CN1132683C - Practical low-temperature CO oxidizing catalyst - Google Patents
Practical low-temperature CO oxidizing catalyst Download PDFInfo
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- CN1132683C CN1132683C CN00122829A CN00122829A CN1132683C CN 1132683 C CN1132683 C CN 1132683C CN 00122829 A CN00122829 A CN 00122829A CN 00122829 A CN00122829 A CN 00122829A CN 1132683 C CN1132683 C CN 1132683C
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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 relates to a load type gold catalyst for catalyzing and oxidizing carbon monoxide at a low temperature, which has the characteristics of low temperature catalytic activity, water steam poisoning resistance, sulfur poisoning resistance, etc. Au is selected as an active component of the present invention, and a carrier is Fe2O3 (or Co3O4, NiO, NiO. Fe2O3, TiO2, Al2O3, TiO2 / forming oxide). When a gas volume air speed is 1.5*10<3>h<-1>, the present invention can be used for catalyzing CO oxidation reaction under the conditions of environment temperature and environment moisture. When the CO concentration in raw gases is 1.0%, the reaction is continuously carried out for 300 minutes, and the CO penetrating concentration does not exceed 94 ppm. The catalyst can be used for devices (such as gas masks, etc.) for eliminating CO or indoor air purification.
Description
The invention catalytically oxidizes trace (0.1-1.0%) CO in air into CO at ambient temperature and humidity2And the pressure drop meets the requirements of gas masks, and the supported gold catalyst can be used practically.
CO is a leading pollutant in the air of many industrial and indoor environments, especially in air of violent battlefields, fire sites, mine tunnels and the like. Since CO binds to human hemoglobin 250 times as much as oxygen, hemoglobin is prevented from delivering absorbed oxygen to human tissues. The air containing 10ppm of CO has toxic action to human body. The short-term tolerance of The human body is also only 300ppm, and its danger to human health has long been valued by scientists (Stewart, R., The effect of CarbonOxide on Humans; Annu. Rev. Pharmacol., 1975, 15, 409-. The low concentration of CO that is widely present in ambient air and the long term exposure to such low concentrations (ppm level) of CO adversely affects human health (great, w.p., et al, environ.sci.tehnol., 1990, 20, 32-33) compel attention to methods of controlling the concentration of CO in ambient air.
The CO catalytic oxidation method has absolute advantages in terms of equipment volume and operational convenience over other methods, such as adsorption (Yaparpalvi, R.And Chuang K.T, Ind.Eng.chem.Res., 1991, 30, 2219-one 2225).
The catalytic oxidation method is to make CO and oxygen (O) in air at ambient temperature2) Catalytic oxidation reaction is carried out to generate CO2：
In recent years, the most studied CO oxidation catalyst is a supported noble metal catalyst (Cooper, B.J., Platinum Metals Rev., 1994, 38[3]: 101-. The reaction temperature is generally above 200 ℃. The common practice of eliminating low concentrations of CO in air, such as gas masks, indoor (workshop, spacecraft, submarine, living room, store, etc.) air purification, etc., must be done at ambient temperature and humidity. This requires that the catalyst not only have extremely high low temperature activity, but also have sufficiently good stability at relative humidities close to 100%.
At present, Hopcalilite catalyst which is a composite oxide catalyst (Lamb, A.B., Bray, W.C, Frazer, J.C.W; Ind.Eng.Chem., 1920, 12, 213) taking CuO-MnOx as a main component is a gas mask catalyst material which has been used in world war I, and has the fatal defect of poor water resistance, so that a drying tank with larger volume and heavier weight needs to be added before an oxidation tank.
The CO low-temperature oxidation catalyst studied in the laboratory also comprises: (1) transition metal oxides series. Such as Co3O4，MnO2，Co2O3(Pitzer, e.c., Frazer, j.c.w, j.phys.chem., 1941, 45, 761), and other metal oxide series (Yung Fang, Yu Tao, j.catal., 1974, 3, 108). (2) Supported oxide series. Such as CoOx/TiO2The catalyst (Moshida, i., et al, j. phys. chem., 1985, 89, 5439) has a high activity towards CO oxidation at room temperature, but after 15 minutes the catalyst deactivates rapidly. (3) Negative poleSupported noble metal catalysts, e.g. Pd/Fe2O3(Pavlova，S.N.，et al.，React.Kinet.Catal.Lett.，1996，59[1]，103-110)，Pt/SnO2(Li Shiyao，Li Beilu，React.Kinet.Catal.Lett.，1997，62[1]，151-156)，Pt(or Pd)/Al2O3(Shannon, M.D., et al., WO90/10394), Pt/oxide (Schlator, J.C., et al, WO90/04930), Pt-Ir/SDB (Styrene-Divinylbenzene Copolymer) (Yaparpalvi, R.And Chuang K.T., Ind.Eng.chem.Res., 1991, 30, 2219-one 2225). These catalysts are cost prohibitive (Lichunhua, Anriton et al, environmental chemistry, 1992, 13[ 3]]37) or at higher reaction temperatures (e.g. Pt-Pt/Al)2O3Etc.) or the appropriate CO concentration is too low (e.g., Pt-Ir/SDB) to be generalized. Heterogenized Wacker-type catalyst (PdCl)2-CuCl2Etc.) are highly active towards CO oxidation at temperatures close to 60 ℃, but only in the presence of water (Desai, m.n., Butt, j.b., j.cat., 1983, 79, 95). (4) A supported gold catalyst. Haruta et al found Fe2O3NiO, and the like oxide-supported gold catalysts have high activity for CO oxidation at room temperature (Haruta, M.Yamada, N., J.Catal., 1989, 115, 301; Hecheng, Anlitton, et al, Chin.Chen.Lett)1995, 6(4), 345 and 6(5), 447; kinet. catet. cat. lett., 1996, 59, 259), but the preparation method is mostly limited to the coprecipitation method (JP 92-3712228, JP 92-281846; anlitong, hechenping, chinese invention patent, CN 1125638), the obtained powdered sample has poor strength and is difficult to put into practical use.
The invention aims to find a catalyst which has high catalytic activity for CO oxidation reaction at the ambient temperature (-10-40 ℃) and the ambient humidity (relative humidity is 60-100%) and has stable performance and pressure drop meeting the practical requirement of gas masks.
The technical scheme is as follows: the preparation method of the supported gold catalyst for eliminating CO at low temperature is characterized in that the active component is gold, and the carrier is Co3O4、NiO、TiO2、Al2O3、TiO2Al2O3 with the atomic ratio of Au to Co, Ni, Ti and Al being 1.0: 1.0X 1031.0: 10. The preparation method adopts a deposition-precipitation method or a coprecipitation method. The catalyst can be used at the ambient temperature (-10-40 ℃) and the ambient humidity, has stable activity,can be directly applied to a device for eliminating CO by a gas mask, and avoids a drying tank before the catalyst.
Compared with the prior art, the invention has the substantial characteristic that ① has good low-temperature catalytic oxidation of CO into CO2② has good resistance to water vapor poisoning, stable activity under the condition that the relative humidity is less than or equal to 100 percent (23 ℃), a drying tank can be omitted before the catalyst bed, ③ the pressure drop of the catalyst bed meets the practical requirement of a gas mask, ④ has good sulfur poisoning resistance.
Detailed description of the invention
The active component of the catalyst is gold, and the carrier is Al2O3、TiO2、Co3O4、NiO、Fe2O3、NiO·Fe2O3Or TiO2/SiO2、TiO2/Al2O3。
The precursor compound of the active component gold can be metallic gold (wire, strip, gold,lump), chloroauric acid (HAuCl)4·H2O), gold trichloride (AuCl)3) And the like.
The precursor compound of the carrier can be nitrate, sulfate, acetate, chloride or metal alkoxide of the corresponding oxide, or the formed oxide.
The catalyst used in the invention is Fe2O3(or Co)3O4、NiO、TiO2、Al2O3) When used as a carrier, the atomic ratio of Au to Fe (Co, etc.) is 1.0: 1.0 × 103～1.0∶10。Fe (Co, etc.) atomic ratio of 1.0: 1.0X 103～1.0∶10。
The preparation method of the catalyst used in the invention can be a coprecipitation method or a deposition-precipitation method.
The coprecipitation method of the catalyst can be prepared by the following steps: adding a proper amount of gold salt solution and carrier metal salt solution dropwise to Na while stirring2CO3(or K)2CO3) And (3) standing, separating, roasting and activating the solution (or the reverse dropping sequence) to obtain the required catalyst.
The preparation process of the catalyst by a deposition-precipitation method can be as follows: vacuum drying preformed oxide carrier with high specific surface area, adding into active component precursor solution at controlled temperature (such as 350K), and adding dropwise alkaline solution (such as Na) under continuous stirring2CO3、K2CO3NaOH, KOH, etc.), controlling the pH value of the solution at a constant temperature to 4.5-8.5 until the precipitation is complete, and obtaining the finished catalyst through settling, filtering, washing, drying, roasting or activating treatment (Haruta, m., et al, in: "Preparation of CatalystVI", Poncelet, G., et al., eds., Elsevier, Amsterdam, 1995, pp 227-235).
The catalyst of the invention is used for evaluating the performance of CO catalytic oxidation reaction on a normal-pressure fixed bed reactor, and the used raw material gas comprises the following components: CO: 0.25-1.0%, and the balance air.
The conversion of CO was determined from the results of gas chromatography analysis, and the minimum detectable amount of CO was 50 ppm.
And partial catalysts are subjected to performance detection on a CO protective performance test device of a detection center of a Shanxi Xinhua chemical plant according to the use standard requirement. The raw material gas composition is as follows: CO: 0.25-1.0%, air is balance gas, and the humidity is controlled to be saturated humidity under 23 ℃.
The implementation mode and the best embodiment of the invention are as follows:
example 1: the catalyst was prepared by a deposition-precipitation method, and 1.0g of Al was formed2O3Adding the spherical carrier into water, adjusting the pH value to 7.5 by using a 1M NaOH solution under stirring, heating and maintaining the temperature at 70 ℃, then dropwise adding 1.04ml of chloroauric acid solution (9.7200gAu/L), maintaining the pH value at 7.5 by using the 1M NaOH solution, reacting for 1h, filtering, washing, drying at 60 ℃ for 12h, roasting at 350 ℃ for 2h under an air atmosphere to obtain Au/Al with the atomic ratio of Au to Al of 1: 4002O3The finished catalyst is granular and dark brown.
The raw material gas composition is as follows: CO: 1 percent; o is2：12％；N2: 87 percent (volume percent) and the gas volume space velocity of 1.5 multiplied by 104h-1In the case of (2), the complete conversion of CO (residual CO less than 50ppm of the spectrum detection limit of the gas phase) to CO2The allowable minimum reaction temperature of (1) (referred to as "minimum total conversion temperature", the same applies hereinafter) was-15 deg.C (258K).
Example 2: the catalyst was prepared by the deposition-precipitation method described in example 1, and 1.0g of TiO was added2Adding the carrier into water, adjusting pH value to 5.0 with 1M NaOH solution under stirring, heating and maintaining temperature at 70 deg.C, then dropwise adding chloroauric acid solution (9.7200gAu/L)1.04ml, maintaining pH value at 5.0 with 1M NaOH solution, reacting for 1h, filtering, washing, drying at 60 deg.C for 12h, and calcining at 300 deg.C for 2h under air atmosphere to obtain Au/TiO with Au/Ti atomic ratio of 1: 2502The finished product of the catalyst is light brown.
The feed gas described in example 1 was used under the same operating conditions with a minimum total CO conversion temperature of-10 ℃ (263K).
Example 3: Au/Fe with Au-Fe atomic ratio of 1: 80 prepared by adopting coprecipitation method2O3Catalyst, the finished product is uniformBlack in color.
The volume space velocity of the raw material gas and the gas in the application example 1 is 7.5 multiplied by 103h-1At the lowest total CO conversion temperatureThe degree is-19 ℃ (254K).
Example 4: Au/Al with Au to Al atomic ratio of 1: 200 prepared by deposition-precipitation method of example 12O3The finished catalyst is granular and dark brown.
The raw material gas composition is as follows: CO: 1.0 percent; the air is balance gas, the relative humidity is 100 percent (23 ℃), and the specific speed is as follows: 0.75L/cm2The test is carried out by using a CO protective performance test device of a measurement test center of Shanxi Xinhua chemical plant, the continuous reaction lasts for 300 minutes, the permeation concentration of CO is lower than 94ppm (standard requirement:<100ppm), the suction resistance after 30L test is less than or equal to 159Pa (standard requirement:<350Pa), and the suction resistance after 85L test is less than or equal to 682Pa (standard requirement:<880 Pa).
Example 5: Au/Al with Au to Al atomic ratio of 1: 200 prepared by deposition-precipitation method of example 12O3The finished catalyst is granular and dark brown.
The raw material gas composition is as follows: CO: 0.25 percent; the air is balance gas, the relative humidity is 100 percent (23 ℃), and the specific speed is as follows: 0.75L/cm2The test is carried out by using the CO protective performance test device in the example 4, the reaction is continuously carried out for 120 minutes, the permeation concentration of CO is lower than 29ppm (the standard requirement is less than 100ppm), the air suction resistance after 30L of test is less than or equal to 184Pa (the standard requirement is less than or equal to 350Pa), and the air suction resistance after 85L of test is less than or equal to 768Pa (the standard requirement is less than or equal to 880 Pa).
Example 6: Au/Al with Au to Al atomic ratio of 1: 200 prepared by deposition-precipitation method of example 12O3The finished catalyst is granular and dark brown.
The raw material gas composition is as follows: CO: 1.0 percent; the air is balance gas, the relative humidity is 100 percent (23 ℃), and the specific speed is as follows: 1.0L/cm2And (3) testing by using the CO protective performance testing device in the example 4, continuously reacting for 120 minutes, wherein the permeation concentration of CO is lower than 158ppm, and the air suction resistance after 30L of test is less than or equal to 241Pa (the standard requirement is less than or equal to 350 Pa).
Example 7: Au/Co with Au/Co atomic ratio of 1: 350 prepared by adopting coprecipitation method3O4The finished product of the catalyst is uniform black.
In example 1, the volume space velocity of the raw material gas and the gas is 7.5X 103h-1The minimum total conversion temperature of CO is-18 ℃.
Example 8: the Au/NiO catalyst prepared by the coprecipitation method and having the atomic ratio of Au to Ni of 1: 250 has a uniform black finished product.
In example 1, the volume space velocity of the raw material gas and the gas is 7.5X 103h-1The minimum total conversion temperature of CO is-14 ℃.
Example 9: in example 1, 15ppm H was added to the feed gas2S the catalyst described in example 1 was subjected to an experiment of sulfur poisoning resistance, and a CO catalytic oxidation reaction was continuously performed at room temperature for 120min, with no detectable change in the catalyst reactivity and no detectable CO concentration in the tail gas.
Example 10: mixing Al2O3Soaking in sol prepared with butyl titanate, filtering, drying, and calcining at 500 deg.C for 1 hr to obtain TiO2-Al2O3Composite support, prepared with 1.0 wt% Au/TiO by the deposition-precipitation method described in example 12-Al2O3The finished catalyst of (1) is uniform light brown.
In example 1, the volume space velocity of the raw material gas and the gas is 7.5X 103h-1The minimum total conversion temperature of CO is-16 ℃.
Example 11: 3 wt% Au/NiO. Fe prepared by the above coprecipitation method2O3The finished product of the catalyst is uniform black.
In example 1, the volume space velocity of the raw material gas and the gas is 7.5X 103h-1The lowest total conversion temperature of CO was-23 deg.C (250K).
Claims (3)
1. A practical low-temp catalytic CO oxidizing catalyst is prepared from Au as active component, Co3O4, NiO, TiO2, Al2O3, TiO2/Al2O3 as carrier, and Au/Co, Ni, Ti and Al in atomic ratio of 1.0: 1.0X 103-1.0∶10。
2. The method for preparing a practical low-temperature CO catalytic oxidation catalyst as set forth in claim 1, wherein the deposition-precipitation method is characterized in that the solution of the active ingredient can be added dropwise to the carrier suspension whose pH value is adjusted with alkali solution, or can be added dropwise in reverse order.
3. The catalyst for eliminating CO according to claim 1, which can be used at ambient temperature (-10 ℃ to 40 ℃) and ambient humidity, has stable activity, can be directly applied to a device for eliminating CO with a gas mask, and eliminates a drying tank before the catalyst.
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| CN00122829A CN1132683C (en) | 2000-08-29 | 2000-08-29 | Practical low-temperature CO oxidizing catalyst |
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| CN00122829A CN1132683C (en) | 2000-08-29 | 2000-08-29 | Practical low-temperature CO oxidizing catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006007774A1 (en) * | 2004-07-21 | 2006-01-26 | Lidun An | Catalyst with stable catalytic performance and the preparation method thereof |
Families Citing this family (9)
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| CN100333833C (en) * | 2004-12-24 | 2007-08-29 | 中国科学院兰州化学物理研究所 | Method for preparing environment friendly catalyst with gold carried |
| CN100435944C (en) * | 2007-03-13 | 2008-11-26 | 浙江大学 | Load type nano-au catalyst and the preparing method |
| CN101920210B (en) * | 2009-06-12 | 2012-01-25 | 中国科学院上海硅酸盐研究所 | Efficient nanocatalyst Au-VSB-5 for CO catalytic oxidation |
| CN101698149B (en) * | 2009-10-14 | 2012-11-07 | 安立敦 | Supported gold-PGM alloy catalyst with stable storage property and preparation method thereof |
| CN103191731A (en) * | 2013-03-26 | 2013-07-10 | 中国科学院山西煤炭化学研究所 | Au-Pd bimetallic catalyst for preparing methyl formate by selective oxidation of methanol as well as preparation method and application thereof |
| CN103301853B (en) * | 2013-06-20 | 2015-11-18 | 武汉大学 | A kind of Au catalyst and preparation and application of removing carbon monoxide, formaldehyde and ethene |
| CN103447060B (en) * | 2013-08-07 | 2015-06-03 | 中国科学院过程工程研究所 | Catalyst and treatment method for upgrading tar by using catalyst |
| CN103908890B (en) * | 2014-03-14 | 2015-10-28 | 中国石油集团工程设计有限责任公司 | sulfur-containing tail gas low-temperature catalytic oxidation process |
| CN104014340B (en) * | 2014-05-28 | 2016-08-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Loaded Cobalto-cobaltic oxide catalyst and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006007774A1 (en) * | 2004-07-21 | 2006-01-26 | Lidun An | Catalyst with stable catalytic performance and the preparation method thereof |
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