Catalyst for removing volatile organic compounds and preparation method therefor

Abstract

The invention discloses a catalyst for removing volatile organic compounds and a preparation method therefor. In the catalyst, aluminum oxide modified by iron, cobalt and nickel is used as a carrier, cordierite honeycomb ceramic is used as a matrix, and an extremely low content of a mixture of platinum and palladium is used as an active component; a molar ratio of platinum to palladium is 0-1:0-9, and an amount of the mixture of platinum and palladium accounts for 0.01% to 0.05% of a mass of the matrix; and an amount of the carrier accounts for 3% to 5% of the mass of the matrix.

Claims

1. A catalyst for removing volatile organic compounds, wherein aluminum oxide modified by iron, cobalt and nickel is used as a carrier, cordierite honeycomb ceramic is used as a matrix, and a mixture of platinum and palladium is used as an active component; a modified aluminum oxide carrier is coated on a cordierite honeycomb ceramic matrix, and the active component is loaded on the modified aluminum oxide carrier; and a molar ratio of platinum to palladium is 0-1: 0-9, and an amount of the mixture of platinum and palladium accounts for 0.01% to 0.05% of a mass of the matrix; and an amount of the carrier accounts for 3% to 5% of the mass of the matrix.

2. A method for preparing a catalyst for removing volatile organic compounds, wherein the catalyst comprises aluminum oxide modified by iron, cobalt and nickel used as a carrier, cordierite honeycomb ceramic used as a matrix, and a mixture of platinum and palladium used as an active component; a modified aluminum oxide carrier is coated on a cordierite honeycomb ceramic matrix, and the active component is loaded on the modified aluminum oxide carrier; and a molar ratio of platinum to palladium is 0-1: 0-9, and an amount of the mixture of platinum and palladium accounts for 0.01% to 0.05% of a mass of the matrix; and an amount of the carrier accounts for 3% to 5% of the mass of the matrix, wherein the method comprises following steps: (1) coating of the carrier: mixing mixed solution of iron salt, cobalt salt and nickel salt with a water-soluble colloid of aluminum hydroxide to obtain mixed liquid of the solution and the colloid; and impregnating the cordierite honeycomb ceramic into the mixed liquid of the solution and the colloid obtained, removing the cordierite honeycomb ceramic, and drying and roasting the cordierite honeycomb ceramic in an air atmosphere to obtain the cordierite honeycomb ceramic matrix coated with the modified aluminum oxide; (2) discharge strengthening pretreatment: placing the obtained cordierite honeycomb ceramic matrix coated with the modified aluminum oxide in a pulse dielectric barrier discharge reaction zone, and performing the discharge strengthening pretreatment to obtain a discharge-strengthening pretreated cordierite honeycomb ceramic matrix coated with the modified aluminum oxide; (3) preparation of an impregnation liquid of the active component: dissolving and mixing a precursor of platinum and a precursor of palladium with deionized water to obtain the impregnation liquid of the active component; and (4) loading and reduction of the active component: impregnating the discharge-strengthening pretreated cordierite honeycomb ceramic matrix coated with the modified aluminum oxide obtained in the step (2) into the impregnation liquid of the active component obtained in the step (3), removing the cordierite honeycomb ceramic matrix, removing the impregnation liquid remaining in a pore channel of the honeycomb ceramic matrix, drying and roasting the cordierite honeycomb ceramic matrix in an air atmosphere, and finally reducing the cordierite honeycomb ceramic matrix to obtain the catalyst for removing the volatile organic compounds.

3. The method for preparing the catalyst for removing the volatile organic compounds according to claim 2, wherein in the step (1), a concentration of the mixed solution of the iron salt, the cobalt salt and the nickel salt ranges from 2.62 g/mL to 4.64 g/mL; and a concentration of the water-soluble colloid of aluminum hydroxide ranges from 3.25 g/mL to 4.93 g/mL.

4. The method for preparing the catalyst for removing the volatile organic compounds according to claim 2, wherein in the step (1), the iron salt, the cobalt salt and the nickel salt are nitrate or acetate of iron, cobalt and nickel; and in the mixed liquid of the solution and the colloid, a molar ratio of the iron to the cobalt, the nickel and the aluminum is 1-2: 1-2: 1-2: 4-7.

5. The method for preparing the catalyst for removing the volatile organic compounds according to claim 2, wherein in the step (1), the impregnating lasts for 20 minutes to 30 minutes; the drying is performed at 120° C. for 3 hours to 6 hours; and the roasting is performed at 500° C. to 700° C. for 1 hour to 3 hours.

6. The method for preparing the catalyst for removing the volatile organic compounds according to claim 2, wherein in the step (2), the discharge strengthening pretreatment is as follows: discharge conditions are that, under an atmospheric pressure, a dielectric thickness ranges from 1 mm to 5 mm, a voltage ranges from 5000 V to 20000 V, a frequency ranges from 50 Hz to 400 Hz, a pulse width ranges from 100 ns to 200 ns, and the strengthening pretreatment lasts for 5 minutes to 10 minutes.

7. The method for preparing the catalyst for removing the volatile organic compounds according to claim 2, wherein in the step (3), the precursor of platinum is chloroplatinic acid; and the precursor of palladium is palladium chloride.

8. The method for preparing the catalyst for removing the volatile organic compounds according to claim 2, wherein in the step (3), a total content of platinum and palladium in the impregnation liquid of the active component ranges from 1.65 g/L to 8.26 g/L.

9. The method for preparing the catalyst for removing the volatile organic compounds according to claim 2, wherein in the step (4), the impregnating lasts for 20 minutes to 30 minutes; the drying is performed at 120° C. for 3 hours to 6 hours; and the roasting is performed at 500° C. to 700° C. for 1 hour to 3 hours.

10. The method for preparing the catalyst for removing the volatile organic compounds according to claim 2, wherein in the step (4), the reducing is performed in an H.sub.2/N.sub.2 atmosphere at 200° C. to 250° C. for 2 hours to 4 hours.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic diagram of a device for pulse dielectric barrier discharge strengthening pretreatment.

DESCRIPTION OF THE EMBODIMENTS

(2) The method for preparing the catalyst is further described in detail hereinafter with reference to the specific embodiments, and meanwhile, performance test results of the method are described in detail, but the present invention is not limited to these embodiments.

(3) A schematic diagram of a device for pulse dielectric barrier discharge strengthening pretreatment used in the embodiments of the present invention is shown in FIG. 1, which includes a high-voltage electrode 1, a dielectric 3 and a grounding electrode 4, cordierite honeycomb ceramic coated with an aluminum oxide carrier modified by iron, cobalt and nickel is used as a matrix 2 and placed in a reaction zone between the high-voltage electrode 1 and the dielectric 3, wherein discharge conditions are that, under an atmospheric pressure, a dielectric thickness ranges from 1 mm to 5 mm, a voltage ranges from 5000 V to 20000 V, a frequency ranges from 50 Hz to 400 Hz, and a pulse width ranges from 100 ns to 200 ns. Under the conditions above, strengthening pretreatment to the cordierite honeycomb ceramic coated with the aluminum oxide carrier modified by iron, cobalt and nickel as the matrix 2 in a pulse dielectric barrier discharge reaction zone lasts for 5 minutes to 10 minutes.

Embodiment 1

(4) (1) Coating of Modified Aluminum Oxide on a Cordierite Honeycomb Ceramic Matrix

(5) A mixed solution of iron salt, cobalt salt and nickel salt was mixed with a water-soluble colloid of aluminum hydroxide, wherein the iron salt, the cobalt salt and the nickel salt were Fe(NO.sub.3).sub.3.Math.9H.sub.2O, Co(AC).sub.3.Math.4H.sub.2O and Ni(NO.sub.3).sub.4.Math.6H.sub.2O. Specifically, 22.5231 g of Fe(NO.sub.3).sub.3.Math.9H.sub.2O, 13.8872 g of Co(AC).sub.3.Math.4H.sub.2O and 16.0482 g of Ni(NO.sub.3).sub.4.Math.6H.sub.2O were dissolved in 20 mL of deionized water, and mixed with a colloid containing 20 mL of deionized water and 65.0166 g of aluminum hydroxide, and then magnetically stirred. In the mixed liquid prepared, a molar ratio of iron to cobalt, nickel and aluminum was 1:1:1:7.

(6) Cordierite honeycomb ceramic was impregnated into the mixed liquid of the salt solutions and the colloid above for 20 minutes, and coated with the modified aluminum oxide with a coating amount accounting for 3% of a mass of the matrix, and finally, the cordierite honeycomb ceramic was dried at 120° C. for 3 hours and roasted at 500° C. for 3 hours in an air atmosphere to obtain the cordierite honeycomb ceramic matrix coated with the modified aluminum oxide.

(7) (2) Discharge Strengthening Pretreatment to the Cordierite Honeycomb Ceramic Matrix Coated with the Modified Aluminum Oxide.

(8) The cordierite honeycomb ceramic matrix coated with the modified aluminum oxide obtained in the step (1) was placed in a pulse dielectric barrier discharge reaction zone to obtain a discharge-strengthening pretreated cordierite honeycomb ceramic matrix coated with the modified aluminum oxide, wherein the discharge conditions were as follows: under an atmospheric pressure, a dielectric thickness was 1 mm, a voltage was 5000 V, a frequency was 50 Hz, a pulse width was 100 ns, and the strengthening pretreatment lasted for 5 minutes.

(9) (3) Preparation of an Impregnation Liquid of an Active Component

(10) An impregnation liquid of an active component of a mixture of platinum and palladium was prepared, wherein chloroplatinic acid and palladium chloride were respectively dissolved with deionized water, and then mixed, and the platinum and the palladium were prepared in a molar ratio of 1:9. Specifically, 0.0915 g of PdCl.sub.2 and 0.0297 g of H.sub.2PtCl.sub.6.Math.6H.sub.2O were dissolved in 40 mL of water to obtain the impregnation liquid of the active component containing 1.65 g/L of the mixture of platinum and palladium.

(11) (4) Loading and Reduction of the Active Component

(12) The pulse dielectric barrier discharge-strengthening pretreated cordierite honeycomb ceramic matrix coated with the modified aluminum oxide obtained in the step (2) was impregnated into the impregnation liquid of the active component obtained in the step (3) for 20 minutes, then the cordierite honeycomb ceramic matrix was taken out, and the impregnation liquid remaining in a pore channel of the honeycomb ceramic matrix was removed, then the cordierite honeycomb ceramic matrix was dried at 120° C. for 3 hours and roasted at 500° C. for 3 hours in an air atmosphere, and finally the cordierite honeycomb ceramic matrix was reduced at 200° C. for 4 hours in an H.sub.2/N.sub.2 atmosphere (H.sub.2/N.sub.2=5:95, V/V) to obtain a catalyst using an extremely low content of the mixture of platinum and palladium as the active component, wherein the active component accounted for 0.01% of the mass of the matrix.

(13) (5) Performance Evaluation of the Catalyst

(14) Pd—Pt/Fe—Co—Ni—O-γ-Al.sub.2O.sub.3/cordierite honeycomb ceramic with a size of 100 mm×100 mm×50 mm was cut into four cylinders with a size of 30 mm (diameter)×50 mm (length), and any one of the four cylinders was loaded into a catalytic reactor.

(15) The performance evaluation of the catalyst was performed in a fixed bed flow reactor, toluene was used as a representative of volatile organic compounds, and immersed in an ice-water mixture for thermal insulation, and air bubbles were used to carry out a toluene-air mixture to form simulated exhaust gas, wherein a content of the toluene was 3490±50 mg.Math.m.sup.−3 and a reaction airspeed was controlled at 15000 h.sup.−1. Concentrations of the toluene at an inlet and an outlet of an evaluation device were analyzed by FID of a gas chromatograph GC2014C.

(16) A conversion rate of the toluene was calculated by a following formula:
conversion rate of toluene(Conv,%)=[(concentration of inlet toluene Conc.sub.i−concentration of outlet toluene Conc.sub.o)/concentration of inlet toluene Conc.sub.i]×100%.

(17) At each temperature, composition analysis was performed, 5 minutes after a catalytic oxidation reaction reached a stable state.

(18) According to the catalyst prepared in the embodiment, Conc.sub.i=3540 mg.Math.m.sup.−3, Conc.sub.o=36 mg.Math.m.sup.−3 and the conversion rate of the toluene Conv was 98.98% at 230° C.

(19) After the catalyst prepared in the embodiment was continuously operated at 500° C. for 200 hours, a catalytic oxidation reaction test was performed on the toluene at 250° C., and test results were as follows: Conc.sub.i=3535 mg.Math.m.sup.−3, Conc.sub.o=39 mg.Math.m.sup.−3, and the conversion rate of the toluene Conv was 98.90%.

Embodiment 2

(20) (1) Coating of Modified Aluminum Oxide on a Cordierite Honeycomb Ceramic Matrix

(21) A mixed solution of iron salt, cobalt salt and nickel salt was mixed with a water-soluble colloid of aluminum hydroxide, wherein the iron salt, the cobalt salt and the nickel salt were Fe(NO.sub.3).sub.3.Math.9H.sub.2O, Co(AC).sub.3.Math.4H.sub.2O and Ni(NO.sub.3).sub.4.Math.6H.sub.2O. Specifically, 39.9530 g of Fe(NO.sub.3).sub.3.Math.9H.sub.2O, 24.6339 g of Co(AC).sub.3.Math.4H.sub.2O and 28.4672 g of Ni(NO.sub.3).sub.4.Math.6H.sub.2O were dissolved in 25 mL of deionized water, and mixed with a colloid containing 15 mL of deionized water and 60.4111 g of aluminum hydroxide, and then magnetically stirred. In the mixed liquid prepared, a molar ratio of iron to cobalt, nickel and aluminum was 1.5:1.5:1.5:5.5.

(22) Cordierite honeycomb ceramic was impregnated into the mixed liquid of the salt solutions and the colloid above for 25 minutes, and coated with the modified aluminum oxide with a coating amount accounting for 4% of a mass of the matrix, and finally, the cordierite honeycomb ceramic was dried at 120° C. for 4 hours and roasted at 600° C. for 2 hours in an air atmosphere to obtain the cordierite honeycomb ceramic matrix coated with the modified aluminum oxide.

(23) (2) Discharge Strengthening Pretreatment to the Cordierite Honeycomb Ceramic Matrix Coated with the Modified Aluminum Oxide

(24) The cordierite honeycomb ceramic matrix coated with the modified aluminum oxide obtained in the step (1) was placed in a pulse dielectric barrier discharge reaction zone to obtain a discharge-strengthening pretreated cordierite honeycomb ceramic matrix coated with the modified aluminum oxide, wherein the discharge conditions were as follows: under an atmospheric pressure, a dielectric thickness was 3 mm, a voltage was 10000 V, a frequency was 200 Hz, a pulse width was 150 ns, and the strengthening pretreatment lasted for 8 minutes.

(25) (3) Preparation of an Impregnation Liquid of an Active Component

(26) An impregnation liquid of an active component of palladium was prepared, wherein palladium chloride was dissolved with deionized water. Specifically, 0.3303 g of PdCl.sub.2 was dissolved in 40 mL of water to obtain the impregnation liquid of the active component containing 4.95 g/L of the palladium.

(27) (4) Loading and Reduction of the Active Component

(28) The pulse dielectric barrier discharge-strengthening pretreated cordierite honeycomb ceramic matrix coated with the modified aluminum oxide obtained in the step (2) was impregnated into the impregnation liquid of the active component obtained in the step (3) for 25 minutes, then the cordierite honeycomb ceramic matrix was taken out, and the impregnation liquid remaining in a pore channel of the honeycomb ceramic matrix was removed, then the cordierite honeycomb ceramic matrix was dried at 120° C. for 4 hours and roasted at 600° C. for 2 hours in an air atmosphere, and finally the cordierite honeycomb ceramic matrix was reduced at 225° C. for 3 hours in an H.sub.2/N.sub.2 atmosphere (H.sub.2/N.sub.2=5:95, V/V) to obtain a catalyst using an extremely low content of the palladium as the active component, wherein the active component accounted for 0.03% of the mass of the matrix.

(29) (5) Performance Evaluation of the Catalyst

(30) Pd/Fe—Co—Ni—O-γ-Al.sub.2O.sub.3/cordierite honeycomb ceramic with a size of 100 mm×100 mm×50 mm was cut into four cylinders with a size of 30 mm (diameter)×50 mm (length), and any one of the four cylinders was loaded into a catalytic reactor.

(31) The performance evaluation of the catalyst was performed in a fixed bed flow reactor, toluene was used as a representative of volatile organic compounds, and immersed in an ice-water mixture for thermal insulation, and air bubbles were used to carry out a toluene-air mixture to form simulated exhaust gas, wherein a content of the toluene was 3490±50 mg.Math.m.sup.−3 and a reaction airspeed was controlled at 15000 h.sup.−1. Concentrations of the toluene at an inlet and an outlet of an evaluation device were analyzed by FID of a gas chromatograph GC2014C.

(32) A conversion rate of the toluene was calculated by a following formula:
conversion rate of toluene(Conv,%)=[(concentration of inlet toluene Conc.sub.i−concentration of outlet toluene Conc.sub.o)/concentration of inlet toluene Conc.sub.i]×100%.

(33) At each temperature, composition analysis was performed, 5 minutes after a catalytic oxidation reaction reached a stable state.

(34) According to the catalyst prepared in the embodiment, Conc.sub.i=3490 mg.Math.m.sup.−3, Conc.sub.o=30 mg.Math.m.sup.−3 and the conversion rate of the toluene Conv was 99.14% at 230° C.

(35) After the catalyst prepared in the embodiment was continuously operated at 600° C. for 200 hours, a catalytic oxidation reaction test was performed on the toluene at 255° C., and test results were as follows: Conc.sub.i=3480 mg.Math.m.sup.−3, Conc.sub.o=35 mg.Math.m.sup.−3, and the conversion rate of the toluene Conv was 98.99%.

Embodiment 3

(36) (1) Coating of Modified Aluminum Oxide on a Cordierite Honeycomb Ceramic Matrix

(37) A mixed solution of iron salt, cobalt salt and nickel salt was mixed with a water-soluble colloid of aluminum hydroxide, wherein the iron salt, the cobalt salt and the nickel salt were Fe(NO.sub.3).sub.3.Math.9H.sub.2O, Co(AC).sub.3.Math.4H.sub.2O and Ni(NO.sub.3).sub.4.Math.6H.sub.2O. Specifically, 59.8240 g of Fe(NO.sub.3).sub.3.Math.9H.sub.2O, 36.8859 g of Co(AC).sub.3.Math.4H.sub.2O and 42.6257 g of Ni(NO.sub.3).sub.4.Math.6H.sub.2O were dissolved in 30 mL of deionized water, and mixed with a colloid containing 10 mL of deionized water and 49.3404 g of aluminum hydroxide, and then magnetically stirred. In the mixed liquid prepared, a molar ratio of iron to cobalt, nickel and aluminum was 2:2:2:4.

(38) Cordierite honeycomb ceramic was impregnated into the mixed liquid of the salt solutions and the colloid above for 30 minutes, and coated with the modified aluminum oxide with a coating amount accounting for 5% of a mass of the matrix, and finally, the cordierite honeycomb ceramic was dried at 120° C. for 6 hours and roasted at 700° C. for 1 hour in an air atmosphere to obtain the cordierite honeycomb ceramic matrix coated with the modified aluminum oxide.

(39) (2) Discharge Strengthening Pretreatment to the Cordierite Honeycomb Ceramic Matrix Coated with the Modified Aluminum Oxide

(40) The cordierite honeycomb ceramic matrix coated with the modified aluminum oxide obtained in the step (1) was placed in a pulse dielectric barrier discharge reaction zone to obtain a discharge-strengthening pretreated cordierite honeycomb ceramic matrix coated with the modified aluminum oxide, wherein the discharge conditions were as follows: under an atmospheric pressure, a dielectric thickness was 5 mm, a voltage was 20000 V, a frequency was 400 Hz, a pulse width was 200 ns, and the strengthening pretreatment lasted for 10 minutes.

(41) (3) Preparation of an Impregnation Liquid of an Active Component

(42) An impregnation liquid of an active component of palladium was prepared, wherein chloroplatinic acid was dissolved with deionized water. Specifically, 0.8770 g of H.sub.2PtCl.sub.6.Math.6H.sub.2O was dissolved in 40 mL of water to obtain the impregnation liquid of the active component containing 8.26 g/L of the platinum.

(43) (4) Loading and Reduction of the Active Component

(44) The pulse dielectric barrier discharge-strengthening pretreated cordierite honeycomb ceramic matrix coated with the modified aluminum oxide obtained in the step (2) was impregnated into the impregnation liquid of the active component obtained in the step (3) for 30 minutes, then the cordierite honeycomb ceramic matrix was taken out, and the impregnation liquid remaining in a pore channel of the honeycomb ceramic matrix was removed, then the cordierite honeycomb ceramic matrix was dried at 120° C. for 6 hours and roasted at 700° C. for 1 hour in an air atmosphere, and finally the cordierite honeycomb ceramic matrix was reduced at 250° C. for 2 hours in an H.sub.2/N.sub.2 atmosphere (H.sub.2/N.sub.2=5:95, V/V) to obtain a catalyst using an extremely low content of the platinum as the active component, wherein the active component accounted for 0.05% of the mass of the matrix.

(45) (5) Performance Evaluation of the Catalyst

(46) Pt/Fe—Co—Ni—O-γ-Al.sub.2O.sub.3/cordierite honeycomb ceramic with a size of 100 mm×100 mm×50 mm was cut into four cylinders with a size of 30 mm (diameter)×50 mm (length), and any one of the four cylinders was loaded into a catalytic reactor.

(47) The performance evaluation of the catalyst was performed in a fixed bed flow reactor, toluene was used as a representative of volatile organic compounds, and immersed in an ice-water mixture for thermal insulation, and air bubbles were used to carry out a toluene-air mixture to form simulated exhaust gas, wherein a content of the toluene was 3490±50 mg.Math.m.sup.−3 and a reaction airspeed was controlled at 15000 h.sup.−1. Concentrations of the toluene at an inlet and an outlet of an evaluation device were analyzed by FID of a gas chromatograph GC2014C.

(48) A conversion rate of the toluene was calculated by a following formula:
conversion rate of toluene(Conv,%)=[(concentration of inlet toluene Conc.sub.i−concentration of outlet toluene Conc.sub.o)/concentration of inlet toluene Conc.sub.i]×100%.

(49) At each temperature, composition analysis was performed, 5 minutes after a catalytic oxidation reaction reached a stable state.

(50) According to the catalyst prepared in the embodiment, Conc.sub.i=3440 mg.Math.m.sup.−3, Conc.sub.o=20 mg.Math.m.sup.−3 and the conversion rate of the toluene Conv was 99.71% at 230° C.

(51) After the catalyst prepared in the embodiment was continuously operated at 700° C. for 200 hours, a catalytic oxidation reaction test was performed on the toluene at 255° C., and test results were as follows: Conc.sub.i=3460 mg.Math.m.sup.−3, Conc.sub.o=30 mg.Math.m.sup.−3, and the conversion rate of the toluene Conv was 99.13%.

(52) It can be seen from the embodiments above that the monolithic catalyst of the present invention has a high catalytic activity in removing volatile organic compounds represented by the toluene at a lower temperature. Even after continuous operation at 500° C. to 700° C. for 200 hours, the catalyst still maintains the ability to completely oxidize the toluene at 255° C. Moreover, the catalyst of the present invention has simple preparation process, extremely low content of noble metals, high thermal stability, low manufacturing cost, easy popularization and wide application prospect.