METHOD FOR PREPARING AMORPHOUS SILICA-ALUMINA ENCAPSULATED METAL OXIDE CATALYST AND APPLICATION THEREOF

Abstract

A field of environmental protection and discloses a method for preparing an amorphous silica-alumina encapsulated metal oxide catalyst and application thereof. The catalyst is prepared by filling silica-alumina precursors in tunnels of a monometallic or bimetallic complex and then performing heat treatment. The catalyst has the advantages that acidic sites and oxygen vacancies are highly dispersed, the pore size range is large and the mass transfer efficiency is high, improves the efficiency of a cracking-oxidation tandem reaction, and achieves full purification of carbon/nitrogen pollutants in landfill leachate. The COD removal rate of the landfill leachate reaches 98.3% or above, and the ammonia nitrogen removal rate thereof reaches 98.0% or above. The COD concentration of oxypyrolysis purified effluent is less than 98.7 mg/L and the ammonia nitrogen concentration thereof is less than 24.9 mg/L.

Claims

1. A method for preparing an amorphous silica-alumina encapsulated metal oxide catalyst, comprising the following steps: placing a metal complex in a vacuum drying device, performing activation at a temperature of 80-120 C. and a vacuum degree of 15-25 Pa for 4-6 h, and then soaking the activated metal complex in a mixed solution of a silicon precursor, an aluminum precursor, an acidic chelating agent and a hydrolysis inhibitor for 3-4 h; and after washing the soaked sample with an alcohol solvent and drying the same to remove the solvent, performing heat treatment on the obtained solid at a high temperature of 500-800 C. for 4-6 h to remove organic components to obtain an MO.sub.x@SiO.sub.2Al2O3 bi-functional oxypyrolysis catalyst with highly dispersed acidic sites and oxygen vacancies and a rich tunnel structure.

2. The method for preparing an amorphous silica-alumina encapsulated metal oxide catalyst according to claim 1, wherein the metal oxide MO.sub.x is one or two of Fe2O3, Co3O4, Cr2O3, CeO2, V2O5, Mn2O3 and CuO.

3. The method for preparing an amorphous silica-alumina encapsulated metal oxide catalyst according to claim 1, wherein the metal complex is one of MIL-101, MIL-100, MIL-68, MOF-808 and PCN-222 crystal structures; the metal complex is one of Fe-MIL-101, Fe-MIL-100, Fe-MIL-68, Fe-MIL-100, Cr-MIL-101, Ce-MOF-808, V-MIL-101, V-MIL-68, Mn-MIL-100 and CuPCN-222; and the metal complex is one of Fe/Cu-MIL-101, Fe/Co-MIL-101, Fe/Mn-MIL-101, V/Cu-MIL-101, Cr/Cu-MIL-101, V/Cr-MIL-101, V/Mn-MIL-101, Fe/Cu-MIL-68, V/Cu-MIL-68, Ce/Cu-MOF-88, Ce/V-MOF-88, Ce/Mn-MOF-88, Ce/Mn-MIL-100, Fe/Cu-MIL-100 and Cu/MnPCN-222.

4. The method for preparing an amorphous silica-alumina encapsulated metal oxide catalyst according to claim 1, wherein the silicon precursor is one of tetramethoxysilane, tetraethyl orthosilicate and methyltrimethoxysilane; and the mass ratio of silicon precursor to metal complex is 9:1 to 11.8:1, and the silicon precursor is the tetramethoxysilane and the tetraethyl orthosilicate.

5. The method for preparing an amorphous silica-alumina encapsulated metal oxide catalyst according to claim 1, wherein the aluminum precursor is one of aluminum isopropoxide, aluminum tri-sec-butoxide, and aluminum di(sec-butoxide) acetoacetate; and the mass ratio of aluminum precursor to silicon precursor is 0.11:1 to 0.37:1.

6. The method for preparing an amorphous silica-alumina encapsulated metal oxide catalyst according to claim 1, wherein the acidic chelating agent is one of acetic acid and oxalic acid, the hydrolysis inhibitor is ethyl acetoacetate and alcohols, and the alcohols are isopropanol or sec-butanol; the mass ratio of ethyl acetoacetate to aluminum precursor is 0.1:1 to 0.3:1; and the mass ratio of alcohols to aluminum precursor is 1.6:1 to 4.7:1.

7. The method for preparing an amorphous silica-alumina encapsulated metal oxide catalyst according to claim 1, wherein the mass ratio of acidic chelating agent to aluminum precursor is 0.21:1 to 0.63:1; and the alcohol solvent is one or two of methanol, ethanol and sec-butanol.

8. The method for preparing an amorphous silica-alumina encapsulated metal oxide catalyst according to claim 1, wherein based on amorphous silica-alumina, the loading capacity of the metal oxide MO.sub.x is 20-35%; the acid content of the bi-functional catalyst is 2.3-4.5 mmol/g, and the hydrogen consumption of an oxidation active component is 8.5-17.5 mmol/g; and the pore volume of the bi-functional catalyst is 0.8 to 1.7 cm.sup.3/g, and the mesoporous pore sizes range from 2.2 nm to 18.5 nm.

9. An amorphous silica-alumina encapsulated metal oxide catalyst, wherein the catalyst is prepared by using the method according to claim 1.

10. An application of an amorphous silica-alumina encapsulated metal oxide catalyst prepared by the preparation method according to claim 1 to oxypyrolysis purification of landfill leachate, wherein further preferably, the catalyst converts carbon/nitrogen pollutants in the landfill leachate into carbon dioxide, water and nitrogen through aerobic cracking tandem reaction.

11. The application according to claim 10, wherein a catalytic reaction is conducted for the oxypyrolysis purification reaction of the landfill leachate in a circulating fluidized bed reactor; both the air and the landfill leachate are fed from the bottom of an oxypyrolysis reactor; the COD concentration of the landfill leachate is 1000-100000 mg/L, and the ammonia nitrogen concentration is 500-5000 mg/L; the reaction pressure is 0.1-0.2 MPa; the catalytic reaction temperature is 250-450 C., preferably 300-400 C.; the feed molar ratio of oxygen to landfill leachate is 0.1 to 5; and the space velocity is 0.5-3.5 h1.

Description

DETAILED DESCRIPTION

[0031] The present disclosure is further explained with the examples below.

Example 1

[0032] 30 mg of monometallic complex Fe-MIL-101 (Chemsoon Co., Ltd., MIL-101 (Fe)) was activated at 100 C. for 5 h in a vacuum device with a vacuum degree of 20 Pa. Then the activated monometallic complex was soaked in a mixed solution of 300 L (300 mg) of silicon precursor tetramethoxysilane, 20 L (20.9 mg) of acidic chelating agent acetic acid, 10 L (10.3 mg) of hydrolysis inhibitor ethyl acetoacetate and an aluminum precursor (0.099 g/150 L, 0.0495 g/150 L and 0.033 g/150 L of aluminum tri-sec-butoxide/sec-butanol). After soaking for 3 h, centrifugal washing was performed on samples three times with 10 mL of sec-butanol and 10 mL of methanol. Then vacuum drying was performed on the samples at 80 C. for 12 h to obtain the following samples: SiAl-1@MIL-101, SiAl-2@MIL-101 and SiAl-3@MIL-101.

[0033] The samples were placed in a tube furnace and heated at a heating rate of 5 C./min in an air atmosphere to 600 C. for 2 h, and the prepared bi-functional catalysts were Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-1, Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-2 and Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-3, respectively.

[0034] The prepared catalysts Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-1, Fe.sub.2O.sub.3SiO.sub.2Al.sub.2O.sub.3-2 and Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-3 were determined by ammonia temperature-programmed desorption for the acid contents, which were 4.5 mmol/g, 3.2 mmol/g and 2.9 mmol/g, respectively. The catalysts Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-1, Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-2 and Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-3 were determined by hydrogen temperature-programmed reduction for hydrogen consumption, which was 17.5 mmol/g, 14.8 mmol/g and 11.5 mmol/g, respectively. The pore volumes of the catalysts were 1.7 cm.sup.3/g, 1.3 cm.sup.3/g, and 0.8 cm.sup.3/g, respectively, and corresponding pore sizes ranged from 2.2 nm to 18.5 mu.

[0035] The performance test of the catalyst was conducted in a three-stage temperature controlled fluidized bed steel reactor, with a COD concentration of landfill leachate of 8327 mg/L and an ammonia nitrogen concentration of 1263 mg/L. Oxypyrolysis purification of landfill leachate was performed with the bi-functional catalyst with different silica-alumina mass ratios. The catalyst was loaded into an oxypyrolysis reactor, and the landfill leachate was added thereinto through a peristaltic pump. The reaction conditions were as follows: the reaction pressure (gage pressure) was 0.1 MPa, the reaction temperature was 350 C., the feed molar ratio of oxygen to landfill leachate was 2.3, and the space velocity was 1.5.Math.h.sup.1. The COD removal rate, the COD concentration, the ammonia nitrogen removal rate, the ammonia nitrogen concentration and the non-methane hydrocarbon concentration of the landfill leachate are listed in Table 1.

TABLE-US-00001 TABLE 1 Oxypyrolysis purification results of landfill leachate by Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3with different silica-alumina ratios COD Ammonia Ammonia removal COD nitrogen nitrogen Non-methane rate concentration removal rate concentration hydrocarbon Catalyst (%) (mg/L) (%) (mg/L) (mg/m.sup.3) Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-1 99.9 8.3 99.5 6.9 12.8 Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-2 99.4 53.6 98.8 14.7 37.3 Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-3 99.0 83.1 98.0 24.9 51.3

[0036] Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3 catalyst in which the mass ratio of aluminum precursor to silicon precursor was 33% had the highest COD and ammonia nitrogen removal rates of the landfill leachate, and the COD and ammonia nitrogen concentrations of purified effluent were 8.3 mg/L and 6.9 mg/L, respectively.

Example 2

[0037] According to the conditions in Example 1, the activated Fe-MIL-101 was immersed in a mixed solution of a different silicon precursor, aluminum precursor and part of hydrolysis inhibitor, in the following three cases:

[0038] case 1: 300 L (300 mg) silicon precursor tetramethoxysilane and the aluminum precursor aluminum isopropoxide/sec-butanol (0.099 g of aluminum isopropoxide was dispersed in 150 L sec-butanol);

[0039] case 2: 300 L (354 mg) silicon precursor tetraethyl orthosilicate and the aluminum precursor aluminum isopropoxide/isopropanol (0.099 g of aluminum isopropoxide was dispersed in 150 L isopropanol); and

[0040] case 3: 300 L. (270 mg) silicon precursor methyltrimethoxysilane and aluminum precursor aluminum di(sec-butoxide) acetoacetate/sec butanol (0.099 g of aluminum di(sec-butoxide) acetoacetate was dispersed in 150 L sec-butanol).

[0041] Other conditions were the same as those in Example 1, and the prepared catalysts were as follows: Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-4, Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O-5 and Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-6.

[0042] The prepared catalysts Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-4, Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-5 and Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-6 were determined by ammonia temperature-programmed desorption for the acid contents, which were 4.5 mmol/g. 4.1 mmol/g and 3.7 mmol/g, respectively. The catalysts Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-4, Fe.sub.2O.sub.3@SiO.sub.2O.sub.3-5 and Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-6 were determined by hydrogen temperature-programmed reduction for hydrogen consumption, which was 16.9 mmol/g, 15.6 mmol/g and 13.5 mmol/g, respectively. The pore volumes of the catalysts were 1.7 cm.sup.3/g, 1.5 cm.sup.3/g, and 1.5 cm.sup.3/g, respectively, and corresponding pore sizes ranged from 2.2 nm to 18.5 nm.

[0043] The performance test of the catalyst was conducted according to Example 1. The selected landfill leachate had a COD concentration of 51422 mg/L and an ammonia nitrogen concentration of 964 mg/L. The COD removal rate, the COD concentration, the ammonia nitrogen removal rate, the ammonia nitrogen concentration and the non-methane hydrocarbon concentration of the landfill leachate are listed in Table 2.

TABLE-US-00002 TABLE 2 Oxypyrolysis purification results of landfill leachate by Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3with different silica-alumina precursor COD Ammonia Ammonia removal COD nitrogen nitrogen Non-methane rate concentration removal rate concentration hydrocarbon Catalyst (%) (mg/L) (%) (mg/L) (mg/m.sup.3) Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-4 99.9 18.3 99.2 7.4 14.2 Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-5 99.8 93.2 98.1 18.5 48.3 Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-6 99.8 98.7 98.2 17.4 32.6

[0044] The catalysts prepared with tetramethoxysilane as the silicon precursor and the aluminum tri-sec-butoxide as the silica-alumina precursor had the highest COD and ammonia nitrogen removal rates of the landfill leachate, which were 99.9% and 99.2%, respectively.

Example 3

[0045] The monometallic complex was V-MIL-101(MIL-101(V)).

[0046] The activation conditions had the following specific three cases:

[0047] case 1: activation at 100 C. for 6 h in a vacuum device of 15 Pa;

[0048] case 2: activation at 100 C. for 6 h in a vacuum device of 20 Pa; and

[0049] case 3: activation at 100 C. for 6 h in a vacuum device of 25 Pa.

[0050] Other conditions were the same as those in Example 1.

[0051] The prepared bi-functional catalysts were as follows: V.sub.2O.sub.5@SiO.sub.2Al.sub.2O.sub.3-15, V.sub.2O.sub.5@SiO.sub.2Al.sub.2O.sub.3-20 and V.sub.2O.sub.5@SiO.sub.2Al.sub.2O.sub.3-25. The performance test of the catalyst was conducted according to Example 1. The COD removal rate, the COD concentration, the ammonia nitrogen removal rate, the ammonia nitrogen concentration and the non-methane hydrocarbon concentration of the landfill leachate are listed in Table 3.

TABLE-US-00003 TABLE 3 Oxypyrolysis purification results of landfill leachate by V.sub.2O.sub.5@SiO.sub.2Al.sub.2O.sub.3 activated at different vacuum degrees Ammonia Ammonia COD COD nitrogen nitrogen removal concen- removal concen- Non-methane Vacuum rate tration rate tration hydrocarbon degree (%) (mg/L) (%) (mg/L) (mg/m.sup.3) 15 99.3 58.2 98.6 17.6 36.5 20 99.9 7.8 99.4 7.8 10.4 25 99.1 75.8 98.3 21.9 51.1

Example 4

[0052] Other conditions were the same as those in Example 1, except that the dosages of the acidic chelating agent were replaced with 30 L (31.4 mg) and 40 L (41.8 mg), respectively.

[0053] The prepared hi-functional catalysts were Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-30 (the dosage of the acidic chelating agent was 30 L) and Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-40 (the dosage of the acidic chelating agent was 40 L). The acid contents of the prepared catalysts were 3.1 mmol/g and 2.3 mmol/g, respectively. The hydrogen consumption of the catalyst was 11.6 mmol/g and 8.5 mmol/g. The pore volumes of the catalysts were 1.3 cm.sup.3/g and 0.8 cm/g, respectively, and the corresponding pore sizes ranged from 3.6 nm to 18.5 nm. The performance test of the catalyst was conducted according to Example 1. The selected landfill leachate had a COD concentration of 5186 mg/L and an ammonia nitrogen concentration of 2045 mg/L. The COD removal rate, the COD concentration, the ammonia nitrogen removal rate, the ammonia nitrogen concentration and the non-methane hydrocarbon concentration of the landfill leachate are listed in Table 4.

TABLE-US-00004 TABLE 4 Oxypyrolysis purification results of landfill leachate by Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3with different addition amounts of acidic chelating agent COD Ammonia Ammonia removal COD nitrogen nitrogen Non-methane rate concentration removal rate concentration hydrocarbon Catalyst (%) (mg/L) (%) (mg/L) (mg/m.sup.3) Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-30 99.0 49.9 99.4 12.3 28.2 Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-40 98.3 88.1 98.9 22.7 51.3

[0054] When the acidic chelating agent was 30 L, the hi-functional catalyst had the highest purification efficiency for organic pollutants and ammonia nitrogen in the landfill leachate. The COD and ammonia nitrogen concentrations of the oxypyrolysis purified effluent were 49.9 mg/L and 12.3 mg/L, respectively. The non-methane hydrocarbon was 28.2 mg/m.sup.3.

Example 5

[0055] Except for the replacement of the monometallic complex Fe-MIL-101 with monometallic complexes Fe-MIL-100(MIL-100(Fe)), Fe-MIL-68(MIL-68(Fe)), Cr-MIL-101(MIL-101(Cr)), Ce-MOF-808(MOF-808(Zr)), V-MIL-101, Mn-MIL-100 and CuPCN-222(PCN-222(Cu)), the rest conditions were the same as those in Example 1. The prepared bi-functional catalysts were Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-7, Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-8, Cr.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3, CeO.sub.2@SiO.sub.2Al.sub.2O.sub.3, V.sub.2O.sub.5@SiO.sub.2Al.sub.2O.sub.3, Mn.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3 and CuO@SiO.sub.2Al.sub.2O.sub.3, respectively.

[0056] The COD concentration of the landfill leachate was 8327 mg/L, and the ammonia nitrogen concentration was 1263 mg/L. The performance test of the catalyst was conducted according to Example 1. The COD removal rate, the COD concentration, the ammonia nitrogen removal rate, the ammonia nitrogen concentration and the non-methane hydrocarbon concentration of the landfill leachate are listed in Table 5.

TABLE-US-00005 TABLE 5 Oxypyrolysis purification results of landfill leachate by different monometallic encapsulated catalysts COD Ammonia Ammonia removal COD nitrogen nitrogen Non-methane rate concentration removal rate concentration hydrocarbon Catalyst (%) (mg/L) (%) (mg/L) (mg/m.sup.3) Fe.sub.2O.sub.3@SiO.sub.2-Al.sub.2O.sub.3-7 99.1 74.9 98.9 14.1 21.7 Fe.sub.2O.sub.3@SiO.sub.2-Al.sub.2O.sub.3-8 98.8 96.4 98.1 24.5 35.2 Cr.sub.2O.sub.3@SiO.sub.2-Al.sub.2O.sub.3 99.9 9.1 99.2 10.1 13.7 CeO.sub.2@SiO.sub.2-Al.sub.2O.sub.3 99.9 11.7 98.7 16.4 14.9 V.sub.2O.sub.5@SiO.sub.2-Al.sub.2O.sub.3 99.8 14.6 98.8 15.2 15.3 Mn.sub.2O.sub.3@SiO.sub.2-Al.sub.2O.sub.3 99.8 16.6 98.1 23.5 22.1 CuO@SiO.sub.2-Al.sub.2O.sub.3 99.7 22.1 99.4 7.6 15.3

[0057] The selected monometallic complex encapsulated amorphous silica-alumina catalyst had a COD removal rate of 98.8% or above and an ammonia nitrogen removal rate of 98.1% or above for the landfill leachate.

Example 6

[0058] Except for the replacement of the monometallic complex Fe-MIL-101 with the bimetallic complexes Fe/Cu-MIL-101, Fe/Co-MIL-101, Fe/Mn-MIL-101, V/Cu-MIL-101, Cr/Cu-MIL-101, V/Cr-MIL-101, V/Mn-MIL-101, Fe/Cu-MIL-68, V/Cu-MIL-68, Ce/Cu-MOF-808, Ce/V-MOF-808, Ce/Mn-MOF-808, Ce/Mn-MIL-100, Fe/Cu-MIL-100 and Cu/MnPCN-222, other conditions were the same as those in Example 1.

[0059] Method for preparing MIL-101 type bimetallic complex: 1.66 g of terephthalic acid, metal 1 (see table below for type and dosage), and metal 2 (see table below for type and dosage) were dissolved in 150 mL of N, N-dimethylformamide solution, and reacted at 110 C. for 30 h in a constant-temperature oven. After the reaction, the bimetallic complex was filtered and washed with 300 mL of N, N-dimethylfomamide, and 300 mL of acetone, and then vacuum drying was performed at 80 C. to obtain a sample Fe/Cu-MIL-101.

[0060] Components and Dosages of MIL-101 Type Bimetallic Complex

TABLE-US-00006 MIL-101 type bimetallic complex Metal 1 (dosage, g) Metal 2 (dosage, g) Fe/Cu-MIL-101 Ferric chloride Copper nitrate hexahydrate (4.5 g) trihydrate (2 g) Fe/Co-MIL-101 Ferric chloride Cobalt nitrate hexahydrate (4.5 g) hexahydrate (2 g) Fe/Mn-MIL-101 Ferric chloride Manganese chloride hexahydrate (4.5 g) tetrahydrate (2 g) V/Cu-MIL-101 Vanadium Copper nitrate chloride (4.5 g) trihydrate (2 g) Cr/Cu-MIL-101 Chromium nitrate Copper nitrate nonahydrate (4.5 g) trihydrate (2 g) V/Cr-MIL-101 Vanadium Chromium nitrate chloride (4.5 g) nonahydrate (2 g) V/Mn-MIL-101 Vanadium Manganese chloride chloride (4.5 g) tetrahydrate (2 g)

[0061] Method for preparing MIL-68 type bimetallic complex: except for changing the reaction temperature to 180 C., other conditions were the same as those of the method for preparing the MIL-101 type bimetallic complex.

[0062] Components and Dosages of MIL-68 Type Bimetallic Complex

TABLE-US-00007 MIL-68 type bimetallic complex Metal 1 (dosage, g) Metal 2 (dosage, g) Fe/Cu-MIL-68 Ferric chloride Copper nitrate hexahydrate (4.5 g) trihydrate (2 g) V/Cu-MIL-68 Vanadium Copper nitrate chloride (4.5 g) trihydrate (2 g)

[0063] Method for preparing MOF-808 type bimetallic complex: except for changing the terephthalic acid to trimesic acid and reaction time to 2 h, other conditions were the same as those of the method for preparing the MIL-101 type bimetallic complex.

[0064] Components and Dosages of MOF-808 Type Bimetallic Complex

TABLE-US-00008 MOF-808 type bimetallic complex Metal 1 (dosage, g) Metal 2 (dosage, g) Ce/Cu-MOF-808 Cerium nitrate Copper nitrate hexahydrate (4.5 g) trihydrate (2 g) Ce/V-MOF-808 Cerium nitrate Vanadium hexahydrate (4.5 g) chloride (2 g) Ce/Mn-MOF-808 Cerium nitrate Manganese chloride hexahydrate (4.5 g) tetrahydrate (2 g)

[0065] Method for preparing MIL-100 type bimetallic complex: except for changing the terephthalic acid to trimesic acid, other conditions were the same as those of the method for preparing the MIL-101 type bimetallic complex.

[0066] Components and Dosages of MIL-100 Type Bimetallic Complex

TABLE-US-00009 MIL-100 type bimetallic complex Metal 1 (dosage, g) Metal 2 (dosage, g) Ce/Mn-MIL-100 Cerium nitrate Manganese chloride hexahydrate (4.5 g) tetrahydrate (2 g) Fe/Cu-MIL-100 Ferric chloride Copper nitrate hexahydrate (4.5 g) trihydrate (2 g)

[0067] Method for preparing PCN-222 type bimetallic complex: except for changing the terephthalic acid to porphyrin and the reaction temperature to 100 C., other conditions were the same as those of the method for preparing the MIL-101 type bimetallic complex.

[0068] Components and Dosages of Cu/MnPCN-222

TABLE-US-00010 Metal 1 (dosage, g) Metal 2 (dosage, g) Cu/Mn-PCN-222 Copper nitrate Manganese chloride trihydrate (4.5 g) tetrahydrate (2 g)

[0069] Thus, the bi-functional catalysts prepared were Fe.sub.2O.sub.3CuO@SiO.sub.2Al.sub.2O.sub.3-1, Fe.sub.2O.sub.3Co.sub.3O.sub.4@SiO.sub.2Al.sub.2O.sub.3, Fe.sub.2O.sub.3Mn.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3, V.sub.2O.sub.5CuO@SiO.sub.2Al.sub.2O.sub.3-1, Cr.sub.2O.sub.3CuO@SiO.sub.2Al.sub.2O.sub.3, V.sub.2O.sub.5Cr.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3, V.sub.2O.sub.5Mn.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3, Fe.sub.2O.sub.3CuO@SiO.sub.2Al.sub.2O.sub.3-2, V.sub.2O.sub.5CuO@SiO.sub.2Al.sub.2O.sub.3-2, CeO.sub.2CuO@SiO.sub.2Al.sub.2O.sub.3, CeO.sub.2V.sub.2O.sub.5@SiO.sub.2Al.sub.2O.sub.3, CeO.sub.2Mn.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3, Fe.sub.2O.sub.3CuO@SiO.sub.2Al.sub.2O.sub.3-3 and CuOMn.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3, respectively.

[0070] The COD concentration of the landfill leachate was 8327 mg/L, and the ammonia nitrogen concentration was 1263 mg/L. The performance test of the catalyst was conducted according to Example 1. The COD removal rate, the COD concentration, the ammonia nitrogen removal rate, the ammonia nitrogen concentration and the non-methane hydrocarbon concentration of the landfill leachate are listed in Table 6.

TABLE-US-00011 TABLE 6 Oxypyrolysis purification results of landfill leachate by different bimetallic encapsulated catalysts COD Ammonia Ammonia removal COD nitrogen nitrogen Non-methane rate concentration removal rate concentration hydrocarbon Catalyst (%) (mg/L) (%) (mg/L) (mg/m.sup.3) Fe.sub.2O.sub.3CuO@SiO.sub.2Al.sub.2O.sub.3-1 99.9 4.6 99.7 3.8 10.6 Fe.sub.2O.sub.3Co.sub.3O.sub.4@SiO.sub.2Al.sub.2O.sub.3 99.9 5.3 99.7 4.1 11.2 Fe.sub.2O.sub.3Mn.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3 99.9 6.8 99.7 4.3 10.5 V.sub.2O.sub.5CuO@SiO.sub.2Al.sub.2O.sub.3-1 99.9 5.3 99.8 2.6 16.7 Cr.sub.2O.sub.3CuO@SiO.sub.2Al.sub.2O.sub.3 99.9 8.4 99.6 5.1 15.2 V.sub.2O.sub.5Cr.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3 99.9 7.6 99.6 4.9 13.5 V.sub.2O.sub.5Mn.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3 99.9 7.2 99.6 4.8 14.3 Fe.sub.2O.sub.3CuO@SiO.sub.2Al.sub.2O.sub.3-2 99.8 15.9 99.4 7.6 16.5 V.sub.2O.sub.5CuO@SiO.sub.2Al.sub.2O.sub.3-2 99.7 21.8 99.2 10.6 22.3 CeO.sub.2CuO@SiO.sub.2Al.sub.2O.sub.3 99.8 16.5 99.3 8.8 19.6 CeO.sub.2V.sub.2O.sub.5@SiO.sub.2Al.sub.2O.sub.3 99.8 17.9 99.3 8.9 18.8 CeO.sub.2Mn.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3 99.9 8.9 99.5 5.7 17.2 Fe.sub.2O.sub.3CuO@SiO.sub.2Al.sub.2O.sub.3-3 99.8 16.3 99.3 8.8 23.6 CuOMn.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3 99.8 15.3 99.3 9.1 12.1

[0071] The selected bimetallic complex encapsulated amorphous silica-alumina catalyst had a COD removal rate of 99.8% or above and an ammonia nitrogen removal rate of 98.1% or above for the landfill leachate.

Example 7

[0072] Landfill leachate generated in different landfill stages was selected, with an LL1: COD concentration of 8327 mg/L and an ammonia nitrogen concentration of 1263 mg/L, an LL-2: COD concentration of 42064 mg/L and an ammonia nitrogen concentration of 853 mg/L, and an LL-3: COD concentration of 78426 mg/L and an ammonia nitrogen concentration of 692 mg/L. The catalyst Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-1 prepared in Example 1 was employed, and the reaction conditions were as follows: the reaction pressure was 0.2 MPa, the reaction temperature was 3501 C., the feed molar ratio of oxygen to landfill leachate was 2.3, and the space velocity was 1.5 h.sup.1. The COD removal rate, the COD concentration, the ammonia nitrogen removal rate, the ammonia nitrogen concentration and the non-methane hydrocarbon concentration of the landfill leachate are listed in Table 7.

TABLE-US-00012 TABLE 7 Oxypyrolysis purification results of landfill leachate at different COD and ammonia nitrogen concentrations Ammonia Ammonia COD COD nitrogen nitrogen removal concen- removal concen- Non-methane rate tration rate tration hydrocarbon Catalyst (%) (mg/L) (%) (mg/L) (mg/m.sup.3) LL-1 99.9 8.7 99.4 7.3 12.6 LL-2 99.9 36.2 99.0 8.8 14.8 LL-3 99.9 93.8 99.2 5.4 13.0

[0073] The Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-1 bi-functional catalyst had a COD removal rate of 99.9% or above and an ammonia nitrogen removal rate of 99.0% or above for pollutants in the leachate.

Example 8

[0074] The oxypyrolysis treatment process of the landfill leachate was also influenced by the temperature of the oxypyrolysis reaction. The catalyst Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-1 prepared in Example 1 was employed. The landfill leachate sample in Example 1 was selected. The temperature of the oxypyrolysis reaction was changed according to the feed molar ratio of oxygen to landfill leachate and the space velocity in the catalyst performance test of Example 3. The COD removal rate, COD concentration and ammonia nitrogen removal rate, ammonia nitrogen concentration, and non-methane hydrocarbon concentration of the landfill leachate are listed in Table 8.

TABLE-US-00013 TABLE 8 Oxypyrolysis purification results of landfill leachate at different reaction temperatures Ammonia Ammonia COD COD nitrogen nitrogen removal concen- removal concen- Non-methane Reaction rate tration rate tration hydrocarbon temperature (%) (mg/L) (%) (mg/L) (mg/m.sup.3) 250 99.4 49.9 99.5 6.5 46.9 350 99.9 7.9 98.6 17.7 12.6 450 99.0 84.8 98.1 24.1 52.1

[0075] When the reaction temperature was 350 C., the removal efficiency of the organic pollutants in the landfill leachate reached the highest.

Example 9

[0076] The oxypyrolysis treatment process of the landfill leachate was also influenced by the feed molar ratio of oxygen to landfill leachate of the oxypyrolysis process. The catalyst Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-1 prepared in Example 1 was employed. The landfill leachate sample in Example 1 was selected. The feed molar ratio of oxygen to landfill leachate was changed according to the reaction temperature and space velocity in the performance test of the catalyst in Example 1. The COD removal rate, COD concentration and ammonia nitrogen removal rate, ammonia nitrogen concentration, and non-methane hydrocarbon concentration of the landfill leachate are listed in Table 9.

TABLE-US-00014 TABLE 9 Oxypyrolysis purification results of landfill leachate at different feed molar ratios of oxygen to landfill leachate Feed molar Ammonia Ammonia ratio of COD COD nitrogen nitrogen oxygen to removal concen- removal concen- Non-methane landfill rate tration rate tration hydrocarbon leachate (%) (mg/L) (%) (mg/L) (mg/m.sup.3) 0.1 99.2 66.6 98.4 20.2 46.5 2.3 99.9 7.4 99.4 7.7 12.4 5.0 99.1 75.8 98.3 21.9 51.1

[0077] When the feed molar ratio of oxygen to landfill leachate was 2.3, the purification efficiency of the landfill leachate was the highest, with COD and ammonia nitrogen concentrations of purified water being 7.4 mg/L and 7.7 mg/L, respectively.

Example 10

[0078] A catalyst stability test was conducted on the catalyst Fe.sub.2O.sub.3@SiO.sub.2Al.sub.2O.sub.3-1 prepared in Example 1 according to Example 1. A leachate oxypyrolysis purification device operated stably for 100 h, and the catalyst did not exhibit obvious inactivation. The catalyst had an excellent purification effect on the organic pollutants in the landfill leachate, and the stability of the catalyst also reached 100 h.

Comparative Example 1

[0079] 1.6875 g of ferric trichloride hexahydrate was completely dissolved in 20 mL of deionized water, After dissolution 9.5 g of HY molecular sieve with a silica-alumina ratio of 5:1 was added and stirred for 12 h, and then the mixture was placed in a 100 C. oil bath pan and stirred slowly to remove water. Then the water-removed mixture was placed in a tube furnace and heated at 5 C./min in an air atmosphere to 600 C. for heat treatment for 3 h. The catalyst was named Fe.sub.2O.sub.3/HY-5. The performance test of the catalyst was conducted in a three-stage temperature controlled fluidized bed steel reactor, with a COD concentration of landfill leachate of 8327 mg/L and an ammonia nitrogen concentration of 1263 mg/L. Oxypyrolysis purification of landfill leachate was performed with the bi-functional catalyst prepared by the above-mentioned method. The catalyst was loaded into a fluidized bed reaction tube, and the landfill leachate was added into a reactor through a peristaltic pump. The reaction conditions were as follows: the reaction temperature was 350 C., the feed molar ratio of oxygen to landfill leachate was 2.3, and the space velocity was 1.5.Math.h.sup.1 The COD removal rate was 92.1%, and the ammonia nitrogen removal rate was 79.5%. The COD concentration of the effluent was as high as 657.8 mg/L, and the ammonia nitrogen concentration was as high as 258.9 mg/L, which did not meet the discharge standards. The long-term stability effect of the purification reaction was poor, and after only for 22 h, there was significant deactivation of the catalyst, so that the catalytic efficiency was greatly reduced.

Comparative Example 2

[0080] 1.1419 g of cerium nitrate hexahydrate was completely dissolved in 20 mL of deionized water. After dissolution, 9.5 g of amorphous silica-alumina with a silica-alumina ratio of 5:1 was added and stirred for 12 h, and then the mixture was placed in a 100 C. oil bath pan and stirred slowly to remove water. Then, the water-removed mixture was placed in a tube furnace and heated at 5 C./min in an air atmosphere to 600 C. for heat treatment for 3 h. The catalyst was named CeO.sub.2/SiO.sub.2Al.sub.2O.sub.3-5. The leachate was purified according to the process conditions of Comparative example 1, and thus, the COD concentration removal rate was 94.6% and the ammonia nitrogen removal rate was 813%. The COD concentration of the effluent was as high as 449.7 mg/L, and the ammonia nitrogen concentration was as high as 236.2 mg/L. The long-term stability of the purification reaction was slightly improved compared to that of the catalyst prepared in Comparative example 1, but only after 42 h, there was a significant deactivation of the catalyst, so that the catalytic efficiency was greatly reduced.