CN108686670A - A kind of anti-H for denitrating flue gas2O,SO2, heavy metal and dust poison multicomponent catalyst - Google Patents
A kind of anti-H for denitrating flue gas2O,SO2, heavy metal and dust poison multicomponent catalyst Download PDFInfo
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- CN108686670A CN108686670A CN201810530813.XA CN201810530813A CN108686670A CN 108686670 A CN108686670 A CN 108686670A CN 201810530813 A CN201810530813 A CN 201810530813A CN 108686670 A CN108686670 A CN 108686670A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 239000000428 dust Substances 0.000 title abstract description 22
- 229910001385 heavy metal Inorganic materials 0.000 title abstract description 17
- 239000002574 poison Substances 0.000 title abstract description 14
- 231100000614 poison Toxicity 0.000 title abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003546 flue gas Substances 0.000 claims abstract description 37
- 229910018605 Ni—Zn Inorganic materials 0.000 claims abstract description 18
- 239000002905 metal composite material Substances 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 229910001868 water Inorganic materials 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 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 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 4
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 28
- 150000004706 metal oxides Chemical class 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 29
- 239000002994 raw material Substances 0.000 description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000003245 coal Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000002468 redox effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical class [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 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
- 230000015689 metaplastic ossification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical class [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
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Abstract
The present invention relates to a kind of anti-H for denitrating flue gas2O,SO2, heavy metal and dust poison multicomponent catalyst, belong to multi-element metal oxide technical field of function materials.The present invention provides a kind of Fe-Ce-Ni-Zn/TiO2Five yuan of metal composite oxide catalysts.The polynary denitrating catalyst that the present invention uses has wider denitration temperature window and preferable low-temperature denitration activity, especially anti-H2O,SO2, that heavy metal and dust poison ability is stronger.
Description
Technical field
The present invention relates to multi-element metal oxide technical field of function materials, and in particular to a kind of for the anti-of denitrating flue gas
H2O,SO2, heavy metal and dust poison multicomponent catalyst more particularly to a kind of multicomponent catalyst for SCR denitrating flue gas and its
Preparation method.
Background technology
Coal, in occupation of absolute leading role, and long-term accounts for China's primary energy consumption in Chinese national economy construction
The ratio of total amount close even higher than 70%.In coal in China consumption, 80% coal is used as steam coal, is directly used in combustion
It burns and generates thermal energy and power.But coal is a kind of low-grade fossil fuel, and there are a large amount of oxysulfides, nitrogen oxygen in combustion product gases
The pollutants such as compound and carbon dioxide.According to statistics:CO, CO of Discharged form Coal Combustion in China2,SO2, NOX and dust account for total fuel combustion
The ratio for burning discharge capacity is followed successively by 71%, 85%, 90%, 70% and 70%.
Although China has obtained significant results to the control of sulfur dioxide and dust, and compared to sulfur dioxide and dust etc.
The reduction of gross contamination emission, discharged nitrous oxides total amount is but quickly increasing, according to scholarly forecast, according to current development
Trend is up to 35,400,000 tons if not taking effective control measure to the year two thousand thirty nitrogen oxide emission, certainly will give China's ecology
Environment and national economy cause huge harm.Meanwhile nitrogen oxides is also in rising trend to the contribution of China's Acid Rain Pollution, acid rain
Middle NO3- concentration obviously increases, and the Acid Rain Pollution of China some areas is just gradually from sulfuric acid type to sulfuric acid, the compound transformation of nitric acid.
Also, nitrogen oxides also has very strong greenhouse effects.Therefore, the discharge for controlling nitrogen oxides, especially controls coal fired thermal power plant
The discharge of nitrogen oxides is trend of the times.
In recent years, in a variety of coal fired thermal power plant denitration technologies, selective catalytic reduction (Selective catalytic
Reduction, SCR), relatively cost-effective because of its denitration efficiency height, oneself becomes the mainstream of current China's coal fired thermal power plant denitration
Technology.Selective catalytic reduction (SCR) denitration is primarily referred to as under the effect of the catalyst, and (coal fired thermal power plant denitration is also for reducing agent
Former agent is mainly urea and NH3, " selective " reacted with NOX in flue gas, generate nontoxic, free of contamination nitrogen and water.
Currently, SCR denitration used in coal-burning power plant of China is vanadium tungsten titanium series, be required for greatly import or
Foreign technology is quoted, therefore first this and the renewal cost dressed up of SCR catalyst is all very high.And due to denitration temperature it is higher (300~
400 DEG C), SCR device can only be arranged between economizer and air preheater.But contain herein there are a large amount of flying dusts in flue gas
There are alkali metal, the substances such as arsenic and mercury inevitably to corrode and poison catalyst, catalyst is caused to be easy inactivation, service life
It does not grow, and complicated component in flue gas, also be easy to cause catalyst poisoning, lead to life time decay;Meanwhile vanadium tungsten titanium series catalyst
Vanadium component is easy to run off in agent, can be caused serious injury to environment and human body.Therefore, catalyst, which has become, restricts China's popularization and application
SCR denitration technology, the principal element for controlling coal fired thermal power plant discharged nitrous oxides.
Therefore, research is nontoxic, denitration performance is good, denitration temperature window mouth width, the SCR denitration of inexpensive, especially
It is that denitration temperature is low, the strong catalyst for denitrating flue gas of anti-poisoning capability, in China there is important practical application to anticipate
Justice, it has also become one of the focus of line research staff's common concern in the industry.
Invention content
The multicomponent catalyst and preparation method thereof that the object of the present invention is to provide a kind of for denitrating flue gas, it is especially a kind of
For the catalyst of SCR denitrating flue gas, the polynary denitrating catalyst that the present invention uses, have wider denitration temperature window and
Preferable low-temperature denitration activity, especially anti-H2O,SO2, that heavy metal and dust poison ability is stronger.
In order to achieve the above objectives, the present invention provides a kind of multicomponent catalyst for denitrating flue gas, specially a kind of Fe-
Ce-Ni-Zn/TiO2Five yuan of metal composite oxide catalysts, wherein
The molar ratio of element of Fe/Ti is (0.2~0.7):1;
The molar ratio of Elements C e/Ti is (0.05~0.8):1;
The molar ratio of element Ni/Ti is (0.2~0.6):1;
The molar ratio of element Zn/Ti is (0.05~0.5):1.
Preferably, the catalyst has porous structure.
Preferably, the granularity of the catalyst is 50~3500 mesh.
Preferably, the porosity of the catalyst is 2.5~1500m2/g。
Preferably, the specific surface area of the catalyst is 0.008~0.48cm3/g。
Invention also provides a kind of preparation methods of above-mentioned multicomponent catalyst for denitrating flue gas, including following step
Suddenly:
A soluble source of iron, soluble cerium source, soluble nickel source, soluble Zn source, titanium dioxide) are dissolved in polyvinyl alcohol
In aqueous solution, a certain amount of titania powder is added and is mixed, dry after being vigorously stirred, irradiation obtains intermediate powder;
B it) will be ground after intermediate powder calcination that above-mentioned steps obtain, obtain the catalyst for denitrating flue gas.
Preferably, the drying is dried using microwave dryer, and drying time is 10-60 minutes.
Preferably, the irradiation is irradiated using low-energy electronic accelerator irradiation devices, irradiation 0.1-0.3MeV,
Irradiation time is 1-3 minutes.
Preferably, the calcination temperature is 400-600 DEG C, and the time is 0.5-2.5 hours.
Preferably, the time being vigorously stirred is 3-5 minutes.
Preferably, the mass concentration of the polyvinyl alcohol water solution is 0.1%-4%.
Preferably, the soluble source of iron includes bivalent soluble source of iron and/or trivalent solubility source of iron.
Preferably, the soluble source of iron includes ferric sulfate, ferrous sulfate, iron chloride, frerrous chloride, ferric nitrate and nitric acid
It is one or more in ferrous iron;
The solubility cerium source includes one or more in cerous sulfate, cerium chloride and cerous nitrate;
The solubility nickel source includes one or more in nickel sulfate, nickel chloride and nickel nitrate;
The soluble Zn source includes one or more in zinc sulfate, zinc chloride and zinc nitrate.
The present invention provides a kind of multicomponent catalysts for denitrating flue gas, are Fe-Ce-Ni-Zn/TiO2Five yuan of metals
Composite oxide catalysts.Compared with prior art, the present invention is toxic for existing vanadium Titanium series catalyst, denitration temperature is high,
The problems such as cost height carry out creative selection and research, it is believed that ferrum-based catalyst has ring in numerous catalyst
The advantages that border is nontoxic, denitration is at low cost is a kind of SCR denitration of great exploitation potential, and is carried out in various metals
Combination, with preferable catalytic performance and on the basis of stability, temperature window is applied in broadening, especially has preferable low temperature
Active and anti-H2O,SO2, heavy metal and dust poison ability, finally obtained the Fe-Ce-Ni-Zn/TiO of the present invention2Five yuan of gold
Belong to composite oxide catalysts.Fe-Ce-Ni-Zn/TiO provided by the invention2Five yuan of metal composite oxide catalysts, can be with
The advantages of regarding as iron-based, titanium-based or cerium base catalyst, and combining above-mentioned catalyst, each component cooperate, and compensate for original
There is the deficiency of single catalyst.The addition of wherein Fe can improve the low temperature active and sulfur poisoning resistance of denitrating catalyst, but
SO in flue gas2It is very big to the activity influence of denitrating catalyst, and also not for the influencing mechanism of different catalyst system and catalyzings
Together, and middle low-temperature denitration activity is still insufficient, and the multi-element metal oxide of the present invention effectively raises the comprehensive of antitoxinization
Conjunction ability;Elements C e is nontoxic, rich reserves, and has excellent redox property, but low temperature active and sulfur poisoning-resistant energy
Power is insufficient, and the multi-element metal oxide of the present invention effectively compensates for its drawbacks described above.Fe-Ce-Ni- provided by the invention
Zn/TiO2Five yuan of metal composite oxide catalysts have anti-H as SCR catalyst for denitrating flue gas2O,SO2, heavy metal and powder
The advantages that toxic dust ability is strong, denitration is at low cost also has higher thermal stability, wider temperature window and preferable low
Warm denitration activity.The experimental results showed that Fe-Ce-Ni-Zn/TiO provided by the invention2Five yuan of metal composite oxide catalysts,
Catalytic efficiency and catalytic activity temperature are adjustable with synthesis component, and water resistant Sulfur tolerance is preferable, in H2O and SO2Existing a certain range
Interior, catalytic efficiency is stablized 91% or more.
Description of the drawings
Fig. 1 is the SEM electromicroscopic photographs of multi-element metal oxide powder prepared by the embodiment of the present invention 1;
Fig. 2 is the EDS energy spectrum diagrams of multi-element metal oxide powder prepared by the embodiment of the present invention 1;
Fig. 3 is the denitration catalyst rate detection figure of multi-element metal oxide powder prepared by the embodiment of the present invention 1.
Specific implementation mode
In order to further appreciate that the present invention, the preferred embodiments of the invention are described with reference to embodiment, but
It is it should be appreciated that these descriptions are only the feature and advantage further illustrated the present invention rather than to patent requirements of the present invention
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to people in the art
It is prepared by conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or metal composite oxygen
The purity of compound field routine.
The present invention provides a kind of multicomponent catalyst for denitrating flue gas, specially a kind of Fe-Ce-Ni-Zn/TiO2Five
First metal composite oxide catalyst.
The definition of the multi-element metal oxide is not particularly limited in the present invention, with well known to those skilled in the art more
First metal oxide or composite oxide of metal.The present invention is to the ingredient of the multi-metal oxide catalyst without spy
It does not limit, those skilled in the art can select and adjust according to practical situations, raw material condition and product requirement.
The present invention is to be more advantageous to SCR denitrating flue gas, is especially more advantageous to the middle low temperature SCR denitration of power-plant flue gas, institute
State element of Fe/Ti, i.e., the molar ratio of the described element of Fe and element ti is preferably (0.2~0.7):1, more preferably (0.2~
0.6):1, more preferably (0.3~0.5):1, most preferably (0.35~0.45):1;The Elements C e/Ti, i.e., the described Elements C e
Molar ratio with element ti is preferably (0.05~0.8):1, more preferably (0.2~0.5):1, more preferably (0.3~0.5):
1, most preferably (0.35~0.45):1;The molar ratio of the element Ni/Ti, i.e., the described element Ni and element ti is preferably (0.2
~0.6):1, more preferably (0.3~0.5):1, more preferably (0.35~0.5):1, most preferably (0.35~0.45):1;Institute
State element Zn/Ti, i.e., the molar ratio of the described element Zn and element ti is preferably (0.05~0.5):1, more preferably (0.1~
0.5):1, more preferably (0.2~0.4):1, most preferably (0.3~0.4):1.
The pattern of the multi-metal oxide catalyst is not particularly limited in the present invention, ripe with those skilled in the art
The pattern for the multi-metal oxide catalyst known is not particularly limited, and those skilled in the art can be according to practical application feelings
Condition, raw material condition and product requirement are selected and are adjusted, and catalyst of the present invention is preferably nano material, the catalysis
The granularity of agent is preferably 50~3500 mesh, more preferably 100~3000 mesh, more preferably 500~3000 mesh, most preferably 1000
~2000 mesh.Catalyst of the present invention preferably has porous structure;The porosity of the catalyst is preferably 2.5~
1500m2/ g, more preferably 10~1000m2/ g, more preferably 100~400m2/ g, most preferably 300~400m2/g;It is described to urge
The specific surface area of agent is preferably 0.008~0.48cm3/ g, more preferably 0.01~0.30cm3/ g, more preferably 0.06~
0.25cm3/ g, most preferably 0.15~0.25cm3/g.Catalyst of the present invention for denitrating flue gas is preferred for SCR cigarettes
The catalyst of qi exhaustion nitre is more preferably used for the catalyst of middle low-temperature smoke air SCR denitration, is more specifically preferred in power-plant flue gas
The catalyst of low temperature SCR denitration.
The present invention is preferably 220~350 DEG C to the temperature in use of the catalyst, more preferably 230~330 DEG C, more excellent
It is selected as 250~280 DEG C, most preferably 260~270 DEG C;Wherein low temperature temperature in use can be 200~250 DEG C, or be 210
~240 DEG C, it is either 220~230 DEG C again or is 220~225 DEG C.
Above-mentioned steps of the present invention provide a kind of Fe-Ce-Ni-Zn/TiO2Five yuan of metal composite oxide catalysts, can be with
The advantages of regarding as iron-based, titanium-based or cerium base catalyst, and combining above-mentioned catalyst, each component cooperate, and compensate for original
There is the deficiency of single catalyst.The present invention further optimizes combination to component, with TiO2For carrier, low temperature is urged during Fe is used as
Change doped body, rare earth metal Ce, transition metal Zn and Ni are prepared for multicomponent Fe-Ce- as enhancing catalytic performance auxiliary agent
Ni-Zn/TiO2Five yuan of metal composite oxide catalysts, each component flexible ratio is adjustable, and not only synthesis cost is relatively low, Er Qiegeng
Add the low temperature SCR denitration suitable for power-plant flue gas.Fe-Ce-Ni-Zn/TiO provided by the invention2Five yuan of metal composite oxidations
Object catalyst has anti-H2O,SO2, heavy metal and dust poison the advantages that ability is strong, denitration is at low cost, also there is higher heat
Stability, wider temperature window and preferable low-temperature denitration activity.
The present invention also provides a kind of preparation methods of above-mentioned multicomponent catalyst for denitrating flue gas, including following step
Suddenly:
A soluble source of iron, soluble cerium source, soluble nickel source, soluble Zn source, titanium dioxide) are dissolved in polyvinyl alcohol
In aqueous solution, a certain amount of titania powder is added and is mixed, dry after being vigorously stirred, irradiation obtains intermediate powder;
B it) will be ground after intermediate powder calcination that above-mentioned steps obtain, obtain the catalyst for denitrating flue gas.
The present invention especially indicates the range of choice and optimum principle of the poly metal oxide nano material, such as nothing,
It is consistent with the range of choice and optimum principle of the catalyst nano material that is previously used for denitrating flue gas, it no longer goes to live in the household of one's in-laws on getting married one by one herein
It states.
Soluble source of iron, soluble cerium source, soluble nickel source, soluble Zn source, titanium dioxide are dissolved in by the present invention first
In polyvinyl alcohol water solution, a certain amount of titania powder is added and is mixed, dry after being vigorously stirred, irradiation obtains centre
Powder.
After low concentration polyethylene alcohol is dissolved in the water, aqueous solution has certain stickiness and mobility, a variety of inorganic metal acid
Salt, which is added in low concentration polyethylene alcohol solution, preferably to be connect by the stickiness of polyvinyl alcohol itself and functional group
Touch reaction.And in high-temperature calcination processing, high molecular polymer polyvinyl alcohol can be completely removed, and not interfere with multi-element metal
The generation of oxide catalyst.The mass concentration of the polyvinyl alcohol water solution is preferably 0.1%-4%.The present invention is to described poly-
The addition of vinyl alcohol aqueous solution is not particularly limited, using the ratio of final products as standard, pilot process consume or real
Border inventory, those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement
It is whole.
The soluble source of iron is not particularly limited in the present invention, is with soluble source of iron well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical situations, raw material condition and product requirement
The bright soluble source of iron preferably includes bivalent soluble source of iron and/or trivalent solubility source of iron, more preferably bivalent soluble
Source of iron or trivalent solubility source of iron;It is of the present invention solubility source of iron specifically preferably include ferric sulfate, ferrous sulfate, iron chloride,
It is one or more in frerrous chloride, ferric nitrate and ferrous nitrate, more specifically preferably ferric sulfate, ferrous sulfate, iron chloride, chlorine
Change ferrous, ferric nitrate or ferrous nitrate, most preferably ferric nitrate.The present invention is not special to the addition of the soluble source of iron
Limitation, using the ratio of final products as standard, pilot process consume or practical inventory, those skilled in the art can roots
It is selected and is adjusted according to practical condition, raw material condition and product requirement.
The soluble cerium source is not particularly limited in the present invention, is with soluble cerium source well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical situations, raw material condition and product requirement
The bright soluble cerium source preferably includes one or more in cerous sulfate, cerium chloride and cerous nitrate, more preferably cerous sulfate, chlorine
Change cerium or cerous nitrate, most preferably cerous nitrate.The addition in the soluble cerium source is not particularly limited in the present invention, with final
The ratio of product is standard, and pilot process consume or practical inventory, those skilled in the art can be according to actual productions
Situation, raw material condition and product requirement are selected and are adjusted.
The soluble nickel source is not particularly limited in the present invention, is with soluble nickel source well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical situations, raw material condition and product requirement
The bright soluble nickel source preferably includes one or more in nickel sulfate, nickel chloride and nickel nitrate, more preferably nickel sulfate, chlorine
Change nickel or nickel nitrate, most preferably nickel nitrate.The addition of the soluble nickel source is not particularly limited in the present invention, with final
The ratio of product is standard, and pilot process consume or practical inventory, those skilled in the art can be according to actual productions
Situation, raw material condition and product requirement are selected and are adjusted.
The soluble Zn source is not particularly limited in the present invention, is with soluble Zn source well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical situations, raw material condition and product requirement
The bright soluble Zn source preferably includes one or more in zinc sulfate, zinc chloride and zinc nitrate, more preferably zinc sulfate, chlorine
Change zinc or zinc nitrate, most preferably zinc nitrate.The addition in the soluble Zn source is not particularly limited in the present invention, with final
The ratio of product is standard, and pilot process consume or practical inventory, those skilled in the art can be according to actual productions
Situation, raw material condition and product requirement are selected and are adjusted.
The addition of the titanium dioxide is not particularly limited in the present invention, using the ratio of final products as standard,
Pilot process consumes or practical inventory, those skilled in the art can be according to practical condition, raw material condition and products
It is required that being selected and being adjusted.
The mode and condition of the drying is not particularly limited in the present invention, with drying side well known to those skilled in the art
Formula and condition, those skilled in the art can select according to practical condition, raw material condition and product requirement
And adjustment.The mode of drying of the present invention is preferably dried using microwave dryer.Microwave drying is a kind of novel do
Dry mode.When dry, microwave energy directly acts on medium molecule and is converted into thermal energy, since there is microwave penetration performance to make in medium
It heats simultaneously outside, heat transfer is not needed, so heating speed is very fast.Simultaneously regardless of object any shape, due to Jie of object
Matter is inside and outside to be heated simultaneously, and the internal-external temperature difference of material is small, and homogeneous heating makes dry mass greatly improve.The time of the drying is excellent
It is selected as 10~60 minutes, more preferably 20~40 minutes, most preferably 20~30 minutes.
The mode and condition of the irradiation is not particularly limited in the present invention, with irradiation side well known to those skilled in the art
Formula and condition, those skilled in the art can select according to practical condition, raw material condition and product requirement
And adjustment.The mode of irradiation of the present invention is preferably irradiated using low-energy electronic accelerator irradiation devices.Electron accelerator
With room temperature, it is not damaged, without residual hazard, environmental protection, low energy consumption, operation it is easy to operate, high degree of automation, be suitable for large-scale industry
The features such as metaplasia is produced.Ultrasound needs 6 hours, and microwave needs 20min (but in fact not enough uniformly effectively, energy or low).It is described
Irradiation is 0.1-0.3MeV, more preferably 0.15-0.25MeV, most preferably 0.18-0.22MeV;The irradiation time is 1-
3 minutes;More preferably 1.5-2.5 minutes, most preferably 1.8-2.2 minutes.
The present invention will finally be ground after intermediate powder calcination that above-mentioned steps obtain, obtain the catalysis for denitrating flue gas
Agent.
The mode and condition of the calcining is not particularly limited in the present invention, with calcining side well known to those skilled in the art
Formula and condition, those skilled in the art can select according to practical condition, raw material condition and product requirement
And adjustment, the mode of calcining of the present invention is preferably Muffle furnace, is more preferably calcined in air atmosphere;The temperature of the calcining
Preferably 400~600 DEG C of degree, more preferably 500~575 DEG C, most preferably 550~560 DEG C;The time of the calcining is specifically excellent
It is selected as 0.5~2.5 hour, more preferably 1~2 hour, most preferably 1.5~1.8 hours.
The mode being vigorously stirred and condition is not particularly limited in the present invention, with play well known to those skilled in the art
Strong agitating mode and condition, those skilled in the art can be according to practical condition, raw material condition and product requirements
It is selected and is adjusted.The time being vigorously stirred is 3-5 minutes.
The mode and condition of the grinding is not particularly limited in the present invention, with grinding side well known to those skilled in the art
Formula and condition, those skilled in the art can select according to practical condition, raw material condition and product requirement
And adjustment, the granularity of grinding of the present invention is preferably 50~3800 mesh, more preferably 100~3000 mesh, more preferably 500~
2500 mesh, most preferably 1000~2000 mesh.
Above-mentioned steps of the present invention provide a kind of multicomponent catalyst for denitrating flue gas, i.e. Fe-Ce-Ni-Zn/TiO2Five
The preparation method of first metal composite oxide catalyst.The present invention particularly prepares the catalyst using hydro-thermal method, Fe, Ce, Ni,
Good interaction occurs for Zn and Ti groups branch, and the interworking of catalyst components can be made to reach more preferably effect, improved whole
The redox property of body metal composite oxide catalyst, low-temperature catalytic oxidation NO are NO2Performance, while helping to be catalyzed
The crystal grain refinement of agent, surface area increase, and provide more activity for SCR reactions, finally denitration performance are promoted to be substantially improved, carried simultaneously
High low temperature SCR denitration activity so that denitration temperature window is substantially widened, and is effectively extended to low-temperature space, effective solution
Low-temperature denitration activity is relatively low in existing ferrum-based catalyst, and preparation process is not mature enough, limit its large-scale industry and answer
Inherent shortcoming is more appropriately applied to the removing of the discharged nitrogen oxides of China's coal fired thermal power plant.The experimental results showed that this
The multi-element metal oxide provided is provided, catalytic efficiency and catalytic activity temperature are adjustable with synthesis component, and water resistant Sulfur tolerance compared with
It is good, anti-H2O,SO2, that heavy metal and dust poison ability is strong, in H2O and SO2In existing a certain range, catalytic efficiency is stablized
91% or more.
In order to further illustrate the present invention, it a kind of is urged with reference to embodiments for denitrating flue gas to provided by the invention
Agent and preparation method thereof is described in detail, but it is to be understood that these embodiments are before being with technical solution of the present invention
It puts and is implemented, give detailed embodiment and specific operating process, only the spy to further illustrate the present invention
It seeks peace advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following embodiments.
Embodiment 1
It is 0.2 by molar ratio:0.05:0.2:0.05:1 0.2g iron chloride, 0.09g cerium chlorides, 0.16g nickel chlorides and
0.04g zinc chloride, 0.5g titania powders are dissolved in 30mL polyvinyl alcohol water solutions (mass concentration 0.1%), are added certain
Amount titania powder is mixed, and is put into microwave dryer 10 minutes after being vigorously stirred 3 minutes, is then placed in low-energy electron and adds
In fast device irradiation devices, irradiation is set as 0.1MeV, and after processing in 1 minute, lower 400 DEG C of air atmosphere is calcined 0.5 hour, is ground into
Powder.Quickly, Fe-Ce-Ni-Zn/TiO is efficiently prepared2Five yuan of metal composite oxide catalysts.
The multi-element metal oxide prepared to the embodiment of the present invention 1 characterizes.Fig. 1 is prepared by the embodiment of the present invention 1
The SEM electromicroscopic photographs of multi-element metal oxide powder.Fig. 2 is multi-element metal oxide powder prepared by the embodiment of the present invention 1
EDS energy spectrum diagrams.Fig. 3 is the XRD spectrum of multi-element metal oxide powder prepared by the embodiment of the present invention 1.Table 1 is multi-element metal oxygen
The atomic percent of each component is corresponded in compound powder.
The atomic percent of each component is corresponded in 1 multi-element metal oxide powder of table
| Element | Atomic percent |
| O | 62.08 |
| Ti | 20.78 |
| Fe | 4.54 |
| Ni | 4.26 |
| Zn | 1.58 |
| Ce | 6.75 |
| Total amount: | 100.00 |
By Fig. 2 and table 1 it is found that the controllable multi-element metal oxide of specific ratio has been prepared in the present invention.
Poly metal oxide nano material prepared by the embodiment of the present invention 1 is carried out using detection.
Test example one
The experimental provision reactor that SCR removes NO uses fixed bed quartz tube reactor, internal diameter 1cm, reaction temperature
By the K-type thermocouple measurement in intercalation reaction device.Simulated flue gas condition is supplied using steel cylinder, flue gas includes Ar (with H2O),
NO/Ar,O2,SO2/ Ar and NH3The flow of/Ar, gas are controlled and are adjusted by mass flowmenter with composition, steam H2O is by Ar
By being taken out of after steam generating means, react using Ar as balanced gas.In the reaction starting stage, it is real first to carry out saturation absorption
It tests, i.e., is re-introduced into NH after reactor inlet and outlet NO, concentration reach balance3Carry out SCR reactions.The practical typical flue gas of simulation
Distribution composition:500ppmNO/Ar, 500ppmNH3/ Ar, 4%O2, Ar is (with H2O(10-30g/m3)) it is carrier gas.Temperature model
It is 75-400 DEG C to enclose, and reaction pressure is normal pressure, and air speed ratio is 10000/h.Wherein NO and NH3Ratio run according to practical power plant
When the mix proportion scheme that uses, be 1:1.The results are shown in Table 2.
Table 2Fe-Ce-Ni-Zn/TiO2Five yuan of composite oxide of metal are in different temperatures and SO2NO reduction conversions under concentration
Rate
By testing result it is found that multi-element metal oxide prepared by the present invention, has wider denitration temperature window (220-
350 DEG C) and preferable low-temperature denitration activity (91% or more).
Test example two
It is urged since the various metallic elements released when the fuel combustions such as coal can be moved to by dust
Agent surface makes to will also result in catalyst poisoning inactivation while catalyst blockage.Denitrating catalyst is urged to investigate dust
Change activity influence, carries out antidusting experimental simulation in this project testing, the dust of experiment is derived from coal-fired boiler in power plant, by weight
The dust of percentage 1%-10% is placed in quartz reactor leading portion, and control N2 air-flows are 200-2000mL/min, experimental temperature model
Enclose is 150-400 DEG C.The SCR catalyst powder for being put among quartz reactor is placed in dust-contained airflow 3-36 hours, then
Dust is removed to measure the denitration activity of SCR catalyst again in the typical reaction atmosphere of SCR denitration test device.Mould
The distribution composition of quasi- practical typical flue gas:500ppmNO/Ar, 500ppmNH3/ Ar, 4%O2, Ar is (with H2O(10-30g/m3))
For carrier gas.Reaction pressure is normal pressure, and air speed ratio is 10000/h.Wherein NO and NH3Ratio use when being run according to practical power plant
Mix proportion scheme, be 1:1.The results are shown in Table 3.
3 Fe-Ce-Ni-Zn/TiO of table2Five yuan of composite oxide of metal are under different weight percentage dust purge time
NO restore conversion ratio
By testing result it is found that multi-element metal oxide prepared by the present invention, there is stronger anti-dust to poison ability,
High NO conversion ratios can be maintained in 36 hours.
Test example three
China's fire coal ingredient is extremely complex, present in impurity many heavy metals can be discharged in burning, these a huge sum of money
Category can be enriched to SCR catalyst surface in catalytic process, and catalyst poisoning is caused to inactivate.The present invention is with regard to several typical cases in flue dust
Heavy metal element (Cu, As, Pb) is tested the activity influence of SCR denitration.It is real that this project carries out preventing from heavy metal
Test tries:By CuO, PbO, A of incorporation weight percent 0.1%-5% respectivelyS2O3Catalyst afterwards carries out the de- of SCR catalyst
The active measurement of nitre simulates the distribution composition of practical typical flue gas:500ppmNO/Ar, 500ppmNH3/ Ar, 4%O2, Ar is (adjoint
H2O(10-30g/m3)) it is carrier gas.Reaction pressure is normal pressure, and air speed ratio is 10000/h.Wherein NO and NH3Ratio according to reality
The mix proportion scheme that power plant uses when running is 1:1.
4 Fe-Ce-Ni-Zn/TiO of table2Five yuan of composite oxide of metal are under the incorporation of different weight percentage heavy metal
NO restores conversion ratio
By testing result it is found that by testing result it is found that multi-element metal oxide prepared by the present invention, has stronger anti-
Heavy metal poisons ability.
Embodiment 2
It is 0.7 by molar ratio:0.8:0.6:0.5:1 1.84g iron chloride, 3.64g cerium chlorides, 1.05g nickel chlorides and
1.09g zinc chloride, 1.3g titania powders are dissolved in 75mL polyvinyl alcohol water solutions (mass concentration 1.6%), are added certain
Amount titania powder is mixed, and is put into microwave dryer 35 minutes after being vigorously stirred 4 minutes, is then placed in low-energy electron and adds
In fast device irradiation devices, irradiation is set as 0.2MeV, and after processing in 2 minutes, lower 550 DEG C of air atmosphere is calcined 2 hours, is pulverized
End.Quickly, Fe-Ce-Ni-Zn/TiO is efficiently prepared2Five yuan of metal composite oxide catalysts.
Poly metal oxide nano material prepared by the embodiment of the present invention 2 is carried out using detection.
Method is the same as embodiment 1.
By testing result it is found that multi-element metal oxide prepared by the present invention, anti-H2O,SO2, dust and heavy metal poison energy
Power is strong, also has higher thermal stability, wider temperature window (220-350 DEG C) and preferable low-temperature denitration activity
(91% or more).
Embodiment 3
It is 0.2 by molar ratio:0.2:0.2:0.2:1 0.44g ferric sulfate, 0.69g cerous sulfates, 0.33g nickel sulfates and
0.54g zinc sulfate, 0.7g titania powders are dissolved in 100mL polyvinyl alcohol water solutions (mass concentration 4%), are added a certain amount of
Titania powder is mixed, and is vigorously stirred and is put into microwave dryer after five minutes 60 minutes, and low-energy electron acceleration is then placed in
In device irradiation devices, irradiation is set as 0.3MeV, and after processing in 3 minutes, lower 600 DEG C of air atmosphere is calcined 2.5 hours, is pulverized
End.Quickly, Fe-Ce-Ni-Zn/TiO is efficiently prepared2Five yuan of metal composite oxide catalysts.
Poly metal oxide nano material prepared by the embodiment of the present invention 3 is carried out using detection.
Method is the same as embodiment 1.
By testing result it is found that multi-element metal oxide prepared by the present invention, anti-H2O,SO2, dust and heavy metal poison energy
Power is strong, also has higher thermal stability, wider temperature window (220-350 DEG C) and preferable low-temperature denitration activity
(91% or more).
Above to the catalyst provided by the present invention for SCR denitrating flue gas, it to be especially used for low-temperature SCR in power-plant flue gas
Catalyst of denitration and preparation method thereof.It is described in detail, specific case used herein is to the principle of the present invention
And embodiment is expounded, the explanation of above example is only intended to help to understand that the method for the present invention and its core are thought
Think, including best mode, and but also any person skilled in the art can put into practice the present invention, including manufactures and use
Any device or system, and implement the method for any combination.It should be pointed out that coming for those skilled in the art
It says, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention, these improvement and modification
It also falls within the protection scope of the claims of the present invention.The range of patent protection of the present invention is defined by the claims, and can
Including those skilled in the art it is conceivable that other embodiment.It is not different from right if these other embodiments have and wants
The structural element of character express is sought, or if they include and equivalent structure of the character express of claim without essence difference
Element, then these other embodiments should also be included in the scope of the claims.
Claims (10)
1. a kind of multicomponent catalyst for denitrating flue gas, which is characterized in that it is Fe-Ce-Ni-Zn/TiO2Five yuan of metal composites
Oxide catalyst.
2. multicomponent catalyst according to claim 1, which is characterized in that wherein,
The molar ratio of element of Fe/Ti is (0.2~0.7):1;
The molar ratio of Elements C e/Ti is (0.05~0.8):1;
The molar ratio of element Ni/Ti is (0.2~0.6):1;
The molar ratio of element Zn/Ti is (0.05~0.5):1.
3. multicomponent catalyst according to claim 1, which is characterized in that the catalyst has porous structure, described to urge
The granularity of agent is 50~3500 mesh, and the porosity of the catalyst is 2.5~1500m2/ g, the specific surface area of the catalyst
For 0.008~0.48cm3/g。
4. a kind of preparation method of the multicomponent catalyst described in claim 1 for denitrating flue gas, which is characterized in that including with
Lower step:
A) by soluble source of iron, soluble cerium source, soluble nickel source, soluble Zn source, that titanium dioxide is dissolved in polyvinyl alcohol is water-soluble
In liquid, a certain amount of titania powder is added and is mixed, dry after being vigorously stirred, irradiation obtains intermediate powder;
B it) will be ground after intermediate powder calcination that above-mentioned steps obtain, obtain the catalyst for denitrating flue gas.
5. preparation method according to claim 4, which is characterized in that the drying is dried using microwave dryer,
Drying time is 10-60 minutes.
6. preparation method according to claim 4, which is characterized in that the irradiation is using low-energy electronic accelerator irradiation dress
It sets and is irradiated, irradiation 0.1-0.3MeV, irradiation time is 1-3 minutes.
7. preparation method according to claim 4, which is characterized in that the calcination temperature is 400-600 DEG C, and the time is
0.5-2.5 hours.
8. preparation method according to claim 4, which is characterized in that the time being vigorously stirred is 3-5 minutes.
9. preparation method according to claim 4, which is characterized in that
The solubility source of iron includes one in ferric sulfate, ferrous sulfate, iron chloride, frerrous chloride, ferric nitrate and ferrous nitrate
Kind is a variety of;
The solubility cerium source includes one or more in cerous sulfate, cerium chloride and cerous nitrate;
The solubility nickel source includes one or more in nickel sulfate, nickel chloride and nickel nitrate;
The soluble Zn source includes one or more in zinc sulfate, zinc chloride and zinc nitrate.
10. preparation method according to claim 4, which is characterized in that the mass concentration of the polyvinyl alcohol water solution is
0.1%-4%.
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