CN112755954A - Preparation method and application of nitrogen and phosphorus removal hydroxy aluminum vermiculite sludge particles - Google Patents

Preparation method and application of nitrogen and phosphorus removal hydroxy aluminum vermiculite sludge particles Download PDF

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CN112755954A
CN112755954A CN202011592403.1A CN202011592403A CN112755954A CN 112755954 A CN112755954 A CN 112755954A CN 202011592403 A CN202011592403 A CN 202011592403A CN 112755954 A CN112755954 A CN 112755954A
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vermiculite
aluminum
sludge
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冉阳
付峥嵘
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Hunan University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12Naturally occurring clays or bleaching earth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid 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
    • B01J20/0248Compounds of B, Al, Ga, In, Tl
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid 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 form
    • B01J20/28016Particle form
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/288Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/58Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/105Phosphorus compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/001Runoff or storm water

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Abstract

The invention relates to a preparation method and application of hydroxyl aluminum vermiculite sludge particles for removing nitrogen and phosphorus, wherein vermiculite is washed by deionized water for multiple times, then is corroded by hydrochloric acid solution, is subjected to solid-liquid separation, is washed to be neutral and is dried to prepare acid modified vermiculite; and (2) oscillating the acid modified vermiculite with an aluminum sulfate solution in ultrasonic oscillation for 30min, soaking for 24h to obtain a mixed solution, dropwise adding a sodium hydroxide solution into the mixed solution until the pH value of the mixed solution is alkalescent, carrying out solid-liquid separation, and drying to obtain the hydroxy aluminum vermiculite. The invention uniformly mixes the hydroxy aluminum vermiculite and the aluminum sludge according to the mass ratio, prepares the mixture solid particles by a ball pressing forming machine, dries the mixture in an automatic program control oven, and finally bakes the mixture for 1 hour at 500 ℃ in a muffle furnace and cools the mixture to prepare the hydroxy aluminum vermiculite sludge particles. The composite particle filler has good stability, changes waste into valuable, has good ammonia nitrogen adsorption performance, and can enhance the generation of phosphorus adsorption precipitation on the particle surface.

Description

Preparation method and application of nitrogen and phosphorus removal hydroxy aluminum vermiculite sludge particles
Technical Field
The invention relates to a preparation method and application of a hydroxy aluminum vermiculite sludge particle filler, in particular to a preparation method and application of hydroxy aluminum vermiculite sludge particles for nitrogen and phosphorus removal, and belongs to the technical field of rainwater treatment.
Background
Due to the development of urbanization and the increase of hardening area of urban areas, rainwater is directly discharged after falling on the ground surface without being treated, and the problem of environmental pollution caused by precipitation runoff is increasingly serious. The traditional urban rainwater drainage system is used for quickly draining rainwater runoff by building a rainwater pipeline system and enlarging the impervious area, so that runoff is increased, the peak time is advanced, and urban waterlogging is aggravated. In heavy rain, rainwater runoff entraps surface settlement pollutants and enters a discharged water body, so that surface water such as natural water body and the like is seriously polluted and even has a stink phenomenon.
With the rising of sponge city construction, the rapid drainage mode of cities is gradually replaced. As one of the contents of sponge city construction, the bioretention facility collects and treats the rainwater and then discharges the rainwater, thereby eliminating the waterlogging caused by rain and the chronic diseases of sewage transverse flow due to the shortage of the drainage facility, relieving the water environment problem caused by rainwater runoff pollution and the like, and promoting and solving the problems of urban waterlogging, rainwater collection and utilization, black and odorous water body treatment and the like. The biological detention pool can effectively remove Total Suspended Solids (TSS), heavy metals/metalloids, pathogens and grease in rainwater, but the removal effect of the biological detention pool on nitrogen and phosphorus is poor, and sometimes, the matrix filler in the biological detention pool even has the phenomenon of nitrogen and phosphorus loss, so that the concentration of total nitrogen and total phosphorus in the effluent of the biological detention pool is increased. In order to overcome the defect that the traditional bioretention pond has poor effect of removing nitrogen and phosphorus in the rainwater treatment of a sponge city, the composite adsorption filler applied to the denitrification and dephosphorization of rainwater needs to be researched and developed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a granular filler of hydroxy aluminum vermiculite sludge, which can strengthen the nitrogen and phosphorus removal effect of rainwater; the second purpose of the invention is to provide the application of the granular filler of the hydroxy aluminum vermiculite sludge in rainwater treatment, solve the inherent defect of poor nitrogen and phosphorus removal effect of the bioretention pond, reduce nutrients in rainwater and facilitate the alleviation of the eutrophication phenomenon of surface water.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of hydroxyl aluminum vermiculite sludge particles for nitrogen and phosphorus removal comprises the following steps:
s1, washing vermiculite with deionized water for multiple times, corroding with a hydrochloric acid solution, oscillating for 3 hours at 25 ℃ in a constant-temperature oscillator, standing, performing solid-liquid separation, washing the acid-treated vermiculite to be neutral, drying for 2 hours in an automatic program control oven, and grinding to obtain acid-modified vermiculite for later use;
s2, adding the acid modified vermiculite obtained through the S1 treatment into a water-soluble trivalent aluminum salt solution, oscillating for 30min in ultrasonic oscillation, soaking for 24h to obtain a mixed solution, dropwise adding a sodium hydroxide solution into the mixed solution until the pH value of the mixed solution is alkalescent, and finally performing solid-liquid separation and drying to obtain the hydroxyl aluminum vermiculite;
s3, the aluminum sludge is derived from water treatment residues of water plants, has high humidity, is naturally dried and then is ground into powder for later use;
s4, uniformly mixing the hydroxy aluminum vermiculite with the aluminum sludge, adding water, fully stirring, preparing into mixed solid particles by using a ball pressing forming machine, drying in an automatic program control oven, roasting in a muffle furnace, and cooling to room temperature to obtain the hydroxy aluminum vermiculite sludge particles.
Further, in S1, the concentration of the dilute hydrochloric acid solution is 1-3mol/L, preferably 1 mol/L; the volume-mass ratio of the vermiculite to the dilute hydrochloric acid solution is 1g: 5-15ml, preferably 1g:10 ml.
Further, in S1, the vermiculite is natural vermiculite.
Further, in S2, Al in the water-soluble trivalent aluminum salt solution3+The concentration of (A) is 0.1-0.5mol/L, preferably 0.3 mol/L; the mass ratio of the water-soluble trivalent aluminum salt to the vermiculite is 2:1-5:1, and preferably 3:1 mol/L.
Further, in S2, the concentration of the sodium hydroxide solution is 0.1 to 1mol/L, preferably 0.1 mol/L.
Further, in S3, the aluminum sludge is derived from excess sludge from waterworks using aluminum and iron salts as coagulating agent.
Further, in S4, the drying time in the automatic program-controlled oven is 2h, and the temperature is 110 ℃.
Further, in S4, the roasting temperature in the muffle furnace is 500 ℃, and the roasting time is 1-3h, preferably 2 h.
In S4, the particle size of the hydroxy aluminum vermiculite sludge particles is 1-3cm, preferably 2 cm.
Based on the same inventive concept, the invention also provides application of the hydroxy aluminum vermiculite sludge particle filler prepared by the preparation method in rainwater denitrification and dephosphorization.
Further, mixing the rainwater to be treated with the hydroxy aluminum vermiculite sludge particle filler, and oscillating at constant temperature; wherein the mass volume ratio of the hydroxy aluminum vermiculite sludge particle filler to the rainwater is 4g:1000 mL; further, NH in the rainwater4 +The initial concentration of (A) is 0.5-3mg/L, and the initial concentration of TP is 0.5-3 mg/L.
The particle filler has large specific surface area, abundant pore structures and rough surface, contains metal ions such as iron and aluminum, is beneficial to adsorbing phosphorus, and can promote chemical precipitation of phosphorus, iron and aluminum ions so that the phosphorus is attached to the surface of the particle filler in a precipitation form.
The particle size of the particle filler is 1-3cm, the particle filler is more stable, the erosion loss of rainwater can be reduced, and resources are utilized to the maximum extent.
The hydroxy aluminum vermiculite sludge particles developed by the invention are particularly suitable for being filled into biological detention facilities for rainwater treatment in sponge cities as fillers.
The vermiculite selected in the invention is a good adsorbent, and the material is widely distributed. Corroding vermiculite with dilute hydrochloric acid to remove surface impurities and increase pore structure so as to facilitate subsequent modification; after the obtained acid modified vermiculite is mixed with a water-soluble trivalent aluminum salt solution, slowly dropwise adding a sodium hydroxide alkaline solution to adjust the pH value to be alkalescent, and finally carrying out solid-liquid separation and drying to obtain hydroxy aluminum vermiculite; uniformly mixing hydroxy aluminum vermiculite and aluminum sludge, adding water, fully stirring, preparing into mixed solid particles by using a ball pressing forming machine, drying in an automatic program control oven, roasting in a muffle furnace, and cooling to room temperature to obtain the hydroxy aluminum vermiculite sludge particles. The invention loads the aluminum hydroxide on the vermiculite, which can realize the separation of the aluminum hydroxide and the water solution, load the aluminum hydroxide on the surface of the vermiculite and enhance the chemical adsorption of phosphorus and the generation of precipitates. In addition, the specific surface area of the hydroxy aluminum vermiculite sludge particles is large, the internal pores are large, the loading capacity of hydroxy aluminum bonded by the vermiculite laminated structure is large, the stability is good, aluminum ion falling and secondary pollution cannot occur, and the excellent adsorption performance of the hydroxy aluminum vermiculite can be fully exerted. After the rainwater is treated by the particles developed by the research, the concentration of nutrients in the rainwater, particularly the concentration of phosphorus in the outlet water can be effectively reduced, and the standard of surface water IV class water can be reached.
Compared with the prior art, the hydroxy aluminum vermiculite sludge particles prepared by the invention and the application thereof have the following advantages: (1) the invention provides a preparation method of hydroxy aluminum vermiculite sludge particles, which combines hydroxy aluminum and aluminum sludge with vermiculite with excellent adsorption performance to realize the reinforced removal of nitrogen and phosphorus in rainwater by adsorption and chemical precipitation modes, so that the effluent quality reaches the surface level IV class water standard.
(2) There are many researches related to vermiculite modification, and there are also a few reports on the research of removing ammonia nitrogen and phosphorus by using the excellent adsorption performance of vermiculite, but the research of preparing particles by mixing the modified vermiculite and water treatment residues and removing nitrogen and phosphorus in rainwater by adopting adsorption and chemical precipitation methods is not reported, and the problem of stably loading aluminum hydroxide on the surface of the vermiculite by adopting the scheme of the invention is not reported in the prior art. The preparation method adopts a precipitation method, and forms aluminum hydroxide (AlOOH) by dropping sodium hydroxide alkaline solution and controlling the reaction temperature, and the aluminum hydroxide is loaded on the surface of the vermiculite, so that the adsorption performance of the vermiculite is further improved.
(3) The preparation method of the invention abandons the traditional direct soaking, and utilizes ultrasonic waves and a constant temperature oscillator to dip, so that aluminum salt and vermiculite can be fully mixed, and the loading efficiency is improved.
(4) The preparation method comprises the steps of uniformly mixing the hydroxy aluminum vermiculite with the water treatment residues, adding water, fully stirring, preparing into mixed solid particles by using a ball pressing forming machine, drying in an automatic program control oven, roasting in a muffle furnace, and cooling to room temperature to obtain the hydroxy aluminum vermiculite sludge particles. After being roasted in a muffle furnace, the hydroxy aluminum vermiculite sludge particles have rich pore diameter structures, good stability and no secondary pollution.
(5) The hydroxy aluminum vermiculite sludge particles have the advantages of low raw material cost, simple method and easy manufacture.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of acid-modified vermiculite under a high magnification lens of example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the acid-modified vermiculite under a low magnification lens of example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the hydroxy aluminum vermiculite under a high power lens in example 1;
FIG. 4 is a Scanning Electron Microscope (SEM) image of the hydroxy aluminum vermiculite under a low magnification lens in example 1;
FIG. 5 is a Scanning Electron Microscope (SEM) image of the water treatment residue of example 1 under a high magnification;
FIG. 6 is a Scanning Electron Microscope (SEM) image of the water treatment residue of example 1 under a low magnification;
FIG. 7 is a Scanning Electron Microscope (SEM) image of the hydroxy aluminum vermiculite sludge particles under a high power lens of example 1;
FIG. 8 is a Scanning Electron Microscope (SEM) image of the hydroxy aluminum vermiculite sludge particles under a low magnification lens of example 1;
FIG. 9 is a Fourier transform Infrared Spectroscopy (FTIR) plot of acid modified vermiculite and hydroxy alumino vermiculite according to example 1;
FIG. 10 is a Fourier Infrared Spectroscopy (FTIR) plot of the hydroxy aluminovermiculite sludge particles of example 1;
FIG. 11 is an X-ray diffraction (XRD) pattern of the acid modified vermiculite and hydroxy aluminium vermiculite of example 1;
FIG. 12 is an X-ray diffraction (XRD) pattern of the hydroxy aluminovermiculite sludge particles of example 1;
FIG. 13 is a graph of the effect of hydroxyaluminum vermiculite sludge particles on the amount of phosphorus adsorbed at different pH's of example 2;
FIG. 14 is the effect of varying the amount of aluminum hydroxy vermiculite sludge particles added on the amount of phosphorus adsorbed in example 3;
FIG. 15 is a graph of the effect of hydroxyaluminum vermiculite sludge particles on the amount of phosphorus adsorbed at different initial concentrations of phosphorus for example 4;
FIG. 16 is the effect of hydroxy alumino vermiculite sludge particles on ammonia nitrogen adsorption capacity at different pH's of example 5;
FIG. 17 is the effect of the change of the feeding amount of the hydroxy aluminum vermiculite sludge particles on the ammonia nitrogen adsorption amount in example 6.
Detailed Description
In order to make the preparation method and application of the present invention easy to understand, the following will be made by combining the specific examples of the present invention and the accompanying drawings to clearly and completely explain the technical scheme of the present invention, but not to limit the present invention.
In the embodiment, the adsorption capacity and removal rate of the hydroxy-aluminous vermiculite sludge particle adsorption material to ammonia nitrogen and phosphate are calculated according to the following formulas:
qe=(C0- Ce)*V/m
QR=(C0- Ce)/ C0*100%
in the formula: q. q.seThe modified vermiculite is used for balancing adsorption capacity (mg/g); qRThe phosphorus removal rate of the modified vermiculite is; c0Is the initial mass concentration (mg/L) of phosphorus; ceThe mass concentration (mg/L) of phosphorus in the supernatant after adsorption equilibrium; v is the volume of the phosphorus solution; m is the mass (g) of the modified vermiculite.
Example 1
In the embodiment, the hydroxy aluminum vermiculite sludge particles are prepared by adopting natural vermiculite through corrosion, soaking, drying, grinding, washing, aluminum modification, mixing, ball pressing, drying and roasting, and the preparation method comprises the following steps:
the method comprises the following steps: preparing 1mol/L hydrochloric acid solution, respectively adding natural vermiculite into the hydrochloric acid solution, oscillating for 3h at 25 ℃ in a constant temperature oscillator, standing for 24h, washing with deionized water until the pH value is about 7.0, drying for 2h in a constant temperature oven at 110 ℃, and finally grinding the dried hydrochloric acid modified vermiculite (HMV) to obtain 200-mesh modified vermiculite powder;
step two: taking 1mol/L hydrochloric acid modified vermiculite as a base, firstly soaking the weighed acid modified vermiculite with 0.03 mol/L1/L aluminum sulfate solution for 24 hours according to the solid-to-liquid ratio of 1:5, then regulating the pH value to be neutral with 0.01mol/L sodium hydroxide solution, finally soaking for 12 hours to prepare hydroxy aluminum vermiculite (AMV), washing the vermiculite with deionized water, and respectively placing the vermiculite into a thermostat and drying at 110 ℃ for later use;
step three: the aluminum sludge is derived from water treatment residues of water plants, has high humidity, is naturally dried and then is ground into powder for later use; uniformly mixing hydroxy aluminum vermiculite and aluminum sludge, adding water, fully stirring, preparing into mixed solid particles by using a ball pressing forming machine, drying at 110 ℃ in an automatic program control oven, finally roasting in a muffle furnace at 500 ℃ for 2 hours, and cooling to room temperature to obtain the hydroxy aluminum vermiculite sludge particles.
Fig. 1 and 2 are Scanning Electron Microscope (SEM) images of the acid-modified vermiculite obtained in the first step under high and low magnification lenses, fig. 3 and 4 are Scanning Electron Microscope (SEM) images of the hydroxy aluminum vermiculite obtained in the second step under high and low magnification lenses, fig. 5 and 6 are Scanning Electron Microscope (SEM) images of aluminum sludge under high and low magnification lenses, and fig. 7 and 8 are Scanning Electron Microscope (SEM) images of hydroxy aluminum vermiculite sludge particles obtained in the third step under high and low magnification lenses. The vermiculite structure is a layered structure, wherein the surface of the hydrochloric acid modified vermiculite is smooth, a rough appearance is not formed, and the vermiculite has an obvious short-crack structure and a certain gap structure after being corroded by hydrochloric acid; the hydroxyl aluminum vermiculite has a relatively rough appearance, and a plurality of fine particles are distributed on the surface of the hydroxyl aluminum vermiculite, so that the hydroxyl aluminum vermiculite can provide a good living environment for the growth of a biological membrane, and can improve the biological load and the ion exchange capacity; observing the surface form of the sludge by water treatment residues under a low power lens to form a honeycomb shape, wherein the particles are irregularly arranged and have rich void structures and large specific surface areas; the surface of the sludge particles is loose and porous under a high power lens, the pores are large, and the specific surface area is high; the hydroxyl aluminum vermiculite sludge particles have large internal pores, rough and loose surfaces, are porous, increase the specific surface area, reduce the zeta potential, are attached with a large amount of metal aluminum ions, and have more active functional groups.
Fig. 9 is a graph of fourier infrared spectroscopy (FTIR) of acid modified vermiculite and hydroxy aluminium vermiculite, and fig. 10 is a graph of fourier infrared spectroscopy (FTIR) of hydroxy aluminium vermiculite sludge particles. The analysis test is carried out on a Fourier infrared spectrum infrared spectrometer, and the modified leech is preparedGrinding stone and hydroxy aluminum vermiculite sludge particles into powder, mixing and tabletting with spectrally pure potassium bromide respectively according to the mass ratio of 1:100, and performing infrared spectrum analysis (the wavelength range is 4000--1). The hydroxy aluminum vermiculite has rich surface active groups compared with acid modified vermiculite, and the hydroxy aluminum vermiculite sludge particles have the characteristics of both the hydroxy aluminum vermiculite and the acid modified vermiculite, and an infrared spectrogram of the hydroxy aluminum vermiculite consists of a plurality of peaks with different intensities and has stretching vibration and bending vibration of hydroxy; stretching vibration of Si-O; C-O stretching vibration; stretching and contracting vibration of Al-O; stretching and contracting vibration of Fe-O.
Fig. 11 is an X-ray diffraction (XRD) pattern of acid-modified vermiculite and hydroxy aluminum vermiculite, and fig. 12 is an X-ray diffraction (XRD) pattern of hydroxy aluminum vermiculite sludge particles. When the modified vermiculite is subjected to X-ray diffraction (XRD) analysis, compared with the hydrochloric acid modified vermiculite, the diffraction characteristic peak intensity of the hydroxy aluminum vermiculite is weakened, and the position of the characteristic peak is unchanged, so that the damage of the hydroxy aluminum loading process to the vermiculite crystal structure is small. In addition, the hydroxy aluminum vermiculite has the characteristics of relatively obvious broadening of diffraction peaks and shortening of diffraction peaks. The diffraction characteristic peak of the hydroxy aluminum vermiculite sludge particles is similar to that of modified vermiculite, but the content of mineral substances is different, and the hydroxy aluminum vermiculite sludge particles are mainly formed by SiO2、KAl2(AlSi3O10)(OH)2、Al2(Si2O5)(OH)4、Ca3Al2Si3O12The contents of the mineral substances are 71%, 15.7%, 11% and 2.3% respectively.
Example 2
The preparation method of the hydroxy aluminum vermiculite sludge particles is the same as the first step, the second step and the third step in the example 1.
Step four: the pH value of 5mg/L phosphorus initial concentration is respectively adjusted to 2, 4, 6, 8, 10 and 12 by using dilute HCl or NaOH, the adding amount of the hydroxy aluminum vermiculite sludge particles is 0.5g/L, the hydroxy aluminum vermiculite sludge particles are added into a 250ml conical flask, the conical flask is oscillated at 150 r/min in a constant temperature oscillator, and the concentration of phosphorus in the sample is measured at regular time until the concentration of phosphorus in the sample is not changed. The results are shown in FIG. 13, which shows the adsorption capacity of aluminum hydroxy vermiculite sludge particles by adjusting the pH in the rain waterThe influence of (3) can be seen that the adsorption capacity initially increased and then decreased with increasing pH, and the maximum adsorption amount of 2.11mg · g was reached at pH =6-1The result shows that the aluminum hydroxy vermiculite sludge particles have better phosphorus adsorption removal performance.
Example 3
The preparation method of the hydroxy aluminum vermiculite sludge particles is the same as the first step, the second step and the third step in the example 1.
Step four: adjusting the pH =6 in the initial phosphorus concentration of 5mg/L, adding the hydroxy aluminum vermiculite sludge particles in the amount of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 g/L respectively, adding the hydroxy aluminum vermiculite sludge particles in the amount of 250ml conical flasks with the initial phosphorus concentration of 5mg/L respectively, oscillating the flasks at the temperature of 25 ℃ at 150 r/min in a constant temperature oscillator, and measuring the phosphorus concentration in the sample at regular time until the phosphorus concentration in the sample is not changed. As a result, as shown in FIG. 14, the phosphorus removal rate rapidly increased as the amount of addition was gradually increased, and the amount of addition was 5 g.L-1When the method is used, the removal rate is close to 80%, and the adsorption quantity is reduced, but the method still has good adsorption effect on phosphorus. When the adding amount exceeds 6 g.L-1In the process, although the removal rate can be stably increased, the adsorption quantity of the unit adsorbent to phosphorus is greatly reduced because adsorption sites on the surfaces of the hydroxy aluminum vermiculite sludge particles are greatly occupied by adsorbed phosphorus.
Example 4
The preparation method of the hydroxy aluminum vermiculite sludge particles is the same as the first step, the second step and the third step in the example 1.
Step four: under the condition that the pH =6 is not changed, the initial phosphorus concentration is 1, 2, 3, 4, 5, 6, 7 and 8mg/L respectively, the adding amount of the hydroxy aluminum vermiculite sludge particles is 0.5g/L, the hydroxy aluminum vermiculite sludge particles are added into a 250ml conical flask, the conical flask is oscillated in a constant temperature oscillator at 25 ℃ and 150 r/min, and the oscillation is carried out fully for 180 min. And (4) filtering the solution subjected to adsorption oscillation by using a 0.45 mu m filter membrane, and then measuring the concentration of phosphorus in the solution. As a result, as shown in fig. 15, as the initial concentration of phosphorus is continuously increased, the electrostatic attraction is gradually increased, the adsorption sites on the surface of the modified vermiculite are more easily occupied, and the adsorption amount of the hydroxy aluminum vermiculite sludge particles is gradually increased. The TP removal rate is increased rapidly when the initial concentration is 1mg/L-3mg/L, the TP removal rate is increased slowly when the initial concentration is 3mg/L-4mg/L, and the highest removal rate can reach 86 percent; after the initial concentration reaches 4mg/L, the TP removal rate is gradually reduced, but the lowest removal rate is more than 70%, and the TP removal rate is reduced probably because the active adsorption sites of the hydroxy aluminum vermiculite sludge particles are reduced after a large number of phosphorus molecules are combined on the adsorption sites.
Example 5
The preparation method of the hydroxy aluminum vermiculite sludge particles is the same as the first step, the second step and the third step in the example 1.
Step four: respectively adjusting the pH value of 5mg/L ammonia nitrogen initial concentration to 2, 4, 6, 8, 10 and 12 by using dilute HCl or NaOH, adding 0.5g/L hydroxyl aluminum vermiculite sludge particles into a 250ml conical flask, oscillating at the temperature of 25 ℃ in a constant temperature oscillator at 150 r/min, and periodically measuring the concentration of ammonia nitrogen in the sample until the concentration of ammonia nitrogen in the sample is not changed. Hydroxyaluminum vermiculite sludge particle pair NH under different pH values4 +The results of the change in the adsorption amount of-N are shown in FIG. 16. When the pH of the solution is lower than 9, NH is added along with the increase of the pH value4 +-the N adsorption capacity increases gradually; when pH =9, the maximum adsorption amount is 15.01mg g-1Followed by NH4 +The adsorption quantity of-N is gradually reduced, which indicates that the hydroxy aluminum vermiculite sludge particles adsorb NH in an alkaline environment4 +The effect of-N is better. However, too high or too low pH of the solution is not favorable for NH4 +-adsorption of N. NH in solution when the pH is too low4 +In its predominant form, a large amount of H is present in solution+,H+Compete for the surface active sites of the aluminum hydroxy vermiculite sludge particles and NH4 +Generating competitive adsorption; while the OH groups present in the solution increase with increasing pHIncrease of OHCan reduce the cationic charge on the surface of the material, thereby promoting the adsorption effect to be enhanced, and when the pH value is too high, OH is added-And NH4 +Formation of weak electrolyte NH3·H2O, influence NH4 +-adsorption effect of N.
Example 6
The preparation method of the hydroxy aluminum vermiculite sludge particles is the same as the first step, the second step and the third step in the example 1.
Step four: adjusting pH =6 in 5mg/L ammonia nitrogen initial concentration, and adding the hydroxy aluminum vermiculite sludge particles respectively at 0.1, 0.2, 0.5, 1.0 and 2.0 g.L-1Respectively adding the mixture into a 250ml conical flask, oscillating the mixture in a constant temperature oscillator at the temperature of 25 ℃ at 150 r/min, and periodically measuring the concentration of ammonia nitrogen in the sample until the concentration of phosphorus in the sample is unchanged. The results are shown in FIG. 17, where the amount of the hydroxy aluminum vermiculite sludge particles added is equal to the amount of NH added4 +The adsorption amount of N is in a positive correlation in a certain range. When the adding amount is less than 0.5 g.L-1When is NH4 +The N adsorption rate increases sharply with the addition of the aluminum hydroxy vermiculite sludge particles; when the adding amount is more than 0.5 g.L-1Then, hydroxy aluminium vermiculite sludge particle pair NH4 +The adsorption amount of N is in a steady trend. This may be due to NH in solution4 +The N concentration is fixed, the more the adding amount of the hydroxy aluminum vermiculite sludge particles is, the more adsorption sites are provided, and NH is4 +The easier N is to bind to active sites on the hydroxy aluminum vermiculite sludge particles and be adsorbed; however, with the increasing dosage of the hydroxy aluminum vermiculite sludge particles, competitive adsorption of binding sites can be generated, so that the adsorption amount per unit area is reduced. When the adding amount of the hydroxy aluminum vermiculite sludge particles reaches 0.5 g.L-1Then, the adsorption capacity tends to be stable, the increase range of the adsorption rate is reduced, and the change of the number of the surface active sites of the adsorbent is reduced.
The foregoing embodiments are set forth so that the present invention will be more clearly understood and appreciated by those skilled in the art, and it will be understood that various changes and modifications may be made without departing from the spirit and scope of the invention, and all changes and modifications that fall within the metes and bounds of the claims appended hereto as well as equivalents thereof.

Claims (10)

1. A preparation method of hydroxyl aluminum vermiculite sludge particles for nitrogen and phosphorus removal is characterized by comprising the following steps:
s1, washing vermiculite with deionized water for multiple times, corroding with a hydrochloric acid solution, oscillating for 3 hours at 25 ℃ in a constant-temperature oscillator, standing, performing solid-liquid separation, washing the acid-treated vermiculite to be neutral, drying for 2 hours in an automatic program control oven, and grinding to obtain acid-modified vermiculite for later use;
s2, adding the acid modified vermiculite obtained through the S1 treatment into a water-soluble trivalent aluminum salt solution, oscillating for 30min in ultrasonic oscillation, soaking for 24h to obtain a mixed solution, dropwise adding a sodium hydroxide solution into the mixed solution until the pH value of the mixed solution is alkalescent, and finally performing solid-liquid separation and drying to obtain the hydroxyl aluminum vermiculite;
s3, the aluminum sludge is derived from water treatment residues of water works, has high humidity, is naturally dried and then is ground into powder for later use;
s4, uniformly mixing the hydroxy aluminum vermiculite with the aluminum sludge, adding water, fully stirring, preparing into mixed solid particles by using a ball pressing forming machine, drying in an automatic program control oven, roasting in a muffle furnace, and cooling to room temperature to obtain the hydroxy aluminum vermiculite sludge particles.
2. The method according to claim 1, wherein the hydrochloric acid solution has a pH value of 1-3 and a standing time of 24h in S1, and is dried in a thermostat for 2h at a temperature of 110 ℃, and finally the dried hydrochloric acid-modified vermiculite is ground to obtain 200-mesh modified vermiculite powder.
3. The method of claim 1, wherein the drying temperatures of S1-S4 in the automatic programmed oven are all 110 ℃.
4. The method according to claim 1, wherein the water-soluble trivalent aluminum salt in S2 is aluminum sulfate or aluminum chloride, preferably aluminum sulfate.
5. The method according to claim 1, wherein in S2, Al in the water-soluble trivalent aluminum salt solution is3+The concentration of (A) is 0.1-1mol/L, acid modified leechSoaking the stone and the aluminum sulfate solution according to the solid-to-liquid ratio of 1: 5.
6. The method according to claim 1, wherein in S3, the aluminum sludge is derived from water plant processing residues using iron and aluminum salts as coagulating agent.
7. The preparation method according to claim 1, wherein in S4, the aluminum sludge and the aluminum hydroxy vermiculite are uniformly mixed according to a mass ratio of 1:1 to prepare pellets with a particle size of 2-3 mm.
8. The method according to claim 1, wherein the dried mixed solid particles in S4 are calcined in a muffle furnace at a temperature of 500 ℃ for a time of 2 hours.
9. The application of the granular filler of the hydroxy aluminum vermiculite sludge prepared by the preparation method of any one of claims 1 to 8 in the denitrification and dephosphorization of rainwater.
10. The application of the hydroxyl aluminum vermiculite sludge as claimed in claim 8, wherein the granular packing of the hydroxyl aluminum vermiculite sludge is good in stability, and waste is used as a treasure, so that the granular packing has good ammonia nitrogen adsorption performance and can enhance the generation of phosphorus adsorption precipitation on the surfaces of granules.
CN202011592403.1A 2020-12-29 2020-12-29 Preparation method and application of nitrogen and phosphorus removal hydroxy aluminum vermiculite sludge particles Pending CN112755954A (en)

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