CN113117684A - Preparation method of ternary oxide ozone catalyst for advanced wastewater treatment - Google Patents

Preparation method of ternary oxide ozone catalyst for advanced wastewater treatment Download PDF

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CN113117684A
CN113117684A CN202110419931.5A CN202110419931A CN113117684A CN 113117684 A CN113117684 A CN 113117684A CN 202110419931 A CN202110419931 A CN 202110419931A CN 113117684 A CN113117684 A CN 113117684A
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ozone catalyst
catalyst
wastewater treatment
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ternary oxide
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柳玉肖
毛旭辉
朱子强
赵建力
王智成
刘卫静
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Hebei Delong Environmental Engineering Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone

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Abstract

The invention discloses a preparation method of a ternary oxide ozone catalyst for advanced wastewater treatment. The invention aims to solve the problems of easy aggregation of catalytic active components and low utilization rate of substrate pore channels in the traditional preparation method of the alumina-based ozone catalyst. The preparation method of the catalyst comprises the following steps: a. gamma-Al with the diameter of 2-5 mm2O3Soaking the mixture in dilute nitric acid for 12 hours, filtering and taking out the mixture, washing the mixture with deionized water until the pH value is unchanged, and drying the mixture for later use; b. preparing stock solution of iron nitrate, copper nitrate and lanthanum nitrate containing metal ion promoters with certain concentration; c. drying the gamma-Al obtained in the step a2O3Adding into the prepared stock solution, and soaking for 24 h; d. impregnating the impregnated gamma-Al2O3Filtering, cleaning and drying, and finally roasting at high temperature to obtain the alumina-based ozone catalyst with uniformly dispersed active substances. The ozone catalyst of the present inventionThe catalyst layer has thick catalytic layer, the active component has good dispersibility, and the method has simple preparation process and low cost, and is easy for engineering macro preparation.

Description

Preparation method of ternary oxide ozone catalyst for advanced wastewater treatment
Technical Field
The invention relates to the field of environmental catalysis and water treatment, in particular to a preparation method of a ternary oxide ozone catalyst for advanced wastewater treatment.
Background
After the rapid economic development of decades, the situation of water resource shortage is further highlighted, and the water resource problems of over exploitation, water source exhaustion, water pollution, water ecosystem destruction and the like are continuously restricting the development of economy and society in China. Under the background, the advanced treatment and recycling of effective sewage are realized, and the utilization efficiency of water resources is improved, which is the current development trend. At present, technologies including physical and chemical methods, biological methods, chemical methods, membrane methods and the like which are continuously used in China can basically meet the treatment requirements of general light industrial wastewater and domestic sewage, but the treatment of most of complex sewage (such as coking wastewater, pharmaceutical wastewater, aquaculture wastewater, garbage percolate and the like) is still in a standstill. Taking the coking wastewater as an example, the method has the characteristics of large discharge amount, complex components, high concentration of toxic organic matters, poor treatment effect of the traditional biochemical method and the like, and is always a big problem in the industrial water treatment industry. With the further tightening of the national sewage discharge standard and the increasing demand of urban and industrial water, the development of a feasible, economical and efficient advanced wastewater treatment technology is urgent.
The ozone catalytic oxidation technology is an efficient technology for treating the organic sewage difficult to degrade, has the advantages of simple and convenient operation, safe implementation, low cost, no sludge and salt generation and the like, and is concerned; however, ozone has a low solubility and insufficient self-oxidation efficiency, and it is necessary to increase the ozone decomposition efficiency by introducing an ozone catalyst, thereby generating a large amount of radicals having high oxidation activity and enhancing the oxidation effect. Therefore, the development of efficient, economical and stable ozone catalyst is the core of the application of the ozone catalytic oxidation process to advanced treatment of complex organic wastewater. Currently, ozone catalysis is dominated by homogeneous catalysis and heterogeneous catalysis. Unlike homogeneous ozone catalyst, which has high cost, easy loss and secondary pollution, the supported heterogeneous catalyst has wide application owing to its advantages of easy preparation, simple separation and recovery, high reusability, etc.
The supported catalyst in the field of ozone catalysis is mainly carbon-based, ceramic-based and alumina-based. The carbon-based ozone catalyst needs inert gas protection in the high-temperature calcination stage, and the preparation process is complex; the ceramic base has a single pore channel structure and relatively insufficient loading capacity of active components; and gamma-Al2O3The catalyst is regarded as an excellent substrate material of the supported ozone catalyst due to the advantages of inherent physicochemical stability, rich pore channel structure and the like. Wherein, the chemical dipping method is adopted to quickly prepare the target gamma-Al2O3The ozone-based catalytic oxidation catalyst is the most widely applied and conventional catalyst preparation method at present. For example, the Chinese patent application (application publication No. CN105289585A) discloses a method for preparing gamma-Al by dipping2O3The patent proposes in-situ chemical precipitation, and a target catalytic ozone oxidant can be obtained without high-temperature calcination, but the actual catalytic service life is greatly shortened due to weaker load firmness between an active component and a carrier. He Dannong et Al (application publication No. CN105381797A) proposed a preparation process of a double rare earth element doped gamma-Al 2O 3-based supported catalyst based on a traditional impregnation-calcination method, but the active components dispersed on the surface of the carrier are easy to seriously aggregate in the high-temperature sintering process, so that the dispersion degree of the active components is reduced, and the activity of the catalyst is weakened to a certain extent. Therefore, the development of a heterogeneous ozone catalyst with strong bonding firmness and uniformly dispersed active components for the ozone water treatment process is urgently needed.
Disclosure of Invention
Technical problem to be solved
Aiming at the problems of easy agglomeration of active components, low utilization rate of substrate pore channels and the like of the existing supported ozone catalyst, the invention provides gamma-Al2O3As a carrierAccording to the preparation method of the ternary Fe, Cu and La oxide ozone oxidant, the accelerant with metal coordination capacity is introduced in the catalyst preparation process, so that the efficiency of immersing ternary Fe, Cu and La metal ions into the substrate can be improved, and the agglomeration phenomenon among the metal ions can be reduced. The ternary composite ozone catalyst has the characteristics of thick catalytic activity layer, uniform dispersion of active species and the like, and can obviously improve the catalytic oxidation efficiency of ozone and the removal efficiency of organic pollutants.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: a preparation method of a ternary oxide ozone catalyst for advanced wastewater treatment comprises the following steps:
the method comprises the following steps: taking 10-20% by mass of dilute nitric acid to Al2O3Dipping and activating, taking out after dipping for a certain time, cleaning and drying for later use;
step two: preparing a metal ion promoter, iron nitrate mixed solution, copper nitrate mixed solution and lanthanum nitrate mixed solution in a certain mass ratio, and fully dissolving all the components through mechanical stirring to obtain impregnation stock solution;
step three: taking a certain amount of Al activated in the first step2O3Adding the precursor into an impregnation stock solution for full impregnation, filtering and drying after the impregnation for a certain time to obtain an ozone catalyst precursor loaded with Fe, Cu and La metal elements;
step four: and D, roasting the precursor obtained in the step three at a high temperature, and obtaining the ternary oxide ozone catalyst after roasting.
Preferably, in the first step, Al is2O3With gamma-Al2O3Mainly, the particle size of the particles is 2-5 mm.
Furthermore, the dipping time in the first step is 10-14 h.
Preferably, in the second step, the metal ion promoter is one or more of ethylenediamine tetraacetic acid, ascorbic acid and N, N-ethylenediamine succinic acid, and the mass ratio of the components in the impregnation stock solution is that the promoter: iron nitrate: manganese nitrate: deionized water is 1-5: 10-30: 5-20: 50 to 200.
Preferably, Al is activated in the third step2O3And adding the mixture into the dipping stock solution for dipping for 12-36 h.
Preferably, in the fourth step, the roasting temperature rise speed is kept between 2 and 6 ℃/min, the roasting temperature is within the range of 400 to 700 ℃, and the ternary oxide ozone catalyst prepared in the fourth step is ternary Fe2O3-CuO-La2O3An oxide co-doped target alumina-based ozone catalyst.
(III) advantageous effects
The invention provides a preparation method of a ternary oxide ozone catalyst for advanced wastewater treatment, which has the following beneficial effects: one or more mixtures of ethylenediamine tetraacetic acid, ascorbic acid and N, N-ethylenediamine succinic acid are used as metal ion promoters, so that an impregnation system is ensured to be in an acidic condition, and the self-hydrolysis reaction of metal ions is inhibited; in addition, the metal ions can be promoted to enter the pore channels of the substrate by the coordination capacity, and the impregnation depth of the active species is improved.
While inventing Fe3+、Cu2+、La3+The ternary metal oxide ozone catalyst with uniformly dispersed active species is prepared by doping in different proportions and combining the chelating effect of the accelerant. Wherein the metal oxide Fe has catalytic activity2O3、CuO、La2O3Evenly distributed on alumina pore canal carrier, reduced ozone and rivers erode and lead to the deactivation phenomenon that catalyst looks mutual friction caused, greatly prolonged catalyzed life, also improved active site simultaneously, realize high-efficient catalytic ozonation, improve the ozone utilization ratio.
Furthermore, the ternary supported ozone catalyst has the advantages of simple preparation method, strong load firmness of active species, good dispersibility, good catalytic stability and reproducibility and reusability, thereby having better broad spectrum and higher practical value.
Description of the drawings:
FIG. 1 is a graph showing the effect of CODcr in removing dye wastewater by ozone oxidation alone, catalytic ozone oxidation by a catalyst in comparative example 1 and catalytic ozone oxidation by a catalyst in example 1;
FIG. 2 is a graph comparing the performance of a catalyst prepared by the conventional impregnation method and the present invention after 10 cycles of degradation;
FIG. 3 is a graph showing the comparison of Fe ion release amounts in water of the ozone catalysts prepared in example 1 of the present invention and comparative example 1;
FIG. 4 shows Fe prepared in example 1 of the present invention2O3-CuO-La2O3/Al2O3A super depth of field map of a cross section of the catalyst.
Detailed Description
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
In order to better understand the technical features of the present invention, the following discussion of Fe of the present invention is made by way of example2O3-CuO-La2O3/Al2O3The catalytic effect of the supported ozone catalyst on ozone oxidation and the removal efficiency of organic matters. The examples are not intended to limit the scope of the invention.
Example 1
A preparation method of a ternary oxide ozone catalyst for advanced wastewater treatment comprises the following steps:
gamma-Al with the particle size of 2-5 mm and the weight of 100g2O3Weight for carrierSoaking in 10% dilute nitric acid solution for 12 hr, washing with deionized water until pH is unchanged, and oven drying;
adding ethylene diamine tetraacetic acid serving as a metal ion promoter into deionized water with a certain volume, and after the metal ion promoter is fully dissolved, sequentially adding ferric nitrate, cupric nitrate and lanthanum nitrate into the solution to prepare the impregnation stock solution. Wherein the weight of each component of the dipping stock solution is as follows: the weight percentages of the ethylene diamine tetraacetic acid, the ferric nitrate, the manganese nitrate and the deionized water are respectively 5g, 15g, 10g and 100 g.
Drying the gamma-Al for later use2O3Adding into prepared stock solution, and soaking for 24 hr.
The gamma-Al dipped in the step (3) is added2O3Taking out, washing and drying with deionized water, transferring into a muffle furnace, keeping the roasting temperature rise speed at 4 ℃/min, the roasting temperature at 500 ℃, the roasting time at 3h, and obtaining the target Fe after the roasting is finished2O3-CuO-La2O3/Al2O3A supported ozone catalyst.
The ozone catalyst is used for degrading simulated dye wastewater, the CODcr of the simulated wastewater is 150mg/L, the UV254 is 0.532, the total volume of the wastewater is 1L, the adding amount of the catalyst is 50g, and the effective volume of a catalytic reactor is 1.5L. And the titanium aeration head is used for aerating the ozone from the bottom of the reactor to the inside of the reaction system in a micro-nano bubble form. The experiment was carried out under constant temperature conditions (reaction temperature was controlled between 25. + -. 2 ℃ C. by cryostat) for 60 min. The results of treatment of the simulated dye wastewater are shown in Table 1.
The results show that Fe in the present invention2O3-CuO-La2O3/Al2O3The removal effect of the ozone catalyst on the organic wastewater is better than the oxidation effect of common ozone, compared with the removal rate of COD and UV254 in single ozone oxidation which is only 25.1 percent and 40.6 percent, the addition of the catalyst obviously improves the removal efficiency of organic matters, and when the reaction time is 60min, the removal rate of CODcr and UV254 is higher67.2% and 83.7%, respectively. Wherein, the comparison result of CODcr removing rate of the simulated wastewater in different time periods is shown in FIG. 2.
Comparative example 1
FeCuLaOx/Al is prepared by adopting the traditional steps of activation, impregnation, drying and calcination2O3An ozone catalyst. The preparation method is the same as that of the example 1 except that the metal ion accelerator ethylene diamine tetraacetic acid is not added.
FeCuLaOx/Al prepared in the above way2O3The ozone catalyst is used for simulating the degradation of dye wastewater, the CODcr in the simulated wastewater is 150mg/L, the UV254 is 0.532, the total volume of the wastewater is 1L, the adding amount of the catalyst is 50g, and the effective volume of the catalytic reactor is 1.5L. And the titanium aeration head is used for aerating the ozone from the bottom of the reactor to the inside of the reaction system in a micro-nano bubble form. The experiment was carried out under constant temperature conditions (reaction temperature was controlled between 25. + -. 2 ℃ C. by cryostat) for 60 min. The results of treatment of the simulated dye wastewater are shown in Table 1.
The results show that FeCuLaOx/Al in the invention2O3The removal rate of CODcr and UV254 in the simulated organic wastewater after the ozone catalyst reacts for 60min is only 50.6 percent and 61.8 percent. The CODcr removal rate of simulated wastewater over different degradation periods is shown in FIG. 3. Compared with the high-efficiency Fe obtained by adding the metal ion promoter in the process of preparing the ozone catalyst2O3-CuO-La2O3/Al2O3Supported ozone catalyst, supported ozone catalyst FeCuLaOx/Al prepared by traditional impregnation method2O3Catalytic ozone is less active.
TABLE 1
Figure BDA0003027467810000061
Example 2
The ozone catalyst used for water treatment in example 1 and comparative example 1 was collected, washed, dried, and then transferred to a 300 ℃ muffle furnace to be calcined for 2 hours, and then cooled and taken out and used for treating simulated dye wastewater, and the degradation test conditions were maintained to be the same as in example 1. The two catalysts are respectively subjected to 10 repeated degradation tests, the test results are shown in fig. 4, and the results show that compared with the traditional impregnation process, the catalyst is easy to cause catalytic species to agglomerate on the surface of a carrier, the introduction of the metal ion accelerant in the catalyst preparation process is beneficial to improving the uniform dispersion of active species, improving the catalytic ozone activity site number and accelerating the ozone catalytic oxidation efficiency, and even after 10 repeated tests, the ozone catalyst prepared by the method still has the performance of efficiently removing organic pollutants.
Example 3
Based on the cycle test performed in example 2, a third cycle degradation experiment was selected, 5mL of the reaction solution was taken out at different time periods, transferred to a 10mL colorimetric tube, 1mL of hydroxylamine hydrochloride with a concentration of 1g/L, 2mL of acetic acid with a concentration of 1mol/L, and 2mL of phenanthroline solution with a concentration of 1g/L were sequentially added, and after standing for 15min, the total iron content dissolved in the reaction solution was determined at a wavelength of 510nm by a spectrophotometric method. The experimental result is shown in FIG. 3, FeCuLaOx/Al is degraded after 60min2O3The total dissolved iron ions in the catalytic system reach 0.19mg/L which is far higher than Fe2O3-CuO-La2O3/Al2O30.08mg/L in the catalytic system. FeCuLaOx/Al2O3The loss of excess active component from the catalytic system demonstrates a reduction in catalytic ozone activity and a reduction in catalyst life.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (8)

1. A preparation method of a ternary oxide ozone catalyst for advanced wastewater treatment is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: taking 10-20% by mass of dilute nitric acidFor Al2O3Dipping and activating, taking out after dipping for a certain time, cleaning and drying for later use;
step two: preparing a metal ion promoter, iron nitrate mixed solution, copper nitrate mixed solution and lanthanum nitrate mixed solution in a certain mass ratio, and fully dissolving all the components through mechanical stirring to obtain impregnation stock solution;
step three: taking a certain amount of Al activated in the first step2O3Adding the precursor into an impregnation stock solution for full impregnation, filtering and drying after the impregnation for a certain time to obtain an ozone catalyst precursor loaded with Fe, Cu and La metal elements;
step four: and D, roasting the precursor obtained in the step three at a high temperature, and obtaining the ternary oxide ozone catalyst after roasting.
2. The method for preparing the ternary oxide ozone catalyst for advanced wastewater treatment according to claim 1, wherein the method comprises the following steps: in the first step, Al is2O3With gamma-Al2O3Mainly, the particle size of the particles is 2-5 mm.
3. The method for preparing the ternary oxide ozone catalyst for advanced wastewater treatment according to claim 1, wherein the method comprises the following steps: the dipping time in the first step is 10-14 h.
4. The method for preparing the ternary oxide ozone catalyst for advanced wastewater treatment according to claim 1, wherein the method comprises the following steps: in the second step, the metal ion promoter is one or more of ethylenediamine tetraacetic acid, ascorbic acid and N, N-ethylenediamine succinic acid.
5. The method for preparing the ternary oxide ozone catalyst for advanced wastewater treatment according to claim 3, wherein the method comprises the following steps: the mass ratio of each component in the dipping stock solution is as follows: iron nitrate: manganese nitrate: deionized water is 1-5: 10-30: 5-20: 50 to 200.
6. The method for preparing the ternary oxide ozone catalyst for advanced wastewater treatment according to claim 1, wherein the method comprises the following steps: al after activation in the third step2O3And adding the mixture into the dipping stock solution for dipping for 12-36 h.
7. The method for preparing the ternary oxide ozone catalyst for advanced wastewater treatment according to claim 1, wherein the method comprises the following steps: in the fourth step, the roasting temperature rise speed is required to be kept between 2 and 6 ℃/min, and the roasting temperature is within the range of 400 to 700 ℃.
8. The method for preparing the ternary oxide ozone catalyst for advanced wastewater treatment according to claim 1, wherein the method comprises the following steps: the ozone catalyst of the ternary oxide prepared in the fourth step is ternary Fe2O3-CuO-La2O3An oxide co-doped target alumina-based ozone catalyst.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114534735A (en) * 2021-12-31 2022-05-27 嘉兴学院 Method for preparing high-dispersion supported metal catalyst by chelation auxiliary strategy
CN114804323A (en) * 2022-04-13 2022-07-29 海天水务集团股份公司 Ozone-based wastewater oxidation treatment method

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Publication number Priority date Publication date Assignee Title
US4040982A (en) * 1976-01-12 1977-08-09 Nalco Chemical Company Ozonization catalyst
CN106964349A (en) * 2017-02-24 2017-07-21 河北科技大学 Ozone catalytic oxidation catalyst, its preparation method and application
CN109092323A (en) * 2017-06-20 2018-12-28 中国石油化工股份有限公司 Low-temperature SCR catalyst for denitrating flue gas and its preparation method and application
CN110115999A (en) * 2018-02-06 2019-08-13 浙江中凯瑞普环境工程股份有限公司 Ozone catalytic oxidation catalyst and preparation method thereof for degradation of organic waste water
CN111282577A (en) * 2020-03-30 2020-06-16 中国环境科学研究院 Supported bi-component metal oxide catalyst for advanced treatment of petrochemical wastewater and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4040982A (en) * 1976-01-12 1977-08-09 Nalco Chemical Company Ozonization catalyst
CN106964349A (en) * 2017-02-24 2017-07-21 河北科技大学 Ozone catalytic oxidation catalyst, its preparation method and application
CN109092323A (en) * 2017-06-20 2018-12-28 中国石油化工股份有限公司 Low-temperature SCR catalyst for denitrating flue gas and its preparation method and application
CN110115999A (en) * 2018-02-06 2019-08-13 浙江中凯瑞普环境工程股份有限公司 Ozone catalytic oxidation catalyst and preparation method thereof for degradation of organic waste water
CN111282577A (en) * 2020-03-30 2020-06-16 中国环境科学研究院 Supported bi-component metal oxide catalyst for advanced treatment of petrochemical wastewater and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114534735A (en) * 2021-12-31 2022-05-27 嘉兴学院 Method for preparing high-dispersion supported metal catalyst by chelation auxiliary strategy
CN114804323A (en) * 2022-04-13 2022-07-29 海天水务集团股份公司 Ozone-based wastewater oxidation treatment method
CN114804323B (en) * 2022-04-13 2023-06-13 海天水务集团股份公司 Wastewater oxidation treatment method based on ozone

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Application publication date: 20210716