WO2006007774A1 - Catalyst with stable catalytic performance and the preparation method thereof - Google Patents

Catalyst with stable catalytic performance and the preparation method thereof Download PDF

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Publication number
WO2006007774A1
WO2006007774A1 PCT/CN2005/000602 CN2005000602W WO2006007774A1 WO 2006007774 A1 WO2006007774 A1 WO 2006007774A1 CN 2005000602 W CN2005000602 W CN 2005000602W WO 2006007774 A1 WO2006007774 A1 WO 2006007774A1
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catalyst
carrier
catalytic performance
solution
stable
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PCT/CN2005/000602
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Chinese (zh)
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Lidun An
Shixue Qi
Xuhua Zou
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Lidun An
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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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • 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
    • B01J23/005—Spinels
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation

Definitions

  • Hopcalite catalyst which is a composite oxide catalyst with Cu0_Mn0x as its main component (Lamb, AB, Bray, IC, Frazer, JCW; Ind. Eng. Chem., 1920, 12, 213).
  • Hopcalite catalyst is a composite oxide catalyst with Cu0_Mn0x as its main component (Lamb, AB, Bray, IC, Frazer, JCW; Ind. Eng. Chem., 1920, 12, 213).
  • Gas mask catalyst materials that have been used in World War I. Its fatal shortcoming is poor water resistance, so a larger, heavier "drying tank” must be added before the "oxidation tank”.
  • the melting point of nano-gold particles is significantly lower than that of bulk metals.
  • the melting point of ⁇ 3 nm gold particles is close to 850K (Huettig Temperature ⁇ 10 °C), ie in use and storage.
  • the growth of gold particles during the process is one of the important reasons for the deactivation of such catalysts.
  • Other reasons for deactivation may also be the formation of carbonate on the surface of the catalyst (Kim Chang Hwan & Thompson LT; "Gold 2003"), the negative effect of water on the stability of the catalyst (Wang Gui-ying, et al. 1557-1562, 2000), and poisoning of ions (such as C1 -, CN” ions) that form complexes with gold.
  • a supported gold catalyst with stable catalytic performance characterized in that: the active component is Au, the carrier is ruthenium, MlIOx modified A1 2 0 3 , Ti0 2 / A1 2 0 3 , Au and ( ⁇ + ⁇
  • the atomic ratio is 1.0: 1.0 to 1.0: 10, and the atomic ratio of ⁇ I to ⁇ is 2.0: 1.0 to 0.2: 1.0; the atomic ratio of Au to A1 is 1.0: 1 ⁇ 0 ⁇ 10 3 ⁇ 1.0: 10.
  • the support can be a shaped oxide or a modified shaped oxide support.
  • the carrier is prepared by a dipping method or a coprecipitation method. After the shaped carrier is loaded with MI0x and Mil Ox, it is calcined at 800 ° C - lOOCTC to form a spinel (AB 2 0 4 ) or perovskite (AB0 3 ) structure. After the catalyst precursor is reduced by hydrogen, a part of Au forms an alloy Au x MI with the easily reductible MI Ox.
  • the invention adopts a composite oxide modified 1 2 0 3 or 1 ⁇ 0 2 as a carrier to prepare a supported nano gold catalyst, and the substantial characteristics thereof are: between the nano gold particles on the surface of the catalyst and the transition metal oxide of the spinel structure.
  • the strong interaction, and some gold particles form an alloy structure with the transition metal, thereby stabilizing the stability of the structure and catalytic activity of the supported nano-gold catalyst during long-term use and storage.
  • the invention Compared with the prior art, the invention also has the following essential features: 1 has good catalytic activity of low temperature catalytic oxidation of CO to co 2 ; 2 has good resistance to water vapor poisoning, and has a relative humidity of 100% (23) In the case of °C), the activity is stable and the drying tank can be omitted before the catalyst bed. 3 has good long-term storage resistance, long-term (years) sealed storage at room temperature, catalyst catalytic performance is not Change. 4 bed pressure drop meets the practical requirements of gas masks. 5 has good resistance to sulfur poisoning. The best way to implement the invention
  • the active component of the catalyst of the present invention is gold, the carrier is ⁇ , ⁇ modified ⁇ 1 2 0 3 ,
  • Ti0 2 /Si0 2 or Ti0 2 /AL0 3 Ti0 2 /Si0 2 or Ti0 2 /AL0 3 .
  • the precursor compound of the above active component gold may be metal gold (filament, bar, block), chloroauric acid (HAuCl 4 ⁇ 0), gold trichloride (AuCl 3 ) or the like.
  • the precursor compound of the carrier may be a nitrate, a sulfate, an acetate, a chloride or a metal alkoxide of the corresponding oxide, or a formed oxide.
  • the modified transition metal oxide M I Ox, the precursor of Mil Ox may be a nitrate, a sulfate, an acetate or a chloride of the corresponding oxide, wherein Ml is Cu, Mil is Fe, or Co, or ⁇ .
  • the atomic ratio of Au to A1 or the like is 1.0: 1.0 ⁇ 10 3 ⁇ 1 ⁇ 0: 10.
  • the atomic ratio of Au to ( ⁇ + ⁇ ) is 1.0: 1.0 to 1.0: 10
  • the atomic ratio of M1 to Mil is 2.0: 1.0 to 0.2: 1.0.
  • the preparation method of the catalyst carrier used in the present invention may be a coprecipitation method or a dipping method.
  • the coprecipitation preparation process of the catalyst carrier may be: adding an appropriate amount of a salt solution of MI and Mil metal salt solution and a carrier metal to the solution of N C0 3 (or K 2 C0 3 ) under stirring, and allowing to stand and separate.
  • the calcination and activation treatments provide the desired catalyst support.
  • the preparation process of the impregnation method of the catalyst carrier may be: impregnating an appropriate amount of MI and Mil metal salt solution with a shaped carrier (such as A1 2 0 3 ), leaving it for at least 1 hour, and drying and calcining to obtain a composite oxide carrier.
  • a shaped carrier such as A1 2 0 3
  • the loading of the nano gold is carried out by a deposition-precipitation method or an anion impregnation method.
  • the nano-gold anion impregnation method uses the patent technology of the applicant's laboratory (An Lidun, Qi Shixue, Suo Zhanghuai, Weng Yonggen, Zou Xuhua; a new preparation method of supported nano-gold catalyst, Chinese invention patent application number: 03138796. 1, application date: July 8, 2003).
  • the catalyst of the present invention is subjected to an evaluation of the performance of the catalytic oxidation of the CO in a normal-pressure fixed-bed reactor.
  • the composition of the raw material gas used is: CO: 0. 25-1. 0%, and the rest is air.
  • Catalyst heat resistance test The finished catalyst was placed in a dry box at 120 ° C for 72 h to test the activity change of the catalyst.
  • Anti-wetting performance test of the catalyst The finished catalyst was placed in a reaction tube and continuously reacted with a water vapor-saturated feed gas at room temperature for 72 h, or continuously treated with water vapor saturated air at room temperature for the same gas velocity for 72 h to test the activity of the catalyst. Variety.
  • the gas volumetric space velocity is 1. 5 X 10 4 h - 1 , complete conversion of CO (residual CO is below the gas chromatographic detection limit of 50 ppm.
  • the allowable minimum reaction temperature for C0 2 (referred to as the "lowest total conversion temperature", the same below) is -18 ° C (255 K). 5°C ⁇ The minimum conversion temperature is 18.5 ° C.
  • the thermal resistance test of the catalyst The finished catalyst was heated in an air atmosphere at 12 CTC for 72 h in a dry box, and the catalytic activity was tested to a minimum full conversion temperature of 20. 0 ° C after cooling to room temperature.
  • the catalyst is tested for its moisture resistance.
  • the catalyst is placed in a reaction tube and the water is saturated with water at room temperature to evaluate the reaction at the same gas rate for 72 hours.
  • the activity of the catalyst is tested.
  • the minimum total conversion temperature is 14.1 ° ( :.
  • the composition of the raw material gas is: C0: 1. 0%;
  • the air is the equilibrium gas, the relative humidity is 100% (23 °C), and the specific speed is: 0.75 L/min. cm 2 , with the measurement and test center of a certain chemical plant in Shanxi
  • the CO protection performance test device was tested, continuous reaction for 300 minutes, C0 permeation concentration was lower than 54ppm (standard requirement: OOpprn), after inhalation resistance 159Pa after 30L test (standard requirement: 350Pa), 85L after test Air resistance 682Pa (standard requirements: 880Pa).
  • Example 4 The catalyst of Example 3 was placed in a jar at room temperature for 1 year, and its catalytic performance was evaluated.
  • the composition of the raw material gas is: CO: 0.25%; the air is the equilibrium gas, the relative humidity is 100% (23 °C), and the specific speed is: 0.65 L/min. cm2, and the CO protection performance test of the measurement and test center of a certain chemical plant in Shanxi
  • the device was tested and continuously reacted for 30 minutes.
  • the CO permeation concentration was less than 2 ppm (standard requirement. ⁇ ⁇ 100 ⁇ )
  • the inspiratory resistance after 184Pa was 184Pa (standard requirement: 350Pa)
  • the inspiratory resistance after 85L was 768Pa (standard requirements: 880Pa;).
  • the catalytically stable supported gold catalyst of the present invention and the preparation method thereof are suitable for use in a gas mask, indoor (workshop, spacecraft, submarine, living room, store, etc.) air purification. ⁇

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

This invention discloses a carried Au catalyst with staff e catalytic performance and the preparation method thereof. The active component of the catalyst is Au and the carrier is A12O3 or TíO2/A12O3 dedicated by MIOx and MIIOx, wherein the atomic ratio of Au to (MI + MII) is 1.0:1.0~1.0:10, MI to MII is 2.0:1.0~0.2:1.0 and Au to A1 is 1.0:1.0 X 103 ~1.0:10. The substantial characteristics of the invention are the strong interaction between the Au nanoparicles and the oxides of transition metal with pinel structure, as well as the alloy structure forming by part of Au nanoparticles and the transition metals. Thus, the stability of structure and catalytic activity of the carried nano-Au catalyst is remained during the long-term use.

Description

催化性能稳定的负载型金催化剂及其制备方法 技术领域  Supported gold catalyst with stable catalytic performance and preparation method thereof
本发明涉及一种金催化剂， 具体地讲， 是在环境温度、 环境湿度下催化 氧化空气中微量（0. 1%〜1. 0%) CO成 C02, 催化性能稳定，且压力降满足防毒 面具和空气净化要求的、 具工业实用性的催化性能稳定的负载型金催化剂及 其制备方法。 背景技术  The invention relates to a gold catalyst, in particular, a catalytically oxidizing air in a small amount (0.1%~1. 0%) CO to C02 under ambient temperature and ambient humidity, the catalytic performance is stable, and the pressure drop satisfies the gas mask And a commercially available catalytically stable supported gold catalyst and a preparation method thereof, which are required for air purification. Background technique
目前， 我国的防毒面具多用 Hopcalite催化剂， 它是以 Cu0_Mn0x为主要 成份的复合氧化物催化剂 （Lamb， A. B.， Bray, I C, Frazer, J. C. W.； Ind. Eng. Chem. , 1920, 12， 213), 是在第一次世界大战中就已经使用过的防毒 面具催化剂材料。 其致命缺点是抗水性差， 因此 "氧化罐"前必须再加一个 体积更大， 重量更重的 "干燥罐" 。负载型金催化剂可在环境温度（-io°c〜 40°C )和环境湿度下消除 CO (安立敦， 齐世学、 邹旭华， 索掌怀； 实用型低 温 CO催化氧化催化剂； 中国发明专利 ZL 00 1 22829. 3 ), 应用于防毒面具 可免去催化剂前干燥罐。 但负载型金催化剂的稳定性是影响其工业应用的关 键因素之一。 TEM 照片表明， 失活催化剂 Au/Ti02 的金颗粒明显大于新鲜 Au/Ti02的金颗粒。 Wronski的计算表明， 纳米金颗粒 （特别是〈10 nm) 的熔 点较块状金属有明显降低， 例如， Φ 3 nm金颗粒的熔点接近 850K ( Huettig Temperature 〜10 °C )， 即在使用和储存过程中金颗粒的长大是这类催化 剂失活的重要原因之一。 失活的其它原因可能还有催化剂表面碳酸盐的生成 (Kim Chang Hwan & Thompson L T ； "Gold 2003 " )，水对催化剂稳定性的 负效应 (Wang Gui- ying，et al.化学学报 58， 1557-1562， 2000)，以及易与金 形成配合物的离子 （如 C1—，CN"离子） 的中毒。 At present, China's gas masks mostly use Hopcalite catalyst, which is a composite oxide catalyst with Cu0_Mn0x as its main component (Lamb, AB, Bray, IC, Frazer, JCW; Ind. Eng. Chem., 1920, 12, 213). Gas mask catalyst materials that have been used in World War I. Its fatal shortcoming is poor water resistance, so a larger, heavier "drying tank" must be added before the "oxidation tank". Supported gold catalyst can eliminate CO at ambient temperature (-io °c~ 40 °C) and ambient humidity (An Lidun, Qi Shixue, Zou Xuhua, Suo Zhanghuai; practical low temperature CO catalytic oxidation catalyst; Chinese invention patent ZL 00 1 22829. 3), applied to the gas mask can eliminate the pre-catalyst drying tank. However, the stability of supported gold catalysts is one of the key factors affecting its industrial application. TEM photographs show that the gold particles of the deactivated catalyst Au/Ti0 2 are significantly larger than the gold particles of fresh Au/Ti0 2 . Wronski's calculations show that the melting point of nano-gold particles (especially <10 nm) is significantly lower than that of bulk metals. For example, the melting point of Φ 3 nm gold particles is close to 850K (Huettig Temperature ~10 °C), ie in use and storage. The growth of gold particles during the process is one of the important reasons for the deactivation of such catalysts. Other reasons for deactivation may also be the formation of carbonate on the surface of the catalyst (Kim Chang Hwan & Thompson LT; "Gold 2003"), the negative effect of water on the stability of the catalyst (Wang Gui-ying, et al. 1557-1562, 2000), and poisoning of ions (such as C1 -, CN" ions) that form complexes with gold.
负载型金催化剂的某些稳定化措施已经建议和试验， 例如， 采用酸性载 体以防止催化剂表面碳酸盐的生成（G C Bond & D T Thompson, Catal. Rev. -Sci. Eng. , 41, 319-388, 1999)， 加入其它氧化物助剂或与其它过渡金属 生成合金以阻止金颗粒在使用和储存过程中长大， 例如， Au/Ti02- Ce02 (Petrov L. A，1998)， Au/Zr02— Ce02 (Plzak, V ， WO 03/068389 Al, 21 Aug 2003) , Au/ Fe203 (or MnOx) _MgO/Al203 (Grisel ， R， et al. , Catalysis Today , 72， 123-132， 2002) 和 Au- Pd/support (DEGUSA AG, 2001) , Au-PGMs/Zr02-Ce02 ( arecot P, 1999) , 或采用不含 CI—离子的金属化合物前 驱体。 Holger Falke, et al. (USP 5068217, Nov 26 1991)曾用 Fe203/ A1203 复合氧化物载体制备出高活性的负载型金催化剂。 Grisel, R J H et al. (Catalysis Today, 64, 69-81， 2001 )还发现， 加入 M0x (M=Cr, Mn, Fe, Co, Ni , Cu and Zn) 到 Au/ A1203中可以提高载体上小金颗粒的热稳定性。 该方案均系加入单一氧化物助剂， 未经长期稳定性实验。 Some stabilization measures for supported gold catalysts have been suggested and tested, for example, with acid loading To prevent the formation of carbonate on the catalyst surface (GC Bond & DT Thompson, Catal. Rev. -Sci. Eng., 41, 319-388, 1999), adding other oxide promoters or alloying with other transition metals. Prevents gold particles from growing during use and storage, for example, Au/Ti0 2 - Ce0 2 (Petrov L. A, 1998), Au/Zr0 2 — Ce0 2 (Plzak, V, WO 03/068389 Al, 21 Aug 2003), Au/Fe 2 0 3 (or MnOx) _MgO/Al 2 0 3 (Grisel, R, et al., Catalysis Today, 72, 123-132, 2002) and Au-Pd/support (DEGUSA AG, 2001 ), Au-PGMs/Zr0 2 -Ce0 2 (arecot P, 1999), or a metal compound precursor containing no CI-ion. Holger Falke, et al. (USP 5068217, Nov 26 1991) used a Fe 2 O 3 / A1 2 3 composite oxide support to prepare a highly active supported gold catalyst. Grisel, RJH et al. (Catalysis Today, 64, 69-81, 2001) also found that the addition of M0x (M=Cr, Mn, Fe, Co, Ni, Cu and Zn) to Au/A1 2 0 3 can be improved. Thermal stability of the small gold particles on the carrier. The program is a single oxide additive that has not been tested for long-term stability.
通常遇到的要消除空气中低浓度的 C0, 例如防毒面罩、 室内 （车间、 航 天器、 潜艇、 居室、 商店等） 空气净化等， 必须在环境温度和湿度下进行。 这就要求催化剂不仅要有极高的低温活性，而且在相对湿度接近 100%情况下 要有足够好的稳定性。 已授权 （安立敦， 齐世学、 邹旭华， 索掌怀； 实用型 低温 C0催化氧化催化剂； ZL 00 1 22829. 3) 和正在进行实质性审查的专利 (安立敦， 齐世学、 邹旭华， 索掌怀； 用于 C0低温催化氧化的负载型纳米金 催化剂； PCT国际申请号: PCT/CN01/01582; 国际申请日： 2001年 11月 23 日）所题专利催化剂可在储存一年的时间内保持高的催化活性，以后其活性便 逐渐降低， 直至不能满足使用要求， 即催化剂的长期储存稳定性尚有不足。 发明的公开  Commonly encountered to eliminate low concentrations of C0 in the air, such as gas masks, indoor (workshops, spacecraft, submarines, homes, shops, etc.) air purification, etc., must be carried out at ambient temperature and humidity. This requires that the catalyst not only has a very high low temperature activity, but also has a sufficiently good stability at a relative humidity of approximately 100%. Authorized (An Lidun, Qi Shixue, Zou Xuhua, Suo Zhanghuai; Practical Low Temperature C0 Catalytic Oxidation Catalyst; ZL 00 1 22829. 3) and patents under substantive review (An Lidun, Qi Shixue, Zou Xuhua, Suo Zhanghuai; Supported nano-gold catalyst for C0 low-temperature catalytic oxidation; PCT International Application No.: PCT/CN01/01582; International filing date: November 23, 2001) The patented catalyst can maintain high catalysis during storage for one year. After the activity, the activity will gradually decrease until the requirements for use are not met, that is, the long-term storage stability of the catalyst is insufficient. Disclosure of invention
本发明的目的在于寻找一种在环境温度（一 10° ( 〜 50°C )和环境湿度（相 对湿度 60%〜100%) 下催化反应活性高、 性能稳定的、 压力降满足防毒面具 和空气净化实用要求的催化剂以及其制备方法。 称为催化性能稳定的负载型 金催化剂及其制备方法。 The object of the present invention is to find a catalytic activity with high pressure and stable performance at ambient temperature (10 ° (~ 50 ° C) and ambient humidity (relative humidity 60% ~ 100%), pressure drop to meet the gas mask And a catalyst for practical purification of air and a preparation method thereof. It is called a supported gold catalyst with stable catalytic performance and a preparation method thereof.
技术方案： 一种催化性能稳定的负载型金催化剂， 其特征在于： 活性组 分为 Au， 载体为 ΜΙΟχ, MlIOx修饰的 A1203、 Ti02/ A1203, Au与（ΜΙ+ΜΠ) 的原子比为 1.0: 1.0〜1.0： 10， Μ I与 ΜΠ的原子比为 2.0： 1.0〜0.2： 1.0; Au与 A1的原子比为 1.0: 1·0Χ103〜1.0: 10。 Technical Solution: A supported gold catalyst with stable catalytic performance, characterized in that: the active component is Au, the carrier is ruthenium, MlIOx modified A1 2 0 3 , Ti0 2 / A1 2 0 3 , Au and (ΜΙ+ΜΠ The atomic ratio is 1.0: 1.0 to 1.0: 10, and the atomic ratio of Μ I to ΜΠ is 2.0: 1.0 to 0.2: 1.0; the atomic ratio of Au to A1 is 1.0: 1·0 Χ 10 3 〜 1.0: 10.
其中 MI为 Cu， Mil为 Fe， 或 Co, 或 Ni。  Where MI is Cu and Mil is Fe, or Co, or Ni.
载体可以是成型氧化物或改性的成型氧化物载体。  The support can be a shaped oxide or a modified shaped oxide support.
载体是采用浸渍方法或共沉淀方法制备， 成型载体负载 MI0x， Mil Ox 后， 经过 800°C- lOOCTC的焙烧， 以生成尖晶石 （AB204) 或钙钛石 （AB03) 结 构，催化剂前体经氢气还原后， 部分 Au与易还原的 M I Ox生成合金 AuxM I。 The carrier is prepared by a dipping method or a coprecipitation method. After the shaped carrier is loaded with MI0x and Mil Ox, it is calcined at 800 ° C - lOOCTC to form a spinel (AB 2 0 4 ) or perovskite (AB0 3 ) structure. After the catalyst precursor is reduced by hydrogen, a part of Au forms an alloy Au x MI with the easily reductible MI Ox.
催化性能稳定的负载型金催化剂的制备方法是： 将预先成型的具有高比 表面积的氧化物载体经真空干燥处理后置入控制温度（例如 350K)下的活性 组分前体溶液中， 在连续搅拌中逐滴加入碱溶液 （如 Na2C03、 K2C03、 Na0H、 K0H等）， 在恒温下控制溶液 pH值为 4.5〜8.5， 直至沉淀完全， 经沉降、 过 滤、 洗涤、 千燥、 焙烧或活化处理得成品催化剂。 The catalytically stable supported gold catalyst is prepared by: pre-forming an oxide carrier having a high specific surface area by vacuum drying and placing it in an active component precursor solution at a controlled temperature (for example, 350 K) in a continuous manner. Add alkali solution (such as Na 2 C0 3 , K 2 C0 3 , Na0H, K0H, etc.) dropwise while stirring, and control the pH of the solution to 4.5~8.5 at constant temperature until the precipitation is complete, after sedimentation, filtration, washing, drying , calcination or activation treatment to obtain a finished catalyst.
本发明采用复合氧化物修饰的 1203或 1^02为载体， 制备负载型纳米金 催化剂， 其实质性特点是： 催化剂表面的纳米金颗粒与尖晶石结构过渡金属 氧化物之间的的强相互作用， 以及部分金颗粒与过渡金属形成合金结构， 从 而稳定了负载型纳米金催化剂在长期使用和储存过程中的结构和催化活性的 稳定性。 The invention adopts a composite oxide modified 1 2 0 3 or 1^0 2 as a carrier to prepare a supported nano gold catalyst, and the substantial characteristics thereof are: between the nano gold particles on the surface of the catalyst and the transition metal oxide of the spinel structure. The strong interaction, and some gold particles form an alloy structure with the transition metal, thereby stabilizing the stability of the structure and catalytic activity of the supported nano-gold catalyst during long-term use and storage.
与已有技术相比， 本发明还具有的实质性特点是： ①具有良好的低温催 化氧化 C0成 co2的催化活性； ②具有良好的抗水蒸汽中毒的性能， 在相对湿 度 100% (23°C) 情况下， 活性稳定， 催化剂床层前可省去干燥罐。 ③具有 良好的耐长期储存性能， 室温下长期 （数年） 密封储存， 催化剂催化性能不 变。 ④床层压力降符合防毒面具实用要求。 ⑤具有良好的抗硫中毒能力。 实现本发明的最佳方式 Compared with the prior art, the invention also has the following essential features: 1 has good catalytic activity of low temperature catalytic oxidation of CO to co 2 ; 2 has good resistance to water vapor poisoning, and has a relative humidity of 100% (23) In the case of °C), the activity is stable and the drying tank can be omitted before the catalyst bed. 3 has good long-term storage resistance, long-term (years) sealed storage at room temperature, catalyst catalytic performance is not Change. 4 bed pressure drop meets the practical requirements of gas masks. 5 has good resistance to sulfur poisoning. The best way to implement the invention
以下是本发明的详细说明。  The following is a detailed description of the invention.
本发明的催化剂的活性组分为金， 载体为 Μΐθχ, ΜΙΙΟχ修饰的 Α1203、The active component of the catalyst of the present invention is gold, the carrier is Μΐθχ, ΜΙΙΟχmodified Α1 2 0 3 ,
Ti02/Si02 或 Ti02/AL03。 Ti0 2 /Si0 2 or Ti0 2 /AL0 3 .
上述活性组分金的前身化合物可以是金属金 （丝、 条、 块）、 氯金酸 (HAuCl4 · 0)， 三氯化金 (AuCl3) 等。 The precursor compound of the above active component gold may be metal gold (filament, bar, block), chloroauric acid (HAuCl 4 · 0), gold trichloride (AuCl 3 ) or the like.
载体的前身化合物可以是对应氧化物的硝酸盐、 硫酸盐、 醋酸盐、 氯化 物或金属醇盐等，或是已成型的氧化物。修饰的过渡金属氧化物 M I Ox, Mil Ox 的前身可以是对应氧化物的硝酸盐、 硫酸盐、 醋酸盐、 氯化物， 其中 Ml为 Cu， Mil为 Fe， 或 Co, 或 Νί。  The precursor compound of the carrier may be a nitrate, a sulfate, an acetate, a chloride or a metal alkoxide of the corresponding oxide, or a formed oxide. The modified transition metal oxide M I Ox, the precursor of Mil Ox may be a nitrate, a sulfate, an acetate or a chloride of the corresponding oxide, wherein Ml is Cu, Mil is Fe, or Co, or Νί.
本发明所用催化剂以 Α1203等为载体时， Au 与 A1 等的原子比为 1.0: 1.0Χ103〜1·0: 10。 Au与（ΜΙ+ΜΠ)的原子比为 1.0: 1.0〜1.0： 10， Ml与 Mil的原子比为 2.0: 1.0 〜0.2: 1.0。 When the catalyst used in the present invention is supported by Α1 2 0 3 or the like, the atomic ratio of Au to A1 or the like is 1.0: 1.0 Χ 10 3 〜1·0: 10. The atomic ratio of Au to (ΜΙ+ΜΠ) is 1.0: 1.0 to 1.0: 10, and the atomic ratio of M1 to Mil is 2.0: 1.0 to 0.2: 1.0.
本发明所用催化剂载体的制备方法可以是共沉淀法， 浸渍法。  The preparation method of the catalyst carrier used in the present invention may be a coprecipitation method or a dipping method.
催化剂载体的共沉淀法制备过程可以是:将适量的 M I和 Mil金属盐溶液 和载体金属的盐溶液于搅拌中滴加到 N C03(或 K2C03)溶液中，经静置、分离、 焙烧、 活化处理即得所需催化剂载体。 The coprecipitation preparation process of the catalyst carrier may be: adding an appropriate amount of a salt solution of MI and Mil metal salt solution and a carrier metal to the solution of N C0 3 (or K 2 C0 3 ) under stirring, and allowing to stand and separate. The calcination and activation treatments provide the desired catalyst support.
催化剂载体的浸渍法制备过程可以是:将适量的 M I和 Mil金属盐溶液用 成型的载体 （如 A1203) 浸渍， 静置至少 lh后， 经干燥、 焙烧得复合氧化物 载体。 The preparation process of the impregnation method of the catalyst carrier may be: impregnating an appropriate amount of MI and Mil metal salt solution with a shaped carrier (such as A1 2 0 3 ), leaving it for at least 1 hour, and drying and calcining to obtain a composite oxide carrier.
纳米金的负载采用沉积-沉淀法或阴离子浸渍法。  The loading of the nano gold is carried out by a deposition-precipitation method or an anion impregnation method.
催化剂的沉积一沉淀法制备过程可以是： 将预先成型的具有高比表面积 的氧化物载体经真空干燥处理后置入控制温度（例如 350K)下的活性组分前 体溶液中， 在连续搅拌中逐滴加入碱溶液（如 N¾C03、 K2C03、 NaOH、 K0H等）， 在恒温下控制溶液 pH值为 4. 5〜8. 5， 直至沉淀完全， 经沉降、 过滤、 洗涤、 干燥、 焙烧或活化处理得成品催化剂。 The deposition-precipitation preparation process of the catalyst may be: pre-forming an oxide support having a high specific surface area by vacuum drying treatment and placing it in front of the active component at a controlled temperature (for example, 350 K). Precursor solution, by continuous stirring was added dropwise a solution of a base (e.g. N¾C0 3, K 2 C0 3, NaOH, K0H , etc.), at a constant temperature control of the solution pH of 4. 5 ~ 8. 5, until the precipitation is complete, the The finished catalyst is settled, filtered, washed, dried, calcined or activated.
纳米金的阴离子浸渍法负载过程采用申请人实验室专利技术 （安立敦， 齐世学、 索掌怀， 翁永根， 邹旭华； 一种新的负载型纳米金催化剂的制备方 法， 中国发明专利申请号： 03138796. 1， 申请日： 2003年 7月 8日）。  The nano-gold anion impregnation method uses the patent technology of the applicant's laboratory (An Lidun, Qi Shixue, Suo Zhanghuai, Weng Yonggen, Zou Xuhua; a new preparation method of supported nano-gold catalyst, Chinese invention patent application number: 03138796. 1, application date: July 8, 2003).
本发明所述的催化剂在常压固定床反应器上进行 CO催化氧化反应性能 评价， 所用原料气组成为： CO: 0. 25-1. 0%, 其余为空气。  The catalyst of the present invention is subjected to an evaluation of the performance of the catalytic oxidation of the CO in a normal-pressure fixed-bed reactor. The composition of the raw material gas used is: CO: 0. 25-1. 0%, and the rest is air.
CO的转化率由气相色谱分析结果求出， C0 的最小可检测量为 50ppm。 部分催化剂在山西某某化工厂检测中心 C0 防护性能试验装置上按实用 国家标准要求进行了性能检测。 原料气组成为： C0: 0. 25-1. 0%， 空气为平衡 气， 控制湿度为 23 °C下的饱和湿度。  The conversion rate of CO was determined by gas chromatography analysis, and the minimum detectable amount of C0 was 50 ppm. Some of the catalysts were tested for performance on the C0 protective performance test equipment of a certain chemical plant testing center in Shanxi according to the requirements of practical national standards. The composition of the feed gas is: C0: 0. 25-1. 0%, air is the balance gas, and the humidity is controlled to be saturated at 23 °C.
催化剂的抗热性能实验： 将成品催化剂置于干燥箱中空气气氛中 120°C 下加 72h， 测试催化剂的活性变化。  Catalyst heat resistance test: The finished catalyst was placed in a dry box at 120 ° C for 72 h to test the activity change of the catalyst.
催化剂的抗湿性能实验： 将成品催化剂置于反应管中用室温下水汽饱和 的原料气连续反应 72h, 或用室温下水汽饱和的空气以评价反应同样的气速 连续处理 72h， 测试催化剂的活性变化。  Anti-wetting performance test of the catalyst: The finished catalyst was placed in a reaction tube and continuously reacted with a water vapor-saturated feed gas at room temperature for 72 h, or continuously treated with water vapor saturated air at room temperature for the same gas velocity for 72 h to test the activity of the catalyst. Variety.
本发明实现方式和最佳实施例：  Implementations and preferred embodiments of the invention:
例 1： 将 0. 0325g CuCl2* 2H20和 0. 0419g FeCl3« 6H20熔于 2. 6 ml水 中， 将成型的 2. 0g A1203球状载体加入到上述溶液中， 摇匀后静置 1 h， 于 80 - 120°C下干燥 4 h,空气气氛下于 80CTC焙烧 3h， 自然冷至室温。量取 0. 75 mlHAuCl4溶液 (20 gAu/L), 加 0. 2 ml 去离子水， 加 0. 25 ml Na OH ( 1 ) 溶液， 调节溶液的 pH =9- 10， 将上述复合载体倒入浸渍， 混匀， 静置 1 h， 用 20 ml氨水 （pH =10-11) 浸泡 24 h, 滤去清夜， 用去离子水洗至无可检 测 （用 AgN03溶液） 的 C1 离子， 60°C干燥 12h， 300°C下氢气还原 1 h， 得 浅褐色成品催化剂。 Example 1: 0. 0325g CuCl 2 * 2H 2 0 and 0. 0419g FeCl 3 « 6H 2 0 melted in 2. 6 ml of water, the formed 2.0 g of A1 2 0 3 spherical carrier was added to the above solution, shake After standing for 1 h, it was dried at 80-120 ° C for 4 h, calcined at 80 CTC for 3 h in an air atmosphere, and naturally cooled to room temperature. 0. 75 mlHAuCl 4 solution (20 gAu / L), add 0. 2 ml deionized water, add 0. 25 ml Na OH (1) solution, adjust the pH of the solution = 9-10, pour the above composite carrier Into the impregnation, mix, stand for 1 h, soak for 24 h with 20 ml of ammonia (pH = 10-11), filter off the night, wash with deionized water to no detectable (with AgN0 3 solution) C1 ion, 60 ° C drying for 12h, hydrogen reduction at 300 ° C for 1 h, Light brown finished catalyst.
在原料气组成为： CO: 1%； 02： 12%； N2: 87% (体积百分比）， 气体体积 空速为 1. 5 X 104h— 1的情况下， CO完全转化 (残余 CO 低于气相色譜检测极限 50ppm) 为 C02的允许最低反应温度 （称为 "最低全转化温度" ， 以下同） 为 —18°C (255K)。 于 27°C下连续反应 3 h， 最低全转化温度为一 18. 5°C。 In the case of the composition of the feed gas: CO: 1%; 0 2 : 12%; N 2 : 87% (volume percent), the gas volumetric space velocity is 1. 5 X 10 4 h - 1 , complete conversion of CO (residual CO is below the gas chromatographic detection limit of 50 ppm. The allowable minimum reaction temperature for C0 2 (referred to as the "lowest total conversion temperature", the same below) is -18 ° C (255 K). 5°C。 The minimum conversion temperature is 18.5 ° C.
催化剂的抗热性能实验： 将成品催化剂置于干燥箱中空气气氛中 12CTC 下加热 72h， 冷至室温后测试其催化活性为最低全转化温度一 20. 0°C。  The thermal resistance test of the catalyst: The finished catalyst was heated in an air atmosphere at 12 CTC for 72 h in a dry box, and the catalytic activity was tested to a minimum full conversion temperature of 20. 0 ° C after cooling to room temperature.
催化剂的抗湿性能实验： 将成品催化剂置于反应管中用室温下水汽饱和 的空气以评价反应同样的气速连续处理 72h， 测试催化剂的活性， 其最低全 转化温度为一 14. 0° (：。  The catalyst is tested for its moisture resistance. The catalyst is placed in a reaction tube and the water is saturated with water at room temperature to evaluate the reaction at the same gas rate for 72 hours. The activity of the catalyst is tested. The minimum total conversion temperature is 14.1 ° ( :.
例 2: 采用例 1所用的复合载体。量取 0. 75 mlHAuCL溶液（20 gAu/L), 加 0. 75 ml 去离子水， 用此金溶液直接浸渍复合载体。 混匀， 静置 1 h， 用 20 ml氨水（pH =10- 11 )浸泡 24 h， 滤去清夜， 用去离子水洗至无可检测（用 AgN03溶液） 的 C1 离子， 60Γ干燥 12h， 300°C下氢气还原 1 h， 得浅褐色 成品催化剂。 其最低全转化温度为一 24. 0°C。 Example 2: The composite carrier used in Example 1 was used. Measure 0.575 ml of HAuCL solution (20 gAu/L), add 0.75 ml of deionized water, and directly impregnate the composite carrier with the gold solution. Mix well, let stand for 1 h, soak for 24 h with 20 ml of ammonia water (pH = 10-11), filter off the night, wash with deionized water to the undetectable (with A g N0 3 solution) C1 ion, 60 Γ dry for 12 h The hydrogen was reduced at 300 ° C for 1 h to obtain a light brown finished catalyst. 0度C。 The minimum full conversion temperature is a 24. 0 ° C.
例 3: 称取 100g A1203球状载体， 采用例 1方法制备复合载体， 量取 75 ml HAuCl4溶液 (20 gAu/L)， 加 20 ml 去离子水， 加 30 ml Na OH ( 1M) 溶 液， 调节溶液的 pH =9-10, 将上述复合载体倒入浸渍， 混匀， 静置 1 h， 用 500 ml氨水 （pH =10-11 ) 浸泡 24 h， 滤去清夜， 用去离子水洗至无可检测 (用 AgN03溶液） 的 C1 离子， 60°C干燥 12h， 300°C下氢气还原 1 h， 得浅 褐色成品催化剂。 其最低全转化温度为一 17. 5°C。 Example 3: Weigh 100 g of A1 2 0 3 spherical carrier, prepare the composite carrier by the method of Example 1, measure 75 ml of HAuCl 4 solution (20 gAu/L), add 20 ml of deionized water, add 30 ml of Na OH (1M) Solution, adjust the pH of the solution = 9-10, pour the above composite carrier into the impregnation, mix, let stand for 1 h, soak for 24 h with 500 ml of ammonia water (pH = 10-11), filter off the night, wash with deionized water To the C1 ion without detectable (with AgN0 3 solution), drying at 60 ° C for 12 h, hydrogen reduction at 300 ° C for 1 h, to obtain a light brown finished catalyst. 5度C。 The minimum full conversion temperature is 17. 5 ° C.
在原料气组成为： C0: 1. 0%; 空气为平衡气， 相对湿度 100% (23°C ), 比速为： 0. 75L/min. cm2， 用山西某某化工厂计量测试中心 CO防护性能试验 装置进行测试， 连续反应 300 分钟， C0 透过浓度低于 54ppm (标准要求： OOpprn), 30L试后吸气阻力 159Pa (标准要求： 350Pa) , 85L试后吸 气阻力 682Pa (标准要求： 880Pa)。 The composition of the raw material gas is: C0: 1. 0%; The air is the equilibrium gas, the relative humidity is 100% (23 °C), and the specific speed is: 0.75 L/min. cm 2 , with the measurement and test center of a certain chemical plant in Shanxi The CO protection performance test device was tested, continuous reaction for 300 minutes, C0 permeation concentration was lower than 54ppm (standard requirement: OOpprn), after inhalation resistance 159Pa after 30L test (standard requirement: 350Pa), 85L after test Air resistance 682Pa (standard requirements: 880Pa).
例 4: 将例 3催化剂放入广口瓶中室温下空气中放置 1年后再评价其催 化性能。在原料气组成为： CO: 0.25%；空气为平衡气，相对湿度 100%(23°C)， 比速为： 0.65 L/min. cm2, 用山西某某化工厂计量测试中心 CO防护性能试验 装置进行测试，连续反应 30分钟， CO透过浓度低于 2ppm (标准要求. ·〈100ρρπι)， 30L试后吸气阻力 184Pa (标准要求： 350Pa)， 85L试后吸气阻力 768Pa (标准要求： 880Pa；)。 工业应用性  Example 4: The catalyst of Example 3 was placed in a jar at room temperature for 1 year, and its catalytic performance was evaluated. The composition of the raw material gas is: CO: 0.25%; the air is the equilibrium gas, the relative humidity is 100% (23 °C), and the specific speed is: 0.65 L/min. cm2, and the CO protection performance test of the measurement and test center of a certain chemical plant in Shanxi The device was tested and continuously reacted for 30 minutes. The CO permeation concentration was less than 2 ppm (standard requirement. · <100ρρπι), the inspiratory resistance after 184Pa was 184Pa (standard requirement: 350Pa), and the inspiratory resistance after 85L was 768Pa (standard requirements: 880Pa;). Industrial applicability
' 本发明的催化性能稳定的负载型金催化剂及其制备方法适用于防毒面 罩、 室内 （车间、 航天器、 潜艇、 居室、 商店等） 空气净化等。 ·  The catalytically stable supported gold catalyst of the present invention and the preparation method thereof are suitable for use in a gas mask, indoor (workshop, spacecraft, submarine, living room, store, etc.) air purification. ·

Claims

权 利 要 求 Rights request
1、一种催化性能稳定的负载型金催化剂， 其特征在于： 活性组分 为 Au，载体为 M I Ox, Mil Ox修饰的 Al203、Ti02/ A1203， Au与（M I +MII) 的原子比为 1.0: 1.0〜1.0: 10, MI与 Mil的原子比为 2.0: 1.0 〜 0.2： 1.0； Au与 Al的原子比为 1.0: 1.0X103〜： L.O: 10。 A supported gold catalyst having stable catalytic performance, characterized in that: the active component is Au, the carrier is MI Ox, Mil Ox modified Al 2 0 3 , Ti0 2 / A1 2 0 3 , Au and (MI + The atomic ratio of MII) is 1.0: 1.0 to 1.0: 10, and the atomic ratio of MI to Mil is 2.0: 1.0 to 0.2: 1.0; the atomic ratio of Au to Al is 1.0: 1.0X10 3 to: LO: 10.
2、如权利要求 1要求所说的催化性能稳定的负载型金催化剂，其 特征在于： 其中 Ml为 Cu， ΜΠ为 Fe， 或 Co， 或 Ni。  A supported gold catalyst having stable catalytic performance as claimed in claim 1, wherein M1 is Cu and ruthenium is Fe, or Co, or Ni.
3、如权利要求 1要求所说的催化性能稳定的负载型金催化剂，其 特征在于： 载体可以是成型氧化物或改性的成型氧化物载体。  3. A catalytically stable supported gold catalyst as claimed in claim 1 wherein the support is a shaped oxide or a modified shaped oxide support.
4、如权利要求 1或 2或 3所说的催化性能稳定的负载型金催化剂 的制备方法， 其特征在于： 载体是采用浸渍方法或共沉淀方法制备， 成型载体负载 ΜΙ0χ， ΜΠΟχ后， 经过 800°C- )0(TC的焙烧， 以生成 尖晶石（AB204) 或钙钛石（AB03) 结构，催化剂前体经氢气还原后， 部 分 Au与易还原的 M I Ox生成合金 AuxM I。 The method for preparing a catalytically stable supported gold catalyst according to claim 1 or 2 or 3, wherein the carrier is prepared by a dipping method or a coprecipitation method, and the shaped carrier is loaded with ΜΙ0χ, ΜΠΟχ, after 800 °C-)0 (calcination of TC to form a spinel (AB 2 0 4 ) or perovskite (AB0 3 ) structure. After the catalyst precursor is reduced by hydrogen, some of the Au and the easily reduced MI Ox form an alloy Au. x MI.
5、如权利要求 1或 2或 3要求所说的催化性能稳定的负载型金催 化剂的制备方法，其特征在于：纳米金的负载采用沉积-沉淀法或阴离 子浸渍法； 其中， 沉积 -沉淀法为： 将预先成型的具有高比表面积的氧 化物载体经真空干燥处理后置入控制温度（例如 350K)下的活性组分 前体溶液中，在连续搅拌中逐滴加入碱溶液（如 Na2C03、 K2C03、 Na0H、 K0H等）， 在恒温下控制溶液 pH值为 4.5〜8.5， 直至沉淀完全， 经沉 降、 过滤、 洗涤、 干燥、 焙烧或活化处理得成品催化剂。  The method for preparing a supported gold catalyst having stable catalytic performance as claimed in claim 1 or 2 or 3, wherein the loading of the nano gold is carried out by a deposition-precipitation method or an anion impregnation method; wherein, the deposition-precipitation method To: pre-form an oxide carrier having a high specific surface area by vacuum drying and then placing it into an active component precursor solution at a controlled temperature (for example, 350K), and adding an alkali solution (such as Na2C03, dropwise) under continuous stirring. K2C03, Na0H, K0H, etc.), the pH of the solution is controlled at a constant temperature of 4.5 to 8.5 until the precipitation is complete, and the finished catalyst is obtained by sedimentation, filtration, washing, drying, calcination or activation.
PCT/CN2005/000602 2004-07-21 2005-04-29 Catalyst with stable catalytic performance and the preparation method thereof WO2006007774A1 (en)

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