CN110589927A - Process method for treating fluorine-containing wastewater by using chitosan and aluminum sulfate composite modified zeolite - Google Patents
Process method for treating fluorine-containing wastewater by using chitosan and aluminum sulfate composite modified zeolite Download PDFInfo
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- CN110589927A CN110589927A CN201910939000.0A CN201910939000A CN110589927A CN 110589927 A CN110589927 A CN 110589927A CN 201910939000 A CN201910939000 A CN 201910939000A CN 110589927 A CN110589927 A CN 110589927A
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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Abstract
The invention provides a process method for treating fluorine-containing mine water by using aluminum sulfate and chitosan composite modified zeolite, which comprises the following steps: (1) screening and drying zeolite to obtain zeolite particles with the same size; (2) dissolving chitosan in acetic acid solution, adding zeolite and kaolin, and stirring; (3) adding Al to zeolite modified by chitosan2(SO4)3Standing, washing and drying to obtain aluminum sulfate and chitosan composite modified zeolite; (4) adding aluminum sulfate and chitosan composite modified zeolite into simulated (F-) containing wastewater. The invention combines chitosan, zeolite and aluminum sulfate, which can reduce cost and improve the adsorption performance of zeolite; in addition, the invention also strictly optimizes the parameters of the aluminum sulfate and chitosan composite modified zeolite in the preparation and use processes, and further improves the adsorption performance of the aluminum sulfate and chitosan composite modified zeolite.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a process method for treating fluorine-containing wastewater by using chitosan and aluminum sulfate composite modified zeolite.
Background
Fluorine is an osteogenic element and is one of trace elements necessary for human growth, a proper amount of fluorine is helpful for preventing dental caries, and when excessive intake of fluorine is caused, the dental caries and fluorosis are common diseases, and the death of people can be caused in serious cases. China is one of high-fluorine water areas in the world, except Shanghai markets, high-fluorine underground water exists in all provinces, the high-fluorine water areas are mainly distributed in arid and semi-arid areas in the northern China, the concentration of fluorine water is mostly between 1mg/L and 10mg/L and exceeds the allowable concentration of 1.0mg/L in the national sanitary Standard for Drinking Water (GB 5949-2006), and fluoride becomes one of the overproof indexes of detection according to the result of underground water quality monitoring in recent years. Therefore, the problem that the fluorine content in the treated water exceeds the standard can be solved, the drinking water safety of people in high-fluorine areas can be guaranteed, the cyclic utilization of water resources can be promoted, and the water using pressure is reduced.
The existing domestic and foreign defluorination methods mainly comprise an adsorption method, a precipitation method, an ion exchange method, a membrane separation technology and the like. The adsorption method is widely applied because the adsorption material is cheap and easy to obtain, the treatment method is simple, and the applicability is good. Commonly used defluorination adsorbents have been developed mainly: active alumina, nano material, binary and multi-element metal oxide adsorbent, zeolite, chitosan, microbial adsorbent and the like. However, the adsorption method has disadvantages such as a low adsorption amount and a long adsorption time, and thus a method of modifying an adsorbent is generally used to enhance the adsorption performance. However, as the pollution phenomenon is continuously deepened, the traditional adsorbent cannot meet the public demand.
Accordingly, there is an urgent need to develop a new adsorbent to obtain a new process for treating wastewater containing fluorine by using the adsorbent.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process method for treating fluorine-containing wastewater by using chitosan and aluminum sulfate composite modified zeolite.
The invention adopts the following technical scheme to solve the technical problems:
a process method for treating fluorine-containing wastewater by utilizing chitosan and aluminum sulfate composite modified zeolite comprises the following specific steps:
(1) sieving zeolite with 16 mesh sieve, washing with water, drying in a constant temperature drying oven at 105 deg.C for 1 hr, and cooling to room temperature in the dryer for use;
(2) selecting 0.6g of chitosan to be dissolved in 80ml of 9% acetic acid solution, placing the solution on a magnetic stirrer, stirring the solution for 60min at the speed of 100r/min, adding 1.0g of dry clean zeolite and 0.5g of kaolin, and continuing stirring the solution for 30min to obtain chitosan modified zeolite;
(3) adding Al with the mass fraction of 25g/L2(SO4)3Uniformly stirring 60ml of the solution to 1.0g of chitosan-modified zeolite on a magnetic stirrer at a speed of 120r/min for 30min, standing for 24h, and performing suction filtration and water washing by using a 0.45-micron microporous filter membrane until the solution is neutral; finally, the mixture is dried in a constant-temperature drying oven at the temperature of 105 ℃ to obtain aluminum sulfate and chitosan composite modified zeolite;
(4) adding 1.00g of aluminum sulfate and chitosan composite modified zeolite into 100ml of simulated F-containing wastewater, wherein the concentration of F-in the simulated F-containing wastewater is 10mg/L, and the pH value is 6; after mixing, the mixture was stirred at 25 ℃ for 4h for adsorption.
As one preferable mode of the present invention, the zeolite particles of step (1) are purchased from analytical grade zeolite particles dedicated to the university laboratory research institute of brocade environmental development.
In a preferred embodiment of the present invention, the above-mentioned H2SO4The acetic acid reagent was analytically pure.
In a preferred embodiment of the present invention, the chitosan is analytically pure chitosan, and the degree of deacetylation is 96.5% or more.
Compared with the prior art, the invention has the advantages that: chitosan and zeolites are commonly used as adsorbent materials; wherein, the chitosan has good adsorption effect but higher price; the zeolite is cheap and easy to obtain, has high mechanical strength and stable property, and has large specific surface area; al in aluminium salts3+Has high affinity to F-, can be subjected to complex precipitation in an aqueous solution, and is Al3+Al (OH) formed during the reaction3Flocs, also possessing ion exchange and adsorption F-The ability of (c); the invention combines chitosan, zeolite and kaolin to make the chitosan and Al3+The zeolite which is used as a surface modifier and is subjected to surface modification is used for treating fluorine-containing wastewater, so that the use amount of chitosan can be saved, the cost can be reduced, and the zeolite can be modified to improve the adsorption performance of the zeolite powder; in addition, the invention also strictly optimizes various parameters in the preparation and use processes of the aluminum sulfate and chitosan composite modified zeolite, and experiments prove that:
(1) when the chitosan is 0.6g, the zeolite is 1.0g, the kaolin is 0.5g, the concentration of aluminum sulfate is 25g/L, and the concentration of acetic acid is 9%, the adsorption effect is optimal;
(2) the theoretical maximum adsorption capacity of 1.9627mg/g was reached when adsorbing at 25 ℃ and a pH of 6 at an F-concentration of 10mg/L for 8 h.
Drawings
FIG. 1 is a graph of F-concentration versus time for different acetic acid concentrations in example 2;
FIG. 2 is a graph of F-concentration over time for different aluminum sulfate volumes in example 2;
FIG. 3 is a graph showing the change in morphology before and after modification of zeolite in example 3 (in the graph, a is before modification, and b is after modification);
FIG. 4 is an X-ray diffraction pattern of zeolite samples before and after modification in example 4
FIG. 5 is an X-ray photoelectron spectrum of a zeolite sample before and after adsorption in example 5
FIG. 6 is a spectrum of zeolite samples before and after adsorption in example 5
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
The process method for treating fluorine-containing wastewater by using the chitosan and aluminum sulfate composite modified zeolite comprises the following specific steps:
(1) sieving zeolite with 16 mesh sieve, washing with water, drying in a constant temperature drying oven at 105 deg.C for 1 hr, and cooling to room temperature in the dryer for use;
(2) selecting 0.6g of chitosan to be dissolved in 80ml of 9% acetic acid solution, placing the solution on a magnetic stirrer, stirring the solution for 60min at the speed of 100r/min, adding 1.0g of dry clean zeolite and 0.5g of kaolin, and continuing stirring the solution for 30min to obtain chitosan modified zeolite;
(3) adding Al with the mass fraction of 25g/L2(SO4)3The solution 60ml to chitosan modified zeolite 1.0g, in a magnetic stirrer with 120r/min uniform stirring for 30min, standing 24h, performing suction filtration and water washing by using a 0.45-micron microporous filter membrane until the solution is neutral; finally, the mixture is dried in a constant-temperature drying oven at the temperature of 105 ℃ to obtain aluminum sulfate and chitosan composite modified zeolite;
(4) 1.00g of aluminum sulfate and chitosan composite modified zeolite is added into 100ml of simulated F-containing zeolite-In waste water, wherein the simulation contains F-F in waste water-The concentration is 10mg/L, and the pH value is 6; after mixing, the mixture was stirred at 25 ℃ for 4h for adsorption.
Further, the zeolite particles in the step (1) are purchased from special analytical grade zeolite particles of university laboratory research units developed in Jinyuan environmental protection.
Further, a reagent H2SO4Acetic acid as analytically pure (Aladdin Industrial Corporation); the chitosan (the deacetylation degree is more than or equal to 96.5%) is analytically pure (chemical reagent of national drug group, Inc.).
Example 2
This example illustrates the influence of three factors, i.e., "acetic acid concentration", "mass ratio of chitosan-zeolite-kaolin", and "aluminum sulfate addition amount" on the "adsorption and fluorine removal effects of zeolite before and after modification" during the preparation process.
1. Effect of acetic acid concentration
Acetic acid-dissolved chitosan will form a better viscous fluid and will reduce the surface tension of chitosan, increase the dissolution rate, better cover the zeolite, and increase the defluorination performance. The acetic acid concentration will have some effect on the modification.
Therefore, the fluorine removal performance of the modified material is tested in the range of 1-11% of acetic acid concentration, the fluorine concentration of the wastewater is 10mg/L, the dosage of the adsorbent is 1.0g, and Al is used2(SO4)3The amount added was 10 ml.
The results of the modified fluorine removal are shown in FIG. 1 (in FIG. 1, the abscissa represents the acetic acid concentration, the left side of the ordinate represents the residual fluorine concentration value, mg/L, and the right side represents the fluorine removal rate,%). As can be seen from FIG. 1, when the acetic acid concentration reaches 3%, the better the modified defluorination effect with the increase of the acetic acid concentration, and reaches the maximum when reaching 9%, the residual fluorine ion concentration is the lowest, and the defluorination rate is the highest. However, when the acetic acid concentration exceeds 9%, the residual fluorine ion concentration increases, indicating that fluorine ions are desorbed again. This may be that the acetic acid concentration is too high, inhibiting the formation of amino groups on the chitosan surface, thus affecting the formation of NHF groups. The results show that the zeolite particles compositely modified by chitosan and aluminum sulfate in the embodiment maintain good defluorination capability at the concentration value of 9 percent acetic acid.
2. Effect of Chitosan-Zeolite-Kaolin Mass ratio
Selecting the chitosan adding amount A1Zeolite addition amount B1And the amount of kaolin C1Three factors, each at 4 levels, establish L16(43) Cross-section of (1) comparing zeolite pairs before and after modification to F-The optimum combination of zeolite modifications was obtained (see table 1 for orthogonal experimental results). Wherein the F-concentration and adsorption efficiency before and after adsorption are measured by ion selective electrode methodc and c0The mass concentration of ions in the solution before and after adsorption, unit: mg/L. Amount of adsorptionv represents the volume of the solution, ml; m is the mass of the added modified material, g.
TABLE 1 results of orthogonal experiments
The results of the modified defluorination are shown in Table 1, and it is understood from Table 1 that the factors have a large influence on the adsorption amount of the adsorbent in the following order: chitosan>Zeolite>Kaolin. In addition, from the experimental results, when 0.6g of chitosan, 9% of acetic acid concentration, 1.0g of zeolite and 0.5g of kaolin are used, the adsorption efficiency is highest, and the optimal combination is A2B1C2。
3. Influence of the amount of aluminum sulfate added
The modified material pair F was tested at the addition of 10 ml-60 ml of aluminum sulfate-The adsorption performance of (c); wherein, the concentration of the modified acetic acid is 9 percent, the adding amount of the modified zeolite is 1.0g, and the temperature is 25 ℃.
The modified fluorine removal structure is shown in FIG. 2 (in FIG. 2, the abscissa represents the amount of aluminum sulfate added, ml, the left side of the ordinate represents the residual fluorine concentration value, mg/L, and the right side represents the fluorine removal rate,%). As can be seen from FIG. 2, as the amount of aluminum sulfate added increases, the fluorine ion concentration decreases and the fluorine removal rate increases. When 60ml of aluminum sulfate was added, the fluoride ion concentration was minimized.
Example 3
This example illustrates the morphology characterization of the aluminum sulfate and chitosan composite modified zeolite of the present invention.
The appearance characterization is carried out by a cold field emission scanning electron microscope (S-4800), the amplification factor is 1K, the accelerating voltage is 2.0kV, and the working distance is 16.3 mm.
The shape change of the zeolite is shown in figure 3, wherein a is before modification, and b is after modification (namely the aluminum sulfate and chitosan composite modified zeolite of the invention). After the zeolite is modified by the chitosan and the zeolite, the porosity of the particles is increased, and the particles have more external expansion structures, and meanwhile, the chitosan has the properties of agglomeration, adsorption and precipitation, thereby further enhancing the F adsorption of the modified zeolite-The ability of the cell to perform. Fig. 3 shows that the micro-morphology of the adsorbent is changed, and the surface area and the porosity are increased, so that the adsorption capacity is improved to a certain extent.
Example 4
This example illustrates the mineral composition analysis (XRD) of the aluminum sulfate and chitosan composite modified zeolite of the present invention.
The mineral composition of zeolite and modified zeolite is determined by XRD (Smart Lab) ray diffractometer, the emitter material is Cu target, the pressure of the generating tube is 40kV, the tube current is 100mA, the scanning range is from 10-90 degrees of 2 theta, the sample is continuously scanned at the speed of 0.01 degrees, the XRD pattern of the sample before and after modification is shown in figure 4, in the figure, (Qtz represents quartz, Kln represents kaolinite, Nac represents nacrite, SiO represents nacrite, etc2Represents dioxySilicon nitride).
The mineral in the zeolite is an existing carrier of trace elements, the stability of the mineral is closely related to the crystal lattice energy of the mineral, and the higher the crystal lattice energy is, the better the stability of the mineral is. The mineral in the modified material is mainly Qtz (quartz), and as can be seen from fig. 4, the silicate mineral has relatively high lattice energy and the modified material has a relatively stable structure.
The chitosan molecule contains more amino groups, and when the chitosan molecule is dissolved in an acidic solution, the chitosan molecule has positive charges and can be combined with molecules on the outer surface of the crystal to form covalent bonds. As the chitosan molecular chain with positive charge is very long, the chitosan molecular chain is difficult to insert into pores of the fly ash crystal, and only a fly ash-chitosan compound is formed. As can be seen from fig. 4, the positions of diffraction peaks before and after coating the zeolite with chitosan and aluminum sulfate did not change, indicating that the crystal structure type of the modified zeolite did not change. Therefore, it can be presumed that the modification mechanism of the fly ash-supported chitosan is the chemical bonding of the fly ash and the positively charged chitosan.
Example 5
This example illustrates the elemental composition (XPS) and content (EDS) analysis of the aluminum sulfate and chitosan composite modified zeolite of the present invention.
Zeolite and modified zeolite elemental compositions were determined by XPS (ESCALAB250Xi) ray photoelectron spectroscopy, energy range: 0-5,000 eV, the area of the X-ray beam spot is from 900 μm to 200 μm, the large beam spot: the sample is scanned under the conditions of Ag3d5/2(FWHM is 0.8eV, and the strength is larger than or equal to 650 kcps), an XPS spectrum of the sample before and after modification is shown in FIG. 5. As can be seen from FIG. 5, elements such as Al 2p, Mg 2s, C ls and O ls appear before and after adsorption, a new strong peak appears at 685.5eV after adsorption (FIG. 5(b)), which proves that F ls is the F ls, and the composite adsorbent has the capability of adsorbing fluorine ions.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. A process method for treating fluorine-containing wastewater by using aluminum sulfate and chitosan composite modified zeolite is characterized by comprising the following specific steps:
(1) sieving zeolite with 16 mesh sieve, washing with water, drying in a constant temperature drying oven at 105 deg.C for 1 hr, and cooling to room temperature in the dryer for use;
(2) selecting 0.6g of chitosan to be dissolved in 80ml of 9% acetic acid solution, placing the solution on a magnetic stirrer, stirring the solution for 60min at the speed of 100r/min, adding 1.0g of dry clean zeolite and 0.5g of kaolin, and continuing stirring the solution for 30min to obtain chitosan modified zeolite;
(3) adding Al with the mass fraction of 25g/L2(SO4)3Uniformly stirring 60ml of the solution to 1.0g of chitosan-modified zeolite on a magnetic stirrer at a speed of 120r/min for 30min, standing for 24h, and performing suction filtration and water washing by using a 0.45-micron microporous filter membrane until the solution is neutral; finally, the mixture is dried in a constant-temperature drying oven at the temperature of 105 ℃ to obtain aluminum sulfate and chitosan composite modified zeolite;
(4) adding 1.0g of aluminum sulfate and chitosan composite modified zeolite into 100ml of simulated F-containing wastewater, wherein the concentration of F-in the simulated F-containing wastewater is 10mg/L, and the pH value is 6; after mixing, the mixture was stirred for 4 hours with an amount of aluminum sulfate added of 60ml for adsorption.
2. The process for treating fluorine-containing wastewater by using chitosan and aluminum sulfate composite modified zeolite as claimed in claim 1, wherein the zeolite particles in step (1) are purchased from analytical grade zeolite particles dedicated to university laboratory research institute provided in jin Yuan environmental protection.
3. The process method for treating fluorine-containing wastewater by using chitosan-aluminum sulfate composite modified zeolite as claimed in any one of claims 1-2, wherein the H is2SO4The acetic acid reagent was analytically pure.
4. The process method for treating fluorine-containing wastewater by using the chitosan-aluminum sulfate composite modified zeolite according to any one of claims 1-2, wherein the chitosan is analytically pure chitosan, and the deacetylation degree is not less than 96.5%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320347A (en) * | 2020-03-16 | 2020-06-23 | 武夷学院 | Treatment method of secondary sedimentation tank sludge of domestic sewage plant |
| CN112777672A (en) * | 2020-12-07 | 2021-05-11 | 江苏海普功能材料有限公司 | Functional silicon dioxide modified defluorination material and preparation and application thereof |
| CN113501599A (en) * | 2021-08-11 | 2021-10-15 | 龙岩学院 | Method for treating fluorine-containing wastewater |
| CN116212824A (en) * | 2022-11-16 | 2023-06-06 | 云南驰宏锌锗股份有限公司 | Defluorination material for zinc hydrometallurgy and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898128A (en) * | 2009-05-25 | 2010-12-01 | 中国科学院生态环境研究中心 | Preparation and application method of aluminum modified red mud defluorinating absorbent |
| CN103058411A (en) * | 2012-12-20 | 2013-04-24 | 中国科学院生态环境研究中心 | Method of removing fluorinions in water |
-
2019
- 2019-09-30 CN CN201910939000.0A patent/CN110589927A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898128A (en) * | 2009-05-25 | 2010-12-01 | 中国科学院生态环境研究中心 | Preparation and application method of aluminum modified red mud defluorinating absorbent |
| CN103058411A (en) * | 2012-12-20 | 2013-04-24 | 中国科学院生态环境研究中心 | Method of removing fluorinions in water |
Non-Patent Citations (2)
| Title |
|---|
| 廖国权等: "交联负载铝壳聚糖树脂对氟的吸附性能研究", 《环境工程学报》 * |
| 陈静娴: "金属改性壳聚糖复合吸附剂的制备及水中除氟性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320347A (en) * | 2020-03-16 | 2020-06-23 | 武夷学院 | Treatment method of secondary sedimentation tank sludge of domestic sewage plant |
| CN112777672A (en) * | 2020-12-07 | 2021-05-11 | 江苏海普功能材料有限公司 | Functional silicon dioxide modified defluorination material and preparation and application thereof |
| CN112777672B (en) * | 2020-12-07 | 2023-07-25 | 江苏海普功能材料有限公司 | Functionalized silica modified defluorination material and preparation and application thereof |
| CN113501599A (en) * | 2021-08-11 | 2021-10-15 | 龙岩学院 | Method for treating fluorine-containing wastewater |
| CN116212824A (en) * | 2022-11-16 | 2023-06-06 | 云南驰宏锌锗股份有限公司 | Defluorination material for zinc hydrometallurgy and preparation method thereof |
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Application publication date: 20191220 |