CN111530412A - Method for synthesizing synchronous denitrification and dephosphorization adsorbent based on natural zeolite - Google Patents
Method for synthesizing synchronous denitrification and dephosphorization adsorbent based on natural zeolite Download PDFInfo
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- B01J20/16—Alumino-silicates
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Abstract
A method for synthesizing a synchronous denitrification and dephosphorization adsorbent based on natural zeolite belongs to the technical field of environmental engineering. Lanthanum is introduced in the process of synthesizing the molecular sieve by natural zeolite to prepare the lanthanum modified molecular sieve adsorbent with synchronous nitrogen and phosphorus removal performance, and the lanthanum modified molecular sieve adsorbent has good adsorption effect on ammonium and phosphate ions. The method is technically characterized in that the synthesis and modification of the molecular sieve are combined together, a lanthanum solution is directly introduced into the synthesis process of the molecular sieve, a lanthanum element is introduced into a reaction mixed solution after crystal grains are generated, and the lanthanum modification and crystal aging process are simultaneously carried out by means of the alkaline condition in the reaction mixed solution. The lanthanum element can be loaded on the surface of the porous structure of the molecular sieve to the maximum extent, and has higher phosphorus adsorption capacity on the basis of not influencing the ammonia nitrogen adsorption performance; meanwhile, the operation steps of synthesizing the molecular sieve and modifying the adsorbent are simplified, and the reagent consumption is saved. The invention has better application prospect for advanced sewage treatment.
Description
Technical Field
The invention relates to a synthetic method of a tail water synchronous denitrification dephosphorization adsorbent suitable for a municipal sewage plant, belonging to the technical field of environmental engineering.
Background
The regeneration treatment and resource reuse of sewage are an effective way to solve the problem of water resources. Limited by the traditional sewage biological treatment process technology, the effluent of the municipal sewage plant still contains nitrogen and phosphorus with certain concentration, and the water body eutrophication problem can be caused when the effluent is reused in landscape water bodies. At present, the function of deep denitrification and dephosphorization is added on the basis of the traditional biological treatment process, and the main purpose of upgrading and reforming the municipal sewage plant is achieved. On the other hand, nitrogen and phosphorus are also important production materials, and especially non-renewable phosphorus ore resources face the problem of gradual depletion. How to realize the recovery of nitrogen and phosphorus resources while removing nitrogen and phosphorus from sewage becomes a technical difficulty in the field of sewage treatment.
The main methods for removing nitrogen and phosphorus from sewage include chemical precipitation, biological method, stripping method and adsorption method. The widely applied biological nitrogen and phosphorus removal process has long flow, complex operation and control and nonideal effect on removing low-concentration nitrogen and phosphorus; the chemical precipitation method and the air stripping method both have the problem of secondary pollution; the adsorption method has the dual functions of pollutant removal and resource recovery: especially, the method has the characteristics of high efficiency and stability in removing low-concentration pollutants, the saturated adsorbent can be repeatedly used after desorption and regeneration, and the desorbed adsorbate can be subjected to resource recovery. At present, the application of an adsorption method in the field of deep nitrogen and phosphorus removal of sewage mainly aims at single nitrogen removal or phosphorus removal, and most adsorbents do not have the capacity of synchronously and effectively adsorbing nitrogen and phosphorus.
The key to the adsorption process is the adsorbent material. Zeolite is a silicate mineral and is known as "zeolite" because it boils when heated. The natural zeolite has large specific surface area and porous structure, and its basic structural unit is similar to molecular sieve, and is made of silicon oxygen (SiO)4) Tetrahedron and aluminum oxide (AlO)4) The tetrahedra are connected with each other through sharing oxygen atoms to form a negatively charged ring-shaped or three-dimensional structure, and have good cation exchange performance, and particularly have certain selective adsorption on positively charged ammonium ions. However, compared with artificially synthesized molecular sieves, the natural zeolite silicon-aluminum has unfixed effective components, high impurity content and uneven pore channel size, and the treatment effect is not reasonable when the natural zeolite silicon-aluminum is directly used as an adsorbentThinking; the conventional acid-base modification treatment cannot radically improve the adsorption performance. The artificial synthesis of zeolite molecular sieve from natural zeolite as raw material is one way to solve the problem. At present, the usual synthesis method is the alkali-soluble conventional process proposed in the patent published in 1981 by Leonard et al in the united states. The process comprises the steps of dissolving clinoptilolite ore powder with high whiteness and purity in alkali, directly mixing the clinoptilolite ore powder with a sodium aluminate solution for reaction and crystallization, and preparing the zeolite molecular sieve which is mainly used as an industrial catalyst and a washing assistant.
The synthetic zeolite molecular sieve has stable silicon oxygen (SiO)4) And aluminum oxide (AlO)4) The tetrahedron structure has large specific surface area and uniform pore canal size, is an ammonium adsorbent with large adsorption capacity and stable adsorption performance, but has poor adsorption performance to phosphate radical with negative charge. Relevant researches show that the rare earth element lanthanum can modify the adsorption material, and the lanthanum-modified adsorbent has a good adsorption removal effect on phosphate. The lanthanum element has good biocompatibility, is friendly to an ecosystem and is safe to apply. The invention introduces the rare earth lanthanum into the zeolite molecular sieve synthesis process, and aims to endow the zeolite molecular sieve with the capability of synchronously removing nitrogen and phosphorus.
Disclosure of Invention
The invention provides a method for synthesizing a synchronous denitrification and dephosphorization adsorbent based on natural zeolite.
The zeolite molecular sieve is synthesized by adopting an alkali-soluble conventional process (figure 1). By controlling the synthesis reaction process, lanthanum is introduced after the molecular sieve crystal grains are basically generated, and the crystal grain growth and aging reaction are continued to generate the lanthanum modified zeolite molecular sieve (figure 2).
The specific preparation process comprises the following steps: taking a certain amount of natural zeolite raw material (grinding and sieving with a 100-mesh sieve) to put into a three-neck flask, adding sodium hydroxide solution with the mass percent concentration of 20% according to the solid-liquid mass ratio of 1:5, putting the flask into a magnetic stirrer, stirring and dissolving alkali for 2h at 95 ℃, measuring the content of silicon element in a dissolution liquid through ICP (attached table one), and measuring the content of silicon element according to SiO2:Al2O3Adding sodium aluminate solution into the mixed solution with the molar ratio of 1:0.5, keeping the temperature unchanged, mixing and crystallizing for 2h, and introducing the mixed solution for crystallization reaction with the mass percentage concentration of0.7 percent lanthanum chloride solution, the volume of which is 2 times that of the added sodium hydroxide solution, aging and reacting for 12 hours at 60 ℃, filtering and washing the mixed solution until the pH value is neutral, and drying to obtain the lanthanum modified zeolite molecular sieve (grinding and sieving with a 80-mesh sieve) (figure 3).
The synthesis process of the lanthanum modified zeolite molecular sieve comprises the following steps: (1) dissolving a silicate component (a silicon source) from natural zeolite in an alkali solution, reacting with an added sodium aluminate solution (an aluminum source) to generate an amorphous substance containing aluminosilicate, and crystallizing at a certain temperature to form zeolite molecular sieve grains; (2) adding lanthanum chloride solution and adding La under alkaline condition2O3The lanthanum modified zeolite molecular sieve is loaded on the surface of a molecular sieve crystal grain, and the crystal grain gradually grows and ages to form a lanthanum modified zeolite molecular sieve crystal product.
TABLE 1 ICP measurement results
| Element(s) | Concentration (g/L) | Dissolution rate |
| Si | 25.94 | 35.7％ |
In order to evaluate the adsorption performance of the adsorbent, a static adsorption experiment is carried out under the condition of laboratory water distribution, and the synchronous adsorption effect of the adsorbent on ammonia nitrogen and phosphate is investigated. The experimental result shows that compared with the natural zeolite raw material, the ammonia nitrogen and phosphate adsorption performance of the lanthanum modified zeolite molecular sieve is greatly improved; compared with a pure zeolite molecular sieve, the phosphorus removal capacity of the lanthanum-modified zeolite molecular sieve is improved by 77%, the phosphorus adsorption capacity is increased from 2.93mg/g to 12.69mg/g, and the ammonia nitrogen adsorption performance is not influenced. Therefore, the adsorbent has certain application potential for advanced nitrogen and phosphorus removal of the effluent of the municipal sewage plant.
Compared with the prior art, the invention has the advantages that:
(1) the invention discovers that the rare earth element lanthanum is introduced in the synthesis process of the zeolite molecular sieve, so that phosphate adsorption performance can be endowed to the zeolite molecular sieve, and the ammonia nitrogen adsorption performance of the molecular sieve can not be greatly influenced. After lanthanum modification, the phosphate adsorption performance of the zeolite molecular sieve is improved by 77%.
(2) Different from the traditional adsorbent matrix modification, in the preparation process of the adsorbent, the lanthanum solution is directly introduced into a zeolite molecular sieve crystallization reaction system, so that the solid-liquid separation process of a synthesized product is omitted, the strong alkaline condition of the reaction system can be fully utilized, and the alkali consumption is saved; meanwhile, lanthanum element can be loaded on the surface of the zeolite molecular sieve porous structure to the maximum extent, and the dephosphorization function is exerted.
(3) The natural zeolite raw material used in the invention is rich in reserves in China, and is cheap and easy to obtain. And the rare earth element resources in China are quite rich, so that the adsorbent disclosed by the invention has a good practical engineering application prospect.
Drawings
FIG. 1 shows a conventional process for alkali dissolution;
FIG. 2 shows a modified preparation process after lanthanum element introduction;
FIG. 3 shows the lanthanum modified zeolite molecular sieve;
FIG. 4 shows the effect of the Si-Al feed ratio on the adsorption performance of the lanthanum-modified molecular sieve;
FIG. 5 the effect of lanthanum solution concentration on the adsorption performance of lanthanum modified molecular sieves;
FIG. 6 is a comparison of the effects of static adsorption experiments.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to illustrate the invention and not to limit the scope of the invention.
The invention is mainly suitable for advanced nitrogen and phosphorus removal of the effluent of the municipal sewage plant.
Firstly, the optimal SiO is preferably selected by changing the adding proportion of silicon and aluminum and the solubility of lanthanum solution in the preparation process of the adsorbent2:Al2O3Proportioning and concentration of lanthanum chloride solution (preferred embodiment).
Then, lanthanum modified zeolite molecular sieve adsorbent is prepared under the optimal preparation conditions, an experimental group taking lanthanum modified zeolite molecular sieve as adsorbent, a control group I taking pure natural zeolite as adsorbent and a control group II taking zeolite molecular sieve as adsorbent are subjected to static adsorption experiment, the adsorption effect of the lanthanum modified zeolite molecular sieve is analyzed through the static experiment result, and the possible nitrogen and phosphorus removal mechanism (example) is further explored.
PREFERRED EMBODIMENTS FOR CARRYING OUT THE INVENTION
(1) Silicon-aluminum material feeding ratio
Set up SiO2:Al2O3The ratio of lanthanum to lanthanum is 1:0.25, 1:0.5, 1:1, 1:1.5 and 1:2 respectively, the concentration of lanthanum solution is 0.8% (mass concentration), and other conditions are the same as the preparation process, so that a series of lanthanum modified zeolite molecular sieves are prepared.
Accurately weighing 0.1g of different lanthanum modified zeolite molecular sieves, and placing the zeolite molecular sieves in a container with 100mL of KH2PO4Concentration 20mg/L (in terms of P), NH4Cl concentration 30mg/L (in N) in an Erlenmeyer flask. After constant temperature oscillation adsorption for 12h at 25 ℃ and 220r/min, taking supernatant to measure the concentration of ammonia nitrogen and phosphate, and calculating the equilibrium adsorption quantity. (FIG. 4)
(2) Concentration of lanthanum solution
The concentration of lanthanum solution is set to be 0, 0.2%, 0.4%, 0.6%, 0.7% and 0.8%, and a series of lanthanum modified zeolite molecular sieves are prepared under the conditions of the optimal silicon-aluminum feed ratio and the same other conditions as the preparation process.
Accurately weighing 0.1g of different lanthanum modified zeolite molecular sieves, and placing the zeolite molecular sieves in a container with 100mL of KH2PO4Concentration 20mg/L (in terms of P), NH4Cl concentration 30mg/L (in N) in an Erlenmeyer flask. After constant temperature oscillation adsorption for 12h at 25 ℃ and 220r/min, taking supernatant to measure the concentration of ammonia nitrogen and phosphate, and calculating the equilibrium adsorption quantity. (FIG. 5)
The experimental results show that the optimal silicon-aluminum ratio in the preparation process of the lanthanum-modified zeolite molecular sieve is SiO2:Al2O3The optimum lanthanum solution concentration was 0.7% (mass concentration) at a molar ratio of 1: 0.5. And the experimental result of figure 5 shows that the phosphate adsorption performance of the modified zeolite molecular sieve is gradually improved along with the increase of the concentration of the lanthanum solution, and the ammonia nitrogen adsorption performance is firstly kept stable and then begins to decline. The reason for the analysis may be the La of the load2O3When the content is too high, the electronegativity of the zeolite molecular sieve is weakened, and the ammonia nitrogen ion exchange adsorption performance is reduced. When the concentration of the lanthanum solution is below 0.7%, the addition of the lanthanum solution does not greatly influence the ammonia nitrogen adsorption performance of the zeolite molecular sieve, and the adsorption capacity of the zeolite molecular sieve is basically kept stable.
Examples
Preparing a lanthanum modified molecular sieve adsorbent: taking a certain amount of natural zeolite raw material (grinding and sieving with a 100-mesh sieve) to put in a three-neck flask, adding sodium hydroxide solution with the mass percent concentration of 20% according to the solid-liquid mass ratio of 1:5, putting the flask in a magnetic stirrer, stirring and dissolving alkali for 2h at 95 ℃, measuring the content of silicon element in the dissolved liquid, and measuring according to SiO2:Al2O3Adding a sodium aluminate solution into the mixed solution at a molar ratio of 1:0.5, keeping the temperature unchanged, mixing and crystallizing for 2 hours, introducing a lanthanum chloride solution with the mass percentage concentration of 0.7% into the crystallization reaction mixed solution, carrying out aging reaction at 60 ℃ for 12 hours, carrying out suction filtration and washing on the mixed solution until the pH value is neutral, and drying to obtain the lanthanum-modified zeolite molecular sieve.
Laboratory simulation water distribution: KH (Perkin Elmer)2PO4Concentration 20mg/L (in terms of P), NH4The Cl concentration was 30mg/L (in terms of N) and 1 mol. L was used-1Hydrochloric acid and 1 mol. L-1And adjusting the pH value of the water distribution to be 5-7 by using a sodium hydroxide solution.
The adsorbents for the experimental group were placed in a 500mL Erlenmeyer flask with 100mL of water using 0.1g of lanthanum modified zeolite molecular sieve (80 mesh sieve). The adsorbents of the control groups I and II respectively adopt natural zeolite and zeolite molecular sieve (passing through a 80-mesh sieve) with the same mass, and the other control conditions are the same as those of the test group. After constant temperature oscillation adsorption for 12h at 25 ℃ and 220r/min, taking supernatant to measure the concentration of ammonia nitrogen and phosphate, and calculating the equilibrium adsorption quantity. (FIG. 6)
As can be seen from the experimental results shown in fig. 6, compared with the natural zeolite, the ammonia nitrogen and phosphate adsorption performances of the lanthanum-modified zeolite molecular sieve are respectively improved by 87% and 95%, while compared with the simple zeolite molecular sieve, the phosphate adsorption performance of the lanthanum-modified zeolite molecular sieve is improved by 77%, and the ammonia nitrogen adsorption performance is basically maintained unchanged. The adsorbent prepared by the invention has high-efficiency ammonia nitrogen and phosphate adsorption performance, and is very suitable for being used as an adsorbent for advanced sewage treatment.
The analysis of the mechanism of phosphorus and nitrogen removal of the lanthanum modified zeolite molecular sieve is as follows:
the basic building block of zeolite molecular sieves is Silica (SiO)4) And aluminum oxide (AlO)4) Tetrahedra, wherein aluminum oxide (AlO)4) The aluminum atoms in the tetrahedra are trivalent and positive, and thus are negatively charged overall, and the cations are associated with aluminum oxide (AlO) according to the conservation of charge4) The tetrahedral bonding is electrically neutral, so that a large number of exchangeable cations, such as Na, are present in the lattice structure of the molecular sieve+And the like, and the ammonium ions in the water are absorbed by the ion exchange. In addition, due to the silicon oxygen (SiO) in the molecular sieve4) And aluminum oxide (AlO)4) The difference of the tetrahedral connection mode causes a plurality of pore channels and cavities to exist in the molecular sieve lattice structure, and provides diffusion channels for ammonium ions in water to enter the molecular sieve lattice structure.
After lanthanum modification, a small amount of lanthanum is La2O3Is loaded on the surface of the molecular sieve crystal structure. In water with a neutral pH range, La2O3Hydroxylation reaction is carried out to generate La-OH and H2PO4 -Or HPO4 2Complexation and electrostatic adsorption take place. The ammonia nitrogen is mainly removed by the cation exchange action in the zeolite molecular sieve lattice structure, the phosphate is mainly removed by the complexation coordination action on the surface of the molecular sieve porous structure, and the adsorption action sites and the action modes of the two are different and have small mutual influence. Therefore, the temperature of the molten metal is controlled,the lanthanum modified zeolite molecular sieve can synchronously adsorb ammonium ions and phosphate ions.
Claims (1)
1. A method for synthesizing a synchronous denitrification and dephosphorization adsorbent based on natural zeolite is characterized in that a natural zeolite raw material is heated and alkali-dissolved in a sodium hydroxide solution, the solid-liquid mass ratio of the natural zeolite to the sodium hydroxide solution is 1:5, the mass percentage concentration of the sodium hydroxide solution is 20%, the temperature is controlled at 95 ℃, and the alkali-dissolving time is 2 hours;
then measuring the content of silicon element in the dissolution liquid, and then according to SiO2:Al2O3Adding a sodium aluminate solution into the mixed solution after alkali dissolution at a molar ratio of 1:0.5, wherein the volume of the sodium aluminate solution is the same as that of the added sodium hydroxide solution, performing crystallization reaction for 2 hours at 95 ℃ to generate zeolite molecular sieve grains, then adding a lanthanum chloride solution with the mass percent concentration of 0.7% into the reaction mixed solution, wherein the volume of the lanthanum chloride solution is 2 times that of the added sodium hydroxide solution, performing reaction for 12 hours at 60 ℃, performing suction filtration on the mixed solution, washing until the pH value is neutral, and drying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108132A (en) * | 2020-09-18 | 2020-12-22 | 扬州大学 | Composite nano material for synchronous nitrogen and phosphorus removal, preparation method and application |
| CN112479647A (en) * | 2020-11-27 | 2021-03-12 | 南京理工大学 | Composite autoclaved porous zeolite filter material with manganese and phosphorus removal functions and preparation method thereof |
| CN116586039A (en) * | 2023-04-03 | 2023-08-15 | 浙江工业大学 | Preparation method and application of lanthanum modified nano chitosan porous ZSM-5 composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921103A (en) * | 2016-05-19 | 2016-09-07 | 四川理工学院 | Preparation method of La(OH)3 modified kieselguhr and molecular sieve adsorption material for simultaneously fixing nitrogen and phosphorus |
| CN106669598A (en) * | 2016-12-21 | 2017-05-17 | 浙江大学 | Novel zeolite adsorbent for removing anionic pollutant in water and preparation method |
| CN109046236A (en) * | 2018-08-31 | 2018-12-21 | 常州大学 | A kind of preparation of the ultrasound for denitrogenation dephosphorizing-lanthanum modified zeolite |
| CN109847691A (en) * | 2019-03-22 | 2019-06-07 | 中国人民大学 | A kind of lanthanum iron modified zeolite dephosphorization adsorbent and the preparation method and application thereof |
-
2020
- 2020-04-28 CN CN202010347937.1A patent/CN111530412A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921103A (en) * | 2016-05-19 | 2016-09-07 | 四川理工学院 | Preparation method of La(OH)3 modified kieselguhr and molecular sieve adsorption material for simultaneously fixing nitrogen and phosphorus |
| CN106669598A (en) * | 2016-12-21 | 2017-05-17 | 浙江大学 | Novel zeolite adsorbent for removing anionic pollutant in water and preparation method |
| CN109046236A (en) * | 2018-08-31 | 2018-12-21 | 常州大学 | A kind of preparation of the ultrasound for denitrogenation dephosphorizing-lanthanum modified zeolite |
| CN109847691A (en) * | 2019-03-22 | 2019-06-07 | 中国人民大学 | A kind of lanthanum iron modified zeolite dephosphorization adsorbent and the preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴忆宁等主编: "第6章（4）沸石分子筛", 《基础环境化学工程原理》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108132A (en) * | 2020-09-18 | 2020-12-22 | 扬州大学 | Composite nano material for synchronous nitrogen and phosphorus removal, preparation method and application |
| CN112108132B (en) * | 2020-09-18 | 2021-06-04 | 扬州大学 | Composite nano material for synchronous nitrogen and phosphorus removal, preparation method and application |
| CN112479647A (en) * | 2020-11-27 | 2021-03-12 | 南京理工大学 | Composite autoclaved porous zeolite filter material with manganese and phosphorus removal functions and preparation method thereof |
| CN116586039A (en) * | 2023-04-03 | 2023-08-15 | 浙江工业大学 | Preparation method and application of lanthanum modified nano chitosan porous ZSM-5 composite material |
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Application publication date: 20200814 |
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| WD01 | Invention patent application deemed withdrawn after publication |