CN115254026B - Bismuth-based adsorption chlorine removal material and preparation method and application thereof - Google Patents
Bismuth-based adsorption chlorine removal material and preparation method and application thereof Download PDFInfo
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- CN115254026B CN115254026B CN202211011893.0A CN202211011893A CN115254026B CN 115254026 B CN115254026 B CN 115254026B CN 202211011893 A CN202211011893 A CN 202211011893A CN 115254026 B CN115254026 B CN 115254026B
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- bismuth
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- chlorine
- phthalocyanine
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 69
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000460 chlorine Substances 0.000 title claims abstract description 59
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 59
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims abstract description 82
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003446 ligand Substances 0.000 claims abstract description 27
- 239000010954 inorganic particle Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 10
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- -1 bismuth salt Chemical class 0.000 claims abstract description 9
- 239000011247 coating layer Substances 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 23
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000006298 dechlorination reaction Methods 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 150000004032 porphyrins Chemical class 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000010419 fine particle Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- KSFOVUSSGSKXFI-GAQDCDSVSA-N CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O Chemical compound CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O KSFOVUSSGSKXFI-GAQDCDSVSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229950003776 protoporphyrin Drugs 0.000 claims description 5
- AQIFPEIUSQBFJF-UHFFFAOYSA-N 4-[10,15,20-tris(4-cyanophenyl)-21,23-dihydroporphyrin-5-yl]benzonitrile Chemical compound N#Cc1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C#N)c2ccc([nH]2)c(-c2ccc(cc2)C#N)c2ccc(n2)c(-c2ccc(cc2)C#N)c2ccc1[nH]2 AQIFPEIUSQBFJF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical class C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229940049676 bismuth hydroxide Drugs 0.000 claims description 3
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- FVHZCBQLLFLQAG-UHFFFAOYSA-N 5,10,15,20-tetrakis(4-nitrophenyl)-21,23-dihydroporphyrin Chemical compound [O-][N+](=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)[N+]([O-])=O)c2ccc([nH]2)c(-c2ccc(cc2)[N+]([O-])=O)c2ccc(n2)c(-c2ccc(cc2)[N+]([O-])=O)c2ccc1[nH]2 FVHZCBQLLFLQAG-UHFFFAOYSA-N 0.000 claims description 2
- UJKPHYRXOLRVJJ-MLSVHJFASA-N CC(O)C1=C(C)/C2=C/C3=N/C(=C\C4=C(CCC(O)=O)C(C)=C(N4)/C=C4\N=C(\C=C\1/N\2)C(C)=C4C(C)O)/C(CCC(O)=O)=C3C Chemical compound CC(O)C1=C(C)/C2=C/C3=N/C(=C\C4=C(CCC(O)=O)C(C)=C(N4)/C=C4\N=C(\C=C\1/N\2)C(C)=C4C(C)O)/C(CCC(O)=O)=C3C UJKPHYRXOLRVJJ-MLSVHJFASA-N 0.000 claims description 2
- 235000019738 Limestone Nutrition 0.000 claims description 2
- 239000006004 Quartz sand Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001621 bismuth Chemical class 0.000 claims description 2
- VFHDWGAEEDVVPD-UHFFFAOYSA-N chembl507897 Chemical compound C1=CC(O)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(O)=CC=1)=C1C=CC(=N1)C(C=1C=CC(O)=CC=1)=C1C=CC(N1)=C1C=2C=CC(O)=CC=2)=C2N=C1C=C2 VFHDWGAEEDVVPD-UHFFFAOYSA-N 0.000 claims description 2
- 229930002875 chlorophyll Natural products 0.000 claims description 2
- 235000019804 chlorophyll Nutrition 0.000 claims description 2
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 229960003569 hematoporphyrin Drugs 0.000 claims description 2
- 239000006028 limestone Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- FDJUBNCEVCSIAV-UHFFFAOYSA-N tetrakis(o-aminophenyl)porphyrin Chemical compound NC1=CC=CC=C1C(C1=CC=C(N1)C(C=1C(=CC=CC=1)N)=C1C=CC(=N1)C(C=1C(=CC=CC=1)N)=C1C=CC(N1)=C1C=2C(=CC=CC=2)N)=C2N=C1C=C2 FDJUBNCEVCSIAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims 4
- 239000002351 wastewater Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- REPFNYFEIOZRLM-UHFFFAOYSA-N chembl376444 Chemical compound C1=CC(N)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(N)=CC=1)=C1C=CC(=N1)C(C=1C=CC(N)=CC=1)=C1C=CC(N1)=C1C=2C=CC(N)=CC=2)=C2N=C1C=C2 REPFNYFEIOZRLM-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000004033 porphyrin derivatives Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- HXHRCHCVCSWZDH-UHFFFAOYSA-N 5-benzo[a]anthracen-1-yl-21,23-dihydroporphyrin Chemical class C1(=CC=CC2=CC=C3C=C4C=CC=CC4=CC3=C12)C1=C2C=CC(C=C3C=CC(=CC=4C=CC(=CC5=CC=C1N5)N4)N3)=N2 HXHRCHCVCSWZDH-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a bismuth-based adsorption chlorine removal material which has a core-shell structure, wherein the core is inorganic particles, the shell is a nitrogen-doped carbon coating layer, and bismuth (bismuth oxide and/or bismuth salt) is uniformly dispersed in the nitrogen-doped carbon coating layer. According to the invention, a bismuth source is dispersed in a mixture, and under the action of a nitrogen-containing ligand, the bismuth source can be uniformly dispersed in the mixture in the presence of a nitrogen-containing auxiliary agent, and has good affinity with inorganic particles, and after sintering, the nitrogen-containing ligand can form a nitrogen-doped carbon coating layer, so that the bismuth-based adsorption chlorine-removing material is obtained. The material is put into the wastewater, or the wastewater passes through a flow column filled with the material, and chlorine in the wastewater can be removed rapidly and effectively through the adsorption chlorine removal effect. The method of the invention saves materials, reduces cost, and can be directly used for the existing equipment and instruments such as a packed tower, a flow column and the like; no impurity is introduced, oxidation-reduction reaction does not occur, separation and recovery are convenient, and secondary pollution is not generated.
Description
Technical Field
The invention relates to the technical field of wastewater dechlorination, in particular to a bismuth-based adsorption dechlorination material, a preparation method and application thereof.
Background
Examples of the method for removing chlorine salts from the aqueous solution include ion exchange method, insoluble salt precipitation method, electrochemical method, layered oxide method, vacuum distillation method, membrane separation method, heat treatment method, solvent extraction method, etc. Most of the methods have the defects and limiting conditions of complex process, high energy consumption, secondary pollution and the like. The precipitation method has simple process, but low removal rate, and sludge needs to be treated; the adsorption method has long reaction time, is easily influenced by temperature, competitive ion, chloride ion concentration and the like, and is difficult to recover the adsorbent; the membrane separation method has more industrial application, but has high cost and is easy to cause blockage and pollution; the electrochemical method has high efficiency but high energy consumption. Because of the different forms of chlorine-containing salts, different chlorine removal technical measures are suitable for the application occasions.
Chloride ions are stable forms of chlorine that cannot be assimilated or decomposed by microorganisms, and most of the chloride is readily soluble and therefore difficult to remove. Chloride ions have obvious harm to industrial production, metal equipment and reinforced concrete. The chlorine-containing wastewater changes the soil structure, causes alkalization salinization, and has an inhibiting effect on the growth of plant seedlings and crops. High concentrations of chloride are very detrimental to human health. Aiming at industrial wastewater treatment, the invention provides the bismuth-based adsorption chlorine removal material which is simple and convenient to use, low in energy consumption, free from introducing impurities and secondary pollution, and the preparation method thereof, and aims at facilitating wastewater reuse, avoiding introducing impurities and preventing oxidation-reduction side reactions.
Bismuth-based chlorine scavengers have found industrial application in metallurgical processes. The bismuth-based adsorption material can effectively remove ionic pollutants in aqueous solution, such as nitrate, fluorine-chlorine ions, arsenic ions and the like, so that general attention of the scientific and technological community is obtained, and related literature reports are more. In CN110357239A, bismuth oxide with the content of more than 95% is used as a chlorine removing agent of a chlorine-containing solution, and the consumption of the chlorine removing agent is 15-20 times of the chloride ion content. Bismuth oxide is large in size and slow in dissolution, so that the chlorine removal efficiency is limited, and the aim of effectively removing chlorine can be fulfilled under the condition of excessive bismuth oxide. CN104479056B reacts the mineral oil solution of polyisobutylene succinic anhydride with bismuth nitrate under the protection of nitrogen, and a high molecular organic bismuth compound is prepared and used as a chlorine removing agent. But the chlorine removal efficiency is still not ideal. CN114835233a discloses a bismuth-based metal organic framework material for rapidly removing chloride ions in wastewater, which is prepared from bismuth salt, trimesic acid and CTAB, and is used for removing chloride in wastewater. The MOFs material with larger specific surface area is utilized, the pore canal is used as a shuttle channel of chloride ions, the structure rapidly collapses under the acidic condition, and the reaction of bismuth and chloride ions is improved. The method has rapid chlorine removal, can remove 78.8% in 1min, and can remove 85.3% in 10 min. However, MOFs materials are complex to prepare, have high cost and are not suitable for industrial production and application.
Disclosure of Invention
The invention is realized by the following technical scheme:
the bismuth-based adsorption chlorine-removing material has a core-shell structure, wherein the core is inorganic particles, the shell is a nitrogen-doped carbon coating layer, and bismuth (bismuth oxide or bismuth salt) is uniformly dispersed in the nitrogen-doped carbon coating layer.
Further, the shell comprises a raw material of a nitrogen-containing ligand, a nitrogen-containing auxiliary agent and a bismuth source, wherein the nitrogen-containing ligand is protoporphyrin or a derivative thereof and phthalocyanine or a derivative thereof; derivatives of porphyrins include hematoporphyrin, chlorophyll, substituted 5,10,15, 20-tetraphenylporphyrins.
Preferably, the mass ratio of the nitrogen-containing ligand, the nitrogen-containing auxiliary agent and the metal bismuth source is 12-18:5-9:2-4.
The invention mixes the nitrogen-containing ligand, the nitrogen-containing auxiliary agent and the metal bismuth source, then adds the inorganic particles, after mixing evenly, preheats and sinters the mixture to form a nitrogen-doped carbon layer on the surface of the inorganic particles, and bismuth is uniformly dispersed in the carbon layer.
Further, the structural formula of the substituted 5,10,15, 20-tetraphenylporphyrin is shown in a formula (I), and the structural formula of the phthalocyanine derivative is shown in a formula (II):
(I) />(II)
R 1 ，R 2 ，R 3 independently selected from H, NH 2 、NO 2 、NCO、CN、OH。
Preferably, in the compounds of formula (I), R are on the same benzene ring 1 ，R 2 One of which is H and the other is selected from NH 2 、NO 2 OH, NCO; in the compound of formula (II), R 3 And not H at the same time.
More preferably, the porphyrin derivative is selected from at least one of tetra (o-aminophenyl) porphyrin, tetra (p-cyanophenyl) porphyrin, tetra (p-nitrophenyl) porphyrin, tetra (o-isocyanatophenyl) porphyrin, tetra (p-hydroxyphenyl) porphyrin; the phthalocyanine derivative is at least one selected from alpha-tetranitro phthalocyanine, alpha-tetraamino phthalocyanine, beta-tetraisocyanato phthalocyanine and alpha-tetrahydroxy phthalocyanine.
Preferably, the nitrogen-containing ligand is porphyrin or a derivative thereof, and the molar ratio of the nitrogen-containing ligand to phthalocyanine or a derivative thereof is 1-3: 1-3. More preferably, the nitrogen-containing ligand is porphyrin or a derivative thereof, and the molar ratio of the nitrogen-containing ligand to phthalocyanine or a derivative thereof is 1 to 1.5: 1-1.5. The porphyrin derivative and the phthalocyanine derivative act together to form a multi-layer sandwich type multi-layer bismuth matching structure, so that bismuth is more uniformly and stably dispersed, and a better chlorine removal effect is achieved.
Further, the nitrogen-containing auxiliary agent is selected from at least one of chitosan, melamine and urea, and the bismuth source is selected from at least one of bismuth oxide, bismuth nitrate and bismuth hydroxide.
Further, the inorganic particles comprise at least one of activated carbon, glass particles, ceramic particles, quartz sand, titanium dioxide, bentonite, porous silica, fly ash and limestone powder; the particle size of the inorganic particles is 0.5-10mm. The specific surface area of the activated carbon is large, more active sites reacting with chlorine can be formed on the surface, so that the chlorine removal effect is better, but the intensity of the activated carbon is lower; the ceramic particles have high specific gravity and high strength, and are suitable for the packing of a fluidized bed or a chromatographic column in wastewater treatment.
Further, the mass ratio of the inorganic fine particles to the raw materials of the shell (the sum of the nitrogen ligand, the nitrogen-containing auxiliary agent, and the bismuth source) is 10 to 40 times; preferably, when the inorganic particles are activated carbon, the mass ratio of the inorganic particles to the shell is 10-15:1; when the inorganic particles are glass particles or ceramic particles, the mass ratio of the inorganic particles to the shell raw materials is 30-40:1. The active carbon has large specific surface area, and can finish the preparation of bismuth-based adsorption chlorine removal material with small dosage.
The invention also provides a preparation method of the bismuth-based adsorption chlorine removal material, which comprises the following steps:
dissolving or dispersing a nitrogen-containing ligand in a water-soluble organic solvent to obtain a first mixture; dissolving or dispersing a nitrogenous additive in water, adding a bismuth source, and ball-milling to obtain a second mixture; and (3) uniformly mixing the inorganic particles with the first mixture and the second mixture, taking out, drying, preheating and sintering to obtain the bismuth-based adsorption dechlorination material.
Further, the inorganic particles are sequentially and uniformly mixed with the first mixture and the second mixture, namely, the inorganic particles are uniformly mixed with 40-60% of the first mixture, then are uniformly mixed with 40-60% of the second mixture, and then the rest of the first mixture and the rest of the second mixture are added for continuous uniform mixing. The addition of the first mixture and the second mixture in portions allows for a more uniform dispersion of the bismuth source in the material.
Further, the water-soluble organic solvent refers to one of acetonitrile, tetrahydrofuran and pyridine.
Further, the ball milling is to grind the materials to 4000-10000 meshes, preferably 5000-6000 meshes in the ball mill. After the bismuth source is ground to a certain fineness, the bismuth source is more beneficial to the uniform dispersion of the bismuth source in the material.
Further, the mass concentration of the nitrogen-containing ligand in the first mixture is 10-30wt%, and the solid content of the second mixture is 20-40%.
Further, the inorganic particles are sequentially mixed with the first mixture and the second mixture uniformly in a roller; specifically, inorganic particles are added into a roller, the first mixture is mixed for 1-2 hours, then the second mixture is added, and the mixture is mixed for 1-2 hours and taken out.
Further, the drying is performed at 90-110 ℃ or at 60-70 ℃ and 0.01-0.1 Mpa; the preheating is to heat for 1-3 hours at 200-260 ℃; the sintering is carried out at the temperature of 450-600 ℃ for 6-12h.
According to the method, the bismuth source is dispersed in the mixture, the bismuth source can be uniformly dispersed in the mixture under the action of the nitrogen-containing ligand and in the presence of the nitrogen-containing auxiliary agent, and has good affinity with inorganic particles, after sintering, the nitrogen-containing ligand can form a nitrogen-doped carbon coating layer, and the bismuth is uniformly dispersed in the coating layer, so that the bismuth-based adsorption chlorine-removing material is obtained. The material is put into the wastewater, or the wastewater passes through a flow column filled with the material, and chlorine in the wastewater can be rapidly and effectively removed through adsorption and chlorine removal, the static equilibrium adsorption chlorine removal rate can reach about 85%, and the preferred embodiment can reach about 90%; when the flow column is used for treating chlorine-containing water, the dynamic chlorine removal rate can reach about 70% at the flow rate of 1-2BV/h (i.e. 1-2 times of column volume per hour), and the rapid chlorine removal effect is shown.
The invention has the beneficial effects that: the inorganic particles are utilized to form the adsorption chlorine removal material with certain particle size and volume, so that the material is saved, the cost is reduced, and the adsorption chlorine removal material can be directly used for existing equipment and instruments such as a packed tower, a flow column and the like; porphyrin and/or phthalocyanine derivative forms a film-shaped adsorption chlorine removal material with bismuth-containing material on the surface of inorganic particles under the action of auxiliaries such as chitosan, melamine, urea and the like; the bismuth-based adsorption chlorine removal material does not introduce impurities, does not generate oxidation-reduction reaction, is convenient for separation and recovery, and does not generate secondary pollution.
Detailed Description
The following detailed description further explains and illustrates the contents of the present invention.
Reagents used in the examples of the present invention were all commercially available.
Example 1
8g of tetra (p-aminophenyl) porphyrin and 8g of alpha-tetra-amino phthalocyanine were dissolved in 100mL acetonitrile to obtain a first mixture; 3g of melamine and 3g of urea are dispersed in 30mL of water, 4g of bismuth nitrate is added, and the mixture is ground to 6000 meshes in a ball mill to obtain a second mixture; 260g of active carbon particles with the average particle size of 3mm are added into a roller, 50% of the first mixture is firstly added and mixed for 1h, then 50% of the second mixture is added, the mixture is mixed for 1h, the mixture is dried at 105 ℃ for 1h, the rest of the first mixture and the second mixture are added and mixed for 1h, then the mixture is taken out, dried at 105 ℃ for 1h, preheated at 230 ℃ for 2h, then heated to 550 ℃, and the mixture is sintered at the temperature of 8 h, thus obtaining the bismuth-based adsorption chlorine removal material.
Example 2
6g of tetra (p-cyanophenyl) porphyrin and 6g of alpha-tetrahydroxyphthalocyanine were dissolved in 80 mL tetrahydrofuran to obtain a first mixture; 5g of melamine and 3g of urea are dissolved in 40mL of water, 4g of bismuth oxide is added, and the mixture is ground to 5000 meshes in a ball mill to obtain a second mixture; 360g of active carbon particles with the average particle size of 1.5mm are added into a roller, 40% of the first mixture is added and mixed for 1h, then 40% of the second mixture is added, mixed for 1h, dried at 105 ℃ for 1h, then the rest of the first mixture and the second mixture are added and mixed for 1h, then the mixture is taken out, dried at 105 ℃ for 1h, preheated at 260 ℃ for 2h, then heated to 600 ℃, and the bismuth-based adsorption chlorine removal material is obtained after heat preservation and sintering for 1 h.
Example 3
9g of tetra (p-cyanophenyl) porphyrin and 9g of beta-tetranitrophthalocyanine are dissolved in 100mL of acetonitrile to obtain a first mixture; 8g of chitosan is dissolved in 30mL of water, 4g of bismuth hydroxide is added, and the mixture is ground to 6000 meshes in a ball mill to obtain a second mixture; adding 1200g of ceramic particles with the particle size of 2mm into a roller, firstly adding 60% of a first mixture, uniformly mixing for 1h, then adding 60% of a second mixture, uniformly mixing for 1h, drying at 105 ℃, then adding the rest of the first mixture and the second mixture, uniformly mixing, drying at 105 ℃ for 1h, preheating at 200 ℃ for 2h, heating to 450 ℃, and carrying out heat preservation and sintering for 12h to obtain the bismuth-based adsorption dechlorination material.
Example 4
The other conditions were the same as in example 1 except that the nitrogen-containing ligand was 16g of tetra (p-aminophenyl) porphyrin, i.e., that no α -tetra-amino phthalocyanine was added.
Example 5
The other conditions were the same as in example 1 except that the nitrogen-containing ligand was 16g of α -tetraminophthalocyanine, i.e., tetra (p-aminophenyl) porphyrin was not added.
Example 6
Other conditions were the same as in example 1 except that the nitrogen-containing ligand was 12g of tetra (p-aminophenyl) porphyrin and 4g of tetra (p-aminophenyl) porphyrin.
Example 7
Other conditions were the same as in example 1 except that the nitrogen-containing ligand was 10g of tetra (p-aminophenyl) porphyrin and 6g of tetra (p-aminophenyl) porphyrin.
Example 8
8g of tetra (p-aminophenyl) porphyrin and 8g of alpha-tetra-amino phthalocyanine were dissolved in 100mL acetonitrile to obtain a first mixture; 3g of melamine and 3g of urea are dispersed in 20mL of water, 4g of bismuth nitrate is added, and the mixture is ground to 1200 meshes in a ball mill to obtain a second mixture; 300g of activated carbon particles with the average particle size of 1.5mm are added into a roller, the first mixture is firstly added and mixed for 1h, then the second mixture is added and mixed for 1h, the mixture is dried at 105 ℃ for 1h, and is preheated at 230 ℃ for 2h, then the temperature is raised to 550 ℃, and the bismuth-based adsorption chlorine removal material is obtained after heat preservation and sintering for 8 h. I.e., in comparison to example 1, in example 8, the first mixture, the second mixture, was added in one portion, rather than two portions as in example 1.
Example 9
Other conditions were the same as in example 1 except that tetra (p-aminophenyl) porphyrin was replaced with protoporphyrin.
Example 10
Other conditions were the same as in example 1 except that alpha-tetraminophthalocyanine was replaced with phthalocyanine.
Example 11
The other conditions were the same as in example 1 except that 5g of melamine and 3g of urea were dissolved in 40mL of water, and 4g of bismuth oxide was added to obtain a second mixture, i.e., without ball milling.
Comparative example 1
8g of tetra (p-aminophenyl) porphyrin and 8g of alpha-tetra-amino phthalocyanine were dissolved in 100mL acetonitrile to obtain a first mixture; 4g of bismuth nitrate was dispersed in 20mL of water and milled in a ball mill to 1200 mesh to give a second mixture; 300g of activated carbon particles with the average particle size of 1.5mm are added into a roller, 50% of the first mixture is added and mixed for 1h, then 50% of the second mixture is added, the mixture is mixed for 1h, the mixture is dried at 105 ℃ for 1h, the rest of the first mixture and the second mixture are added and mixed for 1h, then the mixture is taken out, dried at 105 ℃ for 1h, preheated at 230 ℃ for 2h, then heated to 550 ℃, and the mixture is sintered for 8 h under heat preservation, thus obtaining the bismuth-based adsorption chlorine removal material. I.e., no nitrogen-containing auxiliary was added as compared to example 1.
Application example 1
Dissolving analytically pure NaCl in deionized water to prepare a chloride ion solution with the concentration of 500mg/L, taking 10mL of the aqueous solution in a beaker, respectively adding 0.65g of the bismuth-based adsorption chlorine removal material prepared in the above examples and comparative examples, and stirring and adsorbing for 0.5h at normal temperature to reach adsorption equilibrium. Filtering the suspension, retaining the filtrate, and measuring the concentration of chloride ions in the solution by using a silver nitrate titration method. The chlorine removal rate was calculated and the results are shown in table 1 below:
TABLE 1 static equilibrium dechlorination Effect
| Chlorine scavenger | Chlorine removal rate |
| Example 1 | 91.4% |
| Examples2 | 88.7% |
| Example 3 | 81.6% |
| Example 4 | 88.5% |
| Example 5 | 89.1% |
| Example 6 | 89.9% |
| Example 7 | 90.5% |
| Example 8 | 90.7% |
| Example 9 | 88.2% |
| Example 10 | 87.8% |
| Example 11 | 88.6% |
| Comparative example 1 | 76.5% |
。
Application example 2
The bismuth-based adsorption chlorine removal materials obtained in the above examples and comparative examples were respectively charged into 125mL glass columns (with sand plates and pistons) and filled to 100mL, 100mg/L NaCl aqueous solution containing 0.3% sodium carboxymethylcellulose was injected into the upper portions of the glass columns, the flow rate was controlled to 1.5BV/h (i.e., 1.5 column volumes per hour), the effluent was collected, and the concentration of chloride ions in the solution was measured by silver nitrate titration. And calculating the chlorine removal rate. The results are shown in Table 2 below:
TABLE 2 dynamic dechlorination effect of flow column
| Chlorine scavenger | Chlorine removal rate |
| Example 1 | 71.3% |
| Example 2 | 70.8% |
| Example 3 | 58.7% |
| Example 4 | 67.4% |
| Example 5 | 69.1% |
| Example 6 | 70.2% |
| Example 7 | 70.5% |
| Example 8 | 69.8% |
| Example 9 | 64.4% |
| Example 10 | 67.1% |
| Example 11 | 68.2% |
| Comparative example 1 | 47.2% |
。
As can be seen from the above Table 1 and Table 2, the bismuth-based adsorption chlorine removal material prepared by the present invention can efficiently remove chlorine ions in water, and can achieve a chlorine removal rate of about 70% even at a flow rate of 1.5 BV/h.
As can be seen from a comparison of example 1 and example 8, the addition of the first porphyrin/phthalocyanine mixture, and the second mixture comprising N-aid and bismuth source, in portions, results in a more uniform dispersion of bismuth and thus a better chlorine removal. As can be seen from a comparison of example 1 and examples 9 and 10, the obtained chlorine removal material was better in chlorine removal effect from porphyrin/phthalocyanine having substituent on the benzene ring, probably due to the fact that the benzene ring has substituent (NH) 2 、NO 2 CN, OH, NCO, etc.) have a better dispersing and affinity action on bismuth, and increase the nitrogen content in the material system, leading to a higher nitrogen doping ratio. From a comparison of example 1 and example 11, it was found that a better chlorine removal effect was obtained by ball milling the second mixture containing the bismuth source to a certain particle size and then preparing the bismuth-based adsorption chlorine removal material.
Claims (13)
1. The bismuth-based adsorption chlorine removal material is of a core-shell structure, and is characterized in that the core is inorganic particles, the shell is a nitrogen-doped carbon coating layer, and bismuth oxide and/or bismuth salt are uniformly dispersed in the nitrogen-doped carbon coating layer; the shell comprises a raw material of nitrogen-containing ligand, nitrogen-containing auxiliary agent and bismuth source; the nitrogen-containing ligand is protoporphyrin or a derivative thereof, and phthalocyanine or a derivative thereof; the mass ratio of the nitrogen-containing ligand to the nitrogen-containing auxiliary agent to the metal bismuth source is 12-18:5-9:2-4; the nitrogenous additive is at least one selected from chitosan, melamine and urea; the inorganic particles are at least one selected from activated carbon, glass particles, ceramic particles, quartz sand, titanium dioxide, bentonite, porous silica, fly ash and limestone powder; the particle size of the inorganic particles is 0.5-10mm.
2. Bismuth-based adsorptive chlorine-removing material according to claim 1, characterized in that the derivative of porphyrin is selected from hematoporphyrin, chlorophyll or substituted 5,10,15, 20-tetraphenylporphyrin.
3. The bismuth-based adsorptive chlorine removal material of claim 2, wherein said substituted 5,10,15, 20-tetraphenylporphyrin has a structural formula shown in formula (I), and said phthalocyanine derivative has a structural formula shown in formula (II):
(I) />(II)
R 1 ，R 2 ，R 3 independently selected from H, NH 2 、NO 2 NCO, CN or OH.
4. A bismuth-based adsorptive chlorine removal material according to claim 3, wherein in the compound of formula (I), R on the same benzene ring 1 ，R 2 One of which is H and the other is selected from NH 2 、NO 2 OH or NCO; in the compound of formula (II), R 3 And not H at the same time.
5. The bismuth-based adsorptive chlorine removal material of claim 3, wherein said substituted 5,10,15, 20-tetraphenylporphyrin is selected from at least one of tetra (o-aminophenyl) porphyrin, tetra (p-cyanophenyl) porphyrin, tetra (p-nitrophenyl) porphyrin, tetra (o-isocyanatophenyl) porphyrin, tetra (p-hydroxyphenyl) porphyrin; the phthalocyanine derivative is at least one selected from alpha-tetranitro phthalocyanine, alpha-tetraamino phthalocyanine, beta-tetraisocyanato phthalocyanine and alpha-tetrahydroxy phthalocyanine.
6. The bismuth-based adsorption chlorine-removal material according to claim 2, wherein the nitrogen-containing ligand is protoporphyrin or derivative thereof, and the molar ratio of the nitrogen-containing ligand to phthalocyanine or derivative thereof is 1-3: 1-3.
7. The bismuth-based adsorption chlorine-removal material according to claim 6, wherein the nitrogen-containing ligand is protoporphyrin or derivative thereof, and the molar ratio of the nitrogen-containing ligand to phthalocyanine or derivative thereof is 1-1.5: 1-1.5.
8. The bismuth-based adsorption chlorine-removal material of claim 2, wherein said bismuth source is selected from at least one of bismuth oxide, bismuth nitrate, bismuth hydroxide.
9. The bismuth-based adsorption chlorine-removing material according to claim 2, wherein the mass ratio of the inorganic fine particles to the raw material of the shell is 10 to 40 times.
10. The bismuth-based adsorption chlorine-removing material according to claim 9, wherein when the inorganic fine particles are activated carbon, the mass ratio of the inorganic fine particles to the raw materials of the shell is 10-15:1; when the inorganic particles are glass particles or ceramic particles, the mass ratio of the inorganic particles to the shell raw materials is 30-40:1.
11. The method for preparing the bismuth-based adsorption chlorine removal material as claimed in any one of claims 1 to 10, comprising the steps of:
dissolving or dispersing a nitrogen-containing ligand in a water-soluble organic solvent to obtain a first mixture; dissolving or dispersing a nitrogenous additive in water, adding a bismuth source, and ball-milling in a ball mill to obtain a second mixture; and (3) uniformly mixing the inorganic particles with the first mixture and the second mixture, taking out, drying, preheating and sintering to obtain the bismuth-based adsorption dechlorination material.
12. The method according to claim 11, wherein the inorganic fine particles are mixed with the first mixture and the second mixture in this order, the inorganic fine particles are mixed with 40-60% of the first mixture, then mixed with 40-60% of the second mixture, and then the remaining first mixture and the second mixture are added to continue mixing.
13. Use of the bismuth-based adsorption chlorine-removal material as claimed in any one of claims 1 to 10 for removing chloride ions from water.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004091276A (en) * | 2002-09-02 | 2004-03-25 | Hitachi Plant Eng & Constr Co Ltd | Activated carbon for adsorption of arsenic and its manufacturing method |
| CN107892375A (en) * | 2017-10-19 | 2018-04-10 | 上海交通大学 | The minimizing technology of chloride Chlorine in Solution ion |
| CN109731605A (en) * | 2019-02-28 | 2019-05-10 | 哈尔滨工业大学 | A kind of metal composite situ Nitrogen Doping carbon microspherical catalyst and its application |
| CN112542577A (en) * | 2020-12-03 | 2021-03-23 | 济南大学 | Nano bismuth/nitrogen-doped carbon foam nanosheet two-dimensional composite material and preparation method and application thereof |
| CN113060754A (en) * | 2021-03-16 | 2021-07-02 | 江苏理工学院 | Doped cuprous dechlorinating agent and preparation method and application thereof |
| CN113089017A (en) * | 2021-04-08 | 2021-07-09 | 中国科学院化学研究所 | Metal bismuth nanoparticle composite material and preparation method and application thereof |
| CN113181974A (en) * | 2021-04-08 | 2021-07-30 | 华南理工大学 | Bismuth oxide-carbon nitride-porphyrin composite photocatalyst and preparation method thereof |
| CN114835233A (en) * | 2022-06-01 | 2022-08-02 | 闽江学院 | Method for rapidly removing chloride ions in wastewater by using bismuth-based metal organic framework material |
-
2022
- 2022-08-23 CN CN202211011893.0A patent/CN115254026B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004091276A (en) * | 2002-09-02 | 2004-03-25 | Hitachi Plant Eng & Constr Co Ltd | Activated carbon for adsorption of arsenic and its manufacturing method |
| CN107892375A (en) * | 2017-10-19 | 2018-04-10 | 上海交通大学 | The minimizing technology of chloride Chlorine in Solution ion |
| CN109731605A (en) * | 2019-02-28 | 2019-05-10 | 哈尔滨工业大学 | A kind of metal composite situ Nitrogen Doping carbon microspherical catalyst and its application |
| CN112542577A (en) * | 2020-12-03 | 2021-03-23 | 济南大学 | Nano bismuth/nitrogen-doped carbon foam nanosheet two-dimensional composite material and preparation method and application thereof |
| CN113060754A (en) * | 2021-03-16 | 2021-07-02 | 江苏理工学院 | Doped cuprous dechlorinating agent and preparation method and application thereof |
| CN113089017A (en) * | 2021-04-08 | 2021-07-09 | 中国科学院化学研究所 | Metal bismuth nanoparticle composite material and preparation method and application thereof |
| CN113181974A (en) * | 2021-04-08 | 2021-07-30 | 华南理工大学 | Bismuth oxide-carbon nitride-porphyrin composite photocatalyst and preparation method thereof |
| CN114835233A (en) * | 2022-06-01 | 2022-08-02 | 闽江学院 | Method for rapidly removing chloride ions in wastewater by using bismuth-based metal organic framework material |
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