Catalyst For Catalytic Oxidation Treatment Of Organic Wastewater, Preparation Method Thereof, And Application Thereof

Abstract

A catalyst for catalytic oxidation treatment of organic wastewater, comprising aluminum oxide, and nickel, ferrum, manganese, and cerium supported on the aluminum oxide in oxide form. Based on the weight of aluminum oxide, the contents of the following components in the catalyst are: nickel: 5.0-20 wt %; ferrum: 0.5-5.5 wt %; manganese: 0.5-3.5 wt %; and cerium: 1.5-3.0 wt %. The present invention has a good effect in catalytic oxidation for degrading COD organic pollutants in wastewater and has high reactivity.

Claims

1. A catalyst for catalytic oxidation treatment of organic wastewater, wherein the catalyst comprises alumina and nickel, iron, manganese and cerium loaded on the alumina in oxide form; based on the weight of the alumina, the contents of the following components in the catalyst are as follows: nickel 5.0-20 wt %, preferably 5.5-12.0 wt %; iron 0.5-5.5 wt %, preferably 1.5-5.0 wt %; manganese 0.5-3.5 wt %, preferably 1.0-3.0 wt %; cerium 1.5-3.0 wt %, preferably 2.0-2.8 wt %.

2. The catalyst according to claim 1, wherein the catalyst comprises a cerium-modified alumina carrier and nickel, iron, manganese and cerium loaded on the cerium-modified alumina carrier in oxide form; the cerium-modified alumina carrier comprises alumina and cerium loaded on the alumina in oxide form; based on the weight of the alumina, the cerium content of the cerium-modified alumina carrier is 1.0-2.0 wt %, preferably 1.2-1.5 wt %.

3. The catalyst according to claim 2, wherein based on the weight of the alumina, the content of cerium loaded on the cerium-modified alumina carrier in the catalyst is 0.5-2.0 wt %, preferably 0.6-1.5 wt %.

4. The catalyst according to claim 1, wherein the nickel, iron, manganese and cerium are respectively derived from one or more of nitrates, acetates and carbonates containing corresponding metal elements, preferably nitrates.

5. A preparation method of a catalyst according to claim 2, wherein the preparation method comprises the following steps: (1) adding an impregnation liquid of cerium salt to the alumina, impregnating the alumina for 30-120 min, and then drying and calcining the obtained solid to produce a cerium-modified alumina carrier; (2) adding an impregnation liquid containing a nickel salt, an iron salt, a manganese salt and a cerium salt to the cerium-modified alumina carrier obtained in step (1), impregnating the cerium-modified alumina carrier for 30-120 minutes, and then drying and calcining the obtained solid to produce the catalyst; based on the weight of the alumina, the cerium content in the impregnation liquid of step (1) is 1.0-2.0 wt %, preferably 1.2-1.5 wt %; in the impregnation liquid of step (2), the cerium content is 0.5-2.0 wt %, preferably 0.6-1.5 wt %; the nickel content is 5.0-20 wt %, preferably 5.5-12.0 wt %; the iron content is 0.5-5.5 wt %, preferably 1.5-5.0 wt %; the manganese content is 0.5-3.5 wt %, preferably 1.0-3.0 wt %; the total cerium content in the impregnation liquid of step (1) and step (2) is 1.5-3.0 wt %, preferably 2.0-2.8 wt %.

6. The preparation method according to claim 5, wherein in step (1), the drying temperature is 100-130 C., the drying time is 2-5 h, the calcining temperature is 450-550 C., and the calcining time is 3-6 h; in step (2), the drying temperature is 100-130 C., the drying time is 2-5 h, the calcining temperature is 450-550 C., and the calcining time is 3-6 h; preferably, an equal volume impregnation process is used in both steps (1) and (2) for impregnation.

7. The preparation method according to claim 5, wherein in step (1), a vacuum pretreatment to the alumina is conducted before the impregnation; the vacuum pretreatment time is 10-30 min, and the vacuum degree of the vacuum pretreatment is 96.0-98.0 KPa.

8. The preparation method according to claim 7, wherein the solvent of the impregnation liquid in steps (1) and (2) is selected from the group consisting of water, methanol, ethanol and any combination thereof, preferably water and/or ethanol, more preferably an ethanol aqueous solution having an ethanol concentration of 10-40% by weight.

9. The preparation method according to claim 5, wherein the cerium salt in step (1) and the nickel salt, iron salt, manganese salt and cerium salt in step (2) are all one or more of nitrates, acetates or carbonates containing corresponding metal elements, preferably nitrates.

10. A method for treating organic wastewater, comprising adding the catalyst according to claim 1 to organic wastewater.

11. The method according to claim 10, comprising further adding sodium hypochlorite to treat the organic wastewater by catalytic oxidation; preferably, the pH of the organic wastewater is 7-8, the reaction temperature of the catalytic oxidation is 20-50 C., and the reaction time is 30-90 min.

12. The preparation method according to claim 6, wherein in step (1), a vacuum pretreatment to the alumina is conducted before the impregnation; the vacuum pretreatment time is 10-30 min, and the vacuum degree of the vacuum pretreatment is 96.0-98.0 KPa.

13. The preparation method according to claim 8, wherein the solvent of the impregnation liquid in steps (1) and (2) is selected from the group consisting of water, methanol, ethanol and any combination thereof, preferably water and/or ethanol, more preferably an ethanol aqueous solution having an ethanol concentration of 10-40% by weight.

14. The method according to claim 12, wherein the catalyst comprises a cerium-modified alumina carrier and nickel, iron, manganese and cerium loaded on the cerium-modified alumina carrier in oxide form; the cerium-modified alumina carrier comprises alumina and cerium loaded on the alumina in oxide form; based on the weight of the alumina, the cerium content of the cerium-modified alumina carrier is 1.0-2.0 wt %, preferably 1.2-1.5 wt %.

15. The method according to claim 13, wherein based on the weight of the alumina, the content of cerium loaded on the cerium-modified alumina carrier in the catalyst is 0.5-2.0 wt %, preferably 0.6-1.5 wt %.

16. The method according to claim 13, wherein comprising further adding sodium hypochlorite to treat the organic wastewater by catalytic oxidation; preferably, the pH of the organic wastewater is 7-8, the reaction temperature of the catalytic oxidation is 20-50 C., and the reaction time is 30-90 min.

17. The method according to claim 14, wherein comprising further adding sodium hypochlorite to treat the organic wastewater by catalytic oxidation; preferably, the pH of the organic wastewater is 7-8, the reaction temperature of the catalytic oxidation is 20-50 C., and the reaction time is 30-90 min.

Description

EMBODIMENTS

[0056] The technical solutions of the present invention and the effects thereof will be further described below through specific embodiments. The following examples are merely illustrative of the invention and are not intended to limit the scope of the invention. Simple modifications of the invention are within the scope of the invention as claimed.

Example 1: Preparation of Spherical Alumina Carrier

[0057] 30 g of high-purity aluminum foil (purity >99.9 wt %) were weighed, and 249.7 g of 10 wt % hydrochloric acid solution was added and stirred to dissolve the aluminum foil at 95-105 C. under reflux condition, and filtered to obtain a transparent aluminum sol with an alumina concentration of 18.2 wt %. 50 g of the obtained aluminum sol was weighed, and 12.0 g of urotropine aqueous solution containing 40% by weight of urotropine was added and mixed well, and then dropped into an oil column at 80 C. with a ball dropper to form pellets for 4-5 h; the pellets were separated from the oil and transferred to an aging kettle. After aging at 125 C. for 8 h, the pellets was taken out and rinsed with deionized water, dried at 120 C. for 2 h, then calcined at 600 C. for 6 h, and at last treated with steam at 600 C. for 8 h to obtain a spherical alumina carrier.

[0058] The physicochemical properties of the obtained spherical alumina carrier were as follows: particle size 1.2-1.8 mm, bulk density 0.43 g/ml, water absorption ratio 60 vol %, specific surface area 198 m.sup.2/g, pore volume 1.42 ml/g, and average pore diameter 134 nm.

Example 2: Preparation of Cerium-Modified Alumina Carrier A

[0059] 15 g (about 35 ml) of the spherical alumina carrier prepared in Example 1 was placed in a vacuum impregnation bottle for vacuum pretreatment, the vacuum pretreatment time was 30 min, and the vacuum degree was 98.0 KPa; 3.6 ml of cerium nitrate aqueous solution containing 0.05 g/ml of cerium was added to an ethanol aqueous solution having an ethanol concentration of 40 wt % to obtain 21 ml of impregnation liquid, and the impregnation liquid was added to the vacuum impregnation bottle and mixed evenly to perform an equal volume impregnation on the spherical alumina carrier. After impregnation for 60 min, the carrier was taken out and dried in an oven at 100 C. for 5 h, and then calcined at 450 C. for 6 h in a muffle furnace to obtain cerium-modified alumina carrier A.

[0060] In the obtained cerium-modified alumina carrier A, the content of cerium (Ce) was 1.2 wt % based on the weight of the alumina.

Example 3: Preparation of Cerium-Modified Alumina Carrier B

[0061] 15 g (about 35 ml) of the spherical alumina carrier prepared in Example 1 was placed in a vacuum impregnation bottle for vacuum pretreatment. The vacuum pretreatment time was 10 min, and the vacuum degree was 96.0 KPa; 4.5 ml of cerium nitrate aqueous solution containing 0.05 g/ml of cerium was added to an ethanol aqueous solution having an ethanol concentration of 10 wt % to prepare 21 ml of impregnation liquid, and the impregnation liquid was added to the vacuum impregnation bottle and mixed evenly to perform an equal volume impregnation to the spherical alumina carrier. After impregnation for 120 min, the carrier was taken out and dried in an oven at 130 C. for 2 h, and then calcined at 550 C. for 3 h in a muffle furnace to obtain cerium-modified alumina carrier B.

[0062] In the obtained cerium-modified alumina carrier B, the content of cerium (Ce) was 1.5 wt % based on the weight of the alumina.

Example 4: Preparation of Cerium-Modified Alumina Carrier C

[0063] 15 g (about 30 ml) of spherical alumina carrier from Shandong Yantai Baichuan Huitong Technology Co., Ltd. was taken and placed in a vacuum impregnation bottle for vacuum pretreatment. The vacuum pretreatment time was 20 min and the vacuum degree was 97.5 KPa. 6.0 ml of cerium nitrate aqueous solution containing 0.05 g/ml of cerium was taken and added to an ethanol aqueous solution have an ethanol concentration of 30 wt %, to prepare an impregnation liquid having a volume of 21 ml. The impregnation liquid was added to the vacuum impregnation bottle and mixed evenly to perform an equal volume impregnation on the spherical alumina carrier. After impregnation for 30 min, the carrier was taken out and dried in an oven at 120 C. for 3 h, and then calcined at 550 C. for 4 h in a muffle furnace to obtain cerium-modified alumina carrier C.

[0064] The physicochemical properties of the above spherical alumina carrier derived from Shandong Yantai Baichuan Huitong Technology Co., Ltd. were as follows: particle size 1.5-2.0 mm, bulk density 0.50 g/ml, water absorption rate 70 vol %, specific surface area 250 m.sup.2/g, pore volume 1.20 ml/g, and average pore size 130 nm.

[0065] In the obtained cerium-modified alumina carrier C, the content of cerium (Ce) was 2.0 wt % based on the weight of the alumina.

Example 5: Preparation of Cerium-Modified Alumina Carrier D

[0066] 15 g (about 50 ml) of spherical alumina carrier from Shandong Zibo Wufeng Aluminum Magnesium Co., Ltd. was taken and placed in a vacuum impregnation bottle for vacuum pretreatment, the vacuum pretreatment time was 30 min, and the vacuum degree was 98.0 KPa; 3.0 ml of cerium nitrate aqueous solution containing 0.05 g/ml of cerium was added to an ethanol aqueous solution having an ethanol concentration of 20 wt % to prepare an impregnation liquid having a volume of 25 ml, and the impregnation liquid was added to a vacuum impregnation bottle and mixed evenly to perform an equal volume impregnation on the spherical alumina carrier. After impregnation for 60 min, the carrier was taken out and dried in an oven at 120 C. for 2 h, and then calcined at 450 C. for 5 h in a muffle furnace to obtain cerium-modified alumina carrier D.

[0067] The physicochemical properties of the above spherical alumina carrier derived from Shandong Zibo Wufeng Aluminum Magnesium Co., Ltd. were as follows: particle size 1.0-1.5 mm, bulk density 0.30 g/ml, water absorption rate 50 vol %, specific surface area 150 m.sup.2/g, pore volume 1.80 ml/g, average pore size of 150 nm.

[0068] In the obtained cerium-modified alumina carrier D, the content of cerium (Ce) was 1.0 wt % based on the weight of the alumina.

Example 6: Preparation of 1# Catalyst

[0069] 15 g (about 35 ml) of cerium-modified alumina carrier A obtained in Example 2 was placed in a vacuum impregnation bottle for vacuum pretreatment. The vacuum pretreatment time was 30 min, and the vacuum degree was 97.5 KPa. At the same time, 10 ml of nickel nitrate aqueous solution containing 0.15 g/ml of nickel, 6.3 ml of iron nitrate aqueous solution containing 0.10 g/ml of iron, 1.0 ml of manganese nitrate aqueous solution containing 0.10 g/ml of manganese, and 2.4 ml of cerium nitrate aqueous solution containing 0.05 g/ml of cerium were added to an ethanol aqueous solution having an ethanol concentration of 40 wt % to prepare an impregnation liquid having a total volume of 21 ml. The above impregnation liquid was added to the vacuum impregnation bottle containing cerium-modified alumina carrier A and mixed evenly to perform an equal volume impregnation on the cerium-modified alumina carrier A. After impregnation for 30 min, the carrier was taken out and dried in an oven at 120 C. for 2 h, then calcined at 550 C. for 3 h in a muffle furnace.

[0070] In the obtained 1# catalyst, the contents of the following components were as follows: nickel 10.0 wt %, iron 4.2 wt %, manganese 0.7 wt %, and cerium 1.8 wt %, based on the weight of the alumina.

Example 6: Preparation of 1# Catalyst

[0071] 15 g (about 35 ml) of the spherical alumina carrier prepared in Example 1 was placed in a vacuum impregnation bottle and for vacuum pretreatment. The vacuum pretreatment time was 30 min, and the vacuum degree was 97.5 KPa. At the same time, 10 ml of nickel nitrate aqueous solution containing 0.15 g/ml of nickel, 6.3 ml of iron nitrate aqueous solution containing 0.10 g/ml of iron, 1.0 ml of manganese nitrate aqueous solution containing 0.10 g/ml of manganese, and 1.8 ml of cerium nitrate aqueous solution containing 0.15 g/ml of cerium were added to an ethanol aqueous solution having an ethanol concentration of 40 wt % to prepare an impregnation liquid having a total volume of 21 ml. The above impregnation liquid was added to the vacuum impregnation bottle containing the spherical alumina carrier and mixed evenly to perform an equal volume impregnation on the spherical alumina carrier. After impregnation for 30 min, the carrier was taken out and placed in an oven at 120 C. for 2 h, then calcined in a muffle furnace at 550 C. for 3 h.

[0072] In the obtained 1# catalyst, based on the weight of the alumina, the contents of the following components therein were as follows: nickel 10.0 wt %, iron 4.2 wt %, manganese 0.7 wt %, and cerium 1.8 wt %.

[0073] Comparison of the Effects of the First Group of Catalysts with Prior Art Catalysts:

[0074] Reverse osmosis concentrated water (COD: 298 ppm, pH=7.8) re-concentrated by a reverse osmosis device was taken, then a sodium hypochlorite solution having a concentration of 10 wt % was added thereto, and the addition amount was 7 ml of the sodium hypochlorite solution per liter of the reverse osmosis concentrated water. The mixed solution was divided into four parts and processed through 1# reactor, 2# reactor, 3# reactor and 4# reactor respectively, wherein 1# reactor was loaded with 1# catalyst prepared in Example 6, 2# reactor was loaded with 1# catalyst prepared in Example 6, #3 reactor was loaded with the catalyst of Example 1 in CN 101844828 B, and #4 reactor was loaded with the catalyst of Example 1 in CN 104549316 A. The dosage of each catalyst was 2 L, the residence time in the reactors was 1 h, the amount of influent water was 2 L/h, and the treatment temperature was 40 C.

[0075] The reverse osmosis concentrated water (COD: 298 ppm, pH=7.8) re-concentrated in the reverse osmosis device was taken, then chlor-alkali industrial wastewater was added thereto (the chlor-alkali industrial wastewater contained the following components: NaClO with a content of 4.8 wt %; NaOH with content of 1.5 wt %; Na.sub.2CO.sub.3 with a content of 7.0 wt %; NaCl with a content of 0.8 wt %), and the addition amount was 14.6 ml of the above-mentioned chlor-alkali industrial wastewater per liter of the reverse osmosis concentrated water. The mixed solution was divided into four parts and processed through 5# reactor, 6# reactor, 7# reactor and 8# reactor respectively, wherein 5# reactor was loaded with 1# catalyst prepared in Example 6, and 6# reactor was loaded with 1# catalyst prepared in Example 6, and #7 reactor was loaded with the catalyst of Example 1 in CN 101844828 B, and #8 reactor was loaded with the catalyst of Example 1 in CN 104549316 A. The dosage of each catalyst was 2 L, the residence time in the reactors was 1 h, the amount of influent water was 2 L/h, and the treatment temperature was 40 C.

[0076] The comparison results of the effects of the catalysts in the first group are shown in Table 1.

TABLE-US-00001 TABLE 1 Comparison results of the catalysts in the first group Metal COD COD loss of of COD amount the the re- in the effluent effluent moval effluent water water rate water Reactor Catalyst Oxidant (ppm) (ppm) (%) (mg/L) 1# 1# (two-step sodium 298 48 84 0.1 method) hypo- 2# 1'# (one step chlorite 298 87 71 0.5 method) solution 3# CN 101844828 298 206 31 0.5 B 4# CN 104549316 298 150 50 0.4 A 5# 1# (two-step chlor- 298 45 85 0.1 method) alkali 6# 1'# (one step industrial 298 83 72 0.4 method) waste- 7# CN 101844828 water 298 200 33 0.4 B 8# CN 104549316 298 143 52 0.4 A

[0077] The metal loss amount in the effluent water refers to the content of metal which is from the catalyst and discharged with the effluent water when the wastewater was treated, in mg/L.

Example 7: Preparation of 2# Catalyst

[0078] 15 g (about 50 ml) of cerium-modified alumina carrier D obtained in Example 5 was placed in a vacuum impregnation bottle for vacuum pretreatment. The vacuum pretreatment time was 30 min, and the vacuum degree was 96.0 KPa. At the same time, 12 ml of nickel nitrate aqueous solution containing 0.15 g/ml of nickel, 2.3 ml of iron nitrate aqueous solution containing 0.10 g/ml of iron, 3.0 ml of manganese nitrate aqueous solution containing 0.10 g/ml of manganese, and 1.5 ml of cerium nitrate aqueous solution containing 0.05 g/ml of cerium were added to an ethanol aqueous solution having an ethanol concentration of 10 wt % to prepare an impregnation liquid having a total volume of 25 ml. The above impregnation liquid was added to the vacuum impregnation bottle containing cerium-modified alumina carrier D and mixed evenly to perform an equal volume impregnation on cerium-modified alumina carrier D. After impregnation for 120 minutes, the carrier was taken out and dried in an oven at 110 C. for 3 h, then calcined at 500 C. for 6 h in a muffle furnace.

[0079] In the obtained 2# catalyst, based on the weight of alumina, the content of each component was as follows: nickel 12.0 wt %, iron 1.5 wt %, manganese 2.0 wt %, and cerium 1.5 wt %.

Example 7: Preparation of 2# Catalyst

[0080] 15 g (about 50 ml) of the spherical alumina carrier from Shandong Zibo Wufeng Aluminum Magnesium Co., Ltd. was placed in a vacuum impregnation bottle for vacuum pretreatment. The vacuum pretreatment time was 30 min and the vacuum degree was 96.0 KPa. At the same time, 12 ml of nickel nitrate aqueous solution containing 0.15 g/ml of nickel, 2.3 ml of iron nitrate aqueous solution containing 0.10 g/ml of iron, 3.0 ml of manganese nitrate aqueous solution containing 0.10 g/ml of manganese, and 1.5 ml of cerium nitrate aqueous solution containing 0.15 g/ml of cerium were added to an ethanol aqueous solution having an ethanol concentration of 10 wt % to prepare an impregnation liquid having a total volume of 25 ml. The above impregnation liquid was added to the vacuum impregnation bottle containing the spherical alumina carrier and mixed evenly to perform an equal volume impregnation on the spherical alumina carrier. After impregnation for 120 min, the carrier was taken out and placed in an oven at 110 C. for 3 h, and then calcined in a muffle furnace was at 500 C. for 6 h.

[0081] In the obtained 2# catalyst, based on the weight of alumina, the content of each component was as follows: nickel 12.0 wt %, iron 1.5 wt %, manganese 2.0 wt %, and cerium 1.5 wt %.

[0082] Comparison of the Effects of the Catalysts of Second Group with the Catalysts of Prior Art:

[0083] Reverse osmosis concentrated water (COD 224 ppm, pH=7.2) re-concentrated by a reverse osmosis device was taken, and a sodium hypochlorite solution having a concentration of 10 wt % was added to the reverse osmosis concentrated water, and the addition amount was 5.2 ml of the above sodium hypochlorite solution per liter of the reverse osmosis concentrated water. The mixed solution was divided into four parts and processed through 1# reactor, 2# reactor, 3# reactor and 4# reactor respectively, wherein 1# reactor was loaded with 2# catalyst prepared in Example 7, 2# reactor was loaded with 2# catalyst prepared in Example 7, #3 reactor was loaded with the catalyst of Example 1 in CN 101844828 B, and #4 reactor was loaded with the catalyst of Example 1 in CN 104549316 A. The dosage of each catalyst was 2 L, the residence time in the reactors was 1 h, the amount of influent water was 2 L/h, and the treatment temperature was 20 C.

[0084] The reverse osmosis concentrated water (COD: 224 ppm, pH=7.2) re-concentrated by the reverse osmosis device was taken, then chlor-alkali industrial wastewater was added thereto (the chlor-alkali industrial wastewater contained the following components: NaClO with a content of 5.8 wt %; NaOH with a content of 1.1 wt %; Na.sub.2CO.sub.3, content was 7.3 wt %; NaCl, the content was 1.2 wt %), and the addition amount was 9.0 ml of the above chlor-alkali industrial wastewater per liter of the reverse osmosis concentrated water. The mixed solution was divided into four parts and processed through 5# reactor, 6# reactor, 7# reactor and 8# reactor respectively, wherein 5# reactor was loaded with 2# catalyst prepared in Example 7, 6# reactor was loaded with 2# catalyst prepared in Example 7, 7# reactor was loaded with the catalyst of Example 1 in CN 101844828 B, and 8# reactor was loaded with the catalyst of Example 1 in CN 104549316 A. The dosage of each catalyst was 2 L, the residence time in the reactors was 1 h, the amount of influent water was 2 L/h, and the treatment temperature was 20 C.

[0085] The comparison results of the effects of the catalysts of the second group were shown in Table 2.

TABLE-US-00002 TABLE 2 Comparison results of the catalysts of the second group Metal COD COD loss of of COD amount the the re- in the influent effluent moval effluent water water rate water Reactor Catalyst Oxidant (ppm) (ppm) (%) (mg/L) 1# 2# (two-step sodium 224 43 81 0.2 method) hypo- 2# 2'# (one step chlorite 224 60 73 0.5 method) solution 3# CN 101844828 224 141 37 0.4 B 4# CN 104549316 224 94 58 0.3 A 5# 2# (two-step chlor- 224 35 84 0.2 method) alkali 6# 2'# (one step industrial 224 54 76 0.4 method) waste- 7# CN 101844828 water 224 135 40 0.3 B 8# CN 104549316 224 90 60 0.3 A

Example 8: Preparation of 3# Catalyst

[0086] 15 g (about 35 ml) of cerium-modified alumina carrier B obtained in Example 3 was placed in a vacuum impregnation bottle for vacuum pretreatment. The vacuum pretreatment time was 30 min, and the vacuum degree was 97.0 KPa. At the same time, 6.0 ml of nickel nitrate aqueous solution containing 0.15 g/ml of nickel, 7.5 ml of iron nitrate aqueous solution containing 0.10 g/ml of iron, 2.5 ml of manganese nitrate aqueous solution containing 0.18 g/ml of manganese, and 3.9 ml of the cerium nitrate aqueous solution containing 0.05 g/ml of cerium were added to deionized water to prepare an impregnation liquid having a total volume of 21 ml. The above impregnation liquid was added to the vacuum impregnation bottle containing cerium-modified alumina carrier B and mixed evenly to perform an equal volume impregnation on cerium-modified alumina carrier B. After impregnation for 90 minutes, the carrier was taken out and placed in an oven at 130 C. to dry for 2 h, then calcined at 550 C. for 5 h in a muffle furnace.

[0087] In the obtained #3 catalyst, based on the weight of the alumina, the content of each component was as follows: nickel 6.0 wt %, iron 5.0 wt %, manganese 3.0 wt %, and cerium 2.8 wt %.

Example 8: Preparation of 3# Catalyst

[0088] 15 g (about 35 ml) of the spherical alumina carrier prepared in Example 1 was placed in a vacuum impregnation bottle for vacuum pretreatment. The vacuum pretreatment time was 30 min, and the vacuum degree was 97.0 KPa. At the same time, 6 ml of nickel nitrate aqueous solution containing 0.15 g/ml of nickel, 7.5 ml of iron nitrate aqueous solution containing 0.10 g/ml of iron, 2.5 ml of manganese nitrate aqueous solution containing 0.18 g/ml of manganese, and 2.8 ml of cerium nitrate aqueous solution containing 0.15 g/ml of cerium were added to deionized water to prepare an impregnation liquid having a total volume of 21 ml. The above impregnation liquid was added to the vacuum impregnation bottle containing the spherical alumina carrier and mixed evenly to perform an equal volume impregnation on the spherical alumina carrier. After impregnation for 90 min, the carrier was taken out and placed in an oven at 130 C. for 2 h, then calcined in a muffle furnace was at 550 C. for 5 h.

[0089] In the obtained 3# catalyst, based on the weight of alumina, the content of each component was as follows: nickel 6.0 wt %, iron 5.0 wt %, manganese 3.0 wt %, and cerium 2.8 wt %.

[0090] Comparison of the Effects of the Catalysts of the Third Group with the Catalysts of the Prior Art:

[0091] Reverse osmosis concentrated water (COD: 183 ppm, pH=7.6) re-concentrated by a reverse osmosis device was taken, then a sodium hypochlorite solution having a concentration of 10 wt % was added thereto, and the addition amount was 4.3 ml of the sodium hypochlorite solution per liter of the reverse osmosis concentrated water. The mixed solution was divided into four parts and processed through 1# reactor, 2# reactor, 3# reactor and 4# reactor respectively, wherein 1# reactor was loaded with 3# catalyst prepared in Example 8, 2# reactor was loaded with 3# catalyst prepared in Example 8, and 3# reactor was loaded with the catalyst of Example 1 in CN 101844828 B, and the 4# reactor was loaded with the catalyst of Example 1 in CN 104549316 A. The dosage of each catalyst was 2 L, the residence time in the reactors was 1 h, the amount of influent water was 2 L/h, and the treatment temperature was 50 C.

[0092] The reverse osmosis concentrated water (COD was 183 ppm, pH=7.6) re-concentrated by the reverse osmosis device, then the chlor-alkali industrial wastewater was added thereto (the chlor-alkali industrial wastewater contained the following components: NaClO with a content of 4.6 wt %; NaOH with a content of 1.3 wt %; Na.sub.2CO.sub.3 with a content of 6.5 wt %; NaCl with a content of 1.0 wt %), and the addition amount was 9.3 ml of the above chlor-alkali industrial wastewater per liter of the reverse osmosis concentrated water. The mixed solution was divided into four parts and processed through 5# reactor, 6# reactor, 7# reactor and 8# reactor, wherein 5# reactor was loaded with 3# catalyst prepared in Example 8, 6# reactor was loaded with 3# catalyst prepared in Example 8, 7# reactor was loaded with the catalyst of Example 1 in CN 101844828 B, and 8# reactor was loaded with the catalyst of Example 1 in CN 104549316 A. The dosage of each catalyst was 2 L, the residence time in the reactors was 1 h, the amount of influent water was 2 L/h, and the treatment temperature was 50 C.

[0093] The comparison results of the effects of the catalysts of the third group are shown in Table 3.

TABLE-US-00003 TABLE 3 Comparison results of the catalysts of the third group Metal COD COD Re- loss of of moval amount the the rate in the influent effluent of effluent water water COD water Reactor Catalyst Oxidant (ppm) (ppm) (%) (mg/L) 1# 3# (two-step Sodium 183 27 85 0.1 method) hypo- 2# 3'# (one step chlorite 183 53 71 0.4 method) solution 3# CN 101844828 183 106 42 0.4 B 4# CN 104549316 183 84 54 0.2 A 5# 3# (two-step chlor- 183 31 83 0.2 method) alkali 6# 3'# (one step industrial 183 54 70 0.5 method) waste- 7# CN 101844828 water 183 112 39 0.4 B 8# CN 104549316 183 91 50 0.1 A

Example 9: Preparation of 4# Catalyst

[0094] 15 g (about 30 ml) of cerium-modified alumina carrier C obtained in Example 4 was placed in a vacuum impregnation bottle for vacuum pretreatment. The vacuum pretreatment time was 30 min, and the vacuum degree was 98.0 KPa. At the same time, 16.0 ml of nickel nitrate aqueous solution containing 0.15 g/ml of nickel, 0.9 ml of iron nitrate aqueous solution containing 0.10 g/ml of iron, 0.8 ml of manganese nitrate aqueous solution containing 0.18 g/ml of manganese, and 1.0 ml of cerium nitrate aqueous solution containing 0.15 g/ml of cerium were added to deionized water to prepare an impregnation liquid having a total volume of 21 ml. The above impregnation liquid was added to the vacuum impregnation bottle containing cerium-modified alumina carrier C and mixed evenly to perform an equal volume impregnation on the cerium-modified alumina carrier C. After impregnation for 60 minutes, the carrier was taken out and placed in an oven at 130 C. to dry for 2 h, then calcined in a muffle furnace at 480 C. for 6 h.

[0095] In the obtained #4 catalyst, based on the weight of the alumina, the content of each component was as follows: nickel 16.0 wt %, iron 0.6 wt %, manganese 1.0 wt %, and cerium 3.0 wt %.

Example 9: Preparation of 3# Catalyst

[0096] 15 g (about 30 ml) of the spherical alumina carrier from Shandong Yantai Baichuan Huitong Technology Co., Ltd. was taken and placed in a vacuum impregnation bottle for vacuum pretreatment. The vacuum pretreatment time was 30 min and the vacuum degree was 98.0 KPa. At the same time, 16.0 ml of nickel nitrate aqueous solution containing 0.15 g/ml of nickel, 0.9 ml of iron nitrate aqueous solution containing 0.10 g/ml of iron, 0.8 ml of manganese nitrate aqueous solution containing 0.18 g/ml of manganese, and 3.0 ml of cerium nitrate aqueous solution containing 0.15 g/ml of cerium were added to deionized water to prepare an impregnation liquid having a total volume of 21 ml. The above impregnation liquid was added to the vacuum impregnation bottle containing the spherical alumina carrier and mixed evenly to perform an equal volume impregnation on the spherical alumina carrier. After impregnation for 60 min, the carrier was taken out and placed in an oven at 130 C. for 2 h, and then calcined in a muffle furnace at 480 C. for 6 h.

[0097] In the obtained 3-1# catalyst, based on the weight of alumina, the content of each component was as follows: nickel 16.0 wt %, iron 0.6 wt %, manganese 1.0 wt %, and cerium 3.0 wt %.

[0098] Comparison of the Effects of the Catalysts of the Fourth Group with the Catalysts of the Prior Art:

[0099] Reverse osmosis concentrated water (COD 240 ppm, pH=7.9) re-concentrated by a reverse osmosis device was taken, then a sodium hypochlorite solution having a concentration of 3.0 wt % was added thereto, and the addition amount was 18.7 ml of the sodium hypochlorite solution per liter of the reverse osmosis concentrated water. The mixed solution was divided into four parts and processed through 1# reactor, 2# reactor, 3# reactor and 4# reactor, wherein 1# reactor was loaded with 4# catalyst prepared in Example 9, 2# reactor was loaded with 4# catalyst prepared in Example 9, 3# reactor was loaded with the catalyst of Example 1 in CN 101844828 B, and 4# reactor was loaded with the catalyst of Example 1 in CN 104549316 A. The dosage of each catalyst was 2 L, the residence time in the reactors was 1 h, the amount of influent water was 2 L/h, and the treatment temperature was 40 C.

[0100] The reverse osmosis concentrated water (COD 240 ppm, pH=7.9) re-concentrated by the reverse osmosis device was taken, and chlor-alkali industrial wastewater was added thereto (the chlor-alkali industrial wastewater contained the following components: NaClO with a content of 3.6 wt %; NaOH with a content of 1.0 wt %; Na.sub.2CO.sub.3, with a content of 7.3 wt %; NaCl with a content of 1.6 wt %), and the addition amount was 15.6 ml of the above chlor-alkali industrial wastewater per liter of the reverse osmosis concentrated water. The mixed solution was divided into four parts and processed through 5# reactor, 6# reactor, 7# reactor and 8# reactor, wherein 5# reactor was loaded with 4# catalyst prepared in Example 9, 6# reactor was loaded with 4# catalyst prepared in Example 9, and 7# reactor was loaded with the catalyst of Example 1 in CN 101844828 B, and 8# reactor was loaded with the catalyst of Example 1 in CN 104549316 A. The dosage of each catalyst was 2 L, the residence time in the reactors was 1 h, the amount of influent water was 2 L/h, and the treatment temperature was 40 C.

[0101] The comparison results of the effects of the catalysts of the fourth group are shown in Table 4.

TABLE-US-00004 TABLE 4 Comparison results of the catalysts of the fourth group Metal COD COD Re- loss of of moval amount the the rate in the influent effluent of effluent water water COD water Reactor Catalyst Oxidant (ppm) (ppm) (%) (mg/L) 1# 4# (two-step sodium 240 47 80 0.1 method) hypo- 2# 4'# (one step chlorite 240 70 71 0.5 method) solution 3# CN 101844828 240 130 46 0.3 B 4# CN 104549316 240 96 60 0.1 A 5# 4# (two-step chlor- 240 36 85 0.1 method) alkali 6# 4'# (one step industrial 240 62 74 0.3 method)) waste- 7# CN 101844828 water 240 122 49 0.4 B 8# CN 104549316 240 89 63 0.2 A

[0102] Base on the comparison results of the effects of the catalysts of the above four groups, comparing with the catalysts in the prior art, the catalysts of the present invention can effectively catalyze the oxidation of sodium hypochlorite, thereby effectively degrade the refractory organic pollutants in the organic wastewater. The treatment effect on the organic wastewater is good. The removal rate of COD is high, and the amount of metal loss in the effluent water is small. Among the catalysts with same components and contents of each component, compared with the carrier which is a simple spherical alumina carrier, the carrier which is a cerium modified alumina carrier has a better treatment effect on the organic wastewater, higher the removal rate of COD, and small metal loss in the effluent water, which fully demonstrates that the cerium in the cerium-modified alumina carrier can provide an anchoring effect and dispersing effect, prevent the loss of active metal components, and improve the treatment effect on organic wastewater. Similarly, the catalyst of the present invention can effectively catalyze the oxidation of sodium hypochlorite in industrial wastewater containing sodium hypochlorite (such as chlor-alkali industrial wastewater), and then treat the organic wastewater to achieve the purpose of treating waste by waste and saving resources.