CN113398939A - Iron-cerium composite oxide catalyst for VOCs treatment and preparation method thereof - Google Patents
Iron-cerium composite oxide catalyst for VOCs treatment and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 39
- ZGMCLEXFYGHRTK-UHFFFAOYSA-N [Fe].[Ce] Chemical compound [Fe].[Ce] ZGMCLEXFYGHRTK-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 150000003624 transition metals Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012695 Ce precursor Substances 0.000 claims description 4
- 239000012692 Fe precursor Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229940117389 dichlorobenzene Drugs 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000000376 reactant Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910001268 Ferrocerium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
- F23G2209/142—Halogen gases, e.g. silane
Abstract
The invention provides an iron-cerium composite oxide catalyst for VOCs treatment and a preparation method thereof, wherein the catalyst is prepared from a composite oxide Ce of rare earth metal cerium (Ce) and transition metal iron (Fe)xFeyOzA catalyst in the form of a solid powder; wherein x =2 ~ 40, y =2 ~ 4, and z =7 ~ 86. The iron-cerium composite oxide catalyst disclosed by the invention can be used for efficiently removing Volatile Organic Compounds (VOCs), the low-temperature catalytic combustion activity is high, particularly the spindle-shaped iron-cerium composite oxide catalyst has higher reaction activity, and the temperature is 304 ℃ when the chlorobenzene conversion rate is 90%; has wide application prospect and good economic benefit.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and environmental protection, and particularly relates to an iron-cerium composite oxide catalyst for VOCs treatment and a preparation method thereof.
Background
VOCs refer to organic substances having a boiling point between 50 ℃ and 260 ℃ at normal temperature. VOCs mainly come from industries such as ships, chemical engineering, paints, automobiles and the like, and have the characteristics of stable chemical property and difficult degradation. VOCs can cause atmospheric pollution problems such as haze, photochemical smog and the like, and can threaten the life health of people and restrict the development of social economy. Therefore, VOCs treatment is an urgent task.
In industry, the treatment of VOCs is largely divided into two categories. The first method is a physical method, VOCs are removed by an adsorption method, a condensation method and the like, and the effect is good. However, the physical method only transfers the VOCs from the atmosphere to the surface of the material, and the pollutants are not oxidized and decomposed, so that the problem of secondary pollution is easily caused. The second type of process is a chemical process comprising: direct combustion, pulse corona discharge, osmotic reaction, catalytic hydrodechlorination, biodegradation, gas phase photocatalytic degradation, catalytic combustion, and the like. Compared with other chemical methods, the catalytic combustion method has the advantages of high low-temperature catalytic activity and low energy consumption, and is a mature environment-friendly technology at present.
The catalysts for eliminating VOCs by the catalytic combustion method can be divided into four types: transition metal oxide catalysts, noble metal catalysts, perovskite catalysts, rare earth metal catalysts. The noble metal catalyst shows high catalytic combustion activity on VOCs, but the noble metal catalyst has the defects of high price, easy loss of active components, easy inactivation and the like. Compared with noble metal catalysts, transition metal oxide catalysts have a stronger deactivation resistance. The catalytic combustion activity of highly dispersed rare earth cerium based metal catalysts on VOCs has been reported to approach palladium and platinum based noble metal catalysts. The research and development of the low-temperature bimetallic catalytic combustion catalyst for VOCs treatment not only has important theoretical significance, but also has important practical significance.
Disclosure of Invention
The invention aims to provide an iron-cerium composite oxide catalyst for VOCs treatment and a preparation method thereof, and aims to solve the problems of low VOC degradation activity and high VOC degradation cost in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an iron-cerium composite oxide catalyst for VOCs treatment is characterized in that the catalyst is prepared from a composite oxide Ce of rare earth metal cerium (Ce) and transition metal iron (Fe)xFeyOzA catalyst in the form of a solid powder; wherein x is 2-40, y is 2-4, and z is 7-86.
Preferably, the molar ratio of the cerium element to the iron element in the catalyst is 19: 1-1: 1.
The preparation method of the iron-cerium composite oxide catalyst for VOCs treatment is characterized by comprising the following steps:
(1) uniformly mixing the aqueous solution of the cerium precursor and the aqueous solution of the iron precursor to obtain a metal precursor mixed solution; (2) adding an alkali solution into the hydrothermal reaction kettle to adjust the pH value to 10, and stirring for 15-50 min; (3) heating the hydrothermal reaction kettle to 120-180 ℃, and carrying out hydrothermal reaction for 2-10 h; (4) cooling to room temperature, carrying out suction filtration to obtain a solid, and drying the washed solid at 40-80 ℃ for 2-10 h; obtaining the iron-cerium composite oxide catalyst;
the cerium precursor is one or two of cerium nitrate, cerium sulfate and cerium carbonate; the iron precursor can be one or two of ferric nitrate, ferric sulfate and ferric chloride, and is preferably cerium nitrate or ferric nitrate; the alkali solution is weak alkali solution or strong alkali solution, and the weak alkali solution is one or more of sodium bicarbonate solution, sodium carbonate solution, potassium bicarbonate solution, potassium carbonate solution and ammonia water; the strong alkali solution is sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, in the step (2), the weak base solution is added to adjust the pH to 8-9, and then the strong base solution is added to adjust the pH to 10.
Preferably, the hydrothermal reaction is kept at 140-160 ℃ for 3-5 h.
Preferably, before use, the catalyst for low-temperature catalytic combustion needs to be ground and then screened by a 40-120-mesh screen.
The invention also provides application of the iron-cerium composite oxide catalyst in low-temperature catalytic combustion of volatile organic waste gas.
Further, the application of the iron-cerium composite oxide catalyst comprises the following steps: filling the iron-cerium composite oxide catalyst into a fixed bed reactor, and removing volatile organic compounds in the exhaust gas after catalytic combustion by taking oxygen-containing gas as an oxidant; the catalytic combustion temperature is 150-450 ℃.
Preferably, the fixed bed reactor is a quartz fixed bed reactor; the oxygen-containing gas is air, wherein the volume fraction of the oxygen is 2-20%; the loading of the catalyst is sufficient to completely convert the volatile organic compounds into carbon dioxide and water, and the preferred loading of the catalyst is 25-150 mg; the amount of the catalyst for treating the waste gas per gram is 10-50L/h.
Preferably, the volatile organic compound is a chlorinated aromatic volatile organic compound, such as: chlorobenzene, dichlorobenzene and the like, wherein the concentration of the volatile organic compound in the waste gas is 0.1-5 vol%.
The invention has the following beneficial effects:
the iron-cerium composite oxide catalyst disclosed by the invention can be used for efficiently removing Volatile Organic Compounds (VOCs), the low-temperature catalytic combustion activity is high, particularly, the spindle-shaped iron-cerium composite oxide catalyst has higher reaction activity, and the temperature is 304 ℃ when the chlorobenzene conversion rate is 90%; having a wide range of applications and good economic benefits, some of which will become apparent from the description below or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1: scanning electron micrographs of the iron cerium composite oxide catalyst of example 1.
Detailed Description
It should be understood by those skilled in the art that the present embodiment is only for illustrating the present invention and is not to be used as a limitation of the present invention, and the embodiment can be changed or modified within the scope of the claims of the present invention.
The raw materials used in this example are all commercially available.
Example 1
(1) Mixing 10mL of 0.1mol/L ferric nitrate solution and 10mL of 0.9mol/L cerous nitrate solution to obtain a metal precursor mixed solution; (2) placing the metal precursor mixed solution in a hydrothermal reaction kettle with a polytetrafluoroethylene inner container, adding a sodium carbonate solution to adjust the pH value to 9, continuously adjusting the pH value to 10 by using a sodium hydroxide solution, and continuously stirring for 20 min; (3) putting the hydrothermal reaction kettle into an air-blast drying oven, heating to 150 ℃, and keeping the reaction for 4 hours; (4) cooling to room temperature, performing suction filtration to separate to obtain a solid, and alternately washing with ethanol and water for three times; drying the washed solid in a vacuum oven at 60 deg.C for 4h to obtain spindle-shaped iron-cerium composite oxide catalyst, grinding the catalyst, sieving with a 40 mesh sieve, and naming as Ce9Fe1-A。
Example 2
(1) Mixing 10mL of 0.1mol/L ferric nitrate solution and 10mL of 0.9mol/L cerous nitrate solution to obtain a metal precursor mixed solution; (2) placing the metal precursor mixed solution in a hydrothermal reaction kettle with a polytetrafluoroethylene inner container, adding a potassium carbonate solution to adjust the pH value to 9, continuously adjusting the pH value to 10 by using a sodium hydroxide solution, and continuously stirring for 20 min; (3) putting the hydrothermal reaction kettle into a forced air drying oven, heating to 180 ℃, and keeping for 4 hours; (4) cooling to room temperature, performing suction filtration to separate to obtain a solid, and alternately washing with ethanol and water for three times; drying the washed solid in a vacuum oven at 60 ℃ for 4h to obtain a straight rod-shaped iron-cerium composite oxide catalyst, grinding the catalyst, and sieving the ground catalyst by using a 40-mesh sieve to obtain the catalyst named Ce9Fe1-B。
Example 3
(1) Mixing 10mL of 0.1mol/L ferric nitrate solution and 10mL of 0.9mol/L cerous nitrate solution to obtain a metal precursor mixed solution; (2) placing the metal precursor mixed solution in a hydrothermal reaction kettle with a polytetrafluoroethylene inner container, slowly dropwise adding a sodium hydroxide solution to adjust the pH value to 10, and continuously stirring for 20 min; (3) putting the hydrothermal reaction kettle into a forced air drying oven, heating to 150 ℃, and keeping for 4 hours; (4) cooling to room temperature, performing suction filtration to separate to obtain a solid, and alternately washing with ethanol and water for three times; drying the washed solid in a vacuum oven at 60 ℃ for 4h to obtain the irregular spherical iron-cerium composite metal oxide, grinding the catalyst, and sieving the catalyst by using a 40-mesh sieve to obtain the catalyst named Ce9Fe1-C。
Example 4
A fusiform iron-cerium composite oxide catalyst, having a molar ratio Ce: Fe of 6:1, designated Ce, was obtained as in example 1, with a cerium nitrate solution concentration of 0.6mol/L, the remainder being unchanged6Fe1-A。
Example 5
A fusiform iron-cerium composite oxide catalyst, having a molar ratio Ce: Fe of 3:1, designated C, was obtained as in example 1, with a cerium nitrate solution concentration of 0.3mol/L, the remainder being unchangede3Fe1-A。
Example 6
A fusiform iron-cerium composite oxide catalyst, having a molar ratio Ce: Mn of 1:1, designated as Ce, was obtained as in example 1, with a cerium nitrate solution concentration of 0.1mol/L, the remainder being unchanged1Fe1-A。
Example 7
A fusiform iron-cerium composite oxide catalyst, having a molar ratio Ce: Mn of 10:1, designated as Ce, was obtained as in example 1, wherein the concentration of the cerium nitrate solution was 1.0mol/L, and the balance was unchanged10Fe1-A。
Example 8
A fusiform iron-cerium composite oxide catalyst, having a molar ratio Ce: Mn of 15:1, designated as Ce, was obtained as in example 1, wherein the concentration of the cerium nitrate solution was 1.5mol/L, and the balance was unchanged15Fe1-A。
Application example 1
The applicant researches and discovers that: adjusting the pH value of the metal precursor mixed solution to 8-9 by using a weak base solution such as carbonate or ammonia water, and adjusting the pH value to 10 by using a strong base solution such as sodium hydroxide or potassium hydroxide, and obtaining the iron-cerium composite oxide catalyst in a spindle shape under the condition that the hydrothermal reaction temperature is 120-160 ℃; but at a lower temperature of 120-140 ℃, the obtained iron-cerium composite oxide catalyst is in an irregular spindle shape.
Adjusting the pH value of a metal precursor solution to 8-9 by using a weak base solution such as carbonate or ammonia water and the like, adjusting the pH value of the metal precursor solution to 10 by using a strong base solution such as sodium hydroxide or potassium hydroxide and the like, and obtaining the iron-cerium composite oxide catalyst in a straight rod shape under the condition that the hydrothermal reaction temperature is 160-180 ℃;
and (3) directly adjusting the pH value of the metal precursor solution to 10 by using a strong alkali solution, and obtaining the iron-cerium composite oxide catalyst in an irregular spherical shape under the conditions that the hydrothermal reaction temperature is 120-160 ℃.
The catalytic activity tests of the catalysts obtained in examples 1 to 8 were carried out in a quartz fixed bed reactor having an internal diameter of 3mm, the reactants being chloro-organics chlorobenzene and dichlorobenzene. The prepared ferro-cerium oxide is catalyzedThe catalyst is filled into a fixed bed reactor, VOCs are injected into a vaporization chamber (the whole pipeline is electrically heated) by a 100 series KDS120 micro-injection pump of Stoelting company of America to be vaporized, then the vaporized VOCs are mixed with oxygen-containing gas and enter a reactor, and the gas flow is controlled by a mass flow meter. And (3) monitoring the concentration of VOCs on line by connecting FID detectors with gas chromatography at the inlet and the outlet of the fixed bed reactor in series, and calculating the removal rate of VOC. Reaction conditions are as follows: the dosage of the catalyst is 125mg, the volume fraction of oxygen is 5 percent, and the airspeed of the system is 20000h-1The concentration of the reactant was 1500 ppm. Carrying out quantitative analysis on the reactants by adopting gas chromatography; the activity of the catalyst is expressed in terms of the conversion of chlorobenzene and dichlorobenzene, where T is50And T90The reaction temperatures at which the reactant conversions were 50% and 90%, respectively, were expressed. The relationship between the conversion of VOCs and temperature under the action of different catalysts is shown in table 1.
Table 1 examples 1-8 catalytic combustion activity of catalysts for benzene and toluene
As can be seen from comparison of examples 1 to 3 in Table 1, the spindle-shaped iron-cerium composite oxide catalyst has higher reactivity; as is clear from comparison of example 1 with examples 4 to 7, the highest activity was observed at a Ce/Fe ratio of 9:1, so that the reaction temperature in example 1 was the lowest and the temperature at which the chlorobenzene conversion was 90% was 313 ℃.
Application example 2
The catalyst loading was varied according to the procedure of application example 1, the remaining conditions were kept constant, and the conversion of chlorobenzene and dichlorobenzene on the catalyst of example 1 as a function of the amount of catalyst is shown in Table 2.
TABLE 2 relationship between catalytic combustion activity of chlorobenzene and dichlorobenzene on catalyst and catalyst loading
As can be seen from table 2, the catalyst of example 1 exhibited high catalytic combustion activity for both p-chlorobenzene and dichlorobenzene at catalyst dosages greater than 50mg, and the temperature was 304 ℃ at 90% chlorobenzene conversion.
Claims (10)
1. An iron-cerium composite oxide catalyst for VOCs treatment is characterized in that the catalyst is prepared from a composite oxide Ce of rare earth metal cerium (Ce) and transition metal iron (Fe)xFeyOzA catalyst in the form of a solid powder; wherein x =2 ~ 40, y =2 ~ 4, and z =7 ~ 86.
2. The iron-cerium composite oxide catalyst according to claim 1, wherein a molar ratio of the cerium element to the iron element in the catalyst is 19:1 to 1: 1.
3. The method for preparing an iron-cerium composite oxide catalyst according to claim 1 or 2, comprising the steps of:
(1) uniformly mixing the aqueous solution of the cerium precursor and the aqueous solution of the iron precursor to obtain a metal precursor mixed solution; (2) adding an alkali solution into the hydrothermal reaction kettle to adjust the pH value to 10, and stirring for 15-50 min; (3) heating the hydrothermal reaction kettle to 120-180 ℃, and carrying out hydrothermal reaction for 2-10 h; (4) cooling to room temperature, carrying out suction filtration to obtain a solid, and drying the washed solid at 40-80 ℃ for 2-10 h; obtaining the iron-cerium composite oxide catalyst.
4. The preparation method according to claim 3, wherein the cerium precursor is one or two of cerium nitrate, cerium sulfate and cerium carbonate; the iron precursor is one or two of ferric nitrate, ferric sulfate and ferric chloride; the alkali solution is weak alkali solution or strong alkali solution, and the weak alkali solution is one or more of sodium bicarbonate solution, sodium carbonate solution, potassium bicarbonate solution, potassium carbonate solution and ammonia water; the strong alkali solution is sodium hydroxide solution and/or potassium hydroxide solution.
5. The method according to claim 3, wherein in the step (2), the weak base solution is added to adjust the pH to 8 to 9, and then the strong base solution is added to adjust the pH to 10 to 11.
6. The preparation method according to claim 3, wherein the hydrothermal reaction is maintained at 140-160 ℃ for 3-5 hours.
7. Use of an iron cerium composite oxide catalyst according to claim 1 or 2, characterised in that it is used for low temperature catalytic combustion of volatile organic exhaust gases.
8. Use of an iron cerium composite oxide catalyst according to claim 7, comprising the steps of: filling the iron-cerium composite oxide catalyst into a fixed bed reactor, and removing volatile organic compounds in the exhaust gas after catalytic combustion by taking oxygen-containing gas as an oxidant; the catalytic combustion temperature is 150-450 ℃.
9. The use of the iron cerium composite oxide catalyst according to claim 7, wherein the fixed bed reactor is a quartz fixed bed reactor; the oxygen-containing gas is air, wherein the volume fraction of the oxygen is 2-20%; the loading amount of the catalyst is 25-150 mg; the amount of the catalyst for treating the waste gas per gram is 10-50L/h.
10. The application of the iron-cerium composite oxide catalyst according to claim 7, wherein the volatile organic compound is a chlorinated aromatic hydrocarbon volatile organic compound, and the concentration of the volatile organic compound in the exhaust gas is 0.1-5 vol%.
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