CN113000015A - Preparation method and dephosphorization application of attapulgite-periclase-based hydrotalcite - Google Patents
Preparation method and dephosphorization application of attapulgite-periclase-based hydrotalcite Download PDFInfo
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- CN113000015A CN113000015A CN202110262378.9A CN202110262378A CN113000015A CN 113000015 A CN113000015 A CN 113000015A CN 202110262378 A CN202110262378 A CN 202110262378A CN 113000015 A CN113000015 A CN 113000015A
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- attapulgite
- periclase
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 85
- 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 75
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 75
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 49
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 29
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000010452 phosphate Substances 0.000 claims abstract description 27
- 229960000892 attapulgite Drugs 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 20
- 235000012245 magnesium oxide Nutrition 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 150000001450 anions Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004021 humic acid Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 55
- 235000021317 phosphate Nutrition 0.000 claims description 27
- 239000006228 supernatant Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002860 competitive effect Effects 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000000523 sample Substances 0.000 description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/22—Magnesium silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a preparation method of attapulgite-periclase-based hydrotalcite, which comprises the following steps: s1: and uniformly mixing the periclase and the attapulgite to obtain a mixed sample. S2: adding HNO into the mixed sample3The solution is dissolved. S3: adding alkali liquor into the dissolved solution, and adjusting the pH value. S4: urea is added to the solution obtained in step S3 to obtain a mixed solution. S5: carrying out hydrothermal reaction on the mixed solution, and drying the precipitate obtained after the reactionAnd drying to obtain the PP-LDH. S6: and roasting the PP-LDH to obtain the PP-LDO. The phosphate capture capacity of the attapulgite-periclase hydrotalcite PP-LDO prepared by the invention can reach 448.58mg P/g, which is 10 times higher than that of the traditional magnesium-aluminum hydrotalcite. In addition, the attapulgite-periclase hydrotalcite PP-LDO has high phosphate removal rate in a mixed solution containing competitive anions and humic acid, can meet increasingly strict wastewater discharge standards, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a preparation method of attapulgite-periclase-based hydrotalcite and a dephosphorization application thereof.
Background
Eutrophication of aquatic ecosystems is a global environmental pollution problem that can cause the flowering of dangerous aquatic plants and the consumption of dissolved oxygen, seriously affecting the survival of aquatic organisms and the safety of drinking water supply. In order to cope with increasingly stringent phosphorus load control requirements and increasingly diminishing phosphorus sources, it is highly desirable to develop efficient phosphorus removal strategies and to recover phosphorus as a complete process for sewage treatment plants.
The adsorption process is considered to be an advanced technology, can realize high-grade phosphorus removal even in a solution with extremely low concentration, and has the characteristics of simple operation and economy. Furthermore, it is generally considered a viable option for achieving synergistic removal and recovery of phosphorus. In the prior art, various types of solid adsorbents have been developed to remove phosphates, such as polymeric anion exchangers, zeolites, activated alumina, hydrous iron oxides, steel slag, and the like. However, these materials often capture phosphorus through strong precipitation interactions, increasing the technical difficulty of efficiently recovering phosphorus. Most phosphorus-containing species are recovered by displacement of phosphorus using high-caustic, high-salt regenerants, which results in additional expense and a large waste stream. In view of the major drawbacks in current practice, the development of effective wastewater phosphorus synergistic capture and resource materials has become an urgent need.
Attapulgite (Palygorskite), also known as Palygorskite, is an aquifer chain magnesiosilicate mineral, the crystal microstructure of which is acicular, fibrous or fibrous aggregate, belongs to the sepiolite family in mineralogical classification, and has a unique nanorod crystal structure, so that the attapulgite has high specific surface area and porosity. In addition, the crystal structure of the attapulgite is often doped with a certain amount of metal components such as calcium, magnesium and the like according to different geological conditions of a producing area besides metal elements such as magnesium and aluminum, so that the attapulgite has the potential of forming surface precipitates with phosphate in water.
Hydrotalcite or hydrotalcite-like compounds (LDHs) are a class of anionic materials having brucite-like layered structures, consisting of divalent and trivalent metal cation hydroxides in a two-dimensional layered structure with a large number of exchangeable anions between the layers, which are capable of ion-exchanging with many anionic contaminants in water, so that the anionic contaminants are removed from the water by entering between the layers of the hydrotalcite or hydrotalcite-like compound, and thus the hydrotalcite or hydrotalcite-like compound is very suitable as an anionic adsorbent material in water. In addition, the hydrotalcite or hydrotalcite-like compound has good thermal stability and unique memory effect. However, when the hydrotalcite or hydrotalcite-like compound is calcined at a too high temperature, the crystal structure of the hydrotalcite or hydrotalcite-like compound is irreversibly damaged, and the crystal structure recombination cannot be realized by utilizing the memory effect.
At present, in order to improve the adsorption capacity of the material, the research in the prior art adopts a method of excessively increasing the loading capacity of the exogenous metal active component, which causes a great amount of consumption of chemical agents and greatly increases the synthesis cost of the material. However, based on the deep analysis of the structural composition characteristics of the mineral material, the research of fully utilizing the self metal components and characteristic structures of the mineral material and organically combining with the exogenous active groups is still quite lacking. In addition, the synthesis of hydrotalcite materials requires a certain ratio of divalent to trivalent metal ions and ensures stable nucleation and growth of crystals in the synthesis system. At present, the preparation conditions of the hydrotalcite synthesized by applying natural minerals are not clear, and the research on the removal of phosphate in water is more rarely reported.
Disclosure of Invention
Technical problem to be solved
The invention provides a preparation method of attapulgite-periclase-based hydrotalcite, aiming at solving the problems that the metal components and the characteristic structures of mineral materials are not fully utilized, the preparation conditions of synthesizing the hydrotalcite by using natural minerals are not clear, and the pollutant adsorption capacity is low in the prior art. In order to solve the problems, the invention also provides a dephosphorization application of the attapulgite-periclase-based hydrotalcite
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a preparation method of attapulgite-periclase-based hydrotalcite comprises the following steps:
s1, preparing a mixed sample: uniformly mixing periclase and attapulgite to obtain a mixed sample;
s2, dissolving and mixing a sample: adding HNO into the mixed sample obtained in the step S13Dissolving the solution;
s3, adjusting pH: adding alkali liquor into the dissolved solution obtained in the step S2, and adjusting the pH value;
s4, adding urea: adding urea into the solution obtained in the step S3 to obtain a mixed solution;
s5, hydrothermal reaction: carrying out hydrothermal reaction on the mixed solution obtained in the step S4, and drying a precipitate obtained after the reaction to obtain an attapulgite-periclase based hydrotalcite material PP-LDH;
s6, roasting: and roasting the attapulgite-periclase based hydrotalcite material PP-LDH obtained in the step S5 to obtain a roasted product PP-LDO of the attapulgite-periclase based hydrotalcite material.
In the preparation method described above, preferably, in step S1, the mass ratio of periclase to attapulgite is 1: 1-4: 1.
in the preparation method described above, preferably, in step S2, HNO with a mass fraction of 10% to 20% is added to the mixed sample obtained in step S13And stirring the solution for 2-5 hours under the water bath condition at the temperature of 70-100 ℃.
In the preparation method described above, preferably, in step S3, the mixed sample dissolved in step S1 is centrifuged to extract a supernatant, and the pH of the supernatant is adjusted to 3.0 to 4.0 using 0.5mol/L NaOH or KOH solution.
In the preparation method described above, preferably, in step S4, CO is continuously introduced into the solution at a rate of 50mL/min2And keeping for more than 20min, and then adding urea into the solution.
In the preparation method, preferably, in step S5, the mixed solution is transferred to a polytetrafluoroethylene reaction kettle, and undergoes hydrothermal reaction at 100-120 ℃ for 24-48 h; and centrifuging the solution after reaction, pouring out supernatant, washing the precipitate with deionized water, and drying the precipitate in a thermostat at 60-80 ℃.
In the preparation method, preferably, in step S6, the attapulgite-periclase-based hydrotalcite material PP-LDH obtained in step S5 is calcined at a high temperature of 300-500 ℃ for 2-6 hours to obtain a calcined product PP-LDO of the attapulgite-periclase-based hydrotalcite material.
The invention also provides an application of the attapulgite-periclase-based hydrotalcite material prepared by the preparation method, and the attapulgite-periclase-based hydrotalcite material is used for adsorbing phosphate.
Use as described above, preferably the attapulgite-periclase-based hydrotalcite material is used for adsorbing phosphate in a mixed environment competing for anions and humic acid;
the competing anion comprises SO4 2-、NO3 -、HCO3 -And Cl-。
(III) advantageous effects
The invention has the beneficial effects that:
the attapulgite-periclase hydrotalcite PP-LDO prepared by the preparation method of the invention has good phosphate capture capacity which can reach 448.58mg P/g and is 10 times higher than the phosphate adsorption capacity of the traditional magnesium-aluminum hydrotalcite. In addition, the attapulgite-periclase hydrotalcite PP-LDO material has high phosphate removal rate in a mixed solution containing competitive anions and humic acid, can meet increasingly strict wastewater discharge standards, and has good application prospect as an economic and effective adsorbent.
Drawings
FIG. 1 is a scanning electron micrograph of PLDH, PP-LDH and PP-LDO according to the present invention;
FIG. 1a is a scanning electron micrograph of a PLDH according to the invention;
FIG. 1b is a scanning electron micrograph of PP-LDH according to the present invention;
FIG. 1c is a scanning electron micrograph of a PP-LDO according to the present invention;
FIG. 2 is an X-ray diffraction diagram of periclase, attapulgite and attapulgite-periclase composite material (in the diagram, the Diagram represents Mg)0.72Al0.28(CO3)0.15(OH)1.980.48H2O, where O stands for brucite, ● for MgO);
FIG. 3 is a graph comparing the phosphate adsorption capacity of the natural periclase, attapulgite-periclase composite material of the present invention;
FIG. 4 is a plot of phosphate adsorption isotherms and Langmuir, Freundlich, Sims model fit for PLDH, PP-LDH and PP-LDO according to the present invention.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The embodiment of the invention provides a preparation method of attapulgite-periclase-based hydrotalcite, which comprises the following steps:
s1, preparing a mixed sample: and uniformly mixing the periclase and the attapulgite to obtain a mixed sample.
S2, dissolving and mixing a sample: adding HNO into the mixed sample obtained in the step S13The solution is dissolved.
S3, adjusting pH: adding an alkali solution to the dissolved solution obtained in step S2, and adjusting the pH.
S4, adding urea: urea is added to the solution obtained in step S3 to obtain a mixed solution.
S5, hydrothermal reaction: and (4) carrying out hydrothermal reaction on the mixed solution obtained in the step S4, and drying the precipitate obtained after the reaction to obtain the attapulgite-periclase-based hydrotalcite material PP-LDH.
S6, roasting: and roasting the attapulgite-periclase based hydrotalcite material PP-LDH obtained in the step S5 to obtain a roasted product PP-LDO of the attapulgite-periclase based hydrotalcite material.
The attapulgite-periclase hydrotalcite PP-LDO prepared by the preparation method of the embodiment of the invention has good phosphate capture capacity, wherein the capture capacity can reach 448.58mg P/g, which is 10 times higher than that of the traditional magnesium-aluminum hydrotalcite. In addition, the attapulgite-periclase hydrotalcite PP-LDO material has high phosphate removal rate in a mixed solution containing competitive anions and humic acid, can meet increasingly strict wastewater discharge standards, and has good application prospect as an economic and effective adsorbent.
Preferably, in step S1, the mass ratio of periclase to attapulgite is 1: 1-4: 1.
preferably, in step S2, HNO with the mass fraction of 10% -20% is added to the mixed sample obtained in step S13And stirring the solution for 2-5 hours under the water bath condition at the temperature of 70-100 ℃.
Preferably, in step S3, the mixed sample dissolved in step S1 is centrifuged to extract a supernatant, and the pH of the supernatant is adjusted to 3.0 to 4.0 using 0.5mol/L NaOH or KOH solution.
Preferably, in step S4, CO is continuously introduced into the solution at a rate of 50mL/min2And keeping for more than 20min, and then adding urea into the solution. CO introduced into the solution2React with water to form CO3 2-，CO3 2-Is an interlayer anion required for LDH synthesis. The addition of urea can provide an alkaline environment required by synthesis of LDH layered double hydroxide, and in the prior art, the alkaline environment is adjusted by directly adding NaOH alkali liquor, so that the pH value in the method system is not uniform, and the problem of nonuniform LDH nucleation can be caused. The urea can slowly release alkalescent ammonia and water under the heating condition, can provide a mild acid-base environment, and is more favorable for the crystallization nucleation of the LDH.
Preferably, in step S5, the mixed solution is transferred to a polytetrafluoroethylene reaction kettle, and undergoes hydrothermal reaction at 100-120 ℃ for 24-48 h. And centrifuging the solution after reaction, pouring out supernatant, washing the precipitate with deionized water, and drying the precipitate in a thermostat at 60-80 ℃.
Preferably, in step S6, the attapulgite-periclase based hydrotalcite material PP-LDH obtained in step S5 is roasted at a high temperature of 300-500 ℃ for 2-6 hours to obtain a roasted product PP-LDO of the attapulgite-periclase based hydrotalcite material.
The embodiment of the invention also provides an application of the attapulgite-periclase-based hydrotalcite material prepared by the preparation method, and the attapulgite-periclase-based hydrotalcite material is used for adsorbing phosphate.
Preferably, the capturing capacity of the attapulgite-periclase-based hydrotalcite material to phosphate is 448.58mg P/g at most.
Preferably, the attapulgite-periclase-based hydrotalcite material is used for adsorbing phosphate in a mixed environment competing for anions and humic acid. The competing anion comprises SO4 2-、NO3 -、HCO3 -And Cl-。
Example 1
The embodiment of the invention provides a preparation method of attapulgite-periclase-based hydrotalcite, which comprises the following steps:
s1, preparing a mixed sample: mixing periclase and attapulgite according to the weight ratio of 1: 1, 10g of the mixture was mixed and homogenized to obtain a mixed sample.
S2, dissolving and mixing a sample: the mixed sample obtained in step S1 was dissolved in 100ml of HNO having a mass fraction of 15%3The solution was stirred at 100 ℃ water bath temperature for 2 h.
S3, adjusting pH: centrifuging the solution obtained in the step S2 at the rotation speed of 5000rpm for 5min, then extracting a supernatant, and dropwise and slowly adding a NaOH solution with the concentration of 0.5mol/L into the supernatant under the stirring condition until the pH value of the supernatant reaches 4.0.
S4, adding urea: introducing CO into the solution obtained in the step S3 at a rate of 50mL/min2And after 2 hours, adding 0.5mol of urea into the solution to obtain a mixed solution.
S5, hydrothermal reaction: and (4) transferring the mixed solution obtained in the step S4 to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, and reacting at the temperature of 105 ℃ for 24 hours. And after the hydrothermal reaction is finished, centrifuging, pouring out supernatant, washing the precipitate for 6 times by using deionized water, and drying in a constant temperature oven at 60 ℃ for 12 hours to obtain the attapulgite-periclase-based hydrotalcite material named as PP-LDH-1.
S6, roasting: and (4) roasting the PP-LDH-1 obtained in the step (S5) at the high temperature of 400 ℃ for 4 hours to obtain a roasted product of the attapulgite-periclase based hydrotalcite material, which is named as PP-LDO-1.
Example 2
The embodiment of the invention provides a preparation method of attapulgite-periclase-based hydrotalcite, which comprises the following steps:
s1, preparing a mixed sample: mixing periclase and attapulgite according to the weight ratio of 2: 1, 10g of the mixture was mixed and homogenized to obtain a mixed sample.
S2, dissolving and mixing a sample: the mixed sample obtained in step S1 was dissolved in 100ml of HNO having a mass fraction of 15%3The solution was stirred at 100 ℃ water bath temperature for 2 h.
S3, adjusting pH: centrifuging the solution obtained in the step S2 at the rotation speed of 5000rpm for 5min, then extracting a supernatant, and dropwise and slowly adding a NaOH solution with the concentration of 0.5mol/L into the supernatant under the stirring condition until the pH value of the supernatant reaches 4.0.
S4, adding urea: introducing CO into the solution obtained in the step S3 at a rate of 50mL/min2And after 2 hours, adding 0.5mol of urea into the solution to obtain a mixed solution.
S5, hydrothermal reaction: and (4) transferring the mixed solution obtained in the step S4 to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, and reacting at the temperature of 105 ℃ for 24 hours. And after the hydrothermal reaction is finished, centrifuging, pouring out supernatant, washing the precipitate for 6 times by using deionized water, and drying in a constant temperature oven at 60 ℃ for 12 hours to obtain the attapulgite-periclase-based hydrotalcite material named as PP-LDH-2.
S6, roasting: and (4) roasting the PP-LDH-2 obtained in the step (S5) at the high temperature of 400 ℃ for 4 hours to obtain a roasted product of the attapulgite-periclase based hydrotalcite material, which is named as PP-LDO-2. The attapulgite-periclase-based hydrotalcite prepared by the preparation method of the embodiment of the invention has the strongest adsorption capacity on phosphate, so that the embodiment is the best embodiment.
Example 3
The embodiment of the invention provides a preparation method of attapulgite-periclase-based hydrotalcite, which comprises the following steps:
s1, preparing a mixed sample: mixing periclase and attapulgite according to the weight ratio of 3: 1, 10g of the mixture was mixed and homogenized to obtain a mixed sample.
S2, dissolving and mixing a sample: the mixed sample obtained in step S1 was dissolved in 100ml of HNO having a mass fraction of 15%3The solution was stirred at 100 ℃ water bath temperature for 2 h.
S3, adjusting pH: centrifuging the solution obtained in the step S2 at the rotation speed of 5000rpm for 5min, then extracting a supernatant, and dropwise and slowly adding a NaOH solution with the concentration of 0.5mol/L into the supernatant under the stirring condition until the pH value of the supernatant reaches 4.0.
S4, adding urea: introducing CO into the solution obtained in the step S3 at a rate of 50mL/min2And after 2 hours, adding 0.5mol of urea into the solution to obtain a mixed solution.
S5, hydrothermal reaction: and (4) transferring the mixed solution obtained in the step S4 to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, and reacting at the temperature of 105 ℃ for 24 hours. And after the hydrothermal reaction is finished, centrifuging, pouring out supernatant, washing the precipitate for 6 times by using deionized water, and drying in a constant temperature oven at 60 ℃ for 12 hours to obtain the attapulgite-periclase-based hydrotalcite material named as PP-LDH-3.
S6, roasting: and (4) roasting the PP-LDH-3 obtained in the step (S5) at the high temperature of 400 ℃ for 4 hours to obtain a roasted product of the attapulgite-periclase based hydrotalcite material, which is named as PP-LDO-3.
Example 4
The embodiment of the invention provides a preparation method of attapulgite-periclase-based hydrotalcite, which comprises the following steps:
s1, preparing a mixed sample: mixing periclase and attapulgite according to the weight ratio of 4: 1, 10g of the mixture was mixed and homogenized to obtain a mixed sample.
S2, dissolving and mixing a sample: the mixed sample obtained in step S1 was dissolved in 100ml of HNO having a mass fraction of 15%3In solutionStirring for 2h at the water bath temperature of 100 ℃.
S3, adjusting pH: centrifuging the solution obtained in the step S2 at the rotation speed of 5000rpm for 5min, then extracting a supernatant, and dropwise and slowly adding a NaOH solution with the concentration of 0.5mol/L into the supernatant under the stirring condition until the pH value of the supernatant reaches 4.0.
S4, adding urea: introducing CO into the solution obtained in the step S3 at a rate of 50mL/min2And after 2 hours, adding 0.5mol of urea into the solution to obtain a mixed solution.
S5, hydrothermal reaction: and (4) transferring the mixed solution obtained in the step S4 to a polytetrafluoroethylene reaction kettle for hydrothermal reaction, and reacting at the temperature of 105 ℃ for 24 hours. And after the hydrothermal reaction is finished, centrifuging, pouring out supernatant, washing the precipitate for 6 times by using deionized water, and drying in a constant temperature oven at 60 ℃ for 12 hours to obtain the attapulgite-periclase-based hydrotalcite material named as PP-LDH-4.
S6, roasting: and (4) roasting the PP-LDH-4 obtained in the step (S5) at the high temperature of 400 ℃ for 4 hours to obtain a roasted product of the attapulgite-periclase based hydrotalcite material, which is named as PP-LDO-4.
Comparative example 1
In this comparative example, a control sample was prepared using only 10g of attapulgite, without the addition of periclase, in the same manner as in examples 1-4, and the product obtained was designated as PLDH.
The microscopic morphology of the attapulgite (PLDH), the attapulgite-periclase-based hydrotalcite material (PP-LDH) and the attapulgite-periclase-based hydrotalcite calcined material (PP-LDO) in example 2 of the present invention was studied by using a field emission scanning electron microscope, and the results are shown in fig. 1, and it can be known from fig. 1b that the PP-LDH is a layered double hydroxide composite material. XRD diffraction patterns of the attapulgite (PLDH), the attapulgite-periclase-based hydrotalcite material (PP-LDH) and the attapulgite-periclase-based hydrotalcite calcined material (PP-LDO) in the embodiment 2 are shown in figure 2. The attapulgite-periclase-based hydrotalcite material (PP-LDH-X), the natural periclase and the attapulgite which are prepared according to different proportions are used for adsorbing phosphate, and the phosphate adsorption capacity of the natural periclase, the attapulgite and the attapulgite-periclase composite material shown in figure 3 is obtained by comparing the phosphate adsorption capacity of the natural periclase, the attapulgite and the attapulgite according to the ratio of 4: 1, the attapulgite-periclase composite material prepared by the method has the highest phosphate removal rate. In addition, the compound prepared in example 2 according to 2: the attapulgite-periclase-based hydrotalcite material (PP-LDH-2) prepared in the step 1, a roasted material (PP-LDO-2) thereof and a control sample (PLDH) prepared only by using the attapulgite are used for isothermal phosphate adsorption, phosphate adsorption isotherms and relevant model fitting curves of the PLDH, the PP-LDH and the PP-LDO shown in a figure 4 are obtained by comparison, and the phosphate removal rate of the attapulgite-periclase-based hydrotalcite material (PP-LDH-2) by using the adsorbent in the example 2 is obviously improved compared with other adsorbents.
Tests prove that the attapulgite-periclase-based hydrotalcite material has the mass ratio of the periclase to the attapulgite of 2: the PP-LDH and the calcined derivative PP-LDO synthesized in the 1 st stage show good phosphate capture capacity which is 229.39mg P/g and 448.58mg P/g respectively, and the hydrochloric acid capture capacity of the PP-LDO is 10 times higher than that of the traditional magnesium-aluminum hydrotalcite with the same mass. In addition, the attapulgite-periclase hydrotalcite material prepared by the invention also has higher phosphate removal rate in a mixed solution containing competitive anions and humic acid, can meet increasingly strict discharge standards, and has wider development prospect.
The above embodiments are merely illustrative, and not restrictive, of the scope of the invention, and those skilled in the art will be able to make various changes and modifications within the scope of the appended claims without departing from the spirit of the invention.
Claims (9)
1. A preparation method of attapulgite-periclase-based hydrotalcite is characterized by comprising the following steps:
s1, preparing a mixed sample: uniformly mixing periclase and attapulgite to obtain a mixed sample;
s2, dissolving and mixing a sample: adding HNO into the mixed sample obtained in the step S13Dissolving the solution;
s3, adjusting pH: adding alkali liquor into the dissolved solution obtained in the step S2, and adjusting the pH value;
s4, adding urea: adding urea into the solution obtained in the step S3 to obtain a mixed solution;
s5, hydrothermal reaction: carrying out hydrothermal reaction on the mixed solution obtained in the step S4, and drying a precipitate obtained after the reaction to obtain an attapulgite-periclase based hydrotalcite material PP-LDH;
s6, roasting: and roasting the attapulgite-periclase based hydrotalcite material PP-LDH obtained in the step S5 to obtain a roasted product PP-LDO of the attapulgite-periclase based hydrotalcite material.
2. The preparation method according to claim 1, wherein in the step S1, the mass ratio of periclase to attapulgite is 1: 1-4: 1.
3. the method according to claim 1, wherein in step S2, HNO is added to the mixed sample obtained in step S1 in an amount of 10-20 wt%3And stirring the solution for 2-5 hours under the water bath condition at the temperature of 70-100 ℃.
4. The method according to claim 1, wherein in step S3, the mixed sample obtained by dissolving in step S1 is centrifuged to extract a supernatant, and the pH of the supernatant is adjusted to 3.0 to 4.0 with 0.5mol/L NaOH or KOH solution.
5. The method of claim 1, wherein in step S4, CO is continuously introduced into the solution at a rate of 50mL/min2And keeping for more than 20min, and then adding urea into the solution.
6. The preparation method according to claim 1, wherein in step S5, the mixed solution is transferred to a polytetrafluoroethylene reaction kettle and undergoes hydrothermal reaction at 100-120 ℃ for 24-48 h; and centrifuging the solution after reaction, pouring out supernatant, washing the precipitate with deionized water, and drying the precipitate in a thermostat at 60-80 ℃.
7. The preparation method of claim 1, wherein in step S6, the attapulgite-periclase-based hydrotalcite material PP-LDH obtained in step S5 is calcined at a high temperature of 300-500 ℃ for 2-6 h to obtain a calcined product PP-LDO of the attapulgite-periclase-based hydrotalcite material.
8. The application of the attapulgite-periclase-based hydrotalcite material prepared by the preparation method of any one of claims 1 to 7, wherein the attapulgite-periclase-based hydrotalcite material is used for adsorbing phosphate.
9. Use according to claim 8, wherein the attapulgite-periclase-based hydrotalcite material is used for adsorbing phosphates in a mixed environment competing for anions and humic acid;
the competing anion comprises SO4 2-、NO3 -、HCO3 -And Cl-。
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