental state), and part of the metal catalyst-source material (such as KI) may be swept away by the carbonization atmosphere during carbonization.
- the result of the carbonization step is a carbonaceous body with sulfur and metal catalyst distributed therein.
- this carbonized batch mixture body typically does not have the desired specific surface area for an effective sorption of toxic elements.
- the carbonized batch mixture body is further activated.
- the carbonized batch mixture body may be activated, for example, in a gaseous atmosphere selected from CO 2 , H 2 O, a mixture of CO 2 and H 2 O, a mixture of CO 2 and nitrogen, a mixture ofH 2 O and nitrogen, and a mixture of CO 2 and another inert gas, for example, at an elevated activating temperature in a CO 2 and/or H 2 O-containing atmosphere.
- the atmosphere may be essentially pure CO 2 or H 2 O (steam), a mixture of CO 2 and H 2 O, or a combination of CO 2 and/or H 2 O with an inert gas such as nitrogen and/or argon. Utilizing a combination of nitrogen and CO 2 , for example, may result in cost savings.
- a CO 2 and nitrogen mixture may be used, for example, with CO 2 content as low as 2% or more.
- a mixture of CO 2 and nitrogen with a CO 2 content of 5-50% may be used to reduce process costs.
- the activating temperature can range from 600°C to 1000°C, in certain embodiments from 600°C to 900°C. During this step, part of the carbonaceous structure of the carbonized batch mixture body is mildly oxidized:
- the activating conditions can be adjusted to produce the final product with the desired specific area and composition. Similar to the carbonizing step, due to the high temperature of this activating step, complex chemical reactions and physical changes occur. It is highly desired that at the end of the activation step, the metal catalyst is distributed throughout the activated carbon matrix. It is highly desired that at the end of the activation step, the metal catalyst is distributed substantially homogeneously throughout the activated carbon matrix.
- the metal catalyst is present on at least 30%, at least 40%, at least 50%, at least 60%, or at least 80% of the wall surface area of the pores. It is highly desired that at the end of the activation step, sulfur is distributed throughout the activated carbon matrix. It is highly desired that at the end of the activation step, sulfur is distributed substantially homogeneously throughout the activated carbon matrix. It is highly desired that at the end of the activation step, sulfur is present on at least 30%, at least 40%, at least 50%, at least 60%, or at least 80% of the wall surface area of the pores.
- the batch mixture material is selected such after activation, the sorbent body comprises less than 20% by weight of inorganic materials other than carbon, sulfur, and the metal catalyst (in certain embodiments less than 10%, in certain other embodiments less than 5%).
- the batch mixture material is selected such that, after activation, the sorbent body comprises from 30%-50% by weight of inorganic materials other than carbon, sulfur, and the metal catalyst, based on the total weight of carbon, sulfur, and the metal catalyst.
- all metal catalyst-source materials and all sulfur-source materials are included into the batch mixture body by in-situ forming, such as in-situ extrusion, casting, and the like.
- This process has the advantages of, inter alia: (a) avoiding a subsequent step (such as impregnation) of loading a metal catalyst and/or sulfur onto the activated carbon body, thus potentially reducing process steps, increasing overall process yield, and reducing process costs; (b) obtaining a more homogeneous distribution of active sorption sites (metal catalyst and sulfur) in the sorbent body than what is typically obtainable by impregnation; and (c) obtaining a durable and robust fixation of the metal catalyst and sulfur in the sorbent body, which can withstand the flow of the fluid stream to be treated for a long service period.
- Impregnation can result in preferential distribution of impregnated species (such as metal catalyst and sulfur) on external cell walls, wall surface of large pores (such as those on the micrometer scale). Loading of impregnated species onto a high percentage of the wall surfaces of the nanoscale pores can be time-consuming and difficult. Most of the surface area of activated carbon having high specific area of from 400 to 2000 m ⁇ g "1 are contributed by the nanoscale pores. Thus, it is believed that it is difficult for a typical impregnation step to result in loading of the impregnated species onto a majority of the specific area of such activated carbon material.
- a typical impregnation step can result in a thick, relatively dense layer of the impregnated species on the external cell walls and/or wall surface of large pores, which blocks the fluid passageways into or out of the smaller pores, effectively reducing the sorptive function of the activated carbon.
- the fixation of the impregnated species in a typical impregnation step in the sorbent body is mainly by relatively weak physical force, which may be insufficient for prolonged use in fluid streams. [00123] Nonetheless, in certain embodiments, it is not necessary that all the metal catalyst and/or sulfur is distributed throughout the activated carbon matrix, let alone substantially homogeneously.
- not all of the metal catalyst-source materials and sulfur-source materials are formed in situ into the batch mixture body. It is contemplated that, after the activation step, a step of impregnation of certain metal catalysts and/or sulfur may be carried out. Alternatively, after the activated step, a step of treating the activated body by a sulfur-containing and/or metal catalyst-containing atmosphere may be carried out. Such post-activation loading of metal catalyst is especially useful for metals that cannot withstand the carbonization and/or carbonization steps, such as those based on organometallic compounds, e.g., iron acetylacetonate.
- the activated sorbent body of the invention may be subjected to post- finishing steps, such as pellitizing, grinding, assembling by stacking, and the like. Sorbent bodies of various shapes and compositions of the present invention may then be loaded into a fixed bed which will be placed into the fluid stream to be treated.
- Another aspect of the invention is an extruded batch mixture body comprising:
- a metal catalyst either in elemental form or in a chemical compound comprising the metal; wherein the metal catalyst is distributed substantially homogeneously in the material forming the extruded batch mixture body.
- the particles of sulfur-containing material are distributed substantially homogeneously in the material forming the extruded batch mixture body.
- the sulfur-containing material comprises at least 50% by mole of elemental sulfur.
- the sulfur-containing material comprises elemental sulfur, sulfates, sulfites, sulfides, CS 2 , and other sulfur-containing compounds.
- the extruded batch mixture further comprises:
- the extruded batch mixture comprises less than 20% by weight of inorganic material other than carbon, sulfur-containing inorganic material, water and the metal catalyst, in certain embodiments less than 10%, in certain other embodiments less than 5%.
- the extruded batch mixture comprises from 20% to 50% by weight of an inorganic material other than carbon, sulfur-containing inorganic material, water and the metal catalyst.
- the material is a heat-resistant inorganic material that is chemically stable at 800°C, in certain other embodiments at 1000°C.
- the extruded batch mixture comprises a heat- resistant inorganic material selected from cordierite, mullite, silica, alumina, other oxide glass, other oxide ceramic, other refractory materials, and mixtures and combinations thereof.
- the heat-resistant inorganic material comprises microscale pores.
- An extrusion composition was formulated with 46% liquid phenolic resole resin, 1% lubricating oil, 13% cordierite powder, 9% sulfur powder, 7% iron acetylacetonate, 18% cellulose fiber, 5% Methocel binder and 1 % sodium stearate. This mixture was compounded and then extruded. The extruded honeycomb was then dried and cured in air at 150°C followed by carbonization in nitrogen and activation in carbon dioxide. The activated carbon honeycomb samples were then tested for the mercury removal capability. The test was done at 160 0 C with 22 ⁇ g m "3 inlet elemental mercury concentration.
- the carrier gas for mercury contained N 2 , SO 2 , O 2 and CO 2 .
- the gas flow rate was 750 ml/minute.
- the total mercury removal efficiency was 86% while elemental mercury removal efficiency was 100%.
- the extrusion composition was 59% phenolic resole, 1% phosphoric acid, 1% oil, 9% sulfur powder, 3% iron oxide, 19% cellulose fiber, 7% methocel binder and 1% sodium stearate. These samples were extruded, cured carbonized, activated and tested as in Example 1 for mercury removal performance. The mercury removal efficiency was 87% and 97% for total and elemental mercury, respectively.
- manganese oxide was used as a metal catalyst source with the composition of 6% MnO 2 , 13% cordierite, 7% sulfur, 19% cellulose fiber, 5% methocel binder, 1% sodium stearate, 47% phenolic resole, 1% phosphoric acid and 1% oil.
- the mercury removal efficiency of the samples based on this composition was 92% and 98% for total and elemental mercury, respectively.
- sulfur was added combined with manganese as MnS instead of as elemental sulfur.
- the composition was 15% cordierite, 10% MnS, 20% cellulose fiber, 5% methocel binder, 1% sodium stearate, 47% phenolic resole, and 1% oil.
- sorbent bodies of the invention can demonstrate high mercury removal efficiencies. It is expected that the sorbent bodies of the invention will also be useful for the sorption of other toxic elements such as cadmium, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic and selenium from fluids such as flue gases as well as in coal gasification.
- other toxic elements such as cadmium, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic and selenium from fluids such as flue gases as well as in coal gasification.
- the extrusion composition was 14% charcoal, 47% phenol resin, 7% sulfur, 7% manganese oxide, 18% cellulose fiber, 5% mythical binder and 1% sodium separate. These samples were extruded, cured, carbonized and activated as in Example 1.
- the extrusion composition was 16% cured sulfur-containing phenol resin, 45 % phenol resin, 8% sulfur, 7% manganese oxide, 18% cellulose fiber, 4% mythical binder and 1% sodium separate. These samples were extruded, cured, carbonized and activated as in Example 1. The activated carbon samples were tested as in Example 7. The mercury removal efficiency was 100% and 99% for total and elemental mercury, respectively. See TABLE II below. Thus both Examples 7 and 8 achieved excellent mercury removal results.
- Hg 0 or Hg(O) means elemental mercury
- Hg ⁇ or Hg(T) means total mercury, including elemental and oxidized mercury
- EjJf(Hg 0 ) or EfJf[Hg(O)) means the instant mercury removal efficiency with respect to elemental mercury
- ⁇ ff(Hg ⁇ ) or EjJf[Hg(T)) means instant mercury removal efficiency with respect to mercury at all oxidation states.
- EfJf[Hg(X)) is calculated as follows: where Co is the inlet concentration of Hg(x), and Ci is the outlet concentration of Hg(x), respectively, at a given test time.
- FIG. 1 is a diagram comparing the mercury removal capability of a tested sample of a sorbent according to the present invention and a comparative sorbent over time.
- MSS aggregate amount of mercury per unit mass
- mg-g "1 mercury per unit mass trapped by the tested samples of the tested sorbents.
- EfT(Hg) instant mercury removal efficiency of the tested sorbents
- the horizontal axis is the time the sample was exposed to the test gas. Part of the E#(Hg) data in this figure are also presented in TABLE III below.
- the sorbent according to the present invention comprises sulfur, in-situ extruded MnO 2 as the metal catalyst source and about 45% by weight of cordierite as an inorganic filler.
- Sample 2.2 is a comparative sorbent comprising no in-situ extruded metal catalyst source, comparable amount of sulfur and cordierite, and impregnated FeSO 4 and KI.
- Curves 101 and 103 show the EfJf(Hg) and MSS of the sorbent according to the present invention, respectively.
- Curves 201 and 203 show the Eff(Hg) and MSS of the comparative sorbent, respectively.
- the sorbent did not show an abrupt drop of mercury removal efficiency even after 250 hours of exposure to a simulated flue gas comprising total mercury at about 20 ⁇ g-m "3 , indicating a fairly large amount of mercury can be trapped by the sorbent material before it reaches saturation (or mercury break-through point).
- the curve 201 and data of TABLE III show that the comparative sorbent had an abrupt, continuous drop of instant mercury removal efficiency within 50 hours until about 70 hours when the test was terminated, indicating an early saturation of the sorbent.
- Curves 103 and 203 overlap to a certain extent at the early stage of test period, but 203 ends at about 69 hours.
- the sorbent of this embodiment of the present invention comprising in-situ extruded metal catalyst source, can have much higher mercury removal capability, especially on the long term, than sorbent having an impregnated metal catalyst sources.
- the superior performance of the sorbent of the present invention is due to the more homogeneous distribution of the metal catalyst, and less blockage of the pores in the activated carbon matrix by the metal catalyst.
- FIG. 2 is a diagram showing the inlet mercury concentration (CHgO) and outlet mercury concentration (CHgI) of sorbent bodies according to one embodiment of the present invention various inlet mercury concentrations. This diagram clearly indicates that the sorbent bodies of certain embodiments of the present invention can be used to remove mercury effectively at various mercury concentration (ranging from above 70 to about 25 ⁇ g-m "3 ).
- FIG. 3 is a SEM image of part of a cross-section of a sorbent body according to the present invention comprising in-situ extruded metal catalyst. From the image, preferential accumulation of metal catalyst or sulfur is not observed.
- FIG. 4 is a SEM image of part of a cross-section of a comparative sorbent body comprising post-activation impregnated metal catalyst. The clearly visible white layer of material on the cell wall is the impregnated metal catalyst. It is believed that this relatively dense layer of impregnated layer of metal catalyst can block the entrances into many macroscale and nanoscale pores inside the cell walls, reducing the overall performance of the comparative sorbent body.
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US96655807P | 2007-05-14 | 2007-05-14 | |
| US11/977,843 US7998898B2 (en) | 2007-10-26 | 2007-10-26 | Sorbent comprising activated carbon, process for making same and use thereof |
| PCT/US2008/006082 WO2008143831A2 (en) | 2007-05-14 | 2008-05-13 | Sorbent bodies comprising activated carbon, processes for making them, and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2150337A2 true EP2150337A2 (en) | 2010-02-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08754390A Withdrawn EP2150337A2 (en) | 2007-05-14 | 2008-05-13 | Sorbent bodies comprising activated carbon, processes for making them, and their use |
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| Country | Link |
|---|---|
| EP (1) | EP2150337A2 (en) |
| JP (2) | JP5291092B2 (en) |
| KR (1) | KR101516836B1 (en) |
| CN (1) | CN101687173B (en) |
| CA (1) | CA2686986A1 (en) |
| TW (1) | TW200914126A (en) |
| WO (1) | WO2008143831A2 (en) |
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-
2008
- 2008-05-13 JP JP2010508393A patent/JP5291092B2/en not_active Expired - Fee Related
- 2008-05-13 EP EP08754390A patent/EP2150337A2/en not_active Withdrawn
- 2008-05-13 CA CA002686986A patent/CA2686986A1/en not_active Abandoned
- 2008-05-13 CN CN2008800224132A patent/CN101687173B/en not_active Expired - Fee Related
- 2008-05-13 KR KR1020097025996A patent/KR101516836B1/en not_active Expired - Fee Related
- 2008-05-13 WO PCT/US2008/006082 patent/WO2008143831A2/en not_active Ceased
- 2008-05-14 TW TW097117771A patent/TW200914126A/en unknown
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2013
- 2013-01-04 JP JP2013000083A patent/JP2013126661A/en active Pending
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| Title |
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Also Published As
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| TW200914126A (en) | 2009-04-01 |
| CN101687173A (en) | 2010-03-31 |
| WO2008143831A2 (en) | 2008-11-27 |
| KR20100017793A (en) | 2010-02-16 |
| WO2008143831A3 (en) | 2009-03-26 |
| JP5291092B2 (en) | 2013-09-18 |
| CN101687173B (en) | 2013-11-13 |
| JP2010527288A (en) | 2010-08-12 |
| KR101516836B1 (en) | 2015-04-30 |
| CA2686986A1 (en) | 2008-11-27 |
| JP2013126661A (en) | 2013-06-27 |
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