CN106669598B - Zeolite adsorbent for removing anionic pollutants in water and preparation method thereof - Google Patents
Zeolite adsorbent for removing anionic pollutants in water and preparation method thereof Download PDFInfo
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- CN106669598B CN106669598B CN201611191512.6A CN201611191512A CN106669598B CN 106669598 B CN106669598 B CN 106669598B CN 201611191512 A CN201611191512 A CN 201611191512A CN 106669598 B CN106669598 B CN 106669598B
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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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
- B01J20/0207—Compounds of Sc, Y or Lanthanides
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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
Abstract
The invention discloses a zeolite adsorbent for removing anionic pollutants in water and a preparation method thereof, and relates to the field of materials and the technical field of water purification and sewage treatment. The zeolite adsorbent is characterized in that: the external surface of the zeolite is loaded with a cationic surfactant, and the internal supercage is loaded with rare earth metal lanthanum which can form a complex with anions, so that the internal and external surface areas of the zeolite molecular sieve are more efficiently utilized, and the capability of removing anionic pollutants in water is greatly improved. The adsorbent disclosed by the invention is convenient to prepare, excellent in effect, low in cost, high in utilization rate and very wide in application prospect in treatment of anion-polluted wastewater.
Description
Technical Field
The invention relates to a zeolite adsorbent for removing anionic pollutants in water and a preparation method thereof, belonging to the technical field of materials and water quality purification and pollutant treatment.
Background
For some slightly polluted water bodies in nature, anionic pollutants such as nitrate, phosphate, arsenate and the like are widely existed. The content of pollutants in the water bodies is small, and the water bodies are difficult to reach the standard by a common treatment method under the condition of low investment.
In addition, TN is difficult to reach the standard after various waste water produced in daily life of human beings and industry is treated by a sewage plant, and N in TN mainly exists in the form of nitrate nitrogen. Because the carbon source is insufficient and the nitrate nitrogen content is relatively low, the carbon source enters the biological denitrification device again, and the problems of high investment cost, long process consumption time and difficulty in utilizing trace nitrate nitrogen by microorganisms exist, so that the economy and the feasibility are not realized.
The adsorption method has the advantages of simple and convenient operation, low operation cost and the like, is increasingly used for treating micro pollutants in micro polluted water and biochemical effluent of sewage plants, and has good effect.
Some adsorbents have the limitation of strong unicity when adsorbing pollutants in treated water, and cannot have good removal effect on most or certain types of pollutants. In the past, the modification of zeolite focuses on loading different cationic surfactants on the outer surface of the zeolite so as to improve the capability of removing anionic pollutants in water. However, the cationic surfactant has large molecules and cannot enter the zeolite super cage, so that the adsorbent prepared by the conventional method has relatively low adsorption capacity on nitrate nitrogen. In view of the above, the present invention provides a method for preparing a zeolite adsorbent for removing anionic contaminants in water, so that the zeolite adsorbent has a good removal effect on most of anionic contaminants possibly existing in water.
Disclosure of Invention
The invention aims to overcome the defects of single adsorption and low adsorption quantity of the existing adsorbent and provide a preparation method of a zeolite adsorbent capable of removing various anionic pollutants in water. The adsorbent greatly improves the adsorption of anionic pollutants in water through the electrostatic attraction and ligand exchange action of the cationic surfactant on the outer surface and the complexing action of the supercage lanthanum in the zeolite, thereby achieving the aim of purifying slightly polluted water.
The invention is realized by the following technical scheme:
a method of making a zeolite adsorbent for removing anionic contaminants from water comprising the steps of:
1) taking 2-20 parts by mass of zeolite subjected to impurity removal and performance activation pretreatment into a container, adding deionized water and stirring to form a suspension; adding 0.5-5 parts by mass of lanthanum chloride hydrate, stirring, adjusting the pH value to 8-10 by using NaOH solution, continuously stirring for at least 2 hours, filtering, and washing by using deionized water until no Cl exists-Exist of(ii) a After drying, activating at high temperature to promote the La to form a bond in the zeolite super cage;
2) placing the zeolite obtained after high-temperature activation in the step 1) in a cationic surfactant solution, oscillating for 5-72 h, and filtering and drying to obtain the zeolite adsorbent.
In the above technical solution, the following specific preferred modes can be adopted for each step:
in the step 1), the zeolite is natural clinoptilolite, NaY zeolite molecular sieve or 13X zeolite molecular sieve.
The pretreatment method comprises the following steps: after sieving zeolite, boiling the zeolite for 0.5-2 h by 1+3 hydrochloric acid, washing the zeolite with water, filtering the zeolite, and calcining the zeolite for 2-5h at 400 ℃ in a muffle furnace to remove impurities on the surface of the zeolite and activate the performance of the zeolite.
In the step 1), the particle size of the zeolite is 200-80 meshes.
In the step 1), the mass ratio of the zeolite to the added lanthanum chloride is 10: 1-2: 1.
In the step 1), the concentration range of the NaOH solution is 0.1-3 mol/L.
In the step 2), the cationic surfactant is cetyl trimethyl ammonium bromide, and the concentration range of the cationic surfactant solution is 10-50 mM.
In the step 2), the oscillation speed is 150-300 rpm, and the oscillation temperature is 20-60 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. by loading different substances on the outer surface of the zeolite and in the super cage, the surface adsorption utilization rate of the zeolite molecular sieve is improved, the removal effect of the zeolite molecular sieve on most of anionic pollutants in water is enhanced, and the zeolite molecular sieve has very wide application prospects in purification of biochemical effluent and micro-polluted water in sewage plants.
2. The zeolite raw material has low price, and the cost of the adsorbent is greatly reduced.
3. The adsorption process is convenient to operate, has low requirements on conditions such as temperature, pH and the like, and is more energy-saving and environment-friendly.
Drawings
FIG. 1 is a schematic view of the structure of the adsorbent of the present invention.
Detailed Description
The invention is further illustrated with reference to the accompanying drawings and specific embodiments.
The preparation of the zeolite adsorbent mainly comprises two parts of La load in the zeolite super cage and load modification of external surface HDTMA.
The stable loading of La in the zeolite super cage is realized by adjusting pH and activating at high temperature: taking 2-20 parts by mass of zeolite subjected to impurity removal and performance activation pretreatment into a container, adding deionized water and stirring to form a suspension; adding 0.5-5 parts by mass of lanthanum chloride hydrate, stirring, adjusting the pH value to 8-10 by using NaOH solution, continuously stirring for at least 2 hours, filtering, and washing by using deionized water until no Cl exists-Are present. In this step, La is caused to be La (OH) by adjusting pH2+、[La(OH2)La]4+And [ La (OH)2La]4+Is fixed on the inner surface of the zeolite, promotes the movement of the zeolite to the inner part of the zeolite super cage through high-temperature activation and stabilizes the load.
The load modification of the external surface HDTMA was carried out in a stoppered conical flask. A certain amount of zeolite which is dried and activated at high temperature is put into a cationic surfactant solution (such as HDTMA solution) with excessive concentration, and most HDTMA is loaded on the surface of the zeolite in the form of double-layer molecules by constant-temperature oscillation.
After analysis, the structure of the finally formed zeolite adsorbent is shown in figure 1, and different substances are loaded on the outer surface of the molecular sieve and the inner part of the super cage, so that the surface area of the molecular sieve is more efficiently utilized, and the adsorbent has a better adsorption effect on a specific type of pollutant, namely an anionic pollutant, in water. Specifically, HDTMA loaded on the outer surface of the zeolite molecular sieve adsorbs anionic pollutants in water through the actions of electrostatic attraction, ligand exchange and the like, and the adsorption and removal of the anionic pollutants in water are completed through the actions of lanthanum complexation and the like in the molecular sieve super cage.
In order to verify the effect of the adsorbent prepared by the invention, an adsorption test is also carried out on the adsorbent. The adsorption experiment is carried out in a conical flask with a plug, nitrate solution with certain concentration and prepared zeolite adsorbent are added, the mixture is placed in a constant-temperature oscillation box, after reaction for a certain time, a suction filtration device is used for quickly separating the adsorbent from adsorbate solution, and a part of solution is filtered by a filter and is used for measuring the concentration of the adsorbed nitrate.
The following examples are provided to fully explain the present invention in further detail and to show the adsorption effect.
Example 1
1. And (3) pretreating a certain amount of zeolite which is sieved by a sieve of 80-200 meshes, and then drying for later use. The pretreatment method comprises the following steps: and (3) sieving the NaY zeolite, washing with water, filtering, and calcining in a muffle furnace at 400 ℃ for 3h to activate the surface performance of the zeolite.
2. Respectively weighing 10g of NaY zeolite and 5g of lanthanum chloride hydrate, firstly placing 10g of NaY zeolite in a container, adding deionized water and stirring to form a suspension; then, lanthanum chloride hydrate was added to the zeolite suspension with magnetic stirring at 25 ℃ to mix the two well and keep them in suspension, and stirred for 1 h. And then dropwise adding a sodium hydroxide solution with the concentration of 1.0mol/L into the reaction solution, adjusting the pH to 9, continuously stirring for 2 hours, filtering and separating, and repeatedly washing the solid with deionized water until no chloride ions exist. Drying and activating at high temperature to obtain the zeolite-lanthanum.
3. 100ml of a 10mM hexadecyltrimethylammonium bromide solution was taken in a 250ml conical flask with a stopper, 10g of a zeolite-lanthanum adsorbent was added, and the flask was shaken at 45 ℃ for 24 hours. Filtering, washing and drying to obtain the cationic surfactant modified zeolite-lanthanum composite adsorbent.
4. 0.5g of the cationic surfactant modified zeolite-lanthanum composite adsorbent prepared by the method is weighed and placed in 50ml of phosphate solution with the concentration of 10mg/L, and the solution is placed on a constant-temperature water bath oscillator to be oscillated for 12 hours at the oscillation speed of 150 rpm. After the experiment, no phosphate is detected (lower than the detection limit), namely the experiment shows that the adsorption removal rate of the phosphate with the initial concentration of 10mg/L is close to 100%.
Example 2
1. And (3) pretreating a certain amount of zeolite which is sieved by a sieve of 80-200 meshes, and then drying for later use. The pretreatment method comprises the following steps: and (3) sieving the NaY zeolite, washing with water, filtering, and calcining in a muffle furnace at 400 ℃ for 3h to activate the surface performance of the zeolite.
2. Respectively weighing 10g of NaY zeolite and 5g of lanthanum chloride hydrate, firstly placing 10g of NaY zeolite in a container, adding deionized water and stirring to form a suspension; then, lanthanum chloride hydrate was added to the zeolite suspension with magnetic stirring at 25 ℃ to mix the two well and keep them in suspension, and stirred for 1 h. And then dropwise adding a sodium hydroxide solution with the concentration of 1.0mol/L into the reaction solution, adjusting the pH to 9, continuously stirring for 2 hours, filtering and separating, and repeatedly washing the solid with deionized water until no chloride ions exist. Drying and activating at high temperature to obtain the zeolite-lanthanum.
3. 100ml of a 30mM hexadecyltrimethylammonium bromide solution was taken in a 250ml conical flask with a stopper, 10g of zeolite-lanthanum adsorbent was added, and shaking was carried out at 45 ℃ for 36 hours. Filtering, washing and drying to obtain the cationic surfactant modified zeolite-lanthanum composite adsorbent.
4. 0.1g of the cationic surfactant modified zeolite-lanthanum composite adsorbent prepared by the method is weighed and placed in 50ml of phosphate solution with the concentration of 50mg/L, and the solution is placed on a constant-temperature water bath oscillator to be oscillated for 12 hours at the oscillation speed of 150 rpm. Experiments show that the adsorption capacity of the phosphate with the initial concentration of 50mg/L is 23.98mg/g, and the removal rate reaches 91.25%.
Example 3
1. And (3) pretreating a certain amount of natural clinoptilolite sieved by a sieve of 80-150 meshes, and drying for later use. The pretreatment method comprises the following steps: sieving natural clinoptilolite, boiling with 1+3 hydrochloric acid for 1h, washing with water, filtering, and calcining in a muffle furnace at 400 deg.C for 3h to remove impurities on zeolite surface and activate performance.
2. Respectively weighing 5g of pretreated natural clinoptilolite and 1g of lanthanum chloride hydrate, putting 5g of natural clinoptilolite in a container, adding deionized water, and stirring to form a suspension; then, lanthanum chloride hydrate was added to the zeolite suspension with magnetic stirring at 25 ℃ to mix the two well and keep them in suspension, and stirred for 1 h. And then dropwise adding a sodium hydroxide solution with the concentration of 1.0mol/L into the reaction solution, adjusting the pH to 9, continuously stirring for 2 hours, filtering and separating, and repeatedly washing the solid with deionized water until no chloride ions exist. Drying and activating at high temperature to obtain the zeolite-lanthanum.
3. 100ml of a 30mM hexadecyltrimethylammonium bromide solution was taken in a 250ml conical flask with a stopper, and zeolite-lanthanum adsorbent was added thereto and shaken at 45 ℃ for 24 hours. Filtering, washing and drying to obtain the cationic surfactant modified zeolite-lanthanum composite adsorbent.
4. 0.1g of the cationic surfactant modified zeolite-lanthanum composite adsorbent prepared by the method is weighed and placed in 50ml of nitrate nitrogen solution with the concentration of 50mg/L, and the solution is placed on a constant-temperature water bath oscillator to be oscillated for 12 hours at the oscillating speed of 150 rpm. Experiments show that the adsorption quantity of nitrate nitrogen with the initial concentration of 50mg/L is 14.12mg/g, and the removal rate reaches 56.50%.
The above examples show that the zeolite adsorbent prepared by the invention has a good removal effect on most of anionic pollutants possibly existing in water, and particularly has an extremely outstanding adsorption removal rate on phosphate, which is nearly 100%.
Claims (1)
1. A method for preparing a zeolite adsorbent for removing anionic contaminants from water, comprising the steps of:
1) pretreating zeolite sieved by a sieve of 80-200 meshes and then drying for later use, wherein the pretreatment method comprises the following steps: sieving NaY zeolite, washing with water, filtering, and calcining in a muffle furnace at 400 ℃ for 3h to activate the surface performance of the zeolite;
2) respectively weighing 10g of NaY zeolite and 5g of lanthanum chloride hydrate, firstly placing 10g of NaY zeolite in a container, adding deionized water and stirring to form a suspension; then under the magnetic stirring at 25 ℃, adding hydrated lanthanum chloride into the zeolite suspension to ensure that the hydrated lanthanum chloride and the zeolite suspension are fully mixed and in a suspension state, and stirring for 1 h; then dropwise adding a sodium hydroxide solution with the concentration of 1.0mol/L into the reaction solution, adjusting the pH to 9, continuously stirring for 2 hours, filtering and separating, and repeatedly washing the solid with deionized water until no chloride ions exist; drying and activating at high temperature to prepare zeolite-lanthanum;
3) taking 100mL of 10mM hexadecyl trimethyl ammonium bromide solution to a 250mL conical flask with a plug, adding 10g of zeolite-lanthanum adsorbent, and oscillating for 24h at 45 ℃; filtering, washing and drying to obtain the cationic surfactant modified zeolite-lanthanum composite adsorbent.
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| CN107213866A (en) * | 2017-06-26 | 2017-09-29 | 泉州师范学院 | A kind of preparation method and application for being used to go the zinc oxide modified zeolite adsorbing material of anionic pollutant in water removal |
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| CN111530410A (en) * | 2020-04-28 | 2020-08-14 | 北京工业大学 | Method for preparing phosphorus removal adsorbent based on natural zeolite synthesized molecular sieve waste |
| CN111530412A (en) * | 2020-04-28 | 2020-08-14 | 北京工业大学 | Method for synthesizing synchronous denitrification and dephosphorization adsorbent based on natural zeolite |
| CN112023873A (en) * | 2020-08-25 | 2020-12-04 | 广西桂林新大桂工环境科技中心(有限合伙) | Preparation method of heavy metal scavenging agent for sewage treatment |
| CN112495340A (en) * | 2020-10-20 | 2021-03-16 | 广州振清环保技术有限公司 | Preparation method of modified clinoptilolite and water body purifying agent |
| CN113185671B (en) * | 2021-05-27 | 2022-09-16 | 复旦大学 | Impurity removal and purification method for epoxy resin |
| CN114749143B (en) * | 2022-04-01 | 2024-03-01 | 北京工业大学 | Preparation method and application of synchronous denitrification and dephosphorization adsorbent material based on natural clinoptilolite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380343A (en) * | 2011-08-31 | 2012-03-21 | 环境保护部华南环境科学研究所 | Simultaneous nitrogen and phosphorus removal modified artificial zeolite for micro-polluted water, and preparation method thereof |
| CN103539217A (en) * | 2013-11-06 | 2014-01-29 | 四川大学 | Zeolite modification method for synchronously removing cationic and anionic nitrogen and anionic phosphorus pollutants from sewage |
| CN104959123A (en) * | 2015-07-15 | 2015-10-07 | 江苏大学 | Preparation method and application of novel hierarchical pore composite material |
| CN104971699A (en) * | 2015-07-27 | 2015-10-14 | 南京大学 | Modified zeolite organic matter composite agent for synchronous nitrogen and phosphorus removal of sewage, and preparation method, application and application method of modified zeolite organic matter composite agent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380343A (en) * | 2011-08-31 | 2012-03-21 | 环境保护部华南环境科学研究所 | Simultaneous nitrogen and phosphorus removal modified artificial zeolite for micro-polluted water, and preparation method thereof |
| CN103539217A (en) * | 2013-11-06 | 2014-01-29 | 四川大学 | Zeolite modification method for synchronously removing cationic and anionic nitrogen and anionic phosphorus pollutants from sewage |
| CN104959123A (en) * | 2015-07-15 | 2015-10-07 | 江苏大学 | Preparation method and application of novel hierarchical pore composite material |
| CN104971699A (en) * | 2015-07-27 | 2015-10-14 | 南京大学 | Modified zeolite organic matter composite agent for synchronous nitrogen and phosphorus removal of sewage, and preparation method, application and application method of modified zeolite organic matter composite agent |
Non-Patent Citations (2)
| Title |
|---|
| HDTMA改性沸石同步去除氨氮和磷酸盐的效果及规律研究;姚景等;《安全与环境学报》;20150630;第15卷(第3期);第216页左栏倒数第1段-右栏第1段、第216页第1.2部分 * |
| 镧铈改性沸石对污水除磷性能和机制的比较研究;崔有为等;《中国稀土学报》;20160831;第34卷(第4期);第461页左栏第2段、第1.1、1.2部分 * |
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