CN109336075B - Preparation method of porous titanium hydrogen phosphate material, obtained product and application - Google Patents
Preparation method of porous titanium hydrogen phosphate material, obtained product and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 51
- JWFYORYPRRVBPH-UHFFFAOYSA-J hydrogen phosphate;titanium(4+) Chemical compound [Ti+4].OP([O-])([O-])=O.OP([O-])([O-])=O JWFYORYPRRVBPH-UHFFFAOYSA-J 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000010791 quenching Methods 0.000 claims abstract description 15
- 230000000171 quenching effect Effects 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 14
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910009973 Ti2O3 Inorganic materials 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 230000007797 corrosion Effects 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 11
- 239000002135 nanosheet Substances 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 40
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- 229910019142 PO4 Inorganic materials 0.000 abstract description 10
- 238000005342 ion exchange Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 24
- 238000009826 distribution Methods 0.000 description 15
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 14
- 239000011787 zinc oxide Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 10
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 9
- 229960000907 methylthioninium chloride Drugs 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- -1 hydrogen ions Chemical class 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000011065 in-situ storage Methods 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
- 238000011084 recovery Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910020293 Na2Ti3O7 Inorganic materials 0.000 description 1
- AQVJBQZLOYEZEP-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ti+4].[Cu+2].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Cu+2].P(=O)([O-])([O-])[O-] AQVJBQZLOYEZEP-UHFFFAOYSA-H 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- ORZHVTYKPFFVMG-UHFFFAOYSA-N xylenol orange Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 ORZHVTYKPFFVMG-UHFFFAOYSA-N 0.000 description 1
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0292—Phosphates of compounds other than those provided for in B01J20/048
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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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/12—Compounds containing phosphorus
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention discloses a preparation method of a porous titanium hydrogen phosphate material, an obtained product and application thereof, wherein the porous material is prepared from 0-30mol% of ZnO, 25-60mol% of CuO and 10-15mol% of TiO2And 30mol% of P2O5The preparation method comprises the steps of firstly preparing the raw materials into a mixture, melting the mixture into a melt, and then carrying out rapid cooling molding or water quenching, heat treatment, acid etching and the like to obtain the product. The method adopts inorganic raw materials, has the advantages of easily obtained raw materials, low cost, no use of organic solvents, short preparation period and high yield, is suitable for industrial application and popularization and large-scale production, and provides a brand new thought for the preparation of the porous titanium hydrogen phosphate material. The main crystal phase of the obtained porous material is Ti2O3(H2PO4)2·2H2O, has high specific surface area, large aperture and adjustable size, simultaneously has the functions of adsorption and ion exchange, and can be applied to various fields.
Description
Technical Field
The invention relates to a preparation method of a porous titanium hydrogen phosphate material, an obtained product and application, and belongs to the technical field of porous materials.
Background
The titanium hydrogen phosphate material has excellent ion exchange performance and can be used as a catalyst and a sensor. Due to its characteristic layered structure, the titanium hydrogen phosphate material is also easy to be modified by intercalation. At present, titanium hydrogen phosphate materials are mainly prepared by a wet chemical method and a hydrothermal method, and the adopted titanium sources are mainly titanium isopropoxide, tetrabutyl titanate, layered titanate, titanium trichloride, titanium tetrachloride and the like. There have also been reports of using titanyl sulfate and titanium powder. Organic titanium salt is adopted, and an organic solvent is usually required to be added, so that the cost is high, and the reaction is difficult to control; the use of inorganic titanium sources generally requires long reaction times. E.g. A.I. Bortun et al using layered Na2Ti3O7Or Na4Ti9O20With phosphoric acid as raw material at 130oStirring and refluxing the mixture for 30 days to obtain layered Ti2O3(H2PO4)2·2H2O material (J. mater. Res.1996,11: 2490-; H. takahashi et al uses titanyl sulfate and ammonium dihydrogen phosphate at 70oStirring and mixing under C, adjusting pH and then 100oReacting for 10 days under C to obtain Ti2O3(H2PO4)2·2H2And (3) O material. In addition, the titanium hydrogen phosphate material prepared by the method has larger surface area, mainly comes from atomic scale gaps among layered structures, and is not beneficial to the adsorption of the material to macromolecules.
Disclosure of Invention
Aiming at the defects that the existing titanium hydrogen phosphate material is difficult to produce in a large scale, long in production period or high in cost, difficult to control the production and the like, the invention provides a preparation method of a porous titanium hydrogen phosphate material and an obtained product. The method is based on the principle that multiphase solids are subjected to selective acid corrosion and combined with in-situ chemical reaction, the porous titanium hydrogen phosphate material is prepared, the raw materials are cheap and easy to obtain, the production period is short, large-scale production is facilitated, and the obtained material has a high specific surface area and a large pore diameter.
The specific technical scheme of the invention is as follows:
a preparation method of a porous titanium hydrogen phosphate material comprises the following steps:
(1) according to the mol ratio of ZnO 0-30%, CuO 25-60%, TiO210- 15mol%、P2O5Weighing each raw material according to the component content of 30 mol%;
(2) uniformly mixing the raw materials to obtain a mixture, heating the mixture to be molten, and carrying out rapid cooling molding or water quenching on the obtained molten liquid on a mold;
(3) cooling the sample formed by quenching, or drying the sample formed by quenching in water for later use;
(4) carrying out first-stage heat preservation heat treatment on the sample in the step (3) at 490-520 ℃, and then carrying out second-stage heat preservation heat treatment at 642-665 ℃;
(5) and (4) immersing the sample obtained in the step (4) in hydrochloric acid for corrosion to obtain the porous titanium hydrogen phosphate material.
Further, in the step (1), ZnO, CuO and TiO are provided2 The raw materials of the components are oxides, namely zinc oxide, copper oxide and titanium dioxide, and P is provided2O5The starting material of the component may be directly the oxide P2O5And may be a phosphoric acid solution. In the formula, the total molar weight of all the components is 100%.
Further, in the step (2), when P is introduced by using a phosphoric acid solution2O5Firstly, uniformly mixing other solid powdery raw materials, then adding a phosphoric acid solution and water, uniformly mixing, heating after uniform mixing, and then crushing to obtain a mixture; when P is adopted2O5Introduction of powder P2O5When in use, the raw materials are directly and uniformly mixed to obtain a mixture. Wherein, the heating treatment is carried out at the temperature of 180 ℃ and 250 ℃ for 20-25 hours.
Further, in the step (2), the temperature of the mixed material is increased from room temperature to 1250 ℃ at the temperature increase rate of 5-10 ℃/min, and the mixed material is kept at 1250 ℃ to be completely melted.
Further, in step (3), the sample formed by quenching is cooled to 490-520 ℃ and is directly subjected to heat preservation treatment at the temperature, or the sample formed by quenching is directly cooled to room temperature and is then heated to 490-520 ℃ and is subjected to heat preservation treatment.
Further, in the step (4), the block sample is subjected to heat preservation at 490-520 ℃ for 1 hour and then at 642-665 ℃ for 2 hours; the water-quenched particle sample is subjected to heat preservation and heat treatment at 635-660 ℃.
Further, in the step (5), the concentration of hydrochloric acid is 0.5-1.5 mol/L. When the hydrochloric acid is used for corrosion, the corrosion temperature is 70-90 ℃, and the corrosion time is generally 18-24 hours.
The formation mechanism of the porous titanium hydrogen phosphate material is that firstly, all raw material components fully react in a high-temperature melting state, and are solidified into amorphous opaque black blocks or particles through quenching forming or water quenching. Wherein when the raw material contains 25-30mol% of zinc oxide, the raw material is quenched and formed in the conventional air; when the sample does not contain zinc oxide or the content of zinc oxide is less than 25mol%, the sample surface is required to be kept at room temperature during quenching forming so as to avoid the block from separating out coarse crystals in advance. The method comprises the following steps of carrying out two-section type heat preservation heat treatment on a block sample, carrying out one-section type heat preservation heat treatment on a particle sample to promote uniform nucleation and crystal growth of the sample, so that crystalline phases such as copper titanium phosphate, copper pyrophosphate, copper phosphate, copper oxide, zinc pyrophosphate and the like are separated out through recrystallization, treating multiphase blocks or particles containing the crystalline phases in a hot hydrochloric acid solution, wherein the crystalline phases are different in corrosion speed and corrosion degree, and complex in-situ chemical reaction is also carried out during corrosion to finally form the porous titanium hydrogen phosphate material.
Furthermore, the porous material obtained by the method is blocky or granular, wherein the product formed by rapid cooling is blocky, and the water quenching product is granular. SEM test shows that the interior of the porous material is microscopically composed of nano sheets, and the thickness of the nano sheets is about 30-70 nm. The combination of XRD, NMR and EDS analysis results and literature data shows that the porous material contains Ti2O3(H2PO4)2·2H2Main crystal phase of O, which31The PNMR spectrum has a characteristic peak between-7.0 and-7.3 ppm, and the EDS analysis result shows that the Ti/P molar ratio of the material is about 1.1; when the formulation did not contain zinc oxide, the sample crystallized very weakly and also contained a small amount of alpha-Ti (HPO)4)2·H2And O crystal phase. The relative content of the crystal phase can be judged from the intensity of diffraction peaks in an XRD pattern.
Furthermore, the porous material mainly comes from pores formed by gaps among the nano sheets, and the nano sheets also have pores. The pores are generated when the crystal phase formed by the two-stage heat preservation and heat treatment of the material is selectively dissolved out during acid etching and is regenerated into a new phase. The pore size ranges from meso-porous to macroporous distribution.
The porous material has the advantages of short preparation period, easily obtained raw materials, higher specific surface area, pore size distribution in the range from mesopores to macropores, adsorption and ion exchange functions, large specific gravity, adjustable size, easy separation and recovery, and low cost because the used raw materials are common industrial raw materials. Therefore, the porous titanium hydrogen phosphate material prepared by the method is also within the protection scope of the invention.
Furthermore, the invention also provides application of the porous titanium hydrogen phosphate material as an adsorbent and an ion exchanger. Because the material has porosity, physical adsorption can be directly generated; because the material contains hydrogen ions, ion exchange can occur while adsorption is carried out; after ion exchange, the solution pH drops.
The porous titanium hydrogen phosphate material is prepared by the steps of melting, heat treatment, acid etching and the like, and the method has the advantages of low raw material price, simple operation, easy control and short period, is suitable for industrial application and popularization and large-scale production, and provides a brand new thought for the preparation of the porous titanium hydrogen phosphate material. The resulting porous material has Ti2O3(H2PO4)2·2H2The O main crystal phase has high specific surface area, adjustable size, large specific gravity, easy use, convenient recovery after use, and adsorption and ion exchange functions.
Drawings
FIG. 1 is an XRD diffraction pattern of the materials obtained in examples 1-5.
FIG. 2 is a SEM photograph of the material obtained in example 1.
Fig. 3 is a BJH pore size distribution curve of the materials obtained in example 1 and example 2.
Detailed Description
The invention is further described with reference to the following drawings and detailed description, which are illustrative only and not limiting in nature.
Sample N was measured using a nitrogen isothermal adsorption apparatus (Autosorb iQ-C)2An isothermal adsorption curve, calculating specific surface area according to a BET model, obtaining a pore size distribution curve according to a BJH model, determining a main pore size according to curve peak point data, and determining the pore volume from N2The adsorption curve is determined relative to the amount of adsorption at the maximum pressure. The pore distribution of the sample above 110nm is determined by mercury intrusion porosimetry.
The adsorption experiment was performed with stirring. Ion exchange performance test is carried out under stirring, and the test is respectively carried out on Cu2+、Zn2+And Ni2+Carry out ionThe experiment was exchanged and the pH before and after the solution experiment was determined. Sample adsorption or ion efficiency according to formula Rt=(C0−Ct)/C0X 100% calculation. In the formula, RtEfficiency at time t; c0The concentration of the original solution; ctIs the concentration of the solution at time t.
And (3) measuring the absorbance of the methylene blue in the solution after the sample adsorbs the methylene blue at the position of 665 nm of the wavelength by using a spectrophotometer, and calculating the concentration of the methylene blue in the solution according to a standard curve. Cu in solution before and after ion exchange2+、Zn2+And Ni2+The concentration of the compound is respectively measured by an EDTA spectrophotometry, a xylenol orange spectrophotometry and a PAR spectrophotometry, and the test wavelength is 730 nm, 570 nm and 496 nm.
Example 1
1. According to the formula CuO60%, TiO 210%、P2O530% of molar composition selected from raw materials CuO and TiO2The starting materials of (A) are the oxides themselves, P2O5The starting material of (2) was a phosphoric acid solution (85 wt%).
2. Uniformly mixing copper oxide and titanium oxide powdery raw materials, adding a phosphoric acid solution and a proper amount of water, uniformly mixing, heating at 200 ℃ for 24 hours, and crushing for later use to obtain a mixture.
3. And (3) putting the mixture obtained in the step (2) into a crucible, raising the temperature from room temperature to 1250 ℃ at the heating rate of 5 ℃/min, and keeping the temperature at 1250 ℃ to ensure that the mixture is completely molten. And pouring the molten sample out of the mold, cooling and molding the surface of the sample by water to obtain a block sample, and cooling the block sample to room temperature for later use.
4. And raising the temperature of the block sample to 510 ℃ at the temperature raising rate of 5 ℃/min, preserving the heat for 1h, then raising the temperature from 510 ℃ to 665 ℃ at the temperature raising rate of 5 ℃/min, and preserving the heat for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
5. And (4) soaking the sample obtained in the step (4) in 1mol/L hydrochloric acid at 80 ℃ for 24h, and taking out to obtain the product, namely the porous titanium hydrogen phosphate material.
XRD analysis of the resulting product, as shown in FIG. 1, can be derived from the following: the product has weak crystallization and contains titanium hydrogen phosphateSalt phase Ti2O3(H2PO4)2·2H2O, and also a small amount of alpha-Ti (HPO)4)2·H2And O crystal phase. SEM picture (figure 2) shows that the material is composed of nano-sheets, the thickness of the nano-sheets is 30-70nm, nano-holes are formed in the nano-sheets, and large gaps are formed among the nano-sheets.
Subjecting the product to N2The BET surface area of the product, determined by isothermal adsorption analysis, was 94m2Per g, pore volume of 0.61cm3A broad pore size distribution from 2nm to 110nm, and a pore size distribution curve (FIG. 2) having major pore diameters of 2.2nm and 30.2 nm.
Example 2
1. According to the formula CuO55%, TiO215%、P2O530% of molar composition selected from raw materials CuO and TiO2The starting materials of (A) are the oxides themselves, P2O5The starting material of (2) was a phosphoric acid solution (85 wt%).
2. The same as in example 1.
3. The same as in example 1.
4. The sample is heated to 520 ℃ at the heating rate of 5 ℃/min and is kept warm for 1h, and then is heated to 662 ℃ from 520 ℃ at the heating rate of 5 ℃/min and is kept warm for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
5. And (4) soaking the sample obtained in the step (4) in 1mol/L hydrochloric acid at 80 ℃ for 24h, and taking out to obtain the porous titanium hydrogen phosphate material.
The sample is a block material, and the XRD analysis shows that the product has weak crystallization and contains Ti-hydrogen phosphate phase Ti2O3(H2PO4)2·2H2O, and also a small amount of alpha-Ti (HPO)4)2·H2And O crystal phase. Warp of N2The BET surface area of the product, determined by isothermal adsorption analysis, was 122m2Per g, pore volume of 0.54cm3The pore size distribution is wide from 2nm to 110nm, and the main pore size of a pore size distribution curve is 2.1nm and 17.3-30.3 nm. And measuring that 8000-100,000 nm macropores exist in the sample by using a mercury porosimeter.
Adsorption experiment: 300mg of the block sample is taken and suspended in 100 ml of methylene blue solution with the concentration of 5 mg/L under the dark condition, the adsorption of the sample approaches the balance at 7 hours under the stirring condition, and the removal efficiency of the sample to the methylene blue in the solution reaches 90 percent.
Example 3
1. According to the formula of ZnO15%, CuO40%, TiO215%、P2O530 percent of molar composition selected from raw materials of ZnO, CuO and TiO2The starting materials of (A) are the oxides themselves, P2O5The starting material of (2) was a phosphoric acid solution (85 wt%).
2. Uniformly mixing zinc oxide, copper oxide and titanium oxide powdery raw materials, adding a phosphoric acid solution and a proper amount of water, uniformly mixing, heating at 200 ℃ for 24 hours, and crushing for later use to obtain a mixture.
3. The same as in example 1.
4. And (3) raising the temperature of the sample to 518 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1h, then raising the temperature from 518 ℃ to 646 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
5. And (4) soaking the sample obtained in the step (4) in 1mol/L hydrochloric acid at 80 ℃ for 24h, and taking out to obtain the porous titanium hydrogen phosphate material.
The main crystal phase of the product is Ti by XRD analysis2O3(H2PO4)2·2H2O。
Warp of N2The BET surface area of the obtained product was 119m by isothermal adsorption analysis2Per g, pore volume of 0.52cm3(ii)/g, wide pore size distribution from 2nm to 110nm, and major pore diameters of the pore size distribution curve of 2.0nm and 17.3 nm.
Adsorption experiment: 300mg of the block sample is taken and suspended in 100 ml of methylene blue solution with the concentration of 5 mg/L under the dark condition, the adsorption of the sample approaches the balance at 7 hours under the stirring condition, and the adsorption efficiency of the sample on the methylene blue in the solution reaches 90 percent. The sample adsorbing methylene blue once is calcined at 430 ℃ and then used for adsorbing methylene blue in the solution, the process is repeated for 5 times, the adsorption lasts for 3 hours until the equilibrium is reached, and the adsorption rate still reaches 64%.
Example 4
1. According to the formula of ZnO30%, CuO25%, TiO215%、P2O5Selecting raw materials of ZnO and Cu with a molar composition of 30%O、TiO2The starting materials of (A) are the oxides themselves, P2O5The starting material of (2) was a phosphoric acid solution (85 wt%).
2. Uniformly mixing zinc oxide, copper oxide and titanium oxide powdery raw materials, adding a phosphoric acid solution and a proper amount of water, uniformly mixing, heating at 200 ℃ for 24 hours, and crushing for later use to obtain a mixture.
3. And (3) putting the mixture obtained in the step (2) into a crucible, raising the temperature from room temperature to 1250 ℃ at a temperature raising rate of 5 ℃/min, and preserving the temperature at 1250 ℃ to enable the mixture to be completely molten. Pouring the molten sample out of the die, carrying out quenching and forming on the sample in the air to obtain a block sample, and cooling the block sample to room temperature for later use.
4. The sample is heated to 490 ℃ at the heating rate of 5 ℃/min and is kept warm for 1h, and then is heated from 490 ℃ to 642 ℃ at the heating rate of 5 ℃/min and is kept warm for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
5. And (4) soaking the sample obtained in the step (4) in 1mol/L hydrochloric acid at 80 ℃ for 24h, and taking out to obtain the porous titanium hydrogen phosphate material.
The sample is a block material, and the main crystal phase is Ti through XRD analysis2O3(H2PO4)2·2H2O。
Warp of N2The BET surface area of the obtained product was 111m by isothermal adsorption analysis2Per g, pore volume of 0.55cm3(ii)/g, wide pore size distribution from 2nm to 110nm, and major pore diameters of the pore size distribution curve of 2.2nm and 17.3 nm.
Example 5
1. According to the formula of ZnO25%, CuO30%, TiO215%、P2O530 percent of molar composition selected from raw materials of ZnO, CuO and TiO2、P2O5The raw materials of (A) are all oxides per se.
2. The raw materials are uniformly mixed to obtain a mixture for later use.
3. The batch is put into a crucible, the temperature is raised from room temperature to 1250 ℃ at the set heating rate of 5 ℃/min, the temperature is kept for 2h at 1250 ℃ to completely melt the batch, and then the molten sample is poured into water for water quenching.
4. The water quenched sample was dried and then raised to 635 ℃ at a rate of 5 ℃/min and held for 2 h. And after the heat preservation is finished, cooling the sample to room temperature along with the furnace.
5. And (4) soaking the sample obtained in the step (4) in 1mol/L hydrochloric acid at 80 ℃ for 18h, and taking out to obtain the porous titanium hydrogen phosphate material.
The obtained product is granular in shape. XRD analysis shows that the obtained product has Ti as main crystal phase2O3(H2PO4)2·2H2O; warp of N2Isothermal adsorption analysis, surface area of sample 121m2Per g, pore volume of 0.56cm3The pore size distribution is wide from 2nm to 110nm, and the main pore diameters of the pore size distribution curve are 2.3nm and 17.4 nm.
Ion adsorption and exchange experiments: adding 0.2 g of the sample in the example 5 into 40 mL of nickel ion solution with the concentration of 10 mg/L, and stirring for 1h, wherein the nickel ion concentration is reduced by 55.8%, and the unit adsorption amount is 1.1 mg/g; the pH of the solution decreased from 5.03 to 3.89 indicating that the nickel ions were ion exchanged with the hydrogen ions in the material.
0.2 g of the sample in the example 5 is added into 40 mL of copper ion solution with the concentration of 900 mg/L, and the mixture is stirred for 1h, so that the copper ion concentration is reduced by 35.5 percent, and the unit adsorption capacity is 63.9 mg/g; the pH of the solution was lowered from 5.03 to 3.24, indicating that the copper ions were ion exchanged with the hydrogen ions in the material.
0.2 g of the sample in the example 5 is added into 40 mL of zinc ion solution with the concentration of 50 mg/L, and the mixture is stirred for 2.5 hours, so that the concentration of the zinc ions is reduced by 67.8 percent, and the unit adsorption capacity is 6.8 mg/g; the pH of the solution decreased from 5.5 to 3.84 indicating that the copper ions were ion exchanged with the hydrogen ions in the material.
Can be applied to various fields.
Claims (10)
1. A preparation method of a porous titanium hydrogen phosphate material is characterized by comprising the following steps:
(1) weighing each raw material according to the component content of 0-30mol% of ZnO, 25-60mol% of CuO, 210-15 mol% of TiO and 530 mol% of P2O;
(2) uniformly mixing the raw materials to obtain a mixture, heating the mixture to be molten, and carrying out rapid cooling molding on the obtained molten liquid on a mold to form a block or water quenching to form a particle sample;
(3) cooling the block sample formed by quenching, or drying the particle sample formed by water quenching for later use;
(4) carrying out first-stage heat preservation heat treatment on the block sample in the step (3) at 490-520 ℃, and then carrying out second-stage heat preservation heat treatment at 642-665 ℃; carrying out heat preservation treatment on the water-quenched particle sample at 635-660 ℃;
(5) and (4) immersing the sample obtained in the step (4) in hydrochloric acid for corrosion to obtain the porous titanium hydrogen phosphate material.
2. The method of claim 1, wherein: ZnO, CuO and TiO2 components are introduced by respective oxides, and P2O5 components are introduced by oxides P2O5 or phosphoric acid solution.
3. The method of claim 1, wherein: in the step (2), when a phosphoric acid solution is adopted to introduce P2O5, other solid powdery raw materials are uniformly mixed, then the phosphoric acid solution and water are added to be uniformly mixed, heating treatment is carried out after uniform mixing, and then crushing is carried out to obtain a mixture; when P2O5 powder is adopted to be introduced into P2O5, the raw materials are directly and uniformly mixed to obtain a mixture; the heat treatment is carried out at 180 ℃ and 250 ℃ for 20-25 hours.
4. The method of claim 1, wherein: in the step (2), the temperature of the mixture is increased from room temperature to 1250 ℃ at the heating rate of 5-10 ℃/min, and the mixture is completely melted by heat preservation at 1250 ℃, wherein the heat preservation time is 1 hour.
5. The method of claim 1, wherein: in the step (3), the quenched and formed sample is cooled to 490-520 ℃ and the first stage of heat treatment is directly performed at the temperature, or the quenched and formed sample is directly cooled to room temperature and then heated to 490-520 ℃ and the first stage of heat preservation treatment is performed.
6. The method of claim 1, wherein: in the step (4), the block sample is subjected to heat preservation at 490-520 ℃ for 1 hour and at 642-665 ℃ for 2 hours; the pellet samples were incubated at 635-660 ℃ for 2 hours.
7. The method of claim 1, wherein: in the step (5), the concentration of the hydrochloric acid is 0.5-1.5mol/L, the temperature during corrosion is 70-90 ℃, and the corrosion time is 24 hours.
8. The porous titanium hydrogenphosphate material obtained by the production method according to any one of claims 1 to 7, characterized in that: the porous titanium hydrogen phosphate material is blocky or granular, is composed of nanosheets, and has mesopores and macropores.
9. The porous titanium hydrogenphosphate material according to claim 8, characterized in that: the main crystal phase of the porous titanium hydrogen phosphate material is Ti2O3(H2PO4)2 & 2H 2O.
10. Use of the porous titanium hydrogenphosphate material of claim 8 as an adsorbent or ion exchanger.
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| CN101402035A (en) * | 2008-11-28 | 2009-04-08 | 河北理工大学 | Method for directly producing photocatalysis assembled material with high-titanium furnace cinder |
| CN102417170A (en) * | 2011-08-24 | 2012-04-18 | 华南理工大学 | Sodium zinc phosphate-based pigment with high solar reflection performance and preparation method thereof |
| CN108101015A (en) * | 2017-12-20 | 2018-06-01 | 广东华材实业股份有限公司 | A kind of high entropy phosphate, high-temperature agglomerant and preparation method and application |
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