CN113797886A - Montmorillonite composite material and application thereof in heavy metal adsorption - Google Patents
Montmorillonite composite material and application thereof in heavy metal adsorption Download PDFInfo
- Publication number
- CN113797886A CN113797886A CN202111066836.8A CN202111066836A CN113797886A CN 113797886 A CN113797886 A CN 113797886A CN 202111066836 A CN202111066836 A CN 202111066836A CN 113797886 A CN113797886 A CN 113797886A
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- composite material
- montmorillonite composite
- ferrihydrite
- 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.)
- Pending
Links
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 215
- 239000002131 composite material Substances 0.000 title claims abstract description 156
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 title abstract description 35
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims description 55
- 239000000725 suspension Substances 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 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 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 238000005341 cation exchange Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 claims description 2
- 239000002689 soil Substances 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 229910052604 silicate mineral Inorganic materials 0.000 abstract description 3
- 239000012798 spherical particle Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 75
- 239000011651 chromium Substances 0.000 description 47
- 238000000034 method Methods 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- 239000002243 precursor Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 8
- 229910052793 cadmium Inorganic materials 0.000 description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000004438 BET method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- -1 hydroxyl iron ions Chemical class 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a montmorillonite composite material and application thereof in heavy metal adsorption. The montmorillonite composite material comprises montmorillonite and ferrihydrite; the ferrihydrite is dispersed on the outer surface of the montmorillonite. The montmorillonite composite material has larger BET specific surface area and multilevel pore structure characteristics, not only retains the pore structure characteristics of montmorillonite, but also has the pore structure characteristics of ferrihydrite; the ferrihydrite particles with positive charges are firmly combined with the montmorillonite particles with negative charges on the layer surface to form a stable montmorillonite composite material; the composite material has the structural characteristics of typical layered structure silicate minerals and ferrihydrite, and ferrihydrite nanoparticles are in a spherical particle structure and are wrapped by montmorillonite sheets. The montmorillonite composite material is applied to water bodies of various heavy metals or field soil environments, and can effectively remove the heavy metals in the environments.
Description
Technical Field
The invention relates to the field of mineral materials, in particular to a montmorillonite composite material and application thereof in heavy metal adsorption.
Background
The clay minerals such as montmorillonite and the like have abundant reserves, are cheap and easily available, are environment-friendly and are the predominant non-metallic minerals in China. Montmorillonite materials have special structures and properties such as abundant micropores, higher specific surface area and larger pore volume, and are applied to adsorption and control of toxic substances such as heavy metals and organic pollutants in recent years. Montmorillonite is structurally characterized by two layers of silicon-oxygen tetrahedrons sandwiching a layer of aluminum oxy octahedron. Due to isomorphous substitution (e.g. Al between octahedral layers)3+Is coated with Mg2+Or Fe2+By substitution of Si between tetrahedral layers4+Is covered with Al3+Substitution, etc.) between layers, there is an excess negative charge that attracts Na between montmorillonite layers by electrostatic action+And Ca2+And electrostatic equilibrium is achieved. Because the active sites of the natural montmorillonite are occupied, the binding force of cations and montmorillonite sheets is weak, and the cations can be exchanged by other cations (including inorganic cations and organic cations), so that the adsorption efficiency is low; and the surface of the montmorillonite is usually electronegative, which makes the montmorillonite have poor adsorption effect on anionic heavy metals.
The modified montmorillonite is a commonly used means at present, and the pore structure, the hydrophilicity and the hydrophobicity and the charge property of the montmorillonite can be changed by modifying the montmorillonite, so that the adsorption and removal effects of the montmorillonite on heavy metals and organic pollutants are obviously influenced. In recent years, modification of montmorillonite mainly includes organic modification and inorganic modification. However, most organic reagents are used in the organic modification process, for example, CN112237901A discloses a preparation method of novel composite modified montmorillonite for treating chromium-containing wastewater, the invented material has higher hexavalent chromium adsorption performance, but the preparation process of the material needs to use toxic and harmful substances such as cetylpyridinium chloride and the like, and secondary pollution is caused to the environment. The inorganic modification method is mainly characterized in that the space between montmorillonite layers is increased through pillaring, the specific surface area is increased, for example, CN111718719A discloses a vulcanized nano zero-valent iron-acid activated montmorillonite composite material, and a preparation method and application thereof. Therefore, a composite material which is simple in preparation process, green, pollution-free and low in price and can realize high-efficiency adsorption of heavy metal ions is needed to be found.
Disclosure of Invention
In order to solve the problems of potential environmental pollution caused by modified montmorillonite and low adsorption efficiency of montmorillonite on heavy metals in the prior art, the invention aims to provide a montmorillonite composite material; the second purpose of the invention is to provide a preparation method of the montmorillonite composite material; the invention also aims to provide the application of the montmorillonite composite material in heavy metal adsorption.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a montmorillonite composite material comprises montmorillonite and ferrihydrite; the ferrihydrite is dispersed on the outer surface of the montmorillonite.
Preferably, the specific surface area of the montmorillonite composite material is more than or equal to 146.6m2(ii)/g; further preferably, the specific surface area of the montmorillonite composite material is 146.6 to 250m2(ii)/g; still further preferably, a montmorillonite composite materialHas a specific surface area of 146.6-230.6m2(ii)/g; the specific surface area is measured by a BET method.
Preferably, the total pore volume of the montmorillonite composite material is more than or equal to 0.156cm3(ii)/g; further preferably, the total pore volume of the montmorillonite composite is 0.156 to 0.210cm3(ii)/g; still further preferably, the total pore volume of the montmorillonite composite is 0.156 to 0.198cm3(ii)/g; the total pore volume is measured using the BET method.
Preferably, the cation exchange capacity of the montmorillonite is more than or equal to 90 mmoL/g; further preferably, the cation exchange capacity of montmorillonite is not less than 110 mmoL/g.
The second aspect of the present invention provides a method for producing the above-mentioned montmorillonite composite material.
A preparation method of the montmorillonite composite material comprises the following steps:
1) mixing the iron source solution and the montmorillonite solution to obtain a mixed solution;
2) adding a strong base solution into the mixed solution obtained in the step 1) to obtain a suspension;
3) aging the suspension obtained in the step 2), coagulating and separating the suspension to obtain the montmorillonite composite material.
Preferably, in the preparation method of the montmorillonite composite material, the montmorillonite in the step 1) is calcium-based montmorillonite; further preferably, the purity of the montmorillonite is more than or equal to 70 percent; still more preferably, the purity of montmorillonite is not less than 85%.
In some preferred embodiments of the present invention, the montmorillonite in step 1) of the method for producing the montmorillonite composite material is selected from the group consisting of calcium montmorillonite.
Preferably, in the preparation method of the montmorillonite composite material, in the step 1), the iron source is at least one of ferric chloride or ferric nitrate; further preferably, the iron source in step 1) is ferric chloride.
Preferably, in the preparation method of the montmorillonite composite material, the mass ratio of Fe in the iron source solution in the step 1) to montmorillonite is (0.5-3): 1; further preferably, the mass ratio of Fe to montmorillonite in the iron source solution in the step 1) is 2: 1.
preferably, in the preparation method of the montmorillonite composite material, the pH value of the suspension obtained in the step 2) is 6.5-7.5; it is further preferred that the suspension obtained in step 2) has a pH of 7.0.
Preferably, in the preparation method of the montmorillonite composite material, the strong alkali solution in the step 2) is at least one of a sodium hydroxide solution, a potassium hydroxide solution and a calcium hydroxide solution; further preferably, the strong alkali solution in the step 2) is at least one of sodium hydroxide solution and potassium hydroxide solution; still more preferably, the strong alkali solution in the step 2) is a sodium hydroxide solution.
Preferably, in the preparation method of the montmorillonite composite material, when the strong alkali solution in the step 2) is a sodium hydroxide solution, the concentration of the sodium hydroxide solution is 0.5-2 mol/L; further preferably, the concentration of the sodium hydroxide solution is 0.8-1.5 mol/L; still more preferably, the concentration of the sodium hydroxide solution is 1 mol/L.
Preferably, in the preparation method of the montmorillonite composite material, when the strong alkali solution in the step 2) is a sodium hydroxide solution, the dropping speed of the sodium hydroxide solution added into the mixed solution obtained in the step 1) is 0.1-12 mL/min; further preferably, the dropping speed of the sodium hydroxide solution added into the mixed solution obtained in the step 1) in the step 2) is 0.1-10 mL/min; when the sodium hydroxide solution is added into the mixed solution obtained in the step 1), the dropping speed is 0.1-0.5mL/min when the pH is close to neutral, and when the pH is close to neutral, the dropping speed of the sodium hydroxide solution is too fast, so that the pH is suddenly increased, and precipitates are generated.
Preferably, in the preparation method of the montmorillonite composite material, the aging time in the step 3) is 3-7 h; further preferably, the aging time in the step 3) is 4-6 h; aging is carried out at room temperature.
Preferably, in the preparation method of the montmorillonite composite material, a sodium hydroxide solution is required to be added dropwise in the aging process of the suspension in the step 3); further preferably, the concentration of the sodium hydroxide solution is 0.5-2 mol/L; further preferably, the concentration of the sodium hydroxide solution is 1 mol/L.
Preferably, in the preparation method of the montmorillonite composite material, the pH value of the suspension is 6.5-7.5 when the suspension is coagulated in the step 3); it is further preferred that the pH of the suspension in step 3) is 7.0 when the suspension coagulates.
Preferably, the preparation method of the montmorillonite composite material, step 3), further comprises the steps of freeze drying and grinding the montmorillonite composite material.
The invention also provides application of the montmorillonite composite material in heavy metal adsorption.
Preferably, the montmorillonite composite material is applied to adsorbing at least one of heavy metals of chromium, cadmium, arsenic, lead, copper, zinc, nickel and mercury; further preferably, the montmorillonite composite material is applied to adsorbing at least one of heavy metals of chromium, cadmium, arsenic and lead; still further preferably, the montmorillonite composite material is applied to adsorbing heavy metals of chromium and cadmium.
The invention also provides a method for adsorbing heavy metal by adopting the montmorillonite composite material, which comprises the following steps:
1) mixing the montmorillonite composite material with heavy metal wastewater, and reacting to obtain a mixed solution;
2) separating the mixed liquor in the step 1) to remove solids, thereby realizing the removal of heavy metals in the wastewater.
Preferably, in the method for adsorbing heavy metals by using the montmorillonite composite material, in the step 1), the heavy metal is at least one of chromium, cadmium, arsenic, lead, copper, zinc, nickel and mercury; further preferably, the heavy metal in the step 1) is at least one of chromium, cadmium, arsenic and lead; still further preferably, the heavy metals in step 1) are chromium and cadmium.
Preferably, in the method for adsorbing heavy metal by using the montmorillonite composite material, the mass ratio of the montmorillonite composite material to the heavy metal in the step 1) is 1: (0.01-0.05); further preferably, the mass ratio of the montmorillonite composite material to the heavy metal in the step 1) is 1: (0.02-0.03); still further preferably, the mass ratio of the montmorillonite composite material to the heavy metal in the step 1) is 1: 0.02.
preferably, in the method for adsorbing heavy metal by using the montmorillonite composite material, the concentration of the heavy metal in the heavy metal wastewater in the step 1) is 10-260 mg/L; further preferably, the concentration of the heavy metal in the heavy metal wastewater in the step 1) is 30-80 mg/L; still more preferably, the heavy metal concentration of the heavy metal in step 1) is 50 mg/L.
Preferably, the method for adsorbing heavy metal by the montmorillonite composite material has the advantages that the reaction time in the step 1) is 5-1440 min; further preferably, the reaction time in step 1) is 10 to 1440 min.
Preferably, the method for adsorbing heavy metal by the montmorillonite composite material is that the reaction in the step 1) is carried out under the condition of oscillation or stirring; further preferably, the reaction in step 1) is carried out under shaking conditions.
Preferably, the method for adsorbing heavy metal by the montmorillonite composite material has the advantages that the pH value of the reaction in the step 1) is 3-6; further preferably, the pH of the reaction in step 1) is 4 to 5.
Preferably, in the method for adsorbing heavy metals by the montmorillonite composite material, the separation mode in the step 2) is one of centrifugation and sedimentation; further preferably, the separation in step 2) is performed by centrifugation.
The invention has the beneficial effects that:
(1) the montmorillonite composite material has larger BET specific surface area and multilevel pore structure characteristics, not only retains the pore structure characteristics of montmorillonite, but also has the pore structure characteristics of ferrihydrite; the ferrihydrite particles with positive charges are firmly combined with the montmorillonite particles with negative charges on the layer surface to form a stable montmorillonite composite material; the composite material has the structural characteristics of typical layered structure silicate minerals and ferrihydrite, and ferrihydrite nanoparticles are in a spherical particle structure and are wrapped by montmorillonite sheets.
(2) The montmorillonite composite material prepared by the invention has higher specific surface area and larger pore volume, and the specific surface area can reach 230.6m2The pore volume can reach 0.198cm3The material has higher adsorption capacity to heavy metals, particularly chromium and cadmium, the pore structure distribution of the obtained material is more orderly, and the development of the microporous structure is favorable for the adsorption of the heavy metals.
(3) According to the invention, by adopting a method for synthesizing ferrihydrite, montmorillonite particles are loaded in the ferrihydrite synthesis process, so that the ferrihydrite-loaded montmorillonite composite material is obtained. The material has the advantages that the structure characteristics of montmorillonite are kept, the structure characteristics of the ferrihydrite are also realized, the modification of the pore structure is realized, and a certain effect is realized on the stability of the ferrihydrite. Due to the change of the charge property and the increase of surface groups of the montmorillonite composite material, the montmorillonite composite material has better adsorption effect on anionic heavy metals (such as Cr (VI)) and cationic heavy metals (such as Cd (II)).
(4) The whole synthesis process flow of the montmorillonite composite material is carried out at normal temperature and normal pressure, the energy consumption is low, the adopted process flow and equipment are simple, the operation is convenient, the preparation period is short, the production process cost is low, and the large-scale production is easy; the montmorillonite is a common non-metal mineral resource, is rich in reserves, cheap and easy to obtain, environment-friendly, and free of byproducts such as waste water, waste gas and waste residue which are difficult to control in the implementation process; the montmorillonite composite material is powdery, can be stored in a sealed manner under a dry condition, does not cause any secondary pollution in the preparation process of the composite material, can avoid secondary pollution to the environment while improving the heavy metal adsorption effect, and can be used for solving the problem of heavy metal pollution of water or soil in China.
(5) The montmorillonite composite material has the advantages of high efficiency, low cost, simple and convenient operation and the like, and can be widely used for treating wastewater and soil in a plurality of fields such as tanning, electroplating, metallurgy, pharmacy, ferrochrome smelting, pigment, chromate chemical industry and the like.
Drawings
FIG. 1 is an XRD pattern of a montmorillonite raw material, ferrihydrite and the montmorillonite composite material prepared in example 3;
FIG. 2 is a scanning electron microscope photograph of the montmorillonite composite material prepared in example 3;
FIG. 3 is an infrared spectrum of a montmorillonite raw material, ferrihydrite and the montmorillonite composite material prepared in example 3;
FIG. 4 is a nitrogen isothermal adsorption-desorption graph of the montmorillonite composite prepared in example 3;
FIG. 5 is a Zeta potential diagram of a montmorillonite raw material and a montmorillonite composite material prepared in example 3;
FIG. 6 is a graph showing the adsorption removal of Cr (VI) by the montmorillonite composites prepared in examples 1-3;
FIG. 7 is a graph showing the adsorption removal of Cd (II) by the montmorillonite composite material prepared in example 3-5;
FIG. 8 is a bar graph of the montmorillonite composite material prepared in example 1 used for adsorbing and removing Cr (VI) in contaminated soil.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or equipment used in the examples are, unless otherwise specified, either conventionally commercially available or may be obtained by methods known in the art. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Example 1
The method for preparing the montmorillonite composite material comprises the following steps:
(1) 1.40g of montmorillonite was added to 250mL of FeCl with a concentration of 0.2mol/L3And (3) fully stirring the solution, wherein the initial Fe/montmorillonite mass ratio of the obtained mixed solution is 1: 0.5;
(2) dropwise adding 300mL of NaOH solution with the concentration of 1mol/L into the mixed solution obtained in the step (1) at the speed of 0.5mL/min, and continuously stirring until the pH value is 7.0 to obtain precursor suspension of the composite material;
(3) aging the precursor suspension obtained in the step (2) at room temperature for 4h, and adjusting the pH value to 7.0 by using the NaOH solution obtained in the step (2);
(4) and (4) centrifuging the suspension obtained in the step (3) to obtain a reaction product, namely the montmorillonite composite material, and freeze-drying and storing the montmorillonite composite material.
The specific surface area of the montmorillonite composite material prepared in this example was 230.6m measured by the Brunauer-Emmett-Teller (BET) method2(iv)/g, total pore volume 0.183cm3(iii) the specific surface area of micropores of the montmorillonite composite material was 105.7m2Per g, micropore volume of 0.067cm3/g。
Using potassium dichromate (K)2Cr2O7) As a Cr (VI) source, the Cr (VI) concentrations are respectively 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 100mg/L, 140mg/L, 180mg/L, 220mg/L and 260 mg/L. The montmorillonite composite material is tested for Cr (VI) adsorption capacity by an adsorption experiment under the following experimental conditions: the adsorbent content was 2.5g/L, room temperature, pH 4.5. As a result, the saturated adsorption amount of Cr (VI) by the montmorillonite composite material of the present example was 22.6mg/g at room temperature.
Example 2
The method for preparing the montmorillonite composite material comprises the following steps:
(1) 1.87g of montmorillonite was added to 250mL of FeCl with a concentration of 0.2mol/L3And (3) fully stirring the solution, wherein the initial Fe/montmorillonite mass ratio of the obtained mixed solution is 1.5: 1;
(2) dropwise adding 300mL of NaOH solution with the concentration of 1mol/L into the mixed solution obtained in the step (1) at the speed of 0.5mL/min, and continuously stirring until the pH value is 7.0 to obtain precursor suspension of the composite material;
(3) aging the precursor suspension obtained in the step (2) at room temperature for 4h, and adjusting the pH value to 7.0 by using the NaOH solution obtained in the step (2);
(4) and (4) centrifuging the suspension obtained in the step (3) to obtain a reaction product, namely the montmorillonite composite material, and freeze-drying and storing the montmorillonite composite material.
The specific surface area of the montmorillonite composite prepared in this example was 165.9m measured by the BET method2(ii)/g, total pore volume 0.191cm3/g。
Using potassium dichromate (K)2Cr2O7) As a Cr (VI) source, the Cr (VI) concentrations are respectively 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 100mg/L, 140mg/L, 180mg/L, 220mg/L and 260 mg/L. The montmorillonite composite material is tested for Cr (VI) adsorption capacity by an adsorption experiment under the following experimental conditions: the adsorbent content was 2.5g/L, room temperature, pH 4.5. As a result, the saturated adsorption amount of Cr (VI) by the montmorillonite composite material of the present example was 20.8mg/g at room temperature.
Example 3
The method for preparing the montmorillonite composite material comprises the following steps:
(1) 2.8g of montmorillonite was added to 250mL of FeCl at a concentration of 0.2mol/L3And (3) fully stirring the solution, wherein the initial Fe/montmorillonite mass ratio of the obtained mixed solution is 1: 1;
(2) dropwise adding 300mL of NaOH solution with the concentration of 1mol/L into the mixed solution obtained in the step (1) at the speed of 0.5mL/min, and continuously stirring until the pH value is 7.0 to obtain precursor suspension of the composite material;
(3) aging the precursor suspension obtained in the step (2) at room temperature for 4h, and adjusting the pH value to 7.0 by using the NaOH solution obtained in the step (2);
(4) and (4) centrifuging the suspension obtained in the step (3) to obtain a reaction product, namely the montmorillonite composite material, and freeze-drying and storing the montmorillonite composite material.
The specific surface area of the montmorillonite composite material prepared in this example was 146.6m measured by the BET method2In terms of/g, total pore volume of 0.156cm3/g。
Using potassium dichromate (K)2Cr2O7) As a Cr (VI) source, the Cr (VI) concentrations are respectively 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 100mg/L, 140mg/L, 180mg/L, 220mg/L and 260 mg/L. The montmorillonite composite material is tested for Cr (VI) adsorption capacity by an adsorption experiment under the following experimental conditions: the adsorbent content was 2.5g/L, room temperature, pH 4.5. As a result, the saturated adsorption amount of Cr (VI) to the montmorillonite composite material of the present example was 17.8mg/g at room temperature.
The XRD pattern of the montmorillonite composite material prepared in this example is shown in figure 1, and the d of montmorillonite in the montmorillonite composite material001The value is about 1.29nm, and the pure montmorillonite composite material d001The value is about 1.53nm, and the prior art shows that the montmorillonite loads hydroxyl iron ions d001The value was 1.50. + -. 0.02nm, indicating that the montmorillonite composite prepared in this example had mainly ferric ions and no hydroxyl iron ions in the interlayer region, and had the structural characteristics of typical layered structure silicate minerals and ferrihydrite.
This exampleThe scanning electron microscope image of the prepared montmorillonite composite material is shown in figure 2, and the ferrihydrite nano-particles are in a spherical particle structure and are wrapped by the montmorillonite in a sheet layer. The infrared spectrogram of the montmorillonite composite material prepared in this example is shown in figure 3, the montmorillonite composite material is a mixed phase of ferrihydrite particles wrapping montmorillonite, and the montmorillonite characteristic group Si-O-Si stretching vibration peak (1033 cm) in the mixed phase-1) Si-O-Al stretching vibration peak (519 cm)-1) And Si-O-Si deformation vibration peak (466 cm)-1) Equal cm-1And a hydroxyl group of ferrihydrite structure (3395 cm)-1) Adsorbed water (1618 cm)-1) And (4) waiting for characteristic peaks. Compared with a pure ferrihydrite material, the montmorillonite composite material has the advantages that the characteristic peak of absorbed water is reduced; compared with a pure montmorillonite material, the montmorillonite composite material has the characteristics of the characteristic peaks of ferrihydrite and montmorillonite, and the vibration peak of the structural hydroxyl group is gradually shifted to a low wave number. This is due to the loading of the weakly crystalline ferrihydrite on the surface, which indicates a tight bond between the two phases.
The nitrogen isothermal adsorption-desorption curve of the montmorillonite composite material prepared in the embodiment is shown in the attached figure 4, and it can be seen that the montmorillonite composite material has an obvious H3 type hysteresis loop, and belongs to an IV (a) type isothermal adsorption curve, which shows that the composite material has obvious mesoporous and microporous characteristics, the pore structure distribution of the obtained montmorillonite composite material is more ordered, and the development of the microporous structure is favorable for heavy metal adsorption. FIG. 5 is a Zeta potential diagram of the montmorillonite composite material and the montmorillonite raw material prepared in example 3, and it can be seen from FIG. 5 that pH is in the range of 2-12, the Zeta potential of the montmorillonite raw material is negative, and therefore, the montmorillonite raw material has a strong electrostatic adsorption effect on cationic heavy metals such as Cd, while for the montmorillonite composite material, the Zeta potential is between ferrihydrite and the montmorillonite raw material and gradually approaches a positive value, indicating that the montmorillonite composite material can adsorb anionic heavy metals.
Example 4
The method for preparing the montmorillonite composite material comprises the following steps:
(1) 4.2g of montmorillonite was added to 250mL of FeCl at a concentration of 0.2mol/L3Stirring thoroughly in the solution to obtain the initial Fe/montmorillonite mixed solutionThe mass ratio is 1: 1.5;
(2) dropwise adding 300mL of NaOH solution with the concentration of 1mol/L into the mixed solution obtained in the step (1) at the speed of 0.5mL/min, and continuously stirring until the pH value is 7.0 to obtain precursor suspension of the composite material;
(3) aging the precursor suspension obtained in the step (2) at room temperature for 4h, and adjusting the pH value to 7.0 by using the NaOH solution obtained in the step (2);
(4) and (4) centrifuging the suspension obtained in the step (3) to obtain a reaction product, namely the montmorillonite composite material, and freeze-drying and storing the montmorillonite composite material.
The specific surface area of the montmorillonite composite material prepared in this example was 194.3m measured by the BET method2(iv)/g, total pore volume 0.198cm3/g。
Example 5
The method for preparing the montmorillonite composite material comprises the following steps:
(1) 5.6g of montmorillonite was added to 250mL of FeCl at a concentration of 0.2mol/L3Fully stirring the solution, wherein the initial Fe/montmorillonite mass ratio of the obtained mixed solution is 0.5: 1;
(2) dropwise adding 300mL of NaOH solution with the concentration of 1mol/L into the mixed solution obtained in the step (1) at the speed of 0.5mL/min, and continuously stirring until the pH value is 7.0 to obtain precursor suspension of the composite material;
(3) aging the precursor suspension obtained in the step (2) at room temperature for 4h, and adjusting the pH value to 7.0 by using the NaOH solution obtained in the step (2);
(4) and (4) centrifuging the suspension obtained in the step (3) to obtain a reaction product, namely the montmorillonite composite material, and freeze-drying and storing the montmorillonite composite material.
The specific surface area of the montmorillonite composite prepared in this example was 173.8m measured by the BET method2(ii)/g, total pore volume 0.164cm3/g。
Example 6
The montmorillonite composites prepared in examples 1-3 were subjected to Cr (VI) adsorption experiments.
The specific steps of adsorbing and removing Cr (VI) by the montmorillonite composite material are as follows:
(1) with potassium dichromate (K)2Cr2O7) 300mL of simulated wastewater with a Cr (VI) concentration of 50mg/L and a pH of 4.5 is prepared as a Cr (VI) source.
(2) Weighing 0.10g of the montmorillonite composite material obtained in the examples 1-3, adding the montmorillonite composite material into a 50mL centrifuge tube, adding 40mL of Cr (VI) solution with the initial concentration of 50mg/L, and determining the number of reaction centrifuge tubes to be arranged according to the number of samples and repeated samples;
(3) placing the mixed reaction solution on a horizontal oscillator for oscillation at room temperature;
(4) taking out reaction samples for centrifugation after the reactions are carried out for 5, 10, 60, 180, 360, 720 and 1440min respectively; after the supernatant is diluted by a proper amount, the concentration of heavy metal Cr (VI) ions in the solution is measured by adopting inductively coupled plasma emission spectrometry (ICP-OES), and the removal rate of Cr (VI) in different time is calculated according to the concentration of Cr (VI) ions in the solution before and after adsorption.
FIG. 6 is a graph of the change in Cr (VI) removal rate at different time points. As can be seen from FIG. 6, all three montmorillonite composites can adsorb and remove Cr (VI) in a short time. The Cr (VI) removal rate of Fhy-Mnt-1:0.5 (the mass ratio of Fe/montmorillonite is 1: 0.5) samples in the solution is the highest; at 1440min, the removal rate of Cr (VI) of the montmorillonite composite material prepared by the method 1 reaches 86.3%, the removal rate of Cr (VI) of the montmorillonite composite material prepared by the method 2(Fhy-Mnt-1.5:1) reaches 76.2%, and the removal rate of Cr (VI) of the montmorillonite composite material prepared by the method 3(Fhy-Mnt-1:1) reaches 60.1%.
Example 7
The montmorillonite composites prepared in examples 3-5 were subjected to Cd (II) adsorption experiments.
The method comprises the following steps of (II) adsorbing and removing Cd by the montmorillonite composite material:
(1) cadmium nitrate (Cd (NO)3)2) 300mL of simulated wastewater with a Cd (II) concentration of 50mg/L and a pH of about 4.5 was prepared as a source of Cd (II).
(2) Weighing 0.10g of montmorillonite composite material, adding the montmorillonite composite material into a 50mL centrifuge tube, adding 40mL of Cd (II) solution with the initial concentration of 50mg/L, and determining the number of reaction centrifuge tubes to be arranged according to the number of samples and repeated samples;
(3) placing the mixed reaction solution on a horizontal oscillator for oscillation at room temperature;
(4) after the reaction is carried out for 10 min, 30 min, 60 min, 180 min, 360 min, 960 min and 1440min, three reaction samples are respectively taken out and centrifuged; and (3) after the supernatant is diluted by a proper multiple, determining the concentration of Cd (II) ions in the solution by adopting ICP-OES, and calculating the removal rate of Cd (II) in different time according to the concentration of Cd (II) in the solution before and after adsorption.
FIG. 7 is a graph of the removal rate of Cd (II) at different time points. As can be seen from FIG. 7, all three montmorillonite composites can adsorb and remove Cd (II) in a short time. The removal rate of Cd (II) of Fhy-Mnt-1:1.5 (the mass ratio of Fe to montmorillonite is 1: 1.5) samples in the solution is the highest; at 1440min, the removal rate of Cd (II) of the montmorillonite composite material reaches 68.5%, Fhy-Mnt-0.5:1 (the mass ratio of Fe to montmorillonite is 0.5:1) the removal rate of Cd (II) of the montmorillonite composite material reaches 60.7%, and the removal rate of Cd (II) of the Fhy-Mnt-1:1 (the mass ratio of Fe to montmorillonite is 1:1) of the montmorillonite composite material reaches 55.1%.
Example 8
The montmorillonite composite material prepared in example 1 was used for adsorbing and removing Cr (VI) in contaminated soil, and experimental soil used in this example was soil from Taishan city and county of Taishan city of Guangdong province.
(1) Preparing soil suspension according to the water-soil mass ratio of 10:1, wherein the content of Cr (VI) in the obtained soil suspension is 50 mg/L;
(2) adding the montmorillonite composite material prepared in the example 1 into the soil suspension obtained in the step (1), adding the montmorillonite composite material according to the mass ratio of the montmorillonite composite material to the soil of 1:40, and setting contrast treatment without the montmorillonite composite material;
(3) the mixed reaction system is placed on a horizontal oscillator for 24 hours under the condition of room temperature. After the reaction, the supernatant was diluted by an appropriate factor, and the concentration of Cr (VI) ions in the solution was measured by inductively coupled plasma emission spectrometry (ICP-OES).
FIG. 8 is a graph showing the removal rate of Cr (VI) adsorbed on the soil from the montmorillonite composite, and it can be seen from the content of Cr (VI) in the soil before and after the treatment with the montmorillonite composite that the removal rate of Cr (VI) in the soil after the treatment with the montmorillonite composite is 30.5% higher than that of the control without the montmorillonite composite. From the above results, it is understood that the montmorillonite composite material of the present invention can effectively reduce the content of cr (vi) in soil.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-described preferred embodiment should not be construed as limiting the present invention. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. A montmorillonite composite material, characterized in that the montmorillonite composite material comprises montmorillonite and ferrihydrite; the ferrihydrite is dispersed on the outer surface of the montmorillonite.
2. The montmorillonite composite material as claimed in claim 1, wherein the specific surface area of the montmorillonite composite material is not less than 146.6m2/g。
3. The montmorillonite composite material according to claim 1, wherein the total pore volume of the montmorillonite composite material is not less than 0.156cm3/g。
4. The montmorillonite composite material according to claim 1, wherein the cation exchange capacity of montmorillonite is not less than 90 mmoL/g.
5. The method for producing a montmorillonite composite material as claimed in any one of claims 1 to 4, characterized by comprising the steps of:
1) mixing the iron source solution and the montmorillonite solution to obtain a mixed solution;
2) adding a strong base solution into the mixed solution obtained in the step 1) to obtain a suspension;
3) aging the suspension obtained in the step 2), and coagulating and separating the suspension to obtain the montmorillonite composite material.
6. The method for producing a montmorillonite composite material according to claim 5, wherein the iron source in step 1) is at least one of ferric chloride or ferric nitrate.
7. The method for producing a montmorillonite composite material according to claim 5, wherein the mass ratio of Fe to montmorillonite in the iron source solution in step 1) is (0.5-3): 1.
8. the method for producing a montmorillonite composite material according to claim 5, characterized in that the pH value at which the suspension is obtained in step 2) is 6.5 to 7.5.
9. The method for producing a montmorillonite composite according to claim 5, characterized in that the aging time in step 3) is 3-7 h.
10. Use of the montmorillonite composite of any one of claims 1-4 in adsorbing heavy metals.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111066836.8A CN113797886A (en) | 2021-09-13 | 2021-09-13 | Montmorillonite composite material and application thereof in heavy metal adsorption |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111066836.8A CN113797886A (en) | 2021-09-13 | 2021-09-13 | Montmorillonite composite material and application thereof in heavy metal adsorption |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113797886A true CN113797886A (en) | 2021-12-17 |
Family
ID=78895154
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111066836.8A Pending CN113797886A (en) | 2021-09-13 | 2021-09-13 | Montmorillonite composite material and application thereof in heavy metal adsorption |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113797886A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114774130A (en) * | 2022-04-15 | 2022-07-22 | 哈尔滨工业大学 | Modified clay mineral for repairing arsenic-lead-antimony composite contaminated soil and preparation method and application thereof |
CN115739012A (en) * | 2022-10-28 | 2023-03-07 | 湖南大学 | Silica ferrihydrite coated halloysite nanotube composite adsorbent and preparation method and application thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1369437A (en) * | 2002-03-18 | 2002-09-18 | 浙江大学 | Process for preparing Fe-modified montmorillonite used to remove phosphorus and nitrous-state nitrogen from culturing water |
CN101215041A (en) * | 2008-01-14 | 2008-07-09 | 中国科学院广州地球化学研究所 | Method for treating Cr6+ in waste water and method for preparing montmorillonite-base nano magnetite used thereof |
CN105771880A (en) * | 2015-12-25 | 2016-07-20 | 武汉理工大学 | Iron oxyhydroxide supported montmorillonite adsorption and catalysis double-function material and preparation method thereof |
CN110125161A (en) * | 2019-04-30 | 2019-08-16 | 湖南大学 | A kind of heavy metal soil-repairing agent and method cooperateing with compost based on magnesia-montmorillonite composite material |
US20190352196A1 (en) * | 2016-10-28 | 2019-11-21 | Qatar Foundation For Education, Science And Community Development | Method for adsorption of toxic contaminants from water |
CN113368856A (en) * | 2021-06-03 | 2021-09-10 | 华南师范大学 | Preparation method and application of iron pillared montmorillonite composite catalyst |
-
2021
- 2021-09-13 CN CN202111066836.8A patent/CN113797886A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1369437A (en) * | 2002-03-18 | 2002-09-18 | 浙江大学 | Process for preparing Fe-modified montmorillonite used to remove phosphorus and nitrous-state nitrogen from culturing water |
CN101215041A (en) * | 2008-01-14 | 2008-07-09 | 中国科学院广州地球化学研究所 | Method for treating Cr6+ in waste water and method for preparing montmorillonite-base nano magnetite used thereof |
CN105771880A (en) * | 2015-12-25 | 2016-07-20 | 武汉理工大学 | Iron oxyhydroxide supported montmorillonite adsorption and catalysis double-function material and preparation method thereof |
US20190352196A1 (en) * | 2016-10-28 | 2019-11-21 | Qatar Foundation For Education, Science And Community Development | Method for adsorption of toxic contaminants from water |
CN110125161A (en) * | 2019-04-30 | 2019-08-16 | 湖南大学 | A kind of heavy metal soil-repairing agent and method cooperateing with compost based on magnesia-montmorillonite composite material |
CN113368856A (en) * | 2021-06-03 | 2021-09-10 | 华南师范大学 | Preparation method and application of iron pillared montmorillonite composite catalyst |
Non-Patent Citations (4)
Title |
---|
HENRIK GREEN-PEDERSEN等: "Preparation, characterization, and sorption properties for Ni(II) of iron oxyhydroxide–montmorillonite", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》, vol. 168, pages 133 * |
大井健太: "《无机离子交换材料》", vol. 1, 上海科学技术出版社, pages: 175 * |
姜浩等: "低聚合羟基铁离子-蒙脱石复合体吸附砷的实验研究", 《地球化学》, vol. 31, no. 6, pages 593 - 601 * |
杨彩虹等: "二元体系中水铁矿对Cd( Ⅱ) 和Zn( Ⅱ) 的吸附作用", 《环境化学》, vol. 32, no. 10, pages 1924 - 1930 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114774130A (en) * | 2022-04-15 | 2022-07-22 | 哈尔滨工业大学 | Modified clay mineral for repairing arsenic-lead-antimony composite contaminated soil and preparation method and application thereof |
CN115739012A (en) * | 2022-10-28 | 2023-03-07 | 湖南大学 | Silica ferrihydrite coated halloysite nanotube composite adsorbent and preparation method and application thereof |
CN115739012B (en) * | 2022-10-28 | 2024-04-16 | 湖南大学 | Siliceous ferrihydrite coated halloysite nanotube composite adsorbent and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Enhancement of As (V) adsorption from aqueous solution by a magnetic chitosan/biochar composite | |
Tang et al. | A novel two-dimensional accordion-like titanium carbide (MXene) for adsorption of Cr (VI) from aqueous solution | |
Yang et al. | Simultaneous reductive and sorptive removal of Cr (VI) by activated carbon supported β-FeOOH | |
Jiang et al. | Phosphate adsorption from wastewater using ZnAl-LDO-loaded modified banana straw biochar | |
Yan et al. | High U (VI) adsorption capacity by mesoporous Mg (OH) 2 deriving from MgO hydrolysis | |
Shao et al. | Polypyrrole/bacterial cellulose nanofiber composites for hexavalent chromium removal | |
CN113797886A (en) | Montmorillonite composite material and application thereof in heavy metal adsorption | |
Zhao et al. | Adsorption of Cu (II) by phosphogypsum modified with sodium dodecyl benzene sulfonate | |
Li et al. | The synthesis and characterization of hydrous cerium oxide nanoparticles loaded on porous silica micro-sphere as novel and efficient adsorbents to remove phosphate radicals from water | |
Yu et al. | Removal of methylene blue over low-cost mesoporous silica nanoparticles prepared with naturally occurring diatomite | |
Guo et al. | Synthesis and application of 8-hydroxyquinoline modified magnetic mesoporous carbon for adsorption of multivariate metal ions from aqueous solutions | |
Zhang et al. | Characterization of La–Mg-modified palygorskite and its adsorption of phosphate | |
Zhu et al. | Co-sorption of Cd and phosphate on the surface of a synthetic hydroxyiron-montmorillonite complex | |
Zhou et al. | Development of polymeric iron/zirconium-pillared clinoptilolite for simultaneous removal of multiple inorganic contaminants from wastewater | |
CN114425340B (en) | Preparation of biochar modified cobalt-iron bimetallic composite catalyst and application of biochar modified cobalt-iron bimetallic composite catalyst in catalytic degradation of tetracycline | |
CN114797783B (en) | Adsorbent for selectively removing Cr (VI) and preparation method and application thereof | |
Zhang et al. | Low-price MnO 2 loaded sepiolite for Cd 2+ capture | |
Xu et al. | Preparation of magnetic kaolinite nanotubes for the removal of methylene blue from aqueous solution | |
Lu et al. | Zeolite X/chitosan hybrid microspheres and their adsorption properties for Cu (II) ions in aqueous solutions | |
Peng et al. | A study of adsorption behaviour of Cu (II) on hydroxyapatite-coated-limestone/chitosan composite | |
Dai et al. | Synthesis of MgAl-LDH@ ZIF-8 composites by in situ growth method for highly efficient phosphate removal | |
Wang et al. | Adsorption of metal and metalloid ions onto nanoporous microparticles functionalized by atomic layer deposition | |
Xu et al. | Preparation of MnO2–Al2O3 adsorbent with large specific surface area for fluoride removal | |
Wang et al. | Facile synthesis of novel 3D flower-like magnetic La@ Fe/C composites from ilmenite for efficient phosphate removal from aqueous solution | |
Nascimento et al. | On the adsorption of neodymium species from aqueous solution by beneficiated palygorskite |
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 |