CN106964333B - Rare earth supported catalyst for treating sewage, preparation method and application thereof, and method for treating sewage by catalytic oxidation of ozone - Google Patents
Rare earth supported catalyst for treating sewage, preparation method and application thereof, and method for treating sewage by catalytic oxidation of ozone Download PDFInfo
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- CN106964333B CN106964333B CN201710218613.6A CN201710218613A CN106964333B CN 106964333 B CN106964333 B CN 106964333B CN 201710218613 A CN201710218613 A CN 201710218613A CN 106964333 B CN106964333 B CN 106964333B
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
Abstract
The invention discloses a rare earth supported catalyst for treating sewage, a preparation method and application thereof, and a method for treating sewage by catalytic oxidation of ozone. The rare earth catalyst comprises a modified activated carbon carrier and a rare earth composite active component loaded on the modified activated carbon; the rare earth composite active component consists of lanthanum oxide and gadolinium oxide. The rare earth catalyst prepared by the method has the characteristics of high reaction activity, stable performance, good recoverability and the like; meanwhile, the preparation method has simple process and is easy for large-scale industrial production. The rare earth catalyst can realize the high-efficiency removal of the organic wastewater difficult to degrade by adopting an ozone catalytic advanced oxidation technology, is simple to operate and convenient to maintain, and has good economic and social benefits.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a rare earth supported catalyst for treating sewage, a preparation method and application thereof, and a method for treating sewage by catalytic ozonation.
Background
The catalytic ozone oxidation technology decomposes organic macromolecular substances difficult to degrade into non-toxic or slightly-toxic inorganic substances by generating free radicals with extremely strong oxidability under an alkaline condition, particularly generating substitution, bond breaking, addition and other actions on hydroxyl free radicals and organic pollutants, so that the wastewater can reach the standard and be discharged into the environment.
However, the favored technology without secondary pollution also has certain application limitations, such as: (1) at present, the research on the ozone catalyst at home and abroad is mainly a single-component catalyst, but the research on the supported composite catalyst is less; (2) after the organic wastewater is degraded by heterogeneous catalytic oxidation using a metal oxide as a catalyst, it is difficult to separate and recover the metal oxide.
To date, scholars at home and abroad have found that rare earth elements have various catalytic and catalytic promoting capabilities, and at present, rare earth elements which account for one fourth of the total world production are used for preparing catalysts. The rare earth catalyst generally has the advantages of good stability, high selectivity, short processing period and the like.
The rare earth metal oxide has obvious promotion effect on catalyzing ozone to degrade organic matters, and meanwhile, the supported catalyst has good recoverability and stability, and the problem of metal ion dissolution in the process of catalyzing ozone to degrade pollutants is solved, so that the possibility of secondary pollution is reduced. Therefore, the supported rare earth oxide catalyst combining the advantages of the two is a promising catalytic ozonation catalyst.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a rare earth supported catalyst for treating sewage, which can effectively catalyze ozone oxidation to treat sewage and improve the sewage treatment efficiency; meanwhile, the catalyst has good stability, can be repeatedly used, does not bring secondary pollution, and has good application prospect.
The second purpose of the invention is to provide a preparation method of the rare earth supported catalyst, which is simple in preparation steps and suitable for large-scale industrial production of the rare earth supported catalyst.
The third purpose of the invention is to provide a method for treating sewage by catalytic ozonation, in the method, the rare earth loaded catalyst is used for reaction catalysis, so that the efficiency of sewage oxidation treatment can be effectively improved, and pollution is avoided.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a rare earth supported catalyst for treating sewage comprises a modified activated carbon carrier and rare earth metal oxide loaded on the modified activated carbon carrier;
wherein the rare earth metal oxide is lanthanum oxide and gadolinium oxide.
Meanwhile, the invention also provides a preparation method of the rare earth supported catalyst, which comprises the following steps:
(a) dipping the activated carbon into a mixed solution of sulfuric acid and zinc chloride, and then drying and washing to obtain modified activated carbon;
(b) reacting lanthanum oxide and gadolinium oxide with hydrochloric acid and sodium hydroxide solution in sequence to obtain rare earth active component mixed solution;
(c) adding the modified activated carbon into the rare earth active component mixed solution, mixing, filtering, washing and drying to obtain solid powder, and calcining the solid powder to obtain the rare earth supported catalyst.
Optionally, in the present invention, the preparation of the modified activated carbon in step (a) includes the following steps: mixing sulfuric acid and a zinc chloride solution to prepare a compound solution, dipping active carbon in the compound solution, and performing ultrasonic oscillation at room temperature for 6-18 h; then, filtering the impregnated activated carbon, and washing the activated carbon with deionized water until the surface of the activated carbon is neutral; and drying the washed activated carbon at the temperature of 100-120 ℃ for 6-12 h, grinding and sieving to obtain the modified activated carbon.
Optionally, in the present invention, the preparation of the rare earth active component mixed solution in step (b) includes the following steps: mixing lanthanum oxide and gadolinium oxide powder with hydrochloric acid, and heating for reaction; then, adding a surfactant, and fully stirring and mixing; then, adding distilled water, and cooling to room temperature; adding a sodium hydroxide solution under the stirring condition to enable the pH value of the system to reach 8-10, and continuously stirring for reacting for 1-2 hours to obtain a rare earth hydroxide suspension, namely a rare earth active component mixed solution.
Optionally, in the invention, the molar ratio of lanthanum oxide to gadolinium oxide is (1-2): (1-2).
Optionally, in the invention, the concentration of the hydrochloric acid is 3-5 mol/L;
and/or the concentration of the sodium hydroxide solution is 0.5-1.5 mol/L;
and/or, the surfactant is PEG 20000.
Optionally, in the present invention, the preparation of the solid powder in step (c) includes the following steps: dispersing modified activated carbon in the rare earth active component mixed solution, and then carrying out ultrasonic treatment for 1-3 hours until the modified activated carbon is completely mixed; the resulting mixed solution was vacuum filtered, and the precipitate was washed with distilled water to pH 7; and drying the washed precipitate at 80-90 ℃ for 8-12 h to obtain solid powder.
Alternatively, in the present invention, the calcination in step (c) includes the following steps: under the gas protection condition, placing the solid powder in a tubular furnace, then gradually heating the tubular furnace from room temperature to 550-600 ℃, and preserving heat for 2-3 h; and then naturally cooling to room temperature to obtain the rare earth supported catalyst.
Further, the invention also provides a sewage treatment method, and the method uses the rare earth supported catalyst.
The invention also provides the application of the rare earth supported catalyst prepared by the method in sewage treatment.
Compared with the prior art, the invention has the beneficial effects that:
(1) the rare earth loaded catalyst has good stability and higher catalytic efficiency, is a high-efficiency, economic and practical rare earth catalyst, and can effectively improve the advanced oxidation treatment efficiency of sewage;
(2) the method has the advantages of low price of raw materials, convenient preparation method, suitability for industrial large-scale preparation of the rare earth supported catalyst, and contribution to the application of the cheaper rare earth catalyst in the sewage treatment technology of ozone catalytic advanced oxidation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows the number of times of use of the rare earth-supported catalyst and the COD removal rate in example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The rare earth loaded catalyst not only has good catalytic activity, but also has good stability and reusability, and the rare earth resources in China are rich, so that a novel rare earth loaded catalyst is developed and is used for treating sewage by ozone catalytic advanced oxidation, and the method is an effective method for fully utilizing the rare earth resources.
Specifically, the rare earth supported catalyst provided by the invention comprises a modified activated carbon carrier and a rare earth metal oxide loaded on the modified activated carbon carrier; wherein the rare earth metal oxide is lanthanum oxide and gadolinium oxide.
Through loading, the stability of the catalyst can be improved, and the loaded catalyst can be effectively recycled and reused, which is very beneficial to environmental protection and cost reduction; meanwhile, the supported catalyst has good catalytic activity, and can effectively improve the oxidation treatment efficiency of ozone on organic matters in sewage;
the preparation method of the rare earth supported catalyst comprises the following steps:
(a) dipping activated carbon in a mixed solution of sulfuric acid and zinc chloride, and then drying the dipped activated carbon to obtain modified activated carbon;
in the invention, the active carbon is modified by a chemical method, which specifically comprises the following steps:
mixing sulfuric acid and zinc chloride to prepare a compound solution, preferably, the concentration of the raw material sulfuric acid is 3.0mol/L, and the concentration of the raw material zinc chloride solution is 3.0 mol/L; the volume ratio of the sulfuric acid to the zinc chloride solution is 1: 1;
then, dipping the activated carbon into the compound solution, and ultrasonically oscillating for 6-18 h at room temperature; preferably, the oscillation is performed in an ultrasonic oscillator;
then, filtering the impregnated activated carbon, and washing the activated carbon with deionized water until the surface is neutral; drying the washed activated carbon at 100-120 ℃ for 6-12 h, grinding and sieving to obtain modified activated carbon; preferably, the drying of the activated carbon is carried out in a vacuum drying oven;
(b) lanthanum oxide (La)2O3) And gadolinium oxide (Gd)2O3) Mixing with hydrochloric acid for reaction, and adding sodium hydroxide solution to obtain rare earth active componentMixing the solution;
preferably, in the step, the raw material rare earth oxide is powder, and further preferably, the molar ratio of lanthanum oxide to gadolinium oxide is (1-2): (1-2);
preferably, the concentration of the raw material hydrochloric acid is 3-5 mol/L;
in order to further improve the reaction rate, the reaction is carried out under the heating condition and is carried out until the rare earth oxide is completely dissolved to obtain corresponding rare earth chloride;
then, adding a proper amount of surfactant, and fully stirring to ensure that the surfactant can be fully dissolved and dispersed in the system; preferably, the surfactant is PEG 20000;
then, adding appropriate amount of distilled water, preferably, distilled water, and adding rare earth ion (La)3+And Gd3+Total concentration of (b) to 0.2mol/L, followed by cooling the system to room temperature;
then, under the condition of violent stirring, dropwise adding a NaOH solution into a rare earth chloride solution, enabling the pH of the system to reach 8-10, and continuously stirring for reacting for 1-2 hours to obtain a rare earth hydroxide suspension, namely a rare earth active component mixed solution;
in the step, the generated rare earth hydroxide can be effectively dispersed in the system by adopting violent stirring; meanwhile, the excessive instantaneous generation amount of the hydroxide can be avoided by dropwise adding the sodium hydroxide, so that large agglomerated precipitates are generated, and the effective load on the modified activated carbon is difficult to perform, preferably, the concentration of the sodium hydroxide solution is 0.5-1.5 mol/L, and more preferably, the concentration of the sodium hydroxide solution is 1-1.2 mol/L;
(c) adding modified activated carbon into the rare earth active component mixed solution, mixing, filtering, washing and drying the obtained mixed solution to obtain solid powder; calcining the obtained solid powder in a protective atmosphere, and then cooling to room temperature to obtain a rare earth supported catalyst;
specifically, in the step, firstly, the modified activated carbon is soaked in the rare earth active component mixed solution, and then ultrasonic treatment is carried out for 1-3 hours, so that the rare earth hydroxide can be effectively adsorbed on the surface of the modified activated carbon;
then, the resulting mixed solution was vacuum-filtered, and the precipitate was washed with distilled water to pH 7; then, drying the washed precipitate at 80-90 ℃ for 8-12 h to obtain solid powder; preferably, in this step, the drying is carried out in an oven;
then, the dried solid powder is calcined, and in order to avoid the influence of air on the calcination, the calcination is preferably performed under a gas protection condition, and more preferably, the protection gas is nitrogen;
under the gas protection condition, placing the solid powder in a tubular furnace, then gradually heating the tubular furnace from room temperature to 550-600 ℃, and preserving heat for 2-3 h; then naturally cooling to room temperature to obtain the rare earth supported catalyst; preferably, in this step, the rate of temperature rise is 5 ℃/min.
The rare earth supported catalyst prepared by the method is a rare earth supported catalyst taking modified activated carbon as a carrier and rare earth oxide as an active component.
Furthermore, the preparation process of the rare earth supported catalyst is simple, so that the method is suitable for large-scale industrial production; meanwhile, the raw materials used in the preparation method are low in price, so that the preparation cost of the catalyst is low, and the preparation method is favorable for large-scale application of the rare earth supported catalyst in the aspects of sewage treatment and the like.
The rare earth supported catalyst provided by the invention has good catalytic activity, so that the rare earth supported catalyst can be applied to occasions such as sewage ozone catalytic advanced oxidation treatment and the like; meanwhile, the rare earth loaded catalyst can show good catalytic efficiency in the reaction of treating sewage by ozone catalytic advanced oxidation, and further can improve the sewage treatment efficiency.
Meanwhile, the sewage treatment method provided by the invention can be specifically referred to as follows: the rare earth load catalyst is filled into an ozone catalytic advanced oxidation reaction column, then sewage and ozone are introduced into the reaction column, and the sewage is subjected to ozone catalytic advanced oxidation treatment in a filling area.
Example 1
The preparation method of the rare earth supported catalyst provided by the invention can be specifically referred to as follows:
(a) weighing a proper amount of 3.0mol/L sulfuric acid and 3.0mol/L zinc chloride solution respectively according to the volume ratio of 1:1, and then mixing to obtain a compound solution;
then, dipping the activated carbon in the compound solution, and oscillating for 12 hours in an ultrasonic oscillator at room temperature;
then, filtering the impregnated activated carbon, repeatedly washing the activated carbon by deionized water until the surface of the activated carbon is neutral, then putting the activated carbon into a vacuum drying oven, and drying the activated carbon for 6 hours at 110 ℃; drying, grinding, sieving to obtain modified active carbon, and drying in a dryer.
(b) Respectively weighing a proper amount of lanthanum oxide powder and gadolinium oxide powder according to a molar ratio of 1:1, mixing the lanthanum oxide powder and the gadolinium oxide powder with a proper amount of 3.2mol/L hydrochloric acid, and heating for reaction until the powder is completely dissolved to obtain a mixed system containing lanthanum chloride and gadolinium chloride;
then, PEG20000 is added and fully stirred to completely dissolve and disperse the PEG;
then, adding a proper amount of distilled water to ensure that the concentration of the rare earth ions is 0.2mol/L, and cooling to room temperature;
and finally, dropwise adding NaOH under the condition of violent stirring to enable the pH of the system to reach 8-10, and then reacting for 1h to obtain a rare earth hydroxide suspension, namely the rare earth active component mixed solution.
(c) Adding modified activated carbon into the suspension of the rare earth hydroxide (rare earth active component mixed solution), and then carrying out ultrasonic treatment for 1h to fully mix the modified activated carbon and the rare earth hydroxide;
then, the mixed system was vacuum filtered, and the resulting precipitate was repeatedly washed with distilled water until its pH became 7; drying the washed precipitate in an oven at 80 ℃ for 12h to obtain solid powder;
then, the dried solid powder is placed in a tubular furnace under the nitrogen protection condition, and the flow rate of nitrogen gas is controlled to be 0.2L/min;
and then, heating the tubular furnace from room temperature to 550 ℃ at the heating rate of 5 ℃/min, preserving the heat at the temperature for 2h for calcination, and naturally cooling to room temperature to obtain the prepared rare earth supported catalyst.
Experimental example 1
(1) Testing of modified activated carbon:
the activated carbon modified according to the step (a) of example 1 and the same raw material activated carbon as in example 1 were taken and tested for surface area, average pore diameter and pore volume, respectively, and the test results are shown in the following table:
| sample (I) | Specific surface area/m2·g-1 | Average pore diameter nm | Pore volume/cm3·g-1 |
| Unmodified activated carbon | 322 | 3.20 | 0.18 |
| Modified activated carbon | 579 | 2.80 | 0.26 |
As can be seen from the above test and comparison data, compared with the unmodified activated carbon, the modified activated carbon has a larger increase in specific surface area and pore volume, which is also beneficial to increasing the loading capacity of the activated carbon, and further increasing the catalytic reaction efficiency of the ozone catalytic advanced oxidation reaction.
(2) Sewage treatment experiment:
the rare earth loaded catalyst is filled at the bottom of an ozone catalytic advanced oxidation reaction column, then the reaction column is used for treating industrial wastewater with COD of 300mg/L, the adding amount of ozone is 20mg/L, and the hydraulic retention time is 60 min;
through detection, the COD of the treated water body is less than or equal to 45mg/L, and the removal rate of the COD is 85 percent;
then, the reaction column was subjected to the above-described experiment repeatedly, and the removal rate of COD in each experiment was statistically calculated, and the results are shown in FIG. 1 below. As shown in the test results of FIG. 1, the rare earth supported catalyst prepared by the method of example 1 still has good ability of catalyzing ozone advanced oxidation to remove COD after being recycled for many times; meanwhile, even if the catalyst is used for the 10 th time, the COD catalytic removal rate can still reach 84.8 percent.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (4)
1. A method for treating sewage by catalytic oxidation of ozone is characterized in that: filling a rare earth loaded catalyst at the bottom of an ozone catalytic advanced oxidation reaction column, and using the reaction column for treating industrial wastewater with COD of 300mg/L, wherein the adding amount of ozone is 20mg/L, and the hydraulic retention time is 60 min;
the rare earth supported catalyst comprises a modified activated carbon carrier and a rare earth metal oxide supported on the modified activated carbon carrier; wherein the rare earth metal oxide is lanthanum oxide and gadolinium oxide;
the preparation method comprises the following steps:
(a) dipping the activated carbon into a sulfuric acid and zinc chloride compound solution, mixing, and then drying and washing to obtain modified activated carbon;
mixing sulfuric acid and a zinc chloride solution to prepare a compound solution, dipping active carbon in the compound solution, and performing ultrasonic oscillation at room temperature for 6-18 h; then, filtering the impregnated activated carbon, and washing the activated carbon with deionized water until the surface of the activated carbon is neutral; drying the washed activated carbon at 100-120 ℃ for 6-12 h, grinding and sieving to obtain modified activated carbon;
(b) reacting lanthanum oxide and gadolinium oxide with hydrochloric acid and sodium hydroxide solution in sequence to obtain rare earth active component mixed solution;
mixing lanthanum oxide and gadolinium oxide powder with hydrochloric acid, and heating for reaction; then, adding a surfactant, and fully stirring and mixing; then, adding distilled water, and cooling to room temperature; adding a sodium hydroxide solution under the stirring condition to enable the pH of the system to reach 8-10, and continuously stirring for reacting for 1-2 hours to obtain a rare earth hydroxide suspension, namely a rare earth active component mixed solution; the molar ratio of lanthanum oxide to gadolinium oxide is (1-2): (1-2);
(c) adding the modified activated carbon into the rare earth active component mixed solution, mixing, filtering, washing and drying to obtain solid powder, and calcining the solid powder to obtain the rare earth supported catalyst.
2. The catalytic ozonation process of sewage according to claim 1, wherein the concentration of hydrochloric acid is 3 to 5 mol/L;
and/or the concentration of the sodium hydroxide solution is 0.5-1.5 mol/L;
and/or, the surfactant is PEG 20000.
3. The catalytic ozonation process of sewage water of claim 1, wherein the preparation of solid powder in step (c) comprises the steps of:
dispersing modified activated carbon in the rare earth active component mixed solution, and then carrying out ultrasonic treatment for 1-3 hours until the modified activated carbon is completely mixed; the resulting mixed solution was vacuum filtered, and the precipitate was washed with distilled water to pH 7; and drying the washed precipitate at 80-90 ℃ for 8-12 h to obtain solid powder.
4. The catalytic ozonation process of sewage according to claim 1, wherein the calcination in step (c) comprises the steps of:
under the gas protection condition, placing the solid powder in a tubular furnace, then gradually heating the tubular furnace from room temperature to 550-600 ℃, and preserving heat for 2-3 h; and then naturally cooling to room temperature to obtain the rare earth supported catalyst.
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| CN109012658A (en) * | 2018-09-06 | 2018-12-18 | 杭州恒畅环保科技有限公司 | A kind of ozone oxidation catalyst and preparation method thereof |
| CN112973662A (en) * | 2021-02-25 | 2021-06-18 | 中节能环保投资发展(江西)有限公司 | Method for preparing ozone catalyst by doping rare earth enrichment with excess sludge and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891296A (en) * | 2010-07-19 | 2010-11-24 | 江南大学 | Method for treating ozonization water by taking Y-type zeolite loaded with rare earth oxides of cerium oxide (CeO2) and lanthanum oxide (La2O3) as catalyst |
| CN105268425A (en) * | 2014-07-17 | 2016-01-27 | 中国科学院大连化学物理研究所 | Modified active carbon catalyst, and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101891296A (en) * | 2010-07-19 | 2010-11-24 | 江南大学 | Method for treating ozonization water by taking Y-type zeolite loaded with rare earth oxides of cerium oxide (CeO2) and lanthanum oxide (La2O3) as catalyst |
| CN105268425A (en) * | 2014-07-17 | 2016-01-27 | 中国科学院大连化学物理研究所 | Modified active carbon catalyst, and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 氯化锌二次活化普通椰壳活性炭制备高中孔活性炭;葛晓利 等;《遵义医学院学报》;20140430;第37卷(第2期);第219-222页 * |
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