CN113351155A - Adsorbing material and preparation method and application thereof - Google Patents
Adsorbing material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113351155A CN113351155A CN202110654497.9A CN202110654497A CN113351155A CN 113351155 A CN113351155 A CN 113351155A CN 202110654497 A CN202110654497 A CN 202110654497A CN 113351155 A CN113351155 A CN 113351155A
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- Prior art keywords
- parts
- titanium
- thallium
- based porous
- adsorbing
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 74
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 52
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 239000010936 titanium Substances 0.000 claims abstract description 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 45
- 239000003463 adsorbent Substances 0.000 claims abstract description 29
- 230000003750 conditioning effect Effects 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 29
- 239000002002 slurry Substances 0.000 claims description 26
- 239000011230 binding agent Substances 0.000 claims description 25
- 238000001179 sorption measurement Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000000779 smoke Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 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 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003546 flue gas Substances 0.000 abstract description 19
- 238000005516 engineering process Methods 0.000 abstract description 10
- 208000026015 thallium poisoning Diseases 0.000 abstract description 9
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 12
- 239000004568 cement Substances 0.000 description 11
- 239000003365 glass fiber Substances 0.000 description 11
- 229920000742 Cotton Polymers 0.000 description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 9
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 9
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 9
- 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 9
- 238000000034 method Methods 0.000 description 9
- 235000006408 oxalic acid Nutrition 0.000 description 9
- 239000000428 dust Substances 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000001413 cellular effect Effects 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000012692 Fe precursor Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003476 thallium compounds Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—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
- 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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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0214—Compounds of V, Nb, Ta
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/0218—Compounds of Cr, Mo, W
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- B01J20/0222—Compounds of Mn, Re
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention provides an adsorbing material and a preparation method and application thereof. The adsorbent material comprises: a substrate comprising a titanium-based porous material; and a conditioning aid present on the surface and/or inside of the substrate, the conditioning aid comprising a transition metal element; wherein the adsorbent material has a plurality of pore structures; and the proportion of the pore diameter of 100-250nm in the pore structure is 20-50%, preferably 25-40%. By adopting the adsorbing material disclosed by the invention, the thallium poisoning degree of the denitration catalyst can be effectively reduced, the service life of the SCR denitration catalyst is prolonged, the use cost of a denitration system is reduced, and the adaptability of the denitration catalyst in thallium-containing flue gas is improved; the adsorbing material prepared by the invention can reduce 80% or even more than 80% of thallium on the denitration catalyst, and realizes the wide application of the denitration catalyst technology in thallium-containing flue gas.
Description
Technical Field
The invention relates to an adsorbing material and a preparation method and application thereof; in particular to a thallium adsorption material and a preparation method and application thereof; in particular to a thallium adsorption material for protecting a cement kiln flue gas denitration catalyst, a preparation method and application thereof, belonging to the technical field of denitration catalysts.
Background
The nitrogen oxides are important pollutants of air pollution, and the nitrogen oxide treatment of the coal power plant is mature, so that the requirement of ultralow emission is met. The cement smoke nitrogen oxides are the third pollution source after the fire power and the automobile exhaust. The sources of nitrogen oxides generated during cement production are mainly two: when the temperature range is 500-1500 ℃, fuel type nitrogen oxides are generated in the decomposing furnace and the rotary kiln, and the fuel type nitrogen oxides approximately account for 75-95% of all the nitrogen oxides; and nitrogen oxides generated in the rotary kiln at temperatures greater than 1200 ℃. Therefore, the cement industry is urgently required to find ways in the aspect of nitrogen oxide emission reduction.
At present, the emission of nitrogen oxides can be reduced by low-nitrogen combustion, staged combustion, selective non-catalytic reduction (SNCR) and other denitration technologies, Selective Catalytic Reduction (SCR) denitration technology, and various technologies combined or derived from technical improvement and upgrading. The selective catalytic reduction denitration technology is one of the most widely applied and mature and effective flue gas denitration technologies, and the V-W-Ti denitration catalyst is widely applied to coal-fired power plants due to the advantages of high denitration efficiency, long service life and the like, and is gradually applied to the cement industry along with the promotion of environmental protection at present.
However, because cement flue gas has high dust and high temperature and thallium is contained in ash, thallium is deposited on the surface of a catalyst during flue gas denitration, so that the catalyst is poisoned and the activity is reduced, the influence of thallium contained in cement dust on the denitration catalyst is studied by paradox and the like, the influence of thallium on the performance of the denitration catalyst is studied by indicating medium and low dust (cement, 2015), and the influence of thallium on the performance of the denitration catalyst is studied by indicating thallium has direct negative influence on surface acidity and redox performance (APPL CATAL B-ENVIRON, 2020), but the research on thallium enrichment process mechanism is less, and a more appropriate industrial solution is less seen, so a simple and feasible scheme for reducing catalyst thallium poisoning is needed.
Citation document 1 discloses a thallium poisoning resistant core-shell honeycomb catalyst for cement kiln flue gas denitration and a preparation method thereof, wherein the catalyst is a core-shell catalyst and V-W/TiO with thallium poisoning resistant auxiliary agent added2The core structure is a metal oxide film as a shell structure; the thallium resistant additive comprises element gallium and/or element indium. The thallium poisoning resistance of the prepared denitration catalyst is 2-3 times higher than that of the existing catalyst, the denitration efficiency is stably maintained at more than 90%, and breakthrough of the denitration catalyst technology under the condition of thallium-containing flue gas in a cement kiln is realized. But the catalyst still contains 3-4% of thallium, and the thallium and TiO can be mixed2The reaction occurs, and thus the catalyst is still subject to thallium poisoning by long-term use, thereby affecting the life of the catalyst.
Citation 2 discloses a method for purifying and recovering thallium in smelting flue gas, which takes activated carbon loaded metal chloride as a catalyst to adsorb and catalytically oxidize virulent monovalent thallium compounds in the smelting flue gas; introducing the smelting flue gas subjected to dust removal treatment into a fixed bed reactor filled with a catalyst, capturing a monovalent thallium compound in the gas by the catalyst and carrying out an oxidation reaction on the surface of the catalyst, wherein heavy metal thallium is converted into thallium oxide which is easier to remove from a monovalent compound with high toxicity and high mobility and is attached to the surface of the catalyst; the catalyst after the reaction is electrolyzed after acid washing, and thallium can be recovered and used for preparing medicines, electronic equipment elements and optical elements. This method, which uses electrolysis after acid washing to remove thallium, damages the denitration catalyst, still results in a short catalyst life, and is not suitable for use in cement flue gas.
Citations
Cited document 1: CN111905716A
Cited document 2: CN109364659A
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems in the prior art, the invention provides an adsorbing material, and solves the problems that the activity of the traditional denitration catalyst in thallium-containing flue gas is reduced quickly and thallium poisoning is easy to occur in the prior art.
Furthermore, the invention also provides a preparation method of the adsorbing material, and the preparation method is simple and easy, has easily obtained raw materials, and is suitable for industrial production.
Means for solving the problems
The invention provides an adsorbing material, wherein the adsorbing material comprises:
a substrate comprising a titanium-based porous material; and
a conditioning aid present on the surface and/or inside of the substrate, the conditioning aid comprising a transition metal element; wherein,
the adsorbing material is provided with a plurality of hole structures; and the proportion of the pore diameter of 100-250nm in the pore structure is 20-50%, preferably 25-40%.
The adsorbing material provided by the invention has a specific surface area of 50-70 m2(ii)/g; and/or the total pore volume of the adsorbing material is 0.3-0.6 cm3/g。
The adsorbing material provided by the invention further comprises a binder and/or a proppant on the surface and/or in the adsorbing material.
The adsorption material according to the present invention, wherein the titanium-based porous material includes anatase type titanium dioxide and/or rutile type titanium dioxide; preferably, the particle size D90 of the titanium-based porous material is less than 5 μm; and/or, the content of titanium dioxide is not less than 97.0% by mass of the total mass of the titanium-based porous material.
The adsorbing material of the present invention, wherein the content of the transition metal element in terms of oxide is 0.1 to 1.5%, preferably 0.3 to 1.1%, and more preferably 0.4 to 0.9% based on the total weight of the adsorbing material.
According to the adsorbing material provided by the invention, the transition metal element comprises one or more of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, palladium, silver and gold.
The invention also provides a preparation method of the adsorption material, wherein the preparation method comprises the step of attaching a conditioning aid to the surface and/or the interior of the titanium-based porous material.
The preparation method comprises the following steps:
mixing a titanium-based porous material, a regulating assistant precursor and a pore-forming agent to obtain precursor slurry; preferably, the precursor slurry further comprises one or more of a combination of a binder, a proppant, a stabilizer and a dispersant;
and mixing and extruding the precursor slurry, and roasting to obtain the adsorbing material.
According to the preparation method, the conditioning additive precursor comprises one or more of an oxide of a transition metal, a hydroxide of a transition metal, and a salt of a transition metal.
According to the preparation method, the temperature rise rate of roasting is 1-20 ℃/min, the temperature is finally raised to 400-650 ℃, and the temperature is kept for 1-8 hours.
The invention also provides the use of the adsorption material according to the invention for adsorbing compounds containing thallium; preferably, the adsorption material is used for protecting the denitration catalyst in the smoke containing the thallium element.
ADVANTAGEOUS EFFECTS OF INVENTION
By adopting the adsorbing material disclosed by the invention, the thallium poisoning degree of the denitration catalyst can be effectively reduced, the service life of the SCR denitration catalyst is prolonged, the use cost of a denitration system is reduced, and the adaptability of the denitration catalyst in thallium-containing flue gas is improved; the adsorbing material prepared by the invention can reduce 80% or even more than 80% of thallium on the denitration catalyst, and realizes the wide application of the denitration catalyst technology in thallium-containing flue gas.
Furthermore, the preparation method of the adsorbing material is simple and easy, raw materials are easy to obtain, and the adsorbing material is suitable for industrial mass production.
Further, the adsorbing material of the present invention can be used for the use of the adsorbing material for adsorbing a compound containing a thallium element; in particular, the adsorbing material can be used for protecting a denitration catalyst in a thallium-element-containing flue gas.
Drawings
Fig. 1 shows an electron micrograph of the adsorbent material of the present invention.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, "plural" in "plural", and the like means a numerical value of 2 or more unless otherwise specified.
In this specification, the terms "substantially", "substantially" or "substantially" mean an error of less than 5%, or less than 3% or less than 1% as compared to the relevant perfect or theoretical standard.
In the present specification, "%" denotes mass% unless otherwise specified.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
In the present specification, the term "particle diameter D90" means a particle diameter corresponding to a cumulative number of particle size distributions of samples of 90%. Its physical meaning is that 90% of the particles have a particle size smaller than this.
In the present specification, if "room temperature" or "normal temperature" appears, the temperature may be generally 10 to 40 ℃.
<First aspect>
A first aspect of the invention provides an adsorbent material comprising:
a substrate comprising a titanium-based porous material; and
a conditioning aid present on the surface and/or inside the substrate; wherein,
the adsorbing material has a plurality of pore structures, and the proportion of the pore diameter of 100-250nm in the pore structures is 20-50%, preferably 25-40%, for example: 22%, 28%, 30%, 32%, 35%, 38%, 42%, 45%, 48%, etc.
By adopting the adsorbing material disclosed by the invention, the thallium poisoning degree of the denitration catalyst can be effectively reduced, the service life of the SCR denitration catalyst is prolonged, the use cost of a denitration system is reduced, and the adaptability of the denitration catalyst in thallium-containing flue gas is improved; the adsorbing material prepared by the invention can reduce 80% or even more than 80% of thallium on the denitration catalyst, and realizes the wide application of the denitration catalyst technology in thallium-containing flue gas.
Further, in the invention, the specific surface area of the adsorbing material is 50-70 m2G, for example: 52m2/g、55m2/g、58m2/g、60m2/g、62m2/g、65m2/g、68m2(iv)/g, etc.; and/or the total pore volume of the adsorbing material is 0.3-0.6 cm3In g, e.g. 0.4cm3/g、0.5cm3And/g, etc. When the specific surface area of the adsorbing material is 50-70 m2(ii)/g; and/or the total pore volume of the adsorbent material is0.3～0.6cm3In the case of/g, adsorption of a thallium element-containing substance is utilized.
Typically, the adsorbent material of the invention has an average pore size of 50-100nm, for example: 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, etc.
Base body
The substrate of the present invention comprises a titanium-based porous material. The titanium-based porous material has the advantages of high specific surface area, developed pore structure, adjustable pore size in a certain range and high advantage. However, titanium-based porous materials have a relatively low adsorption rate for target pollutants. Moreover, there still remains a certain difficulty if it is directly applied to the adsorption of a thallium element-containing compound.
As the titanium-based porous material, the present invention is not particularly limited, and there may be mentioned some titanium-based porous materials commonly used in the art, which can be prepared by a conventional preparation method or commercially available. Specifically, in the present invention, the titanium-based porous material may include anatase type titanium dioxide and/or rutile type titanium dioxide. In view of the high cost of rutile titanium dioxide, it is obtained at very high temperatures. Also, the use of anatase titania enables a desired pore diameter to be obtained. Therefore, the present invention preferably uses anatase titania as the titanium-based porous material.
The present invention is not particularly limited with respect to some other parameters of the titanium-based porous material, such as particle size, etc., and can be obtained as desired. Preferably, in order to obtain an adsorbing material with excellent performance, the particle size D90 of the titanium-based porous material of the invention can be 5 μm or less; and/or, the content of titanium dioxide is not less than 97.0% by mass of the total mass of the titanium-based porous material.
Conditioning aids
The inventors of the present invention have found that the adsorption of a thallium element-containing substance by an adsorbing material can be enhanced by using a conditioning aid. In the present invention, the conditioning additive contains a transition metal element. When the transition metal element is contained in the adsorbent, the thallium element-containing substance can be adsorbed more effectively.
The transition metal element is not particularly limited in the present invention, and may be one or a combination of two or more of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, palladium, silver, and gold, which are commonly used in the art.
Specifically, the content of the transition metal element in terms of oxide is 0.1 to 1.5%, preferably 0.3 to 1.1%, and more preferably 0.4 to 0.9%, based on the total weight of the adsorbent material, for example: 0.2%, 0.5%, 0.6%, 0.7%, 0.8%, 1.0%, 1.2%, 1.3%, 1.4%, etc. When the content of the transition metal element in terms of oxide is 0.1 to 1.5%, the effect of adsorbing the thallium element-containing substance is more excellent.
Other ingredients
The adsorbent material of the present invention may also comprise a binder and/or a proppant.
In some specific embodiments, the invention can enable the titanium-based porous material to be bonded more tightly by using the binder, and form the adsorption material with more excellent performance. In the present invention, the binder retained in the adsorbent material is generally an inorganic binder, and preferably, the inorganic binder includes one or a combination of two or more of alkali metal silicate, phosphate, aluminosilicate, silica, and the like. More preferably, the present invention preferably uses silica as the inorganic binder in consideration of the influence of impurities on the adsorption material.
Furthermore, the adsorbing material of the invention can also contain a proppant, so that the adsorbing material is more stable by using the proppant. In the present invention, the proppant may be a fiber-based proppant, such as: one or a combination of two or more of ceramic fiber, glass fiber, carbon fiber, asbestos fiber, and the like. Preferably, the present invention preferably uses glass fibers as a proppant in consideration of the influence of impurities on the adsorbent material.
In addition, the invention also provides an adsorbent which comprises the adsorbing material of the invention, and the adsorbent can also comprise other various adsorbing materials known in the field, such as other activated carbon, molecular sieve, diatomite and the like. In a preferred embodiment of the present invention, the adsorbent material of the present invention is included at least at 60 mass% or more, preferably at 80 mass% or more, and more preferably at 90 mass% or more, based on the total mass of the adsorbent.
<Second aspect of the invention>
In a second aspect, the present invention provides a method for producing the adsorbent material according to the first aspect, which comprises the step of attaching a conditioning aid to the surface and/or the interior of the titanium-based porous material.
In some specific embodiments, the preparation method comprises the steps of:
mixing a titanium-based porous material, a regulating assistant precursor and a pore-forming agent to obtain precursor slurry; preferably, the precursor slurry further comprises one or more of a combination of a binder, a proppant, a stabilizer and a dispersant;
and mixing and extruding the precursor slurry, and roasting to obtain the adsorbing material.
As for the titanium-based porous material, it is the titanium-based porous material according to the first aspect of the present invention. Specifically, in the invention, the titanium-based porous material can be used in an amount of 75-89 parts by mass, for example: 78 parts, 80 parts, 82 parts, 85 parts, 88 parts and the like.
Further, as for the conditioning aid precursor, the conditioning aid precursor includes one or a combination of two or more of an oxide of a transition metal, a hydroxide of a transition metal, and a salt of a transition metal. Taking the iron element as an example, the iron precursor includes one or a combination of two or more of iron oxide, iron hydroxide and iron salt, for example: one or more of ferric oxide, ferrous oxide, ferric hydroxide, ferrous hydroxide, ferric nitrate, ferrous nitrate, etc. Taking the copper element as an example, the copper precursor includes one or a combination of two or more of copper oxide, copper hydroxide, and copper salt, such as copper oxide, cuprous oxide, copper hydroxide, cuprous hydroxide, cupric nitrate, cuprous nitrate, and the like. In the present invention, the addition amount of the conditioning aid precursor may be 3 to 11 parts by mass, for example: 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts and the like. Preferably, in view of the adsorption effect, an iron precursor is preferably used as the conditioning aid precursor.
As for the pore-forming agent, the invention can obtain the adsorbing material with the required pore diameter and pore volume and the proper specific surface area by using the pore-forming agent. The pore-forming agent is not particularly limited in the present invention, and may be any of those commonly used in the art. For example: commonly used small molecular pore-forming agent or high molecular pore-forming agent, etc. According to the invention, the pore-forming agent is used, so that the supporting layer has a proper pore structure, and the adsorption performance of the adsorption material is improved.
Specifically, in the present invention, the polymeric pore-forming agent includes one or a combination of two or more of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), cotton pulp, and the like. The small-molecule pore-forming agent comprises one or the combination of more than two of lithium chloride, calcium chloride or water. However, in view of the requirements of the present invention for pore structure and the influence of impurities in the product on the adsorbent material, it is preferable to use a polymeric pore former such as cotton pulp or the like. In the invention, the pore-forming agent is used in an amount of 0.5 to 2.0 parts by mass, for example: 0.7 part, 0.9 part, 1.1 part, 1.3 parts, 1.5 parts, 1.7 parts, 1.9 parts and the like.
In some embodiments, the invention further comprises a binder. The properties of the adhesive material of the present invention are improved by using a binder or the obtained precursor slurry is made favorable for firing. In view of the most effective exertion of the binder effect, the binder of the present invention is used in an amount of 1.2 to 5.3 parts by mass, for example: 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.7 parts, 3 parts, 3.2 parts, 3.5 parts, 3.7 parts, 4 parts, 4.2 parts, 4.5 parts, 4.7 parts, 5 parts and the like.
On one hand, the invention can enable the titanium-based porous material to be bonded more tightly by using the inorganic binder, thereby forming the adsorbing material with more excellent performance. Preferably, the inorganic binder includes one or a combination of two or more of alkali metal silicate, phosphate, aluminosilicate, silica, and the like. More preferably, the present invention preferably uses silica as the inorganic binder in consideration of the influence of impurities on the adsorption material. Further, in the present invention, the inorganic binder may be added in an amount of 0.5 to 3 parts by mass, for example: 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts and the like.
On the other hand, the present invention can also make the precursor data of the present invention mixed more uniformly by using an organic binder. As the organic binder, the present invention is not particularly limited, and may be some binders commonly used in the art, for example: hydroxypropyl methylcellulose, carboxymethyl cellulose (CMC), polyethylene oxide (PEO), or a combination thereof. Further, in the present invention, the organic binder may be added in an amount of 0.7 to 2.3 parts by mass, for example: 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts and the like.
Furthermore, the adsorbing material of the invention can also contain a proppant, so that the adsorbing material is more stable by using the proppant. In the present invention, the proppant may be a fiber-based proppant, such as: one or a combination of two or more of ceramic fiber, glass fiber, carbon fiber, asbestos fiber, and the like. Preferably, the present invention preferably uses glass fibers as a proppant in consideration of the influence of impurities on the adsorbent material.
Further, in some embodiments, the present invention can make the dissolution of the conditioning aid precursor faster by using the stabilizer, thereby enabling to obtain a uniformly mixed precursor slurry, and can further improve the extrusion efficiency. Specifically, in the present invention, the amount of the stabilizer added may be 0.7 to 6.4 parts by mass, for example: 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts and the like.
Further, the stabilizer of the present invention is not particularly limited, and may be any chemical substance commonly used in the art for facilitating dissolution of a precursor of the conditioning aid, such as: inorganic acids, organic acids, alkaline agents, and the like, and it is preferable to use an organic acid and/or an alkaline agent as a stabilizer in view of the efficacy, stability of the product and the influence of impurities in the product on the adsorbent; wherein, the alkaline agent can be added during extrusion, thereby improving the extrusion efficiency. Specifically, the stabilizer of the present invention may include one or a combination of two or more of oxalic acid, lactic acid, stearic acid, and ammonia water.
In addition, in order to form the precursor slurry, the raw material of the present invention further contains water, and the amount of water used may be 42 to 78 parts by mass, for example: 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts and the like.
Further, the mixing method is not particularly limited in the present invention, and the mixing of the raw materials may be accelerated by stirring.
In some specific embodiments, the preparation method comprises the steps of:
mixing a titanium-based porous material, a regulating aid precursor, a propping agent and a pore-forming agent to obtain an intermediate slurry;
mixing and dissolving a binder and water, and then uniformly mixing the binder, the intermediate slurry and a stabilizer to obtain precursor slurry;
and mixing, extruding and drying the precursor slurry, and roasting to obtain the adsorbing material.
In some specific embodiments, the kneading mode is not particularly limited, and the kneading may be a mode generally used in the art, and is generally carried out at a temperature of 100 ℃.
In some embodiments, the drying conditions of the present invention are not particularly limited, and may be performed according to the drying conditions commonly used in the art, for example: the drying temperature can be 100-120 ℃, and the drying time can be 0.25-2 h.
In some specific embodiments, the baking apparatus is not particularly limited as to the baking, but a baking furnace is preferably used in view of the baking effect.
In the roasting, the temperature rising rate is 1-20 ℃/min, preferably 2-15 ℃/min, and the temperature rising time can be 1-6 h, preferably 2-4 h. Finally, the temperature is raised to 400-650 ℃, preferably to 450-: 500-550 ℃. The temperature can be kept for 1-8 h, preferably 2-6 h, for example: 5-5 h and the like. By performing the heat-insulating treatment in the above temperature range, the specific surface area, pore diameter and pore volume desired in the present invention can be more easily obtained. And then cooling, wherein the cooling rate can be 1-20 ℃/min, and preferably 2-15 ℃/min. And cooling to normal temperature, and preparing the adsorbing material by using a corresponding mould. The time for cooling can be 0.5-4 h, preferably 1-3 h.
<Third aspect of the invention>
A third aspect of the invention provides the use of an adsorption material according to the invention for adsorbing a compound containing thallium element; preferably, the adsorption material is used for protecting the denitration catalyst in the smoke containing the thallium element.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The following examples and comparative examples are parallel runs, with the same processing steps and parameters, unless otherwise indicated. The titanium-based porous material is crystal anatase titanium dioxide, the particle size D90 is less than 5 mu m, the content of the titanium dioxide is not less than 97.0%, and the titanium-based porous material is obtained through commercial purchase.
Example 1
The content of thallium calculated by oxide is less than 0.1% for the working condition of the dust;
mixing Fe (OH)3Mixing with water, stirring for dissolving, and mixing with titanium-based porous material, glass fiber, cotton pulp and Fe2O3Mixing to obtain intermediate slurry;
mixing hydroxypropyl methyl cellulose, silicon dioxide, carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and water, heating to 60 ℃ for dissolving, and then uniformly mixing with the intermediate slurry and oxalic acid to obtain precursor slurry;
mixing the precursor slurry at normal temperature, extruding, drying, heating to 500 ℃ at the heating rate of 15 ℃/min, and roasting for 8 h; then the temperature is reduced to normal temperature at the rate of 10 ℃/min, and 13-hole honeycomb adsorbing materials with the length of 0.3 meter are prepared by using corresponding moulds.
The feed comprises the following raw materials in parts by weight: fe (OH)34 parts of titanium-based porous material 86 parts, 6 parts of glass fiber, 1.5 parts of cotton pulp and Fe2O33 parts, 1 part of hydroxypropyl methyl cellulose, 1.2 parts of silicon dioxide, 0.2 part of carboxymethyl cellulose (CMC), 0.2 part of polyethylene oxide (PEO), 2.8 parts of oxalic acid and 61 parts of water.
The 13-hole honeycomb thallium adsorbing material can be directly installed in front of a 13-hole honeycomb denitration catalyst module (a 13-hole die with the same size as the former) without intervals (direct connection, mutual dislocation and through hole-to-hole connection), and an air soot blower needs to be arranged.
Example 2
The thallium content of the dust calculated by oxide is less than 0.3 percent;
mixing Fe (OH)3Mixing with water, stirring for dissolving, and mixing with titanium-based porous material, glass fiber, cotton pulp and Fe2O3Mixing to obtain intermediate slurry;
mixing hydroxypropyl methyl cellulose, silicon dioxide, carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and water, heating to above 60 ℃ for dissolution, then uniformly mixing with the intermediate slurry and oxalic acid, mixing at 60 ℃, extruding, drying, heating to 500 ℃ at the rate of 15 ℃/min for roasting for 1 h; and then, cooling to normal temperature at the rate of 15 ℃/min to prepare the 11-hole cellular thallium adsorbing material with the length of 0.5 meter.
The feed comprises the following raw materials in parts by weight: fe (OH)33 parts of titanium-based porous material 87 parts, 6 parts of glass fiber, 1.5 parts of cotton pulp and Fe2O35 parts, 0.9 part of hydroxypropyl methyl cellulose, 1.2 parts of silicon dioxide, 0.2 part of carboxymethyl cellulose (CMC), 0.2 part of polyethylene oxide (PEO), 3.0 parts of oxalic acid and 65 parts of water.
The 12-hole honeycomb thallium adsorbing material can be directly and additionally arranged in front of an 11-hole honeycomb denitration catalyst module without intervals (direct connection, mutual dislocation and hole-to-hole direct connection), is directly connected and does not dislocate with each other, and an air soot blower needs to be arranged.
Example 3
The thallium content of the dust calculated by oxide is more than 0.3 percent;
mixing Fe (OH)3Mixing with water, stirring for dissolving, and mixing with titanium-based porous material, glass fiber, cotton pulp and Fe2O3Mixing to obtain intermediate slurry;
mixing hydroxypropyl methyl cellulose, silicon dioxide, carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and water, heating to above 60 ℃ for dissolution, then uniformly mixing with the intermediate slurry and oxalic acid, mixing at normal temperature, extruding, drying, heating to 500 ℃ at the rate of 10 ℃/min, and roasting for 1 h; and then the temperature is reduced to normal temperature at the rate of 5 ℃/min to prepare the 8-hole cellular thallium adsorbing material with the length of 0.8 meter.
The feed comprises the following raw materials in parts by weight: fe (OH)32 parts of titanium-based porous material 88 parts, 6 parts of glass fiber, 1.5 parts of cotton pulp and Fe2O37 parts, 0.9 part of hydroxypropyl methyl cellulose, 1.2 parts of silicon dioxide, 0.3 part of carboxymethyl cellulose (CMC), 0.2 part of polyethylene oxide (PEO), 3.2 parts of oxalic acid and 71 parts of water.
The 8-hole honeycomb thallium adsorbing material can be directly installed at the position of not less than 2 meters in front of an 8-hole honeycomb denitration catalyst module (using an 8-hole mold with the same size) without intervals (direct connection, mutual dislocation and hole-to-hole direct connection), and an air soot blower needs to be configured.
Example 4
The thallium content of the dust calculated by oxide is more than 0.3 percent;
mixing Fe (OH)3Mixing with water, stirring for dissolving, and mixing with titanium-based porous materialGlass fibre, cotton pulp and CuO, Fe2O3Mixing to obtain intermediate slurry;
mixing hydroxypropyl methyl cellulose, silicon dioxide, carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and water, heating to above 60 ℃ for dissolution, then uniformly mixing with the intermediate slurry and oxalic acid, mixing at normal temperature, extruding, drying, heating to 500 ℃ at the rate of 10 ℃/min, and roasting for 1 h; and then the temperature is reduced to normal temperature at the rate of 15 ℃/min to prepare the 8-hole cellular thallium adsorbing material with the length of 0.8 meter.
The feed comprises the following raw materials in parts by weight: fe (OH)32 parts of titanium-based porous material 88 parts, 6 parts of glass fiber, 1.5 parts of cotton pulp, 3 parts of CuO and Fe2O34 parts, 0.9 part of hydroxypropyl methyl cellulose, 1.2 parts of silicon dioxide, 0.3 part of carboxymethyl cellulose (CMC), 0.2 part of polyethylene oxide (PEO), 3.2 parts of oxalic acid and 71 parts of water.
The 8-hole honeycomb thallium adsorbing material can be directly installed at the position of not less than 2 meters in front of an 8-hole honeycomb denitration catalyst module (using an 8-hole mold with the same size) without intervals (direct connection, mutual dislocation and hole-to-hole direct connection), and an air soot blower needs to be configured.
Performance testing
1. The specific surface area and total pore volume of the adsorbent material were measured using a physical adsorption apparatus (macbeche, japan). The specific surface area is calculated by a Brunauer-Emmett-Teller (BET) method, the total pore volume is calculated by a non-local density functional biology (NLDFT) method, the ratio of the pore diameter in the pore structure of 100-250nm is obtained by a mercury intrusion method test, and the result is shown in Table 1.
TABLE 1
As can be seen from Table 1, the specific surface area of the adsorbent of the present invention is 50 to 70m2(ii)/g; the total pore volume of the adsorbing material is 0.3-0.6 cm3In addition, the pore diameter in the pore structure is 100-250nmThe ratio is 20-50%, and the adsorbing material of the invention can adsorb substances containing thallium.
2. Adsorption Performance test
The adsorbent according to examples 1-3 was placed in the flue, in direct contact with the actual flue gas, and after each two months the adsorbent was removed and scanned by X-ray fluorescence spectroscopy (XRF) to obtain the content of Tl in terms of oxides, as shown in table 2 below.
TABLE 2
As can be seen from table 2, the adsorbing material of the present invention can adsorb thallium-containing substances more effectively, and the adsorption rate of the present invention is faster and more than that of a conventional denitration catalyst.
It should be noted that, although the technical solutions of the present invention are described by specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. An adsorbent material, comprising:
a substrate comprising a titanium-based porous material; and
a conditioning aid present on the surface and/or inside of the substrate, the conditioning aid comprising a transition metal element; wherein,
the adsorbing material has a plurality of pore structures, and the proportion of the pore diameter of 100-250nm in the pore structures is 20-50%, preferably 25-40%.
2. The adsorbing material according to claim 1, wherein the specific surface area of the adsorbing material is 50-70 m2(ii)/g; and/or the total pore volume of the adsorbing material is 0.3-0.6 cm3/g。
3. The adsorbent material according to claim 1 or 2, wherein the adsorbent material further comprises a binder and/or a proppant on the surface and/or inside thereof.
4. The adsorption material of any one of claims 1 to 3, wherein the titanium-based porous material comprises anatase titania and/or rutile titania; preferably, the particle size D90 of the titanium-based porous material is less than 5 μm; and/or, the content of titanium dioxide is not less than 97.0% by mass of the total mass of the titanium-based porous material.
5. The adsorbent material according to any one of claims 1 to 4, wherein the transition metal element is present in an amount of 0.1 to 1.5%, preferably 0.3 to 1.1%, and more preferably 0.4 to 0.9%, calculated as oxide, based on the total weight of the adsorbent material.
6. The adsorbent material according to claim 5, wherein the transition metal element comprises one or a combination of two or more of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, palladium, silver, and gold.
7. A method for producing an adsorbing material according to any of claims 1 to 6, comprising a step of attaching a conditioning aid to the surface and/or inside of the titanium-based porous material.
8. The method of manufacturing according to claim 7, comprising the steps of:
mixing a titanium-based porous material, a regulating assistant precursor and a pore-forming agent to obtain precursor slurry; preferably, the precursor slurry further comprises one or more of a combination of a binder, a proppant, a stabilizer and a dispersant;
and mixing and extruding the precursor slurry, and roasting to obtain the adsorbing material.
9. The production method according to claim 7 or 8, wherein the conditioning additive precursor includes one or a combination of two or more of an oxide of a transition metal, a hydroxide of a transition metal, and a salt of a transition metal; and/or the presence of a gas in the gas,
the temperature rising rate of the roasting is 1-20 ℃/min, the temperature is finally raised to 400-650 ℃, and the temperature is kept for 1-8 hours.
10. Use of an adsorption material according to any one of claims 1 to 6 for adsorbing compounds containing thallium elements; preferably, the adsorption material is used for protecting the denitration catalyst in the smoke containing the thallium element.
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| CN115155523A (en) * | 2022-07-22 | 2022-10-11 | 北京清新环境技术股份有限公司 | Composite adsorption catalyst for synergistically removing mercury and sulfur dioxide in flue gas and preparation method and application thereof |
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