CN114873623A - 具有还原性和吸附性的可回收水滑石及其制备方法和应用 - Google Patents
具有还原性和吸附性的可回收水滑石及其制备方法和应用 Download PDFInfo
- Publication number
- CN114873623A CN114873623A CN202210579877.5A CN202210579877A CN114873623A CN 114873623 A CN114873623 A CN 114873623A CN 202210579877 A CN202210579877 A CN 202210579877A CN 114873623 A CN114873623 A CN 114873623A
- Authority
- CN
- China
- Prior art keywords
- hydrotalcite
- stirring
- ldh
- recoverable
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 23
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 23
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012153 distilled water Substances 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 12
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000176 sodium gluconate Substances 0.000 claims abstract description 9
- 229940005574 sodium gluconate Drugs 0.000 claims abstract description 9
- 235000012207 sodium gluconate Nutrition 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000007710 freezing Methods 0.000 claims abstract description 4
- 230000008014 freezing Effects 0.000 claims abstract description 4
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 7
- 238000009830 intercalation Methods 0.000 claims description 6
- 230000002687 intercalation Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 230000001603 reducing effect Effects 0.000 claims 2
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000011651 chromium Substances 0.000 abstract description 59
- 239000000463 material Substances 0.000 abstract description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052804 chromium Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
-
- 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
- B01J20/06—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
- B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Geology (AREA)
- Compounds Of Iron (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明提供具有还原性和吸附性的可回收水滑石及其制备方法和应用，包括以下步骤：S1.制备磁性Fe3O4粒子；S2.Fe3O4分散到去氧蒸馏水中，再加入FeSO4和Al2(SO4)3，将碱溶液缓慢加入反应得到Fe3O4@Fe‑Al LDH前体；Fe3O4@Fe‑Al LDH前体加入到葡萄糖酸钠溶液中，震荡，冲洗过滤，冷冻，真空冷冻干燥，得到赋磁GA@Fe3O4@Fe‑Al LDH。获得的GA@Fe3O4@Fe‑Al LDH对废水中Cr(Ⅵ)和总铬的去除都有很效，材料能应用于实际废水Cr(Ⅵ)的去除。
Description
技术领域
本发明涉及工业污水处理技术领域，具体为一种具有还原性和吸附性的可回收水滑石及其制备方法和应用，以及该材料在废水中去除Cr(VI)并以Cr(III)的形态回收铬的应用。
背景技术
常规Mg-Al水滑石对重金属离子，如铬酸根阴离子，吸附去除率不高，利用阴离子对水滑石插层改性虽然可以提高材料与重金属离子的亲和性，但仍然存在Cr(VI)毒性大，后续资源化、无害化处理困难的问题。同时，水滑石本身呈粉末态，在吸附过程后回收率不高也影响含Cr污水的处理。赋磁虽能实现吸附剂的回收，但也存在大幅削弱水滑石对Cr(VI)去除率的问题。
发明内容
针对上述技术问题，本发明提供一种具有还原性和吸附性的可回收水滑石及其制备方法和应用，提高Cr(VI)去除率。
具体技术方案为：
具有还原性和吸附性的可回收水滑石的制备方法，包括以下步骤：
S1.制备磁性Fe3O4粒子
将蒸馏水加热煮沸后封闭，冷却至室温得到去氧蒸馏水。用NaOH溶解于适量去氧蒸馏水中配制约1mol/L NaOH溶液。另外用去氧蒸馏水配置摩尔浓度约为0.7mol/L的FeSO4和1.4mol/L的FeCl3混合溶液，置于磁力搅拌器上，设置温度为25℃，转数为800r/min进行搅拌，30min后缓慢加入配制的NaOH溶液，待溶液完全变黑后仍继续滴加NaOH溶液直至pH值约为10，继续搅拌约1h，搅拌过程持续通入氮气保护，然后转移至反应釜中，在120℃条件下加热24h，倒入滤袋过滤，用少量蒸馏水和乙醇反复洗涤2次，以洗去表面未反应的杂质离子，然后抽真空冷冻干燥得到Fe3O4粒子。
(1)全程尽量隔绝氧气。
(2)缓慢滴加NaOH溶液直至pH值约为10。
(3)在120℃条件下在反应釜中加热24h
以保证所得Fe3O4粒子均匀细小，成品稳定。
S2.制备赋磁的还原性Fe(II)-Al(III)水滑石前体
在室温下，将约0.5g S1得到的Fe3O4分散到装有100mL去氧蒸馏水中烧杯，于超声仪中超声分散30min，再加入适量的FeSO4和Al2(SO4)3，使他们的浓度分别约为0.8mol/L和0.2mol/L，在烧杯中搅拌溶解，得到混合液A。再将烧杯置于磁力搅拌器上，调节温度为25℃，转数为800r min-1。将浓度约1mol/L碱溶液缓慢加入到混合液A中，控制滴加速度以维持体系pH＝9，搅拌时间30min，整个滴加和搅拌过程通入氮气以防止亚铁离子被氧化。搅拌完成后将产生的悬浮液快速转移至离心管离心处理，将离心得到的沉淀物转移至聚四氟乙烯内村的反应釜中，置于100℃的真空烘箱中反应24h。水热完成后将沉淀物倒入500目的滤袋中，经3次去氧蒸馏水和2次的无水乙醇的充分洗涤后，得到Fe3O4@Fe-Al LDH前体。
(1)原料为FeSO4和Al2(SO4)3。
(2)原料FeSO4和Al2(SO4)3的浓度为0.8mol/L和0.2mol/L；维持滴加体系pH＝9。
(3)使用去氧蒸馏水；整个滴加和搅拌过程通入氮气；置于100℃的真空烘箱中反应24h。
作用在于，前体中的SO4 2-有利于后续过程S3中的葡萄糖酸根阴离子的交换插层；Fe(II)和Al(III)能相对稳定的形成水滑石层板结构；以及防止Fe(II)在过程中氧化。
S3.葡萄糖酸钠插层对赋磁的Fe-Al LDH前体改性
将0.5～4g葡萄糖酸钠溶解到40mL去氧蒸馏水中，配置成一定浓度的葡萄糖酸钠溶液。取S2中约6g经蒸馏水和无水乙醇冲洗过滤后的Fe3O4@Fe-Al LDH前体，加入到配置好的葡萄糖酸钠溶液中，放置于25℃，180r min-1的恒温震荡箱中震荡24h，然后再次用等量蒸馏水和无水乙醇冲洗过滤，于-80℃的冰箱中冷冻，再用真空冷冻干燥机干燥，得到赋磁GA@Fe3O4@Fe-Al LDH。
(1)插层材料为葡萄糖酸钠。
(2)插层要在形成Fe3O4@Fe-Al LDH前体之后。
(3)操作中使用去氧蒸馏水；于-80℃的冰箱中冷冻，再用冷冻干燥机干燥。
作用在于，葡萄糖酸钠易与SO4 2-交换进入层间，进入层间后，可提高材料成品在空气中的稳定性，同时提高材料对Cr(VI)阴离子的交换吸附能力。尽可能避免制备过程中的氧化。
根据申诉制备方法所得的具有还原性和吸附性的可回收水滑石，在pH范围3～9下，12h内能有效去除污水中的Cr(VI)阴离子，各种共存阴阳离子对材料去除Cr(VI)的影响较小。
将Cr(VI)六价铬处理后的吸附材料从液体中分离，烘干，并用一定体积的约1mol/L HCl浸泡、振荡数小时，以回收吸附还原的Cr。回收溶液为约1mol L-1的HCl溶液，总Cr回收率约80％。回收的总Cr中，Cr(III)形态占95％。
附图说明
图1为实施例1中GA@Fe3O4@Fe-Al LDH的扫描电镜图像；
图2A为实施例1中Fe-Al LDH、GA@Fe-Al LDH和GA@Fe3O4@Fe-Al LDH的XRD图谱；
图2B为实施例1中Fe-Al LDH、GA@Fe-Al LDH和GA@Fe3O4@Fe-Al LDH的FTIR图谱；
图3为实施例1中GA@Fe3O4@Fe-Al LDH的磁性表征；
图4为实施例2中不同Cr(Ⅵ)初始浓度下GA@Fe3O4@Fe-Al LDH对Cr(Ⅵ)和总铬去除率随时间的变化；
图5为实施例3中不同赋磁方法合成的材料对Cr(Ⅵ)去除率的影响；
图6A为实施例5中复合材料对Cr(Ⅵ)去除过程中各指标随时间的变化之一；
图6B为实施例5中复合材料对Cr(Ⅵ)去除过程中各指标随时间的变化之二；
图7为实施例7中产品材料对Cr(Ⅵ)的单位材料去除量随pH的变化图；
图8A为实施例7中不同阴干扰离子对GA@Fe3O4@Fe-Al LDH去除Cr(Ⅵ)的影响；
图8B为实施例7中不同阳干扰离子对GA@Fe3O4@Fe-Al LDH去除Cr(Ⅵ)的影响；
图9为实施例8中复合材料去除实际废水中Cr(Ⅵ)和总铬的情况。
具体实施方式
结合实施例说明本发明的具体技术方案。
实施例1
制备过程中半成品、最终产品材料的结构表征，如图1、图2A、图2B、图3；
Fe-Al LDH：除了不加Fe3O4粒子，其他均按S2制备。
GA@Fe-Al LDH：除了不加Fe3O4粒子，其他均按S2、S3顺序制备。
GA@Fe3O4@Fe-Al LDH：完全按S1、S2、S3顺序制备。
实施例2
GA@Fe3O4@Fe-Al LDH对Cr(VI)和总铬的去除率，如图4；
实验条件为Cr(VI)初始浓度20～50mg/L，0.05g吸附剂，200mL Cr(Ⅵ)待处理液，pH＝7，25℃180r/min恒温振荡器。
结果为当Cr(VI)初始浓度20mg/L，Cr(Ⅵ)去除率约90％。
实施例3
三种不同方法赋磁对产品Cr(VI)去除能力的影响，如图5；
方法一：将适量S1中获得的Fe3O4和事先制备好的Fe-Al LDH混合到100mL去氧蒸馏水中，于超声仪中超声分散30min，然后方法同S2。
方法二：权利要求中的方法赋磁。
方法三：将适量预先制备好的Fe-Al LDH加入到100mL水中，超声分散30min，再加入适量FeSO4和FeCl3，维持体系pH＝9，在氮气保护下搅拌1h，后续处理与S2一致。
以上三种方法中物料用量比例一致。
结果为，用权利要求中的方法赋磁，对水滑石Cr(VI)去除能力的抑制最小。
实施例4
赋磁方法对产品Cr(VI)去除能力的影响，如表1；
表1赋磁对插层水滑石材料的Cr(Ⅵ)和总铬的单位质量材料去除量的影响
结果为，用权利要求中的方法赋磁，对单位质量水滑石材料的Cr(VI)和总铬去除能力的抑制较小。
实施例5
Cr(VI)去除实验中材料还原性的表现，如图6A和图6B；
实施条件为Cr(VI)初始浓度为30mg/L，其他条件同实施例2。
结果为，溶液中出现了少量Cr(III)，材料表现出一定还原性。
实施例6
Cr回收实验中材料还原性的表现，如表2；
表2中间材料及最终产品上的铬的回收情况
实施条件为，Cr(Ⅵ)去除实验后，分离和收集沉淀物。在105℃的电加热鼓风箱中干燥24h。置于装有100ml 1mol L-1的HCl溶液的烧杯中，25℃恒温振荡20h，取上清液，稀释，过0.45μm滤膜，测定Cr(Ⅵ)和总铬含量。
结果为，GA@Fe3O4@Fe-Al LDH上约80％的Cr能重新回到溶液中，且其中Cr(III)的比例高达95％。材料表现出很强的还原性。
实施例7
Cr(VI)去除实验中环境条件的影响，如图7、图8A和图8B；
图8中，不同小写字母表示在不同处理下Cr(VI)的剩余浓度差异显著(P<0.05)。
结果为，在3～9的pH范围，GA@Fe3O4@Fe-Al LDH对Cr(VI)去除都有很好表现；共存的阴阳离子对Cr(VI)去除影响不大。
实施例8
GA@Fe3O4@Fe-Al LDH对实际电镀废水中Cr(VI)和总铬的去除能力，如图9；
企业取得的实际电镀废水，测得指标情况表如表3：
表3实际电镀废水中各指标的含量
实施条件，将上述实际废水稀释1倍后，取100ml稀释废水加入0.05g GA@Fe3O4@Fe-Al LDH材料，25℃，转速为180r/min的恒温振荡器振荡20h。
图9中模拟废水情况为，pH＝3，Cr(Ⅵ)浓度为100mg/L，Cu2+、Cd2+、Ni2+、Zn2+、NO3 -、CO3 2-、SO4 2-离子浓度均约为50mg/L，实验条件同实际废水。
空白为pH＝3，仅含有100mg/LCr(Ⅵ)，无其他离子。
实施结果为，GA@Fe3O4@Fe-Al LDH产品对实际废水和模拟废水中Cr(Ⅵ)和总铬的去除都有很效，材料能应用于实际废水Cr(Ⅵ)的去除。
Claims (6)
1.具有还原性和吸附性的可回收水滑石的制备方法，其特征在于，包括以下步骤：
S1.制备磁性Fe3O4粒子
FeSO4和FeCl3溶于蒸馏水中，搅拌，然后缓慢加入NaOH溶液，待溶液完全变黑后仍继续滴加NaOH溶液直至pH值为10，持续搅拌；
搅拌过程持续通入氮气保护，然后转移至反应釜中，加热，反应结束后过滤，洗涤，抽真空冷冻干燥得到Fe3O4粒子；
S2.制备赋磁的还原性Fe(II)-Al(III)水滑石前体
Fe3O4分散到去氧蒸馏水中，再加入FeSO4和Al2(SO4)3，搅拌溶解，得到混合液A；
搅拌器上，将碱溶液缓慢加入到混合液A中，控制滴加速度以维持体系pH＝9；
滴加和搅拌过程通入氮气；
搅拌完成后将产生的悬浮液快速转移至离心管，得到的沉淀物转移至聚四氟乙烯内村的反应釜中进行反应，反应完成后将得到的沉淀物倒入滤袋中，冲洗后，得到Fe3O4@Fe-AlLDH前体；
S3.葡萄糖酸钠插层对赋磁的Fe-Al LDH前体改性
取S2中得到的Fe3O4@Fe-Al LDH前体，加入到葡萄糖酸钠溶液中，震荡，冲洗过滤，冷冻，真空冷冻干燥，得到赋磁GA@Fe3O4@Fe-Al LDH。
2.根据权利要求1所述的具有还原性和吸附性的可回收水滑石的制备方法，其特征在于，S1中，NaOH溶液浓度为1mol/L；
FeSO4和FeCl3的摩尔浓度分别为0.7mol/L和1.4mol/L，FeSO4和FeCl3溶于蒸馏水中后搅拌条件为：温度25℃，转数800r/min；
30min后缓慢加入NaOH溶液，滴加NaOH后，继续搅拌约1h；
反应釜中，条件为：120℃条件，加热24h。
3.根据权利要求1所述的具有还原性和吸附性的可回收水滑石的制备方法，其特征在于，S2中，FeSO4和Al2(SO4)3的摩尔浓度分别为0.8mol/L和0.2mol/L，搅拌条件为：温度25℃，转数为800r min-1；碱溶液浓度为1mol/L，搅拌时间30min；
反应釜中条件为：100℃，反应24h。
4.根据权利要求1所述的具有还原性和吸附性的可回收水滑石的制备方法，其特征在于，S3中，震荡条件为：25℃，180r min-1，24h。
5.具有还原性和吸附性的可回收水滑石，其特征在于，根据权利要求1到4任一项所述的制备方法所得。
6.根据权利要求5所述的具有还原性和吸附性的可回收水滑石的应用，其特征在于，用于去除污水中的Cr(VI)阴离子。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210579877.5A CN114873623B (zh) | 2022-05-25 | 2022-05-25 | 具有还原性和吸附性的可回收水滑石及其制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210579877.5A CN114873623B (zh) | 2022-05-25 | 2022-05-25 | 具有还原性和吸附性的可回收水滑石及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114873623A true CN114873623A (zh) | 2022-08-09 |
| CN114873623B CN114873623B (zh) | 2023-02-03 |
Family
ID=82678522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210579877.5A Active CN114873623B (zh) | 2022-05-25 | 2022-05-25 | 具有还原性和吸附性的可回收水滑石及其制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114873623B (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114620920A (zh) * | 2022-03-15 | 2022-06-14 | 中国科学院生态环境研究中心 | 一种活化过硫酸盐调理污泥的磁性材料制备方法 |
| CN116119725A (zh) * | 2023-01-16 | 2023-05-16 | 河北师范大学 | 一种还原型含铁水滑石材料的制备方法 |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5514281A (en) * | 1992-11-24 | 1996-05-07 | B. Braun Melsungen Ag | Process for the selective elimination of inorganic phosphate from liquids by means of adsorbent materials modified with polynuclear metal oxyhydroxides |
| JP2012229140A (ja) * | 2011-04-26 | 2012-11-22 | Osaka Prefecture Univ | 鉄系層状複水酸化物の製造方法 |
| CN102847513A (zh) * | 2012-09-19 | 2013-01-02 | 常州大学 | 一种制备有机水滑石的方法 |
| CN102874880A (zh) * | 2012-10-09 | 2013-01-16 | 湖南大学 | 纳米亚铁铝类水滑石及其超声共沉淀制备方法和应用 |
| AU2014358120A1 (en) * | 2013-12-03 | 2016-03-03 | Kyowa Chemical Industry Co., Ltd. | Magnetic hydrotalcite composite and process for manufacturing same |
| CN106861605A (zh) * | 2017-03-31 | 2017-06-20 | 四川农业大学 | 活性炭负载纳米Fe‑Al（氢）氧化物颗粒复合材料的制备方法及其应用 |
| CN110102246A (zh) * | 2019-04-28 | 2019-08-09 | 华东交通大学 | 一种磁性层状双金属氢氧化物吸附剂及其除磷除铬应用 |
| CN111498921A (zh) * | 2020-04-15 | 2020-08-07 | 北京化工大学 | 一种去除污染水中污染物的复合材料及方法 |
| CN111559760A (zh) * | 2020-06-16 | 2020-08-21 | 北京化工大学 | 一种磁性水滑石及其制备方法和应用 |
| CN114195246A (zh) * | 2021-09-29 | 2022-03-18 | 河南力浮科技有限公司 | 纳米级FeS/LDH复合材料制备及钝化去除水中铬的应用 |
-
2022
- 2022-05-25 CN CN202210579877.5A patent/CN114873623B/zh active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5514281A (en) * | 1992-11-24 | 1996-05-07 | B. Braun Melsungen Ag | Process for the selective elimination of inorganic phosphate from liquids by means of adsorbent materials modified with polynuclear metal oxyhydroxides |
| JP2012229140A (ja) * | 2011-04-26 | 2012-11-22 | Osaka Prefecture Univ | 鉄系層状複水酸化物の製造方法 |
| CN102847513A (zh) * | 2012-09-19 | 2013-01-02 | 常州大学 | 一种制备有机水滑石的方法 |
| CN102874880A (zh) * | 2012-10-09 | 2013-01-16 | 湖南大学 | 纳米亚铁铝类水滑石及其超声共沉淀制备方法和应用 |
| AU2014358120A1 (en) * | 2013-12-03 | 2016-03-03 | Kyowa Chemical Industry Co., Ltd. | Magnetic hydrotalcite composite and process for manufacturing same |
| CN106861605A (zh) * | 2017-03-31 | 2017-06-20 | 四川农业大学 | 活性炭负载纳米Fe‑Al（氢）氧化物颗粒复合材料的制备方法及其应用 |
| CN110102246A (zh) * | 2019-04-28 | 2019-08-09 | 华东交通大学 | 一种磁性层状双金属氢氧化物吸附剂及其除磷除铬应用 |
| CN111498921A (zh) * | 2020-04-15 | 2020-08-07 | 北京化工大学 | 一种去除污染水中污染物的复合材料及方法 |
| CN111559760A (zh) * | 2020-06-16 | 2020-08-21 | 北京化工大学 | 一种磁性水滑石及其制备方法和应用 |
| CN114195246A (zh) * | 2021-09-29 | 2022-03-18 | 河南力浮科技有限公司 | 纳米级FeS/LDH复合材料制备及钝化去除水中铬的应用 |
Non-Patent Citations (2)
| Title |
|---|
| XINHONGQIU ET AL.: ""One-step synthesis of layered double hydroxide-intercalated gluconate for removal of borate"", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
| 闫春燕 等: ""葡萄糖酸根插层水滑石的制备、表征及对硼的吸附研究"", 《离子交换与吸附》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114620920A (zh) * | 2022-03-15 | 2022-06-14 | 中国科学院生态环境研究中心 | 一种活化过硫酸盐调理污泥的磁性材料制备方法 |
| CN116119725A (zh) * | 2023-01-16 | 2023-05-16 | 河北师范大学 | 一种还原型含铁水滑石材料的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114873623B (zh) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114873623B (zh) | 具有还原性和吸附性的可回收水滑石及其制备方法和应用 | |
| Son et al. | A novel approach to developing a reusable marine macro-algae adsorbent with chitosan and ferric oxide for simultaneous efficient heavy metal removal and easy magnetic separation | |
| Zhou et al. | Adsorption of mercury (II) with an Fe 3 O 4 magnetic polypyrrole–graphene oxide nanocomposite | |
| Ren et al. | Chromium (VI) adsorption from wastewater using porous magnetite nanoparticles prepared from titanium residue by a novel solid-phase reduction method | |
| Venkateswarlu et al. | Surfactant-free green synthesis of Fe 3 O 4 nanoparticles capped with 3, 4-dihydroxyphenethylcarbamodithioate: stable recyclable magnetic nanoparticles for the rapid and efficient removal of Hg (II) ions from water | |
| Long et al. | Removal of phosphate from aqueous solution by magnetic Fe–Zr binary oxide | |
| Fang et al. | Facile upscaled synthesis of layered iron oxide nanosheets and their application in phosphate removal | |
| Shahid et al. | Characterization and application of magnetite Particles, synthesized by reverse coprecipitation method in open air from mill scale | |
| Chen et al. | One-step hydrothermal synthesis of hydrophilic Fe 3 O 4/carbon composites and their application in removing toxic chemicals | |
| Kraus et al. | Synthesis of MPTS-modified cobalt ferrite nanoparticles and their adsorption properties in relation to Au (III) | |
| Yang et al. | La-EDTA coated Fe3O4 nanomaterial: preparation and application in removal of phosphate from water | |
| US11713253B2 (en) | Magnesium-aluminum hydrotalcite-loaded nano zero-valent iron composite material, method for preparing same and use thereof | |
| CN108704610B (zh) | 磁性碳修饰的镁铁水滑石复合材料及其制备方法和应用 | |
| Zhang et al. | Synthesis of KMnO4-treated magnetic graphene oxide nanocomposite (Fe3O4@ GO/MnOx) and its application for removing of Cu2+ ions from aqueous solution | |
| CN114195246B (zh) | 纳米级FeS/LDH复合材料制备及钝化去除水中铬的应用 | |
| Abdolmaleki et al. | Efficient heavy metal ion removal by triazinyl-β-cyclodextrin functionalized iron nanoparticles | |
| CN113042000A (zh) | 一种鸡粪衍生生物炭负载纳米零价铁复合材料及其制备方法和应用 | |
| Yan et al. | Evenly distribution of amorphous iron sulfides on reconstructed Mg-Al hydrotalcites for improving Cr (VI) removal efficiency | |
| Olusegun et al. | Comparative characteristics and enhanced removal of tetracycline and ceftriaxone by Fe3O4-lignin and Fe3O4-carbon-based lignin: mechanism, thermodynamic evaluation, and DFT calculation | |
| CN110479203A (zh) | 一种甘氨酸改性FeMg-LDH及其制备和应用 | |
| Liang et al. | Magnetic mesoporous carbon hollow microspheres adsorbents for the efficient removal of Cr (III) and Cr (III)-EDTA in high salinity water | |
| CN115501858B (zh) | 磁性硫氮掺杂生物炭复合材料及其制备方法和在共吸附抗生素与重金属离子中的应用 | |
| Chaudhary et al. | Removal of coomassie brilliant blue R-250 dye from water using γ-Fe2O3 nanoparticles | |
| CN114797782B (zh) | 磁性氧化石墨烯-金属有机框架纳米复合材料及其制备方法和应用 | |
| CN111701569B (zh) | 双金属有机骨架衍生多孔炭及其制备方法和用途 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |