CN110354797B - Porous nano iron oxide material and preparation method and application thereof - Google Patents
Porous nano iron oxide material and preparation method and application thereof Download PDFInfo
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- CN110354797B CN110354797B CN201810311491.XA CN201810311491A CN110354797B CN 110354797 B CN110354797 B CN 110354797B CN 201810311491 A CN201810311491 A CN 201810311491A CN 110354797 B CN110354797 B CN 110354797B
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000000463 material Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 229910052742 iron Inorganic materials 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000006259 organic additive Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 231100000331 toxic Toxicity 0.000 claims description 6
- 230000002588 toxic effect Effects 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000011343 solid material Substances 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000010865 sewage Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910052785 arsenic Inorganic materials 0.000 description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 6
- 150000002505 iron Chemical class 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- -1 and2 Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004876 x-ray fluorescence Methods 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000000877 morphologic effect Effects 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 159000000014 iron salts Chemical class 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
- 230000005389 magnetism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Compounds Of Iron (AREA)
Abstract
The invention relates to the field of porous nano materials, and discloses a porous nano iron oxide material and a preparation method and application thereof, wherein the porous nano iron oxide material comprises the following main components in mass ratio of Fe, Cu, K, M1, M2, M3, S1, 100, 0-10, 0.1-30; wherein the material has a microscopic morphology of at least one of rod-like, spindle-shaped, linear, needle-like, spherical and sheet-like, and has a specific surface area of 140-358m2(ii)/g, the average pore diameter is 6-18 nm. The invention also discloses a preparation method and application of the porous nano iron oxide material. The invention prepares the environment-friendly nano iron oxide material with different shapes, porous structures and high specific surface area by utilizing the tailing product generated in the production process of the precipitated iron catalyst, and has wide application prospect. The method has low equipment investment, is simple and feasible, changes waste into valuable, and greatly improves the added value of the waste generated in the traditional precipitated iron catalyst production process.
Description
Technical Field
The invention relates to the field of porous nano materials, in particular to a porous nano iron oxide material and a preparation method and application thereof.
Background
Fischer-Tropsch (F-T) synthesis is the core technology of coal indirect liquefaction, and synthesis gas (CO + H) is usually prepared by the action of F-T synthesis catalysts such as precipitated iron base or supported cobalt2) The catalytic reaction is carried out to synthesize liquid hydrocarbon/wax hydrocarbon products. Precipitated iron-based catalysts, which are readily available in raw materials, are suitable for the reaction operating temperature and the H content of synthesis gas2The advantages of wider/CO ratio, lower methane selectivity and the like are still the key points of research and development in the industry.
At present, with the popularization and development of the domestic indirect coal liquefaction (Fischer-Tropsch synthesis) industry, the production scale of the precipitated iron-based Fischer-Tropsch synthesis catalyst is gradually increased. In the industrial production process of the precipitated iron catalyst, a large amount of unqualified products with the particle size of less than 50 mu m are inevitably generated, and how to efficiently utilize the unqualified products is not inconstant from the aspect of environmental protection and the aspect of improving the production benefit for the industrial production of the catalyst. In recent years, inorganic nanomaterials with special morphology have been the hot point of research of material scientists. The porous nano iron oxide is used as an adsorbent, can be used for removing anions such as phosphorus-containing compounds in sewage, and can also be used as a removing agent of highly toxic metal ions such as Gr.
For example, CN1248486A discloses an iron-rare earth element composite water treatment adsorbent and a preparation method thereof, the iron-rare earth element composite water treatment adsorbent is synthesized by reacting 2-valent and 3-valent iron salts (such as ferrous chloride, ferric chloride or ferrous sulfate ferric sulfate, etc.) and rare earth element salts (such as cerium lanthanum salt, etc.) under an alkaline condition, wherein the molar percentage ranges of the three salts are 40-60% of 3-valent iron salt, 20-35% of 2-valent iron salt and 10-35% of rare earth element. The three salts react in alkaline solution with the pH value of 7-11 at normal temperature to generate a precipitate, and the precipitate is washed by deionized water and dried to prepare the salt. The composite water treatment adsorbent is used for treating phosphorus-containing sewage or arsenic-containing drinking water, and compared with a common activated alumina adsorbent, the adsorption amount of phosphorus or arsenic under different temperature and different pH values is obviously increased, the adsorption speed is obviously accelerated, and the adsorption amount is slightly influenced by the change of the pH value. However, the preparation of the composite water treatment adsorbent requires the preparation of the iron oxide adsorbent from the precipitation of the raw material solution, the preparation process is long, a large amount of sewage is generated, and the raw materials mostly contain chlorine or sulfur.
CN1486783A discloses a high-activity iron oxide adsorbent and a preparation method thereof, wherein the high-activity iron oxide adsorbent is prepared by adding soluble trivalent inorganic iron salt (such as ferric chloride, ferric nitrate or ferric sulfate, the molar concentration of the aqueous solution is 0.2-1.5M) into an aqueous solution of water-soluble hydroxyl polymer (polyvinyl alcohol, the mass concentration of the aqueous solution is 0.1-2.0 wt%) or water-soluble amido polymer (polyacrylamide, the mass concentration of the aqueous solution is 0.1-2.0 wt%), stirring to completely dissolve the soluble trivalent inorganic iron salt, adding a strong base solution with the concentration of 1.0-10.0M under the condition of stirring, controlling the pH value of the reaction solution between 2.5 and 5.5 to obtain a precipitated product, and then washing, dehydrating and drying the precipitated product to obtain the high-activity iron oxide adsorbent. The preparation of the high-activity iron oxide adsorbent also needs to prepare the iron oxide adsorbent from the precipitation of a raw material solution, the preparation process is long, and a large amount of sewage can be generated.
CN103272553A discloses a preparation method of a magnetic nano iron oxide adsorbent for removing arsenic in water, which comprises the following steps: the first step, mixing iron salt water solution and alkali water solution to prepare ferric hydroxide, centrifugally separating the ferric hydroxide, adding glacial acetic acid, stirring until forming hydrated ferric oxide colloidal solution, the second step, adding organic solvent into the colloidal solution, reacting the hydrated ferric oxide with the organic solvent to form compound precipitate, separating, drying and roasting to obtain the magnetic nano ferric oxide adsorbent. The preparation of the magnetic nano iron oxide adsorbent also needs to prepare the iron oxide adsorbent from the precipitation of a raw material solution, the preparation process is long, the preparation process is complex, and a large amount of sewage can be generated.
CN105107480A discloses a preparation method of a mesoporous iron oxyhydroxide adsorbent for adsorbing a highly toxic pollutant Cr (6+), which is to mix an inorganic iron salt solution, a urea solution and an ethanol solution of a Pluronic triblock copolymer, stir the mixture evenly and heat the mixture in a drying oven to obtain a mesoporous iron oxyhydroxide-Pluronic triblock copolymer suspension, and the suspension is sequentially subjected to centrifugal separation, distilled water washing, ethanol washing and vacuum drying at room temperature to prepare the mesoporous iron oxyhydroxide-Pluronic triblock copolymer adsorbent. The preparation of the mesoporous iron oxyhydroxide adsorbent also needs to prepare the iron oxide adsorbent from the precipitation of a raw material solution, the preparation process is long, the preparation process is complex, and a large amount of sewage can be generated.
In conclusion, the iron oxide adsorbent is basically prepared from the precipitation of raw material solution, the operation flow is long, the preparation process is complex, the raw materials relate to complex and difficult-to-treat compounds, and the preparation process generates a large amount of sewage.
Disclosure of Invention
The invention aims to solve the problems of long operation flow, complex preparation process, large amount of sewage generation and the like of the prior art that the preparation is started from the precipitation of a raw material solution, and provides a porous nano iron oxide material and a preparation method and application thereof.
In order to achieve the above object, the present invention provides a porous nano iron oxide material, which has a main composition in mass ratio of Fe: Cu: K: M1: M2: M3: S1 of 100: (0-10): 0.1-30), wherein M1 is selected from at least one of Li, Na, Ba, Ca and Sr;m2 is at least one selected from Zr, Gr, Y, Ti, Mn, Mo, V, Co, Ni and Zn; m3 is selected from at least one of Nd, Ce, Ld, Ta and Sm; s1 is selected from SiO2、Al2O3、TiO2And ZrO2At least one of; wherein the material has a microscopic morphology of at least one of rod-like, spindle-shaped, linear, needle-like, spherical and sheet-like, and has a specific surface area of 140-358m2(ii)/g, the average pore diameter is 6-18 nm.
The second aspect of the invention provides a preparation method of a porous nano iron oxide material, which comprises the following steps:
(1) mixing precipitated iron catalyst tailings, an organic additive and water to obtain a mixture;
(2) heating the mixture obtained in the step (1) under a sealed condition;
(3) and after the temperature is reduced or the pressure is reduced, liquid is pumped out, and the residual solid materials are dried.
The third aspect of the invention provides a porous nano iron oxide material prepared by the method.
The invention provides an application of the porous nano iron oxide material in wastewater treatment.
Compared with the prior art, the invention has the following beneficial effects:
1) the environment-friendly nano iron oxide material with different morphological characteristics, porous structure and high specific surface area is prepared by utilizing a tailing product generated in the production process of the precipitated iron catalyst. Compared with the prior catalyst tailing, the specific surface area of the nano iron oxide material is improved by at least more than 40 percent.
2) The precipitated iron catalyst tailings after the improvement of the invention have wide application prospects according to the characteristics of morphological characteristics, adsorption capacity, strong and weak magnetism, photoinduction and the like, for example, the precipitated iron catalyst tailings have no pollution and are environment-friendly when being used as a high-efficiency adsorbent, and have the function of adsorbing and removing pollutants in water such as phosphorus-containing compounds and the like or other toxic heavy metals and the like.
3) The method has low equipment investment, is simple and feasible, changes waste into valuable, and greatly improves the added value of the waste generated in the traditional precipitated iron catalyst production process.
Drawings
FIG. 1 is the electron microscope image of the rod-shaped porous nano iron oxide in example 1.
FIG. 2 is the electron microscope image of the spindle-shaped porous nano iron oxide of example 2.
FIG. 3 is the electron microscope image of the linear porous nano iron oxide of example 3.
Fig. 4 is an electron microscope image of the needle-shaped porous nano iron oxide of example 4.
FIG. 5 is the electron microscope image of the spherical porous nano iron oxide of example 5.
FIG. 6 is the electron microscopic image of the flaky porous nano iron oxide of example 6.
Figure 7 is the XRD pattern of porous nano-iron oxide of example 1.
Fig. 8 is the XRD pattern of the porous nano-iron oxide of example 2.
Figure 9 is the XRD pattern of porous nano-iron oxide of example 3.
Figure 10 is the XRD pattern of porous nano-iron oxide of example 4.
Fig. 11 is the XRD pattern of porous nano-iron oxide of example 5.
Figure 12 is the XRD pattern of porous nano-iron oxide of example 6.
FIG. 13 is a graph of the calibration results of the crystal phase structure of the porous nano-iron oxide HRTEM as shown in FIG. 1 of example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a porous nano iron oxide material, which mainly comprises the following components in mass ratio of Fe, Cu, K, M1, M2, M3, S1, 100, (0-10) and (0-10) to (0.1-30), wherein M1 is selected from at least one of Li, Na, Ba, Ca and Sr, M2 is selected from at least one of Zr, Gr, Y, Ti, Mn, Mo, V, Co, Ni and Zn, M3 is selected from at least one of Nd, Ce, Ld, Ta and Sm, S1 is selected from at least one of SiO2、Al2O3、TiO2And ZrO2At least one of; wherein the material has a microscopic morphology of at least one of rod-like, spindle-shaped, linear, needle-like, spherical and sheet-like, and has a specific surface area of 140-358m2(ii)/g, the average pore diameter is 6-18 nm.
The invention relates to an environment-friendly nano iron oxide material with different morphological characteristics, porous structure and high specific surface area, which is obtained by improving precipitated iron catalyst tailings. Compared with the prior catalyst tailing, the specific surface area of the nano iron oxide material is improved by at least more than 40 percent.
In the invention, the crystalline phase composition of the porous nano iron oxide material is controllable. According to the invention, the crystalline phase composition of the porous nano iron oxide material is mainly alpha-Fe2O3。
The invention provides a preparation method of a porous nano iron oxide material, which comprises the following steps:
(1) mixing precipitated iron catalyst tailings, an organic additive and water to obtain a mixture;
(2) heating the mixture obtained in the step (1) under a sealed condition;
(3) and after the temperature is reduced or the pressure is reduced, liquid is pumped out, and the residual solid materials are dried.
The invention uses water and organic additive as reaction solvent, and creates a high-temperature high-pressure reaction environment by heating, thereby inducing the system to generate chemical reaction different from the normal state. The method of the invention has high efficiency and low cost, and can effectively control the morphology characteristics, the crystal phase composition, the pore size distribution and the like of the porous nano iron oxide material through temperature and pressure. The method has low equipment investment, is simple and feasible, changes waste into valuable, and greatly improves the added value of the waste generated in the traditional precipitated iron catalyst production process.
In the present invention, in step (1), the precipitated iron catalyst heel: water: the mass ratio of the organic additive is 1 (5-50) to 0.0001-0.1, which is beneficial to the formation of the porous nano iron oxide material.
In the invention, the precipitated iron catalyst tailings are widely available, and in the step (1), the precipitated iron catalyst tailings are at least one of precipitated iron catalyst spray drying tailings, precipitated iron catalyst tabletting and crushing tailings, precipitated iron catalyst screening tailings and tailings in the form of any filter cake generated in the catalyst production process.
In the invention, the precipitated iron catalyst tailing is a product with unqualified particle size generated in the industrial production process of the precipitated iron catalyst, and in the step (1), the particle size of the precipitated iron catalyst tailing is less than 50 mu m.
According to the invention, in step (1), the main components of the precipitated iron catalyst tailings have a molar ratio of Fe: Cu: K: M1: M2: M3: S1 of 100: (0-10): (0.1-30), wherein M1 is selected from at least one of Li, Na, Ba, Ca and Sr, M2 is selected from at least one of Zr, Gr, Y, Ti, Mn, Mo, V, Co, Ni and Zn, M3 is selected from at least one of Nd, Ce, Ld, Ta and Sm, S1 is selected from at least one of SiO, Ce, Ld, Ta and Sm, and2、Al2O3、TiO2and ZrO2At least one of (1).
In the present invention, the kind of the organic additive is not particularly limited, and may be any of various organic additives conventionally used in the art as long as it can function as a pore-forming agent, and in the step (1), the organic additive is at least one of an organic acid, an organic alcohol, an organic aldehyde, and an organic ketone. Preferably, the organic acid is acetic acid, oxalic acid or propionic acid, the organic alcohol is methanol or ethanol, the organic aldehyde is formaldehyde or acetaldehyde, and the organic ketone is acetone or propanedione.
In the invention, the morphology characteristics, the crystal phase composition, the pore size distribution and the like of the porous nano iron oxide material can be effectively controlled through the controllability of temperature and pressure. In the step (2), the temperature is controlled at 100-450 ℃, the pressure is controlled at 0.1-6MPa, and the heating time is 0.1-48 hours.
Preferably, the temperature is controlled at 150 ℃ and 250 ℃, the pressure is controlled at 0.5-3MPa, and the heating time is 1-36 hours.
The invention provides a porous nano iron oxide material prepared by the method.
The invention provides application of a porous nano iron oxide material in wastewater treatment, wherein the wastewater is preferably wastewater containing phosphorus compounds or toxic heavy metals.
The porous nano iron oxide material has the function of adsorbing and removing pollutants in water such as phosphorus-containing compounds or toxic heavy metals, and is pollution-free and environment-friendly. Experiments prove that the removal rate of the phosphorus compounds or the toxic heavy metals can reach 99 percent.
The present invention will be described in detail below by way of examples. In the following examples:
specific surface area and pore volume of precipitated iron catalyst tails and porous nano iron oxide materials: the specific surface area is measured by a BET specific surface method, and the pore volume is measured by a low-temperature nitrogen adsorption method.
The precipitated iron catalyst tailing comprises the following components in percentage by weight: the analysis was carried out using an X-ray fluorescence spectrometer (XRF).
Microstructure of the nanomaterial: HRTEM test is adopted.
The crystalline phase structure of the nano material is as follows: XRD test or HRTEM test result calibration is adopted.
Example 1
The precipitated iron catalyst spray-dried cyclone tailings are analyzed by an X-ray fluorescence spectrometer (XRF), and the main components and the contents of the precipitated iron catalyst spray-dried cyclone tailings are Fe, Cu, K, Na and SiO2100: 3.0: 5.0: 0.4: 0.3: 23.5. Weighing 20.0g precipitated iron catalyst spray drying cyclone tailings, placing in a pressure vessel, adding 200mL deionized water, then weighing 0.05g methanol and acetic acid, adding into the tailings, then sealing the vessel, placing in a forced air drying oven, addingHeating to 220 ℃, keeping the pressure at 1.5MPa, keeping the temperature for 32 hours, taking out the oven after cooling, absorbing all liquid phase by a suction pipe, putting the residual wet catalyst powder into the oven, and drying overnight to obtain the porous nano iron oxide material.
The porous nano iron oxide material sample was subjected to HRTEM test, as shown in fig. 1. As can be seen from FIG. 1, the porous nano iron oxide material has a rod-like shape, a diameter of about 3-5nm, and a length of about 20-110 nm. The porous nano iron oxide material sample is calibrated by XRD test and HRTEM test results, as shown in figures 7 and 13. As can be seen from FIGS. 7 and 13, the crystalline phase structure of the porous nano iron oxide material is a-Fe2O3。
Example 2
The precipitated iron catalyst spray-dried cyclone tailings are analyzed by an X-ray fluorescence component analyzer (XRF), and the main components and the contents of the precipitated iron catalyst spray-dried cyclone tailings are Fe, Cu, K, Mn, Ca, Ce and SiO2100: 5.0: 7.0: 6.0: 1.5: 3.0: 15.5. Weighing 20.0g of precipitated iron catalyst spray drying cyclone tailings, placing the weighed materials in a pressure container, adding 200mL of deionized water, weighing 0.05g of ethanol and 0.01g of acetone, adding the weighed materials into the tailings, sealing the container, placing the container in a forced air drying oven, heating to 180 ℃, keeping the temperature at 1.1MPa for 32 hours, taking out the oven after cooling, absorbing all liquid phases by using a suction pipe, placing the residual wet catalyst powder in the oven, and drying overnight to obtain the porous nano iron oxide material.
The porous nano iron oxide material sample was subjected to HRTEM test, as shown in fig. 2. As shown in FIG. 2, the porous nano iron oxide material has a spindle-shaped morphology, a width of about 3-5nm, a thickness of about 1-2nm, and a length of about 20-110 nm. The porous nano iron oxide material sample was tested by XRD and shown in fig. 8. As can be seen from FIG. 8, the crystalline phase structure of the porous nano iron oxide material is a-Fe2O3。
Example 3
The precipitated iron catalyst tabletting and crushing tailings are analyzed by an X-ray fluorescence component analyzer (XRF), and the main components and the contents of the precipitated iron catalyst tabletting and crushing tailings are Fe, Cu, K, Li, Nd and NdZr∶SiO2100: 1.0: 3.0: 0.3: 2.0: 4.5: 25. Weighing 20.0g of precipitated iron catalyst tabletting and crushing tailings, placing the crushed tailings in a pressure container, adding 200mL of deionized water, then weighing 0.05g of ethanol and 0.01g of acetone, adding the ethanol and the acetone into the tailings, then sealing the container, placing the container in a forced air drying oven, heating to 250 ℃, keeping the temperature at 0.7MPa, keeping the temperature for 24 hours, taking out the drying oven after cooling, absorbing all liquid phases by using a suction pipe, placing the residual wet catalyst powder in the drying oven, and drying at night to obtain the porous nano iron oxide material.
The porous nano iron oxide material sample was subjected to HRTEM test, as shown in fig. 3. As can be seen from FIG. 3, the porous nano iron oxide material has a linear shape, a diameter of about 2-5nm and a length of about 20-120 nm. The porous nano iron oxide material sample was tested by XRD and shown in fig. 9. As can be seen from FIG. 9, the crystalline phase structure of the porous nano iron oxide material is a-Fe2O3。
Example 4
The porous nano iron oxide material was prepared according to the method of example 1, except that the precipitated iron catalyst tailing was precipitated iron catalyst screening tailing, heated to 450 ℃, heated at a pressure of 3.0MPa, and maintained at the temperature for 1.0 hour.
The porous nano iron oxide material sample was subjected to HRTEM test, as shown in fig. 4. As shown in FIG. 4, the porous nano iron oxide material has a needle-like shape, a width of about 2-5nm, a thickness of about 1-3nm, and a length of about 20-100 nm. The porous nano iron oxide material sample was tested by XRD and shown in fig. 10. As can be seen from FIG. 10, the crystalline phase structure of the porous nano iron oxide material is a-Fe2O3。
Example 5
A porous nano iron oxide material was prepared according to the method of example 1, except that the temperature was heated to 260 ℃ under a pressure of 1.5MPa and the temperature was maintained for 0.1 hour.
The porous nano iron oxide material sample was subjected to HRTEM test, as shown in fig. 5. As can be seen from FIG. 5, the porous nano iron oxide material is spherical and has a diameter of about 5-16 nm. The porous nano iron oxide material sample was tested by XRD and shown in fig. 11. As can be seen from FIG. 11, the porous nano iron oxide materialThe crystal phase structure of the material is a-Fe2O3。
Example 6
A porous nano iron oxide material was prepared according to the method of example 1, except that the temperature was heated to 100 ℃ under a pressure of 0.8MPa and the temperature was maintained for 48 hours.
The porous nano iron oxide material sample was subjected to HRTEM test, as shown in fig. 6. As shown in FIG. 6, the porous nano iron oxide material has a shape of a sheet, a width of about 2-6nm, a thickness of about 0.5-3nm, and a length of about 10-130 nm. The porous nano iron oxide material sample was tested by XRD and shown in fig. 12. As can be seen from FIG. 12, the crystalline phase structure of the porous nano iron oxide material is a-Fe2O3。
Comparative example 1
The catalyst tailing was the same as in example 1, and the porous nano iron oxide material was prepared according to the method of example 1, except that 0.05g of methanol and acetic acid was added without adding deionized water to prepare the iron oxide material.
Comparative example 2
The catalyst tailing was the same as in example 1, and the porous nano iron oxide material was prepared according to the method of example 1, except that the iron oxide material was prepared by heating to 500 ℃ and a pressure of 3.0 MPa.
Comparative example 3
The catalyst tailing was the same as in example 1, and the porous nano iron oxide material was prepared according to the method of example 1, except that the iron oxide material was prepared by heating to 90 ℃ under a pressure of 1.5 MPa.
Test example
(1) Macroscopic texture parameters of the porous nano iron oxide materials prepared in examples 1-6 and comparative examples 1-3 and the precipitated iron catalyst tailings selected in examples 1-6 and comparative examples 1-3 were measured by a low temperature nitrogen physical adsorption BET specific surface method. The results are shown in tables 1 and 2.
TABLE 1
TABLE 2
As can be seen from the comparison of the results in tables 1 and 2, the BET specific surface area of the porous nano iron oxide materials prepared in examples 1-6 is improved by at least 40%.
Application example 1
Application of the porous nano iron oxide material, 1.0g of the porous nano iron oxide material prepared in example 1 is put into 1.0L of wastewater containing phosphorus compound, wherein the concentration of the wastewater containing phosphorus compound (measured by the mass of phosphorus) is 0.2g/L, and the removal rate of the phosphorus compound is 99.7 percent.
Application example 2
Application of the porous nano iron oxide material, 1.0g of the porous nano iron oxide material prepared in example 1 was put into 1.0L of arsenic-containing wastewater, wherein the concentration of the arsenic-containing wastewater was 0.4g/L, and the removal rate of arsenic was determined to be 99.95%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A porous nanometer iron oxide material is characterized in that the material mainly comprises the following components in mass ratio of Fe, Cu, K, M1, M2, M3, S1 = 100, (0-10) and (0.1-30), and the content of Cu and K is not 0; wherein M1 is selected from at least one of Li, Na, Ba, Ca and Sr, M2 is selected from at least one of Zr, Gr, Y, Ti, Mn, Mo, V, Co, Ni and Zn, M3 is selected from at least one of Nd, Ce, Ld, Ta and Sm, S1 is selected from SiO2、Al2O3、TiO2And ZrO2At least one of; wherein the material isThe micro-morphology is at least one of rod-shaped, spindle-shaped, thread-shaped, needle-shaped, spherical and flake-shaped, and the specific surface area of the material is 140-2(ii)/g, the average pore diameter is 6-18 nm;
the preparation method of the material comprises the following steps:
(1) mixing precipitated iron catalyst tailings, an organic additive and water to obtain a mixture;
(2) heating the mixture obtained in the step (1) under a sealed condition;
(3) after the temperature is reduced or the pressure is reduced, liquid is pumped out, and the residual solid materials are dried;
in the step (1), the organic additive is at least one of organic acid, organic alcohol, organic aldehyde and organic ketone;
in the step (2), the heating temperature is controlled at 100-450 ℃, the pressure is controlled at 0.1-6MPa, and the heating time is 0.1-48 hours.
2. The porous nano-iron oxide material of claim 1, wherein the porous nano-iron oxide material has a crystalline phase composition of primarily α -Fe2O3。
3. The preparation method of the porous nano iron oxide material according to claim 1 or 2, characterized by comprising the following steps:
(1) mixing precipitated iron catalyst tailings, an organic additive and water to obtain a mixture;
(2) heating the mixture obtained in the step (1) under a sealed condition;
(3) after the temperature is reduced or the pressure is reduced, liquid is pumped out, and the residual solid materials are dried;
in the step (1), the organic additive is at least one of organic acid, organic alcohol, organic aldehyde and organic ketone;
in the step (2), the heating temperature is controlled at 100-450 ℃, the pressure is controlled at 0.1-6MPa, and the heating time is 0.1-48 hours.
4. The method of claim 3, wherein in step (1), the precipitated iron catalyst tails: water: the mass ratio of the organic additive is 1: 5-50: 0.0001-0.1.
5. The method according to claim 3 or 4, wherein in step (1), the precipitated iron catalyst tailings are at least one of precipitated iron catalyst spray-drying tailings, precipitated iron catalyst tabletting and crushing tailings, precipitated iron catalyst screening tailings and filter cake-form tailings generated in the catalyst production process;
and/or the particle size of the precipitated iron catalyst tailings is less than 50 mu m.
6. The method of claim 3 or 4, wherein in step (1), the main components of the precipitated iron catalyst tailings are in mass ratios of Fe: Cu: K: M1: M2: M3: S1 = 100: (0-10): (0.1-30), and the content of Cu and K is different from 0; wherein M1 is selected from at least one of Li, Na, Ba, Ca and Sr, M2 is selected from at least one of Zr, Gr, Y, Ti, Mn, Mo, V, Co, Ni and Zn, M3 is selected from at least one of Nd, Ce, Ld, Ta and Sm, S1 is selected from SiO2、Al2O3、TiO2And ZrO2At least one of (1).
7. The method according to claim 3 or 4, wherein in step (1), the organic acid is acetic acid, oxalic acid or propionic acid, the organic alcohol is methanol or ethanol, the organic aldehyde is formaldehyde or acetaldehyde, and the organic ketone is acetone or propanedione.
8. The method as claimed in claim 3 or 4, wherein in the step (2), the heating temperature is controlled to be 150 ℃ and 250 ℃, the pressure is controlled to be 0.5-3MPa, and the heating time is 1-36 hours.
9. A porous nano iron oxide material prepared according to the method of any one of claims 3-8.
10. The porous nano iron oxide material of any one of claims 1, 2 and 9
Application in the treatment of waste water.
11. The use of the porous nano iron oxide material of claim 10 in the treatment of wastewater, which is a wastewater containing phosphorus compounds or toxic heavy metals.
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