CN105413697A - Preparation method of magnetic rare earth barium ferrite purification nano-catalyst - Google Patents
Preparation method of magnetic rare earth barium ferrite purification nano-catalyst Download PDFInfo
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- CN105413697A CN105413697A CN201510698343.4A CN201510698343A CN105413697A CN 105413697 A CN105413697 A CN 105413697A CN 201510698343 A CN201510698343 A CN 201510698343A CN 105413697 A CN105413697 A CN 105413697A
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- denitration
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 78
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 78
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000746 purification Methods 0.000 title claims abstract description 20
- 239000011943 nanocatalyst Substances 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 229910001868 water Inorganic materials 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 91
- 239000000843 powder Substances 0.000 claims description 66
- 239000003054 catalyst Substances 0.000 claims description 61
- 238000004140 cleaning Methods 0.000 claims description 55
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 32
- 239000000919 ceramic Substances 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000005554 pickling Methods 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000001879 gelation Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 7
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 5
- 229920001285 xanthan gum Polymers 0.000 claims description 5
- 235000020097 white wine Nutrition 0.000 claims description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims description 4
- 241000208367 Euonymus Species 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 101100203596 Caenorhabditis elegans sol-1 gene Proteins 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 18
- 238000004065 wastewater treatment Methods 0.000 abstract description 6
- 238000007796 conventional method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 20
- 238000003860 storage Methods 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000010842 industrial wastewater Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 7
- 239000010865 sewage Substances 0.000 description 7
- 229910052779 Neodymium Inorganic materials 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 5
- 238000007885 magnetic separation Methods 0.000 description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 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
- 230000015556 catabolic process Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 150000004831 organic oxygen compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 244000191761 Sida cordifolia Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J23/005—Spinels
-
- 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
-
- 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- 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
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Compounds Of Iron (AREA)
Abstract
The present invention relates to a preparation method of a magnetic rare earth barium ferrite purification nano-catalyst, and belongs to the manufacturing field of wastewater treatment agents. The preparation method comprises the working procedures of solution dissolution and preparation, proportioning and mixing, high-temperature ultrasonic dispersing solation, microwave negative pressure gelatinization, microwave negative pressure mionectic denitration and roasting. The preparation method is characterized in that after the working procedure of proportioning and mixing, the working procedures of high-temperature ultrasonic dispersion, microwave negative pressure gelatinization, microwave negative pressure mionectic denitration and roasting are performed. According to the preparation method, by utilizing microwave negative pressure mionectic denitration, ammonium nitrate is directly converted into nitrogen, oxygen and water. In the preparation process, no nitrogen oxide is generated, and secondary pollution of nitrogen oxides generated in the preparation process of a conventional method is eliminated.
Description
Technical field
The present invention is used for chemical oxygen demand COD, sulphur-containing substance and nitrogenous thing process in metallurgical industry, chemical industry effluent, is specifically related to a kind of preparation method of magnetic rare earth barium ferrite nanometer cleaning catalyst.
Background technology
In metallurgy, the chemical industry strategy of sustainable development, the low cost purified treatment of waste water and waste gas is a wherein important ring.Process waste water, waste gas need just can be completed by the physical-chemical reaction process of complexity mostly, and this type of reaction needed catalytic purification agent most is done auxiliary, as the aspects such as exhaust fume catalytic reaction and liquid waste processing need environment protection catalytic cleanser in a large number.Environment protection catalytic cleanser require high, active high, the mithridatism of mechanical strength and stability strong, selective good, and to use by repeated regeneration.Require that equipment is simple, technique is terse in the application, do not produce secondary pollution to reduce environmental protection investments, be convenient to user and accept.But find and a kind ofly can meet all these catalytic purification agent required and be difficult to accomplish in one move, therefore scientific research personnel meets in exploitation the exploration that the new catalytic scavenging material of ecological requirements and new catalytic process aspect do one's utmost.
The catalysis material developed at present and researching and developing has precious metal catalytic material, Zeolite molecular sieve catalysis material, TiO
2catalysis material and electrode catalytic materials and living things catalysis biomaterial, ionic liquid at room temperature etc.Wherein noble metal catalyst has realized suitability for industrialized production and large-scale application, satisfactory for result, but because Precious Metals Resources is rare, be difficult to the requirement meeting environmental protection industry (epi) develop rapidly, in addition catalysis material is in development mostly, therefore develop the cheap and scope of application wide, respond well catalyst just becomes the task of top priority.
Summary of the invention
The invention provides a kind of cheap and preparation method of innovative magnetic Nano rare earth barium ferrite cleaning catalyst.
Technical scheme of the present invention:
A preparation method for magnetic rare earth barium ferrite nanometer cleaning catalyst, comprises and moltenly joins solution, proportioning and mixing, high temperature ultrasonic dispersion sol, the gelation of microwave negative pressure, the few oxygen denitration of microwave negative pressure, calcining process; High temperature ultrasonic dispersion, the gelation of microwave negative pressure, the few oxygen denitration of microwave negative pressure, calcining process is carried out after it is characterized in that proportioning and mixed processes;
A kind of magnetic rare earth barium ferrite nanometer cleaning catalyst, general formula is Ba
xre
yme
zfe
mo
n, wherein x is 0.1 ~ 3.0, y be 0 ~ 2.0, z be 0 ~ 2, m be 1 ~ 24, n is 3 ~ 48; Wherein, Me is Cu or Zn or Mn or Co, Re is La or Ce or Nd or Pr or Sc or Y.
Magnetic rare earth barium ferrite nanometer cleaning catalyst is Ba
0.9nd
0.1fe
12o
19or Ba
0.8nd
0.2fe
2o
4or BaLa
0.1co
0.9fe
16o
27;
A kind of preparation method of magnetic rare earth barium ferrite nanometer cleaning catalyst, comprise and moltenly join solution, proportioning and mixing, high temperature ultrasonic dispersion sol, the gelation of microwave negative pressure, the few oxygen denitration of low-temperature microwave negative pressure, calcining process, make innovative magnetic rare earth barium ferrite nanometer cleaning catalyst, better applied in sewage disposal to make magnetic rare earth barium ferrite nanometer cleaning catalyst.
Preparation principle is for utilizing citric acid by metallic ion coordination, form chelate, by sol-gal process by its dispersing and disintegrating, obtain required magnetic rare earth barium ferrite nanometer cleaning catalyst finally by roasting, and utilize this magnetic rare earth barium ferrite nanometer cleaning catalyst to make cleaning catalyst to carry out catalytic purification reaction in disposing of sewage.
1. moltenly join solution
1. ferric nitrate deionized water is made into the iron nitrate solution that molar concentration is 0.4 ~ 0.8mol/L;
2. barium nitrate deionized water is made into the barium nitrate solution that molar concentration is 0.25 ~ 0.5mol/L;
3. rare earth oxide (as lanthanum, cerium, neodymium, praseodymium and mishmetal) is made into by deionized water the re chloride that mol ratio content concn is 0.03 ~ 0.10mol/L with after dissolving with hydrochloric acid;
2. proportioning and mixing
1. by barium nitrate solution, iron nitrate solution, earth solution, citric acid, according to Ba
2+: Fe
3+: Re
n+: the mol ratio of citric acid is (0.1 ~ 3.00): (1 ~ 24): (0 ~ 2.0): the proportioning of (3 ~ 20), measure solution respectively and weigh solid, then add citric acid after barium nitrate solution, iron nitrate solution and earth solution being mixed, be uniformly mixed solution until citric acid is complete clearly molten; Now Fe
3+, Ba
2+, Re
n+form chelating ion with citrate ion, reaction equation is as follows:
H
3L+Fe
3+→FeL+3H
+
H
3L+Ba
2+→(BaL)
-+3H
+
H
3L+Nd
3+→NdL+3H
+
In formula
2. with ammoniacal liquor, the mixed solution pH value of step 1. gained is transferred to 6.5 ~ 7.5,
NH
3·H
2O+HNO
3→NH
4NO
3+H
2O
NH
3·H
2O+HCl→NH
4Cl+H
2O
Treat that next step uses after mixed solution prepares;
3. high temperature ultrasonic dispersion sol
1. xanthans being added pH value by 1g ~ 5g/L or pickling elm rubber powder 10 ~ 25g/L is in the mixed solution of 6.5 ~ 7.5, continues to stir to become thick colloidal solution;
2. above-mentioned colloidal solution is placed in glass container, at the temperature of 50 ~ 80 DEG C, carry out ultrasonic disperse with 600W/40kHz ultrasonic disperse instrument, jitter time is 60 ~ 120min; After High Temperature Disperse process, metal ion fully disperses in colloidal solution, treats that next step uses;
4. microwave negative pressure gelation:
1. step 3 gained colloidal solution being placed in ceramic vessel with cover is placed in microwave reactor, and stove internal gas pressure controls to-(0.1 ~ 0.5) kPa;
2. be that in the microwave reactor of 2.45GHz, regulating power is 140 ~ 280W, carries out microwave drying treatment in frequency, control temperature 110 ~ 150 DEG C, time 10 ~ 35min, extracts the moisture evaporated out, makes gel after cooling during process;
3. obtained gel grinder ground, grind, sieve and repeatedly carry out, to making gel fine powder by 200 mesh sieves, gel fine particle diameter≤0.075mm;
5. the few oxygen denitration of microwave negative pressure:
1. gel fine powder is put into ceramic vessel with cover and be placed in microwave reactor, reactor internal gas pressure controls to-(1 ~ 2) KPa;
2. be that in the microwave reactor of 2.45GHz, setting power is 360 ~ 500W in frequency, carry out microwave denitration process, control temperature is 200 ~ 240 DEG C, and the time is 5 ~ 10min; In gel fine powder, a small amount of ammonium chloride is decomposed into ammonia and hydrogen chloride in the process, and decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reacts as follows:
3. close microwave reactor, make it naturally cool to 25 DEG C;
4. from microwave reactor, take out ceramic vessel, collect fine powder also with grinder grinding, by 200 eye mesh screens, namely this fine powder is product after denitration and denitration gel fine powder, and particle diameter≤0.075mm, treats that next step uses;
6. roasting:
1. the crucible filling denitration gel fine powder is placed in the roaster after purification;
2. open roaster controller, control temperature is progressively warming up to 550 ~ 850 DEG C by 25 DEG C, at this temperature 60 ~ 120min; In the process, organic substance decomposing is carbon dioxide and water, and the chelating ion of baric, iron, other metal ions and rare earth becomes the agent of nano rare earth barium ferrite catalytic purification through calcining;
3. close roaster controller, product powder is placed in crucible and naturally cools to 25 DEG C with stove;
4. open roaster, take out crucible, collect fine powder, this fine powder is nano-magnetic rare earth barium ferrite cleanser, and its character is as shown in table 1:
Table 1 nano-magnetic rare earth barium ferrite cleanser character
The method that magnetic rare earth barium ferrite nanometer cleaning catalyst is disposed of sewage:
By the waste water in storage tank with being pumped in suspended-bed reactor, and in proportion magnetic rare earth barium ferrite nanometer cleaning catalyst is joined in suspended-bed reactor, open compressed air require switch and supersonic generator simultaneously, make compressed air (or oxygen, ozone) through dispersion plate be separated into after fine gas bubbles with waste water, magnetic rare earth barium ferrite nanometer cleaning catalyst Homogeneous phase mixing, ultrasonic wave stirring rod starts vibration simultaneously, stir containing air (or oxygen, ozone) and the mixed liquor of magnetic rare earth barium ferrite nanometer cleaning catalyst, separator is entered through magnetic separation after gas and waste water fully react, Water Sproading through purification does it and uses, the magnetic rare earth barium ferrite nanometer cleaning catalyst that recovery obtains returns in suspended-bed reactor to be reused, the gas that purified treatment produces is emptying after inspection, if desired high temperature purification, then utilize steam(-)coil to heat, if there is accident, the waste water carrying out purified treatment enters as emergency pool from guard valve.
The step that magnetic rare earth barium ferrite nanometer cleaning catalyst is disposed of sewage is as follows:
(1) deliver in suspended-bed reactor by waste water pump from storage tank, flow is 80 ~ 150L/min;
(2) magnetic rare earth barium ferrite nanometer cleaning catalyst is pressed 100 ~ 300g/m
3add in suspended-bed reactor;
(3) by compressed air (or pure oxygen, ozone) with the flow of 20L/min through dispersion plate be separated into after fine gas bubbles with waste water, magnetic rare earth barium ferrite nanometer cleaning catalyst Homogeneous phase mixing;
(4) 20KHz/2000W ultrasonic stirrer agitated liquid is opened, COD (COD) in such waste water and oxygen adsorb at catalyst surface, enrichment, there is heterogeneous catalytic reaction, larger molecular organics valence link is ruptured, generate the organic oxygen compound of lower molecular weight, oxidation step of going forward side by side decomposes, and molecule is diminished.Organic matter is progressively from hydrocarbon → alcohol (aldehyde) → acid → CO
2+ H
2o, wherein acid degradation is controlling unit wherein; In processing procedure, reaction is as follows:
After purified treatment containing the water of the rare earth barium ferrite nanometer cleaning catalyst that is magnetic at separator through magnetic separation, reclaim magnetic rare earth barium ferrite nanometer cleaning catalyst and return in suspended-bed reactor and reuses, the gas CO that purified treatment produces
2through check harmless after emptying, recovery of purifying waste water do its use;
Beneficial effect of the present invention:
1, the present invention utilizes sol-gel method to prepare magnetic rare earth barium ferrite nanometer cleaning catalyst, utilize xanthans or pickling elm rubber powder as gelatinizing agent, ultrasonic wave does dispersion treatment, good dispersion, be conducive to the dispersiveness of crystal grain thinning and raising powder, reduce cost of material;
2, the present invention utilizes the gelation of microwave negative pressure, and compared with conventional method, gelation speed is fast, and technique is simple, and production efficiency is high;
3, the present invention utilizes the few oxygen denitration of microwave negative pressure, make ammonium nitrate be converted into nitrogen, oxygen and water, preparation process does not have the generation of nitrogen oxide, eliminates the secondary pollution phenomenon producing nitrogen oxide in conventional method preparation process, the denitration time is short, and denitration fine particle is even;
4, after roasting, gained magnetic rare earth barium ferrite nanometer cleaning catalyst cubic system spinel-type crystallite dimension is 40 ~ 90nm, and specific saturation magnetization is 28 ~ 40emu/g; Hexaplanar M type crystallite dimension is 30 ~ 80nm, and specific saturation magnetization is 20 ~ 50emu/g, stable chemical nature, and be easy to itself and liquid to separate by magnetic separation after catalytic reaction terminates, by washing methods Direct Regeneration, life cycle is long; Can be used for TOC, COD in process industrial wastewater, sulphur-containing substance and nitrogenous thing.
Temperature is that before 20 ~ 70 DEG C of Industrial Wastewater Treatment, COD content is 500 ~ 800mg/L; Add magnetic rare earth barium ferrite nanometer cleaning catalyst 100g/m
3, after the process of 0.5 ~ 1 hour, COD content is 10 ~ 20mg/L, COD clearance is 95%;
Temperature is that before 20 ~ 70 DEG C of Industrial Wastewater Treatment, COD content is 500 ~ 800mg/L; Add magnetic rare earth barium ferrite nanometer cleaning catalyst 200g/m
3, after the process of 0.5 ~ 1 hour, industrial wastewater COD content is 3 ~ 5mg/L, COD clearance>=99%;
Accompanying drawing explanation
Fig. 1 is the process chart utilizing magnetic rare earth barium ferrite nanometer cleaning catalyst of the present invention to carry out suspension bed to dispose of sewage.
Fig. 2 is the TEM figure of the magnetic rare earth barium ferrite nanometer cleaning catalyst of the embodiment of the present invention 1.
Fig. 3 is the TEM figure of the magnetic rare earth barium ferrite nanometer cleaning catalyst of the embodiment of the present invention 2.
Fig. 4 is the magnetic rare earth barium ferrite nanometer cleaning catalyst X-ray diffractogram of the embodiment of the present invention 1.
Fig. 5 is the magnetic rare earth barium ferrite nanometer cleaning catalyst X-ray diffractogram of the embodiment of the present invention 2.
In Fig. 1: 1 is waste water, 2 is storage tank, and 3 is suction pump, 4 is suspended-bed reactor, and 5 is compressed air, and 6 is flow switch, 7 is ultrasonic wave stirring rod, and 8 is supersonic generator, and 9 is separator, 10 is the purified gas of discharging, and 11 for purifying waste water, and 12 is circulating pump, 13 is guard valve, and 14 is emergency pool, and 15 is steam(-)coil, 16 is magnetic rare earth barium ferrite nanometer cleaning catalyst, and 17 is dispersion plate.
Detailed description of the invention
Embodiment 1: preparation method is as follows for magnetic rare earth barium ferrite nanometer cleaning catalyst:
1, selected chemical substance material
To carry out selected to the chemical substance material needed for preparation, and carry out quality purity control:
2, roaster is cleared up
To clear up the roaster that preparation uses, remove in-furnace dust dirt and harmful gas material with compressed air, make in stove clean;
3, dry process
Take neodymia 200g ± 5g and be placed in quartz boat, be placed in vacuum drying chamber dry, baking temperature 120 DEG C ± 2 DEG C, vacuum-18Pa, drying time 30min;
4, obtain solution
(1) taking 1 ± 0.001mol nine water ferric nitrate deionized water, to be prepared into 0.5 ± 0.001mol/L iron nitrate solution at 2000 milliliters of volumetric flasks stand-by;
(2) take 0.25 ± 0.001mol barium nitrate deionized water to be prepared into 0.25 ± 0.001mol/L at 1000 milliliters of volumetric flasks and to prepare barium nitrate solution for later use;
(3) take 0.05 ± 0.001mol neodymia, 0.1 ± 0.001mol/L dissolving with hydrochloric acid, be then prepared into 0.05 ± 0.001mol/L neodymium chloride solution by deionized water at 1000 milliliters of volumetric flasks stand-by;
5, proportioning and mixing
By Fe
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-be 2:0.8:0.2:6 by molal quantity ratio, measure iron nitrate solution, barium nitrate solution, re chloride weigh citric acid respectively:
Iron nitrate solution, barium nitrate solution and neodymium chloride solution are mixed and stir, then citric acid is added, continue to stir until solution is clarified completely, dripping ammoniacal liquor regulates solution ph to 7.0 ± 0.01, adds deionized water by metal ion in solution concentration adjustment to 0.24 ± 0.01mol/L with 500ml volumetric flask; Treat after mixed solution prepares that next step operation uses;
6, high temperature ultrasonic dispersion sol
(1) xanthans being added pH value by 2 ± 0.001g/L is in the mixed solution of 7.0 ± 0.01, continues stirring and makes it be dissolved into colloidal solution;
(2) colloidal solution is placed in glass container, at the temperature of 60 ± 1 DEG C, carry out ultrasonic disperse with 600W/40kHz ultrasonic disperse instrument, jitter time is 90 ± 0.1min; After High Temperature Disperse process, metal ion fully disperses in colloidal solution, treats that next step uses;
7, microwave negative pressure gelation:
(1) step 6 gained colloidal solution being placed in ceramic vessel with cover is placed in microwave reactor, and stove internal gas pressure controls to-(0.2 ± 0.01) kPa;
(2) in frequency be 2.45GHz microwave reactor in, carry out microwave drying treatment with the microwave that setting power is 200W, treatment temperature 125 ± 1 DEG C, time 25 ± 0.01min, during process, extract the moisture that evaporates out, after its cooling, make gel;
(3) made gel grinder ground, grind, sieve and repeatedly carry out, until make gel fine powder by 200 mesh sieves, gel fine particle diameter≤0.075mm;
8, the few oxygen denitration of microwave negative pressure:
(1) gel fine powder is put into ceramic vessel with cover and be placed on microwave reactor, reactor internal gas pressure controls to-(1.5 ± 0.01) kPa;
(2) in 2.45GHz frequency microwave reactor, setting power is that the microwave of 450W carries out denitration process, control temperature 220 ± 1 DEG C, time 6 ± 0.01min; In the process, in gel fine powder, ammonium chloride is decomposed into ammonia and hydrogen chloride, and decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reacts as follows:
(3) close microwave reactor, make it naturally cool to 25 DEG C;
(4) from microwave reactor, take out ceramic vessel, after collecting reaction, fine powder also grinds with grinder, and extremely by 200 mesh sieves, namely this fine powder is the product after denitration is denitration gel fine powder, and particle diameter≤0.075mm, treats that next step uses;
9, roasting:
(1) ceramic vessel filling denitration gel fine powder is placed in the roaster of purification;
(2) open roaster controller, control temperature is progressively warming up to 650 ± 1 DEG C by 25 DEG C, and in this temperature roasting, roasting time is 60 ± 0.01min; In the process, organic substance decomposing is carbon dioxide and water, and the chelating ion of baric, iron and rare earth synthesizes the agent of nano rare earth barium ferrite catalytic purification through calcining;
(3) close roaster controller, make fine powder naturally cool to 25 DEG C with stove;
(4) open roaster, take out ceramic vessel, collect fine powder, this fine powder is nano-magnetic rare earth barium ferrite cleanser;
(5) the nano-magnetic rare earth barium ferrite cleanser that this technique is produced is powdery, and its average-size: 75.5nm, structural formula is Ba
0.8nd
0.2fe
2o
4, be cubic system spinel ferrite body structure, specific saturation magnetization 37emu/g.
The TEM figure of the magnetic rare earth barium ferrite nanometer cleaning catalyst shown in Fig. 2 shows Ba
0.8nd
0.2fe
2o
4for irregular class square sheet-like particle, crystallite dimension between 40 ~ 90nm, average-size 75.5nm.
The XRD diffracted intensity collection of illustrative plates of the magnetic rare earth barium ferrite nanometer cleaning catalyst shown in Fig. 4, ordinate is diffracted intensity, abscissa is the angle of diffraction 2 θ, peak value has been there is at the angle of diffraction 28.428 °, 32.716 °, 33.266 °, 42.464 °, 46.405 °, 54.906 °, 62.515 °, 65.743 ° places, match with standard x RD spectrogram PDF46-0113, for Bb21m (36) type cubic crystal structure, in magnetic rare earth barium ferrite nanometer cleaning catalyst, introduce Nd
3+, both do not caused the disappearance of diffraction maximum also obviously not occur other diffraction maximums, whole series of samples is single-phase, and Nd is described
3+occupy part Ba
2+position.
Embodiment 2:
With embodiment 1 unlike Fe in material composition proportioning
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-molal quantity ratio be 9:0.8:0.2:20, calcining process sintering temperature is 750 DEG C, and other techniques are identical with embodiment 1.
1, selected chemical substance material
To carry out selected to the chemical substance material needed for preparation, and carry out quality purity control:
2, roaster is cleared up
To clear up the roaster that preparation uses, remove in-furnace dust dirt and harmful gas material with compressed air, make in stove clean;
3, dry process
Takes neodymia 200g ± 5g and be placed in quartz boat, and it is dry quartz boat to be placed in vacuum drying chamber, baking temperature 120 DEG C ± 2 DEG C, vacuum-18Pa, drying time 30min;
4, obtain solution
(1) taking 1 ± 0.001mol nine water ferric nitrate deionized water, to prepare 0.5 ± 0.001mol/L iron nitrate solution at 2000 milliliters of volumetric flasks stand-by;
(2) take 0.25 ± 0.001mol barium nitrate deionized water to prepare 0.25 ± 0.001mol/L at 1000 milliliters of volumetric flasks and prepare barium nitrate solution for later use;
(3) take 0.05 ± 0.001mol neodymia, 0.1 ± 0.001mol/L dissolving with hydrochloric acid, then prepare 0.05 ± 0.001mol/L neodymium chloride solution by deionized water at 1000 milliliters of volumetric flasks stand-by;
5, proportioning and mixing
According to Fe
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-molal quantity ratio be 9:0.8:0.2:20, measure iron nitrate solution, barium nitrate solution respectively, weigh citric acid containing neodymium solution:
By iron nitrate solution, barium nitrate solution and mix and stir containing neodymium solution, then citric acid is added, continue to stir until solution is clarified completely, dripping ammoniacal liquor regulates solution ph to 7.0 ± 0.01, add deionized water at 500ml volumetric flask and solution concentration is adjusted to 0.4 ± 0.01mol/L, treat that subsequent processing uses;
6, high temperature ultrasonic dispersion sol
(1) 1 ± 0.001g xanthans being added pH value is in 500 ± 0.01ml mixed solution of 7.0 ± 0.01, continues stirring and makes it be dissolved into colloidal solution gradually;
(2) above-mentioned colloidal solution is placed in glass container, at the temperature of 60 ± 0.01 DEG C, carry out ultrasonic disperse with 600W/40kHz ultrasonic disperse instrument, jitter time is 90 ± 0.01min; After High Temperature Disperse process, metal ion fully disperses in colloidal solution, and treats that next step uses;
7, microwave negative pressure gelation:
(1) 6 gained colloidal solutions being placed in ceramic vessel with cover is placed in microwave reactor, and stove internal gas pressure controls to-(0.2 ± 0.01) kPa;
(2) in frequency be 2.45GHz microwave reactor in, carry out microwave drying treatment with the microwave that setting power is 200W, treatment temperature 125 ± 1 DEG C, time 25 ± 0.01min, during process, extract the moisture that evaporates out, after its cooling, make gel;
(3) made gel grinder is ground, cross 200 mesh sieves; Grind, sieve and repeatedly carry out, become gel fine powder, gel fine particle diameter≤0.075mm;
8, the few oxygen denitration of microwave negative pressure
(1) gel fine powder is put into ceramic vessel with cover and be placed on microwave reactor, reactor internal gas pressure controls to-(1.5 ± 0.01) kPa;
(2) in 2.45GHz frequency microwave reactor, use the microwave that setting power is 450W to carry out denitration process, treatment temperature is 220 ± 1 DEG C, and the time is 6 ± 0.1min; In gel fine powder, a small amount of ammonium chloride is decomposed into ammonia and hydrogen chloride in the process, and decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reacts as follows:
(3) close microwave reactor, make it naturally cool to 25 DEG C;
(4) from microwave reactor, take out ceramic vessel, fine powder after collecting reaction also grinds with grinder, and cross 200 mesh sieves, namely gained fine powder is the product after denitration is denitration gel fine powder, and particle diameter≤0.075mm, treats that next step uses;
9, roasting
(1) ceramic vessel filling denitration gel fine powder is placed in the roaster after purification;
(2) open roaster controller, regulate temperature to be progressively warming up to 750 ± 1 DEG C by 25 DEG C, at this temperature, roasting time 60 ± 0.1min; In the process, organic substance decomposing is carbon dioxide and water, and the chelating ion of baric, iron and rare earth synthesizes the agent of nano rare earth barium ferrite catalytic purification through calcining;
(3) close roaster controller, make fine powder naturally cool to 25 DEG C with stove;
(4) open roaster, take out ceramic vessel and interior fine powder thereof, this fine powder is nano-magnetic rare earth barium ferrite cleanser;
(5) the nano-magnetic rare earth barium ferrite cleanser that this technique is produced is powdery, and its average-size is 62.3nm, and structural formula is Ba
0.8nd
0.2fe
9o
19, belong to hexaplanar M type ferrite structure, magnetic saturation intensity 37emu/g;
10, product storage
To the rare earth barium ferrite cleanser powder storage of preparation in the glass container of amber transparent, be airtightly stored in cool place, drying, clean environment, the erosion of moistureproof, sun-proof, anti-acid-alkali salt, storage temperature 20 DEG C ± 10 DEG C, relative humidity≤10%.
Magnetic rare earth barium ferrite nanometer cleaning catalyst TEM figure shown in Fig. 3 shows Ba
0.8nd
0.2fe
12o
19for irregular class hexagon sheet-like particle, crystallite dimension between 30 ~ 80nm, average-size 62.3nm;
The XRD diffracted intensity collection of illustrative plates of the magnetic rare earth barium ferrite nanometer cleaning catalyst shown in Fig. 5, ordinate is diffracted intensity, abscissa is the angle of diffraction 2 θ, the angle of diffraction 22.972 °, 30.295 °, 31.261 °, 32.148 °, 34.089 °, 35.571 °, 37.046 °, 40.278 °, 42.758 °, 49.992 °, 50.252 °, 55.005 °, 56.886 °, there is peak value in 63.002 ° of places, coincide with XRD standard spectrogram PDF39-1433, for P63/M-mmc (194)) type M type hexagonal system structure, Nd in magnetic rare earth barium ferrite nanometer cleaning catalyst
3+existence, both do not caused the disappearance of diffraction maximum also obviously not occur other diffraction maximums, whole series of samples is single-phase, and Nd is described
3+occupy part Ba
2+position.
Embodiment 3:
The present embodiment and embodiment 1 are unlike Fe in material composition proportioning
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-molal quantity ratio 2:0.9:0.1:6, adopt pickling elm rubber powder to carry out solation process, other techniques are identical with embodiment 1.
1, selected chemical substance material
To carry out selected to the chemical substance needed for preparation, and carry out quality purity control:
2, roaster is cleared up
To clear up the roaster that preparation uses, remove in-furnace dust dirt and harmful gas material with compressed air, make in stove clean;
3, dry process
Take neodymia 200 ± 5g and be placed in quartz boat respectively, be placed in vacuum drying chamber dry, baking temperature 120 DEG C ± 2 DEG C, vacuum-18Pa, drying time 30min;
4, pickling elm rubber powder preparation
1. choose 5 years raw elm extra dry white wine skin 2000 ± 5g and be broken into the fritter that granularity is 2 ~ 3mm;
2. by step 1. gained elm extra dry white wine skin fritter 0.1mol/L hydrochloric acid 3L repeatedly clean three times, remove Ca wherein
2+, Mg
2+; And then by washed with de-ionized water three times;
3. by step 2. gained pickling Radix Ulmi Tonkinesis Rhizoma Euonymus to be again placed in vacuum drying chamber dry, baking temperature 110 ± 2 DEG C, vacuum-18Pa, drying time 60 ± 2min;
4. pickling Radix Ulmi Tonkinesis Rhizoma Euonymus after step 3. gained drying is placed in grinding machine for grinding, cross the fine powder that 200 mesh sieves obtain particle diameter≤0.075mm, this fine powder is pickling elm rubber powder, is placed in drier and treats that next step uses;
5, obtain solution
1. taking 1 ± 0.001mol nine water ferric nitrate deionized water, to prepare 0.5 ± 0.001mol/L iron nitrate solution at 2000 milliliters of volumetric flasks stand-by;
2. take 0.25 ± 0.001mol barium nitrate deionized water to prepare 0.25 ± 0.001mol/L at 1000 milliliters of volumetric flasks and prepare barium nitrate solution for later use;
3. take 0.05 ± 0.001mol neodymia, 0.1 ± 0.001mol/L dissolving with hydrochloric acid, then prepare 0.05 ± 0.001mol/L neodymium chloride solution by deionized water at 1000 milliliters of volumetric flasks stand-by;
6, proportioning and mixing
According to Fe
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-molal quantity ratio be 2:0.9:0.1:6, measure iron nitrate solution, barium nitrate solution respectively, weigh citric acid containing neodymium solution:
By iron nitrate solution, barium nitrate solution and mix and stir containing neodymium solution, then citric acid is added, continue to stir until solution is clarified completely, dripping ammoniacal liquor regulates solution ph to 7.0 ± 0.01, add deionized water at 500ml volumetric flask and solution concentration is adjusted to 0.6 ± 0.01mol/L, treat that next step uses;
7, high temperature ultrasonic dispersion sol
1. 12 ± 0.001g pickling elm rubber powder being added pH value is in 500 ± 0.01ml mixed solution of 7.0 ± 0.01, continues stirring and makes it be dissolved into colloidal solution gradually;
2. above-mentioned colloidal solution is placed in glass container, at the temperature of 60 ± 0.01 DEG C, carry out ultrasonic disperse with 600W/40kHz ultrasonic disperse instrument, jitter time is 90 ± 0.01min; After High Temperature Disperse process, metal ion fully disperses in colloidal solution, and treats that next step uses;
8, microwave negative pressure gelation:
1. 6 gained colloidal solutions being placed in ceramic vessel with cover is placed in microwave reactor, and stove internal gas pressure controls to-(0.2 ± 0.01) kPa;
2. be in the microwave reactor of 2.45GHz in frequency, carry out microwave drying treatment with the microwave that setting power is 200W, treatment temperature 125 ± 1 DEG C, time 25 ± 0.01min, during process, extract the moisture evaporated out, after its cooling, make gel;
3. made gel grinder ground, grind, sieve and repeatedly carry out, to making gel fine powder by 200 mesh sieves, gel fine particle diameter≤0.075mm;
9, the few oxygen denitration of microwave negative pressure:
1. gel fine powder is put into ceramic vessel with cover and be placed on microwave reactor, reactor internal gas pressure controls to-(1.5 ± 0.01) kPa;
2., in 2.45GHz frequency microwave reactor, use the microwave that setting power is 450W to carry out denitration process, treatment temperature is 220 ± 1 DEG C, and the time is 6 ± 0.1min; In gel fine powder, a small amount of ammonium chloride is decomposed into ammonia and hydrogen chloride in the process, and decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reacts as follows:
3. close microwave reactor, make it naturally cool to 25 DEG C;
4. from microwave reactor, take out ceramic vessel, fine powder after collecting reaction also grinds with grinder, and cross 200 mesh sieves, namely gained fine powder is the product after denitration is denitration gel fine powder, and particle diameter≤0.075mm, treats that next step uses;
10, roasting:
1. the ceramic vessel filling denitration gel fine powder is placed in the roaster after purification;
2. open roaster controller, regulate temperature to be progressively warming up to 650 ± 1 DEG C by 25 DEG C, at this temperature, roasting time 60 ± 0.1min; In the process, organic substance decomposing is carbon dioxide and water, and the chelating ion of baric, iron and rare earth synthesizes the agent of nano rare earth barium ferrite catalytic purification through calcining;
3. close roaster controller, make fine powder naturally cool to 25 DEG C with stove;
4. open roaster, take out ceramic vessel and interior fine powder thereof, this fine powder is nano-magnetic rare earth barium ferrite cleanser;
5. the nano-magnetic rare earth barium ferrite cleanser that this technique is produced is powdery, and its average-size: 65.7nm, structural formula is Ba
0.9nd
0.1fe
2o
4, belong to cubic system spinel type ferrite structure, magnetic saturation intensity 45emu/g;
(11) product storage
To the rare earth barium ferrite cleanser powder storage of preparation in the glass container of amber transparent, be airtightly stored in cool place, drying, clean environment, the erosion of moistureproof, sun-proof, anti-acid-alkali salt, storage temperature 20 ± 10 DEG C, relative humidity≤10%.
The embodiment utilizing magnetic rare earth barium ferrite nanometer cleaning catalyst to dispose of sewage is:
1, utilize technological process that magnetic rare earth barium ferrite nanometer cleaning catalyst is disposed of sewage as shown in Figure 1, the waste water 1 in storage tank 2 is delivered in suspended-bed reactor 4 with pump 3, and by 100 ~ 300g/ waste water m
3ratio magnetic rare earth barium ferrite nanometer cleaning catalyst 16 is joined in suspended-bed reactor 4, open compressed air 5 flow switch 6 and supersonic generator 8 simultaneously, make compressed air (or oxygen, ozone) 5 through dispersion plate 17 be separated into after fine gas bubbles with waste water 1, magnetic rare earth barium ferrite nanometer cleaning catalyst 16 Homogeneous phase mixing, simultaneously ultrasonic wave stirring rod 7 starts Vibratory Mixing and contains air (or oxygen, ozone) 5 and the mixed liquor of magnetic rare earth barium ferrite nanometer cleaning catalyst 16, separator 9 is entered through magnetic separation after air and waste water fully react, water 11 through purification reclaims and does its use, magnetic rare earth barium ferrite nanometer cleaning catalyst is returned in suspended-bed reactor 4 by circulating pump 13 to be reused, the gas 10 that purified treatment produces is emptying after inspection, if desired high temperature purification, then utilize steam(-)coil 15 to heat, if there is accident, the waste water carrying out purified treatment enters as emergency pool 14 from guard valve 13,
2, magnetic rare earth barium ferrite nanometer cleaning catalyst is pressed 200 ± 0.01g/m
3add in suspension bed;
3, the waste water containing COD is delivered in suspended-bed reactor by pump from storage tank, and flow velocity is 100 ± 0.01L/min;
4, by oxygen (or ozone) with the flow of 20 ± 0.01L/min through dispersion plate be separated into after fine gas bubbles with waste water, catalyst granules three-phase Homogeneous phase mixing; Open 20kHz/2000W ultrasonic stirrer agitated liquid simultaneously, make COD and oxygen by being adsorbed on catalyst surface enrichment like this, there is heterogeneous catalytic reaction, larger molecular organics valence link is ruptured, generate the organic oxygen compound of lower molecular weight, oxidation step of going forward side by side decomposes, and makes molecule continue to diminish.Organic matter is progressively from hydrocarbon → alcohol (aldehyde) → acid → CO
2+ H
2o, wherein acid degradation is controlling unit wherein; In processing procedure, reaction is as follows, as:
Through the water of purified treatment at separator through magnetic separation, reuse in reclaiming clean catalyst Returning reactor; The gas that reaction produces is harmless rear directly emptying after testing;
5, COD index contrast in waste water before and after process:
Temperature is that before 50 ± 0.01 DEG C of Industrial Wastewater Treatment, COD content is 723mg/L; Add magnetic rare earth barium ferrite nanometer cleaning catalyst 100g/m
3, after the process of 45 ± 0.01 minutes, COD content is 30mg/L, COD clearance is 95.85%;
Temperature is that before 50 ± 0.01 DEG C of Industrial Wastewater Treatment, COD content is 732mg/L; Add magnetic rare earth barium ferrite nanometer cleaning catalyst 200g/m
3, after the process of 45 ± 0.01 minutes, industrial wastewater COD content is 7mg/L, COD clearance is 99.04%;
Temperature is that before 50 ± 0.01 DEG C of Industrial Wastewater Treatment, COD content is 728mg/L; Add magnetic rare earth barium ferrite nanometer cleaning catalyst 300g/m
3, after the process of 45 ± 0.01 minutes, industrial wastewater COD content is 6mg/L, COD clearance is 99.18%.
The process of magnetic rare earth barium ferrite nanometer cleaning catalyst is containing NO
x, VOC and CO exhaust-gas treatment method:
1, magnetic rare earth barium ferrite nanometer cleaning catalyst is placed in porous material, and the porous material that magnetic rare earth barium ferrite nanometer cleaning catalyst is housed is made the cylindrical form matched with discharge duct, this cylinder is reactor; Reactor is placed in discharge duct, when the gas containing nitrogen oxide, carbon monoxide, hydrocarbon passes through, gas molecule is adsorbed on its surface and produces Local enrichment by magnetic rare earth barium ferrite nanometer cleaning catalyst, and it is N that nitrogen oxide, carbon monoxide, hydrocarbon a series of redox reaction can occur by gas transition
2, water and CO
2, as:
2, before and after process, in waste gas, gas is at 180 ~ 300 DEG C, CO entrance concentration 8000 ~ 15000mg/m
3, exit concentration 75 ~ 120mg/m
3, conversion ratio>=99%, HC entrance concentration 500 ~ 1000mg/m
3, exit concentration 0.00mg/m
3, conversion ratio 100%, NO
xentrance concentration 300 ~ 1000mg/m
3, exit concentration 2.5 ~ 8mg/m
3, conversion ratio>=99%.
Claims (2)
1. a preparation method for magnetic rare earth barium ferrite nanometer cleaning catalyst, is characterized in that comprising high temperature ultrasonic dispersion sol, the gelation of microwave negative pressure, the few oxygen denitration of low-temperature microwave negative pressure, roasting;
Described high temperature ultrasonic dispersion sol chemical industry sequence is:
(1) xanthans 1g ~ 5g/L or pickling elm rubber powder 10 ~ 25g/L being added pH value is in the mixed solution of 6.5 ~ 7.5, stirs and becomes colloidal solution;
(2) described mixed solution is mol ratio is barium nitrate solution: iron nitrate solution: earth solution: citric acid=0.1 ~ 3.00:1 ~ 24:0 ~ 2.0:3 ~ 20;
(3) colloidal solution is placed in glass container, at the temperature of 50 ~ 80 DEG C, carry out ultrasonic disperse with 600W/40kHz ultrasonic disperse instrument, jitter time is 60 ~ 120min; After High Temperature Disperse process, metal ion fully disperses in colloidal solution;
The step of described microwave negative pressure gel process is:
(1) colloidal solution after high temperature ultrasonic dispersion sol be placed in ceramic vessel with cover and be placed on the microwave reactor that air pressure is-0.1 ~-0.5kPa;
(2) in frequency be 2.45GHz microwave reactor in, regulating power is 140 ~ 280W, carries out microwave drying treatment, control temperature 110 ~ 150 DEG C, time 10 ~ 35min, extracts the moisture that evaporates out during process, after its cooling, become gel;
(3) obtained gel is carried out grind, sieve as the gel fine powder of particle diameter≤0.075mm;
The step of the few oxygen denitration operation of described microwave negative pressure is:
(1) gel fine powder is put into ceramic vessel with cover and be placed in the microwave reactor that setting power is 360 ~ 500W, frequency is 2.45GHz, air pressure is-1 ~-2kPa, carry out microwave denitration process; The control temperature of microwave denitration process is 200 ~ 240 DEG C, and the time is 5 ~ 10min;
In microwave denitration processing procedure, in gel fine powder, ammonium chloride is decomposed into ammonia and hydrogen chloride, and decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reaction equation is as follows:
(2) close microwave reactor, make it naturally cool to 25 DEG C;
(3) from microwave reactor, take out ceramic vessel, collect fine powder, grind, sieve, make the denitration gel fine powder of particle diameter≤0.075mm;
The step of described calcining process is:
(1) crucible filling denitration gel fine powder is placed in the roaster after purification;
(2) open roaster controller, control temperature is 550 ~ 850 DEG C, at this temperature 60 ~ 120min; Obtained nano rare earth barium ferrite catalytic purification agent.
2. the preparation method of a kind of magnetic rare earth barium ferrite nanometer cleaning catalyst according to claim 1, is characterized in that comprising the steps:
(1) material purity requires:
Neodymia purity is 99.9%;
Nine water ferric nitrate purity are 99.9%;
Barium nitrate purity is 99.9%;
Ammoniacal liquor purity is 28%;
Citric acid purity is 99.9%;
Hydrochloric acid purity is 40%;
Pickling elm glue purity is 99.5%;
(2) dry process:
Taking neodymia 200 ± 5g, to be placed in vacuum be that the vacuum drying chamber of-18Pa is dry, baking temperature 120 ± 2 DEG C, drying time 30min;
(3) pickling elm rubber powder preparation:
1. choose 5 years raw elm extra dry white wine skin 2000 ± 5g and be broken into the fritter that granularity is 2 ~ 3mm;
2. by step 1. gained elm extra dry white wine skin fritter 0.1mol/L hydrochloric acid 3L repeatedly clean three times, remove Ca wherein
2+, Mg
2+; And then by washed with de-ionized water three times;
3. by step 2. gained pickling Radix Ulmi Tonkinesis Rhizoma Euonymus to be again placed in vacuum drying chamber dry, baking temperature 110 ± 2 DEG C, vacuum-18Pa, drying time 60 ± 2min; Grind and the pickling elm rubber powder of the obtained particle diameter≤0.075mm that sieves;
(4) obtain solution:
1. taking 1 ± 0.001mol nine water ferric nitrate deionized water, to prepare 0.5 ± 0.001mol/L iron nitrate solution at 2000 milliliters of volumetric flasks stand-by;
2. take 0.25 ± 0.001mol barium nitrate deionized water to prepare 0.25 ± 0.001mol/L at 1000 milliliters of volumetric flasks and prepare barium nitrate solution for later use;
3. take 0.05 ± 0.001mol neodymia, 0.1 ± 0.001mol/L dissolving with hydrochloric acid, then prepare 0.05 ± 0.001mol/L neodymium chloride solution by deionized water at 1000 milliliters of volumetric flasks stand-by;
(5) proportioning and mixing:
According to Fe
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-molal quantity ratio be 2:0.9:0.1:6, measure iron nitrate solution, barium nitrate solution, neodymium chloride solution respectively, weigh citric acid simultaneously;
Iron nitrate solution, barium nitrate solution and neodymium chloride solution are mixed and stir, then citric acid is added, continue to stir until solution is clarified completely, dripping ammoniacal liquor regulates solution ph to 7.0 ± 0.01, adds at 500ml volumetric flask the mixed solution that solution concentration to be adjusted to 0.6 ± 0.01mol/L by deionized water;
(7) high temperature ultrasonic dispersion sol
1. 12 ± 0.001g pickling elm rubber powder being added pH value is in 500 ± 0.01ml mixed solution of 7.0 ± 0.01, continues stirring and makes it be dissolved into colloidal solution gradually;
2. colloidal solution is placed in glass container, at the temperature of 60 ± 0.01 DEG C, carry out ultrasonic disperse with the ultrasonic disperse instrument of 600W/40kHz, jitter time is 90 ± 0.01min; After High Temperature Disperse process, metal ion is fully separated into High Temperature Disperse colloidal solution in colloidal solution;
(8) microwave negative pressure gelation:
1. High Temperature Disperse colloidal solution is placed in ceramic vessel with cover to put into the microwave reactor that air pressure is-0.2 ± 0.01kPa, frequency is 2.45GHz, setting power is 200W and carry out microwave drying treatment, treatment temperature 125 ± 1 DEG C, time 25 ± 0.01min, extract the moisture evaporated during process out, after it cools naturally, make gel;
2. by gel abrasive, the gel fine powder being screened into particle diameter≤0.075mm;
(9) the few oxygen denitration of microwave negative pressure:
1. gel fine powder is put into ceramic vessel with cover and be-(1.5 ± 0.01) kPa at air pressure, frequency is 2.45GHz, setting power is 450W microwave reactor carries out denitration and is treated to denitration gel fine powder; Wherein denitration treatment temperature is 220 ± 1 DEG C, and the time is 6 ± 0.1min; Have ammonium chloride to be decomposed into ammonia and hydrogen chloride in the process in gel fine powder, decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reacts as follows:
(10) roasting:
1. the ceramic vessel filling denitration gel fine powder is placed in roaster;
2. roaster controller is opened, at 650 ± 1 DEG C of roasting temperature 60 ± 0.1min; Naturally being cooled to average-size is 58.6nm, and molecular formula is Ba
0.9nd
0.1fe
2o
4, magnetic saturation intensity is the nano-magnetic rare earth barium ferrite cleanser of the cubic system spinel type ferrite structure of 45emu/g;
In the process, organic substance decomposing is carbon dioxide and water, and the chelating ion of baric, iron and rare earth synthesizes the agent of nano rare earth barium ferrite catalytic purification through calcining.
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| CN108283884A (en) * | 2017-01-09 | 2018-07-17 | 高雄应用科技大学 | With the Ferrite catalyst and its method of selective media reductive reaction treatment exhaust gas nitrogen oxides |
| CN111470606A (en) * | 2020-04-14 | 2020-07-31 | 中稀(宜兴)稀土新材料有限公司 | Lossless medicament adding process for dissolving and preparing rare earth |
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| CN108906065A (en) * | 2018-07-02 | 2018-11-30 | 合肥萃励新材料科技有限公司 | A kind of Nd doping LaFeO3The preparation method of nano particle |
| CN115920889A (en) * | 2022-11-07 | 2023-04-07 | 上海交通大学 | Preparation and application of foamed spinel catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108283884A (en) * | 2017-01-09 | 2018-07-17 | 高雄应用科技大学 | With the Ferrite catalyst and its method of selective media reductive reaction treatment exhaust gas nitrogen oxides |
| CN111470606A (en) * | 2020-04-14 | 2020-07-31 | 中稀(宜兴)稀土新材料有限公司 | Lossless medicament adding process for dissolving and preparing rare earth |
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