CN108465471A - The production system and method for the cerium base catalyst of a kind of cooperation-removal bioxin and nitrogen oxides - Google Patents
The production system and method for the cerium base catalyst of a kind of cooperation-removal bioxin and nitrogen oxides Download PDFInfo
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- CN108465471A CN108465471A CN201810359165.6A CN201810359165A CN108465471A CN 108465471 A CN108465471 A CN 108465471A CN 201810359165 A CN201810359165 A CN 201810359165A CN 108465471 A CN108465471 A CN 108465471A
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- Prior art keywords
- oxalic acid
- reaction chamber
- catalyst
- nitrogen oxides
- pond
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 41
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 232
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 238000002156 mixing Methods 0.000 claims abstract description 52
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000005457 ice water Substances 0.000 claims abstract description 18
- 238000009413 insulation Methods 0.000 claims abstract description 17
- 238000003287 bathing Methods 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 71
- 230000000694 effects Effects 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 16
- 230000007246 mechanism Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 11
- 239000000112 cooling gas Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 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
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 238000009830 intercalation Methods 0.000 claims description 2
- 230000002687 intercalation Effects 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 23
- 238000005245 sintering Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 7
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 55
- 239000000047 product Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 239000011572 manganese Substances 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 titanium dioxide) Chemical compound 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005764 inhibitory process 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- VGGGRWRBGXENKI-UHFFFAOYSA-N 1-chlorodibenzo-p-dioxin Chemical compound O1C2=CC=CC=C2OC2=C1C=CC=C2Cl VGGGRWRBGXENKI-UHFFFAOYSA-N 0.000 description 1
- OGBQILNBLMPPDP-UHFFFAOYSA-N 2,3,4,7,8-Pentachlorodibenzofuran Chemical compound O1C2=C(Cl)C(Cl)=C(Cl)C=C2C2=C1C=C(Cl)C(Cl)=C2 OGBQILNBLMPPDP-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 241000258920 Chilopoda Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000270322 Lepidosauria Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000239226 Scorpiones Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 241000271897 Viperidae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 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 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 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
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
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- 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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
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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
- 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
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/63—Pore volume
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- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- 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
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
-
- 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
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The production system and method for a kind of cooperation-removal bioxin of the present invention and the cerium base catalyst of nitrogen oxides, belong to sintering flue gas Treatment process field.The present invention includes the evenly mixing device, preparation facilities and calciner set gradually；Wherein evenly mixing device is for mixing reactive component solution；Preparation facilities is used to prepare catalyst product, the preparation facilities includes reaction chamber and oxalic acid pond, the top of reaction chamber is provided with oxalic acid pond, the oxalic acid pond is arranged with oxalic acid dropper, oxalic acid pond and the outside of oxalic acid dropper are provided with heating and thermal insulation component, and heating and thermal insulation component is used to carry out heating and thermal insulation to oxalic acid pond and oxalic acid dropper；The outside of the reaction chamber is provided with ice water bathing pool；The calciner is for roasting the product of preparation.Cerium base catalyst prepared by the present invention improves the removal efficiency of bioxin and nitrogen oxides, it is possible to reduce the discharge of dioxin in flue gas and nitrogen oxides.
Description
Technical field
The invention belongs to sintering flue gas Treatment process fields, are related to a kind of cerium base of cooperation-removal bioxin and nitrogen oxides
The production system and method for catalyst.
Background technology
With the rising year by year of output of steel, the more chloro dibenzodioxin English and more chloros that are generated during iron ore sintering
Dibenzofurans (PCDDs/PCDFs) pollution is also more serious therewith.Bioxin has strong carcinogenic teratogenesis , bioxin
Because of its high toxicity, extremely difficult degradation in the environment can be enriched with by food chain, have fat-solubility, being capable of long distance in an atmosphere
Region is influenced from transmission or even global environment is referred to as " poison in century ".As human society recognizes bioxin harm
Know, on May 17th, 2004《Convention of Stockholm about persistence organic pollutant》It is formally effective in the whole world.Then
In June, 2012, China promulgated《Steel sintering, pelletizing industrial air pollution object discharge standard》, wherein specified in more detail enterprise
Particulate matter limit value is 20mg/m in sintering flue gas3, sulfur dioxide limit value be 200mg/m3, nitrogen oxides limit value be 300mg/m3, two
Evil English limit values are 0.5ng-TEQ/m3.And newly issue《Steel sintering, pelletizing industrial air pollution object discharge standard》(modification meaning
See original text) in regulation from 1 day January in 2019, in sintering flue gas particulate matter limit value be 20mg/m3, sulfur dioxide limit value be 50mg/
m3, nitrogen oxides limit value be 100mg/m3, bioxin limit values are 0.5ng-TEQ/m3, the wherein cities 2+26 were from October 1 in 2017
It rises day and implements.The country has more than 1000 iron ore sintering processes at present, possess Tuo bioxin equipment less than 10, therefore compel
Being essential will study for sintering flue gas bioxin removing sulfuldioxides.
It is former in sintering that sintered fume nitric oxide, bioxin removing sulfuldioxides, which mainly have three classes, the first kind, both at home and abroad at present
The compound containing amino or sulphur is added in material, forming complex compound using lone pair electrons and the catalyst of sulphur inhibits bioxin generation anti-
It answers, or is reacted with chlorion using sulfur dioxide, amine groups, reduce chlorine source and bioxin is inhibited to generate, the method effect is
Although upper have preferable inhibition to PCDD, very low to the inhibition of PCDF, and cannot remove sulfide；Second class is
Active carbon adsorption achievees the effect that adsorbing and removing bioxin, but activated carbon method is set using the porous adsorption capacity of activated carbon
Standby investment operating cost is high, and the activated carbon after absorption how to handle and new problem；Third class is selective catalysis Tuo bis- Evil
English, key are to select suitable catalyst, although vanadium Ti-base catalyst can reach higher bioxin removal efficiency,
It is at high price；Catalyst window temperature is unreasonable, and sintering flue gas needs to be again heated to 300-450 DEG C or so progress Tuo bioxin,
And the generation again of bioxin can occur for this temperature；The V2O5 that catalyst after reaction contains is extremely toxic substance, to environment and life
Object has serious pollution, and how to handle is also new problem.In recent years, cerium is because its outstanding storage oxygen, release oxygen ability, outstanding
Oxidation-reduction quality is used in the research of persistence organic pollutant (POPs) catalysis, and cerium is that richness is most in rare element
A kind of high element, price are very low.Therefore, there is an urgent need to develop a kind of catalysis suitable for iron ore sintering flue gas Tuo bioxin
Agent provides effective guarantee for steel industry clean manufacturing.
Through retrieval, innovation and creation it is entitled：Flue gas SCO denitration catalyst and preparation method thereof (number of patent application：
CN201310465375.0, the applying date:2013.09.30), by infusion process by ferric nitrate, ceria (0.1-0.5%),
Aging system is kneaded after titanium dioxide (mass content 80-90%), tungstic acid (2-10%) mixing with forming agent to calcine, wherein forging
It is DEG C calcination time 24-72 hours from room temperature to 650-750 to burn temperature.This application is disadvantageous in that：Price need to be used high
High titanium dioxide (20,000/ton) and tungstic acid (150,000/ton).
Through retrieval, innovation and creation it is entitled：A kind of rare-earth-based complex multi-component denitration, the preparation of Tuo bioxin catalyst
Method (number of patent application：CN201410467844.7, the applying date:2014.09.16), pass through a kind of rare-earth-based complex multi-component
Denitration, Tuo bioxin catalyst preparation method, using titanium dioxide (i.e. titanium dioxide), silica flour as carrier, with ammonium metatungstate, inclined vanadium
Sour ammonium, cerous nitrate and lanthanum nitrate are active component, in auxiliary material under, are made by mixing, kneading, molding, drying, roasting；
The wherein described accessory package includes monoethanolamine, citric acid, ammonium hydroxide, lactic acid, stearic acid, glass fibre, polyphosphazene polymer condensating fiber RP-
CHOP, hydroxypropyl methyl cellulose, polyethylene glycol oxide and water.This application is disadvantageous in that：It needs by being repeatedly kneaded
Journey, complicated for operation, although can reduce to flue gas dioxin content, Dui bioxin emission reduction effects are limited.
Invention content
1. technical problems to be solved by the inivention
It is an object of the present invention to for the Catalyst Plant and producer of existing removing bioxin and nitrogen oxides
Method is poor so that the performance for the catalyst being prepared is poor, provides a kind of cerium base of cooperation-removal bioxin and nitrogen oxides
The production system and method for catalyst；The catalyst prepared by the production system can improve sintering flue gas dioxin and nitrogen
The removal efficiency of oxide, it is possible to reduce the discharge of dioxin in flue gas and nitrogen oxides.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention is：
The production system of a kind of cooperation-removal bioxin of the present invention and the cerium base catalyst of nitrogen oxides, including set successively
Evenly mixing device, preparation facilities and the calciner set；Wherein evenly mixing device is for mixing reactive component solution；Prepare dress
It sets and is used to prepare catalyst product, which includes reaction chamber and oxalic acid pond, and the top of reaction chamber is provided with oxalic acid pond, should
Oxalic acid pond is arranged with oxalic acid dropper, and the outside of oxalic acid pond and oxalic acid dropper is provided with heating and thermal insulation component, heating and thermal insulation component
For carrying out heating and thermal insulation to oxalic acid pond and oxalic acid dropper；The outside of the reaction chamber is provided with ice water bathing pool；The roasting dress
It sets and is roasted for the product to preparation.
Preferably, further include grinding device, which is set to the rear end of calciner, and grinding device is used for roasting
Product after burning is ground to obtain catalyst.
Preferably, evenly mixing device includes mixing pond and rabbling mechanism, and rabbling mechanism is set to the top in mixing pond, and stirs
The stirring blade of actuator base extends to the inside in mixing pond.
Preferably, hot gas jet pipe is provided in reaction chamber, the hot gas nozzle at the top of hot gas jet pipe is corresponding with oxalic acid dropper to be set
It sets.
Preferably, the bottom in mixing pond is connected by pipeline with preparation facilities, and control valve is provided on pipeline.
Preferably, hot gas jet pipe is connected with the first gas tank, and is provided with gas heater on hot gas jet pipe, gas heating
Device is for heating the first gas tank.
Preferably, the hot gas nozzle of hot gas jet pipe is blown into heat gas to reaction chamber, and the temperature of heat gas is 60~80
℃。
Preferably, cold air jet pipe is provided on the side wall of reaction chamber, the front end of cold air jet pipe intercalation reaction intracavitary is provided with
Cold air nozzle.
Preferably, cold air nozzle tilts upward setting, and cold air nozzle is used to be blown into cooling gas, cooling gas to reaction chamber
Temperature be 0~3 DEG C.
Mixing is added in ferrous sulfate, manganese chloride, cerous nitrate and water by a kind of production method of cerium base catalyst of the present invention
In device, it is uniformly mixed so as to obtain catalyst activity component solution；Catalyst activity component solution is transferred to the reaction of preparation facilities again
In chamber, the ice water bathing pool outside reaction chamber is cooled to 0~5 DEG C to catalyst activity component solution, then the oxalic acid in oxalic acid pond is molten
Liquid is added to by oxalic acid dropper in catalyst activity component solution, and it is heavy that reaction chamber hybrid reaction during stirring generates
Form sediment, precipitation is filtered, is washed, dry after be added in calciner and roast, catalyst is made after roasting.
3. advantageous effect
Using technical solution provided by the invention, compared with prior art, have the advantages that：
(1) production system of the cerium base catalyst of of the invention a kind of cooperation-removal bioxin and nitrogen oxides, including according to
Evenly mixing device, preparation facilities and the calciner of secondary setting；Wherein evenly mixing device is for mixing reactive component solution；System
Standby device is used to prepare catalyst product, and the top of reaction chamber is provided with oxalic acid pond, which is arranged with oxalic acid dropper, grass
Sour pond and the outside of oxalic acid dropper are provided with heating and thermal insulation component, and the outside of reaction chamber is provided with ice water bathing pool, ensure that preparation
The stability of product and the performance of product, and can guarantee that the oxalic acid solution of instillation uniformly, can be mixed rapidly with reaction solution again
It closes, to promote the preparation of cerium base catalyst；
(2) production method of the cerium base catalyst of of the invention a kind of cooperation-removal bioxin and nitrogen oxides, by sulfuric acid
Ferrous iron, manganese chloride, cerous nitrate and water are added in evenly mixing device, are uniformly mixed so as to obtain catalyst activity component solution；Catalyst is lived again
Property component solution is transferred in the reaction chamber of preparation facilities, and the ice water bathing pool outside reaction chamber is cold to catalyst activity component solution
But to 0~5 DEG C, then the oxalic acid solution in oxalic acid pond is added to by oxalic acid dropper in catalyst activity component solution, reaction chamber
Hybrid reaction generates precipitation during stirring, precipitation is filtered, is washed, dry after be added in calciner and carry out
Catalyst is made in roasting after roasting, serious compared to containing higher metal environmental pollutions of bio-toxicities such as vanadium, and the present invention
Catalyst does not have bio-toxicity, and ce metal is that reserves are maximum in rare metal, possesses outstanding redox ability, price
Cheaply；And the cerium base catalyst of the present invention appoints so and has higher catalytic effect at low temperature.
Description of the drawings
Fig. 1 is the structure of the production system of a kind of cooperation-removal bioxin of the present invention and the cerium base catalyst of nitrogen oxides
Schematic diagram；
Fig. 2 is the structural schematic diagram of the preparation facilities of the present invention；
Fig. 3 is the connection diagram of the evenly mixing device and preparation facilities of the present invention；
Fig. 4 is the electron microscopic picture of cerium base catalyst prepared by the present invention；
Fig. 5 is the flow chart of the production method of the cerium base catalyst of the present invention.
Label declaration in attached drawing：
10, evenly mixing device；20, preparation facilities；30, calciner；40, grinding device；
100, reaction chamber；110, ice water bathing pool；111, water inlet；112, water outlet；120, mixing component；
130, hot air injection unit；131, the first gas tank；132, gas heater；133, hot gas jet pipe；134, hot gas nozzle；
140, cold air injection unit；141, the second gas tank；142, gas cooler；143, cold air jet pipe；144, cold air nozzle；
151, rotary supporting rod；152, retractable support arm；153, clamping device；
200, oxalic acid pond；201, electromagnetic agitation mechanism；202, mechanical agitator；
210, oxalic acid dropper；220, heating and thermal insulation component；230, oxalic acid valve；
300, mixing pond；301, control valve；310, rabbling mechanism；311, stirring blade.
Specific implementation mode
To facilitate the understanding of the present invention, below with reference to relevant drawings to invention is more fully described, in attached drawing
Several embodiments of the present invention are given, still, the present invention can realize in many different forms, however it is not limited to this paper institutes
The embodiment of description, on the contrary, purpose of providing these embodiments is make it is more thorough and comprehensive to the disclosure.
It should be noted that when element is referred to as " being fixedly arranged on " another element, it can be directly on another element
Or there may also be elements placed in the middle；When an element is considered as " connection " another element, it can be directly connected to
To another element or it may be simultaneously present centering elements；Term as used herein " vertical ", " horizontal ", " left side ",
" right side " and similar statement are for illustrative purposes only.
Unless otherwise defined, all of technologies and scientific terms used here by the article and belong to the technical field of the present invention
The normally understood meaning of technical staff is identical；Used term is intended merely to description tool in the description of the invention herein
The purpose of the embodiment of body, it is not intended that in the limitation present invention；Term " and or " used herein includes one or more phases
Any and all combinations of the Listed Items of pass.
Embodiment 1
With reference to shown in attached drawing 1, a kind of production of the cerium base catalyst of of the invention cooperation-removal bioxin and nitrogen oxides
System, including the evenly mixing device 10, preparation facilities 20 and the calciner 30 that set gradually；Wherein evenly mixing device 10 is used for reaction
Component solution is mixed, and evenly mixing device 10 includes mixing pond 300 and rabbling mechanism 310, and rabbling mechanism 310 is set to mixing pond
300 top, and the stirring blade 311 of 310 bottom of rabbling mechanism extends to the inside in mixing pond 300, the bottom in mixing pond 300
It is connected with preparation facilities 20 by pipeline, control valve 301 is provided on pipeline.
As shown in Figures 2 and 3, above-mentioned preparation facilities 20 is used to prepare catalyst product, which includes anti-
It answers chamber 100 and oxalic acid pond 200, the top of reaction chamber 100 to be provided with oxalic acid pond 200, electromagnetic agitation is provided in the oxalic acid pond 200
Mechanism 201 and mechanical agitator 202；Electromagnetic agitation mechanism 201 and mechanical agitator 202 are used for the oxalic acid in oxalic acid pond 200
Solution is stirred.
Oxalic acid pond 200 is arranged with oxalic acid dropper 210, and the top of reaction chamber 100 is provided with retractable support arm 152, stretches
Support arm 152 is connected by rotary supporting rod 151 with the top of reaction chamber 100, and the end set of retractable support arm 152 has clamping
Mechanism 153, for clamping device 153 for accommodating oxalic acid dropper 210, oxalic acid dropper 210 is fixed on reaction chamber by clamping device 153
100 top；It can be by the collapsing length of the rotational angle and retractable support arm 152 of adjusting rotary supporting rod 151, to make
It obtains oxalic acid dropper 210 to be correspondingly arranged with hot gas jet pipe 133 so that the liquid that hot gas jet pipe 133 sprays is only to oxalic acid dropper
The liquid of 210 corresponding positions is heated.Oxalic acid valve 230 is provided on oxalic acid dropper 210, the oxalic acid valve 230 is for controlling grass
The flow of acid solution.
Oxalic acid pond 200 and the outside of oxalic acid dropper 210 are provided with heating and thermal insulation component 220, and heating and thermal insulation component 220 is used for
Heating and thermal insulation is carried out to oxalic acid pond 200 and oxalic acid dropper 210；The outside of reaction chamber 100 is provided with ice water bathing pool 110, ice-water bath
Pond 110 is used to carry out water-bath cooling to reaction chamber 100, and the water-bath cooling of ice water bathing pool 110 can keep urging in reaction chamber 100
Agent active component solution A is cooled down, and catalyst activity component solution A is maintained at metastable thermotonus area
Between, the stability of product and the performance of product are prepared to ensure that, and then mesoporous performance and the catalysis of catalyst can be improved
Performance；The product that the calciner 30 is used to prepare preparation facilities 20 roasts.
Be provided with hot gas jet pipe 133 in the reaction chamber 100 of the present embodiment, the hot gas nozzle 134 at 133 top of hot gas jet pipe with
Oxalic acid dropper 210 is correspondingly arranged, and hot gas jet pipe 133 is connected with the first gas tank 131, and is provided with gas on hot gas jet pipe 133 and adds
Hot device 132, which is used to carry out heating heat to the first gas tank 131, and collectively forms hot air injection unit 130, should
Hot air injection unit 130 is for heating the liquid on surface layer.The hot gas nozzle 134 of hot gas jet pipe 133 is blown to reaction chamber 100
Enter heat gas, the temperature of heat gas is 60~80 DEG C.Temperature sensor is provided on hot gas nozzle 134, and for detecting
Hot gas nozzle 134 sprays the temperature of gas, regulates and controls the heating power of gas heater 132, so as to adjust the temperature of gas is sprayed
Maintain 60~80 DEG C.The hot gas nozzle 134 is set as disperse state, and ejects diffusion to the solution on 100 top of reaction chamber
The thermal current of shape, it should be noted that the distance between hot gas nozzle 134 and liquid level of solution 101 are less than or equal to 3cm, so that
Hot gas nozzle 134 spray hot gas the liquid on 101 surface layer of liquid level of solution is heated, and especially pair with oxalic acid dropper
The liquid on the surface layer of 210 corresponding positions is heated so that by oxalic acid dropper 210 instill reaction chamber 100 in oxalic acid solution with
Catalyst activity component solution A solution is uniformly mixed rapidly, and under the promotion and stirring of hot gas, it is rapid to promote oxalic acid solution
It is mixed with solution, and does not generate local surplus, improve the efficiency of catalyst preparation, and then the preparation of catalyst can be improved
Quality.To ensure that the performance of the stability and product that prepare product, and it can guarantee that the oxalic acid solution of instillation can be again
It is even, rapidly mix with reaction solution.
Further it should be noted that being provided with cold air jet pipe 143 on the side wall of reaction chamber 100, cold air jet pipe 143 is inserted into instead
The front end in chamber 100 is answered to be provided with cold air nozzle 144, cold air nozzle 144 is connected simultaneously through cold air jet pipe 143 with the second gas tank 141
Cold air injection unit 140 is constituted, gas cooler 142 is provided on cold air jet pipe 143, which is used for gas
It is cooled down, cold air injection unit 140 into reaction chamber 100 for spraying into cooling gas；The cold air nozzle 144, which tilts upward, to be set
It sets, in the penetrating reaction chamber 100 that cooling gas tilts upward.Cold air nozzle 144 is used to be blown into cooling gas to reaction chamber 100,
The temperature of cooling gas is 0~3 DEG C；Cooling gas is prepared for being cooled down to the liquid in reaction chamber 100 to ensure that
The stability of product and the performance of product, at the same time, the cooling gas of ejection accelerate the stirring of solution in reaction chamber 100,
So that reaction is more uniform, avoid producing local surplus, and then the mesoporous performance and catalytic performance of catalyst can be improved.
It is worth noting that the distance between hot gas nozzle 134 and liquid level of solution 101 are less than cold air nozzle 144 and solution liquid
The distance between face 101；I.e. the level height of cold air nozzle 144 be located at hot gas nozzle 134 level height it is low, cold air nozzle
144 with the slanted angle of vertical direction be 30~60 °.Further it should be noted that the jet velocity of cold air nozzle 144 is more than
The jet velocity of hot gas nozzle 134 will control the jet velocity of hot gas nozzle 134, and make hot gas nozzle 134 to surface layer liquid
Body does not generate splash.
The lower part of reaction chamber 100 is provided with mixing component 120, mixing component 120 be used for the solution in reaction chamber 100 into
Row stirring, when mixing component 120 turns to vertical direction, the top of mixing component 120 and hot gas nozzle 134 are in same horizontal line
On, the collective effect of mixing component 120 and cold air nozzle 144 improves the uniformity of mixing.In addition, ice water bathing pool 110 1
The bottom of side is provided with water inlet 111, and ice water bathing pool is provided with water outlet 112 at the top of 110 other side, and ice water is through water inlet
111 flow into ice water bathing pool 110, and are flowed out by water outlet 112, to improve cooling of the ice water bathing pool 110 to reaction chamber 100
Effect.
Embodiment 2
The present embodiment using a kind of above-mentioned cooperation-removal bioxin and the cerium base catalyst of nitrogen oxides production system
Production catalyst method be：Ferrous sulfate, manganese chloride, cerous nitrate and water are added in evenly mixing device 10, catalysis is uniformly mixed so as to obtain
Agent active component solution；Catalyst activity component solution is transferred in the reaction chamber 100 of preparation facilities 20 again, reaction chamber 100
External ice water bathing pool 110 is cooled to 0~5 DEG C to catalyst activity component solution, then the oxalic acid solution in oxalic acid pond 200 is passed through
Oxalic acid dropper 210 is added in catalyst activity component solution, and it is heavy that hybrid reaction during stirring of reaction chamber 100 generates
Form sediment, precipitation is filtered, is washed, dry after be added in calciner 30 and roast, catalyst is made after roasting.
S100, active component solution is prepared
Take 3.3~6.6 parts of FeSO4·7H2O, 9.5 parts of MnCl2·4H2O, 1.3~5.2 parts of Ce (NO3)3·6H2O and go from
Sub- water, which is added to, to be added in evenly mixing device 10, mixing speed 200r/min, the mixing time 30min of evenly mixing device 10；In mixing
Catalyst activity component solution A is mixed to get in device 10；It is worth noting that, the FeSO for taking 3.3g of the present embodiment4·
7H2O, the MnCl of 9.5g2·4H2O, the Ce (NO of 1.3g3)3·6H2O and deionized water are added to be added in evenly mixing device 10 and mix
Conjunction obtains catalyst activity component solution A；
S200, oxalic acid solution is prepared
It adds water in the oxalic acid pond 200 of preparation facilities 20, opens heating and thermal insulation component 220, heating and thermal insulation component 220
For carrying out heating and thermal insulation to oxalic acid pond 200 and oxalic acid dropper 210, and the fluid temperature in oxalic acid pond 200 is kept to reach 60 DEG C, then
Oxalic acid powder, mixing speed 200r/min, mixing time 30min are added into solution, and is uniformly mixed obtained oxalic acid aqueous solution
B；
S300, precipitation solution is prepared
1) catalyst activity component solution A is added to by evenly mixing device 10 in reaction chamber 100, passes through 110 He of ice water bathing pool
Cold air injection unit 140 cools down the catalyst activity component solution A in reaction chamber 100, by catalyst activity component solution A
It is cooled to 0~5 DEG C；
2) collapsing length of the rotational angle and retractable support arm 152 of rotary supporting rod 151 is adjusted so that oxalic acid dropper
210 are correspondingly arranged with hot gas jet pipe 133, open hot air injection unit 130, and hot gas nozzle 134 sprays into heating gas into reaction chamber 100
Body, hot gas heat the liquid on 100 surface layer of reaction chamber, then and by oxalic acid aqueous solution B are added to catalyst activity component
The oxalic acid aqueous solution B that temperature is 60 DEG C is added in the catalyst activity component solution A of reaction chamber 100 again in solution A, and
Oxalic acid solution is added dropwise in position corresponding with hot gas nozzle 134, continues to stir to get obtained precipitation solution C；
400, the preparation of catalyst
Sediment is obtained by filtration in precipitation solution C, and the sediment of gained is washed with deionized, is filtered three times, then
It washed, filtered three times with ethanol solution, by the sediment of gained in 70 DEG C of dry 12h, the sediment after drying is added
To being roasted in calciner 30, wherein calcination temperature is 300~500 DEG C, heating rate in roasting process is 1~2 DEG C/
min；Oxidizing roasting time is 1~1.5 hour；The calcination temperature of the present embodiment is 400 DEG C, and the heating rate in roasting process is
2℃ /min；Oxidizing roasting time is 1 hour, obtains product of roasting.Roasting product of roasting is added to grinding device again
It is ground in 40, the percent of pass that grinding obtains -40 mesh of particle of catalyst is more than 90%, obtains cerium base catalyst.This implementation
The cerium base catalyst of example includes Ce：Mn and Fe, wherein Ce：The molar ratio of Mn is that 0.25, Fe is auxiliary agent, adding proportion range
Fe：The molar ratio 0.25 of Mn.The specific surface area that detection obtains cerium base catalyst is 84m-2/g；The Kong Rongwei 0.17m of catalyst-2/
G, aperture is 5.5nm.Prepare to cerium base catalyst electron microscopic picture as shown in figure 4, by figure analyze it can be found that prepare
Obtained cerium base catalyst is mesoporous state, and the specific surface area of catalyst is bigger, and the catalytic activity of catalysis is higher.
Embodiment 3
The substance of the present embodiment with embodiment 2, the difference is that：In step 400, the preparation process of catalyst
In, additive is added in product of roasting, then by the mixture of product of roasting and additive be added in grinding device 40 into
Row grinding, wherein additive includes that potassium permanganate either under heating conditions can by potassium manganate potassium permanganate or potassium manganate
Oxygen and manganese oxide are decomposited, oxygen is conducive to catalytic effect, and manganese oxide is conducive to supplement the consumption of catalyst manganese.
Embodiment 4
The substance of the present embodiment with embodiment 2, the difference is that：In step 400, the preparation process of catalyst
In, additive is added in product of roasting, then by the mixture of product of roasting and additive be added in grinding device 40 into
Row grinding, wherein additive includes potassium permanganate, activated carbon and sinter return fine powder, to flue gas in the process of processing,
Potassium permanganate, activated carbon and sinter return fine powder in additive and catalyst collective effect so that to the nitrogen in flue gas
Oxide keeps preferable emission reduction condition, so that catalyst has pollutant He during bioxin progress emission reduction
Preferable treatment effect.Be conducive to the component manganese oxide in catalytic effect, especially additive to be conducive to supplement in catalyst
The consumption of effective element not only increases emission reduction efficiency, and can improve the service life of catalyst.
Embodiment 5
A kind of method based on the denitration of cerium base catalyst emission reduction sintering flue gas, Tuo bioxin of the present embodiment, flue gas pass through
Load has the emission reduction device of cerium base catalyst, and NH is blasted into emission reduction device3And air, wherein cerium base catalyst includes Ce：
Mn and Fe, wherein Ce：The molar ratio of Mn is that 0.25~1, Fe is auxiliary agent, adding proportion range Fe：The molar ratio 0.25- of Mn
0.5.The cerium base catalyst of the present embodiment includes Ce：Mn and Fe, wherein Ce：The molar ratio of Mn is that 0.25, Fe is auxiliary agent, addition
Proportional region Fe：The molar ratio 0.25 of Mn.
Wherein NH310~20% that quality is nitrogen oxide mass content in sintering flue gas are sprayed into, the present embodiment takes 10%；
The straying quatity of air is the 5~10% of sintering flue gas other contents, and the present embodiment takes 8%, without in addition being heated to sintering flue gas.
It is 50% that detection, which obtains the emission reduction efficiency that denitration efficiency is 85% , bioxin,.However, sintering flue gas outlet temperature is in 100-200
In DEG C, and existing catalyst shows quite high catalytic activity at 300 DEG C or more, and when less than 300 DEG C, and catalytic activity is often very
Low, sintering flue gas, which reheats, certainly will consume mass energy, increase energy consumption.And the present invention realizes under low-temperature condition, does not have to
It, can be to the nitrogen oxides in flue gas He bioxin progress emission reduction, realizes dirt using cerium base catalyst in the case of heating
Contaminate the low-temperature catalyzed degradation of object.
Emission reduction mechanism therein is that cerium base catalyst promotes NH during being catalyzed reduction3By the nitrogen oxygen in flue gas
Compound also original production N2, cerium base catalyst promotes by flue gas Zhong bioxin reduction decompositions, to generate being catalyzed the during of restoring
The substance of the five poisonous creatures: scorpion, viper, centipede, house lizard, toad.Under the action of metallic catalyst, chemical degradation can occur the PCDD/Fs of gas phase for low temperature, generate final production
Object CO2、 H2O and HCl.Reaction process is as follows：
C12HnCl8-nO2+(9+0.5n)O2→(n-4)H2O+12CO2+(8-n)HCl
C12HnCl8-nO+(9.5+0.5n)O2→(n-4)H2O+12CO2+(8-n)HCl
Certain embodiment of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as；It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range；Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of production system of the cerium base catalyst of cooperation-removal bioxin and nitrogen oxides, it is characterised in that：Including successively
Evenly mixing device (10), preparation facilities (20) and the calciner (30) of setting；Wherein evenly mixing device (10) is used for reactive component
Solution is mixed；Preparation facilities (20) is used to prepare catalyst product, which includes reaction chamber (100) and grass
The top of sour pond (200), reaction chamber (100) is provided with oxalic acid pond (200), which is arranged with oxalic acid dropper
(210), oxalic acid pond (200) and the outside of oxalic acid dropper (210) are provided with heating and thermal insulation component (220), heating and thermal insulation component
(220) it is used to carry out heating and thermal insulation to oxalic acid pond (200) and oxalic acid dropper (210)；The outside of the reaction chamber (100) is provided with
Ice water bathing pool (110)；The calciner (30) is for roasting the product of preparation.
2. the production system of the cerium base catalyst of a kind of cooperation-removal bioxin according to claim 1 and nitrogen oxides,
It is characterized in that：Further include grinding device (40), which is set to the rear end of calciner (30), grinding device
(40) it is used to that the product after roasting to be ground to obtain catalyst.
3. the production system of the cerium base catalyst of a kind of cooperation-removal bioxin according to claim 1 and nitrogen oxides,
It is characterized in that：Evenly mixing device (10) includes mixing pond (300) and rabbling mechanism (310), and rabbling mechanism (310) is set to mixing
The top in pond (300), and the stirring blade (311) of rabbling mechanism (310) bottom extends to the inside of mixing pond (300).
4. the production system of the cerium base catalyst of a kind of cooperation-removal bioxin according to claim 1 and nitrogen oxides,
It is characterized in that：It is provided with hot gas jet pipe (133) in reaction chamber (100), the hot gas nozzle (134) at the top of hot gas jet pipe (133)
It is correspondingly arranged with oxalic acid dropper (210).
5. the production system of the cerium base catalyst of a kind of cooperation-removal bioxin according to claim 2 and nitrogen oxides,
It is characterized in that：The bottom in mixing pond (300) is connected by pipeline with preparation facilities (20), and control valve is provided on pipeline
(301)。
6. the production system of the cerium base catalyst of a kind of cooperation-removal bioxin according to claim 4 and nitrogen oxides,
It is characterized in that：Hot gas jet pipe (133) is connected with the first gas tank (131), and is provided with gas heater on hot gas jet pipe (133)
(132), the gas heater (132) is for heating the first gas tank (131).
7. the production system of the cerium base catalyst of a kind of cooperation-removal bioxin according to claim 4 and nitrogen oxides,
It is characterized in that：The hot gas nozzle (134) of hot gas jet pipe (133) is blown into heat gas, the temperature of heat gas to reaction chamber (100)
Degree is 60~80 DEG C.
8. the production system of the cerium base catalyst of a kind of cooperation-removal bioxin according to claim 4 and nitrogen oxides,
It is characterized in that：Cold air jet pipe (143), cold air jet pipe (143) intercalation reaction chamber are provided on the side wall of reaction chamber (100)
(100) front end in is provided with cold air nozzle (144).
9. the production system of the cerium base catalyst of a kind of cooperation-removal bioxin according to claim 8 and nitrogen oxides,
It is characterized in that：Cold air nozzle (144) tilts upward setting, and cold air nozzle (144) is used to be blown into cooling air to reaction chamber (100)
The temperature of body, cooling gas is 0~3 DEG C.
10. a kind of production method of cerium base catalyst, it is characterised in that：Ferrous sulfate, manganese chloride, cerous nitrate and water are added mixed
In even device (10), it is uniformly mixed so as to obtain catalyst activity component solution；Catalyst activity component solution is transferred to preparation facilities again
(20) in reaction chamber (100), the external ice water bathing pool (110) of reaction chamber (100) is cooled to 0 to catalyst activity component solution
~5 DEG C, then the oxalic acid solution of oxalic acid pond (200) is added to by oxalic acid dropper (210) in catalyst activity component solution, instead
Answer chamber (100) during stirring hybrid reaction generate precipitation, to precipitation be filtered, wash, dry after be added to roasting
Device is roasted in (30), and catalyst is made after roasting.
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| NL2022095A NL2022095B1 (en) | 2018-04-20 | 2018-11-29 | System and method for producing cerium-based catalyst for combined removal of dioxins and nitrogen oxides |
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| WO2019200852A1 (en) * | 2018-04-20 | 2019-10-24 | 安徽工业大学 | Method for reducing emission of nitrogen oxides and dioxins of sintering flue gas on basis of cerium-based catalyst |
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