[go: up one dir, main page]

CN119186489A - Zirconium element-loaded MER type molecular sieve and preparation method and application thereof - Google Patents

Zirconium element-loaded MER type molecular sieve and preparation method and application thereof Download PDF

Info

Publication number
CN119186489A
CN119186489A CN202411699164.8A CN202411699164A CN119186489A CN 119186489 A CN119186489 A CN 119186489A CN 202411699164 A CN202411699164 A CN 202411699164A CN 119186489 A CN119186489 A CN 119186489A
Authority
CN
China
Prior art keywords
molecular sieve
mer
loaded
zirconium
fly ash
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
Application number
CN202411699164.8A
Other languages
Chinese (zh)
Inventor
李常艳
候鹏
任丽瑶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Inner Mongolia University
Original Assignee
Inner Mongolia University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Inner Mongolia University filed Critical Inner Mongolia University
Priority to CN202411699164.8A priority Critical patent/CN119186489A/en
Publication of CN119186489A publication Critical patent/CN119186489A/en
Pending legal-status Critical Current

Links

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
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • 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
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses a zirconium element-loaded MER molecular sieve and a preparation method and application thereof, and belongs to the technical field of molecular sieve preparation. The method comprises the steps of taking fly ash as a raw material, carrying out high-temperature hydrothermal reaction on the fly ash and potassium hydroxide solution to obtain the MER type molecular sieve, wherein the specific surface area of the MER type molecular sieve is 22.2079m 2/g, the aperture is about 10.7306nm, mixing and grinding the MER type molecular sieve and ZrOCl 2 solid phase, dissolving the mixed powder in water, stirring for 22-24 h at 55-65 ℃ to obtain suspension, centrifuging, washing and drying the suspension, and the removal rate of phosphate in sewage by the MER type molecular sieve loaded with zirconium element is up to 99.65%.

Description

Zirconium element-loaded MER type molecular sieve and preparation method and application thereof
Technical Field
The invention belongs to the technical field of molecular sieve preparation, and particularly relates to a zirconium element-loaded MER molecular sieve, and a preparation method and application thereof.
Background
The fly ash is a complex multiphase solid waste material remained after the coal is combusted in a combustion boiler, the fly ash not only contains silicide, iron compounds, aluminide and the like, but also contains a small amount of elements such as boron, magnesium, calcium, sodium, phosphorus, potassium and the like, and the fly ash yield is increased along with the gradual standardization and institutional treatment of the atmosphere in China, the dust removal, desulfurization and denitration technology of the thermal power plant is mature increasingly.
The fly ash cannot realize good protection to the environment, so that the efficient development and utilization of the fly ash have very important significance. The chemical composition of the fly ash is similar to that of zeolite molecular sieve, the fly ash has porous property, the specific surface area is larger, the adsorption performance of the fly ash can be enhanced by modification, and the synthesis of the molecular sieve with higher cost performance and higher utilization rate by utilizing silicon and aluminum rich in the fly ash is considered as one of effective methods for the high-value application of the fly ash. In recent years, with the intensive research on molecular sieve adsorption technology, various novel molecular sieve materials and modification methods have been developed, so that molecular sieves are widely applied and developed, and therefore, if fly ash can be largely utilized, the fly ash can be prepared into usable molecular sieve carriers, and the molecular sieve carriers are modified, the method becomes a good method for solving the environmental problem, and good economic and social benefits can be obtained.
Disclosure of Invention
Aiming at the prior art, the invention provides the zirconium element-loaded MER type molecular sieve and the preparation method and application thereof, which solve the technical problems of how to efficiently utilize fly ash and how to prepare the zirconium element-loaded MER type molecular sieve with strong adsorption capacity with low cost and low energy consumption.
In order to achieve the above purpose, the technical scheme adopted by the invention is that the method for preparing the MER type molecular sieve loaded with zirconium element by using the fly ash comprises the following steps:
S1, mixing fly ash and potassium hydroxide solution, stirring the mixture at 170-180 ℃ for reaction for 15-17 hours, then carrying out solid-liquid separation, and collecting a solid product;
S2, washing and drying the solid product to obtain the MER type molecular sieve, wherein the drying temperature is 110-130 ℃ and the drying time is 3.5-4.5 hours;
S3, mixing and grinding the MER molecular sieve and ZrOCl 2, dissolving the mixed powder in water, and stirring for 22-24 hours at 55-65 ℃ to obtain a suspension;
And S4, centrifuging, washing and drying the suspension to obtain the nano-particle.
Further, the concentration of the potassium hydroxide solution is 2 to 5mol/L.
Further, the mass ratio of the fly ash to the potassium hydroxide in the mixture is 1:0.27-0.67.
Further, in the step S1, the stirring rotation speed is 280-320 rpm.
Further, the reaction temperature in step S1 was 175℃and the reaction time was 16 hours, and the drying temperature in step S2 was 120℃and the drying time was 4 hours.
Further, the mass ratio of the MER molecular sieve to the ZrOCl 2 in the mixed powder in the step S3 is 1 g:17.8-125 mg, and the concentration of the ZrOCl 2 in the suspension is 0.001-0.007mol/L.
Further, in the step S4, the centrifugal speed is 5000-6000 rpm, the centrifugal time is 5-6 mm, washing is carried out by using water until the water after washing does not contain chloride ions, the drying temperature is 75-85 ℃ in the step S4, and the drying time is 11-12 h.
The invention also discloses the MER type molecular sieve loaded with the zirconium element and prepared by the preparation method.
The invention also discloses application of the zirconium element-loaded MER type molecular sieve in preparing a catalyst or an adsorbent
Further, the adsorbent is used for adsorbing phosphate ions in the wastewater, the solid-to-liquid ratio of the MER molecular sieve loaded with zirconium element in the adsorbent to the wastewater is 1 g:10-1000 mL, the pH value of the wastewater is 2-8, the adsorption temperature is 20-80 ℃, and the adsorption time is 180-240 min.
The beneficial effects of the invention are as follows:
1. compared with other methods for preparing the molecular sieve, the preparation method is simple, does not need aging operation, does not need adding molecular sieve seed crystal, does not need high-temperature calcination treatment, has a yield larger than that of laboratory reagent synthesis, and can realize batch production.
2. The fly ash has wide sources and low price, and the prepared MER molecular sieve has stable lattice structure, larger specific surface area, larger aperture and uniform distribution.
3. The MER type molecular sieve prepared firstly contains potassium ions, then the MER type molecular sieve and ZrOCl 2 are subjected to solid phase mixing grinding, the MER type molecular sieve and ZrOCl 2 are promoted to be fully mixed, then mixed powder is stirred in water, zirconium ions are promoted to enter pores of molecules by utilizing electrostatic action, the replacement reaction of the potassium ions and the zirconium ions is facilitated, the zirconium ion content in the molecular sieve is 2.5-3wt% and the potassium ion content is 6-7wt%, when the molecular sieve is applied to adsorbing phosphate ions in wastewater, the zirconium ions have positive charges and form stable chemical bonds with phosphate, so that the phosphate ions are adsorbed, and the removal rate of the phosphate ions in the wastewater can reach 99.65%.
Drawings
FIG. 1 is an XRD pattern of the MER type molecular sieve prepared in example 1;
FIG. 2 is an XRD pattern of the molecular sieve prepared in comparative example 1;
FIG. 3 is XRD patterns of samples prepared in examples 1 to 3 and comparative examples 1 to 3;
FIG. 4 is an SEM image of an MER type molecular sieve prepared in example 1;
FIG. 5 is an EDS spectrum of the MER type molecular sieve prepared in example 1;
FIG. 6 is a Fourier infrared spectrum of the MER type molecular sieve prepared in example 1;
FIG. 7 is a Fourier infrared spectrum of the samples prepared in examples 1 to 3 and comparative examples 1 to 3;
FIG. 8 is an XPS survey of the MER type molecular sieve prepared in example 1;
FIG. 9 is an XPS diagram of O elements in the MER type molecular sieve prepared in example 1;
FIG. 10 is an N 2 adsorption-desorption isotherm and pore size distribution plot of the MER molecular sieve prepared in example 1;
FIG. 11 is a kinetic profile of zirconium element-loaded MER molecular sieves prepared in example 1 versus adsorbed phosphate ions;
fig. 12 is an adsorption pattern diffusion model of the MER-type molecular sieve loaded with zirconium element prepared in example 1 to adsorb phosphate ions.
Detailed Description
The raw materials used in the invention are that the fly ash is from a Happy gold bridge thermal power plant, and potassium hydroxide (KOH, analytical pure AR, 85-90%).
The following describes the present invention in detail with reference to examples.
Example 1
The MER type molecular sieve loaded with the zirconium element is prepared through the following steps:
S1, weighing 43.2g of potassium hydroxide, dissolving in water to prepare a 2mol/L potassium hydroxide aqueous solution, adding 160g of fly ash and the prepared potassium hydroxide aqueous solution into a 1L electric lifting mechanical stirring reaction kettle, stirring and reacting for 16 hours at 175 ℃, wherein the stirring rotation speed is 320rpm, filtering after the reaction is finished, and collecting a solid product;
s2, washing the solid product by deionized water until the pH value of the solid product is neutral, and then putting the solid product into an oven for drying for 4 hours at the drying temperature of 120 ℃ to obtain the MER molecular sieve.
S3, taking 1g of MER molecular sieve and 125mgZrOCl 2 to mix and grind in a mortar, then dissolving the mixed powder in 100mL of water, and stirring for 23h at 60 ℃ to obtain a suspension;
And S4, centrifuging the suspension at 6000rpm for 5min, washing the solid with water until the washed water does not contain chloride ions, and drying for 11h at 80 ℃ to obtain the silver nitrate.
Example 2
The MER type molecular sieve loaded with the zirconium element is prepared through the following steps:
S1, weighing 67.72g of potassium hydroxide, dissolving the potassium hydroxide in water to prepare 5mol/L potassium hydroxide aqueous solution, adding 160g of fly ash and the prepared potassium hydroxide aqueous solution into a 1L electric lifting mechanical stirring reaction kettle, stirring and reacting for 16 hours at 170 ℃, wherein the stirring rotation speed is 300rpm, filtering after the reaction is finished, and collecting a solid product;
s2, washing the solid product by deionized water until the pH value of the solid product is neutral, and then putting the solid product into an oven for drying for 4.5 hours at the drying temperature of 130 ℃ to obtain the MER type molecular sieve.
S3, taking 1g of MER type molecular sieve and 54mgZrOCl 2 to mix and grind in a mortar, then dissolving the mixed powder in 100mL of water, and stirring for 22 hours at 55 ℃ to obtain a suspension;
and S4, centrifuging the suspension at a rotational speed of 5000rpm for 6min, washing the solid with water until the washed water does not contain chloride ions, and drying at 75 ℃ for 12h to obtain the silver nitrate.
Example 3
The MER type molecular sieve loaded with the zirconium element is prepared through the following steps:
S1, weighing 107.2g of potassium hydroxide, dissolving in water to prepare 3mol/L potassium hydroxide aqueous solution, adding 160g of fly ash and the prepared potassium hydroxide aqueous solution into a 1L electric lifting mechanical stirring reaction kettle, stirring and reacting for 17 hours at 180 ℃, wherein the stirring rotation speed is 280rpm, filtering after the reaction is finished, and collecting a solid product;
S2, washing the solid product by deionized water until the pH value of the solid product is neutral, and then putting the solid product into an oven for drying for 3.5 hours at the drying temperature of 110 ℃ to obtain the MER type molecular sieve.
S3, taking 1g of MER molecular sieve and 17.8mgZrOCl 2 in a mortar, mixing and grinding, dissolving the mixed powder in 100mL of water, and stirring for 23h at 60 ℃ to obtain a suspension;
And S4, centrifuging the suspension at 6000rpm for 6min, washing the solid with water until the washed water does not contain chloride ions, and drying for 11h at 85 ℃ to obtain the silver nitrate.
Example 4
The MER type molecular sieve loaded with the zirconium element is prepared through the following steps:
S1, weighing 89.6g of potassium hydroxide, dissolving in water to prepare a 2mol/L potassium hydroxide aqueous solution, adding 160g of fly ash and the prepared potassium hydroxide aqueous solution into a 1L electric lifting mechanical stirring reaction kettle, stirring and reacting for 15 hours at 175 ℃, wherein the stirring rotation speed is 300rpm, filtering after the reaction is finished, and collecting a solid product;
s2, washing the solid product by deionized water until the pH value of the solid product is neutral, and then putting the solid product into an oven for drying for 4 hours at the drying temperature of 120 ℃ to obtain the MER molecular sieve.
S3, taking 1g of MER molecular sieve and 100mgZrOCl 2 to mix and grind in a mortar, then dissolving the mixed powder in 100mL of water, and stirring for 24 hours at 65 ℃ to obtain a suspension;
and S4, centrifuging the suspension at 5500rpm for 6min, washing the solid with water until the water after washing does not contain chloride ions, and drying at 75 ℃ for 12h to obtain the silver nitrate.
Comparative example 1
A molecular sieve prepared by the steps of:
S1, weighing 67.72g of potassium hydroxide, dissolving the potassium hydroxide in water to prepare a potassium hydroxide aqueous solution of 2mol/L, adding 160g of fly ash and the prepared potassium hydroxide aqueous solution into a 1L electric lifting mechanical stirring reaction kettle, stirring and reacting for 12 hours at 175 ℃, wherein the stirring rotation speed is 300rpm, filtering after the reaction is finished, and collecting a solid product;
S2, washing the solid product by deionized water until the pH value of the solid product is neutral, and then putting the solid product into an oven for drying for 4 hours at the drying temperature of 120 ℃ to obtain the product.
Comparative example 2
A molecular sieve prepared by the steps of:
S1, weighing 43.2g of potassium hydroxide, dissolving in water to prepare a 2mol/L potassium hydroxide aqueous solution, adding 160g of fly ash and the prepared potassium hydroxide aqueous solution into a 1L electric lifting mechanical stirring reaction kettle, stirring and reacting for 16 hours at 175 ℃, wherein the stirring rotation speed is 320rpm, filtering after the reaction is finished, and collecting a solid product;
s2, washing the solid product by deionized water until the pH value of the solid product is neutral, and then putting the solid product into an oven for drying for 4 hours at the drying temperature of 120 ℃ to obtain the MER molecular sieve.
S3, taking 1g of MER molecular sieve and 250mgZrOCl 2 to mix and grind in a mortar, then dissolving the mixed powder in 100mL of water, and stirring for 23h at 60 ℃ to obtain a suspension;
And S4, centrifuging the suspension at 6000rpm for 5min, washing the solid with water until the washed water does not contain chloride ions, and drying for 11h at 80 ℃ to obtain the silver nitrate.
Comparative example 3
A molecular sieve prepared by the steps of:
S1, weighing 43.2g of potassium hydroxide, dissolving in water to prepare a 2mol/L potassium hydroxide aqueous solution, adding 160g of fly ash and the prepared potassium hydroxide aqueous solution into a 1L electric lifting mechanical stirring reaction kettle, stirring and reacting for 16 hours at 175 ℃, wherein the stirring rotation speed is 320rpm, filtering after the reaction is finished, and collecting a solid product;
s2, washing the solid product by deionized water until the pH value of the solid product is neutral, and then putting the solid product into an oven for drying for 4 hours at the drying temperature of 120 ℃ to obtain the MER molecular sieve.
S3, taking 1g of MER type molecular sieve and 534mgZrOCl 2 to mix and grind in a mortar, then dissolving the mixed powder in 100mL of water, and stirring for 23h at 60 ℃ to obtain a suspension;
And S4, centrifuging the suspension at 6000rpm for 5min, washing the solid with water until the washed water does not contain chloride ions, and drying for 11h at 80 ℃ to obtain the silver nitrate.
Comparative example 4
A molecular sieve prepared by the steps of:
S1, weighing 96g of potassium hydroxide, dissolving in water to prepare 5mol/L potassium hydroxide aqueous solution, adding 160g of fly ash and the prepared potassium hydroxide aqueous solution into a 1L electric lifting mechanical stirring reaction kettle, stirring and reacting for 15h at 180 ℃, wherein the stirring rotation speed is 320rpm, filtering after the reaction is finished, and collecting a solid product;
S2, washing the solid product by deionized water until the pH value of the solid product is neutral, and then putting the solid product into an oven for drying for 3.5 hours at the drying temperature of 110 ℃ to obtain the MER type molecular sieve.
S3, taking 1g of MER molecular sieve and 178mgZrOCl 2 to mix and grind in a mortar, then dissolving the mixed powder in 100mL of water, and stirring for 22 hours at 65 ℃ to obtain a suspension;
And S4, centrifuging the suspension at 6000rpm for 6min, washing the solid with water until the washed water does not contain chloride ions, and drying for 11h at 85 ℃ to obtain the silver nitrate.
Comparative example 5
A molecular sieve prepared by the steps of:
S1, weighing 43.2g of potassium hydroxide, dissolving in water to prepare a 2mol/L potassium hydroxide aqueous solution, adding 160g of fly ash and the prepared potassium hydroxide aqueous solution into a 1L electric lifting mechanical stirring reaction kettle, stirring and reacting for 16 hours at 175 ℃, wherein the stirring rotation speed is 320rpm, filtering after the reaction is finished, and collecting a solid product;
s2, washing the solid product by deionized water until the pH value of the solid product is neutral, and then putting the solid product into an oven for drying for 4 hours at the drying temperature of 120 ℃ to obtain the MER molecular sieve.
S3, taking 1g of MER molecular sieve and 125mgZrOCl 2 g of MER molecular sieve in a mortar, mixing and grinding, dissolving the mixed powder in 100mL of water, adding 5mL of 25wt% ammonia water, and stirring at 60 ℃ for 23h to obtain a suspension;
And S4, centrifuging the suspension at 6000rpm for 5min, washing the solid with water until the washed water does not contain chloride ions, and drying for 11h at 80 ℃ to obtain the silver nitrate.
Experimental example
The MER type molecular sieves prepared in 6 examples of the invention have similar properties, and the properties of related products are described by taking example 1 as an example.
1. Structure testing
The MER type molecular sieve prepared in example 1 and the molecular sieve prepared in comparative example 1 were subjected to X-ray diffraction (XRD) analysis by using a PANalytical diffractometer, cukα1 radiation λ= 1.54178 a, the bragg angle range is 5 to 80 °, the XRD pattern is shown in fig. 1 to 2, it can be seen from the XRD pattern that the MER type molecular sieve prepared in example 1 exhibits a single crystal phase corresponding to Merl K 10.32(Si22.7Al10.3O64)(H2O)24.32 (JCPDS 86-1110), the unit cell constant a= 14.0948 (6), b= 14.2026 (6), c= 10.0421 (5), orthogonal space group Immm, the peak of the sample prepared in comparative example 1 is not in the same position as that of (JCPDS 86-1110), and the comparative example sample is affected by the preparation process, and the framework structure thereof is destroyed, resulting in more framework defect sites. The samples prepared in examples 1-3 and comparative examples 2-3 were also subjected to X-ray diffraction analysis, and XRD patterns are shown in FIG. 3, so that the characteristic diffraction peaks of the samples of the comparative examples are obviously disappeared, and the characteristic diffraction peaks are changed into amorphous characteristic diffraction peaks, so that the crystal structure of the molecular sieve is changed.
Structural observations of the MER type molecular sieve prepared in example 1 were carried out by using a hitachi S4800 field emission scanning electron microscope, and SEM images are shown in fig. 4, from which it can be seen that the morphology of the prepared MER type molecular sieve takes the shape of rectangular bars, and part takes the shape of thinner plates. And the MER type molecular sieve prepared in example 1 was subjected to component analysis using an energy chromatograph, the analysis chart being shown in figure 5,
Functional group analysis was performed on the MER type molecular sieve prepared in example 1 using fourier infrared spectrometer (FT-IR), as shown in fig. 6, it can be seen from the figure that the bands in the frequency range of 785 to 780 cm −1 and 642 to 640cm −1 are due to Al-O-Si stretching, that the high frequency narrow band around 1638cm −1 and 1633cm −1 is due to δ (O-H) of adsorbed water molecules, that the peaks at about 1025cm −1 and 1031cm −1 correspond to binding vibrations v (Si-O-Si) and v (Si-O-Al), and that the bands in the frequency range of 785 to 780 cm −1 and 642 to 640cm −1 are due to Al-O-Si stretching, and that finally, the peaks at 439 to 431cm −1 are due to v (SiO 4) and v (AlO 4) tetrahedral rings. The samples prepared in examples 1-3 and comparative examples 2-3 were also subjected to structural analysis by a Fourier infrared spectrometer, and the spectra are shown in FIG. 7, wherein the peak corresponds to Zr-O-Zr-O four-ring vibration of the zirconia cluster in the range of 600-700 cm -1, reflecting the interaction between Zr atoms and O atoms, and slight energy band transfer (energy transfer from low to higher energy) can prove that ZrO 2+ ions are successfully incorporated into the MER molecular sieve structure.
X-ray photoelectron spectroscopy (XPS) of the MER type molecular sieve prepared in example 1 was measured with VGScientificESCALABMarkII spectrometer, VGScientificESCALABMarkII spectrometer was equipped with two ultra-high vacuum (UHV) chambers, XPS full spectrum of the MER type molecular sieve was shown in FIG. 8, it can be seen from full spectrum that the MER type molecular sieve contains Si and Al elements, XPS spectrum of O element in the MER type molecular sieve was shown in FIG. 9, 531eV and 531.5eV were respectively Al-O bond and Si-O bond.
The zirconium element-loaded MER type molecular sieves prepared in examples 1 to 3 and comparative examples 2 to 5 were subjected to elemental analysis by a high resolution inductively coupled plasma mass spectrometer, the results of the potassium ion and zirconium ion contents in the samples are shown in Table 1,
TABLE 1
From the table, it can be seen that the zirconium element-loaded MER type molecular sieve in the examples has a zirconium ion content of 2.5-3 wt% and a potassium ion concentration of 6-7 wt%.
2. Adsorption Performance test
① The MER type molecular sieve prepared in example 1 was subjected to an N 2 adsorption-desorption test on an ASAP2020 system, and the N 2 adsorption-desorption isotherm and pore size distribution obtained in example 1 are shown in fig. 10, and it can be seen that the gas adsorption isotherm generated by the nonporous or macroporous material belongs to a type II adsorption isotherm, and the gas adsorption isotherm generated by the nonporous or macroporous material shows a reversible type II isotherm, the linear shape reflects unrestricted monolayer-multilayer adsorption, the adsorption amount rapidly rises under lower relative pressure due to stronger interaction of the adsorbents on the surface, the curve rises, the isotherm inflection point usually appears near the monolayer adsorption, the multilayer adsorption gradually forms as the relative pressure continues to increase, and when the saturated vapor pressure is reached, the adsorption layer does not reach saturation, and the thickness of the multilayer adsorption seems to increase infinitely. The retention ring was judged to be H3-shaped according to the International Union of Pure and Applied Chemistry (IUPAC) classification, and the H3-shaped reflected pores include flat plate slit structures, wedge structures, and the like. The H3 type hysteresis loop is given by a flaky particle material or a slit hole material, and does not show adsorption saturation in a higher relative pressure area, which is consistent with the appearance shown by an SEM image of the MER type molecular sieve. The surface areas were tested as shown in Table 2.
TABLE 2
② Preparing 100mL of aqueous solution with 50ppm phosphate ion concentration and 5 pH value as simulated wastewater, respectively taking 1g of the zirconium element-loaded MER type molecular sieve prepared in examples 1-3 and comparative examples 2-5, adsorbing for 4 hours at 40 ℃, recording data such as adsorption time, adsorption amount and solution concentration in detail, calculating the removal rate of the zirconium element-loaded MER type molecular sieve on the phosphate ion according to the concentration of the phosphate ion in the wastewater, and calculating the calculation results shown in Table 3,
TABLE 3 Table 3
The table shows that the removal rate of phosphate ions in wastewater by the MER molecular sieve loaded with zirconium element in the example can reach 99.65%, the phase structure of the molecular sieve in the comparative example is obviously changed, and the removal capacity of phosphate is obviously reduced.
According to experimental data of the adsorption process of the sample of example 1, an adsorption kinetics curve is drawn, as shown in fig. 11, the adsorption kinetics behavior of phosphate ions on a molecular sieve belongs to secondary kinetics (PSO), and fig. 12 is an adsorption pattern diffusion model of the MER-type molecular sieve loaded with zirconium element of example 1, which shows that the adsorption process comprises three stages, the first stage, the slope is the largest, the adsorption rate is driven by the phosphate concentration difference, and the adsorption rate is controlled by the concentration difference. In the second stage, phosphate gradually migrates into the pores, is absorbed by the surface under the influence of Zr@MER molecular sieve pores, and the slope slowly increases, so that the secondary diffusion of the phosphate in the Zr@MER controls the adsorption rate. According to zeta potential, zr@MER has positive charges, zr ions have positive charges, form stable chemical bonds with phosphate, have higher binding capacity to phosphate, increase adsorption capacity and improve removal capacity. And in the third stage, the slope is gentle, and the adsorption and desorption in the holes reach equilibrium.
While specific embodiments of the invention have been described in detail in connection with the examples, it should not be construed as limiting the scope of protection of the patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.

Claims (10)

1.一种粉煤灰制备负载锆元素的MER型分子筛的方法，其特征在于，包括以下步骤：1. A method for preparing a zirconium-loaded MER molecular sieve from fly ash, characterized in that it comprises the following steps: S1：将粉煤灰和氢氧化钾溶液混合，混合物于170~180℃下搅拌反应15~17h，然后固液分离，收集固体产物；S1: Fly ash and potassium hydroxide solution are mixed, the mixture is stirred at 170-180°C for 15-17h, and then the solid-liquid separation is performed to collect the solid product; S2：洗涤并干燥所述固体产物，得到MER型分子筛；干燥温度为110~130℃，干燥时间为3.5~4.5h；S2: washing and drying the solid product to obtain a MER type molecular sieve; the drying temperature is 110-130° C., and the drying time is 3.5-4.5 h; S3：将所述MER型分子筛与ZrOCl2混合研磨，然后将混合粉末溶于水中，在55~65℃条件下搅拌22~24h，得到悬浮液；S3: Mix and grind the MER molecular sieve and ZrOCl 2 , then dissolve the mixed powder in water, and stir at 55-65° C. for 22-24 hours to obtain a suspension; S4：对所述悬浮液进行离心、洗涤和干燥，即得。S4: centrifuging, washing and drying the suspension to obtain. 2.根据权利要求1所述的粉煤灰制备负载锆元素的MER型分子筛的方法，其特征在于：所述氢氧化钾溶液的浓度为2~5mol/L。2. The method for preparing a zirconium-loaded MER molecular sieve from fly ash according to claim 1, wherein the concentration of the potassium hydroxide solution is 2-5 mol/L. 3.根据权利要求1所述的粉煤灰制备负载锆元素的MER型分子筛的方法，其特征在于：所述混合物中粉煤灰和氢氧化钾的质量比为1：0.27~0.67。3. The method for preparing a zirconium-loaded MER molecular sieve from fly ash according to claim 1, characterized in that the mass ratio of fly ash to potassium hydroxide in the mixture is 1:0.27-0.67. 4.根据权利要求1所述的粉煤灰制备负载锆元素的MER型分子筛的方法，其特征在于：步骤S1中搅拌转速为280~320rpm。4. The method for preparing a zirconium-loaded MER molecular sieve from fly ash according to claim 1, characterized in that the stirring speed in step S1 is 280-320 rpm. 5.根据权利要求1所述的粉煤灰制备负载锆元素的MER型分子筛的方法，其特征在于：步骤S1中反应温度为175℃，反应时间为16h；步骤S2中干燥温度为120℃，干燥时间为4h。5. The method for preparing a zirconium-loaded MER molecular sieve from fly ash according to claim 1, characterized in that: in step S1, the reaction temperature is 175°C and the reaction time is 16 hours; in step S2, the drying temperature is 120°C and the drying time is 4 hours. 6.根据权利要求1所述的粉煤灰制备负载锆元素的MER型分子筛的方法，其特征在于：步骤S3混合粉末中MER型分子筛和ZrOCl2的质量比为1g：17.8~178mg；悬浮液中ZrOCl2的浓度为0.001~0.007mol/L。6. The method for preparing zirconium-loaded MER molecular sieve from fly ash according to claim 1, characterized in that: the mass ratio of the MER molecular sieve and ZrOCl 2 in the mixed powder in step S3 is 1g:17.8~178mg; and the concentration of ZrOCl 2 in the suspension is 0.001~0.007mol/L. 7.根据权利要求1所述的粉煤灰制备负载锆元素的MER型分子筛的方法，其特征在于：步骤S4中离心转速为5000~6000rpm，离心时间为5~6mim；洗涤为用水洗涤至洗涤后的水中不含有氯离子；步骤S4中干燥温度为75~85℃；干燥时间为11~12h。7. The method for preparing a zirconium-loaded MER molecular sieve from fly ash according to claim 1, characterized in that: in step S4, the centrifugal speed is 5000-6000 rpm, and the centrifugal time is 5-6 min; washing is washing with water until the washed water does not contain chloride ions; in step S4, the drying temperature is 75-85°C; and the drying time is 11-12 h. 8.一种负载锆元素的MER型分子筛，其特征在于：采用权利要求1~7任一项所述的粉煤灰制备负载锆元素的MER型分子筛的方法制备得到。8. A zirconium-loaded MER molecular sieve, characterized in that it is prepared by the method for preparing a zirconium-loaded MER molecular sieve using fly ash as claimed in any one of claims 1 to 7. 9.一种负载锆元素的MER型分子筛的应用，其特征在于：将权利要求8所述的负载锆元素的MER型分子筛用于制备催化剂或吸附剂。9. An application of a zirconium-loaded MER type molecular sieve, characterized in that the zirconium-loaded MER type molecular sieve according to claim 8 is used to prepare a catalyst or an adsorbent. 10.根据权利要求9所述的负载锆元素的MER型分子筛的应用，其特征在于：所述吸附剂用于吸附废水中的磷酸根离子，吸附剂中负载锆元素的MER型分子筛与废水的固液比为1g：10~1000mL，废水pH值为2~8，吸附温度为20~80℃，吸附时间为180~240min。10. The use of the zirconium-loaded MER molecular sieve according to claim 9, characterized in that: the adsorbent is used to adsorb phosphate ions in wastewater, the solid-liquid ratio of the zirconium-loaded MER molecular sieve in the adsorbent to the wastewater is 1g:10~1000mL, the pH value of the wastewater is 2~8, the adsorption temperature is 20~80°C, and the adsorption time is 180~240min.
CN202411699164.8A 2024-11-26 2024-11-26 Zirconium element-loaded MER type molecular sieve and preparation method and application thereof Pending CN119186489A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202411699164.8A CN119186489A (en) 2024-11-26 2024-11-26 Zirconium element-loaded MER type molecular sieve and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202411699164.8A CN119186489A (en) 2024-11-26 2024-11-26 Zirconium element-loaded MER type molecular sieve and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN119186489A true CN119186489A (en) 2024-12-27

Family

ID=94074529

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202411699164.8A Pending CN119186489A (en) 2024-11-26 2024-11-26 Zirconium element-loaded MER type molecular sieve and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN119186489A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102524160A (en) * 2012-01-16 2012-07-04 中国环境科学研究院 Water treatment system adopting molecular sieves prepared from flyash of power plants for filtration
US20140079616A1 (en) * 2011-04-08 2014-03-20 Joseph M. Fedeyko Catalysts for the reduction of ammonia emission from rich-burn exhaust
MX2018003805A (en) * 2018-03-27 2019-09-30 Centro De Investig Y De Estudios Avanzados Del I P N Method for the preparation of zeolitic materials from industrial by-products and other abundant and low-cost raw materials, and their use in the treatment of contaminated aqueous effluents.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140079616A1 (en) * 2011-04-08 2014-03-20 Joseph M. Fedeyko Catalysts for the reduction of ammonia emission from rich-burn exhaust
CN102524160A (en) * 2012-01-16 2012-07-04 中国环境科学研究院 Water treatment system adopting molecular sieves prepared from flyash of power plants for filtration
MX2018003805A (en) * 2018-03-27 2019-09-30 Centro De Investig Y De Estudios Avanzados Del I P N Method for the preparation of zeolitic materials from industrial by-products and other abundant and low-cost raw materials, and their use in the treatment of contaminated aqueous effluents.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YOUNESS ABDELLAOUI ET AL.: "Synthesis and Surface Modification of Small Pore Size Zeolite W for Improving Removal Efficiency of Anionic Contaminants from Water", BULLETIN OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY, 2 November 2020 (2020-11-02) *

Similar Documents

Publication Publication Date Title
CN109012575B (en) Method for improving specific surface area and adsorption capacity of calcined diatomite
CN106518794B (en) A kind of metal-organic framework materials of carboxyl-functional and the preparation method and application thereof
CN110559998A (en) Loaded biochar functional material for adsorbing heavy metal ions as well as preparation and application thereof
Yang et al. Facile synthesis of nitrogen-defective gC 3 N 4 for superior photocatalytic degradation of rhodamine B
Shao et al. Porous functionalized MOF self-evolution promoting molecule encapsulation and Hg 2+ removal
CN109174060B (en) Phosphonic acid group-containing chelate resin and method for separating and enriching thorium under high acidity
CN113042003B (en) Zirconium-based metal-organic framework material and preparation method and application thereof
CN113398876A (en) Titanium-based functionalized nano composite microsphere efficient adsorbent for treating uranium-containing wastewater and preparation method thereof
Zhang et al. Phosphorylated-CNC/MWCNT thin films-toward efficient adsorption of rare earth La (III)
Liu et al. UO22+ capture using amidoxime grafting low-cost activated carbon (AO-AC) from solution: Adsorption kinetic, isotherms and interaction mechanism
CN111229167A (en) Thiosemicarbazide modified magnetic graphene oxide adsorbent and preparation method and application thereof
CN119186489A (en) Zirconium element-loaded MER type molecular sieve and preparation method and application thereof
CN113559825A (en) Preparation method, product and application of ZIF-8/sodium bentonite composite material
CN108948366A (en) A kind of preparation and its desulfurization application of the Fe-MOF catalyst with abundant Lewis acidic site
CN101485970A (en) Method for developing high-efficient arsenic-removing sorbent Fe-Zr composite oxide
CN115501858B (en) Magnetic sulfur-nitrogen doped biochar composite material, preparation method thereof and application thereof in co-adsorption of antibiotics and heavy metal ions
CN115672263B (en) Preparation method of halloysite nanotube composite material and application of halloysite nanotube composite material in uranium pollution treatment
CN113813930B (en) Modified biomass-based composite adsorption material for treating radioactive pollutants
CN115337897B (en) High temperature CO 2 Adsorbent and preparation method thereof
CN116459785A (en) Preparation method of halloysite nanotube composite material and application of halloysite nanotube composite material in uranium pollution treatment
CN114522663A (en) Modified fly ash material and preparation method and application thereof
CN112452303A (en) Galla chinensis tannin/dendritic fiber-shaped mesoporous silica nanoparticle composite material and application thereof in gallium recovery
JP2018008861A (en) Manufacturing method of zirconium carrier and zirconium carrier
CN107469773B (en) A silicon-coated carbonized nitrogen-containing carbon-based adsorption material capable of well adsorbing radionuclide uranium and its application method
CN111747421A (en) A kind of method for improving the activity of expanded perlite material

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