CN106215940A - 一种铁铜铈改性二氧化钛催化剂的制备方法及其应用 - Google Patents
一种铁铜铈改性二氧化钛催化剂的制备方法及其应用 Download PDFInfo
- Publication number
- CN106215940A CN106215940A CN201610534311.5A CN201610534311A CN106215940A CN 106215940 A CN106215940 A CN 106215940A CN 201610534311 A CN201610534311 A CN 201610534311A CN 106215940 A CN106215940 A CN 106215940A
- Authority
- CN
- China
- Prior art keywords
- preparation
- parts
- haydite
- catalyst
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- -1 cerium modified titanium Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 13
- 239000010949 copper Substances 0.000 title claims abstract description 13
- 239000002351 wastewater Substances 0.000 claims abstract description 18
- 239000010802 sludge Substances 0.000 claims abstract description 15
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 150000000703 Cerium Chemical class 0.000 claims abstract description 5
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 5
- 150000001879 copper Chemical class 0.000 claims abstract description 4
- 235000011054 acetic acid Nutrition 0.000 claims abstract description 3
- 150000001243 acetic acids Chemical class 0.000 claims abstract description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 235000013339 cereals Nutrition 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000002360 explosive Substances 0.000 claims description 4
- 239000010881 fly ash Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000002910 solid waste Substances 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 23
- 239000000203 mixture Substances 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- 238000002386 leaching Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000003361 porogen Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical group [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 239000000015 trinitrotoluene Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241001300078 Vitrea Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical compound PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011863 silicon-based powder Substances 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
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 210000004127 vitreous body Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种铁铜铈改性二氧化钛催化剂的制备方法及其应用,催化剂的制备包括以下步骤,按体积份:(1)向反应容器中加入300~400份无水乙醇、5~8份乙酰丙酮、3~6份冰乙酸后混合均匀,再加入20~50份钛酸丁酯,搅拌混合得溶液A;(2)在20~30份无水乙醇中,加入0.1~0.5M的可溶性铈盐1~3mL、0.2~1M的可溶性铜盐2~3mL、0.1~0.5M可溶性亚铁盐量3~5ml,混合均匀后,再与溶液A混合得到溶液B;(3)将溶液B加热至60~90℃,加入1~4份模板剂,反应0.5~2h,得到预聚体;(4)将陶粒浸泡于所述预聚体中5~20秒,取出沥干,经干燥后,于400~500℃煅烧0.5~2h,得到铁铜铈改性二氧化钛催化剂。该催化剂对废水的催化处理效果好;同时催化剂的制备还可以利用固体废弃物市政污泥。
Description
技术领域
本发明涉及一种铁铜铈改性二氧化钛催化剂的制备方法及其应用,属于处理工业废水中的催化剂材料技术领域。
背景技术
过硫酸盐高级氧化是近几年发展起来的一种处理难降解有机废水的有效方法,其氧化机理是在催化剂作用下,产生比·OH氧化电位更高的·SO4 -过氧基,主要的催化方式有热催化、光催化和化学催化。化学催化主要是以金属或过渡金属离子如Fe0、Fe2+、Co2+、Ce2+等激活·SO4 -。张盛汉等在《硫酸亚铁/过硫酸钾体系深度处理印染废水》(东华大学学报Vol.39N6.P814)、万小娇等在《过硫酸盐深度催化氧化垃圾渗滤液膜浓缩液》(有色金属设计与研究Vol.35No.1P33)及张乃东等人的发明专利:201110149719.8介绍了化学催化氧化的研究进展。沈迅伟等在《二氧化钛悬浆体系中过硫酸盐对苯酚光催化降解的影响》(环境科学学报Vol.25No.5P631)、沙俊鹏等在《纳米TiO2/介孔ZSM-5协同过硫酸盐光催化降解硝基苯酚废水》(安徽工业大学学报Vol.30No.1P32)介绍了过硫酸盐协同光催化氧化方面的研究进展。
从上述介绍来看,过渡金属催化,是通过过渡金属的价态变化直接激发·SO4 -的产生,而二氧化钛催化则是通过光激发二氧化钛产生导带电子和价带空穴,光生空穴迁移到表面与吸附态羟基和水反应生成羟基自由基;而光生电子与电子受体产生·O- 2自由基,进而激发过硫酸盐产生·SO4 -。催化剂在过硫酸盐氧化的过程中的作用是至关重要的。
资料显示,金属及金属离子催化过硫酸盐氧化时,金属离子是以离子态溶解在待处理废液中,不仅造成金属离子的流失,而且需要增加金属离子与废水的分离工序。如果将金属离子负载到固体载体上,就可解决上述问题。在进行二氧化钛光催化反应时,有人将二氧化钛负载到载体上,如:范峰等人的发明专利《一种ZSM-5沸石的改性处理方法》(专利号:20111092779.8)、翟庆洲等人的发明专利《MCM-41分子筛与钛纳米复合材料及其制备方法》(专利号:200410096181.9)。
过渡金属离子激发过硫酸盐的催化氧化与二氧化钛的光催化氧化共同作用于难降解有机废水的降解会起到叠加的协调效应。
发明内容
本发明解决的技术问题是,提供一种催化效果良好的催化剂,可以用于处理工业废水,特别是炸药废水;同时,这种催化剂的制备方法简便,还可以利用市政污泥,得到的陶瓷载体溶出率低。
本发明的技术方案是,提供一种改性二氧化钛催化剂的制备方法,包括以下步骤,各步骤中的物料均按体积份计算:
(1)向反应容器中加入300~400份无水乙醇,5~8份乙酰丙酮,3~6份冰乙酸后混合均匀,再加入20~50份钛酸丁酯,搅拌混合得溶液A;
(2)在20~30份无水乙醇中,加入0.1~0.5M的可溶性铈盐1~3份,0.2~1M的可溶性铜盐2~3份、0.1~0.5M可溶性亚铁盐份,混合均匀后,再与溶液A混合得到溶液B;
(3)将溶液B加热至60~90℃,加入1~4份模板剂,反应0.5~2h,得到预聚体;
(4)将陶粒浸泡于所述预聚体中5~20秒,取出沥干,经干燥后,于400~500℃煅烧0.5~2h,得到铁铜铈改性二氧化钛催化剂。
本发明掺杂的金属离子是在溶液中的掺杂,掺杂后的物质在微观结构上是均相的,即在微观尺度上,掺杂原子的分布也是均匀的;这与普通的物理掺杂(如:两种粉末混合)具有明显的区别。所以说,此掺杂属于均相掺杂。
进一步地,所述步骤(2)中,可溶性铈盐为硝酸铈铵。
进一步地,所述步骤(2)中,可溶性铜盐为硫酸铜。
进一步地,所述步骤(2)中,可溶性亚铁盐为硫酸亚铁铵。
进一步地,所述步骤(3)中,模板剂为聚乙二醇。
进一步地,所述陶粒由以下方法制得:(1)按重量份,以市政污泥20-60份、粘土10-20份、高岭土10-20份、粉煤灰10-20份、硅源2-5份为原料;将原料中的各组分混匀,再经挤压得陶粒坯料;所述硅源为水玻璃、气相二氧化硅和硅粉中的一种或几种;
(2)将所述陶粒坯料干燥后烧结,冷却,得到多孔陶粒载体;所述烧结是将干燥后的陶粒坯料先升温至300-600℃下预烧10-40min,再升温至950-1150℃,保温10-40min。
进一步地,所述市政污泥的含水率不高于85%,市政污泥中有机质的干基含量为50~60%,无机质的干基含量为40~50%。无机质的主要成分为:三氧化二铝、二氧化硅及氧化铁、氧化钙、氧化镁等。
进一步地,所述陶粒的抗压强度为20~30MPa
进一步地,所述陶粒的孔隙率为45~55%,比表面积为200~400m2/g。
本发明进一步地提供上述催化剂在废水处理,特别是炸药废水处理方面的应用。
铜、铈、铁的掺杂量分别为二氧化钛(重量比)的0.05~0.1、0.1~0.2、0.2~0.4。
锐钛型二氧化钛在可见/紫外光作用下,会激发产生光电子,进而产生羟基自由基,通过掺杂在二氧化钛晶格中人为制造缺陷,利用铁离子、铈离子的价态变化,在紫外光作用下产生光电子-空穴,使产生的羟基自由基的湮灭速度降低,有效自由基的浓度增加,氧化效率提高。铁和铈造成的晶格缺陷不同,起到协同催化的作用,。铜离子的作用是降低反应自由能,使氧化反应更容易进行。
铁和铈离子还可以直接催化分解过硫酸盐产生·SO4自由基,硫酸自由基比羟基自由基具有更高的氧化电位。可以使更难降解的有机物被氧化分解降解。
将制备好的二氧化钛预聚体涂敷在陶粒表面,通过煅烧得到锐钛型二氧化钛晶体。
目前污泥制备陶粒更多使用水底淤泥、或者低含水率污泥,含水市政污泥的粘性大,与物料的混合比较困难,使用比较少。而且目前制得陶粒开孔率不高,作为建材使用的附加值较低。针对该情况,本发明了利用富含有机质的市政污泥作为致孔剂制备多孔载体材料。本发明的市政污泥添加量大,可达60%,有机质含量高,可占固形物中的15-20%,不需额外添加致孔剂,市政污泥不经过干燥直接使用,可以节省能源。
普通多孔陶瓷的主要成分为硅铝酸盐,原料包括高岭土、硅藻土、粘土等,成孔剂为碳酸盐类、有机物等可在高温下挥发成气体的物质。添加市政污泥制备陶粒利用其中有机物作为致孔剂,无机物作为陶粒成分;有机物在300-600℃(预烧)时氧化分解,挥发产生气体,溢出形成孔隙;而污泥中无机物质以SiO2、Al2O3、CaO、Fe2O3元素为主,是硅铝酸盐陶瓷烧制的原材料。陶粒的原料以SiO2和Al2O3为主体成分,为陶粒形成强度和结构的主要结构基础,Al2O3占10-25%,SiO2占40-79%,本发明中适当添加硅源(水玻璃、气相二氧化硅和硅粉),以增加SiO2的含量,调整Al2O3与SiO2的比例;本发明的硅源还可以作为粘结剂,为陶粒胚料的形成提供结构强度,使胚料的强度提高,易于成型。
在污泥陶粒烧制建筑陶粒过程中,有机物预烧时分解,在陶粒内部形成细微通孔,当温度上升到一定程度后,原料中SiO2、Al2O3、CaO、Fe2O3开始相互熔融(冷却后会形成矿物),当烧结温度到达1200℃后或者烧结时间延长时,在颗粒表面形成一定厚度的玻璃相熔融体,冷却后成为闭孔陶粒,这种陶粒密度小、强度高。烧制多孔的载体陶粒(开孔)时,不能在颗粒表面形成玻璃体,造成闭孔;同时又要求内部各组分充分熔融,有足够的物理强度,因此对烧结温度及烧结时间的把握更加精确。CaO、Fe2O3等可以作为SiO2、Al2O3高温液化的助熔剂(不需要单独添加其他的助溶剂,如硼砂),降低形成玻璃体的温度,根据本研究中开孔陶粒的原料成分,烧制温度在950-1150℃,烧制温度为10-40min。在烧制过程中需要控制升温速率和冷却降温速率,升温速度过快使得颗粒表面与内部受热不均,表面容易熔融,易形成闭孔;降温速度快将使得颗粒的物理性质发生变化,容易形成裂缝。
综上所述,载体陶粒与建筑陶粒的最大区别在于:建筑陶粒要求强度高、质轻,内部多孔,表面封闭,无贯穿性空隙,对孔径没有要求。载体陶粒要求表面有贯穿性微孔,比表面积大,孔径均匀,对强度要求相对较低,因此,对温度的控制更加精确,需要经过大量的试验和包括相图分析在内的大量数据分析才能够确定。建筑陶粒对所构成的原材料成分没有严格要求,而载体陶粒对原材料的成分要求严格,需要外加硅源进行成分调整,微小的成分差别都会影响其性能,需要通过大量实验和包括表面扫描、孔径测量,结构分析等大量数据分析及应用试验才能够确定。
本发明制备的多孔陶粒载体有以下特征:表面粗糙、疏松多孔,颗粒孔隙率高达45-55%,比表面积达200-400m2/g;化学性质稳定,1+1盐酸溶出率<1%;重金属浸出量在标准以下,无浸出毒性造成的二次污染;机械强度高,抗压强度达到20-30MPa,甚至更高。可替代传统的天然多孔材料或者人工多孔材料,作为废水处理中的催化剂与吸附剂的载体材料。本发明利用污泥制备多孔陶粒材料,原料简单、价格便宜、性能优异、使用方便。
本发明的有益效果是,对于难降解的有机废水处理效果好;特别是对于含氨基、膦酸基、苯环、稠环等难降解的有机废水降解率更高,还可以利用市政污泥制备陶粒,实现废物利用。
具体实施方式
下面通过几天实施例对本发明做具体介绍,以下实例不构成对本发明的限定。
实施例一
1、陶粒载体制备
取污泥2.0kg、粘土1.0kg、高岭土1.0kg、粉煤灰1.0kg、水玻璃0.2kg,充分混合均匀,造成柱状陶粒坯料,在高温炉中以10℃温度升温至500℃,恒温预烧30min,再以5℃/min速率升温至1100℃,烧结20min,以10℃/min速率冷却至300℃以下,取出自然冷却,得多孔陶粒载体外观为砖红色短柱状固体颗粒。经检查无浸出毒性物质,拥有较好的表观密度与孔隙率,可用作催化剂载体材料。
制得陶粒陶瓷表面粗糙、疏松多孔,颗粒孔隙率高达55%,比表面积达380m2/g;化学性质稳定,1+1盐酸溶出率<0.1%;重金属浸出量在危废排放标准以下,无浸出毒性造成的二次污染;机械强度高,抗压强度达到27MPa。
2、二氧化钛预聚体合成
1)向反应容器中加入350L无水乙醇,再分别加入7.8L乙酰丙酮,4.5L冰乙酸混合均匀,再加入40L钛酸丁酯,搅拌混合。
2)另外量取27L无水乙醇,加入0.1M硝酸铈铵1L;加入0.2M的硫酸铜2L,加入0.1M硫酸亚铁铵3L;混合均匀后,缓慢加入到步骤1)中,搅拌反应。
3)水浴加热至80℃,称3L聚乙二醇,溶解后反应1h,得到铁铜铈改性二氧化钛的预聚体,冷却备用。
3、将步骤1得到的陶瓷载体,浸泡到步骤2得到的预聚体中,并快速取出,沥干预聚体,经干燥后,于450℃煅烧2h,得到铁铜铈改性二氧化钛催化剂。
实施例二:
1、陶粒载体制备
取污泥2.4kg、粘土0.5kg、高岭土0.5kg、粉煤灰0.4kg、气相二氧化硅0.15kg,充分混合均匀,造成柱状陶粒坯料,在高温炉中以10℃温度升温至500℃,恒温预烧40min,再以5℃/min速率升温至1100℃,烧结20min,以10℃/min速率冷却至300℃以下,取出自然冷却,烧得多孔陶粒载体外观为微黄短柱状固体颗粒。经检查无浸出毒性物质,拥有较好的表观密度与孔隙率,可用作催化剂载体材料。
制得陶粒陶瓷表面粗糙、疏松多孔,颗粒孔隙率高达45%,比表面积达220m2/g;化学性质稳定,1+1盐酸溶出率<0.1%;重金属浸出量在危废排放标准以下,无浸出毒性造成的二次污染;机械强度高,抗压强度达到30MPa。
2、二氧化钛预聚体合成
1)向反应容器中加入400L无水乙醇,再分别加入5.5L乙酰丙酮,4L冰乙酸混合均匀,再加入30L钛酸丁酯,搅拌混合。
2)另外量取20L无水乙醇,加入0.1的硝酸铈铵1L;加入0.5M的硫酸铜3L,0.5M硫酸亚铁5L混合均匀后,缓慢加入到步骤1)中,搅拌反应。
3)水浴加热至60℃,称4L聚乙二醇,溶解后反应2h,得到铁铜铈改性二氧化钛的预聚体,冷却备用。
3、将步骤1得到的陶瓷载体,浸泡到步骤2得到的预聚体中,并快速取出,沥干预聚体,经干燥后,于400℃煅烧2h,得到铁铜铈改性二氧化钛催化剂。
催化效果
将实施例一和实施例二所合成的催化剂用于某火药生产企业所产生的炸药废水净化试验,分别得到以下实验结果:
对比例一:纯二氧化钛做催化剂,不进行掺杂,其他与实施例一相同。
对比例二:不加催化剂,在相同功率紫外灯和相同量的过硫酸钾条件下反应,对炸药废水进行氧化,结果如下表。
对比例三:催化剂中不加铜离子改性,其他与实施例一相同。
对比例四:降低硝酸铈用量至0.5L,其他与实施例一相同。
其中,COD表示化学需氧量;TN表示总氮;TNT表示三硝基甲苯;RDX表示环三亚甲基三硝胺。
Claims (10)
1.一种铁铜铈改性二氧化钛催化剂的制备方法,包括以下步骤,各步骤中的物料均按体积份计算:
(1)向反应容器中加入300~400份无水乙醇,5~8份乙酰丙酮,3~6份冰乙酸后混合均匀,再加入20~50份钛酸丁酯,搅拌混合得溶液A;
(2) 在20~30份无水乙醇中加入0.1~0.5M的可溶性铈盐1~3份、0.2~1M的可溶性铜盐2~3 份、0.1~0.5M可溶性亚铁盐3~5份,混合均匀后,再与溶液A混合得到溶液B;
(3) 将溶液B加热至60~90℃,加入1~4份模板剂,反应0.5~2h,得到预聚体;
(4) 将陶粒浸泡于所述预聚体中5~20秒,取出沥干,经干燥后,于400~500℃煅烧0.5~2h,得到铁铜铈改性二氧化钛催化剂。
2.如权利要求1所述的制备方法,其特征在于,所述步骤(2)中,可溶性铈盐为硝酸铈铵,可溶性铜盐为硫酸铜。
3.如权利要求1所述的制备方法,其特征在于,所述步骤(2)中,可溶性亚铁盐为硫酸亚铁铵。
4.如权利要求1所述的制备方法,其特征在于,所述步骤(3)中,模板剂为聚乙二醇。
5. 如权利要求1所述的制备方法,其特征在于,所述陶粒由以下方法制得:(1) 按重量份,以市政污泥20-60份、粘土10-20份、高岭土10-20份、粉煤灰10-20份、硅源2-5份为原料;将原料中的各组分混匀,再经挤压得陶粒坯料;所述硅源为水玻璃、气相二氧化硅和硅粉中的一种或几种;
(2) 将所述陶粒坯料干燥后烧结,冷却,得到多孔陶粒载体;所述烧结是将干燥后的陶粒坯料先升温至300-600℃下预烧10-40min,再升温至950-1150℃,保温10-40min。
6.如权利要求5所述的制备方法,其特征在于,所述市政污泥的含水率不高于85%,市政污泥中有机质的干基含量为50~60%,无机质的干基含量为40~50%。
7.如权利要求1所述的制备方法,其特征在于,所述陶粒的抗压强度为20~30MPa。
8.如权利要求1所述的制备方法,其特征在于,所述陶粒的孔隙率为45~55%,比表面积为200~400m2/g。
9.权利要求1-8任一项所述的制备方法获得催化剂在废水处理方面的应用。
10.如权利要求9所述的应用,其特征在于,所述废水为炸药废水。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610534311.5A CN106215940B (zh) | 2016-07-08 | 2016-07-08 | 一种铁铜铈改性二氧化钛催化剂的制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610534311.5A CN106215940B (zh) | 2016-07-08 | 2016-07-08 | 一种铁铜铈改性二氧化钛催化剂的制备方法及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106215940A true CN106215940A (zh) | 2016-12-14 |
CN106215940B CN106215940B (zh) | 2018-10-02 |
Family
ID=57519152
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610534311.5A Active CN106215940B (zh) | 2016-07-08 | 2016-07-08 | 一种铁铜铈改性二氧化钛催化剂的制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106215940B (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107445647A (zh) * | 2017-09-25 | 2017-12-08 | 贵州开磷磷石膏综合利用有限公司 | 一种磷石膏页岩陶粒及其制备方法 |
CN107917351A (zh) * | 2017-10-27 | 2018-04-17 | 中山市汉庭照明科技有限公司 | 一种具有除甲醛效果的 led 灯泡及制备方法 |
CN108816178A (zh) * | 2018-06-07 | 2018-11-16 | 暨南大学 | 一种负载纳米铁氧化物的多孔陶粒及制备方法 |
CN113318608A (zh) * | 2021-05-17 | 2021-08-31 | 浙江理工大学 | 一种动态催化的水处理陶瓷膜及其应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1583252A (zh) * | 2004-06-15 | 2005-02-23 | 中国科学院新疆理化技术研究所 | 可见光响应型二氧化钛光触媒室内空气净化剂的制备方法 |
CN101905154A (zh) * | 2010-08-20 | 2010-12-08 | 中国林业科学研究院林产化学工业研究所 | 提高可见光响应的掺杂型M-TiO2/AC光催化剂的效率的方法 |
CN104030657A (zh) * | 2014-07-02 | 2014-09-10 | 东华大学 | 一种利用剩余污泥制备具有催化功能陶粒的方法 |
CN104190429A (zh) * | 2014-09-04 | 2014-12-10 | 昆明理工大学 | 一种hcn水解催化剂的制备方法 |
CN104190416A (zh) * | 2014-08-15 | 2014-12-10 | 李建明 | 一种制备金属掺杂的TiO2纳米晶体颗粒的方法 |
-
2016
- 2016-07-08 CN CN201610534311.5A patent/CN106215940B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1583252A (zh) * | 2004-06-15 | 2005-02-23 | 中国科学院新疆理化技术研究所 | 可见光响应型二氧化钛光触媒室内空气净化剂的制备方法 |
CN101905154A (zh) * | 2010-08-20 | 2010-12-08 | 中国林业科学研究院林产化学工业研究所 | 提高可见光响应的掺杂型M-TiO2/AC光催化剂的效率的方法 |
CN104030657A (zh) * | 2014-07-02 | 2014-09-10 | 东华大学 | 一种利用剩余污泥制备具有催化功能陶粒的方法 |
CN104190416A (zh) * | 2014-08-15 | 2014-12-10 | 李建明 | 一种制备金属掺杂的TiO2纳米晶体颗粒的方法 |
CN104190429A (zh) * | 2014-09-04 | 2014-12-10 | 昆明理工大学 | 一种hcn水解催化剂的制备方法 |
Non-Patent Citations (2)
Title |
---|
王灵: ""纳米TiO_2光催化氧化难降解有机物研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
邵琳琳: ""掺杂纳米二氧化钛的制备及其光催化性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107445647A (zh) * | 2017-09-25 | 2017-12-08 | 贵州开磷磷石膏综合利用有限公司 | 一种磷石膏页岩陶粒及其制备方法 |
CN107445647B (zh) * | 2017-09-25 | 2020-06-26 | 贵州开磷磷石膏综合利用有限公司 | 一种磷石膏页岩陶粒及其制备方法 |
CN107917351A (zh) * | 2017-10-27 | 2018-04-17 | 中山市汉庭照明科技有限公司 | 一种具有除甲醛效果的 led 灯泡及制备方法 |
CN108816178A (zh) * | 2018-06-07 | 2018-11-16 | 暨南大学 | 一种负载纳米铁氧化物的多孔陶粒及制备方法 |
CN113318608A (zh) * | 2021-05-17 | 2021-08-31 | 浙江理工大学 | 一种动态催化的水处理陶瓷膜及其应用 |
Also Published As
Publication number | Publication date |
---|---|
CN106215940B (zh) | 2018-10-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106215940A (zh) | 一种铁铜铈改性二氧化钛催化剂的制备方法及其应用 | |
Sugrañez et al. | Enhanced photocatalytic degradation of NOx gases by regulating the microstructure of mortar cement modified with titanium dioxide | |
Ji et al. | Geopolymers produced from drinking water treatment residue and bottom ash for the immobilization of heavy metals | |
Mukherjee et al. | Green synthesis of α-Fe2O3 nanoparticles for arsenic (V) remediation with a novel aspect for sludge management | |
Yue et al. | Research on the characteristics of red mud granular adsorbents (RMGA) for phosphate removal | |
Razak et al. | Agricultural and industrial waste-derived mesoporous silica nanoparticles: A review on chemical synthesis route | |
Hasegawa et al. | Facile preparation of hierarchically porous TiO2 monoliths | |
Criado et al. | Alkali activation of fly ash. Part III: Effect of curing conditions on reaction and its graphical description | |
CN105753505B (zh) | 一种多孔陶粒载体及其制备方法 | |
Zhang et al. | Acid activation for pre-desilicated high-alumina fly ash | |
Jin et al. | Formulation and durability of a geopolymer based on metakaolin/tannery sludge | |
Dhmees et al. | Preparation and characterization of nano SiO2@ CeO2 extracted from blast furnace slag and uranium extraction waste for wastewater treatment | |
CN105688917A (zh) | 一种多孔陶粒芬顿催化剂及其制备方法 | |
CN106179367A (zh) | 一种铜铈改性二氧化钛催化剂及其制备方法和应用 | |
CN108484115A (zh) | 一种利用固体废弃物制备的多孔材料 | |
Tang et al. | Self-foaming high strength artificial lightweight aggregates derived from solid wastes: expansion mechanism and environmental impact | |
Zhang et al. | Co-vitrification of municipal solid waste incinerator fly ash and bottom slag: Glass detoxifying characteristics and porous reformation | |
Samanta et al. | Physico-chemical and adsorption study of hydrothermally treated zeolite A and FAU-type zeolite X prepared from LD (Linz–Donawitz) slag of the steel industry | |
CN104817272B (zh) | 吸附有金属离子的吸附剂作为着色剂的应用、所得着色剂及其制备和应用 | |
CN103007954B (zh) | 一种多相催化臭氧氧化催化剂及其制备方法 | |
Feng et al. | Study of triethanolamine on regulating early strength of fly ash-based chemically foamed geopolymer | |
Si et al. | Simultaneous removal of nitrogen and phosphorus by magnesium-modified calcium silicate core-shell material in water | |
CN115385577A (zh) | 一种飞灰保温棉及其制备方法 | |
Zhang et al. | Effect of oxalic acid pretreatment on the mechanical properties and microstructure of phosphogypsum | |
Du et al. | The hydration mechanism of magnesium oxysulfate cement prepared by magnesium desulfurization byproducts |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB02 | Change of applicant information | ||
CB02 | Change of applicant information |
Address after: 410330 the 319 National Road of Liuyang National Economic Development Zone, Changsha, Hunan. Applicant after: HUNAN YONKER ENVIRONMENTAL PROTECTION RESEARCH INSTITUTE CO., LTD. Applicant after: Shenzhen Yongqing water limited liability company Address before: 410330 the 319 National Road of Liuyang National Economic Development Zone, Changsha, Hunan. Applicant before: HUNAN YONKER ENVIRONMENTAL PROTECTION RESEARCH INSTITUTE CO., LTD. Applicant before: HUNAN YONKER WATER CO., LTD. |
|
GR01 | Patent grant | ||
GR01 | Patent grant |