CN1676216A - Catalyst irontrioxide for carbon monoxide oxidation reaction and its preparing method - Google Patents

Catalyst irontrioxide for carbon monoxide oxidation reaction and its preparing method Download PDF

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CN1676216A
CN1676216A CNA2004100145454A CN200410014545A CN1676216A CN 1676216 A CN1676216 A CN 1676216A CN A2004100145454 A CNA2004100145454 A CN A2004100145454A CN 200410014545 A CN200410014545 A CN 200410014545A CN 1676216 A CN1676216 A CN 1676216A
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intermediate product
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CN1319646C (en
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谢毅
熊宇杰
李正全
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The present invention belongs to a gas-phase reaction catalyst and its preparation technique. In particular, it relates to a catalyst Fe2O3 for CO oxidation reaction and its preparation method. The matter phase of said catalyst is alpha-Fe2O3, its microstructure is nano line which contains 10-20 nano mesopore and whose outer diameter is 40-60 nano. Besides, said invention also provides the concrete steps of its preparation technique.

Description

Be used for catalyst di-iron trioxide of carbon monoxide oxidation reaction and preparation method thereof
Technical field
The invention belongs to the catalyst and the preparing technical field thereof that use in the gas-phase reaction, particularly relate to the catalyst Fe for the Oxidation of Carbon Monoxide reaction 2O 3And preparation method thereof.
Background technology
The catalytic oxidation process of CO gas all has higher utility at the aspects such as elimination of eliminating environmental pollution, purify air, seal carbon monoxide in internal-circulation type carbon dioxide laser, CO gas sensor, carbon monoxide gas mask and the closed system.Select appropriate catalyst extremely important for the oxidation of carbon monoxide.Low-cost, high transformation efficiency and good recycling performance are the Considerations of selecting catalyst.The catalyst of the oxidation reaction of carbon monoxide has a variety of, can be divided into the catalyst of low temperature conversion and pyrolytic conversion basically.The catalyst of low temperature conversion generally is the composite based on noble metal, and the catalyst of pyrolytic conversion mostly is oxide.High temperature shift catalysts can be used in vehicle exhaust and handle, commonly the compound of Ca-Ti ore type and spinel structure.Holland " catalysis wall bulletin " (Catalysis Letters, 1993 the 21st the volume 77 pages-87 pages), China's " natural gas chemistry magazine " (English edition, Journal of Natural Gas Chemistry, volume was 121 pages-127 pages in 1999 the 8th) and Switzerland's " materials chemistry and physics " (Materials Chemistry and Physics, volume was 355 pages-362 pages in 1993 the 38th) all report to some extent, but its synthetic method relates to technology such as sol-gel process, more complicated, and cost is also high.Holland " applied catalysis B " (Applied Catalysis B, volume was 151 pages-162 pages in 2003 the 43rd) has reported that average diameter is the commercial Fe of 3 nanometers recently 2O 3Nano particle is used for the situation of catalysis CO gas oxidation reaction, and the complete conversion temperature of first circulation is about 350 ℃, and the complete conversion temperature of second and third circulation then is more than 450 ℃, and this shows that its recycling performance is not fine.
Disclose a kind of in water solution system in the Chinese patent application 03132256.5, utilize low temperature and condition of normal pressure, the aqueous synthesis method of the beta-FeOOH nano-wire for preparing the homophase substrate and align, gained beta-FeOOH nano-wire product has semiconducting behavior, is applicable to the anode material of lithium battery.If prepare α-Fe as intermediate product 2O 3Product, the existence owing to its substrate makes to have a small amount of nano particle in the product, thereby has affected the catalytic performance in the Oxidation of Carbon Monoxide reaction.
Summary of the invention
The objective of the invention is to, propose a kind of catalyst Fe for the Oxidation of Carbon Monoxide reaction 2O 3And preparation method thereof, recycling performance is not so good in the existing catalyst, synthetic technology is complicated and the high in cost of production defective to overcome.
Catalyst Fe for the Oxidation of Carbon Monoxide reaction of the present invention 2O 3, it is characterized in that its phase is α-Fe 2O 3, micro-structural be contain the 10-20 mesoporous nano, external diameter is the nano wire of 40-60 nanometer.
The present invention is used for the catalyst Fe of Oxidation of Carbon Monoxide reaction 2O 3The preparation method, comprise that at first the mol ratio according to 1: 3 adds reactant ferrous chloride (FeCl in vessel 2) and Phen (1,10-phenanthroline), and add water and make frerrous chloride (FeCl 2) concentration reach 0.05mol/L, it is characterized in that, then mentioned solution was reacted under 10-40 ℃ more than 10 hours, filtration obtains crude product, the crude product water is carried out routine washing, drying, obtain the beta-FeOOH nano-wire intermediate product of powdery, wherein optimal reaction temperature is 15-25 ℃; At last the beta-FeOOH nano-wire intermediate product is heated to 520-540 ℃ of constant temperature 12-16 hour and gets catalyst Fe in vacuum environment 2O 3Product, wherein said vacuum are more than 99.99%.
By methods such as electron microscopic observation and pore-size distributions to the gained catalyst Fe 2O 3Product is tested and is learnt, its phase is α-Fe 2O 3, micro-structural be contain the 10-20 mesoporous nano, external diameter is the nano wire of 40-60 nanometer.
In the process of above-mentioned preparation beta-FeOOH nano-wire intermediate product, weight according to gained beta-FeOOH nano-wire intermediate product is calculated last frerrous chloride content in the aqueous solution that stays after the filtration, supply frerrous chloride content in solution then, make frerrous chloride and Phen raw material keep 1: 3 mol ratio, continue again to operate and obtain the beta-FeOOH nano-wire intermediate product by reaction condition, perhaps, utilize fluorescence photometer to detect and filter last frerrous chloride content in the aqueous solution that stays behind the beta-FeOOH nano-wire intermediate product, supply frerrous chloride content in solution then, make frerrous chloride and Phen raw material keep 1: 3 mol ratio, continue to operate obtaining the beta-FeOOH nano-wire intermediate product again by reaction condition.
Among the preparation method of the present invention, take two-step reaction to prepare the catalyst Fe that reacts for Oxidation of Carbon Monoxide 2O 3: the first step is reacted in the aqueous solution and is obtained the beta-FeOOH nano-wire intermediate product; Second step obtains catalyst Fe in 520-540 ℃ of lower vacuum environment 2O 3(α-Fe 2O 3The meso-porous nano line) product.Prepare in the course of reaction of beta-FeOOH nano-wire in the first step, only consumed frerrous chloride and water, and the utilization of part Phen energy iterative cycles does not have the consumption of use, has saved cost.Because frerrous chloride and water price are lower, make the cost of whole preparation process lower.
The catalyst Fe that adopts the inventive method to prepare 2O 3, in catalysis Oxidation of Carbon Monoxide course of reaction, the complete conversion temperature of its first circulation is 320 ℃, second and third circulation then is respectively 332 ℃ and 348 ℃, this illustrates that its complete conversion temperature is lower, and it is recycling functional, and being better than average diameter is the commercial Fe of 3 nanometers 2O 3Nano particle.This is to participate in reaction because the meso-hole structure of product can hold more gas molecule, thereby has reduced complete conversion temperature.This product is to prepare under the high temperature more than 500 ℃ on the other hand, so its good thermal stability, and recycling performance is also better.
Adopt the inventive method Kaolinite Preparation of Catalyst Fe 2O 3, its raw material is cheap and easy to get, and is easy and simple to handle, and technological process is simple, need not complex device, course of reaction is short; Environmentally safe; Productive rate is higher, and the raw material Phen can be recycled, utilization rate 100%, and cost is low; Product catalyst Fe 2O 3Catalytic performance good, be suitable for the batch production, industrial production has a extensive future.
Description of drawings
Fig. 1 is the catalyst Fe to the present invention's preparation 2O 3X-ray powder diffraction (XRD) style figure.
Fig. 2 is the catalyst Fe of the present invention's preparation 2O 3Field emission scanning electron microscope (FE-SEM) photo.
Fig. 3 is transmission electron microscope (TEM) photo of the product of the present invention's preparation.
Fig. 4 is the catalyst Fe of the present invention's preparation 2O 3Heating curve and the pore size distribution curves such as nitrogen suction-desorption.
Fig. 5 is the catalyst Fe of the present invention's preparation 2O 3The catalytic performance curve of three circulations in the oxidation reaction of carbon monoxide.
The specific embodiment
Embodiment 1:
In glass jar, add 2.5mmol frerrous chloride (FeCl 2) and part 7.5mmol Phen (1,10-phenanthroline), add 50ml water again, in 10 ℃ of constant temperature 24 hours; Filter products therefrom and wash with water 2 times, place 60 ℃ of dryings of vacuum drying chamber promptly to get intermediate product β-FeOOH powder 0.05g in 3 hours.The aqueous solution that stays after the filtration, weight 0.05g (0.56mmol) calculating according to products therefrom learns that frerrous chloride content last in the solution is 1.94mmol, supply 0.56mmol frerrous chloride in the aqueous solution that after filtration, stays then, continue reaction again, allow the utilization rate of Phen reach 100%.The β that obtains-FeOOH powder is heated to 520 ℃ of insulations namely got α-Fe in 16 hours in vacuum environment 2O 3Product, vacuum are 99.99%.
Embodiment 2:
In glass jar, add 2.5mmol frerrous chloride (FeCl 2) and part 7.5mmol Phen (1,10-phenanthroline), add 50ml water again, in 15 ℃ of constant temperature 18 hours; Filter products therefrom and wash with water 2 times, place 40 ℃ of dryings of vacuum drying chamber promptly to get intermediate product β-FeOOH powder 0.05g in 5 hours.The aqueous solution that stays after the filtration, weight 0.05g (0.56mmol) calculating according to products therefrom learns that frerrous chloride content last in the solution is 1.94mmol, supply 0.56mmol frerrous chloride in the aqueous solution that after filtration, stays then, continue reaction, allow the utilization rate of Phen reach 100%.The β that obtains-FeOOH powder is heated to 530 ℃ of insulations namely got α-Fe in 14 hours in vacuum environment 2O 3Product, vacuum are 99.99%.
Embodiment 3:
In glass jar, add 2.5mmol frerrous chloride (FeCl 2) and part 7.5mmol Phen (1,10-phenanthroline), add 50ml water again, in 25 ℃ of constant temperature 12 hours; Filter products therefrom and wash with water 2 times, place 80 ℃ of dryings of vacuum drying chamber promptly to get intermediate product β-FeOOH powder 0.05g in 1 hour.The aqueous solution that stays after the filtration utilizes fluorescence photometer to detect frerrous chloride content last in the solution and also is 1.94mmol, and supply 0.56mmol frerrous chloride in the aqueous solution that stays after filtration then continues reaction, allows the utilization rate of Phen reach 100%.The β that obtains-FeOOH powder is heated to 540 ℃ of insulations namely got α-Fe in 12 hours in vacuum environment 2O 3Product, vacuum are 99.99%.
Embodiment 4:
In glass jar, add 2.5mmol frerrous chloride (FeCl 2) and part 7.5mmol Phen (1,10-phenanthroline), add 50ml water again, in 25 ℃ of constant temperature 24 hours; The filtration products therefrom washes with water 2 times, dries naturally promptly to get intermediate product β-FeOOH powder 0.10g in 24 hours.The aqueous solution that stays after the filtration utilizes fluorescence photometer to detect frerrous chloride content last in the solution and also is 1.38mmol, and supply 1.12mmol frerrous chloride in the aqueous solution that stays after filtration then continues reaction, allows the utilization rate of Phen reach 100%.The β that obtains-FeOOH powder is heated to 530 ℃ of insulations namely got α-Fe in 14 hours in vacuum environment 2O 3Product, vacuum are 99.99%.
For the product that obtains in the foregoing description is characterized, adopting changes target X-ray powder diffraction (XRD), field emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), thermal cycle and the tests of the catalytic performance in the carbon monoxide oxidation reaction such as nitrogen suction-desorption, wherein product to the catalytic performance test condition of carbon monoxide oxidation reaction is: the 100 milligrams of samples of stainless steel tube splendid attire that with the diameter are 0.25cm, 3.11% carbon monoxide, the gaseous mixture of 8.03% oxygen and 88.86% nitrogen is given vent to anger with the gas chromatographic detection of FULI9750 conductance cell with the flow velocity air inlet of 360mL/min.
The product XRD style figure that provides according to Fig. 1 and standard style figure more as can be known, the phase of this product is α-Fe 2O 3
Show among FE-SEM photo Fig. 2 that the pattern of products obtained therefrom is a nano wire, external diameter is within 40-60nm, and length is 1-2 μ m, and white line segment is the length of the scale of 250nm among the figure.
Explanation product nano wire is meso-hole structure (is hollow structure, is similar to nanotube) among TEM photo Fig. 3, about mesoporous aperture 10-20nm.
Fig. 4 has expressed the result that hot testers such as nitrogen suction-desorption are tested product, can learn that from the pore size distribution curve analysis aperture of this product is 10-20nm, and average pore size is 15nm; By heating curves such as nitrogen suction-desorptions as can be known, its specific area is 19.06m 2/ g.
Fig. 5 is the catalytic performance curve of three circulations of this product oxidation reaction of being used for carbon monoxide, and as seen from the figure, the complete conversion temperature of first circulation is 320 ℃, and the complete conversion temperature of second and third circulation is respectively 332 ℃ and 348 ℃.Illustrate that it is recycling functional, be better than the Fe in the prior art that average diameter is 3 nanometers 2O 3Nano particle is a kind of catalyst of the oxidation reaction that is used for carbon monoxide well.

Claims (5)

1. one kind is used for the catalyst Fe that Oxidation of Carbon Monoxide reacts 2O 3, it is characterized in that its phase is α-Fe 2O 3, micro-structural be contain the 10-20 mesoporous nano, external diameter is the nano wire of 40-60 nanometer.
2. one kind is used for the catalyst Fe that Oxidation of Carbon Monoxide reacts 2O 3The preparation method, comprise that at first the mol ratio according to 1: 3 adds reactant ferrous chloride (FeCl in vessel 2) and Phen (1,10-phenanthroline), and add water and make frerrous chloride (FeCl 2) concentration reach 0.05mol/L, it is characterized in that, then mentioned solution was reacted under 10-40 ℃ more than 10 hours, filter and to obtain crude product, again the crude product water is carried out that routine washed, drying, obtain the beta-FeOOH nano-wire intermediate product of powdery; At last the beta-FeOOH nano-wire intermediate product is heated to 520-540 ℃ of constant temperature 12-16 hour and namely gets catalyst Fe in vacuum environment 2O 3Product, described vacuum are more than 99.99%.
3. catalyst Fe as claimed in claim 2 2O 3The preparation method, it is characterized in that the optimal reaction temperature of described preparation crude product is 15-25 ℃.
4. catalyst Fe as claimed in claim 2 2O 3The preparation method, it is characterized in that, in the process of above-mentioned preparation beta-FeOOH nano-wire intermediate product, weight according to gained beta-FeOOH nano-wire intermediate product is calculated last frerrous chloride content in the aqueous solution that stays after the filtration, in solution, resupply then frerrous chloride content, so that frerrous chloride and Phen raw material are kept 1: 3 mol ratio, continue again to operate by reaction condition and obtain the beta-FeOOH nano-wire intermediate product.
5. catalyst Fe as claimed in claim 2 2O 3The preparation method, it is characterized in that, in the process of above-mentioned preparation beta-FeOOH nano-wire intermediate product, utilize fluorescence photometer to detect and filter last frerrous chloride content in the aqueous solution that stays behind the beta-FeOOH nano-wire intermediate product, in solution, resupply then frerrous chloride content, so that reaction raw materials is kept 1: 3 mol ratio, continue again to operate by reaction condition and obtain the beta-FeOOH nano-wire intermediate product.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1331730C (en) * 2006-01-12 2007-08-15 天津大学 Method for preceding to oxidize CO in hydrogen-riched air
CN100369703C (en) * 2006-03-28 2008-02-20 华中师范大学 Fe nanowire and preparation method thereof
CN1986427B (en) * 2005-12-21 2010-04-14 中国科学院化学研究所 Nano ferric oxide material and its preparing process and use in water treatment
CN105056719A (en) * 2015-07-30 2015-11-18 福州大学化肥催化剂国家工程研究中心 Preparation method of FeOOH low-temperature desulfurizer and desulfurizer prepared through same
CN110205748A (en) * 2019-04-30 2019-09-06 西南石油大学 A kind of composite nano-fiber membrane and the preparation method and application thereof of β-FeOOH/ polyacrylonitrile

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102134103A (en) * 2011-02-18 2011-07-27 中山火炬职业技术学院 Method for preparing hydroxyl iron oxide nanowire

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4597958A (en) * 1984-09-17 1986-07-01 Mitsui Mining & Smelting Co., Ltd. Method of producing hydrated iron oxide
CN1186266C (en) * 2003-08-07 2005-01-26 中国科学技术大学 Water phase synthetically preparing method of homophase base oriented arranged hydroxy iron oxide nano line

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1986427B (en) * 2005-12-21 2010-04-14 中国科学院化学研究所 Nano ferric oxide material and its preparing process and use in water treatment
CN1331730C (en) * 2006-01-12 2007-08-15 天津大学 Method for preceding to oxidize CO in hydrogen-riched air
CN100369703C (en) * 2006-03-28 2008-02-20 华中师范大学 Fe nanowire and preparation method thereof
CN105056719A (en) * 2015-07-30 2015-11-18 福州大学化肥催化剂国家工程研究中心 Preparation method of FeOOH low-temperature desulfurizer and desulfurizer prepared through same
CN105056719B (en) * 2015-07-30 2017-10-10 福州大学化肥催化剂国家工程研究中心 The preparation method and desulfurizing agent obtained by this method of a kind of FeOOH low-temp desulfurization agent
CN110205748A (en) * 2019-04-30 2019-09-06 西南石油大学 A kind of composite nano-fiber membrane and the preparation method and application thereof of β-FeOOH/ polyacrylonitrile
CN110205748B (en) * 2019-04-30 2022-04-01 西南石油大学 Composite nanofiber membrane of beta-FeOOH/polyacrylonitrile as well as preparation method and application thereof

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