CN110876917B - Superparamagnetic response nano phosphorus adsorbent and preparation method thereof - Google Patents
Superparamagnetic response nano phosphorus adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention provides a superparamagnetic response nano phosphorus adsorbent and a preparation method thereof, wherein the superparamagnetic response nano phosphorus adsorbent is in a granular core-shell structure, and the inner core is Fe 3 O 4 The outer shell of the material is sequentially SiO from inside to outside 2 And Mg-Al-LDHs on which a transition metal oxide is complexed; the average diameter of the particles is 30-80 nm, and the average thickness of the shell is 10-20 nm. The adsorbent can be applied to high-phosphorus sewage treatment to produce high-purity phosphorus-containing fertilizer. The preparation method of the phosphorus adsorbent is simple, and the obtained adsorbent has large adsorption capacity, good phosphate selectivity, strong regeneration capacity, high purity and uniform dispersion; the magnetic responsiveness of the adsorbent enables the adsorbent to be separated from the dehydrated waste liquid under the action of an external magnetic field, so that the adsorbent captures phosphate. The method of the invention makes the phosphorus-containing wastewater become a novel 'phosphorite', and avoids the resource waste caused by the discharge of a large amount of phosphorus along with the effluent or the landfill of residual sludge.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and relates to a preparation method of a superparamagnetic response nano phosphate adsorbent.
Background
Phosphorus recovery technology of municipal sewage plants is one of the hot spots of research; for a sewage treatment plant, phosphorus in sewage is easily accumulated in sludge digestion liquid, especially dewatered sludge waste liquid. Chemical phosphorus removal includes calcium phosphate crystallization, struvite precipitation, ion exchange adsorption, etc., but these materials or methods have small adsorption of phosphate. The operation conditions of the method are slightly harsh, the selectivity to phosphate is poor, the regeneration is difficult, even more difficult-to-treat phosphorus-containing sludge is generated, the problem of wastewater is converted into the problem of waste, more importantly, some interference components in dehydrated sludge influence the adsorption and the phosphate fertilizer generation effect, and the method becomes one of barriers for recycling phosphorus-containing pollutants. Therefore, there is a need to find new adsorption materials and methods for treating high phosphorus wastewater.
Disclosure of Invention
Aiming at the problems of low phosphorus removal adsorption quantity, difficult regeneration of the adsorbent, harsh conditions and low purity of the phosphate fertilizer in the prior art, the invention provides the magnetic nano adsorbent capable of efficiently adsorbing the phosphate fertilizer, which has high adsorption quantity and is renewable.
The invention also aims to provide a method for preparing the compound phosphate fertilizer by using the adsorbent and the dehydrated sludge waste liquid as raw materials.
Still another object of the present invention is to provide an apparatus for preparing a composite phosphate fertilizer from dehydrated sludge waste liquid, in which the steps of phosphorus separation and phosphorus recovery and adsorbent regeneration can be completed, and the equipment volume and the process steps can be reduced.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
The super paramagnetic response nanometer phosphorus adsorbent has granular core-shell structure with Fe as the inner core 3 O 4 The outer shell of the shell is from inside to outsideSiO in turn outside 2 And magnesium aluminum double metal hydroxides (Mg-Al-LDHs) on which transition metal oxides are complexed; the average diameter of the particles is 30-80 nm, and the average thickness of the shell is 10-20 nm; the transition metal is selected from lanthanum, cerium or hafnium.
In the superparamagnetic response nano phosphorus adsorbent, the mass percentage of the magnesium-aluminum double metal hydroxide and the transition metal oxide is 20% -60%; preferably 30% -60%; the mass percentage of the transition metal oxide calculated by metal is 20-60% of the total mass of the magnesium-aluminum double metal hydroxide and the transition metal oxide.
The saturation magnetization intensity of the superparamagnetic response nano phosphorus adsorbent is 65-70 emu/g, and the specific surface area is 130-150 m 2 /g。
The preparation method of the superparamagnetic response nano phosphorus adsorbent comprises the following steps:
(1) Adding aluminum chloride, magnesium chloride and transition metal chloride into the NaOH solution to obtain a magnesium-aluminum double metal hydroxide solution loaded with transition metal oxide;
(2) SiO is made of 2 Wrapped Fe 3 O 4 And (3) adding the particles into the solution obtained in the step (1), stirring, pressurizing and carrying out ultrasonic treatment to obtain the superparamagnetic response nano phosphorus adsorbent.
In the step (1), the molar ratio of aluminum chloride to magnesium chloride to transition metal chloride is 1-17:1:1-226.
Preferably, the concentration of the transition metal oxide-loaded magnesium aluminum double metal hydroxide solution is 0.8 to 1wt%.
In step (2), siO 2 Wrapped Fe 3 O 4 The content of the particles in the solution obtained in the step (1) is 10-15 wt percent.
In the step (2), the ultrasonic frequency is 35-40 kH, the power is 180-200W, and the time is 1-2 min.
In the step (2), the pressure is 0.40-0.45 Mpa.
The SiO is 2 Wrapped Fe 3 O 4 The preparation method of the particles comprises the following steps:
(i) FeCl is added 3 ·6H 2 O and FeCl 2 ·4H 2 O is dissolved in the double distilled water, fully stirred with ammonia monohydrate under the condition of introducing nitrogen, and then nitric acid solution is added to prepare Fe 3 O 4 A nano-magnetic core precursor suspension;
(ii) Slowly injecting the trimethylsiloxysilicate solution into the microemulsion prepared in the step (1), heating, magnetically separating precipitate, cleaning, and drying to obtain SiO 2 Wrapped Fe 3 O 4 And (3) particles.
In step (i), the FeCl 3 ·6H 2 O、FeCl 2 ·4H 2 The molar ratio of O to ammonia monohydrate was 2:1:0.92.
In step (i), fe 3 O 4 The pH value of the nano magnetic core precursor suspension is 3.0-3.5.
In step (ii), the trimethylsiloxysilicate is reacted with FeCl 3 ·6H 2 The molar ratio of O is 0.014:1-0.015:1. The heating temperature and time were 50 ℃ for 3min then 60 ℃ for 3min then 70 ℃ for 3min.
The application of the adsorbent in sewage treatment.
A method for removing phosphorus from wastewater by using the adsorbent, which comprises the following steps:
(1) Mixing and stirring the adsorbent and the wastewater to finish the adsorption of phosphate, thereby obtaining ammonia nitrogen-rich waste liquid;
(2) And separating out the adsorbent for adsorbing phosphate by adopting a magnetic adsorption device to finish dephosphorization.
Further, the method further comprises the step of recovering the adsorbent after the step (2): and leaching the phosphate on the adsorbent by using NaOH solution to obtain a phosphorus-containing solution, and magnetically absorbing and recovering the adsorbent. Further, the method also comprises the steps of mixing the phosphorus-containing solution, the magnesium chloride solution and the ammonia nitrogen-rich waste liquid, crystallizing, and drying to obtain the phosphate fertilizer.
COD of the wastewater is less than or equal to 2000 mg/L, BOD 5 500. 500mg/L or less, 500mg/L or less of ammonia nitrogen, 80 mgP/L or less of phosphate and pH 6.0-7.0.
The dosage of the adsorbent is 300-400 mg/L of wastewater.
The action mechanism of the invention is as follows:
the adsorbent is fully mixed with the wastewater, has high selectivity, can adsorb phosphate in the water, and other substances in the wastewater remain in the wastewater to form wastewater rich in ammonia nitrogen. The adsorbent with adsorbed phosphate is collected after magnetic separation, and then eluted by alkali liquor, and the adsorbent is regenerated and recycled. The eluent is rich in phosphate, enters a crystallization reactor to carry out crystallization reaction with magnesium chloride solution and waste liquid rich in ammonia nitrogen, and a compound phosphate fertilizer-magnesium ammonium phosphate crystal is generated. Thus, the phosphate in the dehydrated sludge waste liquid is recovered and converted into the composite phosphate fertilizer with agricultural value.
The invention has the following advantages:
the preparation method of the phosphorus adsorbent is simple, and the obtained adsorbent has the advantages of large adsorption capacity, good phosphate selectivity, strong regeneration capacity, high purity and uniform dispersion. The magnetic responsiveness of the adsorbent enables the adsorbent to be separated from the dehydrated waste liquid under the action of an external magnetic field, so that the adsorbent captures phosphate. Because the purity of the phosphate recovered by the nano adsorbent is higher, compared with the struvite precipitation extracted by the sludge treatment section, the purity of the compound fertilizer is higher and the operability is higher. The invention prepares the compound phosphate fertilizer by utilizing ammonia nitrogen in the inlet water and an externally added magnesium chloride solution through crystallization reaction, and the produced phosphate fertilizer has low impurity content. The method of the invention makes the phosphorus-containing wastewater become a novel 'phosphorite', and avoids the resource waste caused by the discharge of a large amount of phosphorus along with the effluent or the landfill of residual sludge.
Drawings
FIG. 1 is a scanning electron microscope image of the adsorbent in example 1;
FIG. 2 is a transmission electron microscope image of the adsorbent in example 1.
Detailed Description
The present invention will be further described with reference to examples and drawings, but the present invention is not limited to the examples.
Example 1 preparation of a nano phosphate adsorbent with superparamagnetic response
（1）N 2 Under the protection, 0.42mol/L FeCl 3 Solution and 0.21mol/L FeCl 2 Mixing and stirring the solution and 25wt% of ammonia monohydrate solution according to the volume ratio of 1:1:2, adding 0.50mol/L nitric acid, and regulating the pH value to 3 to obtain Fe 3 O 4 Nano-magnetic core precursor suspension 66 mL;
(2) Slowly injecting 5mL of ethanol solution of 10wt% trimethylsiloxysilicate into the suspension prepared in the step (1) under the condition of water bath heating at 70 ℃ until the concentration of sodium silicate is 2.5wt%, magnetically separating precipitate, then washing and drying to obtain SiO 2 Wrapped Fe 3 O 4 5.2g of particles;
(3) 3.65g of magnesium chloride hexahydrate (18 mmol), 0.3176g of aluminum trichloride hexahydrate (3 mmol) and 1.11g of lanthanum chloride heptahydrate (3 mmol) were added to 400mL of NaOH solution with a concentration of 1.5mol/L to obtain a lanthanum oxide-supported magnesium aluminum double hydroxide (Mg-Al-LDHs-La) solution with a concentration of 0.85wt%;
(4) Adding the particles obtained in the step (2) into the solution obtained in the step (3) to enable SiO to be obtained 2 Wrapped Fe 3 O 4 The concentration of the particles in the solution reaches 1.27wt%, stirring for 1min under the pressure of 0.40Mpa, then carrying out ultrasonic treatment for 2min at the frequency of 35 kH and the power of 180W, and obtaining about 8.46g of adsorbent after magnetic separation.
The scanning electron microscope image of the adsorbent is shown in fig. 1, and the transmission electron microscope image is shown in fig. 2; scanning electron microscopy of the adsorbent shows the polycrystalline structure of the adsorbent: the relatively regular shaped adsorbent particles are packed together to form a rough surface morphology. High power transmission electron micrographs clearly show the core-shell structure of black magnetite (ferroferric oxide) particles ranging in diameter from 35-50nm with a shell thickness of about 10nm. Although the silica coating and the double metal hydroxide cause surface roughness, the original structure of magnetite remains generally unchanged. Under the normal temperature 298K, the SQUID magnetic test shows that the material is a superparamagnetic response material, and the saturation magnetization is 65.43emu/g; the specific surface area of the material measured by BET-N2 is 132.5m 2 /g。
Comparative example 1 preparation of superparamagnetic response nanophosphate adsorbent
An adsorbent is prepared according to the method, the steps and the raw material proportion in the example 1, except that the reaction in the step (4) is carried out under normal pressure to obtain the adsorbent, and the SQUID magnetic test shows that the material is a superparamagnetic response material, and the saturation magnetization is 65.10emu/g; the specific surface area of the material measured by BET-N2 is 124.6m 2 /g。
Comparative example 2 preparation of superparamagnetic response nanophosphate adsorbent
An adsorbent is prepared according to the method, the steps and the raw material proportion in the embodiment 1, except that aluminum chloride and magnesium chloride solution are not added in the step (3), so as to obtain the adsorbent, and the SQUID magnetic test shows that the material is a superparamagnetic response material, and the saturation magnetization is 68.80emu/g; the specific surface area of the material measured by BET-N2 is 120.5m 2 /g。
EXAMPLE 2 adsorption Effect of different adsorbents
Adsorption data were fitted using Langmuir and Freundlich models, and the parameters after fitting are shown in table 1:
TABLE 1 adsorption model parameters for different adsorbents
Table 1 shows the parameters of the adsorbents prepared according to the procedure of the different examples after fitting the adsorption capacities of the adsorbents to the Langmuir and Freundlich adsorption isothermal models. R is R 2 The closer to 1, the better the fitting effect, and therefore, the Langmuir model can more accurately simulate the adsorption process of the adsorbent to phosphate. In addition, parameter q m Maximum adsorption capacity parameter. As is clear from the data in table 1, the adsorbent in example 1 has the greatest maximum adsorption capacity for phosphate and the best adsorption effect. This means that during the synthesis of the adsorbent, pressurization can increase its adsorption capacity for phosphate; the magnesium-aluminum double metal hydroxide loaded with lanthanum oxide is used as the outer layer of the adsorbent, so that more phosphate can be adsorbed than the magnesium-aluminum double metal hydroxide is used as the outer layer of the adsorbent, and the adsorption capacity is stronger.
Comparative example 3 preparation of superparamagnetic response nanophosphate adsorbent
An adsorbent was prepared in the same manner as in example 1, except that the trimethylsilyloxy silicate solution in step (2) was replaced with 0.9mL of a 70wt% sodium silicate solution to obtain an adsorbent.
The same phosphate solutions were subjected to adsorption-regeneration using example 1 and comparative example 3, and the corresponding adsorption capacity changes are shown in table 2:
TABLE 2 adsorption Performance variation of trimethylsilyloxy silicate and sodium silicate materials
The elemental composition of the different adsorbents prepared in example 1 and comparative example 3 was measured, and the results showed that the Fe content was reduced by about 5%, the Mg and Al content was reduced by about 10%, and the lanthanum content was reduced by 15% over 50 cycles of adsorption-regeneration cycles. As can be seen from the data in table 2, the adsorption capacity loss rate of the phosphate adsorbent prepared from the organosilicon as a raw material was lower than that of the inorganic silicon.
Example 3 preparation of a superparamagnetic responsive nanophosphate adsorbent
(1) 11 parts of Fe were prepared in the same manner as in step (1) of example 1 3 O 4 A nano-magnetic core precursor suspension;
(2) 11 parts of SiO were prepared in the same manner as in step (2) of example 1 2 Wrapped Fe 3 O 4 Particles;
(3) Adding magnesium chloride hexahydrate, aluminum trichloride hexahydrate and lanthanum chloride heptahydrate into 400mL of NaOH solution with the concentration of 1.5mol/L according to the mass shown in the table 3 to obtain a lanthanum oxide-loaded magnesium aluminum double metal hydroxide (Mg-Al-LDHs-La) solution;
(4) And (3) respectively adding the particles obtained in the step (2) into the solution obtained in the step (3), stirring for 1min under the pressure of 0.40Mpa, and then carrying out ultrasonic treatment for 2min at the frequency of 35 kH and the power of 180W to obtain the adsorbent.
Phosphate solution with concentration of 20mg/L is prepared, the prepared adsorbent is added into the phosphate solution according to 500mg/L, the concentration of the residual phosphate radical in the solution is detected when adsorption balance is carried out, and the adsorption capacity (mg/g) of different adsorbents is calculated, and the results are shown in Table 3:
TABLE 3 raw material ratios, adsorbent compositions and adsorption capacities of different adsorbents
Example 4 preparation of a superparamagnetic responsive nanophosphate adsorbent
(1) Preparation of multiple Fe parts by the same procedure as in step (1) of example 1 3 O 4 A nano-magnetic core precursor suspension;
(2) Preparation of multiple SiO portions as in step (2) of example 1 2 Wrapped Fe 3 O 4 Particles;
(3) Adding magnesium chloride hexahydrate, aluminum trichloride hexahydrate, hafnium oxychloride octahydrate or cerium chloride to 400mL of NaOH solution with concentration of 1.5mol/L according to the mass shown in the table 4 to obtain magnesium aluminum double metal hydroxide (Mg-Al-LDHs-Hf or Mg-Al-LDHs-Ce) solution loaded with hafnium or cerium oxide;
(4) And (3) respectively adding the particles obtained in the step (2) into the solution obtained in the step (3), stirring for 1min under the pressure of 0.40Mpa, and then carrying out ultrasonic treatment for 2min at the frequency of 35 kH and the power of 180W to obtain the adsorbent.
Phosphate solution with concentration of 20mg/L is prepared, the prepared adsorbent is added into the phosphate solution according to 500mg/L, the concentration of the residual phosphate radical in the solution is detected when adsorption balance is carried out, and the adsorption capacity (mg/g) of different adsorbents is calculated, and the results are shown in Table 4:
TABLE 4 adsorbent raw material composition and adsorption Capacity for hafnium/cerium oxide Supported adsorbent
The diameter of the adsorbent loaded with hafnium oxide ranges from 32 nm to 60nm, and the shell thickness is about 10nm. At normal temperature 298K, through SQUID magnetic testThe material is proved to be a superparamagnetic response material, and the saturation magnetization is 66.13emu/g; the specific surface area of the material measured by BET-N2 is 136.2m 2 /g。
The diameter of the adsorbent loaded with cerium oxide ranges from 40 nm to 55nm, and the shell thickness is about 8nm. Under the normal temperature 298K, the SQUID magnetic test shows that the material is a superparamagnetic response material, and the saturation magnetization is 69.21emu/g; the specific surface area of the material measured by BET-N2 is 139.10m 2 /g。
Claims (10)
1. A superparamagnetic response nano phosphorus adsorbent is characterized by being in a granular core-shell structure, wherein the inner core is Fe 3 O 4 The outer shell of the material is sequentially SiO from inside to outside 2 And a magnesium aluminum double metal hydroxide on which a transition metal oxide is complexed; the average diameter of the particles is 30-80 nm, and the average thickness of the shell is 10-20 nm; the transition metal is selected from lanthanum, cerium or hafnium;
the preparation method of the superparamagnetic response nano phosphorus adsorbent comprises the following steps:
(1) Adding aluminum chloride, magnesium chloride and transition metal chloride into the NaOH solution to obtain a magnesium-aluminum double metal hydroxide solution loaded with transition metal oxide;
(2) SiO is made of 2 Wrapped Fe 3 O 4 Adding particles into the solution obtained in the step (1), stirring, pressurizing and carrying out ultrasonic treatment to obtain the superparamagnetic response nano phosphorus adsorbent;
the SiO is 2 Wrapped Fe 3 O 4 The preparation method of the particles comprises the following steps:
(i) FeCl is added 3 ·6H 2 O and FeCl 2 ·4H 2 O is dissolved in double distilled water, fully stirred with ammonia monohydrate under the condition of introducing nitrogen, and then nitric acid solution is added to prepare Fe 3 O 4 A nano-magnetic core precursor suspension;
(ii) Slowly injecting the trimethylsiloxysilicate solution into the microemulsion prepared in the step (i), heating, magnetically separating precipitate, cleaning, and drying to obtain SiO 2 Wrapped Fe 3 O 4 And (3) particles.
2. The phosphorus sorbent of claim 1, wherein in step (i), the feci 3 ·6H 2 O、FeCl 2 ·4H 2 The molar ratio of O to ammonia monohydrate is 2:1:0.92;
in step (i), fe 3 O 4 The pH value of the nano magnetic core precursor suspension is 3.0-3.5;
in step (ii), the trimethylsiloxysilicate is reacted with FeCl 3 ·6H 2 The mol ratio of O is 0.014:1-0.015:1;
in step (ii), the heating temperature and time are 50 ℃ for 3min, then 60 ℃ for 3min, then 70 ℃ for 3min.
3. The phosphorus adsorbent of claim 1, wherein the mass percent of magnesium aluminum double metal hydroxide and transition metal oxide in the superparamagnetic response nano phosphorus adsorbent is 20% -60%; the mass percentage of the transition metal oxide calculated by metal is 20-60% of the total mass of the magnesium-aluminum double metal hydroxide and the transition metal oxide.
4. The phosphorus adsorbent of claim 1, wherein the mass percent of magnesium aluminum double metal hydroxide and transition metal oxide in the superparamagnetic response nano-phosphorus adsorbent is 30% -60%.
5. The phosphorus adsorbent of claim 1, wherein said superparamagnetic responsive nano-phosphorus adsorbent has a saturation magnetization of 65-70 emu/g and a specific surface area of 130-150 m 2 /g。
6. A method for preparing the superparamagnetic response nano-phosphorus adsorbent according to any one of claims 1-5, comprising the steps of:
(1) Adding aluminum chloride, magnesium chloride and transition metal chloride into the NaOH solution to obtain a magnesium-aluminum double metal hydroxide solution loaded with transition metal oxide;
(2) SiO is made of 2 Wrapped Fe 3 O 4 And (3) adding the particles into the solution obtained in the step (1), stirring, pressurizing and carrying out ultrasonic treatment to obtain the superparamagnetic response nano phosphorus adsorbent.
7. The method of claim 6, wherein in step (1), the molar ratio of aluminum chloride, magnesium chloride and transition metal chloride is 1-17:1:1-226;
the concentration of the magnesium-aluminum double metal hydroxide solution loaded with the transition metal oxide is 0.8-1wt percent.
8. The method according to claim 6, wherein in the step (2), siO 2 Wrapped Fe 3 O 4 The content of the particles in the solution obtained in the step (1) is 10-15 wt percent;
the ultrasonic frequency is 35-40 kH, the power is 180-200W, and the time is 1-2 min;
the pressure is 0.40-0.45 Mpa.
9. Use of a phosphorus adsorbent as defined in any one of claims 1 to 5 in wastewater treatment.
10. The use according to claim 9, wherein the sewage has a COD of 2000 mg/L, BOD5 500mg/L or less, an ammonia nitrogen of 500mg/L or less, a phosphate of 80 mgP/L or less, and a pH of 6.0-7.0;
the dosage of the adsorbent is 300-400 mg/L of wastewater.
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