CN116251599B - Dioxin removal catalyst and preparation method thereof - Google Patents
Dioxin removal catalyst and preparation method thereof Download PDFInfo
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- CN116251599B CN116251599B CN202211100291.2A CN202211100291A CN116251599B CN 116251599 B CN116251599 B CN 116251599B CN 202211100291 A CN202211100291 A CN 202211100291A CN 116251599 B CN116251599 B CN 116251599B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 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 title claims abstract 13
- 238000002360 preparation method Methods 0.000 title abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910001868 water Inorganic materials 0.000 claims abstract description 57
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000460 chlorine Substances 0.000 claims abstract description 40
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 10
- 229910018516 Al—O Inorganic materials 0.000 claims abstract description 5
- 229910018553 Ni—O Inorganic materials 0.000 claims abstract description 5
- 229910007746 Zr—O Inorganic materials 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims description 81
- 239000000843 powder Substances 0.000 claims description 55
- 239000008367 deionised water Substances 0.000 claims description 53
- 229910021641 deionized water Inorganic materials 0.000 claims description 53
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 230000007935 neutral effect Effects 0.000 claims description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 14
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 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 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 8
- 239000011609 ammonium molybdate Substances 0.000 claims description 8
- 229940010552 ammonium molybdate Drugs 0.000 claims description 8
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 8
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 150000003754 zirconium Chemical class 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 7
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 7
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 7
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000001844 chromium Chemical class 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 150000002751 molybdenum Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 150000003376 silicon Chemical class 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- 150000003657 tungsten Chemical class 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- 239000002574 poison Substances 0.000 abstract description 3
- 231100000614 poison Toxicity 0.000 abstract description 3
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 50
- 238000005303 weighing Methods 0.000 description 20
- 230000001105 regulatory effect Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000002013 dioxins Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 208000018569 Respiratory Tract disease Diseases 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 208000029028 brain injury Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
-
- 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
- B01J23/84—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
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a dioxin removal catalyst and a preparation method thereof, wherein the catalyst comprises a three-layer core-shell structure consisting of an inner core, a water-resistant shell layer and a chlorine-resistant shell layer, the inner core is Ce-Ti-Mn-W-Sn-Ni-O x composite oxide, the water-resistant shell layer is Cr-Mo-Al-O x composite oxide, and the chlorine-resistant shell layer is Si-Al-Zr-O x composite oxide. The invention uses the water-resistant shell layer and the chlorine-resistant shell layer of the catalyst core-shell structure to isolate the contact of substances such as water vapor, chloride ions and the like with the active site of the catalyst inner core, thereby effectively solving the problem that the catalyst is easy to poison and deactivate in the process of catalyzing and removing dioxin, prolonging the service time of the catalyst and optimizing the removal performance of the dioxin.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a dioxin removal catalyst and a preparation method thereof.
Background
With the rapid development of economy and the continuous improvement of living standard of people, the production amount and the cleaning amount of the household garbage are increased, and the solid waste is increased, so that a large amount of toxic and harmful gases such as dioxin are generated in the heat treatment of the waste. Dioxins comprise 75 polychlorinated dibenzo (p) dioxin isomers and 135 polychlorinated dibenzo-furan isomers. The main sources of dioxin in nature are two modes of high-temperature gas phase reaction generation and low-temperature heterogeneous reaction generation. The high-temperature gas phase reaction is mainly generated because incomplete combustion products in the high-temperature combustion section and an oxidizing chlorine source form dioxin compounds in a short time through polymerization reaction; the heterogeneous reaction at low temperature is to polymerize chlorine-containing organic matters after being cooled from a hearth at high temperature, and to generate dioxin through molecular recombination catalytic reaction. The main source of dioxin in life is produced by insufficient combustion of household garbage.
Dioxin has strong toxicity, has irritation to mucous membrane of organism, paralyzes central nerve, causes respiratory tract diseases and brain injury, and can participate in photolysis complex chemical process in stratosphere to destroy ozone layer and form ozone layer cavity. In addition, dioxins are carcinogenic, teratogenic, mutagenic and bioaccumulative. It is therefore particularly important to reduce dioxin emissions during heat treatment.
Currently, the dioxin removal technology mainly includes the following two types: one is an adsorption technology, in which an adsorbent such as activated carbon is used to adsorb dioxin, but the adsorbed dioxin still needs to be treated in a concentrated manner; the other is to directly catalyze and remove dioxin by using a catalyst, and the final product is CO 2、H2O、Cl- and the like, however, H 2O、Cl- and the like in the product can be adsorbed and accumulated on the surface of the catalyst so as to cover active sites in the catalyst and can also be in competitive adsorption with reaction gas, so that the catalyst can be quickly poisoned and deactivated in the use process. The reasons severely restrict and prevent the popularization and application of the dioxin catalytic removal technology.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a dioxin removal catalyst and a preparation method thereof, wherein a water-resistant shell layer and a chlorine-resistant shell layer of a catalyst core-shell structure are utilized to isolate substances such as water vapor, chloride ions and the like from contacting active sites of a catalyst core, so that the problem that the catalyst is easy to poison and deactivate in the process of catalyzing and removing dioxin is effectively solved, the service time of the catalyst is prolonged, and the dioxin removal performance is optimized.
The invention provides the following technical scheme:
In a first aspect, a dioxin removal catalyst is provided, which comprises a three-layer core-shell structure consisting of an inner core, a water-resistant shell layer and a chlorine-resistant shell layer, wherein the inner core is a Ce-Ti-Mn-W-Sn-Ni-O x composite oxide, the water-resistant shell layer is a Cr-Mo-Al-O x composite oxide, and the chlorine-resistant shell layer is a Si-Al-Zr-O x composite oxide.
Further, the mass of the water-resistant shell layer is 20-40% of the mass of the core, and the mass of the chlorine-resistant shell layer is 10-20% of the mass of the core.
Further, the molar ratio of Ce, ti, mn, W, sn, ni elements in the Ce-Ti-Mn-W-Sn-Ni-O x composite oxide is 1: (0.1-0.5): (0.1-0.5): (0.1-0.5): (0.1-0.5): (0.1-0.5), wherein the molar ratio of Cr, mo and Al elements in the Cr-Mo-Al-O x composite oxide is 1: (0.5-1): (0.1-0.5), wherein the molar ratio of Si, al and Zr elements in the Si-Al-Zr-O x composite oxide is 1: (0.5-1): (0.1-0.5).
In a second aspect, there is provided a method for preparing the dioxin removal catalyst of the first aspect, comprising the steps of:
Mixing cerium salt, titanium salt, manganese salt, tungsten salt, tin salt and nickel salt with deionized water, heating and stirring, aging to obtain a precipitate, and carrying out suction filtration, washing, drying and calcination on the precipitate in the precipitate to obtain kernel powder;
Mixing chromium salt, molybdenum salt and aluminum salt with deionized water, stirring until the chromium salt, the molybdenum salt and the aluminum salt are completely dissolved, adding the kernel powder, performing ultrasonic dispersion, adjusting the pH value of the solution by sulfuric acid, transferring to a reaction kettle for polymerization reaction, cooling after the reaction is finished, centrifugally separating and precipitating, washing the precipitate with deionized water until the precipitate is neutral, and drying to obtain kernel/water-resistant shell powder;
Mixing silicon salt, aluminum salt and zirconium salt with deionized water, stirring until the silicon salt, aluminum salt and zirconium salt are completely dissolved, adding the core/water-resistant shell powder, performing ultrasonic dispersion, adjusting the pH of the solution with sulfuric acid, transferring to a reaction kettle for polymerization reaction, cooling after the reaction is finished, centrifugally separating and precipitating, washing the precipitate with deionized water until the precipitate is neutral, and drying to obtain the core/water-resistant shell/chlorine-resistant shell powder;
And (3) carrying out oxidative roasting on the inner core/water-resistant shell/chlorine-resistant shell powder to obtain the dioxin removal catalyst.
Further, the specific steps for preparing the core powder include: cerium salt, titanium salt, manganese salt, tungsten salt, tin salt and nickel salt are mixed with deionized water according to a ratio of 1: (0.5-2), stirring for 20-100 min at a rotating speed of 100-1000 r/min at 20-80 ℃, aging for 4-6 h at 90-100 ℃ to obtain a precipitate, carrying out suction filtration and washing on the precipitate in the precipitate, drying for 4-8 h at 50-100 ℃, and calcining the precipitate in a muffle furnace at 300-950 ℃ for 4-12 h to obtain the core powder.
Further, the specific steps for preparing the core/water resistant shell powder include: chromium, molybdenum and aluminum salts were combined with deionized water at 1: mixing (1-5) in mass ratio, stirring at 20-60 ℃ at a rotating speed of 100-500 r/min for 50-120 min until the mixture is completely dissolved, adding the kernel powder, performing ultrasonic dispersion for 10-30 min, adjusting the pH of the solution to 1-6 by sulfuric acid, transferring the solution into a polytetrafluoroethylene lining hydrothermal reaction kettle, performing polymerization reaction at 80-150 ℃ for 24-72 h, cooling to room temperature after the reaction is finished, performing centrifugal separation to precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying at 40-100 ℃ for 6-10 h to obtain the kernel/water-resistant shell powder.
Further, the specific steps for preparing the core/water-resistant shell/chlorine-resistant shell powder include: mixing silicon salt, aluminum salt and zirconium salt with deionized water according to a ratio of 1: mixing (1-5) in mass ratio, stirring at 20-60 ℃ at a rotating speed of 100-500 r/min for 50-120 min until the mixture is completely dissolved, adding the core/water-resistant shell powder, performing ultrasonic dispersion for 10-30 min, adjusting the pH of the solution to 1-6 by sulfuric acid, transferring the solution into a polytetrafluoroethylene lining hydrothermal reaction kettle, performing polymerization reaction at 80-150 ℃ for 24-72 h, cooling to room temperature after the reaction is finished, performing centrifugal separation to precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying at 50-100 ℃ for 8-10 h to obtain the core/water-resistant shell/chlorine-resistant shell powder.
Further, the temperature of the oxidation roasting of the core/water-resistant shell/chlorine-resistant shell powder is 550-900 ℃, the time is 40-80 min, and the oxygen concentration is 5-20%.
Further, the cerium salt is any one of cerium nitrate, cerium chloride and cerium acetate; the titanium salt is any one of titanyl sulfate, titanium chloride and titanium acetate; the manganese salt is any one of manganese nitrate, manganese chloride and manganese sulfate; the tungsten salt is any one of ammonium tungstate and ammonium metatungstate; the tin salt is any one of tin chloride and tin bromide; the nickel salt is any one of nickel nitrate and nickel chloride.
Further, the chromium salt is any one of ammonium dichromate and chromium chloride; the molybdenum salt is any one of ammonium molybdate and lithium molybdate; the aluminum salt is any one of aluminum nitrate, aluminum chloride and aluminum sulfate; the silicon salt is any one of ammonium silicate and lithium silicate; the zirconium salt is any one of zirconium oxychloride and zirconyl nitrate.
Compared with the prior art, the invention has the beneficial effects that:
(1) The dioxin removal catalyst provided by the invention comprises a three-layer core-shell structure consisting of the inner core, the water-resistant shell layer and the chlorine-resistant shell layer, wherein the water-resistant shell layer and the chlorine-resistant shell layer can effectively isolate substances such as water vapor, chloride ions and the like from contacting with the active site of the inner core of the catalyst, reduce the competitive adsorption of the substances with dioxin, effectively solve the problem that the catalyst is easy to poison and deactivate in the process of catalyzing and removing the dioxin, are beneficial to prolonging the service time of the catalyst, and have important significance for popularization and application of the technology of catalyzing and removing the dioxin;
(2) The dioxin removal catalyst provided by the invention has excellent dioxin removal performance, and the dioxin removal rate reaches more than 90% in the temperature range of 250-400 ℃;
(3) The preparation method of the dioxin removal catalyst provided by the invention is simple to operate, has low requirements on production environment and production equipment, and is beneficial to realizing large-scale production and application.
Detailed Description
The invention is further described below. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
(1) Preparation of the catalyst inner core
According to the mole ratio Ce: ti: mn: w: sn: ni=1: 0.2:0.4:0.1:0.3:0.5 weighing cerous nitrate, titanium chloride, manganese sulfate, ammonium metatungstate, tin bromide and nickel chloride with certain mass, putting the cerous nitrate, the titanium chloride, the manganese sulfate, the ammonium metatungstate, the tin bromide and the nickel chloride into a beaker with 500ml, and based on the total mass of the salt, setting the mass ratio of the salt to deionized water as 1:0.5 adding deionized water, and stirring at 50deg.C and 500r/min for 60min; aging for 5 hours at 95 ℃ to obtain a precipitation solution; and (3) carrying out suction filtration and washing on the precipitate in the precipitation liquid, putting the precipitate into a crucible, drying the precipitate for 6 hours at the temperature of 75 ℃, and then putting the precipitate into a muffle furnace to calcine the precipitate for 4 hours at the temperature of 300 ℃ to obtain the core powder of the Ce-Ti-Mn-W-Sn-Ni-Ox composite oxide.
(2) Preparation of water-resistant shell layer of catalyst
The mass of the water-resistant shell layer is 30% of the mass of the inner core, and the molar ratio is Cr: mo: al=1: 0.7:0.5 weighing ammonium dichromate, ammonium molybdate and aluminum nitrate, and adding the ammonium dichromate, the ammonium molybdate and the aluminum nitrate into a beaker according to the mass ratio of the total mass of the ammonium dichromate, the ammonium molybdate and the aluminum nitrate to deionized water of 1:2, weighing deionized water and adding into a beaker; stirring at 40deg.C at 300r/min for 75min; adding the kernel powder obtained in the step (1), performing ultrasonic dispersion for 10min, and regulating the pH value of the solution to 1 by using sulfuric acid; transferring the suspension into a polytetrafluoroethylene lining hydrothermal reaction kettle, and carrying out polymerization reaction for 24 hours at 80 ℃; cooling to room temperature after the reaction is finished, centrifugally separating the precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying the precipitate for 8 hours at 60 ℃ to obtain the core/water-resistant shell powder.
(3) Preparation of chlorine-resistant shell of catalyst
The mass of the chlorine-resistant shell layer is 18 percent of the mass of the core, and the molar ratio Si: al: zr=1: 0.8:0.4 weighing ammonium silicate, aluminum nitrate and zirconyl nitrate, and adding the ammonium silicate, the aluminum nitrate and the zirconyl nitrate into a beaker according to the mass ratio of the total mass of the ammonium silicate, the aluminum nitrate and the zirconyl nitrate to deionized water of 1: weighing deionized water and adding into a beaker; stirring at 60deg.C at 400r/min for 85min; adding the kernel/water-resistant shell powder obtained in the step (2), performing ultrasonic dispersion for 10min, and regulating the pH of the solution to 1 by using sulfuric acid; transferring the suspension into a polytetrafluoroethylene lining hydrothermal reaction kettle, and carrying out polymerization reaction for 24 hours at 80 ℃; cooling to room temperature after the reaction is finished, centrifugally separating the precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying the precipitate for 10 hours at 75 ℃ to obtain the core/water-resistant shell/chlorine-resistant shell powder.
(4) Preparation of dioxin removal catalyst
And (3) oxidizing and roasting the core/water-resistant shell/chlorine-resistant shell powder obtained in the step (3) for 60 minutes at the temperature of 700 ℃ and the oxygen concentration of 15%, thereby obtaining the dioxin removal catalyst with the three-layer core-shell structure.
Example 2
(1) Preparation of the catalyst inner core
According to the mole ratio Ce: ti: mn: w: sn: ni=1: 0.4:0.3:0.1:0.2:0.2 weighing cerium chloride, titanium acetate, manganese nitrate, ammonium metatungstate, tin bromide and nickel chloride with certain mass, putting the cerium chloride, the titanium acetate, the manganese nitrate, the ammonium metatungstate, the tin bromide and the nickel chloride into a beaker with 500ml, and taking the total mass of the salt as the reference, wherein the mass ratio of the salt to deionized water is 1:2 adding deionized water, and stirring at a speed of 300r/min for 60min at 30 ℃; aging for 6 hours at 100 ℃ to obtain a precipitation solution; and (3) carrying out suction filtration and washing on the precipitate in the precipitation liquid, putting the precipitate into a crucible, drying the precipitate for 8 hours at the temperature of 100 ℃, and then putting the precipitate into a muffle furnace to calcine the precipitate for 6 hours at the temperature of 400 ℃ to obtain the core powder of the Ce-Ti-Mn-W-Sn-Ni-Ox composite oxide.
(2) Preparation of water-resistant shell layer of catalyst
The mass of the water-resistant shell layer is 20% of the mass of the inner core, and the molar ratio is Cr: mo: al=1: 0.8:0.4 weighing ammonium dichromate, lithium molybdate and aluminum sulfate, and adding the ammonium dichromate, the lithium molybdate and the aluminum sulfate into a beaker according to the mass ratio of the total mass of the ammonium dichromate, the lithium molybdate and the aluminum sulfate to deionized water of 1: weighing deionized water and adding into a beaker; stirring at 50deg.C at a rotational speed of 100r/min for 110min; adding the kernel powder obtained in the step (1), performing ultrasonic dispersion for 15min, and regulating the pH value of the solution to 3 by using sulfuric acid; transferring the suspension into a polytetrafluoroethylene lining hydrothermal reaction kettle, and carrying out polymerization reaction for 24 hours at 90 ℃; cooling to room temperature after the reaction is finished, centrifugally separating the precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying the precipitate for 10 hours at 80 ℃ to obtain the core/water-resistant shell powder.
(3) Preparation of chlorine-resistant shell of catalyst
The mass of the chlorine-resistant shell layer is 10% of the mass of the core, and the molar ratio Si: al: zr=1: 0.5:0.5, weighing lithium silicate, aluminum nitrate and zirconium oxychloride, and adding the lithium silicate, the aluminum nitrate and the zirconium oxychloride into a beaker according to the mass ratio of the total mass of the lithium silicate, the aluminum nitrate and the zirconium oxychloride to deionized water of 1:2, weighing deionized water and adding into a beaker; stirring at 40deg.C at 150r/min for 50min; adding the core/water-resistant shell powder obtained in the step (2), performing ultrasonic dispersion for 15min, and regulating the pH of the solution to 3 by using sulfuric acid; transferring the suspension into a polytetrafluoroethylene lining hydrothermal reaction kettle, and carrying out polymerization reaction for 24 hours at the temperature of 100 ℃; cooling to room temperature after the reaction is finished, centrifugally separating the precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying the precipitate for 6 hours at 80 ℃ to obtain the core/water-resistant shell/chlorine-resistant shell powder.
(4) Preparation of dioxin removal catalyst
And (3) oxidizing and roasting the core/water-resistant shell/chlorine-resistant shell powder obtained in the step (3) for 80 minutes at the temperature of 550 ℃ and the oxygen concentration of 10%, thereby obtaining the dioxin removal catalyst with the three-layer core-shell structure.
Example 3
(1) Preparation of the catalyst inner core
According to the mole ratio Ce: ti: mn: w: sn: ni=1: 0.1:0.3:0.4:0.5:0.1 weighing cerium nitrate, manganese chloride, ammonium tungstate, tin chloride and nickel chloride with certain mass, putting the cerium nitrate, the manganese chloride, the ammonium tungstate, the tin chloride and the nickel chloride into a 500ml beaker, and taking the total mass of the salt as the basis, according to the mass ratio of the salt to deionized water as 1:1 adding deionized water, and stirring at 50 ℃ for 80min at a rotating speed of 600 r/min; aging for 5 hours at 105 ℃ to obtain a precipitation solution; and (3) carrying out suction filtration and washing on the precipitate in the precipitate liquid, putting the precipitate into a crucible, drying the precipitate for 6 hours at the temperature of 80 ℃, and then putting the precipitate into a muffle furnace to calcine the precipitate for 8 hours at the temperature of 550 ℃ to obtain the core powder of the Ce-Ti-Mn-W-Sn-Ni-Ox composite oxide.
(2) Preparation of water-resistant shell layer of catalyst
The mass of the water-resistant shell layer is 25% of the mass of the inner core, and the molar ratio is Cr: mo: al=1: 0.5:0.5, weighing chromium chloride, ammonium molybdate and aluminum chloride, and adding the chromium chloride, the ammonium molybdate and the aluminum chloride into a beaker according to the mass ratio of the total mass of the chromium chloride, the ammonium molybdate and the aluminum chloride to deionized water of 1:1, weighing deionized water and adding into a beaker; stirring at 45deg.C at a rotation speed of 350r/min for 100min; adding the kernel powder obtained in the step (1), performing ultrasonic dispersion for 20min, and regulating the pH value of the solution to 2 by using sulfuric acid; transferring the suspension into a polytetrafluoroethylene lining hydrothermal reaction kettle, and carrying out polymerization reaction for 48 hours at 120 ℃; cooling to room temperature after the reaction is finished, centrifugally separating the precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying the precipitate for 10 hours at 80 ℃ to obtain the core/water-resistant shell powder.
(3) Preparation of chlorine-resistant shell of catalyst
The mass of the chlorine-resistant shell layer is 15% of the mass of the core, and the molar ratio Si: al: zr=1: 0.9:0.4, weighing lithium silicate, aluminum sulfate and zirconium oxychloride, adding into a beaker, and according to the mass ratio of the total mass of the lithium silicate, the aluminum sulfate and the zirconium oxychloride to deionized water of 1:1, weighing deionized water and adding into a beaker; stirring at 50deg.C at 150r/min for 50min; adding the core/water-resistant shell powder obtained in the step (2), performing ultrasonic dispersion for 15min, and regulating the pH of the solution to 2 by using sulfuric acid; transferring the suspension into a polytetrafluoroethylene lining hydrothermal reaction kettle, and carrying out polymerization reaction for 48 hours at 120 ℃; cooling to room temperature after the reaction is finished, centrifugally separating the precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying the precipitate for 10 hours at 80 ℃ to obtain the core/water-resistant shell/chlorine-resistant shell powder.
(4) Preparation of dioxin removal catalyst
And (3) oxidizing and roasting the core/water-resistant shell/chlorine-resistant shell powder obtained in the step (3) for 60 minutes at the temperature of 800 ℃ and the oxygen concentration of 15%, thereby obtaining the dioxin removal catalyst with the three-layer core-shell structure.
Example 4
(1) Preparation of the catalyst inner core
According to the mole ratio Ce: ti: mn: w: sn: ni=1: 0.3:0.5:0.4:0.2:0.3 weighing cerium acetate, titanyl sulfate, manganese nitrate, ammonium metatungstate, tin bromide and nickel chloride with certain mass, putting into a beaker with 500ml, and based on the total mass of the salt, according to the mass ratio of the salt to deionized water as 1:1.5 adding deionized water, and stirring at 50deg.C and 200r/min for 30min; aging for 5 hours at 90 ℃ to obtain a precipitation solution; and (3) carrying out suction filtration and washing on the precipitate in the precipitate liquid, putting the precipitate into a crucible, drying for 7h at the temperature of 80 ℃, and then putting the crucible into a muffle furnace to calcine for 6h at the temperature of 800 ℃ to obtain the core powder of the Ce-Ti-Mn-W-Sn-Ni-Ox composite oxide.
(2) Preparation of water-resistant shell layer of catalyst
The mass of the water-resistant shell layer is 40% of the mass of the inner core, and the molar ratio is Cr: mo: al=1: 1:0.4, weighing chromium chloride, lithium molybdate and aluminum sulfate, and adding the chromium chloride, the lithium molybdate and the aluminum sulfate into a beaker according to the mass ratio of the total mass of the chromium chloride, the lithium molybdate and the aluminum sulfate to deionized water of 1: weighing deionized water and adding into a beaker; stirring at 50deg.C at 500r/min for 90min; adding the kernel powder obtained in the step (1), performing ultrasonic dispersion for 30min, and regulating the pH of the solution to 6 by using sulfuric acid; transferring the suspension into a polytetrafluoroethylene lining hydrothermal reaction kettle, and carrying out polymerization reaction for 72h at 150 ℃; cooling to room temperature after the reaction is finished, centrifugally separating the precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying the precipitate for 6 hours at 80 ℃ to obtain the core/water-resistant shell powder.
(3) Preparation of chlorine-resistant shell of catalyst
The mass of the chlorine-resistant shell layer is 15% of the mass of the core, and the molar ratio Si: al: zr=1: 1:0.5 weighing ammonium silicate, aluminum nitrate and zirconyl nitrate, adding into a beaker, and according to the mass ratio of the total mass of the heavy ammonium silicate, the aluminum nitrate and the zirconyl nitrate to deionized water of 1: weighing deionized water and adding into a beaker; stirring at 60deg.C at 500r/min for 100min; adding the core/water-resistant shell powder obtained in the step (2), performing ultrasonic dispersion for 15min, and regulating the pH of the solution to 6 by using sulfuric acid; transferring the suspension into a polytetrafluoroethylene lining hydrothermal reaction kettle, and carrying out polymerization reaction for 48 hours at 120 ℃; cooling to room temperature after the reaction is finished, centrifugally separating the precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying the precipitate for 8 hours at 80 ℃ to obtain the core/water-resistant shell/chlorine-resistant shell powder.
(4) Preparation of dioxin removal catalyst
And (3) oxidizing and roasting the core/water-resistant shell/chlorine-resistant shell powder obtained in the step (3) for 90min at 600 ℃ under the condition that the oxygen concentration is 10%, so as to obtain the dioxin removal catalyst with the three-layer core-shell structure.
Comparative example
This comparative example provides a Cr 2O3-CeO2/Al2O3 catalyst for dioxin removal. The preparation method of the catalyst comprises the following steps:
The catalyst is prepared by adopting a citric acid complexation method, 6.9g of cerium nitrate hexahydrate and 6.4g of chromium nitrate nonahydrate are respectively added into 20mL of deionized water, the solution is fully stirred and dissolved, 1.0g of citric acid monohydrate is added into the solution, stirring is continued until the solution is fully dissolved, the solution is magnetically stirred and heated until sol is formed, 5.0g of strip Al 2O3 carrier is immersed for 2h, the solution is taken out and then dried for 12h at 80 ℃, then baked for 4h at 500 ℃ in a muffle furnace, and the excessive powder is removed by sieving through a square hole screen after being taken out, so that the Cr/Ce material is prepared, wherein the mass ratio of the Cr/Ce is 1:1, the metal oxidation loading of the Cr 2O3-CeO2/Al2O3 catalyst is 20wt%, and the mass ratio of citric acid to metal ion substances is 1:6.
The catalysts of examples 1 to 4 and comparative examples were used for the dioxin removal test in the following manner:
The experimental device consists of a gas distribution system, a flow control (mass flowmeter), a gas mixer, a gas preheater, a catalytic reactor and a flue gas analysis system; the catalytic reactor is a quartz tube with an inner diameter of 10mm, and then the reactor is put into a fixed tubular reactor; the simulated flue gas composition was: o 2 (8%), dioxin (3.2 ngI-TEQNm -3) and carrier gas N 2, wherein the airspeed is 20000h -1, and the reaction temperature is controlled at 300 ℃; the gas flow is controlled by a mass flowmeter; the gas is mixed by a gas mixer before entering the reactor and then heated by a heater; the concentration of dioxin at the air inlet and the air outlet is determined by high resolution chromatography and high resolution mass spectrum; in order to eliminate the influence of surface adsorption, the system starts to collect and test after the ventilation operation is stable for 20-30 min, and the initial removal rate of the catalyst to dioxin and the removal rate after continuous test for 200h are respectively obtained, and the results are shown in Table 1.
Wherein the dioxin removal rate of the catalyst is calculated by the following formula:
Dioxin removal rate= [ (X 0-X)/X0 ] ×100%
Wherein X 0 is the initial concentration of dioxin, and X is the concentration of dioxin after catalytic treatment.
TABLE 1 Dioxin removal rates for the catalysts of examples 1-4 and comparative examples
| Sample of | Temperature (. Degree. C.) | Initial removal rate (%) | Removal rate after 200h of continuous test (%) |
| Example 1 | 300 | 90.99 | 90.09 |
| Example 2 | 300 | 94.58 | 92.12 |
| Example 3 | 300 | 99.62 | 99.31 |
| Example 4 | 300 | 93.54 | 92.52 |
| Comparative example | 300 | 88.46 | 50.45 |
As can be seen from Table 1, the initial removal rate of dioxin by the dioxin removal catalyst prepared by the application and the catalyst in the comparative example can reach more than 90%. However, after 200 hours of continuous test, the removal rate of dioxin by the comparative catalyst is reduced to 50.45%, which indicates that the catalyst is poisoned and deactivated; the removal rate of the dioxin is still kept above 90%, which shows that the application effectively improves the poisoning resistance and the service life of the dioxin removal catalyst.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (8)
1. The dioxin removal catalyst is characterized by comprising a three-layer core-shell structure composed of an inner core, a water-resistant shell layer and a chlorine-resistant shell layer, wherein the inner core is a Ce-Ti-Mn-W-Sn-Ni-O x composite oxide, the water-resistant shell layer is a Cr-Mo-Al-O x composite oxide, and the chlorine-resistant shell layer is a Si-Al-Zr-O x composite oxide;
The mass of the water-resistant shell layer is 20-40% of the mass of the core, and the mass of the chlorine-resistant shell layer is 10-20% of the mass of the core;
The molar ratio of Ce, ti, mn, W, sn, ni elements in the Ce-Ti-Mn-W-Sn-Ni-O x composite oxide is 1: (0.1-0.5): (0.1-0.5): (0.1-0.5): (0.1-0.5): (0.1-0.5), wherein the molar ratio of Cr, mo and Al elements in the Cr-Mo-Al-O x composite oxide is 1: (0.5-1): (0.1-0.5), wherein the molar ratio of Si, al and Zr elements in the Si-Al-Zr-O x composite oxide is 1: (0.5-1): (0.1-0.5).
2. A method for preparing the dioxin removal catalyst of claim 1, characterized by comprising the steps of:
Mixing cerium salt, titanium salt, manganese salt, tungsten salt, tin salt and nickel salt with deionized water, heating and stirring, aging to obtain a precipitate, and carrying out suction filtration, washing, drying and calcination on the precipitate in the precipitate to obtain kernel powder;
Mixing chromium salt, molybdenum salt and aluminum salt with deionized water, stirring until the chromium salt, the molybdenum salt and the aluminum salt are completely dissolved, adding the kernel powder, performing ultrasonic dispersion, adjusting the pH value of the solution by sulfuric acid, transferring to a reaction kettle for polymerization reaction, cooling after the reaction is finished, centrifugally separating and precipitating, washing the precipitate with deionized water until the precipitate is neutral, and drying to obtain kernel/water-resistant shell powder;
mixing silicon salt, aluminum salt and zirconium salt with deionized water, stirring until the silicon salt, aluminum salt and zirconium salt are completely dissolved, adding the core/water-resistant shell powder, performing ultrasonic dispersion, adjusting the pH of the solution with sulfuric acid, transferring to a reaction kettle for polymerization reaction, cooling after the reaction is finished, centrifugally separating and precipitating, washing the precipitate with deionized water until the precipitate is neutral, and drying to obtain the core/water-resistant shell/chlorine-resistant shell powder;
And (3) carrying out oxidative roasting on the inner core/water-resistant shell/chlorine-resistant shell powder to obtain the dioxin removal catalyst.
3. The method for preparing the dioxin removal catalyst of claim 2, characterized in that the specific steps for preparing the core powder include: cerium salt, titanium salt, manganese salt, tungsten salt, tin salt and nickel salt are mixed with deionized water according to a ratio of 1: (0.5-2), stirring for 20-100 min at a rotating speed of 100-1000 r/min at 20-80 ℃, aging for 4-6 h at 90-100 ℃ to obtain a precipitate, carrying out suction filtration and washing on the precipitate in the precipitate, drying for 4-8 h at 50-100 ℃, and calcining the precipitate in a muffle furnace at 300-950 ℃ for 4-12 h to obtain the core powder.
4. The method for preparing the dioxin removal catalyst of claim 2, characterized in that the specific steps for preparing the core/water resistant shell powder include: chromium, molybdenum and aluminum salts were combined with deionized water at 1: mixing (1-5) in mass ratio, stirring at 20-60 ℃ at a rotating speed of 100-500 r/min for 50-120 min until the mixture is completely dissolved, adding the kernel powder, performing ultrasonic dispersion for 10-30 min, adjusting the pH of the solution to 1-6 by sulfuric acid, transferring the solution into a polytetrafluoroethylene lining hydrothermal reaction kettle, performing polymerization reaction at 80-150 ℃ for 24-72 h, cooling to room temperature after the reaction is finished, performing centrifugal separation to precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying at 40-100 ℃ for 6-10 h to obtain the kernel/water-resistant shell powder.
5. The method for preparing the dioxin removal catalyst of claim 2, characterized in that the specific steps for preparing the core/water resistant shell/chlorine resistant shell powder include: mixing silicon salt, aluminum salt and zirconium salt with deionized water according to a ratio of 1: mixing (1-5) in mass ratio, stirring at 20-60 ℃ at a rotating speed of 100-500 r/min for 50-120 min until the mixture is completely dissolved, adding the core/water-resistant shell powder, performing ultrasonic dispersion for 10-30 min, adjusting the pH of the solution to 1-6 by sulfuric acid, transferring the solution into a polytetrafluoroethylene lining hydrothermal reaction kettle, performing polymerization reaction at 80-150 ℃ for 24-72 h, cooling to room temperature after the reaction is finished, performing centrifugal separation to precipitate, washing the precipitate with deionized water until the precipitate becomes neutral, and drying at 50-100 ℃ for 8-10 h to obtain the core/water-resistant shell/chlorine-resistant shell powder.
6. The method for preparing the dioxin removal catalyst according to claim 2, wherein the temperature of the oxidation roasting of the core/water-resistant shell/chlorine-resistant shell powder is 550-900 ℃, the time is 40-80 min, and the oxygen concentration is 5-20%.
7. The method for preparing a catalyst for removing dioxin according to claim 2, characterized in that the cerium salt is any one of cerium nitrate, cerium chloride and cerium acetate; the titanium salt is any one of titanyl sulfate, titanium chloride and titanium acetate; the manganese salt is any one of manganese nitrate, manganese chloride and manganese sulfate; the tungsten salt is any one of ammonium tungstate and ammonium metatungstate; the tin salt is any one of tin chloride and tin bromide; the nickel salt is any one of nickel nitrate and nickel chloride.
8. The method for producing a dioxin removal catalyst according to claim 2, characterized in that the chromium salt is any one of ammonium dichromate and chromium chloride; the molybdenum salt is any one of ammonium molybdate and lithium molybdate; the aluminum salt is any one of aluminum nitrate, aluminum chloride and aluminum sulfate; the silicon salt is any one of ammonium silicate and lithium silicate; the zirconium salt is any one of zirconium oxychloride and zirconyl nitrate.
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