CN113134340B - Chromium ion adsorbent, preparation method, application and regeneration method thereof, and treatment method of chromium in leather tail water - Google Patents
Chromium ion adsorbent, preparation method, application and regeneration method thereof, and treatment method of chromium in leather tail water Download PDFInfo
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- CN113134340B CN113134340B CN202110454887.1A CN202110454887A CN113134340B CN 113134340 B CN113134340 B CN 113134340B CN 202110454887 A CN202110454887 A CN 202110454887A CN 113134340 B CN113134340 B CN 113134340B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0292—Phosphates of compounds other than those provided for in B01J20/048
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/22—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
- C02F2103/24—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof from tanneries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a chromium ion adsorbent, a preparation method, an application method and a regeneration method thereof, and a treatment method of chromium in leather tail water, and relates to the technical field of chromium adsorption materials. The chromium ion adsorbent provided by the invention comprises silica, nano zero-valent iron and zirconium phosphate filled in the pores of the silica. In the chromium ion adsorbent provided by the invention, the nano zero-valent iron can realize reduction of Cr (VI); zirconium phosphate has strong affinity to heavy metals, and can realize the efficient adsorption of Cr (III) in high-salt low-concentration chromium wastewater through inner layer complexation; under the combined action of zirconium phosphate, nano zero-valent iron and silicon dioxide, the chromium ion adsorbent can realize synchronous and efficient removal of Cr (III) and Cr (VI), and has excellent heavy metal chromium ion adsorption effect in high-salt leather tail water.
Description
Technical Field
The invention relates to the technical field of chromium adsorption materials, in particular to a chromium ion adsorbent, a preparation method, an application method and a regeneration method thereof, and a treatment method of chromium in leather tail water.
Background
The leather industry is taken as a pillar industry of the light industry in China and is an important component of national economy. However, the large amount of chrome tanning agent used in the leather production and processing process causes that the leather wastewater often contains high-concentration heavy metal chrome, and the heavy metal chrome is discharged into the environment to cause serious harm to the ecological environment. The phenomenon that Cr (VI) and total chromium are difficult to reach the standard and discharge still often occurs in the leather tail water after the multistage treatment, and the discharge standard of Cr (VI) and total chromium of leather wastewater in China is further limited in the official implementation of the discharge standard of industrial water pollutants for leather making and fur processing in 3 months and 1 day 2014. Therefore, the research on the advanced treatment method of the heavy metal chromium in the leather tail water has very important significance for development of leather industry and ecological environment protection.
The industrial treatment method for chromium-containing wastewater mainly comprises a chemical precipitation method, an adsorption method, an ion exchange method, a membrane separation method and the like, wherein the adsorption method has the advantages of high efficiency, low consumption, no secondary pollution, convenient and easy control of operation and the like, has the characteristic of easy recovery and recycling of the removed product, and is considered as the water treatment technology with the most development prospect and research significance.
Chinese patent CN109046293a discloses a trivalent chromium ion adsorbent, namely a 2-acetylthiophene modified mesoporous material, with an adsorption rate of more than 95% for Cr (III). Chinese patent CN106914219a discloses a magnetic carbon microsphere chromium adsorbent, which has abundant oxygen-containing groups and amino groups on the surface, and can efficiently adsorb Cr (VI) in water, and meanwhile, the adsorbent has the advantage of magnetic separation, and is convenient for recycling. However, the above adsorbent is difficult to achieve simultaneous removal of Cr (III) and Cr (VI). Chinese patent CN109261133a discloses a ferromagnetic composite sphere chromium ion adsorbent which is easy to recycle, and is prepared by placing biochar, zero-valent iron powder and hollow glass microspheres in sodium alginate solution, dripping the biochar, zero-valent iron powder and hollow glass microspheres into calcium chloride solution by peristaltic pump after uniformly mixing, and washing the calcium chloride solution with deionized water after crosslinking, wherein the adsorbent not only can remove Cr (III) and Cr (VI) in wastewater, but also can be magnetically separated, recycled and reused; however, the adsorbent is easily interfered by coexisting ions in water when treating leather tail water with high salt and low concentration, so that the adsorption capacity of the adsorbent on chromium ions is limited, and the adsorption effect is poor. In summary, the existing water chromium ion adsorbent has the defect that synchronous removal of Cr (III) and Cr (VI) is difficult to realize or the adsorption capacity of chromium ions is limited.
Disclosure of Invention
In view of the above, the invention aims to provide a chromium ion adsorbent, a preparation method, an application method and a regeneration method thereof, and a treatment method of chromium in leather tail water.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a chromium ion adsorbent, which comprises silica, nano zero-valent iron and zirconium phosphate filled in the pores of the silica.
Preferably, the mass ratio of the zirconium phosphate to the nano zero-valent iron to the silicon dioxide is 1: (15-20): (3-4).
Preferably, the specific surface area of the chromium ion adsorbent is 600-700 m 2 And/g, the grain diameter is 0.2-0.3 mm.
The invention provides a preparation method of the chromium ion adsorbent, which comprises the following steps:
mixing the nano magnet, tetraethoxysilane, zirconium oxychloride solution, ethanol-ammonia water mixed solution and phosphoric acid solution, and aging to obtain ferroferric oxide-silicon dioxide-zirconium phosphate;
and mixing the ferroferric oxide-silicon dioxide-zirconium phosphate and calcium hydride, and carrying out a reduction reaction to obtain the chromium ion adsorbent.
Preferably, the mass ratio of the tetraethoxysilane to the nano-magnet is 1: (2-3);
the concentration of the zirconium oxychloride solution is 0.3-0.5 mol/L;
the volume ratio of the tetraethoxysilane to the zirconium oxychloride solution is 1: (0.5-1);
the concentration of the phosphoric acid solution is 0.4-0.6 mol/L;
the volume ratio of the phosphoric acid solution to the zirconium oxychloride solution is 1: (0.5-1).
Preferably, the aging temperature is 45-60 ℃ and the time is 10-12 h.
Preferably, the mass ratio of the ferroferric oxide-silicon dioxide-zirconium phosphate to the calcium hydride is 1: (5-10);
the temperature of the reduction reaction is 400-600 ℃ and the time is 40-48 h.
The invention provides an application of the chromium ion adsorbent in treating leather tail water.
The invention provides a method for treating chromium in leather tail water, which comprises the following steps: adjusting the pH value of the leather tail water to 4.5-5, adding a chromium ion adsorbent for adsorption reaction, and gathering and recycling the used chromium ion adsorbent;
the chromium ion adsorbent is the chromium ion adsorbent according to the technical scheme or the chromium ion adsorbent obtained by the preparation method according to the technical scheme.
The invention also provides a method for regenerating the chromium ion adsorbent, which comprises the following steps: the used chromium ion adsorbent is soaked in hydrochloric acid solution for desorption regeneration.
The invention provides a chromium ion adsorbent, which comprises silica, nano zero-valent iron and zirconium phosphate filled in the pores of the silica. In the chromium ion adsorbent provided by the invention, the nano zero-valent iron can realize reduction of Cr (VI); zirconium phosphate has strong affinity to heavy metals, and can realize the efficient adsorption of Cr (III) in high-salt low-concentration chromium wastewater through inner layer complexation; the silicon dioxide is used as a porous material and serves as a framework of a chromium ion adsorbent and is used for fixedly loading nano zero-valent iron and zirconium phosphate; under the combined action of zirconium phosphate, nano zero-valent iron and silicon dioxide, the chromium ion adsorbent can realize synchronous and efficient removal of Cr (III) and Cr (VI), and has excellent heavy metal chromium ion adsorption effect in high-salt leather tail water.
In addition, the chromium ion adsorbent provided by the invention can be magnetically separated through an external magnetic field after being adsorbed and saturated, is easy to recycle, and has good application prospect in treating leather wastewater.
The invention provides a preparation method of the chromium ion adsorbent, which comprises the following steps: mixing the nano magnet, tetraethoxysilane, zirconium oxychloride solution, ethanol-ammonia water mixed solution and phosphoric acid solution, and aging to obtain ferroferric oxide-silicon dioxide-zirconium phosphate; and mixing the ferroferric oxide-silicon dioxide-zirconium phosphate and calcium hydride, and carrying out a reduction reaction to obtain the chromium ion adsorbent. The preparation method provided by the invention has the advantages of simple preparation process and suitability for industrial production.
The invention provides a method for treating chromium in leather tail water, which comprises the following steps: adjusting the pH value of the leather tail water to 4.5-5, adding a chromium ion adsorbent for adsorption reaction, and gathering and recycling the used chromium ion adsorbent; the chromium ion adsorbent is the chromium ion adsorbent according to the technical scheme or the chromium ion adsorbent obtained by the preparation method according to the technical scheme. The treatment method provided by the invention has high removal rate of Cr (III) and Cr (VI) in the leather tail water, and can flexibly change the dosage of the chromium ion adsorbent according to the treatment effect, thereby achieving good economic benefit and environmental benefit.
The invention also provides a method for regenerating the chromium ion adsorbent, which comprises the following steps: the used chromium ion adsorbent is soaked in hydrochloric acid solution for desorption regeneration. According to the regeneration method provided by the invention, the treatment cost of heavy metal chromium in the leather tail water is reduced to a great extent through desorption and regeneration of hydrochloric acid.
Drawings
FIG. 1 is a graph showing the effect of examples 4 to 12 on Cr (III) and Cr (VI) removal.
Detailed Description
The invention provides a chromium ion adsorbent, which comprises silica, nano zero-valent iron and zirconium phosphate filled in the pores of the silica.
In the invention, the mass ratio of the zirconium phosphate, the nano zero-valent iron and the silicon dioxide is preferably 1: (15-20): (3-4), more preferably 1: (16-19): (3.2 to 3.8), most preferably 1: (17-18): (3.5-3.6).
In the present invention, the particle diameter of the chromium ion adsorbent is preferably 0.2 to 0.3mm, more preferably 0.22 to 0.28mm, and most preferably 0.25 to 0.26mm; the specific surface area of the chromium ion adsorbent is preferably 600-700 m 2 Preferably 620 to 680m 2 Preferably from 650 to 660m per gram 2 And/g. The chromium ion adsorbent provided by the invention has the advantages of small particle size and large specific surface area, can realize synchronous and efficient removal of Cr (III) and Cr (VI), and also has an excellent heavy metal chromium ion adsorption effect in high-salt leather tail water.
The invention provides a preparation method of the chromium ion adsorbent, which comprises the following steps:
mixing the nano magnet, tetraethoxysilane, zirconium oxychloride solution, ethanol-ammonia water mixed solution and phosphoric acid solution, and aging to obtain ferroferric oxide-silicon dioxide-zirconium phosphate;
and mixing the ferroferric oxide-silicon dioxide-zirconium phosphate and calcium hydride, and carrying out a reduction reaction to obtain the chromium ion adsorbent.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
According to the invention, the nano magnet, the tetraethoxysilane, the zirconium oxychloride solution, the ethanol-ammonia water mixed solution and the phosphoric acid solution are mixed and aged to obtain the ferroferric oxide-silicon dioxide-zirconium phosphate.
In the present invention, the particle diameter of the nanomagnet is preferably 1 to 100nm, more preferably 20 to 80nm, and most preferably 50 to 60nm. In the present invention, the concentration of the zirconium oxychloride solution is preferably 0.3 to 0.5mol/L, more preferably 0.35 to 0.45mol/L, and most preferably 0.4mol/L. In the present invention, the concentration of the phosphoric acid solution is preferably 0.4 to 0.6mol/L, more preferably 0.45 to 0.55mol/L, and most preferably 0.5mol/L. In the present invention, the mass ratio of the tetraethyl orthosilicate (TEOS) to the nano-magnet is preferably 1: (2-3), more preferably 1: (2.2 to 2.8), most preferably 1: (2.5-2.6). In the invention, the volume ratio of the tetraethoxysilane to the zirconium oxychloride solution is preferably 1: (0.5 to 1), more preferably 1: (0.6 to 0.9), most preferably 1: (0.7-0.8). In the present invention, the volume ratio of the phosphoric acid solution and the zirconium oxychloride solution is preferably 1: (0.5 to 1), more preferably 1: (0.6 to 0.9), most preferably 1: (0.7-0.8). In the invention, the ethanol-ammonia water mixed solution is prepared from absolute ethanol, liquid ammonia and water, wherein the volume ratio of the absolute ethanol to the liquid ammonia to the water is preferably (20-30): (1-2): 5, more preferably (22 to 28): (1.2-1.8): 5, most preferably (25 to 26): (1.5-1.6): 5. in the present invention, the ratio of the mass of the nanomagnet to the volume of the ethanol-ammonia water mixed solution is preferably 2g: (15-20) mL, more preferably 2g: (16-19) mL, most preferably 2g: (17-18) mL.
In the invention, the mixing sequence of the nano magnet, the tetraethoxysilane, the zirconium oxychloride solution, the ethanol-ammonia water mixed solution and the phosphoric acid solution is preferably that the nano magnet and the ethanol-ammonia water mixed solution are mixed for the first time to obtain a first dispersion liquid; the first dispersion liquid, tetraethoxysilane and zirconium oxychloride solution are mixed for the second time to obtain a second dispersion liquid; a phosphoric acid solution is added dropwise to the second dispersion. In the present invention, the first mixing mode is preferably ultrasonic mixing, and the power and time of the ultrasonic mixing are not particularly limited, and the nanomagnet may be dispersed in an ethanol-ammonia water mixed solution. In the present invention, the second mixing means is preferably stirring mixing, and the speed and time of the stirring mixing are not particularly limited, and ethyl orthosilicate and zirconium oxychloride may be dissolved. In the present invention, the dropping is preferably performed under stirring, and the speed of the dropping is not particularly limited, and the dropping may be performed dropwise at a constant speed.
In the present invention, the aging is preferably water bath aging; the aging temperature is preferably 45-60 ℃, more preferably 50-55 ℃, and most preferably 52 ℃; the aging time is preferably 10 to 12 hours, more preferably 10.5 to 11.5 hours, and most preferably 11 hours. In the invention, in the aging process, tetraethoxysilane generates silicon dioxide, zirconium oxychloride and phosphoric acid react to generate zirconium phosphate, and then the nano magnet, the silicon dioxide and the zirconium phosphate are uniformly mixed to obtain the ferroferric oxide-silicon dioxide-zirconium phosphate.
After the aging, the method preferably further comprises the steps of washing the aged product with water and then drying to obtain the ferroferric oxide-silicon dioxide-zirconium phosphate. In the present invention, the number of times of the water washing is preferably 3 to 5 times, more preferably 4 times, the purpose of the water washing being to remove unreacted raw materials; the drying temperature is preferably 80-120 ℃, more preferably 100 ℃; the drying time is preferably 8 to 10 hours, more preferably 9 hours.
After ferroferric oxide-silicon dioxide-zirconium phosphate is obtained, the ferroferric oxide-silicon dioxide-zirconium phosphate and calcium hydride are mixed for reduction reaction, and the chromium ion adsorbent is obtained.
In the present invention, the mass ratio of the ferroferric oxide-silicon dioxide-zirconium phosphate to the calcium hydride is preferably 1: (5 to 10), more preferably 1: (6-9), most preferably 1: (7-8).
In the present invention, the mixing means is preferably a grinding mixing means, and the grinding mixing means known to those skilled in the art may be used in the present invention without particular limitation.
In the present invention, the temperature of the reduction reaction is preferably 400 to 600 ℃, more preferably 450 to 550 ℃, and most preferably 500 ℃; the reduction reaction time is preferably 40 to 48 hours, more preferably 42 to 46 hours, and most preferably 44 to 45 hours; the reduction reaction is preferably carried out in a muffle furnace; the reduction reaction is preferably carried out under a protective atmosphere, and the protective atmosphere is not particularly limited in the present invention, and a protective atmosphere well known to those skilled in the art, such as nitrogen, may be used. In the invention, during the reduction reaction, the nano ferroferric oxide powder is reduced into zero-valent iron.
After the reduction reaction, the invention preferably further comprises the steps of sequentially cooling, washing, drying, grinding and sieving the product of the reduction reaction to obtain the chromium ion adsorbent. The present invention is not particularly limited in the manner of coolingIt is to be understood that cooling means well known to those skilled in the art may be employed. In the present invention, the reagent used for the washing is preferably a methanol solution of ammonium chloride, and the concentration of the methanol solution of ammonium chloride is preferably 0.1 to 0.5mol/L, more preferably 0.3mol/L; the number of times of the washing is preferably 3 to 5 times, more preferably 4 times; the purpose of the washing is to remove unreacted CaH 2 Oxidation product impurities. In the present invention, the drying temperature is preferably 50 to 80 ℃, more preferably 60 ℃; the drying time is preferably 20 to 24 hours, more preferably 22 to 23 hours; the drying mode is preferably vacuum drying. In the present invention, the crushing means is preferably grinding, and the grinding operation is not particularly limited, and grinding means well known to those skilled in the art may be used. The size of the screen mesh is not particularly limited, the particle size of the chromium ion adsorbent can be guaranteed to be 0.2-0.3 mm, and the part under the screen is the chromium ion adsorbent.
The invention provides an application of the chromium ion adsorbent in treating leather tail water.
The invention provides a method for treating chromium in leather tail water, which comprises the following steps: adjusting the pH value of the leather tail water to 4.5-5, adding a chromium ion adsorbent for adsorption reaction, and gathering and recycling the used chromium ion adsorbent;
the chromium ion adsorbent is the chromium ion adsorbent according to the technical scheme or the chromium ion adsorbent obtained by the preparation method according to the technical scheme.
The source of the leather tail water is not particularly limited, and biochemical effluent of leather waste water is well known to the person skilled in the art. In the invention, the concentration of chromium ions in the leather tail water is preferably less than or equal to 20mg/L. In an embodiment of the present invention, the leather tail water is preferably a simulated wastewater, and the simulated wastewater is preferably prepared by adding chromium nitrate and potassium dichromate to tap water.
In the present invention, the acid used for the pH adjustment is preferably an inorganic acid, preferably including hydrochloric acid or sulfuric acid; the concentration and the dosage of the inorganic acid are not particularly limited, and the pH value of the leather tail water can be adjusted to 4.5-5.
In the invention, the mass ratio of the chromium ion adsorbent to the leather tail water is preferably 1: (100-800), more preferably 1:500.
In the present invention, the adsorption reaction is preferably carried out under stirring conditions, and the stirring speed is preferably 100 to 200rpm, more preferably 150 to 160rpm; the time of the adsorption reaction is preferably 90 to 120 minutes, more preferably 80 to 100 minutes.
In the present invention, the aggregation recovery is preferably performed by an externally applied magnetic field, specifically, aggregation recovery using a magnet.
The invention also provides a method for regenerating the chromium ion adsorbent, which comprises the following steps: the used chromium ion adsorbent is soaked in hydrochloric acid solution for desorption regeneration. In the present invention, the hydrochloric acid solution is preferably used in an amount of 0.2 to 0.8mol/L, more preferably 0.6mol/L; the desorption regeneration temperature is preferably room temperature. In the desorption regeneration process, trivalent chromium adsorbed by the used chromium ion adsorbent is desorbed again under an acidic condition and is dissolved in a hydrochloric acid solution.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Placing 16.1mL of ethanol, 0.7mL of liquid ammonia and 3.2mL of distilled water in a beaker, and stirring and mixing uniformly to obtain an ethanol-ammonia water mixed solution; adding 2g of nano magnet (with the particle size of 60 nm) into the ethanol-ammonia water mixed solution for ultrasonic dissolution, then adding 1g of TEOS and 0.5mL of 0.3mol/L zirconium oxychloride solution for stirring dissolution, dropwise adding 0.5mL of 0.45mol/L phosphoric acid solution under stirring, aging for 12h in a water bath at 60 ℃, washing with deionized water for 5 times to neutrality, and drying for 10h at 100 ℃ to obtain the ferroferric oxide-silicon dioxide-zirconium phosphate.
2g of zirconium-silica-phosphate and 16g of CaH 2 Grinding, mixing, putting into muffle furnace, reducing at 400 deg.C for 48 hr, cooling to room temperature, and adding NH with concentration of 0.3mol/L 4 Washing with Cl-methanol solution for 5 times, vacuum drying at 60 ℃ for 24 hours, grinding, and sieving with a 60-mesh sieve to obtain the chromium ion adsorbent with the particle size of 0.25 mm.
Example 2
Placing 16.1mL of ethanol, 0.7mL of liquid ammonia and 3.2mL of distilled water in a beaker, and stirring and mixing uniformly to obtain an ethanol-ammonia water mixed solution; adding 2.5g of nano magnet (with the particle size of 60 nm) into the ethanol-ammonia water mixed solution for ultrasonic dissolution, then adding 1g of TEOS and 0.5mL of 0.3mol/L zirconium oxychloride solution for stirring dissolution, dropwise adding 0.5mL of 0.45mol/L phosphoric acid solution under stirring, aging for 12h in a water bath at 60 ℃, washing with deionized water for 5 times to neutrality, and drying for 10h at 100 ℃ to obtain the ferroferric oxide-silicon dioxide-zirconium phosphate.
2g of zirconium-silica-phosphate and 16g of CaH 2 Grinding, mixing, putting into muffle furnace, reducing at 400 deg.C for 48 hr, cooling to room temperature, and adding NH with concentration of 0.3mol/L 4 Washing with Cl methanol solution for 5 times, vacuum drying at 60 ℃ for 24 hours, grinding, and sieving with a 60-mesh sieve to obtain the chromium ion adsorbent with the particle size of 0.25 mm.
Example 3
Placing 16.1mL of ethanol, 0.7mL of liquid ammonia and 3.2mL of distilled water in a beaker, and stirring and mixing uniformly to obtain an ethanol-ammonia water mixed solution; adding 3g of nano magnet (with the particle size of 60 nm) into the ethanol-ammonia water mixed solution for ultrasonic dissolution, then adding 1g of TEOS and 0.5mL of 0.3mol/L zirconium oxychloride solution for stirring dissolution, dropwise adding 0.5mL of 0.45mol/L phosphoric acid solution under stirring, aging for 12h in a water bath at 60 ℃, washing with deionized water for 5 times to neutrality, and drying for 10h at 100 ℃ to obtain the ferroferric oxide-silicon dioxide-zirconium phosphate.
2g of zirconium-silica-phosphate and 16g of CaH 2 Grinding and mixing uniformlyPlacing in a muffle furnace, reducing at 400deg.C for 48h, cooling to room temperature, and using NH with concentration of 0.3mol/L 4 Washing with Cl methanol solution for 5 times, vacuum drying at 60 ℃ for 24 hours, grinding, and sieving with a 60-mesh sieve to obtain the chromium ion adsorbent with the particle size of 0.25 mm.
Example 4
Chromium nitrate and potassium dichromate are added into tap water to prepare simulated wastewater with the Cr (III) concentration of 4.5mg/L, cr (VI) concentration of 0.3 mg/L.
100mL of simulated wastewater is adjusted to pH 5, 0.2g of the chromium ion adsorbent prepared in example 1 is added and mixed uniformly, the mixture is oscillated for 120min at 30 ℃ and 120rpm in a constant temperature oscillator to perform adsorption reaction, the mixture is stood, the concentration of Cr (III) and Cr (VI) in the supernatant is tested, and the test results are shown in Table 1 and FIG. 1.
Example 5
Taking 100mL of certain leather tail water, and measuring the concentration of Cr (III) in the water to be 3.16mg/L and the concentration of Cr (VI) to be 0.414mg/L. The pH value of the leather tail water was adjusted to 5, 0.2g of the chromium ion adsorbent prepared in example 1 was added and mixed uniformly, and the mixture was oscillated for 120min at 30℃and a rotational speed of 120rpm in a constant temperature oscillator, and the mixture was allowed to stand, and the concentrations of Cr (III) and Cr (VI) in the supernatant were measured, and the measurement results are shown in Table 1 and FIG. 1.
Example 6
Taking 100mL of certain leather tail water, and measuring the concentration of Cr (III) in the water to be 6.49mg/L and the concentration of Cr (VI) to be 0.382mg/L. The pH value of the leather tail water was adjusted to 5, 0.2g of the chromium ion adsorbent prepared in example 1 was added and mixed uniformly, and the mixture was oscillated for 120min at 30℃and a rotational speed of 120rpm in a constant temperature oscillator, and the mixture was allowed to stand, and the concentrations of Cr (III) and Cr (VI) in the supernatant were measured, and the measurement results are shown in Table 1 and FIG. 1.
Example 7
Taking 100mL of certain leather tail water, and measuring the concentration of Cr (III) in the water to be 4.14mg/L and the concentration of Cr (VI) to be 0.539mg/L. The pH value of the leather tail water was adjusted to 5, 0.2g of the chromium ion adsorbent prepared in example 1 was added and mixed uniformly, and the mixture was oscillated for 120min at 30℃and a rotational speed of 120rpm in a constant temperature oscillator, and the mixture was allowed to stand, and the concentrations of Cr (III) and Cr (VI) in the supernatant were measured, and the measurement results are shown in Table 1 and FIG. 1.
Example 8
Taking 100mL of certain leather tail water, and measuring the concentration of Cr (III) in the water to be 2.09mg/L and the concentration of Cr (VI) to be 0.817mg/L. The pH value of the leather tail water was adjusted to 5, 0.2g of the chromium ion adsorbent prepared in example 1 was added and mixed uniformly, and the mixture was oscillated for 120min at 30℃and a rotational speed of 120rpm in a constant temperature oscillator, and the mixture was allowed to stand, and the concentrations of Cr (III) and Cr (VI) in the supernatant were measured, and the measurement results are shown in Table 1 and FIG. 1.
Example 9
Taking 100mL of certain leather tail water, and measuring the concentration of Cr (III) in the water to be 3.54mg/L and the concentration of Cr (VI) to be 0.213mg/L. The pH value of the leather tail water was adjusted to 5, 0.2g of the chromium ion adsorbent prepared in example 1 was added and mixed uniformly, and the mixture was oscillated for 120min at 30℃and a rotational speed of 120rpm in a constant temperature oscillator, and the mixture was allowed to stand, and the concentrations of Cr (III) and Cr (VI) in the supernatant were measured, and the measurement results are shown in Table 1 and FIG. 1.
Example 10
Taking 100mL of certain leather tail water, and measuring the concentration of Cr (III) in the water to be 3.16mg/L and the concentration of Cr (VI) to be 0.414mg/L. The pH value of the leather tail water was adjusted to 5, 0.2g of the chromium ion adsorbent prepared in example 2 was added and mixed uniformly, and the mixture was oscillated for 120min at 30℃and a rotational speed of 120rpm in a constant temperature oscillator, and the mixture was allowed to stand, and the concentrations of Cr (III) and Cr (VI) in the supernatant were measured, and the measurement results are shown in Table 1 and FIG. 1.
Example 11
Taking 100mL of certain leather tail water, and measuring the concentration of Cr (III) in the water to be 3.16mg/L and the concentration of Cr (VI) to be 0.414mg/L. The pH value of the leather tail water was adjusted to 5, 0.2g of the chromium ion adsorbent prepared in example 3 was added and mixed uniformly, and the mixture was oscillated for 120min at 30℃and a rotational speed of 120rpm in a constant temperature oscillator, and the mixture was allowed to stand, and the concentrations of Cr (III) and Cr (VI) in the supernatant were measured, and the measurement results are shown in Table 1 and FIG. 1.
Example 12
Placing the chromium ion adsorbent used in the example 6 in 0.6mol/L hydrochloric acid solution for desorption regeneration to obtain regenerated chromium ion adsorbent;
taking 100mL of certain leather tail water, and measuring the concentration of Cr (III) in the water to be 6.49mg/L and the concentration of Cr (VI) to be 0.382mg/L. Adjusting the pH value of the leather tail water to 5, adding 0.2g of the regenerated chromium ion adsorbent and uniformly mixing, oscillating for 120min at the temperature of 30 ℃ and the rotating speed of 120rpm in a constant-temperature oscillator, standing, and testing the concentration of Cr (III) and Cr (VI) in the supernatant, wherein the test results are shown in Table 1 and FIG. 1.
Example 13
Chromium nitrate, potassium dichromate, sodium chloride and sodium sulfate are added into tap water to prepare simulated wastewater with the concentration of Cr (III) of 4.5mg/L, cr (VI) of 0.3mg/L, the concentration of sodium chloride of 1000mg/L and the concentration of sodium sulfate of 1000 mg/L.
100mL of simulated wastewater is adjusted to pH 5, 0.2g of the chromium ion adsorbent prepared in example 1 is added and mixed uniformly, the mixture is oscillated for 120min at 30 ℃ and 120rpm in a constant temperature oscillator to perform adsorption reaction, the mixture is stood, the concentration of Cr (III) and Cr (VI) in the supernatant is tested, and the test results are shown in Table 1 and FIG. 1.
Example 14
Chromium nitrate, potassium dichromate, sodium chloride and sodium sulfate are added into tap water to prepare simulated wastewater with the concentration of Cr (III) of 4.5mg/L, cr (VI) of 0.3mg/L, the concentration of sodium chloride of 1500mg/L and the concentration of sodium sulfate of 1500 mg/L.
100mL of simulated wastewater is adjusted to pH 5, 0.2g of the chromium ion adsorbent prepared in example 1 is added and mixed uniformly, the mixture is oscillated for 120min at 30 ℃ and 120rpm in a constant temperature oscillator to perform adsorption reaction, the mixture is stood, the concentration of Cr (III) and Cr (VI) in the supernatant is tested, and the test results are shown in Table 1 and FIG. 1.
TABLE 1 effects of examples 4 to 14 on removal of Cr (III) and Cr (VI)
As can be seen from Table 1 and FIG. 1, the chromium ion adsorbent prepared by the invention has a removal rate of 86.12-94% for Cr (III) in leather tail water, 84.04-92.67% for Cr (VI) and 85.99-93.92% for the total removal rate of Cr (III) and Cr (VI), and can simultaneously and efficiently remove Cr (III) and Cr (VI).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. A chromium ion adsorbent comprising silica and nano zero-valent iron and zirconium phosphate filled in the pores of the silica; the specific surface area of the chromium ion adsorbent is 600-700 m 2 G, the grain diameter is 0.2-0.3 mm;
the preparation method of the chromium ion adsorbent comprises the following steps:
mixing the nano magnet, tetraethoxysilane, zirconium oxychloride solution, ethanol-ammonia water mixed solution and phosphoric acid solution, and aging to obtain ferroferric oxide-silicon dioxide-zirconium phosphate;
mixing the ferroferric oxide-silicon dioxide-zirconium phosphate and calcium hydride, and carrying out a reduction reaction to obtain a chromium ion adsorbent;
the mass ratio of the tetraethoxysilane to the nano magnet is 1: (2-3);
the concentration of the zirconium oxychloride solution is 0.3-0.5 mol/L;
the volume ratio of the tetraethoxysilane to the zirconium oxychloride solution is 1: (0.5-1);
the concentration of the phosphoric acid solution is 0.4-0.6 mol/L;
the volume ratio of the phosphoric acid solution to the zirconium oxychloride solution is 1: (0.5-1);
the aging temperature is 45-60 ℃ and the aging time is 10-12 hours;
the mass ratio of the ferroferric oxide-silicon dioxide-zirconium phosphate to the calcium hydride is 1: (5-10);
the temperature of the reduction reaction is 400-600 ℃ and the time is 40-48 h.
2. The chromium ion adsorbent according to claim 1, wherein the mass ratio of zirconium phosphate, nano zero-valent iron and silica is 1: (15-20): (3-4).
3. The method for preparing the chromium ion adsorbent according to any one of claims 1 to 2, characterized by comprising the steps of:
mixing the nano magnet, tetraethoxysilane, zirconium oxychloride solution, ethanol-ammonia water mixed solution and phosphoric acid solution, and aging to obtain ferroferric oxide-silicon dioxide-zirconium phosphate;
mixing the ferroferric oxide-silicon dioxide-zirconium phosphate and calcium hydride, and carrying out a reduction reaction to obtain a chromium ion adsorbent;
the mass ratio of the tetraethoxysilane to the nano magnet is 1: (2-3);
the concentration of the zirconium oxychloride solution is 0.3-0.5 mol/L;
the volume ratio of the tetraethoxysilane to the zirconium oxychloride solution is 1: (0.5-1);
the concentration of the phosphoric acid solution is 0.4-0.6 mol/L;
the volume ratio of the phosphoric acid solution to the zirconium oxychloride solution is 1: (0.5-1);
the aging temperature is 45-60 ℃ and the aging time is 10-12 hours;
the mass ratio of the ferroferric oxide-silicon dioxide-zirconium phosphate to the calcium hydride is 1: (5-10);
the temperature of the reduction reaction is 400-600 ℃ and the time is 40-48 h.
4. The use of the chromium ion adsorbent according to any one of claims 1-2 or the chromium ion adsorbent obtained by the preparation method according to claim 3 in the treatment of leather tail water.
5. The method for treating the chromium in the leather tail water is characterized by comprising the following steps of: adjusting the pH value of the leather tail water to 4.5-5, adding a chromium ion adsorbent for adsorption reaction, and gathering and recycling the used chromium ion adsorbent;
the chromium ion adsorbent is the chromium ion adsorbent according to any one of claims 1 to 2 or the chromium ion adsorbent obtained by the preparation method according to claim 3.
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