CN112007694A - Embedded catalyst, preparation method thereof and application thereof in wastewater denitrification - Google Patents

Embedded catalyst, preparation method thereof and application thereof in wastewater denitrification Download PDF

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Publication number
CN112007694A
CN112007694A CN202010973962.0A CN202010973962A CN112007694A CN 112007694 A CN112007694 A CN 112007694A CN 202010973962 A CN202010973962 A CN 202010973962A CN 112007694 A CN112007694 A CN 112007694A
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sodium alginate
solution
embedded
tannate
catalyst
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张瑞娜
刘颖
刘春�
张静
赵秀梅
陈晓轩
张磊
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NORTH CHINA PHARMACEUTICAL CORP
Hebei University of Science and Technology
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NORTH CHINA PHARMACEUTICAL CORP
Hebei University of Science and Technology
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • B01J35/51—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • 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
    • 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
    • C02F2101/163—Nitrates

Abstract

The invention provides an embedded catalyst, a preparation method thereof and application thereof in wastewater denitrification, wherein the catalyst is prepared by the following steps: a. dissolving sodium alginate in deionized water at normal temperature to obtain a sodium alginate solution with the concentration of 10-40 mg/mL; b. adding CaCl2Dissolving in deionized water to obtain CaCl2A solution; c. b, uniformly mixing the sodium alginate solution prepared in the step a with ferric tannate powder to obtain a mixed solution; d. by usingAnd d, dripping the mixed liquid containing the black iron tannate powder prepared in the step c into a calcium chloride solution by using a syringe to quickly form gel spheres, and standing for 10-14 h to fully crosslink the gel spheres so as to obtain the sodium alginate-embedded iron tannate gel spheres. The invention has the advantages of simple preparation, easy solid-liquid separation, high catalyst stability, good denitrification effect and the like.

Description

Embedded catalyst, preparation method thereof and application thereof in wastewater denitrification
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to an embedded catalyst, a preparation method thereof and application thereof in wastewater denitrification.
Background
With the development of modern industry, a large amount of nitrogen-containing sewage is discharged into a water body, so that the content of nitrogen elements in the water body exceeds the self-purification capacity of the water body, and the eutrophication phenomenon of the water body occurs. Therefore, the research on the denitrification materials and technologies of sewage is more and more focused. In order to control nitrogen pollution, biological denitrification technology is mainly adopted at home and abroad at present, and the basic principle is to convert nitrogen in various forms into nitrogen through the nitrification and denitrification of microorganisms. The traditional biological denitrification technology has the defects of high energy consumption and high cost. The physical and chemical denitrification mainly comprises an adsorption method and a catalysis method. The simple adsorption method has a problem that regeneration of the adsorbent is difficult, and the simple catalytic method has a problem that the cost is high.
The patent application publication No. CN 103041856A of China and the application publication date of 2013, 4 months and 17 days discloses that ferric tannate as a novel adsorption catalyst can simultaneously adsorb ammonia nitrogen and nitrite nitrogen in water and catalyze the ammonia nitrogen and nitrite nitrogen to be converted into nitrogen. The preparation process comprises the following steps: firstly FeCl3Mixing the solution and tannic acid solution in certain proportion, reacting completely, and adding saturated NaHCO3Adjusting pH of the mixed solution to neutral, centrifuging the neutral mixed solution, washing with distilled water, centrifuging, and freeze drying to obtain blue-black solidThe iron adsorbs the catalytic material. However, the ferric tannate material prepared in the early stage has the problems of difficult solid-liquid separation and unsatisfactory denitrification effect.
Disclosure of Invention
The invention aims to provide an embedded catalyst, a preparation method thereof and application thereof in wastewater denitrification, so as to solve the problems that ferric tannate materials are difficult to separate and recover and the denitrification effect is not ideal in the prior art.
The technical scheme adopted by the invention is as follows: an embedded catalyst, which is embedded iron tannate, and is prepared by the following method:
a. dissolving sodium alginate in deionized water at normal temperature to obtain a sodium alginate solution with the concentration of 10-40 mg/mL;
b. adding CaCl2Dissolving in deionized water to obtain CaCl2A solution;
c. b, uniformly mixing the sodium alginate solution prepared in the step a with ferric tannate powder to obtain a mixed solution; wherein, the ratio of the ferric tannate to the sodium alginate solution is 0.01-0.06 g to 1 mL;
d. c, dropwise adding the mixed liquid containing the black iron tannate powder prepared in the step c into a calcium chloride solution by using a syringe to quickly form gel spheres, and standing for 10-14 h to fully crosslink the gel spheres so as to obtain sodium alginate-embedded iron tannate gel spheres;
e. and d, washing the gel balls prepared in the step d with distilled water for 3-4 times to obtain the embedded iron tannate catalyst, and storing the embedded iron tannate catalyst in water at normal temperature.
Preferably, in the step a, the concentration of the sodium alginate solution is 20-30 mg/mL.
Preferably, in step b, CaCl2The dosage ratio of the deionized water to the deionized water is 12 g: 400 mL.
Preferably, in step c, the iron tannate to sodium alginate solution is 0.04g to 1 mL.
A preparation method of an embedded catalyst, wherein the embedded catalyst is embedded iron tannate, and the preparation method comprises the following steps:
a. dissolving sodium alginate in deionized water at normal temperature to obtain a sodium alginate solution with the concentration of 10-40 mg/mL;
b. adding CaCl2Dissolving in deionized water to obtain CaCl2A solution;
c. b, uniformly mixing the sodium alginate solution prepared in the step a with ferric tannate powder to obtain a mixed solution; wherein, the ratio of the ferric tannate to the sodium alginate solution is 0.01-0.06 g to 1 mL;
d. c, dropwise adding the mixed liquid containing the black iron tannate powder prepared in the step c into a calcium chloride solution by using a syringe to quickly form gel spheres, and standing for 10-14 h to fully crosslink the gel spheres so as to obtain sodium alginate-embedded iron tannate gel spheres;
e. and d, washing the gel balls prepared in the step d with distilled water for 3-4 times to obtain the embedded iron tannate catalyst, and storing the embedded iron tannate catalyst in water at normal temperature.
Preferably, in the step a, the concentration of the sodium alginate solution is 20-30 mg/mL; in step b, CaCl2The dosage ratio of the deionized water to the deionized water is 12g to 400 mL; in step c, the ratio of the ferric tannate to the sodium alginate solution is 0.04g to 1 mL.
An application of the embedded catalyst in denitrification of wastewater.
The application specifically comprises the following steps: adding the embedded catalyst to a solution containing NH4 +And/or NO2 -And (2) stirring or shaking and mixing the waste water, and carrying out adsorption treatment for 2-4 h, wherein the pH value of the mixed liquid is controlled to be 6-7 and the temperature is controlled to be 10-25 ℃ during the adsorption treatment, and filtering and recovering the embedded catalyst after the treatment is finished.
The adding amount of the embedded catalyst and NH in the wastewater4 +The mass ratio of (A) to (B) is 100-110: 1; adding amount of embedded catalyst and NO in wastewater2 -The mass ratio of (A) to (B) is 250-280: 1.
And controlling the pH value of the mixed solution to be 6-7 and the temperature to be 15 ℃ during adsorption treatment.
Compared with the prior art, the invention has the obvious advantage that the embedded ferric tannate is prepared by reacting ferric tannate powder with sodium alginate solutionThe microsphere catalyst prepared by the method has the advantages of simple preparation method, smooth and elastic microsphere surface, uniform size, 3mm average diameter and good adsorption effect, and can simultaneously adsorb NH4 +-N、NO2 -N and converting it to nitrogen. The embedded ferric tannate has good stability, the denitrification effect is obviously superior to that of the prior art, and the embedded ferric tannate can be used for a long time, thereby solving the problem that the original ferric tannate is difficult to separate from water. The invention has low cost, easy recovery and no secondary pollution.
Drawings
FIG. 1 is a photograph of an embedded catalyst obtained in example 3 of the present invention. Wherein, a is iron tannate powder, and b is the embedded catalyst gel ball of the invention.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
Procedures and methods not described in detail in the following examples are conventional methods well known in the art, and reagents used in the examples are commercially available or prepared by methods well known to those of ordinary skill in the art unless otherwise specified. The following examples all achieve the objects of the present invention.
Example 1:
1) preparation of sodium alginate solution: at normal temperature, 5g of sodium alginate is dissolved in 250mL of deionized water to prepare a 2% (w/v) sodium alginate solution;
2)CaCl2preparation of the solution: adding 12g of CaCl2Dissolving in 400mL of deionized water to prepare 3% (w/v) calcium chloride solution;
3) preparing a mixed solution of sodium alginate and ferric tannate: adding 2.5g of iron tannate powder (the embedding amount is 0.01g/mL) into the sodium alginate solution obtained in the step 1), and carrying out ultrasonic treatment and stirring to uniformly mix the iron tannate powder and the iron tannate powder;
4) preparing gel balls: dripping the mixed solution containing the ferrous tannate powder in the step 3) into a 3% calcium chloride solution by using a 10mL syringe to quickly form gel spheres, and standing for 12h to fully crosslink the gel spheres so as to obtain sodium alginate-embedded ferric tannate gel spheres;
5) washing: washing the gel balls obtained in the step 4) with distilled water for 3-4 times to obtain black gel balls with uniform sizes, and storing the black gel balls in water at normal temperature.
The embedded catalyst is applied to the denitrification of wastewater, and comprises the following specific steps:
1) preparing simulated wastewater: at room temperature, 100mL of NH was prepared4Cl and NaNO2The mixed solution of (1), wherein, NH4Cl concentration 25mg/L, NaNO2The concentration is 50 mg/L;
2) adding amount of gel balls: adding 50mL of gel balls into 100mL of simulated wastewater (the simulated wastewater is aerated by He until the dissolved oxygen is lower than 1 mg/L);
3) the operation conditions are as follows: running in a shaking table at 15 ℃ for 3h, wherein the pH of the mixed solution is 6.3;
4) and (3) determination of a water sample: sampling every half an hour, filtering with 0.45 μm filter membrane, and determining NH in water sample by national standard method4 +-N and NO2 --N。
Example 2
1) Preparation of sodium alginate solution: at normal temperature, 5g of sodium alginate is dissolved in 250mL of deionized water to prepare a 2% (w/v) sodium alginate solution;
2)CaCl2preparation of the solution: adding 12g of CaCl2Dissolving in 400mL of deionized water to prepare 3% (w/v) calcium chloride solution;
3) preparing a mixed solution of sodium alginate and ferric tannate: adding 5g of iron tannate powder (the embedding amount is 0.02g/mL) into the sodium alginate solution obtained in the step 1), and performing ultrasonic treatment and stirring to uniformly mix the iron tannate powder and the iron tannate powder;
4) preparing gel balls: dripping the mixed solution containing the ferrous tannate powder in the step 3) into a 3% calcium chloride solution by using a 10mL syringe to quickly form gel spheres, and standing for 12h to fully crosslink the gel spheres so as to obtain sodium alginate-embedded ferric tannate gel spheres;
5) washing: washing the gel balls obtained in the step 4) with distilled water for 3-4 times to obtain black gel balls with uniform sizes, and storing the black gel balls in water at normal temperature.
The denitrification application was as in example 1.
Example 3
1) Preparation of sodium alginate solution: at normal temperature, 5g of sodium alginate is dissolved in 250mL of deionized water to prepare a 2% (w/v) sodium alginate solution;
2)CaCl2preparation of the solution: adding 12g of CaCl2Dissolving in 400mL of deionized water to prepare 3% (w/v) calcium chloride solution;
3) preparing a mixed solution of sodium alginate and ferric tannate: adding 10g of iron tannate powder (the embedding amount is 0.04g/mL) into the sodium alginate solution obtained in the step 1), and performing ultrasonic treatment and stirring to uniformly mix the iron tannate powder and the iron tannate powder;
4) preparing gel balls: dripping the mixed solution containing the ferrous tannate powder in the step 3) into a 3% calcium chloride solution by using a 10mL syringe to quickly form gel spheres, and standing for 12h to fully crosslink the gel spheres so as to obtain sodium alginate-embedded ferric tannate gel spheres;
5) washing: washing the gel balls obtained in the step 4) with distilled water for 3-4 times to obtain black gel balls with uniform sizes, and storing the black gel balls in water at normal temperature.
The denitrification application was as in example 1.
Example 4
1) Preparation of sodium alginate solution: at normal temperature, 5g of sodium alginate is dissolved in 250mL of deionized water to prepare a 2% (w/v) sodium alginate solution;
2)CaCl2preparation of the solution: adding 12g of CaCl2Dissolving in 400mL of deionized water to prepare 3% (w/v) calcium chloride solution;
3) preparing a mixed solution of sodium alginate and ferric tannate: adding 15g of iron tannate powder (the embedding amount is 0.06g/mL) into the sodium alginate solution obtained in the step 1), and carrying out ultrasonic stirring to uniformly mix the iron tannate powder and the iron tannate powder;
4) preparing gel balls: dripping the mixed solution containing the ferrous tannate powder in the step 3) into a 3% calcium chloride solution by using a 10mL syringe to quickly form gel spheres, and standing for 12h to fully crosslink the gel spheres so as to obtain sodium alginate-embedded ferric tannate gel spheres;
5) washing: washing the gel balls obtained in the step 4) with distilled water for 3-4 times to obtain black gel balls with uniform sizes, and storing the black gel balls in water at normal temperature.
The denitrification application was as in example 1.
The denitrification effects of examples 1-4 are shown in Table 1:
table 1:
Figure BDA0002685080630000051
as is clear from Table 1, the amount of iron tannate embedded directly affects the denitrification efficiency under the same water quality conditions. Iron tannate is a porous material with a large amount of oxygen anions and Fe on the surface3+NH can be adsorbed by electrostatic interaction and coordination4 +-N and NO2 —N, then carrying out catalytic oxidation reaction on the active group Fe-O to generate nitrogen, wherein the best effect is achieved when the embedding amount is 0.04g/mL, and NH4 +-N and NO2 -The removal rate of-N reaches 85% and 77% respectively.
Example 5
1) Preparation of sodium alginate solution: at normal temperature, 2.5g of sodium alginate is dissolved in 250mL of deionized water to prepare 1% (w/v) sodium alginate solution;
2)CaCl2preparation of the solution: adding 12g of CaCl2Dissolving in 400mL of deionized water to prepare 3% (w/v) calcium chloride solution;
3) preparing a mixed solution of sodium alginate and ferric tannate: adding 10g of iron tannate powder (the embedding amount is 0.04g/mL) into the sodium alginate solution obtained in the step 1), and performing ultrasonic treatment and stirring to uniformly mix the iron tannate powder and the iron tannate powder;
4) preparing gel balls: dripping the mixed solution containing the ferrous tannate powder in the step 3) into a 3% calcium chloride solution by using a 10mL syringe to quickly form gel spheres, and standing for 12h to fully crosslink the gel spheres so as to obtain sodium alginate-embedded ferric tannate gel spheres;
5) washing: washing the gel balls obtained in the step 4) with distilled water for 3-4 times to obtain black gel balls with uniform sizes, and storing the black gel balls in water at normal temperature.
The denitrification application was as in example 1.
Example 6
1) Preparation of sodium alginate solution: at normal temperature, 7.5g of sodium alginate is dissolved in 250mL of deionized water to prepare a 3% (w/v) sodium alginate solution;
2)CaCl2preparation of the solution: adding 12g of CaCl2Dissolving in 400mL of deionized water to prepare 3% (w/v) calcium chloride solution;
3) preparing a mixed solution of sodium alginate and ferric tannate: adding 10g of iron tannate powder (the embedding amount is 0.04g/mL) into the sodium alginate solution obtained in the step 1), and performing ultrasonic treatment and stirring to uniformly mix the iron tannate powder and the iron tannate powder;
4) preparing gel balls: dripping the mixed solution containing the ferrous tannate powder in the step 3) into a 3% calcium chloride solution by using a 10mL syringe to quickly form gel spheres, and standing for 12h to fully crosslink the gel spheres so as to obtain sodium alginate-embedded ferric tannate gel spheres;
5) washing: washing the gel balls obtained in the step 4) with distilled water for 3-4 times to obtain black gel balls with uniform sizes, and storing the black gel balls in water at normal temperature.
The denitrification application was as in example 1.
Example 7
1) Preparation of sodium alginate solution: dissolving 10g of sodium alginate in 250mL of deionized water at normal temperature to prepare 4% (w/v) sodium alginate solution;
2)CaCl2preparation of the solution: adding 12g of CaCl2Dissolving in 400mL of deionized water to prepare 3% (w/v) calcium chloride solution;
3) preparing a mixed solution of sodium alginate and ferric tannate: adding 10g of iron tannate powder (the embedding amount is 0.04g/mL) into the sodium alginate solution obtained in the step 1), and performing ultrasonic treatment and stirring to uniformly mix the iron tannate powder and the iron tannate powder;
4) preparing gel balls: dripping the mixed solution containing the ferrous tannate powder in the step 3) into a 3% calcium chloride solution by using a 10mL syringe to quickly form gel spheres, and standing for 12h to fully crosslink the gel spheres so as to obtain sodium alginate-embedded ferric tannate gel spheres;
5) washing: washing the gel balls obtained in the step 4) with distilled water for 3-4 times to obtain black gel balls with uniform sizes, and storing the black gel balls in water at normal temperature.
The denitrification application was as in example 1.
The deamination effects of examples 3 and 5 to 7 are shown in Table 2.
Table 2:
Figure BDA0002685080630000061
as can be seen from Table 2, 2% SA-TA-Fe vs. NH made from SA4 +-N and NO2 -The removal rate of-N is highest, and is 85% and 77% respectively. And the SA solution with the concentration of 2% is uniform in sphere, and the elasticity is better than that of 1%. The gel balls prepared from the 1% SA solution are softer, are not easy to form and have poorer elasticity.
Example 8
The embedded catalyst obtained in the example 3 is applied to the denitrification of wastewater, and the specific steps are as follows:
1) preparing simulated wastewater: at room temperature, 100mL of NH was prepared4Cl and NaNO2The mixed solution of (1), wherein, NH4Cl concentration 25mg/L, NaNO2The concentration is 50 mg/L;
2) adding amount of gel balls: adding 50mL of gel balls into 100mL of simulated wastewater (the simulated wastewater is aerated by He until the dissolved oxygen is lower than 1 mg/L);
3) the operation conditions are as follows: running in a shaking table at 15 ℃ for 3h, wherein the pH of the mixed solution is 3;
4) and (3) determination of a water sample: sampling every half an hour, filtering with 0.45 μm filter membrane, and determining NH in water sample by national standard method4 +-N and NO2 --N。
Example 9
The embedded catalyst obtained in the example 3 is applied to the denitrification of wastewater, and the specific steps are as follows:
1) preparing simulated wastewater: at room temperature, 100mL of NH was prepared4Cl and NaNO2The mixed solution of (1), wherein, NH4Cl concentration 25mg/L, NaNO2The concentration is 50 mg/L;
2) adding amount of gel balls: adding 50mL of gel balls into 100mL of simulated wastewater (the simulated wastewater is aerated by He until the dissolved oxygen is lower than 1 mg/L);
3) the operation conditions are as follows: running in a shaking table at 15 deg.C for 3h, and adjusting pH of the mixed solution to 5;
4) and (3) determination of a water sample: sampling every half an hour, filtering with 0.45 μm filter membrane, and determining NH in water sample by national standard method4 +-N and NO2 --N。
Example 10
The embedded catalyst obtained in the example 3 is applied to the denitrification of wastewater, and the specific steps are as follows:
1) preparing simulated wastewater: at room temperature, 100mL of NH was prepared4Cl and NaNO2The mixed solution of (1), wherein, NH4Cl concentration 25mg/L, NaNO2The concentration is 50 mg/L;
2) adding amount of gel balls: adding 50mL of gel balls into 100mL of simulated wastewater (the simulated wastewater is aerated by He until the dissolved oxygen is lower than 1 mg/L);
3) the operation conditions are as follows: running in a shaking table at 15 deg.C for 3h, and adjusting pH of the mixed solution to 7;
4) and (3) determination of a water sample: sampling every half an hour, filtering with 0.45 μm filter membrane, and determining NH in water sample by national standard method4 +-N and NO2 --N。
Example 11
The embedded catalyst obtained in the example 3 is applied to the denitrification of wastewater, and the specific steps are as follows:
1) preparing simulated wastewater: at room temperature, 100mL of NH was prepared4Cl and NaNO2The mixed solution of (1), wherein, NH4Cl concentration 25mg/L, NaNO2The concentration is 50 mg/L;
2) adding amount of gel balls: adding 50mL of gel balls into 100mL of simulated wastewater (the simulated wastewater is aerated by He until the dissolved oxygen is lower than 1 mg/L);
3) the operation conditions are as follows: running in a shaking table at 15 deg.C for 3h, and adjusting pH of the mixed solution to 9;
4) and (3) determination of a water sample: sampling every half an hour, filtering with 0.45 μm filter membrane, and determining NH in water sample by national standard method4 +-N and NO2 --N。
The denitrification effects of examples 3 and 8 to 11 are shown in Table 3.
Table 3:
examples pH NH4 +-N removal (%) NO2 --N removal (%)
3 6.3 85 77
8 3 31 70
9 5 22 72
10 7 50 68
11 9 3 40
As can be seen from Table 3, iron tannate was present in weakly acidic NH within a certain range4 +-N and NO2 -The catalytic denitrification effect is best in the-N mixed solution. NH at pH 6.34 +-N and NO2 -The removal rate of-N can reach 82% and 74% at most. Under the strong alkaline condition, the sodium alginate microspheres swell, the structure is destroyed, the ferric tannate dissolves out, and the pH value is>Soluble iron tannate at 7, NH at pH 94 +-N and NO2 -The removal rate of-N is extremely low. At pH 3 and 5, NO swelling occurs, NO2 -The removal rate of-N can reach 70% and 72%, which is probably because the change of the pH value of the solution can affect the charge and the species of the surface of the adsorbent, and a large amount of H exists in the solution+Will occupy the adsorption sites on the surface of the gel sphere, resulting in NH4 +N competes for sufficient adsorption sites, NH4 +The removal rate of-N is limited.
Example 12
The embedded catalyst obtained in the example 3 is applied to the denitrification of wastewater, and the specific steps are as follows:
1) preparing simulated wastewater: at room temperature, 100mL of NH was prepared4Cl and NaNO2The mixed solution of (1), wherein, NH4Cl concentration 25mg/L, NaNO2The concentration is 50 mg/L;
2) adding amount of gel balls: adding 50mL of gel balls into 100mL of simulated wastewater (the simulated wastewater is aerated by He until the dissolved oxygen is lower than 1 mg/L);
3) the operation conditions are as follows: running in a shaking table at the temperature of 5 ℃ for 3h, wherein the pH of the mixed solution is 6.3;
4) and (3) determination of a water sample: sampling every half an hour, filtering with 0.45 μm filter membrane, and determining NH in water sample by national standard method4 +-N and NO2 --N。
Example 13
The embedded catalyst obtained in the example 3 is applied to the denitrification of wastewater, and the specific steps are as follows:
1) preparing simulated wastewater: at room temperature, 100mL of NH was prepared4Cl and NaNO2The mixed solution of (1), wherein, NH4Cl concentration 25mg/L, NaNO2The concentration is 50 mg/L;
2) adding amount of gel balls: adding 50mL of gel balls into 100mL of simulated wastewater (the simulated wastewater is aerated by He until the dissolved oxygen is lower than 1 mg/L);
3) the operation conditions are as follows: running in a shaking table at 25 ℃ for 3h, wherein the pH of the mixed solution is 6.3;
4) and (3) determination of a water sample: sampling every half an hour, filtering with 0.45 μm filter membrane, and determining NH in water sample by national standard method4 +-N and NO2 --N。
Example 14
The embedded catalyst obtained in the example 3 is applied to the denitrification of wastewater, and the specific steps are as follows:
1) preparing simulated wastewater: at room temperature, 100mL of NH was prepared4Cl and NaNO2The mixed solution of (1), wherein, NH4Cl concentration 25mg/L, NaNO2The concentration is 50 mg/L;
2) adding amount of gel balls: adding 50mL of gel balls into 100mL of simulated wastewater (the simulated wastewater is aerated by He until the dissolved oxygen is lower than 1 mg/L);
3) the operation conditions are as follows: running in a shaking table at 35 ℃ for 3h, wherein the pH of the mixed solution is 6.3;
4) and (3) determination of a water sample: samples were taken every half hour, 0.Filtering with 45 μm filter membrane, and determining NH in water sample by national standard method4 +-N and NO2 --N。
The denitrification effects of example 3 and examples 12 to 14 are shown in Table 4.
Table 4:
examples Temperature (. degree.C.) Removal Rate (%) Removal Rate (%)
12 5 35 26
3 15 85 77
13 25 65 50
14 35 50 44
As can be seen from Table 4, NH showed the best denitrification performance at 15 ℃4 +-N and NO2 -The maximum removal rates of-N are 85% and 77% respectively, desorption is accelerated at high temperature, and the influence of embedded iron tannate on NH is caused4 +-N and NO2 -Adsorption of-N, decrease in adsorption amount, decrease in removal rate.

Claims (10)

1. An embedded catalyst is characterized in that the embedded catalyst is embedded iron tannate, and the catalyst is prepared by the following method:
a. dissolving sodium alginate in deionized water at normal temperature to obtain a sodium alginate solution with the concentration of 10-40 mg/mL;
b. adding CaCl2Dissolving in deionized water to obtain CaCl2A solution;
c. b, uniformly mixing the sodium alginate solution prepared in the step a with ferric tannate powder to obtain a mixed solution; wherein, the weight ratio of the ferric tannate to the sodium alginate solution is = 0.01-0.06 g: 1 mL;
d. c, dropwise adding the mixed liquid containing the black iron tannate powder prepared in the step c into a calcium chloride solution by using a syringe to quickly form gel spheres, and standing for 10-14 h to fully crosslink the gel spheres so as to obtain sodium alginate-embedded iron tannate gel spheres;
e. and d, washing the gel balls prepared in the step d with distilled water for 3-4 times to obtain the embedded iron tannate catalyst, and storing the embedded iron tannate catalyst in water at normal temperature.
2. The embedded catalyst according to claim 1, wherein in step a, the concentration of the sodium alginate solution is 20-30 mg/mL.
3. The embedded catalyst according to claim 1, wherein in step b, CaCl is added2The dosage ratio of the deionized water to the deionized water is 12 g: 400 mL.
4. The embedded catalyst according to claim 1, wherein in step c, the iron tannate to sodium alginate solution =0.04 g: 1 mL.
5. A preparation method of an embedded catalyst is characterized in that the embedded catalyst is embedded iron tannate, and the preparation method comprises the following steps:
a. dissolving sodium alginate in deionized water at normal temperature to obtain a sodium alginate solution with the concentration of 10-40 mg/mL;
b. adding CaCl2Dissolving in deionized water to obtain CaCl2A solution;
c. b, uniformly mixing the sodium alginate solution prepared in the step a with ferric tannate powder to obtain a mixed solution; wherein, the weight ratio of the ferric tannate to the sodium alginate solution is = 0.01-0.06 g: 1 mL;
d. c, dropwise adding the mixed liquid containing the black iron tannate powder prepared in the step c into a calcium chloride solution by using a syringe to quickly form gel spheres, and standing for 10-14 h to fully crosslink the gel spheres so as to obtain sodium alginate-embedded iron tannate gel spheres;
e. and d, washing the gel balls prepared in the step d with distilled water for 3-4 times to obtain the embedded iron tannate catalyst, and storing the embedded iron tannate catalyst in water at normal temperature.
6. The preparation method of claim 5, wherein in the step a, the concentration of the sodium alginate solution is 20-30 mg/mL; in step b, CaCl2The dosage ratio of the deionized water to the deionized water is 12g to 400 mL; in step c, the solution of ferric tannate and sodium alginate is =0.04 g: 1 mL.
7. Use of the embedded catalyst of any one of claims 1 to 4 in the denitrification of wastewater.
8. Use according to claim 7, wherein the embedded catalyst is added to the solution containing NH4 +And/or NO2 -The wastewater is stirred or vibrated and mixed, and is subjected to adsorption treatment for 2-4 hours, wherein the pH value of a mixed solution is controlled to be 6-7 during the adsorption treatment, the temperature is controlled to be 10-25 ℃, and the wastewater is filtered and recovered after the treatmentThe embedded catalyst.
9. Use according to claim 8, wherein the embedded catalyst is added in an amount corresponding to the amount of NH in the wastewater4 +The mass ratio of (A) to (B) is 100-110: 1; adding amount of embedded catalyst and NO in wastewater2 -The mass ratio of (A) to (B) is 250-280: 1.
10. The use according to claim 8, wherein the pH of the mixture is controlled to 6-7 and the temperature is controlled to 15 ℃ during the adsorption treatment.
CN202010973962.0A 2020-09-16 2020-09-16 Embedded catalyst, preparation method thereof and application thereof in wastewater denitrification Pending CN112007694A (en)

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