CN112960726A - Iron-carbon composite material and preparation method and application thereof - Google Patents
Iron-carbon composite material and preparation method and application thereof Download PDFInfo
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- CN112960726A CN112960726A CN202110284620.2A CN202110284620A CN112960726A CN 112960726 A CN112960726 A CN 112960726A CN 202110284620 A CN202110284620 A CN 202110284620A CN 112960726 A CN112960726 A CN 112960726A
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- iron
- composite material
- carbon
- carbon composite
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- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 155
- 239000002245 particle Substances 0.000 claims abstract description 110
- 229910052742 iron Inorganic materials 0.000 claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 37
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- 239000011230 binding agent Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 150000002505 iron Chemical class 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 238000003892 spreading Methods 0.000 claims description 8
- 230000007480 spreading Effects 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 6
- 239000001923 methylcellulose Substances 0.000 claims description 6
- 235000010981 methylcellulose Nutrition 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229960004887 ferric hydroxide Drugs 0.000 claims description 5
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000004277 Ferrous carbonate Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 4
- 235000019268 ferrous carbonate Nutrition 0.000 claims description 4
- 229960004652 ferrous carbonate Drugs 0.000 claims description 4
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 229940032147 starch Drugs 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002907 Guar gum Polymers 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229960002413 ferric citrate Drugs 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 229960001781 ferrous sulfate Drugs 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000230 xanthan gum Substances 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 235000010493 xanthan gum Nutrition 0.000 claims description 3
- 229940082509 xanthan gum Drugs 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 21
- 239000003344 environmental pollutant Substances 0.000 abstract description 10
- 231100000719 pollutant Toxicity 0.000 abstract description 10
- 238000005469 granulation Methods 0.000 abstract description 6
- 230000003179 granulation Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 37
- 230000001276 controlling effect Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 238000011068 loading method Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 5
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 4
- 230000027455 binding Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000010802 Oxidation-Reduction Activity Effects 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 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
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- 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
- C02F2101/103—Arsenic compounds
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- 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
-
- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an iron-carbon composite material and a preparation method and application thereof, and belongs to the technical field of environment-friendly materials. The invention takes carbon particles and ferric salt as raw materials, and adopts a technical method of adhesive granulation, carbothermic reduction and surface coating to prepare the material, wherein the prepared material takes the carbon particles as a carrier, and an iron particle cluster as a load. Wherein the molar ratio of the iron particles to the carbon particles is 1: 0.2-1: 10. The iron particles are of a core-shell structure, the core is simple substance iron with the particle size of 50-200 nm, and the shell is ferroferric oxide with the thickness of 1-10 nm. The carbon particles are spheroidal and have a particle size of 0.3 to 20 μm. The composite material is externally coated with a layer of water-soluble film for isolating air, and the mass of the film accounts for 0.05-0.5% of the total mass of the material. The material can efficiently remove heavy metal pollutants in water, improves the treatment rate, reduces the treatment cost, shortens the treatment flow, and is a novel water treatment material which has wide application prospect and is easy to realize industrial production and application.
Description
Technical Field
The invention belongs to the technical field of environment-friendly materials, and particularly relates to an iron-carbon composite material and a preparation method and application thereof.
Background
In the environmental protection field, heavy metals mainly refer to mercury, cadmium, lead, chromium, metalloid arsenic and other heavy elements with significant biological toxicity. With increasing activities of mining, smelting, processing and the like of heavy metals in human society, a large amount of heavy metals are discharged into water, and increasingly severe water pollution and drinking water safety problems are caused. In recent years, scholars at home and abroad develop various novel water treatment materials based on the concepts of stabilization and harmlessness of heavy metal pollutants.
The nanoscale iron particles have the advantages of excellent water treatment performance, environmental friendliness, low cost and the like, and are a novel water treatment material with a very wide application prospect. The iron nanoparticles have large specific surface area, low reduction potential and easy generation of Fe3+The method has the characteristics of strong adsorption, reduction, flocculation precipitation and the like, and has obvious removal effect on heavy metal pollutants in water. But the method is limited by the inherent defects of the iron nanoparticles, such as easy agglomeration, easy oxidation, poor mobility, low selectivity to target pollutants and the like, and modification treatment is often required in practical use, wherein the treatment mode mainly comprises two major types, namely loading and surface modification. The carbon particle is an excellent carrier substance and has the characteristics of strong chemical stability, large specific surface area, inertness in aqueous solution and the like. The iron nano particles are loaded on the surfaces of the carbon particles, so that the dispersibility of the carbon nano particles can be effectively improved, an iron-carbon micro-electrolysis effect can be formed, and the removal of heavy metal pollutants in a water body is facilitated.
Through retrieval, relevant patents are published on methods for removing heavy metals in water by adopting iron-carbon composite materials. For example, the Chinese patent application number is: 200710012160.8, filing date: no. 7 and 17 in 2007, the invention and creation name is: a preparation method of a load type nano adsorbent for removing arsenic from drinking water. The preparation steps of the application are as follows: (1) the pore volume is 0.100-0.500 cm3Pretreating the activated carbon material per gram; (2) firstly, soaking activated carbon in a soluble iron salt solution for 10-120 minutes; (3) adding an alcoholic solution into the ferric salt solution as a dispersing agent; (4) under the protection of inert gas at room temperature, titrating ferric salt by using a strong reducing agent potassium borohydride or sodium borohydride, and stirring under the protection of inert gas; after the titration of the potassium borohydride or sodium borohydride solution is finished, continuously stirring for 10-120 minutes; (5) after stirring, centrifuging; washing with anaerobic water for 1-3 times, washing with an organic solvent for 1-3 times, and vacuum drying at 40-100 ℃ for 12-48 h to obtain the product. In the application, the main method for loading iron nanoparticles on a carbon particle carrier is an iron salt solution impregnation method, wherein iron ions are firstly adsorbed on the surface of a carbon-containing substance, and then liquid-phase reduction is carried out through a reducing agent such as sodium borohydride and the like. The method has the following defects: the loading of iron nanoparticles is low, generally not more than 10%; the iron nanoparticles and the carbon particles have weak binding force and are easy to fall off; a large amount of ferric salt waste liquid is generated in the preparation process; the preparation process is long and the efficiency is low.
Disclosure of Invention
1. Problems to be solved
The invention aims to solve the problems of low loading capacity, weak binding force between iron nanoparticles and carbon particles, long preparation process time and low efficiency when iron nanoparticles are loaded on the surfaces of carbon particles by adopting an iron salt solution impregnation method to prepare an iron-carbon composite material, and provides an iron-carbon composite material, and a preparation method and application thereof. The technical scheme of the invention can effectively solve the problems, is used for removing heavy metal pollutants in water, has the advantages of high reaction rate, good removal effect and the like, greatly shortens the treatment process, is favorable for reducing the cost, and is suitable for industrial popularization and application.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the iron-carbon composite material takes carbon particles as a carrier and iron particle clusters as a load; the iron particles are of a core-shell structure, the inner core is nano-scale simple substance iron, and the shell is nano-thickness ferroferric oxide; wherein the carbon particles are spheroidal and have micron-sized particle sizes; the outer surface of the iron-carbon composite material is coated with a layer of water-soluble film capable of isolating air.
Furthermore, the particle size of the carbon particles is 0.3-20 mu m, the particle size of the iron particles is 50-200 nm, and the thickness of the shell layer of the ferroferric oxide is 1-10 nm; the molar ratio of the iron particles to the carbon particles in the iron-carbon composite material is 1: 0.2-1: 10, and the water-soluble film accounts for 0.05-0.5% of the total mass of the iron-carbon composite material.
The preparation method of the iron-carbon composite material comprises the following steps:
uniformly mixing carbon particles, iron salt and a binder, granulating, drying and screening to obtain a precursor for preparing the iron-carbon composite material;
step two, putting the precursor obtained in the step one into a heating furnace, carrying out heat preservation treatment in an inert atmosphere, and then cooling to normal temperature;
and step three, adding the film-forming agent solution into the product obtained in the step two, stirring, filtering and drying to obtain the iron-carbon composite material.
Furthermore, in the second step, the powder spreading thickness of the precursor in the heating furnace is 1-30 mm; the inert gas is one of nitrogen and argon, and the partial pressure of the inert gas in the heating furnace is more than or equal to 90 percent; the heating rate is 5-20 ℃/min, the heat preservation temperature is controlled to be 600-1000 ℃, and the heat preservation time is 15-240 min.
Furthermore, in the second step, when the temperature is lower than 200 ℃, the heating rate is controlled to be 5-9 ℃/min; when the temperature is higher than 200 ℃, the heating rate is controlled to be 10-20 ℃/min.
Further, in the step one, iron salt and carbon particles are added, wherein the molar ratio of iron to carbon is 1: 11-1: 1.2; the dosage of the binder is 1-10% of the total mass of the material.
Furthermore, in the first step, the grain diameter of the granulated powder is 1-30 μm; the drying time is 2-4 h; in the third step, the concentration of the added film forming agent is 0.1-2%, the stirring time is 0.5-1.5 h, the drying temperature is 40-60 ℃, the drying time is 2-4 h, and the drying mode is vacuum drying.
Furthermore, in the first step, the ferric salt is one or more of ferrous sulfate, ferrous carbonate, ferric hydroxide, ferric nitrate, ferrous oxalate, ferric citrate and ferric acetate; the carbon particles adopt any one or more of coal powder, activated carbon, carbon black and graphite powder; the binder is any one or combination of stearic acid, methyl cellulose, polyvinyl alcohol and polyethylene glycol.
Furthermore, in the third step, the film forming agent is any one of polyvinylpyrrolidone, carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, sodium polystyrene sulfonate, polyethylene oxide, polyethylene glycol, starch, xanthan gum and guar gum.
The application of the iron-carbon composite material provided by the invention is that the prepared iron-carbon composite material is put into a water body containing heavy metals to remove the heavy metals, wherein the heavy metal elements include but are not limited to any one or more of lead, cadmium, chromium, mercury, copper, zinc, nickel, cobalt, arsenic, selenium, tellurium and thallium.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the iron-carbon composite material, the specific structure is optimally designed, on one hand, the carbon particles are used as a carrier, the iron nanoparticle cluster is used as a load, the specific surface area and the effective utilization rate of the iron nanoparticles are increased, so that the obtained composite material has high activity and adsorptivity, and when the iron-carbon composite material is used for sewage treatment, the reaction rate is high, the effect is good, the treatment process is greatly shortened, and the cost is reduced. On the other hand, the surface of the material contains a ferroferric oxide shell layer, so that a large amount of loss of zero-valent iron can be effectively avoided under the high-acid condition. Meanwhile, the surface of the nano iron-carbon composite material is coated with the film-forming agent, so that the nano iron-carbon composite material can stably exist in the air and is not easy to oxidize.
(2) According to the iron-carbon composite material, the carbon particles are optimally designed according to the particle size of the iron particles, the thickness of the ferroferric oxide shell layer, the molar ratio of the iron particles to the carbon particles in the core-shell structure and the quality of the water-soluble film, so that the performance and the using effect of the iron-carbon composite material can be effectively guaranteed. The method takes the carbon particles as the carrier, is low in price, green and safe, can improve the agglomeration effect of the nano iron, can provide the iron-carbon micro-electrolysis effect, and accelerates the oxidation reduction effect of zero-valent iron when the acidity is low.
(3) According to the preparation method of the iron-carbon composite material, through the design of the preparation method and the process steps, compared with the traditional method of adopting an iron salt solution impregnation method to load iron nano particles on the surfaces of carbon particles, the loading capacity is obviously improved, so that a micro-electrolysis effect with stronger oxidation-reduction activity and longer service life can be formed when heavy metal sewage is treated, and the degradation and removal capacity of pollutants is obviously enhanced. Meanwhile, a certain amount of specific organic binder is added in the mixing and granulating process of the carbon particles and the iron salt, so that the surface of the iron salt nano particles is coated with a layer of organic binder phase, and then the iron salt nano particles are aggregated into micron-scale iron salt particles through the binding action of the binder and are bonded with the carbon particles together, the bonding strength between the carbon particles and the iron nano particles is improved through in-situ carbothermic reduction reaction, and the falling off of the iron nano particles caused by the action of external force in the processes of transportation, use and the like is avoided.
(4) According to the preparation method of the iron-carbon composite material, the film-forming agent solution with specific type and concentration is added into the prepared iron-carbon composite material and is dried, a ferroferric oxide shell layer with nanometer thickness is formed on the surface of the iron nano particles, and meanwhile, a water-soluble organic film capable of isolating air is coated outside the iron-carbon composite material, so that the oxidation resistance of the material is effectively improved, and the using effect of the material is guaranteed. Meanwhile, the process is optimized, so that the thickness of the ferroferric oxide shell layer is convenient to control, the release speed of the iron component in the using process is favorably controlled, harmful side reactions caused by the excessively high release speed of the iron component in the using process in the acid environment, the oxidizing environment and other environments are inhibited, and the effective utilization rate of the iron component can be improved.
(5) When the iron-carbon composite material is used for treating sewage containing heavy metals, particularly when the treated heavy metal elements include but are not limited to any one or more of lead, cadmium, chromium, mercury, copper, zinc, nickel, cobalt, arsenic, selenium, tellurium and thallium, the iron-carbon composite material can efficiently remove heavy metal pollutants in water, improves the treatment rate, reduces the treatment cost, shortens the treatment process, and is a novel water treatment material which has wide application prospect and is easy to realize industrial production and application.
Drawings
FIG. 1 is an XRD pattern of an iron-carbon composite material obtained in example 1 of the present invention;
FIG. 2 is an SEM photograph of an iron-carbon composite material obtained in example 1 of the present invention;
FIG. 3 is a TEM image of an iron-carbon composite material obtained in example 1 of the present invention.
Detailed Description
The carbon particles are an excellent carrier substance, have strong chemical stability and large specific surface area, are inert in aqueous solution, and load the iron nanoparticles on the surfaces of the carbon particles, so that the dispersibility of the carbon particles can be effectively improved, and an iron-carbon micro-electrolysis effect can be formed, thereby being beneficial to removing pollutants in water. However, the current carbon-supported iron nanoparticles mainly have the following problems:
(1) the loading of iron nanoparticles is low. The conventional iron salt soaking method can only adsorb a small amount of iron ions on the surfaces of carbon particles, the load capacity of iron nanoparticles in the prepared product is generally not more than 10%, and the active ingredients are too low;
(2) iron nanoparticles are susceptible to oxidative deactivation. The carbon-supported iron nanoparticles prepared by the conventional method are very easy to oxidize active iron and even spontaneously combust when stored in air, so that the activity of the carbon-supported iron nanoparticles is reduced, and the safety risk is increased;
(3) the iron-carbon bonding strength is low. Iron and carbon in the carbon-supported iron nanoparticles prepared by the conventional method are mainly combined together through weak intermolecular force, and are easy to fall off in practical use;
(4) the release rate of the iron component during use cannot be controlled. When the carbon-supported iron nanoparticles prepared by the conventional method are used in acidic and oxidative environments, the release speed of the iron component is too high, harmful side reactions are easily caused, and the effective utilization rate of the carbon-supported iron nanoparticles is reduced.
In order to solve the problems, the invention provides an iron-carbon composite material, which takes carbon particles as a carrier and iron particle clusters as a load, wherein the molar ratio of the iron particles to the carbon particles is 1: 0.2-1: 10. The iron particles are of a core-shell structure, the inner core is simple substance iron with the particle size of 50-200 nm, and the shell is ferroferric oxide with the thickness of 1-10 nm; the carbon particles are spherical, the particle size is 0.3-20 mu m, and the iron-carbon composite material is coated with a layer of water-soluble film, the mass of the water-soluble film accounts for 0.05-0.5% of the total mass of the iron-carbon composite material and is used for isolating air. The material disclosed by the invention has excellent adsorption, reduction and precipitation performances on heavy metals in water, can effectively remove heavy metal pollutants in waste acid and waste water, improves the treatment rate, reduces the treatment cost, shortens the treatment flow, and is a novel water treatment material which has a wide application prospect and is easy to realize industrial production and application. The preparation method mainly comprises the following steps:
step one
And fully and uniformly mixing carbon particles and ferric salt which meet the iron-carbon molar ratio of 1: 1.2-1: 11, and a proper amount of binder, controlling the particle size of the particles to be 1-30 mu m, granulating, drying in an air-blast drying oven for 2-4 h, grinding and screening to obtain the precursor for preparing the iron-carbon composite material. The carbon particles are any one or a combination of more of coal powder, activated carbon, carbon black and graphite powder, the ferric salt is any one or a combination of more of ferrous sulfate, ferrous carbonate, ferric hydroxide, ferric nitrate, ferrous oxalate, ferric citrate and ferric acetate, and the binder is any one or a combination of more of stearic acid, methyl cellulose, polyvinyl alcohol and polyethylene glycol.
Step two
And (2) putting the precursor obtained in the step one into a heating furnace, introducing inert atmosphere for heat preservation, wherein the inert atmosphere adopts nitrogen or argon, the flow rate of the inert atmosphere is controlled to be 100-5000 ml/min, the powder spreading thickness of the precursor is 1-30 mm, the partial pressure of the inert gas in the whole reaction system is ensured to be more than or equal to 90%, the temperature rising rate is set to be 5-20 ℃/min, the heat preservation is carried out for 15-240 min at the temperature of 600-1000 ℃, and then the reaction system is cooled to the normal temperature. Specifically, during temperature rise, when the temperature is lower than 200 ℃, the temperature rise rate is controlled to be 5-9 ℃/min; when the temperature is higher than 200 ℃, the heating rate is controlled to be 10-20 ℃/min.
Step three
And (3) adding a certain amount of film-forming agent solution with the concentration of 0.1-2% into the product obtained in the step two, stirring for 0.5-1.5 h, filtering, and drying in vacuum at 40-60 ℃ for 2-4 h to obtain the iron-carbon composite material. Specifically, the added film forming agent can be any one of polyvinylpyrrolidone, carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, sodium polystyrene sulfonate, polyethylene oxide, polyethylene glycol, starch, xanthan gum and guar gum.
It should be noted that the preparation method of the iron-carbon composite material is optimally designed to have a special structure, so that the problem of low loading capacity of the existing cluster-shaped iron nanoparticles is effectively solved, the iron-carbon composite material has high activity and adsorptivity, and when the iron-carbon composite material is used for sewage treatment, the reaction rate is high, the effect is good, the treatment process is greatly shortened, and the cost is reduced. Specifically, a certain amount of specific organic binder is added in the mixing and granulating process of carbon particles and iron salt, so that the surface of iron salt nano particles is coated with a layer of organic binder phase, and the iron salt nano particles are aggregated into micron-scale iron salt particles through the binding action of the binder and are bonded with the carbon particles to form a precursor. In the subsequent roasting process, ferric salt forms clusters of iron nanoparticles through pyrolysis-reduction and is combined with carbon particles in situ, so that the loading capacity of the iron nanoparticles is effectively improved, and the active ingredients are high.
Secondly, a ferroferric oxide shell layer with a nanometer thickness can be formed on the surface of the iron nanoparticles by adding a specific film-forming agent solution into the prepared iron-carbon composite material and drying the solution, and meanwhile, a water-soluble organic film capable of isolating air is coated outside the iron-carbon composite material, so that the oxidation resistance of the iron nanoparticles in the air can be improved by the formed ferroferric oxide shell layer and the water-soluble organic film, the problem that the existing iron nanoparticles are easy to oxidize and inactivate is effectively solved, and the safety risk is reduced.
Finally, the iron-carbon bonding strength can be effectively improved through iron-carbon metallurgical bonding. In the roasting process, mutual diffusion reaction occurs between the iron nano particles and the carbon particles at the interface to form micro welding, so that the iron-carbon bonding strength is improved, and the iron nano particles and the carbon particles are not easy to fall off in use. Meanwhile, the release speed of the iron component in the using process is controlled by regulating and controlling the thickness of the ferroferric oxide shell layer. In addition, the applicant discovers through a large number of experimental researches that the thickness of the ferroferric oxide shell layer can be regulated and controlled by changing the polarity of the solvent and the type of the film forming agent in the process of surface coating, so that the release speed of the iron component can be controlled in the using process, the phenomenon that the harmful side reaction is caused by the excessively high release speed of the iron component is effectively avoided when the ferroferric oxide shell layer is used in an acidic environment and an oxidizing environment, and the effective utilization rate of the material is further improved.
The invention is further described with reference to specific examples.
Example 1
The preparation method of the iron-carbon composite material of the embodiment is as follows:
(1) coal powder and ferrous sulfate are used as reaction raw materials, and methylcellulose is used as a binder. The precursor for preparing the iron-carbon composite material is prepared by mixing the components according to the iron-carbon molar ratio of 1:1.2 and the using amount of the binder of 1 percent, uniformly mixing, controlling the particle size of powder particles to be about 1 mu m through granulation, then drying the powder particles in a blast drying box at 60 ℃ for 4 hours, grinding and screening the powder particles to obtain the precursor for preparing the iron-carbon composite material.
(2) And (3) putting 5g of the precursor obtained in the step one into a heating furnace, controlling the nitrogen flow rate to be 100ml/min, controlling the powder spreading thickness of the precursor to be 1mm, keeping the inert gas partial pressure in the whole reaction system to be 90-95%, preserving the heat at 600 ℃ for 240min, and immediately cooling to the normal temperature. Specifically, during temperature rise, when the temperature is lower than 200 ℃, the temperature rise rate is controlled to be 5 ℃/min; when the temperature is higher than 200 ℃, the heating rate is controlled to be 10 ℃/min.
(3) And (3) adding 100ml of polyvinylpyrrolidone with the concentration of 0.1% into the product obtained in the step two, stirring for 0.5h, filtering, and vacuum-drying at 40 ℃ for 4h to obtain the iron-carbon composite material with the iron particle size of about 50nm, the thickness of the ferroferric oxide shell layer of about 10nm and the iron-carbon molar ratio of about 1: 0.2.
The iron-carbon composite material is added into 100ml of arsenic (V) -containing solution with the concentration of 3g/L according to the adding amount of 10g/L, the solution is stirred for 2 hours at the temperature of 40 ℃, and then the solution is filtered, and the removal rate of the arsenic (V) is 95 percent.
In addition, XRD, SEM and TEM characterization were performed on the iron-carbon composite material obtained in this example, and specific results are shown in fig. 1, fig. 2 and fig. 3. As can be seen from FIG. 1, the main crystal phase of the iron-carbon composite material is elementary iron, and then is ferroferric oxide. No diffraction peak was observed in the figure, indicating that the carbon in the sample was amorphous. In fig. 2, large particles with micron scale are carbon particles, small particles with nanometer scale are iron particles, and the iron nanoparticles are aggregated into clusters and attached around the carbon particles. In FIG. 3, the surface of the iron particle is coated with a continuous crystalline shell layer, and the shell layer is ferroferric oxide with the thickness of about 10 nm. And an amorphous film layer which is discontinuously distributed is arranged outside the ferric oxide shell, is an amorphous carbon layer with the thickness of 1-2 nm and is formed by pyrolyzing a binder.
Example 2
The preparation method of the iron-carbon composite material of the embodiment is as follows:
(1) graphite powder and ferric nitrate are used as reaction raw materials, and stearic acid is used as a binder. The precursor for preparing the iron-carbon composite material is prepared by mixing the materials according to the iron-carbon molar ratio of 1:11 and the using amount of the binder of 10%, uniformly mixing, controlling the particle size of powder particles to be about 30 mu m through granulation, then drying the powder particles in a blast drying oven for 2h at 80 ℃, grinding and screening the powder particles to obtain the precursor for preparing the iron-carbon composite material.
(2) And (3) putting 100g of the precursor obtained in the step one into a heating furnace, controlling the nitrogen flow rate to be 5000ml/min, controlling the powder spreading thickness of the precursor to be 30mm, keeping the inert gas partial pressure in the whole reaction system at 91-96%, preserving the temperature for 120min at 1000 ℃, and immediately cooling to the normal temperature. Specifically, during temperature rise, when the temperature is lower than 200 ℃, the temperature rise rate is controlled to be 9 ℃/min; when the temperature is higher than 200 ℃, the heating rate is controlled to be 20 ℃/min.
(3) And (3) adding 1000ml of 2% polyvinyl alcohol into the product obtained in the step two, stirring for 1.5h, filtering, and drying in vacuum at 60 ℃ for 2h to obtain the iron-carbon composite material with the iron particle size of about 200nm, the thickness of the ferroferric oxide shell layer of about 1nm and the iron-carbon molar ratio of about 1: 10.
The iron-carbon composite material is added into 100ml of nickel-containing solution with the concentration of 1g/L according to the adding amount of 5g/L, the mixture is stirred for 2 hours at the temperature of 25 ℃, the pH value is adjusted to 10, and the removal rate of nickel after filtration is 98%.
The iron-carbon composite material obtained in this example was characterized by XRD, SEM and TEM, and the specific results are substantially as shown in fig. 1, fig. 2 and fig. 3.
Example 3
The preparation method of the iron-carbon composite material of the embodiment is as follows:
(1) active carbon and ferrous carbonate are used as reaction raw materials, and polyvinyl alcohol is used as a binder. The precursor for preparing the iron-carbon composite material is prepared by mixing the materials according to the iron-carbon molar ratio of 1:5 and the using amount of the binder of 5%, uniformly mixing, controlling the particle size of powder particles to be about 10 mu m through granulation, then placing the powder particles into a blast drying oven, drying the powder particles for 3h at 70 ℃, grinding and screening the powder particles to obtain the precursor for preparing the iron-carbon composite material.
(2) And (3) putting 30g of the precursor obtained in the step one into a heating furnace, controlling the nitrogen flow rate to be 1000ml/min, controlling the powder spreading thickness of the precursor to be 10mm, keeping the inert gas partial pressure in the whole reaction system at 90-96%, preserving the temperature at 800 ℃ for 180min, and immediately cooling to the normal temperature. Specifically, during temperature rise, when the temperature is lower than 200 ℃, the temperature rise rate is controlled to be 6 ℃/min; when the temperature is higher than 200 ℃, the heating rate is controlled to be 15 ℃/min.
(3) And (3) adding 200ml of 0.5% polyoxyethylene into the product obtained in the step two, stirring for 1h, filtering, and vacuum-drying at 60 ℃ for 2h to obtain the iron-carbon composite material with the iron particle size of about 100nm, the thickness of the ferroferric oxide shell layer of about 5nm and the iron-carbon molar ratio of about 1: 5.
The iron-carbon composite material is added into 100ml of lead-containing solution with the concentration of 1g/L according to the adding amount of 2g/L, and the mixture is stirred for 1h at the temperature of 25 ℃, so that the removal rate of lead is 96 percent.
The iron-carbon composite material obtained in this example was characterized by XRD, SEM and TEM, and the specific results are substantially as shown in fig. 1, fig. 2 and fig. 3.
Example 4
The preparation method of the iron-carbon composite material of the embodiment is as follows:
(1) carbon black and ferrous acetate are used as reaction raw materials, and polyethylene glycol is used as a binder. The precursor for preparing the iron-carbon composite material is prepared by mixing the materials according to the iron-carbon molar ratio of 1:4 and the binder amount of 6%, uniformly mixing, controlling the particle size of powder particles to be about 15 mu m through granulation, then drying the powder particles in a blast drying oven at 80 ℃ for 3h, grinding and screening the powder particles to obtain the precursor for preparing the iron-carbon composite material.
(2) And (3) putting 20g of the precursor obtained in the step one into a heating furnace, controlling the nitrogen flow rate to be 800ml/min, controlling the powder spreading thickness of the precursor to be 15mm, keeping the inert gas partial pressure in the whole reaction system to be 90-95%, preserving the temperature at 900 ℃ for 100min, and immediately cooling to the normal temperature. Specifically, during temperature rise, when the temperature is lower than 200 ℃, the temperature rise rate is controlled to be 5 ℃/min; when the temperature is higher than 200 ℃, the heating rate is controlled to be 12 ℃/min.
(3) And (3) adding 200ml of 0.5% sodium polystyrene sulfonate into the product obtained in the step two, stirring for 1h, filtering, and drying in vacuum at 60 ℃ for 2h to obtain the iron-carbon composite material with the iron particle size of about 140nm, the thickness of a ferroferric oxide shell layer of about 3nm and the iron-carbon molar ratio of about 1: 4.
The iron-carbon composite material is added into 100ml of hexavalent chromium-containing solution with the concentration of 0.5g/L according to the adding amount of 2g/L, the pH value is adjusted to 10 after the solution is stirred for 1h at the temperature of 25 ℃, and the removal rate of chromium is 97%.
The iron-carbon composite material obtained in this example was characterized by XRD, SEM and TEM, and the specific results are substantially as shown in fig. 1, fig. 2 and fig. 3.
Example 5
The preparation method of the iron-carbon composite material of the embodiment is as follows:
(1) taking coal powder, carbon black, ferrous sulfate and ferric hydroxide as reaction raw materials, wherein the mass ratio of the coal powder to the carbon black is 4:1, and the mass ratio of the ferrous sulfate to the ferric hydroxide is 3: 1; stearic acid and methylcellulose are used as binders, wherein the mass ratio of stearic acid to methylcellulose is 2: 1. The precursor for preparing the iron-carbon composite material is prepared by mixing the components according to the iron-carbon molar ratio of 1:3.5 and the using amount of the binder of 8 percent, uniformly mixing, controlling the particle size of powder particles to be about 20 mu m through granulation, then drying the powder particles in a blast drying box at 80 ℃ for 3 hours, grinding and screening the powder particles to obtain the precursor for preparing the iron-carbon composite material.
(2) And (3) putting 25g of the precursor obtained in the first step into a heating furnace, controlling the nitrogen flow rate to be 1000ml/min, controlling the powder spreading thickness of the precursor to be 25mm, keeping the inert gas partial pressure in the whole reaction system to be 90-96%, preserving the heat at 900 ℃ for 90min, and immediately cooling to the normal temperature. Specifically, during temperature rise, when the temperature is lower than 200 ℃, the temperature rise rate is controlled to be 7 ℃/min; when the temperature is higher than 200 ℃, the heating rate is controlled to be 15 ℃/min.
(3) And (3) adding 200ml of starch with the concentration of 2% into the product obtained in the step two, stirring for 1h, filtering, and vacuum-drying at 50 ℃ for 3h to obtain the iron-carbon composite material with the iron particle size of about 120nm, the thickness of the ferroferric oxide shell layer of about 6nm and the iron-carbon molar ratio of about 1: 3.5.
The iron-carbon composite material is added into 100ml of solution with lead concentration of 0.3g/L, cadmium concentration of 0.05g/L and arsenic (V) concentration of 0.2g/L according to the adding amount of 2g/L, and the solution is stirred for 1h at the temperature of 25 ℃, wherein the removal rate of lead is 95%, the removal rate of cadmium is 90% and the removal rate of arsenic (V) is 98%.
The iron-carbon composite material obtained in this example was characterized by XRD, SEM and TEM, and the specific results are substantially as shown in fig. 1, fig. 2 and fig. 3.
Claims (10)
1. An iron-carbon composite material, characterized in that: carbon particles are used as a carrier, and iron particle clusters are used as a load; the iron particles are of a core-shell structure, the inner core is nano-scale simple substance iron, and the shell is nano-thickness ferroferric oxide; wherein the carbon particles are spheroidal and have micron-sized particle sizes; the outer surface of the iron-carbon composite material is coated with a layer of water-soluble film capable of isolating air.
2. The iron carbon composite material as claimed in claim 1, wherein: the particle size of the carbon particles is 0.3-20 microns, the particle size of the iron particles is 50-200 nm, and the shell thickness of the ferroferric oxide is 1-10 nm; the molar ratio of the iron particles to the carbon particles in the iron-carbon composite material is 1: 0.2-1: 10, and the water-soluble film accounts for 0.05-0.5% of the total mass of the iron-carbon composite material.
3. A method of preparing an iron-carbon composite material as claimed in claim 1 or 2, comprising the steps of:
uniformly mixing carbon particles, iron salt and a binder, granulating, drying and screening to obtain a precursor for preparing the iron-carbon composite material;
step two, putting the precursor obtained in the step one into a heating furnace, carrying out heat preservation treatment in an inert atmosphere, and then cooling to normal temperature;
and step three, adding the film-forming agent solution into the product obtained in the step two, stirring, filtering and drying to obtain the iron-carbon composite material.
4. The method for preparing an iron-carbon composite material according to claim 3, wherein: in the second step, the powder spreading thickness of the precursor in the heating furnace is 1-30 mm; the inert gas is one of nitrogen and argon, and the partial pressure of the inert gas in the heating furnace is more than or equal to 90 percent; the heating rate is 5-20 ℃/min, the heat preservation temperature is controlled to be 600-1000 ℃, and the heat preservation time is 15-240 min.
5. The method for preparing an iron-carbon composite material according to claim 4, wherein the method comprises the following steps: in the second step, when the temperature is lower than 200 ℃, the heating rate is controlled to be 5-9 ℃/min; when the temperature is higher than 200 ℃, the heating rate is controlled to be 10-20 ℃/min.
6. The method for preparing an iron-carbon composite material according to claim 3, wherein: in the first step, the iron salt and the carbon particles are added in a proportion that the molar ratio of iron to carbon is 1: 1.2-1: 11; the dosage of the binder is 1-10% of the total mass of the iron-carbon composite material.
7. The method for producing an iron-carbon composite material according to any one of claims 3 to 6, wherein: in the first step, the grain diameter of the granulated powder is 1-30 μm; the drying time is 2-4 h; in the third step, the concentration of the added film forming agent is 0.1-2%, the stirring time is 0.5-1.5 h, the drying temperature is 40-60 ℃, the drying time is 2-4 h, and the drying mode is vacuum drying.
8. The method for preparing an iron-carbon composite material according to any one of claims 3 to 6, wherein the method comprises the following steps: in the first step, the ferric salt is one or more of ferrous sulfate, ferrous carbonate, ferric hydroxide, ferric nitrate, ferrous oxalate, ferric citrate and ferric acetate; the carbon particles adopt any one or more of coal powder, activated carbon, carbon black and graphite powder; the binder is any one or combination of stearic acid, methyl cellulose, polyvinyl alcohol and polyethylene glycol.
9. The method for preparing an iron-carbon composite material according to any one of claims 3 to 6, wherein the method comprises the following steps: in the third step, the film forming agent is any one of polyvinylpyrrolidone, carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, sodium polystyrene sulfonate, polyethylene oxide, polyethylene glycol, starch, xanthan gum and guar gum.
10. Use of an iron-carbon composite material according to any one of claims 1 to 9, wherein: and (3) putting the prepared iron-carbon composite material into a water body containing heavy metals to remove the heavy metals, wherein the heavy metal elements comprise any one or more of lead, cadmium, chromium, mercury, copper, zinc, nickel, cobalt, arsenic, selenium, tellurium and thallium.
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