CN115106051A - Rapid settling defluorinating agent and preparation method and application method thereof - Google Patents
Rapid settling defluorinating agent and preparation method and application method thereof Download PDFInfo
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Abstract
The invention discloses a rapid-settling defluorinating agent and a preparation method and an application method thereof. The rapid sedimentation defluorinating agent is spherical-like particles or regular spherical particles, the sphericity is 0.6-1, the interior of the rapid sedimentation defluorinating agent is of a solid structure, no complex pore canal with the surface communicated with the interior is formed, the particle size is 50-800 mu m, the small particle size is beneficial to strengthening the diffusion characteristic, and the density is 1.5-2.3 g/cm 3 The influence of fluid buoyancy is small, and the flow-around resistance is more favorably reduced in the same particle size interval, so that the gravity can be used forSedimentation is very easy to separate from water, the sedimentation time is only 2-5 s, and the defect of difficult separation of the powder defluorinating agent in practical application is overcome. Meanwhile, the preparation method of the defluorinating agent is simple, the particle size, the sphericity and the density of the geopolymer microsphere carrier meet the separation requirement through material proportion and parameter optimization in the dispersion-suspension-curing process, and the defluorinating agent has certain mechanical strength, is not easy to damage, has high durability, is beneficial to large-scale production and commercialization, and has the advantage of operation cost, and inorganic active functional components are stable and do not fall off.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a rapid settling defluorinating agent for defluorinating drinking water, surface water, underground water and industrial wastewater, and a preparation method and an application method thereof.
Background
Fluorine pollution mainly comes from the production and application of phosphate fertilizers, the aluminum industry, the glass industry, the steel smelting, the coal combustion process and the like. In industrial enterprises, industrial wastewater such as electroplating, metal processing and the like and washing water for treating fluorine-containing waste gas by a washing method contain a certain amount of fluorine, and the settlement of fluorine-containing smoke dust or leaching of precipitation can pollute soil and underground water. Although fluorine is one of the essential trace elements of human body, excessive intake of fluorine can harm human body, and mild people suffer from symptoms such as mottled glaze, waist soreness and backache, and severe people suffer from fluorosis, resulting in malformation of patient skeleton. The environmental quality standard of surface water in China (GB 3838-2002) stipulates that the standard limits of fluoride in I-III and IV/V water areas are 1.0mg/L and 1.5mg/L (calculated as F < - >). Therefore, the development of the deep purification technology for trace fluorine in water has important significance for realizing the safety control of the water body.
The prior fluorine removal technology with application scale mainly takes a chemical precipitation method and an adsorption method. The chemical precipitation technology is difficult to reach the effluent standard of 1.0mg/L, and a large amount of fluorine-containing sludge is generated. The fluorine removal agent used in the fluorine removal by the adsorption method is usually powder, so that the contact between fluorine ions and the fluorine removal agent is improved, but the problems of easy loss and difficult sedimentation exist in the practical application.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a defluorinating agent capable of rapidly settling and a preparation method and an application method thereof, so as to solve the problems that the existing powder defluorinating agent is easy to run off and difficult to settle when used for treating fluorine-containing wastewater.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a rapid sedimentation defluorinating agent, which is in the shape of spheroidal particles or regular spheroidal particles, the sphericity is 0.6-1, the particle size is 50-800 mu m, and the density is 1.5g/cm 3 ～2.3g/cm 3 。
Furthermore, the rapid sedimentation fluorine removal agent takes geopolymer microspheres as a carrier and nanometer lanthanum oxide as an inorganic functional adsorbent; wherein the surface of the geopolymer microsphere is rough and has no internal communicating pore canal, and the specific surface area is 8m 2 /g～12m 2 (ii)/g; the nanometer lanthanum oxide is short rod-shaped nanometer particles with the diameter range of 5 nm-8 nm, and is a cubic crystal system.
The invention provides a preparation method of a rapid sedimentation fluorine removal agent, which comprises the following steps: preparing activated kaolin in advance; mixing the prepared activated kaolin and an alkaline compound, stirring to form slurry, slowly pouring the slurry into continuously stirred organic liquid, and dispersing, suspending and curing to obtain a geopolymer precursor; curing the geopolymer precursor to obtain a geopolymer microsphere; and soaking the geopolymer microspheres in an alkali solution, sequentially adding the geopolymer microspheres into a lanthanum salt solution and an alkali solution to react, filtering out solids, burning the solids, and then cleaning and drying to obtain the rapid settling defluorinating agent.
Further, the method specifically comprises the following steps: s101, calcining kaolin in a muffle furnace at 400-900 ℃ for 1-12 h to obtain activated kaolin; s102, adding 1 part of alkaline compound into 1.5-3.3 parts of water to prepare an alkaline solution; then adding 1 part of the alkaline solution into 2.2-4.2 parts of the activated kaolin obtained in the S101, and continuously stirring at 2000rpm for 3-10 min to completely mix into slurry; the viscosity is 500mm 2 /s～1500mm 2 In a/s ofPlacing the organic liquid in a container, continuously stirring at the speed of 300-800 rpm, keeping the temperature at 55-70 ℃, and keeping the height from the liquid level of the organic liquid to the bottom of the container at 8-25 cm; slowly pouring the slurry into the stirred organic liquid at the flow rate of 0.5-2.0 ml/s, continuously stirring for 10-30 min, stopping stirring, and collecting solid particles at the bottom of a container to obtain a geopolymer precursor; s103, placing the geopolymer precursor obtained in the step S102 into a container, placing the container into a water bath kettle, maintaining for 3-12 h at 50-80 ℃, taking out the container, placing the container into a drying oven, curing and drying for 6-24 h at 50-80 ℃, then transferring into a muffle furnace, burning for 6h at 400-650 ℃ to remove the organic liquid on the surface, cooling, taking out, washing with distilled water to be neutral, drying for 4h at 80 ℃, and sealing and storing to obtain the geopolymer microspheres; s104, putting 1 part of the geopolymer microspheres obtained in the S103 into a container, adding 25 parts of 3 wt% of alkali solution, soaking for 2 hours, filtering out solid particles, adding the solid particles into 50 parts of 1 wt% -10 wt% of lanthanum salt solution, soaking and stirring for 6 hours-24 hours, filtering out solidified particles, adding 75 parts of 20 wt% -25 wt% of alkali solution into the solidified particles, immediately sealing and oscillating for 12 hours-36 hours; then filtering and separating out solid, putting the solid in a muffle furnace to be burnt for 3 to 9 hours at the temperature of between 400 and 650 ℃, taking out the solid, naturally cooling the solid to room temperature, and then washing and drying the solid by using distilled water to obtain the rapid sedimentation defluorinating agent.
Further, the alkaline compound is one or more of sodium silicate, potassium hydroxide or sodium hydroxide; the organic liquid is dimethyl silicone oil, polyethylene glycol or triglyceride oil.
Further, the alkali used in the alkali solution is one or more of sodium hydroxide, potassium hydroxide or ammonia water.
Further, the lanthanum salt used in the lanthanum salt solution is one or more of lanthanum chloride, lanthanum nitrate or lanthanum sulfate.
The third aspect of the invention provides an application method of the rapid sedimentation fluorine removal agent, which comprises the following steps: s201, placing 1 part of rapid settling defluorinating agent in a batch reactor; s202, injecting 1000-5000 parts of fluorine-containing water into the batch reactor, wherein the fluorine-containing waterThe concentration of the fluorine ions is 1mg/L to 50mg/L, the pH is 2 to 8, and SO 4 2- 、Cl-、NO 3- 、PO 4 3- HA and the like coexisting materials have a concentration of 0mg/L to 1000 mg/L; s203, starting a stirring switch, setting the stirring speed to be 200-800 rpm, setting the treatment temperature to be 10-60 ℃, continuously reacting for 10-30 min, and stopping stirring; s204, after stopping stirring for 2-5S, settling the defluorinating agent to the bottom of the reactor through self gravity, and sampling at a water outlet of the reactor to measure the concentration of the fluorine ions; and S205, repeating the steps from S202 to S204 until the concentration of the fluorine ions in the effluent does not meet the water quality standard requirement, and stopping operation.
The fourth aspect of the invention also provides an application method of the rapid sedimentation fluorine removal agent, which is characterized by comprising the following steps: s301, filling 1 part of rapid settling defluorinating agent into a reaction column of a continuous reactor; s302, continuously injecting fluorine-containing water into the reaction column at a flow rate of 50-250 parts/h, and controlling the temperature at 10-60 ℃; wherein the fluorine ion concentration in the fluorine-containing water is 1 mg/L-50 mg/L, the pH is 2-8, and SO is added 4 2- 、Cl - 、NO 3- 、PO 4 3- HA and the like coexisting materials are 0mg/L to 1000 mg/L; s303, collecting the treated effluent or sampling to determine the concentration of the fluorine ions until the concentration of the fluorine ions in the effluent does not meet the requirement of the water quality standard.
Further, the method also comprises the following steps: s401, taking the rapid sedimentation fluorine removal agent in the batch reactor or the continuous reactor into a clean container; s402, adding 100 parts of 4 wt% sodium hydroxide solution, stirring and eluting for 6-12 h, and then cleaning the rapid sedimentation defluorinating agent with distilled water to be neutral; and S403, taking out the rapid settling defluorinating agent in the step S402, adding 100 parts of 5 wt% sodium chloride solution, stirring for 6-12 h, taking out the defluorinating agent, washing with distilled water for 2 times, drying, and drying to obtain the regenerated rapid settling defluorinating agent which can be matched with intermittent operation or continuous operation again.
Compared with the prior art, the technical scheme provided by the invention at least has the following advantages:
the rapid sedimentation defluorinating agent provided by the invention is spherical-like particles or regular spheres in appearanceThe particle has a sphericity of 0.6-1, a solid structure inside, no surface and internal communicated complex pore canal, a particle size of 50-800 μm, a small particle size favorable for enhancing diffusion characteristics, and a density of 1.5-2.3 g/cm 3 The influence of fluid buoyancy is small, and the reduction of the flow resistance is facilitated in the same particle size interval, so that the powder defluorinating agent can be separated from water very easily by means of gravity settling, the settling time is only 2-5 s, and the defect of difficult separation of the powder defluorinating agent in practical application is overcome.
The rapid sedimentation defluorinating agent is composed of geopolymer microspheres and nano lanthanum oxide, the geopolymer microspheres are rough in surface, lanthanum precursors are effectively dispersed by means of a unique structure of the surfaces of the microspheres, and the problems that nano powder is easy to agglomerate when fluorine-containing wastewater is treated and the treatment effect is poor are solved through the dispersion effect of a carrier on active functional components. The concentration of fluorine ions is 1 mg/L-50 mg/L, SO 4 2- 、Cl - 、NO 3- 、PO 4 3- The HA coexisting wastewater with the concentration as high as 900mg/L HAs the removal efficiency as high as more than 98 percent, and the fluorine ions in the effluent meet the environmental quality standard of surface water (GB 3838-. And by controlling the concentration of the lanthanum precursor and the concentrated ammonia water, the lanthanum oxide obtained by impregnation conversion has a nanoscale, so that the lanthanum oxide is favorably and uniformly dispersed on the surface of the microsphere, the affinity to water is strong, the mass transfer speed is high, the utilization efficiency of the rapid sedimentation defluorinating agent is improved, the sewage treatment time is short, the removal efficiency is high, the adsorption capacity is large, the adding amount is small, and the treated water amount is large.
Meanwhile, the preparation method of the rapid sedimentation defluorinating agent is simple, the particle size, the sphericity and the density of the geopolymer microsphere carrier meet the separation requirements through material proportion and parameter optimization in the dispersion-suspension-curing process, the geopolymer microsphere carrier has certain mechanical strength and is not easy to damage, inorganic active functional components are stable and do not fall off, the durability is high, the large-scale production and commercialization are facilitated, the rapid sedimentation defluorinating agent is suitable for common reactors such as intermittent, continuous and semi-continuous reactors and different operation and stirring modes such as fixing, moving, fluidizing, mechanical stirring, aerating and magnetic stirring, sedimentation separation can be directly completed in intermittent reactors or conventional precipitation equipment, the application operation steps are few, the equipment is simple, the applicability is strong, the application scene is wide, and the operation cost advantage is achieved.
Drawings
One or more embodiments are illustrated by corresponding figures in the drawings, which are not to be construed as limiting the embodiments, unless expressly stated otherwise, and which are not intended to be limiting in scale.
FIG. 1a is a microscopic topography (at 100 μm) of the fluorine removing agent in example 1 of the present invention;
FIG. 1b is a microscopic topography (at 20 μm) of the fluorine removing agent in example 1 of the present invention;
FIG. 2 is a lanthanum distribution on the surface of a fluorine removing agent in example 2 of the present invention;
FIG. 3 is an XRD pattern of the fluorine removing agent in example 2 of the present invention;
FIG. 4 is a TEM photograph of a fluorine-removing agent in example 3 of the present invention;
FIG. 5a is a graph showing the effect of the precipitation of the fluorine-removing agent (left) in example 1 of the present invention compared with the lanthanum oxide powder (right) in the comparative example (0 s at the time of stopping the stirring);
FIG. 5b is a graph showing the effect of the precipitation of the fluorine-removing agent (left) in example 1 of the present invention compared with the lanthanum oxide powder (right) in the comparative example (at 5 seconds when the stirring was stopped).
Detailed Description
As known from the background art, the prior fluorine removal technology mainly comprises a chemical precipitation method and an adsorption method.
In the chemical precipitation technology, medicaments such as lime, soluble salt and the like are used for reacting with high-concentration fluoride ions (about 1000mg/L) in industrial wastewater to form insoluble fluoride precipitate or coprecipitation, and then the formed fluorine-containing sludge is separated from water by equipment such as a sedimentation tank and the like, so that the aim of removing fluorine is fulfilled. The sedimentation tank in the field of water treatment has long development history and mature operation technology, and is widely applied to the treatment of fluorine-containing sewage, and the fluorine concentration of the effluent after sedimentation and separation is generally about several to more than ten mg/L. However, the method has insufficient purification depth for the fluorine-containing water with a low concentration of less than 10mg/L, particularly for the surface water with a concentration of less than 5mg/L, and the chemical precipitation technology is difficult to reach the effluent standard of 1.0mg/L, and a large amount of fluorine-containing sludge is generated, so that the effective treatment and resource utilization technology for the dangerous waste is still explored at present.
The adsorption method for removing fluorine mainly uses active alumina, lanthanum oxide and the like as fluorine removal agents, has the advantages of large specific surface area and many active sites, and fluorine ions are adsorbed on the fluorine removal agents after the mass transfer process from a liquid phase to a solid phase, so that the adsorption method is particularly suitable for removing low-concentration fluorine in water. In laboratory studies, the removal efficiency of lanthanum-magnesium-loaded activated alumina to 10mg/L fluoride ions can reach 94.5% (Korea, Lihongyan, Bengentian, etc.. preparation of lanthanum-magnesium-loaded activated alumina and research on fluoride removal performance. environmental engineering, 2015). However, the inventor finds that the fluorine removing agent is usually powder, and although the contact between fluorine ions and the fluorine removing agent is improved, the fluorine removing agent has the problems of easy loss and difficult sedimentation in practical application, so that the fluorine removing agent is difficult to separate in a traditional sedimentation tank by means of gravity. To solve this problem, the conventional technical solutions in the field of water treatment can be used: (1) preparing an adsorbent with a large particle size of more than 1.0mm, and intercepting the adsorbent in equipment by combining refined adsorption equipment such as a fixed bed, a moving bed or a fluidized bed; (2) preparing adsorption film and other bulk material, and combining the film assembly and apparatus to complete defluorination. For example, commercial D201 anion exchange resins have a particle size of 1mm and a density of about 1.0g/cm 3 The fluorine removal is used in cooperation with an adsorption column; ZL.201010252501.0 defluorinates by filling a fixed bed adsorption column with 2mm granular adsorbent prepared by extrusion molding; ZL.201310113037.0 adopts an activated aluminum oxide defluorination adsorption material to complete solid-liquid separation by adopting complex equipment such as a cyclone separator, a centrifugal separator, a medium filter, a membrane filter and the like; CN 111282556A is processed by electrostatic spinning and calcium source solution to prepare a defluorination composite fiber membrane; CN 113104925A adopts a surface film and an alumina modified internal supporting layer to form a composite film component for defluorination; CN 111995119A discloses can clear up the inside impurity's of filter core embrane method defluorination clarification plant, including preprocessing device, charge device, defluorination device, belt cleaning device, wherein the defluorination device part is equipped with a plurality of defluorination urceolus. Through research, the inventor finds that although the conventional technical schemes are applied to the design, preparation and application of the fluorine removal agent, the separation problem of the powder fluorine removal agent can be solved to a certain extent,but at the cost of: (1) compared with a powder fluorine removal agent, the preparation is more complex, the price is higher, the adsorption capacity is smaller, and the treatment time is longer; (2) compared with a sedimentation tank, the device has larger head loss, complex components and higher maintenance difficulty and cost.
Aiming at the problems, the invention aims to provide a defluorinating agent capable of rapidly settling and a preparation and application method thereof, so as to overcome the defects that the existing powder defluorinating agent is easy to run off, difficult to settle and difficult to separate by gravity only when used for treating fluorine-containing wastewater.
The invention provides a rapid sedimentation defluorinating agent, which is in the shape of spheroidal particles or regular spheroidal particles, the sphericity is 0.6-1, the particle size is 50-800 mu m, and the density is 1.5g/cm 3 ～2.3g/cm 3 。
The second aspect of the invention provides a preparation method of a rapid sedimentation fluorine removal agent, which comprises the following steps: preparing activated kaolin in advance; mixing the prepared activated kaolin and an alkaline compound, stirring to form slurry, slowly pouring the slurry into continuously stirred organic liquid, and dispersing, suspending and curing to obtain a geopolymer precursor; wherein the viscosity of the organic liquid is adjustable; curing the geopolymer precursor to obtain a geopolymer microsphere; and soaking the geopolymer microspheres in an alkali solution, sequentially adding the geopolymer microspheres into a lanthanum salt solution and an alkali solution to react, filtering out solids, burning the solids, and then cleaning and drying to obtain the rapid settling defluorinating agent.
The third aspect of the invention provides an application method of the rapid sedimentation fluorine removal agent, which comprises the following steps: s201, placing 1 part of rapid settling defluorinating agent in a batch reactor; s202, injecting 1000-5000 parts of fluorine-containing water into the batch reactor, wherein the concentration of fluorine ions in the fluorine-containing water is 1-50 mg/L, the pH value is 2-8, and SO is added 4 2- 、Cl - 、NO 3- 、PO 4 3- HA and the like coexisting materials have a concentration of 0mg/L to 1000 mg/L; s203, starting a stirring switch, setting the stirring speed to be 200-800 rpm, setting the treatment temperature to be 10-60 ℃, continuously reacting for 10-30 min, and stoppingStirring; s204, after stopping stirring for 2-5S, settling the defluorinating agent to the bottom of the reactor by self gravity, and sampling at a water outlet of the reactor to determine the concentration of fluorine ions; and S205, repeating the steps from S202 to S204 until the concentration of the fluorine ions in the effluent does not meet the water quality standard requirement, and stopping operation.
The fourth aspect of the invention also provides an application method of the rapid sedimentation fluorine removal agent, which is characterized by comprising the following steps: s301, filling 1 part of rapid settling defluorinating agent into a reaction column of a continuous reactor; s302, continuously injecting fluorine-containing water into the reaction column at a flow rate of 50-250 parts/h, and controlling the temperature at 10-60 ℃; wherein the fluorine ion concentration in the fluorine-containing water is 1 mg/L-50 mg/L, the pH is 2-8, and SO is added 4 2- 、Cl - 、NO 3- 、PO 4 3- HA and the like coexisting materials are 0mg/L to 1000 mg/L; s303, collecting the treated effluent or sampling to determine the concentration of the fluorine ions until the concentration of the fluorine ions in the effluent does not meet the requirement of the water quality standard.
The present invention will be described in detail with reference to the following embodiments.
Example 1
Embodiment 1 provides a method for preparing a rapid-settling fluorine removal agent, which specifically comprises the following steps:
the kaolin was calcined at 500 ℃ for 12 hours in a muffle furnace to obtain Activated Kaolin (AK).
Mixing the raw materials in a ratio of 1: 2, adding dry NaOH into water, and then adding the dry NaOH into the water according to the mass ratio of AK: NaOH 2.5: 1, activated kaolin AK was added and fully mixed to a slurry with continuous stirring at 2000rpm for 5 min. The viscosity is 1000mm 2 And (3) placing the simethicone in a container, continuously stirring at the speed of 500rpm, keeping the temperature at 55 ℃, and keeping the height from the liquid level of the simethicone to the bottom of the container to be 10 cm. Slowly pouring the slurry into the stirred dimethyl silicone oil at the flow rate of 0.5ml/L, continuously stirring for 20min, stopping stirring, and collecting solid particles at the bottom of the container, namely the geopolymer precursor.
Putting the obtained geopolymer precursor into a container, putting the container into a water bath kettle, maintaining for 4h at 55 ℃, taking out the container, putting the container into an oven, and curing and drying at 55 DEG CAnd 8h, burning for 6h at 450 ℃ in a muffle furnace to remove surface dimethyl silicone oil, cooling, taking out, washing to be neutral by using distilled water, drying for 4h at 80 ℃, and sealing and storing to obtain the geopolymer microspheres. The prepared geopolymer microspheres have rough surfaces, no internal communicated pore passages and specific surface areas of 10.37m 2 /g。
Putting 2.0g of geopolymer microspheres into a container, adding 50ml of 3 wt% sodium hydroxide solution, soaking for 2h, filtering out solid particles, adding the solid particles into 100ml of 3 wt% lanthanum chloride solution, soaking and stirring for 12h, filtering, taking out the solidified particles, adding 150ml of 15 wt% concentrated ammonia water, immediately sealing and oscillating for 12 h. Then filtering and separating out solid, putting the solid in a muffle furnace for ignition for 4h at 400 ℃, taking out the solid, naturally cooling the solid to room temperature, washing the solid with distilled water, and drying the solid to obtain the rapid sedimentation defluorinating agent.
The rapid sedimentation fluorine-removing agent obtained in example 1 had a particle size of 120 μm and a density of 1.6g/cm 3 The microscopic topography is shown in FIG. 1.
Application example 1
Application example 1 provides an application method of a rapid sedimentation fluorine removal agent, which is an intermittent operation and specifically comprises the following steps:
0.6g of the quick-settling fluorine-removing agent obtained in example 1 was taken out in a batch reactor. Opening the water inlet of the reactor, injecting 1L of fluorine-containing water into the reactor, controlling the temperature at 20 ℃, and controlling the initial pH of the fluorine-containing water to be 6.2, F - The concentration was 10 mg/L. And starting a stirring switch, setting the stirring speed to be 200rpm, continuously reacting for 10min, and stopping stirring. 3s after stopping stirring, the defluorinating agent is settled to the bottom of the reactor by self gravity. Opening the water outlet of the reactor to discharge water, and sampling and measuring the water outlet of the reactor F - Concentration, calculated to obtain F - The removal rate was 98.8%. And opening the water inlet of the reactor again, and repeatedly using the fluorine removal agent until the concentration of fluorine ions in the effluent does not meet the water quality standard requirement.
Example 2
Embodiment 2 provides a method for preparing a rapid-settling fluorine removal agent, which specifically comprises the following steps:
and placing the kaolin into a muffle furnace, and calcining at 800 ℃ for 12 hours to obtain AK.
Mixing the raw materials in a ratio of 1: 3, adding dry NaOH into water, and then adding the dry NaOH into the water according to the mass ratio of AK: NaOH is 4: 1 mass ratio, adding activated kaolin AK, and mixing completely to obtain slurry under continuous stirring at 2000rpm for 5 min. The viscosity is 1500mm 2 The simethicone/s is put into a container and stirred continuously at the speed of 800rpm, the temperature is kept at 65 ℃, and the height from the liquid level of the simethicone to the bottom of the container is 25 cm. Slowly pouring the slurry into the stirred dimethyl silicone oil at the flow rate of 2.0ml/L, continuously stirring for 30min, stopping stirring, and collecting solid particles at the bottom of the container, namely the geopolymer precursor.
And putting the obtained geopolymer precursor into a container, putting the container into a water bath kettle, maintaining for 6 hours at 65 ℃, taking out the container, putting the container into a drying oven, curing and drying for 24 hours at 65 ℃, then transferring the container into a muffle furnace, burning for 6 hours at 650 ℃ to remove surface dimethyl silicone oil, cooling, taking out, washing with distilled water to be neutral, drying for 4 hours at 80 ℃, and sealing and storing to obtain the geopolymer microsphere.
Putting 2.0g of geopolymer microspheres into a container, adding 50ml of 3 wt% sodium hydroxide solution, soaking for 2h, filtering out solid particles, adding the solid particles into 100ml of 10 wt% lanthanum chloride solution, soaking and stirring for 24h, filtering, taking out solidified particles, adding 150ml of 25 wt% concentrated ammonia water, immediately sealing and oscillating for 36 h. Then filtering and separating out solid, placing the solid in a muffle furnace for ignition for 9 hours at 650 ℃, taking out the solid, naturally cooling the solid to room temperature, and then washing and drying the solid with distilled water to obtain the rapid sedimentation defluorinating agent.
The distribution of lanthanum element of the rapid sedimentation fluorine removal agent obtained in example 2 is shown in fig. 2, and the XRD pattern is shown in fig. 3, wherein typical characteristic peaks of cubic lanthanum oxide are shown, which illustrates that a composite material containing lanthanum oxide is obtained by the preparation method.
5g of the quick-settling fluorine removal agent obtained in the above preparation was placed in a beaker, 100ml of distilled water was added, and the mouth of the beaker was sealed with a sealing film. The beaker was placed in a constant temperature water bath shaker and shaken at 1000rpm for 48h at 90 ℃. After the shaking was stopped, the fluorine removing agent was fished out with a 80-mesh sieve, 500ml of distilled water was used to wash the fluorine removing agent, and the washing liquid was collected in the above beaker. The entire liquid in the beaker was filtered through filter paper. The above liquid-filtered filter paper was dried at 80 ℃ for 24 hours, and no particles or powder visible to the naked eye was observed on the filter paper. And randomly selecting 50 particles in the fluorine removal agent, observing under a microscope, wherein the sampled fluorine removal agent particles still have a complete spherical appearance, and no broken particles are observed. The defluorination agent has certain mechanical strength and is not easy to be damaged in the defluorination operation process.
And (3) putting 0.5g of the rapid sedimentation fluorine removal agent obtained by the preparation operation in a beaker, adding 100ml of distilled water, stirring for 24 hours, and measuring the concentration of lanthanum in the distilled water by adopting an azoarsine III spectrophotometry to calculate that the mass of the lanthanum accounts for 1.8% of the total mass of the lanthanum in the fluorine removal agent of 0.5 g. The nano lanthanum oxide on the surface of the rapid sedimentation defluorinating agent is firmly combined on the surface of the geopolymer microsphere and is not easy to fall off.
Application example 2
Application example 2 provides an application method of a rapid sedimentation fluorine removal agent, which is an intermittent operation and specifically comprises the following steps:
1g of the quick-settling fluorine removal agent obtained in example 2 was taken to perform a batch operation in a batch reactor. The water inlet of the reactor was opened, and 1L of the fluorine-containing water was injected into the reactor, the temperature was controlled at 40 ℃, the initial pH of the fluorine-containing water was 4, and the F-concentration was 10 mg/L. And starting a stirring switch, setting the stirring speed to be 300rpm, and stopping stirring after continuously reacting for 5 min. 5s after stopping stirring, the defluorinating agent is settled to the bottom of the reactor by self gravity. Opening the water outlet of the reactor to discharge water, and sampling and measuring the water outlet of the reactor F - Concentration, calculated to obtain F - The removal rate was 99.5%.
Application example 2 also provides an application method of the rapid sedimentation fluorine removal agent, which is a continuous operation and specifically comprises the following steps:
1g of the quick-settling fluorine removal agent obtained in example 2 was charged into the reaction column of the continuous reactor. Opening the water inlet of the reactor, continuously injecting simulated fluorine-containing underground water into the reaction column at the flow rate of 10BV/h, and simulating F in the fluorine-containing underground water - At a concentration of 5mg/L, Ca 2+ The concentration is 103mg/L, Na + At a concentration of 186Mg/L, Mg 2+ Concentration 142mg/L, Cl - The concentration was 30.7mg/L and the pH was 6. Go intoThe temperature of the water was controlled at 30 ℃. Opening the water outlet of the reactor, continuously collecting the treated effluent, sampling and determining the concentration of fluorine ions until the effluent F - The concentration is more than or equal to 1.0mg/L, and the water inlet and the water outlet are closed in sequence. Calculated according to the proportion, each kg of the defluorinating agent can treat about 1200L of simulated fluorine-containing underground water.
It can be seen that the rapid sedimentation fluorine removal agent provided by the invention can be used for removing F in fluorine-containing water with different components - The good removal effect is realized, the dosage of the defluorinating agent is small, the treated water amount is large, and the defluorinating efficiency is high.
Example 3
Embodiment 3 provides a method for preparing a rapid-settling fluorine removal agent, which specifically comprises the following steps:
and placing the kaolin into a muffle furnace, and calcining for 6 hours at 800 ℃ to obtain AK.
The method comprises the following steps of 1: 2, adding dry NaOH into water, and then adding AK: NaOH is 3: 1 mass ratio, adding activated kaolin AK, and mixing completely to obtain slurry under continuous stirring at 2000rpm for 5 min. The viscosity is 1000mm 2 The simethicone/s is put into a container and stirred continuously at the speed of 500rpm, the temperature is kept at 60 ℃, and the height from the liquid level of the simethicone to the bottom of the container is 15 cm. Slowly pouring the slurry into the stirred dimethyl silicone oil at the flow rate of 1.0ml/L, continuously stirring for 20min, and then stopping stirring, and collecting solid particles at the bottom of the container, namely the geopolymer precursor.
And putting the obtained geopolymer precursor into a container, putting the container into a water bath kettle, maintaining for 6h at 60 ℃, taking out the container, putting the container into a drying oven, curing and drying for 12h at 60 ℃, then transferring into a muffle furnace, burning for 6h at 550 ℃ to remove surface dimethyl silicone oil, cooling, taking out, washing with distilled water to be neutral, drying for 4h at 80 ℃, and sealing and storing to obtain the geopolymer microsphere.
Putting 2.0g of geopolymer microspheres into a container, adding 50ml of 3 wt% sodium hydroxide solution, soaking for 2h, filtering out solid particles, adding the solid particles into 100ml of 8 wt% lanthanum chloride solution, soaking and stirring for 12h, filtering, taking out the solidified particles, adding 150ml of 20 wt% concentrated ammonia water, immediately sealing and oscillating for 24 h. And then, filtering and separating out a solid, putting the solid in a muffle furnace for ignition for 6 hours at 500 ℃, taking out the solid, naturally cooling the solid to room temperature, washing the solid with distilled water, and drying the solid to obtain the rapid sedimentation defluorinating agent.
A TEM photograph of the fast settling fluorine removal agent obtained in example 3 is shown in fig. 4, and it can be seen that nano lanthanum oxide is a short rod-like nanoparticle having a diameter of about 8 nm.
Application example 3
Application example 3 provides an application method of a rapid sedimentation fluorine removal agent, which is a continuous operation and specifically comprises the following steps:
1g of the rapid settling defluorinating agent is filled into a reaction column of a continuous reactor. The water inlet of the reactor is opened, and the simulated fluorine-containing water is continuously injected into the reaction column at the flow rate of 50 BV/h. The concentration of the simulated fluorine-containing water is 50mg/L, SO 4 2- 、Cl-、NO 3- 、PO 4 3- The concentration of five coexisting substances of HA (Humic acid) and HA (Humic acid) is 1000mg/L, and the initial pH value is 4. The temperature was controlled at 40 ℃. Opening the water outlet of the reactor, continuously collecting the treated effluent, sampling and measuring F - And (4) concentration. The fluorine-containing underground water can be treated by about 1100L of simulated fluorine-containing underground water per kg of fluorine removal agent.
Example 4
Embodiment 4 provides a method for preparing a rapid-settling fluorine removal agent, which specifically comprises the following steps:
and placing the kaolin into a muffle furnace, and calcining at 400 ℃ for 1h to obtain AK.
Mixing the raw materials in a ratio of 1: 1.5 adding dry NaOH into water, and then adding AK: NaOH 2.2: 1, adding activated kaolin AK, and continuously stirring for 5min at 2000rpm to completely mix into slurry; the viscosity is 500mm 2 And (3) placing the simethicone in a container, continuously stirring at the speed of 300rpm, keeping the temperature at 55 ℃, and keeping the height from the liquid level of the simethicone to the bottom of the container to be 25 cm. Slowly pouring the slurry into the stirred dimethyl silicone oil at the flow rate of 0.5ml/L, continuously stirring for 10min, stopping stirring, and collecting solid particles at the bottom of the container, namely the geopolymer precursor.
And putting the obtained geopolymer precursor into a container, putting the container into a water bath kettle, maintaining for 3 hours at 50 ℃, taking out the container, putting the container into an oven, curing and drying for 6 hours at 50 ℃, then transferring into a muffle furnace, burning for 6 hours at 400 ℃ to remove surface dimethyl silicone oil, cooling, taking out, washing with distilled water to be neutral, drying for 4 hours at 80 ℃, and sealing and storing to obtain the geopolymer microsphere.
Putting 2.0g of geopolymer microspheres into a container, adding 50ml of 3 wt% sodium hydroxide solution, soaking for 2h, filtering out solid particles, adding the solid particles into 100ml of 1 wt% lanthanum chloride solution, soaking and stirring for 6h, filtering, taking out the solidified particles, adding 150ml of 20 wt% concentrated ammonia water, immediately sealing and oscillating for 12 h. Then filtering and separating out solid, putting the solid in a muffle furnace to be burnt for 3.0h at the temperature of 400 ℃, taking out the solid, naturally cooling the solid to room temperature, washing the solid with distilled water, and drying the solid to obtain the rapid sedimentation defluorinating agent.
Application example 4
Application example 4 provides an application method of a rapid sedimentation fluorine removal agent, which is an intermittent operation and specifically comprises the following steps:
for example, 0.3g of a fast settling fluorine removal agent is taken in a batch reactor. The water inlet of the reactor was opened and 1L of simulated fluorine-containing water was injected into the reactor. F in simulated fluorine-containing water - Concentration 10mg/L, coexisting substance SO 4 2- 、Cl - 、NO 3- 、PO 4 3- HA concentration is 450mg/L, which is 45 times of fluoride ion concentration, initial pH is 6.8, and temperature is controlled at 20 ℃. And starting a stirring switch, setting the stirring speed to be 250rpm, continuously reacting for 30min, and stopping stirring. And 3s after stopping stirring, the defluorinating agent is settled to the bottom of the reactor by self gravity, water is discharged from a water outlet of the reactor, the concentration of the fluorine ions is measured by sampling, and the removal rate of the fluorine ions is calculated to be 97.4 percent, which is 97.5 percent of the coexisting material concentration under the same condition when the coexisting material concentration is 0.
As another example, 0.3g of the fast settling fluorine removal agent was taken in a batch reactor. The water inlet of the reactor was opened and 1L of simulated fluorine-containing water was injected into the reactor. F in simulated fluorine-containing water - Concentration 10mg/L, coexisting substance SO 4 2- 、Cl - 、NO 3- 、PO 4 3- HA concentration was 900mg/L, which was 90 times the fluoride ion concentration, initial pH was 6.8, and temperature was controlled at 20 ℃. Turning on the stirring switch, settingThe stirring speed was 250rpm, and the reaction was continued for 30min, after which the stirring was stopped. And 3s after stopping stirring, the defluorinating agent is settled to the bottom of the reactor by self gravity, water is discharged from a water outlet of the reactor, the concentration of the fluorine ions is sampled and measured, and the removal rate of the fluorine ions is calculated to be 95.7 percent which is 95.8 percent of the coexisting material concentration under the same condition when the coexisting material concentration is 0.
In conclusion, the rapid sedimentation fluorine removal agent provided by the invention takes lanthanum as an active functional center, and compared with aluminum and iron materials, the rapid sedimentation fluorine removal agent has stronger affinity to fluorine ions, especially in the conventional competitive ion SO 4 2- 、Cl - 、NO 3- 、PO 4 3- And HA and the like coexist, and the fluorine removing agent still HAs high selective fluorine removing capacity through ligand exchange and complexation, the removing efficiency is up to more than 98 percent, and the concentration of the fluorine ions after treatment meets the environmental quality standard of surface water (GB 3838-.
Application example 5
The rapid settling fluorine removal agent used in application example 1 was taken out to a clean container and subjected to a regeneration operation. Adding 100ml of 4 wt% sodium hydroxide solution, stirring and eluting for 12h, then washing the fluorine removal agent with distilled water to be neutral, then taking out the fluorine removal agent, adding 100ml of 5 wt% sodium chloride solution, stirring for 12h, and then taking out the fluorine removal agent. Washing with distilled water for 2 times, drying, and regenerating the defluorinating agent. The regenerated defluorinating agent can be added into the batch reactor again for continuous use. After 5 times of regeneration cycle, the F-concentration of the effluent can still be reduced to below 1.0mg/L by the rapid sedimentation defluorinating agent.
It should be noted that the batch operation and the continuous operation provided in the above application examples may be used either singly or in combination. Also, the regeneration operation may be applied after a batch operation and/or a continuous operation.
Comparative example
Lanthanum oxide is a conventional powder fluorine removal agent, and commercially available lanthanum oxide powder has a particle size of about 30 μm and a density of 6.5g/cm 3 . As shown in FIG. 5a and FIG. 5b, 1g of the rapid-settling fluorine removal agent obtained in example 1 and 1g of commercially available lanthanum oxide powder were put in a left bottle and a right bottle, respectively, 250ml of distilled water was added thereto, and the mixture was stirred for 5 minutes to mix the preparation with the powderThe water is mixed thoroughly. The stirring is stopped, and when the time is 5s, the rapid sedimentation fluorine removal agent is completely settled, but the commercially available lanthanum oxide powder has no obvious sedimentation separation tendency. After the lanthanum oxide powder system is still kept for 20 hours, the lanthanum oxide powder system still appears as suspended powder, which indicates that the commercially available lanthanum oxide powder is difficult to settle in water and is not suitable for being directly applied to a batch reactor or a precipitation device for separation.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the present application, and that various changes in form and details may be made therein without departing from the spirit and scope of the present application in practice. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the application, and it is intended that the scope of the application be limited only by the claims appended hereto.
Claims (10)
1. The rapid sedimentation fluorine removal agent is characterized by being in the form of spheroidal particles or regular spheroidal particles, the sphericity of the rapid sedimentation fluorine removal agent is 0.6-1, the particle size of the rapid sedimentation fluorine removal agent is 50-800 mu m, and the density of the rapid sedimentation fluorine removal agent is 1.5g/cm 3 ～2.3g/cm 3 。
2. The rapid settling fluorine removing agent according to claim 1, wherein the rapid settling fluorine removing agent takes geopolymer microspheres as a carrier, and nano lanthanum oxide as an inorganic functional adsorbent;
wherein the surface of the geopolymer microsphere is rough and has no internal communicating pore canal, and the specific surface area is 8m 2 /g～12m 2 /g；
The nanometer lanthanum oxide is short rod-shaped nanometer particles with the diameter range of 5 nm-8 nm, and is a cubic crystal system.
3. The method for preparing the rapid settling fluorine removal agent according to claim 1, comprising the steps of:
preparing activated kaolin in advance;
mixing the prepared activated kaolin and an alkaline compound, stirring to obtain slurry, slowly pouring the slurry into continuously stirred organic liquid, and dispersing, suspending and curing to obtain a geopolymer precursor;
curing the geopolymer precursor to obtain a geopolymer microsphere;
and (2) soaking the geopolymer microspheres in an alkali solution, sequentially adding the geopolymer microspheres into a lanthanum salt solution and an alkali solution to react, filtering out solids, burning the solids, cleaning and drying to obtain the rapid sedimentation defluorinating agent.
4. The preparation method of the rapid sedimentation fluorine removal agent according to claim 3, which comprises the following steps:
the following are all parts by mass,
s101, placing kaolin in a muffle furnace, and calcining for 1-12 hours at 400-900 ℃ to obtain activated kaolin;
s102, adding 1 part of alkaline compound into 1.5-3.3 parts of water to prepare an alkaline solution; then adding 1 part of the alkaline solution into 2.2-4.2 parts of the activated kaolin obtained in the S101, and continuously stirring at 2000rpm for 3-10 min to completely mix into slurry;
the viscosity is 500mm 2 /s～1500mm 2 Putting the organic liquid in a container, continuously stirring at the speed of 300-800 rpm, keeping the temperature at 55-70 ℃, and keeping the height from the liquid level of the organic liquid to the bottom of the container at 8-25 cm;
slowly pouring the slurry into the stirred organic liquid at the flow rate of 0.5-2.0 ml/s, continuously stirring for 10-30 min, stopping stirring, and collecting solid particles at the bottom of a container to obtain a geopolymer precursor;
s103, placing the geopolymer precursor obtained in the step S102 into a container, placing the container into a water bath kettle, maintaining for 3-12 h at 50-80 ℃, taking out the container, placing the container into a drying oven, curing and drying for 6-24 h at 50-80 ℃, then transferring into a muffle furnace, burning for 6h at 400-650 ℃ to remove the organic liquid on the surface, cooling, taking out, washing with distilled water to be neutral, drying for 4h at 80 ℃, and sealing and storing to obtain the geopolymer microspheres;
s104, putting 1 part of the geopolymer microspheres obtained in the S103 into a container, adding 25 parts of 3 wt% of alkali solution, soaking for 2 hours, filtering out solid particles, adding the solid particles into 50 parts of 1 wt% -10 wt% of lanthanum salt solution, soaking and stirring for 6 hours-24 hours, filtering out solidified particles, adding 75 parts of 20 wt% -25 wt% of alkali solution into the solidified particles, immediately sealing and oscillating for 12 hours-36 hours; then filtering and separating out solid, putting the solid in a muffle furnace to be burnt for 3 to 9 hours at the temperature of between 400 and 650 ℃, taking out the solid, naturally cooling the solid to room temperature, and then washing and drying the solid by using distilled water to obtain the rapid sedimentation defluorinating agent.
5. The method for preparing the rapid-settling defluorinating agent according to claim 3 or 4, wherein the alkaline compound is one or more of sodium silicate, potassium hydroxide or sodium hydroxide; the organic liquid is dimethyl silicone oil, polyethylene glycol or triglyceride oil.
6. The method for preparing the rapid settling defluorinating agent according to claim 3 or 4, wherein the alkali used in the alkali solution is one or more of sodium hydroxide, potassium hydroxide or ammonia water.
7. The method for preparing the rapid settling fluorine removal agent as claimed in claim 3 or 4, wherein the lanthanum salt used in the lanthanum salt solution is one or more of lanthanum chloride, lanthanum nitrate or lanthanum sulfate.
8. The application method of the rapid sedimentation fluorine removal agent according to claim 1, which comprises the following steps:
s201, placing 1 part of rapid settling defluorinating agent in a batch reactor;
s202, injecting 1000-5000 parts of fluorine-containing water into the batch reactor, wherein the concentration of fluorine ions in the fluorine-containing water is 1-50 mg/L, the pH value is 2-8, and SO is added 4 2- 、Cl - 、NO 3- 、PO 4 3- HA and the like coexisting materials have a concentration of 0mg/L to 1000 mg/L;
s203, starting a stirring switch, setting the stirring speed to be 200-800 rpm, setting the treatment temperature to be 10-60 ℃, continuously reacting for 10-30 min, and stopping stirring;
s204, after stopping stirring for 2-5S, settling the defluorinating agent to the bottom of the reactor through self gravity, and sampling at a water outlet of the reactor to measure the concentration of the fluorine ions;
and S205, repeating the steps from S202 to S204 until the concentration of the fluorine ions in the effluent does not meet the water quality standard requirement, and stopping operation.
9. The application method of the rapid sedimentation fluorine removal agent according to claim 1, which comprises the following steps:
s301, filling 1 part of rapid settling defluorinating agent into a reaction column of a continuous reactor;
s302, continuously injecting fluorine-containing water into the reaction column at a flow rate of 50-250 parts/h, and controlling the temperature at 10-60 ℃; wherein the fluorine ion concentration in the fluorine-containing water is 1 mg/L-50 mg/L, the pH is 2-8, and SO 4 2- 、Cl - 、NO 3- 、PO 4 3- HA and the like coexisting materials are 0mg/L to 1000 mg/L;
s303, collecting the treated effluent or sampling to determine the concentration of the fluorine ions until the concentration of the fluorine ions in the effluent does not meet the requirement of the water quality standard.
10. The method for applying the rapid-settling fluorine removing agent according to claim 8 or 9, further comprising the steps of:
s401, taking the rapid settling fluorine removal agent in the batch reactor or the continuous reactor into a clean container;
s402, adding 100 parts of 4 wt% sodium hydroxide solution, stirring and eluting for 6-12 h, and then cleaning the rapid sedimentation defluorinating agent with distilled water to be neutral;
and S403, taking out the rapid settling defluorinating agent in the step S402, adding 100 parts of 5 wt% sodium chloride solution, stirring for 6-12 h, taking out the defluorinating agent, washing with distilled water for 2 times, drying, and drying to obtain the regenerated rapid settling defluorinating agent which can be matched with intermittent operation or continuous operation again.
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