CN113477211A - Rare earth composite salt-alkali modified zeolite and preparation method thereof - Google Patents
Rare earth composite salt-alkali modified zeolite and preparation method thereof Download PDFInfo
- Publication number
- CN113477211A CN113477211A CN202110798513.1A CN202110798513A CN113477211A CN 113477211 A CN113477211 A CN 113477211A CN 202110798513 A CN202110798513 A CN 202110798513A CN 113477211 A CN113477211 A CN 113477211A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- zeolite
- alkali
- modified zeolite
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- B01J20/165—Natural alumino-silicates, e.g. zeolites
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to rare earth composite salt and alkali modified zeolite and a preparation method thereof, wherein the rare earth composite salt and alkali modified zeolite comprises the following steps: crushing and sieving zeolite, mixing the zeolite with a salt solution of rare earth metal, filtering, washing and drying the zeolite after ultrasonic oscillation, and roasting the dried zeolite to obtain rare earth modified zeolite; and mixing the rare earth modified zeolite obtained in the previous step with an alkali aqueous solution, soaking, washing, putting into a magnesium chloride solution, soaking, washing and drying to obtain the rare earth composite saline-alkali modified zeolite. According to the invention, the zeolite modified by the rare earth metals of lanthanum, cerium and praseodymium and the saline alkali has a good ammonia nitrogen removal effect, the removal rates of the zeolite can respectively reach 99.27%, 98.85% and 98.54%, meanwhile, the zeolite modified by the rare earth metals of lanthanum, praseodymium and the saline alkali also has a good phosphorus removal effect, the removal rates of the zeolite can respectively reach 98.90% and 98.36%, and the zeolite has a good application prospect in the field of sewage treatment.
Description
Technical Field
The invention relates to the technical field of zeolite modification, in particular to rare earth composite salt and alkali modified zeolite and a preparation method thereof.
Background
In recent years, with the continuous development of social economy, a large amount of domestic sewage, industrial wastewater and the like are directly discharged into lakes, rivers or gulf waters, so that the nitrogen and phosphorus concentration in the water body is higher, the water body is eutrophicated, and the adverse effects on the environment and the human health are caused. Therefore, the research on the denitrification and dephosphorization technology needs to be carried out urgently to improve the quality of the global environment and guarantee the health of human bodies.
The natural zeolite has rich pore channels and cation exchange adsorption performance and can adsorb NH4+The natural zeolite has certain selective adsorption, but the natural zeolite has small adsorption capacity due to high mineral impurity content and non-uniform structural pore channels, so that the natural zeolite is easily limited in engineering application. At present, modification regulation and control research aiming at natural zeolite does not fundamentally solve the defects of material composition and structure, and the adsorption performance is not ideal. The modification treatment of zeolite can make up the defects of easy blockage of zeolite pore channel and small adsorption capacity, and can make the modified zeolite possess strong ion exchange capacity and large adsorption capacity, and these properties can make the zeolite be extensively used in the field of environmental protection.
At present, the application of rare earth and zeolite in the field of sewage treatment in environmental protection is gradually becoming a new technical hotspot. Patent application CN104971699A discloses a modified zeolite organic compound agent for synchronous nitrogen and phosphorus removal of sewage and a preparation method thereof, wherein a mixed solution of cetyl trimethyl ammonium bromide and lanthanum chloride is used as a modification solution to modify zeolite, and then the modified zeolite and polyaluminum ferric chloride (PAFC) are compounded into the modified zeolite organic compound agent in different proportions, the modified zeolite organic compound agent is applied to biochemical tail water of a sewage treatment plant, the treatment effects of nitrate nitrogen and total phosphorus are greatly improved, but the treatment effect of ammonia nitrogen is only 65-75%, and free ammonia (NH3) and ammonium ions (NH 4) in sewage are difficult to effectively remove+) The presence of nitrogen in the form limits the effectiveness of its use.
Disclosure of Invention
The invention aims to solve the problem of poor ammonia nitrogen treatment effect of the existing modified zeolite, and provides rare earth composite saline-alkali modified zeolite and a preparation method thereof.
The specific scheme is as follows:
a preparation method of rare earth composite salt-alkali modified zeolite comprises the following steps:
step 1: crushing and sieving zeolite, mixing the zeolite with a salt solution of rare earth metal, filtering, washing and drying the zeolite after ultrasonic oscillation, and roasting the dried zeolite to obtain rare earth modified zeolite;
step 2: and mixing the rare earth modified zeolite obtained in the previous step with an alkali aqueous solution, soaking, washing, putting into a magnesium chloride solution, soaking, washing and drying to obtain the rare earth composite saline-alkali modified zeolite.
Further, in the step 1, the zeolite is crushed and sieved, and the mesh number is 10-40 meshes;
optionally, in step 1, the salt solution of the rare earth metal is an aqueous solution of a soluble lanthanum salt, an aqueous solution of a soluble cerium salt, or an aqueous solution of a soluble praseodymium salt, and the mass concentration of the rare earth metal element in the solution is 0.15% -0.85%.
Further, in step 1, the pH of the rare earth metal salt solution is adjusted to 9-10 before use, and the addition amount of zeolite: a 20% volume fraction salt solution of a rare earth metal ═ 5 to 15 g: 200 ml;
optionally, in the step 1, the time of ultrasonic oscillation is not less than 16h, the roasting temperature is 450-.
Further, in the step 2, the aqueous solution of the alkali is an aqueous solution of sodium hydroxide or potassium hydroxide, the concentration is 0.5-1.5mol/L, and the time for soaking the rare earth modified zeolite in the aqueous solution of the alkali is 1-5 h;
optionally, in step 2, the magnesium chloride solution is soaked for 1-5 days.
The invention also discloses a preparation method of the rare earth composite saline-alkali modified zeolite and the prepared rare earth composite saline-alkali modified zeolite.
Furthermore, the removal rate of the rare earth composite saline-alkali modified zeolite to ammonia nitrogen in sewage is more than or equal to 95%.
The invention also discloses a sewage purification method, which adopts the rare earth composite saline-alkali modified zeolite and is characterized in that: the method comprises the steps of adjusting the pH value of the sewage to 6.5-7.5, putting the rare earth composite saline-alkali modified zeolite into the sewage, wherein the adding amount of the rare earth composite saline-alkali modified zeolite is as follows: the volume of the sewage is 5-20 mg: 120-280ml, and shaking for 1-3h at constant temperature of 25-30 ℃.
Further, according to the preparation method of the rare earth composite saline-alkali modified zeolite, rare earth metal lanthanum is adopted to obtain the lanthanum composite saline-alkali modified zeolite, and the lanthanum composite saline-alkali modified zeolite is prepared by performing the following steps on sewage with initial ammonia nitrogen concentration of 25mg/L in an environment with pH of 7 according to the addition of zeolite: the volume of the sewage is 10-15 g: 200ml, shaking for 1-3h at constant temperature of 25-30 ℃, and the ammonia nitrogen removal rate is more than or equal to 98 percent.
Further, according to the preparation method of the rare earth composite saline-alkali modified zeolite, the rare earth metal cerium is adopted to obtain the cerium composite saline-alkali modified zeolite, and the cerium composite saline-alkali modified zeolite is prepared by adding the following components in parts by weight to sewage with initial ammonia nitrogen concentration of 25mg/L in an environment with pH of 7: the volume of the sewage is 10-15 g: 200ml, shaking for 1-3h at constant temperature of 25-30 ℃, and the ammonia nitrogen removal rate is more than or equal to 98 percent.
Further, according to the preparation method of the rare earth composite saline-alkali modified zeolite, rare earth metal praseodymium is adopted to obtain the praseodymium composite saline-alkali modified zeolite, and the praseodymium composite saline-alkali modified zeolite is prepared by adding the following components in an amount of zeolite in an environment with pH of 7 to sewage with initial ammonia nitrogen concentration of 25 mg/L: the volume of the sewage is 10-15 g: 200ml, shaking for 1-3h at constant temperature of 25-30 ℃, and the ammonia nitrogen removal rate is more than or equal to 97 percent.
Has the advantages that: the preparation method of the rare earth composite saline-alkali modified zeolite adopts ultrasonic oscillation, facilitates the attachment of rare earth elements in the zeolite through the ultrasonic oscillation, and plays a role in promoting diffusion.
Furthermore, in order to increase the pollutant removal performance of the product, saline-alkali modification is adopted on the basis of ultrasonic oscillation to expand micropores in the zeolite and increase adsorption sites, so that the removal rate of the product on ammonia nitrogen is improved.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is an SEM image of a rare earth modified zeolite obtained by lanthanum modification of a zeolite provided in accordance with an embodiment of the present invention;
FIG. 2 is an SEM image of a rare earth modified zeolite obtained by cerium modification of a zeolite provided in accordance with an embodiment of the present invention;
fig. 3 is an SEM image of a rare earth modified zeolite obtained by praseodymium modification of the zeolite provided in one embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1 study on adsorption time of rare earth metal-loaded zeolite to ammonia nitrogen
Preparing a solution with the lanthanum (cerium and praseodymium) ion mass fraction of 0.35%, pouring 200ml of the prepared solution into a beaker, adjusting the pH to 10 by using 1mol/L sodium hydroxide solution, respectively adding a certain amount of zeolite which is subjected to crushing, sieving and pretreatment into the beaker, soaking for more than 16h, leaching the zeolite from the solution, washing for 2-3 times by using ultrapure water, then placing the zeolite into an oven for drying at 60 ℃, placing the dried zeolite into a muffle furnace for roasting for 1h at 500 ℃ to prepare the rare earth modified zeolite, namely the zeolite adsorbent.
Treating 200ml of simulated wastewater containing 25mg/L of nitrogen concentration by using rare earth metal lanthanum, cerium and praseodymium modified zeolite with different dosages at 25-30 ℃, adjusting the pH value of the system to be 7 by using sodium hydroxide and hydrochloric acid solution, placing the system into a constant-temperature oscillation box for constant-temperature oscillation at 30 ℃, sampling at intervals (1h, 3h, 5h and the like are determined according to adsorption conditions), and measuring the nitrogen and phosphorus concentration in the solution by using a nano-grade reagent spectrophotometry and a molybdate spectrophotometry, wherein the nitrogen and phosphorus concentrations are found: the adsorption conditions of the zeolite modified by the rare earth metals lanthanum, cerium and praseodymium on ammonia nitrogen are basically consistent, the adsorption rate of the zeolite modified by the rare earth metals on the ammonia nitrogen is higher in the first 1h, then the adsorption rate on the ammonia nitrogen is gradually reduced, the adsorption state tends to be saturated in 24h, and the zeolite is basically not adsorbed any more in the later 24 h. The removal efficiency of the rare earth metal lanthanum, cerium and praseodymium modified zeolite on ammonia nitrogen can respectively reach 95.98%, 95.43% and 96.52%.
Example 2 study on adsorption conditions of rare earth metal-loaded zeolite for Ammonia Nitrogen
In the embodiment, the influence of the rare earth metal type, the sieved particle size of the zeolite and the addition amount of the zeolite on the ammonia nitrogen adsorption effect is researched, the experimental method refers to the embodiment 1, and the results are shown in the table 1.
TABLE 1 removal efficiency of ammonia nitrogen by rare earth metal modified zeolites
As can be seen from Table 1, the zeolite modified by the rare earth metals of lanthanum, cerium and praseodymium has better adsorption capacity on ammonia nitrogen, the adding amount and the particle size of the zeolite have influence on the ammonia nitrogen removal effect, the more the adding amount is, the smaller the particle size is, the better the removal effect is, but the adding amount of the zeolite has larger influence on the particle size; the 3 experimental groups with the best ammonia nitrogen removal effect after 48 hours of each experimental group are experimental group 3 (lanthanum, 30 meshes, 20g, 95.98%), experimental group 5 (cerium, 20 meshes, 20g, 95.43%) and experimental group 7 (praseodymium, 10 meshes, 20g, 96.52%); the praseodymium modified zeolite has the particle size of 10 meshes, the adsorption effect is optimal when the adding amount is 20g, and the removal rate can reach 96.52 percent.
Example 3 study on adsorption time of rare earth metal and salt and alkali modified zeolite on ammonia nitrogen
Preparation method of rare earth modified zeolite referring to example 1, the obtained rare earth modified zeolite is placed in a beaker, a sodium hydroxide solution with concentration of 1mol/L which can submerge the surface of the zeolite is poured into the beaker, stirring and soaking are carried out for 1h, then the surface of the zeolite is washed for a plurality of times by pure water, a magnesium chloride solution with volume fraction of 20% is prepared, the washed zeolite after being soaked by alkali liquor is placed in the beaker and soaked by the magnesium chloride solution for 2 days, the zeolite is washed by pure water and dried in a drying oven at 60 ℃, and the rare earth composite saline-alkali modified zeolite is obtained and stored in a dry glass bottle for standby.
Treating 200ml of simulated wastewater containing 25mg/L of nitrogen at the temperature of 25-30 ℃ by using rare earth composite saline-alkali modified zeolite with different dosages at the temperature of 25-30 ℃, adjusting the pH value of the system to be 7 by using sodium hydroxide and hydrochloric acid solution, placing the system into a constant-temperature oscillation box for constant-temperature oscillation at the temperature of 30 ℃, sampling at intervals (1h, 3h, 5h and the like are determined according to adsorption conditions), and measuring the concentration of nitrogen and phosphorus in the solution by using a nano-reagent spectrophotometry and a molybdate spectrophotometry, wherein the discovery is as follows: in the first 8h, the ammonia nitrogen adsorption conditions of different rare earth metals and the zeolite subjected to salt and alkali superposition modification are basically consistent, the ammonia nitrogen concentration of a 10g zeolite experimental group is increased in 1h, and the ammonia nitrogen adsorption rate of 5g and 20g of zeolite subjected to rare earth metal and salt and alkali superposition modification is higher in the first 8h, and the ammonia nitrogen concentration is not increased; after 8 hours of adsorption, the adsorption rate of each zeolite experimental group on ammonia nitrogen is gradually slowed until the basic adsorption saturation is reached, and the ammonia nitrogen concentration of 5g of the zeolite experimental group modified by the superposition of cerium and saline and alkali is increased within 8-24 hours, which is probably caused by the fluctuation of the external environment; the 10g and 20g zeolite experimental groups can almost completely remove ammonia nitrogen in water in 30h, while the 5g zeolite experimental groups still can not reach the ammonia nitrogen removal amount of 10g and 20g in 8h, which shows that the removal effect of the experimental groups with the zeolite addition amount of 10g and 20g is optimal; the maximum removal rate of the zeolite modified by the lanthanum, cerium, praseodymium and saline-alkali can reach 99.27%, 98.85% and 98.54%, and the ammonia nitrogen in the wastewater can be effectively removed.
Example 4 analysis of adsorption conditions of rare earth metal and salt/alkali-modified zeolite on Ammonia Nitrogen
In the embodiment, the influence of the rare earth metal types, the sieved particle size of the zeolite and the addition amount of the zeolite on the ammonia nitrogen adsorption effect is researched, the experimental method refers to the embodiment 3, and the results are shown in the table 2.
As can be seen from Table 2, the adsorption rates of the experimental groups for ammonia nitrogen are different, but the worst ammonia nitrogen removal rate can also reach more than 80%, the final adsorption rate of eight experimental groups in nine experimental groups reaches more than 90%, the ammonia nitrogen removal rate of the experimental group with the zeolite addition amount of 5g can reach more than 80%, and the ammonia nitrogen removal rates of the experimental groups with the zeolite addition amounts of 10g and 20g are more than 97%; the best removal was found to be experiment 3 (lanthanum, 40 mesh, 20 g).
The results of the analysis of table 2 in comparison with table 1 are shown in table 3, and it can be seen from table 3 that when the zeolite dosage is small, the adsorption of ammonia nitrogen can be accelerated by the rare earth metal and the salt and alkali superposition modification, the removal rate of ammonia nitrogen is improved, and the maximum increase can be 12.52%.
TABLE 2 Total phosphorus removal efficiency of rare earth metal and salt/alkali modified zeolites
TABLE 3 comparison of removal efficiency of ammonia nitrogen by rare earth metal modified and rare earth metal superimposed salt-alkali modified zeolite
Example 5 removal of Total phosphorus from Sewage by lanthanum and praseodymium modified zeolites
The rare earth composite saline-alkali modified zeolite prepared in example 4, in which the rare earth elements are lanthanum and praseodymium, is used for treating 200ml of simulated wastewater with a phosphorus concentration of 6mg/L at a temperature of 25-30 ℃, the pH value of the system is adjusted to 7 by using sodium hydroxide and hydrochloric acid solution, the system is placed in a constant temperature oscillation box for constant temperature oscillation at a temperature of 30 ℃, samples are taken at intervals (1h, 3h, 5h and the like are determined according to adsorption conditions), and the nitrogen and phosphorus concentrations in the solution are determined by using a nano-grade reagent spectrophotometry and a molybdate spectrophotometry, and the results are shown in table 4.
From table 4, it can be found that 10-20g of lanthanum, praseodymium and saline-alkali modified zeolite: the removal rate of the total phosphorus in 200ml of sewage can reach more than 95 percent, and the total phosphorus in water can be effectively removed.
TABLE 4 Total phosphorus removal efficiency of rare earth metal and salt/alkali modified zeolites
Example 6
The modified zeolite prepared in the above example was subjected to morphology analysis, and the results are shown in fig. 1, fig. 2, and fig. 3, where fig. 1 shows rare earth modified zeolite (not treated with alkali salt) obtained by modifying 40 mesh zeolite with lanthanum, fig. 2 shows rare earth modified zeolite (not treated with alkali salt) obtained by modifying 40 mesh zeolite with cerium, and fig. 3 shows rare earth modified zeolite (not treated with alkali salt) obtained by modifying 40 mesh zeolite with praseodymium.
As can be seen from fig. 1-3, the rare earth modified zeolite has a dense structure and a rough surface; the surface of the zeolite modified by lanthanum and praseodymium is covered with a layer of strip-shaped substances, because the rare earth metal ions are loaded on the surface of the zeolite, the rare earth metal ions on the surface of the zeolite increase adsorption sites of the zeolite, and form a complex bond with strong binding capacity with nitrogen and phosphorus in the adsorption process, so that the zeolite can effectively adsorb the nitrogen and phosphorus; the zeolite modified by the rare earth metal cerium is in a compact block shape and a sheet shape, and strip-shaped metal ions are not attached to the surface of the zeolite, which may be the reason that the adsorption effect of the zeolite on nitrogen and phosphorus is slightly poor.
Similarly, the shape of the zeolite modified by the lanthanum, the praseodymium and the saline-alkali superposition is analyzed, and the following results are found: the zeolite with the size of 40 meshes is modified by lanthanum, praseodymium and saline alkali, the shape of the zeolite is flaky, the pores of the zeolite modified by the rare earth metal and the saline alkali are enlarged, and the adsorption sites are increased, so that the adsorption of nitrogen and phosphorus is enhanced; the zeolite modified by the rare earth metal cerium is blocky, so that the original sheet structure of the zeolite modified by only cerium is changed, and the adsorption sites of the zeolite are increased, so that the adsorption effect on nitrogen and phosphorus is enhanced.
The specific surface areas of the zeolites prepared in the examples are analyzed, and the results are shown in table 5, and it can be seen from table 5 that the specific surface areas of the 40-mesh modified zeolites are about twice as large as those of the 10-mesh modified zeolites, and the specific surface areas of the rare earth modified zeolites are reduced by saline alkali modification, because the rare earth metal ions are loaded on the surfaces of the zeolites, partial small holes of the zeolites are blocked, so that the specific surface areas of the zeolites are slightly reduced, and the rare earth metals on the surfaces of the zeolites are adsorption sites of the modified zeolites for nitrogen and phosphorus, which are the largest reasons for removing nitrogen and phosphorus, so that the adsorption sites are increased while the specific surface areas are reduced, and nitrogen and phosphorus in water can be effectively removed.
TABLE 5 modified Zeolite specific surface areas
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of rare earth composite salt-alkali modified zeolite is characterized by comprising the following steps: the method comprises the following steps:
step 1: crushing and sieving zeolite, mixing the zeolite with a salt solution of rare earth metal, filtering, washing and drying the zeolite after ultrasonic oscillation, and roasting the dried zeolite to obtain rare earth modified zeolite;
step 2: and mixing the rare earth modified zeolite obtained in the previous step with an alkali aqueous solution, soaking, washing, putting into a magnesium chloride solution, soaking, washing and drying to obtain the rare earth composite saline-alkali modified zeolite.
2. The method for preparing the rare earth composite saline-alkali modified zeolite according to claim 1, which is characterized in that: in the step 1, the zeolite is crushed and sieved, and the mesh number is 10-40 meshes;
optionally, in step 1, the salt solution of the rare earth metal is an aqueous solution of a soluble lanthanum salt, an aqueous solution of a soluble cerium salt, or an aqueous solution of a soluble praseodymium salt, and the mass concentration of the rare earth metal element in the solution is 0.15% -0.85%.
3. The method for preparing the rare earth composite saline-alkali modified zeolite according to claim 1, which is characterized in that: in step 1, the pH of the rare earth metal salt solution is adjusted to 9-10 before use, and the addition amount of zeolite is as follows: a 20% volume fraction salt solution of a rare earth metal ═ 5 to 15 g: 200 ml;
optionally, in the step 1, the time of ultrasonic oscillation is not less than 16h, the roasting temperature is 450-.
4. The method for preparing the rare earth composite saline-alkali modified zeolite according to claim 1, which is characterized in that: in the step 2, the aqueous solution of the alkali is aqueous solution of sodium hydroxide or potassium hydroxide, the concentration is 0.5-1.5mol/L, and the time for soaking the rare earth modified zeolite in the aqueous solution of the alkali is 1-5 h;
optionally, in step 2, the magnesium chloride solution is soaked for 1-5 days.
5. The rare earth composite saline-alkali modified zeolite prepared by the method for preparing the rare earth composite saline-alkali modified zeolite according to any one of claims 1 to 4.
6. The rare earth composite salt-alkali modified zeolite of claim 5, wherein: the removal rate of the rare earth composite saline-alkali modified zeolite to ammonia nitrogen in sewage is more than or equal to 95%.
7. A sewage purification method, which adopts the rare earth composite saline-alkali modified zeolite in claim 5 or 6, and is characterized in that: the method comprises the steps of adjusting the pH value of the sewage to 6.5-7.5, putting the rare earth composite saline-alkali modified zeolite into the sewage, wherein the adding amount of the rare earth composite saline-alkali modified zeolite is as follows: the volume of the sewage is 5-20 mg: 120-280ml, and shaking for 1-3h at constant temperature of 25-30 ℃.
8. The sewage purification method according to claim 7, wherein: the method for preparing rare earth composite salt-alkali modified zeolite according to any one of claims 1 to 4, wherein lanthanum is adopted to obtain lanthanum composite salt-alkali modified zeolite, and the lanthanum composite salt-alkali modified zeolite is prepared by adding the following components in an amount of zeolite under the condition that the pH is 7 for sewage with initial ammonia nitrogen concentration of 25 mg/L: the volume of the sewage is 10-15 g: 200ml, shaking for 1-3h at constant temperature of 25-30 ℃, and the ammonia nitrogen removal rate is more than or equal to 98 percent.
9. The sewage purification method according to claim 7, wherein: the method for preparing rare earth composite salt-alkali modified zeolite according to any one of claims 1 to 4, wherein the rare earth metal cerium is used to obtain cerium composite salt-alkali modified zeolite, and the cerium composite salt-alkali modified zeolite is prepared by adding the following components in terms of zeolite addition amount in an environment with pH of 7 for sewage with initial ammonia nitrogen concentration of 25 mg/L: the volume of the sewage is 10-15 g: 200ml, shaking for 1-3h at constant temperature of 25-30 ℃, and the ammonia nitrogen removal rate is more than or equal to 98 percent.
10. The sewage purification method according to claim 7, wherein: the method for preparing rare earth composite saline-alkali modified zeolite according to any one of claims 1 to 4, wherein praseodymium is adopted as a rare earth metal to obtain the praseodymium composite saline-alkali modified zeolite, and the praseodymium composite saline-alkali modified zeolite is prepared by adding the following components in an amount of zeolite under the condition that the pH is 7 for sewage with the initial ammonia nitrogen concentration of 25 mg/L: the volume of the sewage is 10-15 g: 200ml, shaking for 1-3h at constant temperature of 25-30 ℃, and the ammonia nitrogen removal rate is more than or equal to 97 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110798513.1A CN113477211A (en) | 2021-07-15 | 2021-07-15 | Rare earth composite salt-alkali modified zeolite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110798513.1A CN113477211A (en) | 2021-07-15 | 2021-07-15 | Rare earth composite salt-alkali modified zeolite and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113477211A true CN113477211A (en) | 2021-10-08 |
Family
ID=77939374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110798513.1A Pending CN113477211A (en) | 2021-07-15 | 2021-07-15 | Rare earth composite salt-alkali modified zeolite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113477211A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170307A (en) * | 2013-04-15 | 2013-06-26 | 北京中地泓科环境科技有限公司 | Magnesium-loaded natural zeolite materials for removing fluorine in water |
| CN108793305A (en) * | 2018-06-19 | 2018-11-13 | 佛山陵朝新材料有限公司 | A kind of ammonia nitrogen removal agent |
| 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 |
| CN110193375A (en) * | 2018-02-26 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of preparation method of magnesium salts deposition modification Y type molecular sieve |
| CN112237899A (en) * | 2020-11-02 | 2021-01-19 | 湘潭大学 | Lanthanum-magnesium modified sepiolite for removing phosphorus from black and odorous water body |
| CN112707465A (en) * | 2020-12-30 | 2021-04-27 | 中国科学院南京土壤研究所 | Composite material for rare earth mining area acidic wastewater treatment and preparation method and application thereof |
-
2021
- 2021-07-15 CN CN202110798513.1A patent/CN113477211A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170307A (en) * | 2013-04-15 | 2013-06-26 | 北京中地泓科环境科技有限公司 | Magnesium-loaded natural zeolite materials for removing fluorine in water |
| CN110193375A (en) * | 2018-02-26 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of preparation method of magnesium salts deposition modification Y type molecular sieve |
| CN108793305A (en) * | 2018-06-19 | 2018-11-13 | 佛山陵朝新材料有限公司 | A kind of ammonia nitrogen removal agent |
| 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 |
| CN112237899A (en) * | 2020-11-02 | 2021-01-19 | 湘潭大学 | Lanthanum-magnesium modified sepiolite for removing phosphorus from black and odorous water body |
| CN112707465A (en) * | 2020-12-30 | 2021-04-27 | 中国科学院南京土壤研究所 | Composite material for rare earth mining area acidic wastewater treatment and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 刘亚清等: "超声-镧改性沸石吸附氮磷的特性", vol. 31, no. 2, pages 76 - 81 * |
| 姚忠平等: "《环境水处理药剂》", 四川大学出版社, pages: 131 * |
| 孙兴滨等: "沸石的改性及除磷性能研究", vol. 26, no. 2, pages 161 - 164 * |
| 杨淑佳;王翠红;张智烨;张涛;江荣风;: "人造沸石负载纳米氧化镁同步脱氮除磷的研究", 环境保护科学, no. 01 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105541009B (en) | A kind of processing method of anionic azo dyes waste water | |
| CN101780421B (en) | Ammonia nitrogen adsorbent and preparation method and application method thereof | |
| CN109534432B (en) | Preparation method of biochar modified material for removing phosphorus in eutrophic water body | |
| CN102423684B (en) | A kind of modified zeolite ammonia nitrogen adsorbent and use thereof and renovation process | |
| CN109012565A (en) | A kind of method of the magnetic carbon material Adsorption heavy metal ions in wastewater of nitrating | |
| US11247197B1 (en) | Core-shell structured catalyst, preparation method thereof and method for treating industrial tail gas | |
| CN110743549B (en) | Preparation method of copper-based heterogeneous catalyst taking activated carbon spheres as carrier for wet oxidation | |
| WO2022088309A1 (en) | Biomass-based hydroxyapatite composite material, preparation method therefor and application thereof | |
| CN105617981A (en) | Sepiolite modification method and application of modified sepiolite to wastewater treatment | |
| CN102489245A (en) | Modified pumice absorbing material and preparation method as well as application thereof | |
| CN111408351A (en) | Production method of rare earth adsorbent | |
| CN112156752A (en) | Modified activated carbon with reproducible adsorbability and application thereof in wastewater treatment | |
| CN103706326A (en) | Preparation method of natural mineral-loaded nanometer fluorine removal agent | |
| Su et al. | Preparation of a surface molecular‐imprinted adsorbent for Ni2+ based on Penicillium chrysogenum | |
| CN101773817A (en) | Composite absorption material for wastewater treatment and preparation method thereof | |
| CN107096498A (en) | A kind of modified zeolite ball preparation method and application | |
| CN111632579A (en) | Defluorination resin and preparation method thereof | |
| CN115505166B (en) | Thiourea modified resin-based nano material, preparation method and method for deeply removing selenate in water | |
| CN113477211A (en) | Rare earth composite salt-alkali modified zeolite and preparation method thereof | |
| CN114713184B (en) | Heavy metal adsorbent for removing cadmium ions in water body and preparation method and application thereof | |
| CN106582513A (en) | Composite adsorption material for treatment of heavy metal wastewater and preparation method thereof | |
| CN104607160B (en) | There is the difunctional aqueous phase sorbing material of zwitterion eutectoid content characteristic | |
| CN112452312A (en) | Ammonia nitrogen adsorbent and method for removing ammonia nitrogen in water body | |
| CN108993387A (en) | A kind of method of contents of many kinds of heavy metal ion in the carbon-based magnetic material Adsorption waste water of fluorine doped | |
| CN107162139B (en) | Flocculant for synchronously removing ammonia nitrogen and phosphorus and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |