Supported solid phase catalyst, and preparation method and use thereof

Abstract

The present invention belongs to the flue gas desulfuration field. Specifically, the present invention relates to a supported solid-phase catalyst for oxidizing the by-product magnesium sulfite in a magnesium desulfuration process, and to preparation method and use thereof. The catalyst uses an activated carbon particle as a support, and cobalt nitrate, manganese nitrate, copper nitrate and ferrous nitrate as catalytically active components. The preparation method is as follows: mixing the pre-treated activated carbon support with the catalytically active components, followed by oscillating, standing under microwave irradiation, filtrating, drying, baking, so as to obtain the supported solid-phase catalyst. Raw materials of the present invention are inexpensive and easily available; the preparation process is simple; the catalyst has prominent catalytic effect and can be widely used in the magnesium desulfuration process in medium-sized and small-sized boilers of 75t or more to improve the recovery rate of the desulfuration by-product and reduce energy consumption of the oxidation system; the catalyst has a low amount of catalytically active components and causes low residue in the solution and hence no secondary pollution problem, and has a high generalization value.

Claims

1. A method for preparing a supported solid-phase catalyst using an activated carbon particle as the support, comprising: (1) heating and refluxing the activated carbon particle in a nitric acid solution, followed by ultrasonic oscillation, filtration, washing to neutral, and drying, to obtain a pre-treated activated carbon support; and (2) mixing the pre-treated activated carbon support with cobalt nitrate, manganese nitrate, copper nitrate and ferrous nitrate, followed by oscillating, standing under microwave irradiation, filtrating, drying, and baking, to obtain the supported solid-phase catalyst, wherein the molar ratio of cobalt nitrate, manganese nitrate, copper nitrate, and ferrous nitrate is (2-7):(1-4):(1-4):(1-4).

2. The method according to claim 1, wherein step (2) comprises: immersing the obtained activated carbon support in a mixed solution of cobalt nitrate, manganese nitrate, copper nitrate and ferrous nitrate, immersing at 2000 r/min in a thermostatic oscillator for 5 h, and standing for 12 h under microwave irradiation, filtrating, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, to obtain the supported solid-phase catalyst.

3. The method according to claim 2, wherein in the mixed solution, concentration of cobalt nitrate ranges from 0.001 mol/L to 0.102 mol/L, concentration of manganese nitrate ranges from 0.001 mol/L to 0.051 mol/L, concentration of copper nitrate ranges from 0.001 mol/L to 0.075 mol/L, and concentration of ferrous nitrate ranges from 0.001 mol/L to 0.045 mol/L.

4. The method according to claim 1, wherein the total amount of metal ions is 0.01-0.2 percent by mass of the catalyst.

5. The method according to claim 1, wherein the activated carbon particle is one or more of coal-based spheral activated carbon, coconut shell-based activated carbon, nutshell-based activated carbon, wood-based activated carbon, bamboo-based activated carbon and coal-based columnar activated carbon.

6. The method according to claim 1, wherein the activated carbon particle has a particle size in the range of 0.1 mm to 10 mm and an average pore size in the range of 1 nm to 100 nm.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a graph of the catalytic reaction effects of accelerating oxidation of magnesium sulfite using supported solid-phase catalyst having different types of activated carbon.

(2) FIG. 2 is a graph of the catalytic reaction effects of accelerating oxidation of magnesium sulfite using supported solid-phase catalysts having different molar ratios of catalytically active components.

(3) FIG. 3 is a graph of the catalytic reaction effects of accelerating oxidation of magnesium sulfite using different concentrations of the supported solid-phase catalyst.

(4) FIG. 4 is a graph of the catalytic reaction effects of accelerating oxidation of magnesium sulfite using supported solid-phase catalysts having different catalyst particle sizes.

EMBODIMENTS

(5) The present invention relates to a supported solid-phase catalyst, preparation method and use thereof, which are described as below in detail by way of exemplified examples.

(6) Activated carbon support used in the following examples was pre-treated as follows: activated carbon was heated and refluxed in a concentrated nitric acid of 50% concentration for 1 h, then ultrasonically oscillated at 40 Hz for 40 min, stood, filtrated, washed to neutral, dried at 120 C. for 5 h, so as to obtain the activated support for use.

(7) Method for determining the reaction rate of magnesium sulfite under catalytic condition was as follows: an amount of the catalyst was added into the oxidation reaction system of magnesium sulfite, the reaction conditions were: reaction solution volume: 200 ml, reaction temperature: 45 C., initial concentration of magnesium sulfite: 20 g/L, pH: 8.0, forced air flow rate: 60 L/h. The concentration of sulfate ion in the reactor was tested at intervals, production amount of sulfate ion in a unit time representing the oxidation reaction rate of magnesium sulfite; the reaction rate of magnesium sulfite under catalytic condition was thus obtained.

1. Preparation and Application of Catalysts Having Different Types of Activated Carbon Particles

Example 1

(8) In an oxidation reaction system of magnesium sulfite, no additive was added, the reaction solution volume was 200 ml, the reaction temperature was 45 C., the initial concentration of magnesium sulfite was 20 g/L, pH was 8.0, the forced air flow rate was 60 L/h, under such conditions, the reaction rate was 0.0087 mmol/(L.Math.s), as shown by case 0 in FIG. 1.

Example 2

(9) After pre-treatment, 10.000 g of coal-based columnar activated carbon (CYC) having a diameter of 0.5 mm was added into a mixed solution of 1.4797 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.4932 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.6840 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.4840 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O, then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(10) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0207 mmol/(L.Math.s), as shown by case 1 in FIG. 1, and increased by 3.5 times compared with the non-catalytic condition.

Example 3

(11) After pre-treatment, 10.000 g of wood-based activated carbon (WC) having a diameter of 2-4 mm was added into a mixed solution of 1.4797 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.4932 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.6840 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.4840 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O, then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(12) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0260 mmol/(L.Math.s), as shown by case 2 in FIG. 1, and increased by 2.2 times compared with the non-catalytic condition.

Example 4

(13) After pre-treatment, 10.000 g of bamboo-based activated carbon (BC) having a diameter of 2-4 mm was added into a mixed solution of 1.4797 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.4932 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.6840 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.4840 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O, then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(14) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0238 mmol/(L.Math.s), as shown by case 3 in FIG. 1, and increased by 1.73 times compared with the non-catalytic condition.

Example 5

(15) After pre-treatment, 10.000 g of coconut shell-based activated carbon (CC) having a diameter of 2-4 mm was added into a mixed solution of 1.4797 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.4932 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.6840 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.4840 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O, then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(16) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0282 mmol/(L.Math.s), as shown by case 4 in FIG. 1, and increased by 1.93 times compared with the non-catalytic condition.

Example 6

(17) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 1.4797 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.4932 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.6840 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.4840 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O, then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0392 mmol/(L.Math.s), as shown by case 5 in FIG. 1, and increased by 1.37 times compared with the non-catalytic condition.

2. Preparation and Application of Catalysts Having Different Molar Ratios of Catalytically Active Components

Example 7

(18) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 0.2910 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.2510 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.3420 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.2420 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 1:1:1:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(19) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0181 mmol/(L.Math.s), as shown by case 1 in FIG. 2, and increased by 2.1 times compared with the non-catalytic condition.

Example 8

(20) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 0.873 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.7530 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.6840 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.4840 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 3:3:2:2), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(21) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0210 mmol/(L.Math.s), as shown by case 2 in FIG. 2, and increased by 2.4 times compared with the non-catalytic condition.

Example 9

(22) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 1.1640 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.5020 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.6840 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.4840 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 4:2:2:2), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(23) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0280 mmol/(L.Math.s), as shown by case 3 in FIG. 2, and increased by 3.2 times compared with the non-catalytic condition.

Example 10

(24) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 1.4550 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.4932 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.6840 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.4840 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 5:2:2:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(25) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0332 mmol/(L.Math.s), as shown by case 1 in FIG. 2, and increased by 3.8 times compared with the non-catalytic condition.

Example 11

(26) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 2.0370 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.2510 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.3420 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.2420 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 7:1:1:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(27) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0391 mmol/(L.Math.s), as shown by case 1 in FIG. 2, and increased by 4.5 times compared with the non-catalytic condition.

Example 12

(28) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 2.0370 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.2510 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.3420 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.2420 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 7:1:1:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(29) 0.5 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0299 mmol/(L.Math.s), as shown by case 1 in FIG. 3, and increased by 3.4 times compared with the non-catalytic condition.

Example 13

(30) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 2.0370 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.2510 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.3420 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.2420 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 7:1:1:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(31) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0342 mmol/(L.Math.s), as shown by case 2 in FIG. 3, and increased by 3.9 times compared with the non-catalytic condition.

Example 14

(32) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 2.0370 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.2510 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.3420 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.2420 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 7:1:1:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(33) 2 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0457 mmol/(L.Math.s), as shown by case 3 in FIG. 3, and increased by 5.3 times compared with the non-catalytic condition.

Example 15

(34) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 2.0370 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.2510 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.3420 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.2420 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 7:1:1:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(35) 4 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0558 mmol/(L.Math.s), as shown by case 4 in FIG. 3, and increased by 6.4 times compared with the non-catalytic condition.

Example 16

(36) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 2.0370 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.2510 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.3420 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.2420 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 7:1:1:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(37) 8 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0781 mmol/(L.Math.s), as shown by case 5 in FIG. 3, and increased by 9.0 times compared with the non-catalytic condition.

Example 17

(38) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 0.5-1 mm was added into a mixed solution of 2.0370 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.2510 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.3420 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.2420 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 7:1:1:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(39) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0349 mmol/(L.Math.s), as shown in FIG. 4, and increased by 3.9 times compared with the non-catalytic condition.

Example 18

(40) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 1-2 mm was added into a mixed solution of 2.0370 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.2510 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.3420 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.2420 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 7:1:1:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(41) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0306 mmol/(L.Math.s), as shown in FIG. 4, and increased by 3.5 times compared with the non-catalytic condition.

Example 19

(42) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 2-4 mm was added into a mixed solution of 2.0370 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.2510 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.3420 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.2420 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 7:1:1:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(43) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0217 mmol/(L.Math.s), as shown in FIG. 4, and increased by 2.5 times compared with the non-catalytic condition.

Example 20

(44) After pre-treatment, 10.000 g of nutshell-based activated carbon (FC) having a diameter of 4-6 mm was added into a mixed solution of 2.0370 g of Co(NO.sub.3).sub.2.Math.6H.sub.2O, 0.2510 g of Mn(NO.sub.3).sub.2.Math.4H.sub.2O, 0.3420 g of Fe(NO.sub.3).sub.2.Math.9H.sub.2O, and 0.2420 g of Cu(NO.sub.3).sub.2.Math.3H.sub.2O (in a molar ratio of 7:1:1:1), then went through dynamical immersion at 2000 r/min in a thermostatic oscillator for 5 h, standing for 12 h under microwave irradiation, filtration, drying at 120 C. for 6 h, one-time calcining at 250 C. for 2 h, baking at 400 C. for 3 h, so as to obtain the supported solid-phase catalyst.

(45) 1 g of the obtained catalyst was added into the oxidation reaction system of magnesium sulfite having a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.0206 mmol/(L.Math.s), as shown in FIG. 4, and increased by 2.4 times compared with the non-catalytic condition.