WO2003043732A1 - Catalyseur en or sur support pour l'oxydation catalytique de co a basse temperature - Google Patents

Catalyseur en or sur support pour l'oxydation catalytique de co a basse temperature Download PDF

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Publication number
WO2003043732A1
WO2003043732A1 PCT/CN2001/001582 CN0101582W WO03043732A1 WO 2003043732 A1 WO2003043732 A1 WO 2003043732A1 CN 0101582 W CN0101582 W CN 0101582W WO 03043732 A1 WO03043732 A1 WO 03043732A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
temperature
catalytic oxidation
solution
low
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PCT/CN2001/001582
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English (en)
Chinese (zh)
Inventor
Lidun An
Shixue Qi
Xuhua Zou
Zhanghuai Suo
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Lidun An
Shixue Qi
Xuhua Zou
Zhanghuai Suo
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Application filed by Lidun An, Shixue Qi, Xuhua Zou, Zhanghuai Suo filed Critical Lidun An
Priority to AU2002221503A priority Critical patent/AU2002221503A1/en
Priority to PCT/CN2001/001582 priority patent/WO2003043732A1/fr
Publication of WO2003043732A1 publication Critical patent/WO2003043732A1/fr

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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
    • B01J23/38—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
    • 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
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide

Definitions

  • the invention relates to a chemical catalyst, in particular to a practical supported gold catalyst that catalyzes the oxidation of trace amounts (0.01% ⁇ 1.0%) of CO into co 2 in the air at ambient temperature and humidity, and the pressure drop meets the requirements of gas masks. . Background technique
  • CO is the primary pollutant in many industrial environments and indoor ambient air, especially deadly poisons in the air such as fierce battlefields, fire scenes, mine tunnels and the like. Because the binding capacity of CO to human hemoglobin is 250 times that of oxygen, it can prevent hemoglobin from delivering absorbed oxygen to human tissues. The presence of 10 ppm CO in the air has a toxic effect on the human body, and the short-term tolerance of the human body is only 300 ppm. Its harm to human health has long attracted scientists' attention (Stewart, R., The effect of Carbon Monoxide on Humans; Annu Rev. Pharmacol, 1975, 15, 409-423).
  • CO catalytic oxidation Compared with other methods, such as adsorption, CO catalytic oxidation has absolute advantages in terms of equipment volume and ease of operation (Yaparpalvi, R. And Chuang K. T., Ind. Eng. Chem. Res., 1991, 30, 2219- 2225
  • the catalytic oxidation method refers to the catalytic oxidation reaction between CO and oxygen (o 2 ) in the air at ambient temperature to generate co 2:
  • Hopcalilte catalysts which are CuO-MnOx-based composite oxide catalysts (Lamb, AB, Bray, WC, Frazer, JCW; Ind. Eng. Chem., 1920, 12, 213).
  • the gas mask catalyst material that has been used in the First World War has a fatal shortcoming that it is poor in water resistance. Therefore, a larger and heavier "drying tank” must be added before the "oxidation tank”.
  • the CO low-temperature oxidation catalysts studied in the laboratory include: (1) Transition metal oxide series. Such as Co 3 0 4 , Mn0 2 , Co 2 0 3 (Pitzer, E. C "Frazer, JCW, J. Phys. Chem., 1941, 45, 761), and other metal oxide series (Yung Fang, Yu Tao , J: Catal, 1974, 3 , 108) (2) oxide-supported e.g. CoO x / Ti0 2 catalyst (Moshida, I., et al, J. Phys Chem, 1985, 89, 5439 doi ) High activity for CO oxidation at room temperature, but the catalyst deactivates quickly after 15 minutes, and has the same poor water resistance as the type (1) catalyst.
  • Transition metal oxide series Such as Co 3 0 4 , Mn0 2 , Co 2 0 3 (Pitzer, E. C "Frazer, JCW, J. Phys. Chem., 1941, 45, 761), and other metal oxide series (
  • the purpose of the present invention is to find a kind of catalytic oxidation CO at high ambient temperature (-10 ° C ⁇ 40 ° C) and ambient humidity (relative humidity 0 ⁇ 100%) with high reactivity, stable performance, and pressure drop to meet the practical requirements of gas masks.
  • New catalyst is to find a kind of catalytic oxidation CO at high ambient temperature (-10 ° C ⁇ 40 ° C) and ambient humidity (relative humidity 0 ⁇ 100%) with high reactivity, stable performance, and pressure drop to meet the practical requirements of gas masks.
  • New catalyst is to find a kind of catalytic oxidation CO at high ambient temperature (-10 ° C ⁇ 40 ° C) and ambient humidity (relative humidity 0 ⁇ 100%) with high reactivity, stable performance, and pressure drop to meet the practical requirements of gas masks.
  • the present invention provides a supported gold catalyst for low-temperature CO elimination, which is characterized in that the active component is gold and the carrier is A1 2 0 3 (or Co 3 0 4 , Ti0 2 , Ti0 2 / non-transition metal oxidation). Catalyst), the atomic ratio of Au to A1 (or Co, Ti) is 1.0: 10 ⁇ 1.0: 1.0X 10 3 , and the support of the catalyst may be a shaped oxidation support.
  • the preparation method adopts a deposition-precipitation method or a co-precipitation method, and the activation treatment of the catalyst is a method of reduction with hydrogen or roasting and decomposition.
  • This CO-removing catalyst can be used at ambient temperature (-10 ° C; ⁇ 40 ⁇ ) and ambient humidity. It is stable in activity and can be directly applied to CO-removing devices such as gas masks. Air drying device.
  • the present invention has the following essential features:
  • carrier-supported gold catalyst is free of Fe 2 0 3 of A1 2 0 3 (or Co 3 0 4, Ti0 2,
  • the catalyst is activated by hydrogen reduction or roasting decomposition method.
  • a catalyst not only has good low-temperature catalytic activity for CO oxidation catalyst into C0 2, but also has good water vapor intoxication properties, the relative humidity in the range of 0 to 100%, active stabilization, the catalyst bed can be saved Go to the drying jar.
  • the catalyst is granular, and its particle size and mechanical strength ensure that the pressure drop and impact resistance of the bed can meet the practical requirements of gas masks.
  • the active component of the catalyst of the present invention is gold, and the support may be one of A1 2 0 3 , Co 3 0 4 , Ti0 2 , Ti0 2 / Si0 2 or Ti0 2 / Al 2 0 3 .
  • the precursor compounds of the above active component gold may be metal gold (filament, bar, block), chloroauric acid (HAuCl 4 ⁇ H 2 0), gold trichloride (AuCl 3 ), and the like.
  • the precursor compounds of the support may be nitrates, sulfates, acetates, chlorides or metal alkoxides of the corresponding oxides, or formed oxides.
  • the atomic ratio of Au to A1 (or Co, Ti, etc.) is 1.0: 10 ⁇ 1.0:
  • the range of 1.0 X 10 3 , Au and A1 (or Co, Ti, etc.) atoms is preferably 1.0: 200 to 1.0: 400.
  • the preparation method of the catalyst used in the present invention may be a deposition-precipitation method or a co-precipitation method.
  • the catalyst deposition-precipitation method can be prepared as follows: the oxide support having a high specific surface area formed in advance is vacuum-dried and placed in an active component precursor solution at a controlled temperature (for example, 350K) under continuous stirring Add an alkaline solution (such as Na 2 C0 3 , K 2 C0 3 , NaOH, KOH, etc.) dropwise, and control the pH of the solution at a constant temperature of 4.5 ⁇ 8.5 until the precipitation is complete. After sedimentation, filtration, washing, drying, and hydrogen Reduction treatment or calcination in the stream yields the finished catalyst.
  • an alkaline solution such as Na 2 C0 3 , K 2 C0 3 , NaOH, KOH, etc.
  • the preparation process of the catalyst co-precipitation method may be: adding an appropriate amount of a gold salt solution and a salt solution of a support metal to a Na 2 C0 3 (or K 2 C0 3 ) solution dropwise while stirring (or the reverse dropwise order),
  • the desired catalyst can be obtained by standing, separating, roasting or reducing and activating in a hydrogen stream.
  • the detection method in the following examples of the present invention is to evaluate the performance of the catalyst on the catalytic oxidation reaction of CO on an atmospheric fixed-bed reactor.
  • the composition of the feed gas used is: CO: 0.25% to 1.0%, and the rest is air.
  • the conversion rate of CO was determined from the results of gas chromatography analysis, and the minimum detectable amount of CO was 50 ppm.
  • Part of the catalyst was tested on the CO protective performance test device of the Testing Center of Shanxi Xinhua Chemical Plant in accordance with the requirements of gas mask use standards.
  • the composition of the raw material gas is: CO: 0.25% ⁇ 1.0%, the air is a balanced gas, and the controlled humidity is a saturated humidity at 23 ° C. detailed description
  • the minimum total conversion temperature of CO is-10 ° C (263K).
  • Example 3 Au / Al 2 0 3 catalyst prepared by using the deposition-precipitation method of Example 1 with an atomic ratio of Au to Al of 1: 200.
  • the finished product is granular and dark brown.
  • the composition of the raw material gas is: CO: 1.0%; the air is a balanced gas, the relative humidity is 100% (23 ° C), and the specific speed is: 0.75L / cm 2 .min, tested with a CO protective performance test device, continuous reaction 300 In minutes, the CO transmission concentration is lower than 94ppm (standard requirement: ⁇ 100ppm), the inhalation resistance after 30L test is 159Pa (standard requirement: 350Pa), and the inhalation resistance after 85L test is 682Pa (standard requirement: 880Pa).
  • Example 4 The Au / Al 2 0 3 catalyst having an atomic ratio of Au to Al of 1: 200 prepared by the deposition-precipitation method of Example 1 is granular and has a dark brown finished product.
  • the composition of the raw material gas is: CO: 0.25%; the air is a balanced gas, and the relative humidity is 100% (23 ° C), Than the speed of: 0.75L / C m m in, to test the CO 3 in protective performance test apparatus embodiment, a continuous reaction was 120 minutes, through the CO concentration is less than 29ppm. (Standard: ⁇ 100ppm), 30L test The rear suction resistance is 184Pa (standard requirement: 350Pa), and the 85L test suction resistance is 768Pa (standard requirement: 880Pa).
  • Example 5 The Au / Al 2 0 3 catalyst having an atomic ratio of Au to Al of 1: 200 prepared by the deposition-precipitation method of Example 1 is granular and has a dark brown finished product.
  • the composition of the raw material gas is: CO: 1.0%; the air is a balanced gas, the relative humidity is 100% (23 ° C), and the specific speed is: 1.0 L / cm 2 -min, and tested with the CO protective performance test device described in Example 4 , Continuous reaction for 120 minutes, CO permeation concentration is lower than 158ppm, and the inhalation resistance after the 30L test is 241Pa (standard requirement: 350Pa).
  • Example 6 (1) The Au / Co 3 0 4 catalyst having an atomic ratio of Au to Co prepared by the above co-precipitation method of 1: 250, and the finished product was uniform black.
  • the minimum total conversion temperature of CO is -18 ° C.
  • Example 7 The raw material gas described in Example 1 was compounded with 15 ppm H 2 S.
  • the catalyst described in Example 1 was tested for sulfur poisoning resistance. At room temperature, the CO catalytic oxidation reaction was continuously performed for 120 min. The catalyst had no reactive activity. Detectable change, no detectable CO concentration in tail gas.
  • Example 8 A1 2 0 3 was immersed in a sol prepared with butyl titanate, and filtered and dried at 500 ° C. for 1 h to obtain a Ti0 2 -A1 2 0 3 composite support.
  • the precipitation method prepared a catalyst with a loading of 1.0 wt% Au / TiO 2 —Al 2 O 3 , and the finished product was uniform light brown.
  • the minimum total CO conversion temperature is -35 ° (:.
  • Example 9 A catalyst was prepared by a deposition-precipitation method.
  • a 1.0 g spherical support of 1.0 g A1 2 0 3 was added to water, and the pH was adjusted to 7.5 with a 1M NaOH solution under stirring, and the temperature was maintained at C, and then dropwise.
  • Add 1.04 ml of chloroauric acid solution (9.7200 g Au / L), and maintain pH 7.5 with 1M NaOH solution. After reacting for 1 h, filter, wash, dry at 60 ° C for 12 h, and then roast at 350 ° C for 2 h in air atmosphere.
  • Example 10 An Au / Al 2 0 3 catalyst having an atomic ratio of Au to A1 of 1: 400 is obtained, and the finished product is granular and has a dark brown color.
  • the composition of the raw material gas is: CO: 1%; 0 2 : 12%; N 2 : 87% (volume percentage), and the volumetric space velocity of the gas is 1.5 X lO 1
  • the minimum total conversion temperature of CO can reach -15 ° C (258K) o
  • the catalyst was prepared by the deposition-precipitation method of Example 1, 1.0 g of Ti0 2 support was added to water, and the pH was adjusted to 5.0 with a 1M NaOH solution under stirring, and the temperature was maintained at 70 ° C.
  • the minimum total conversion temperature of CO is-10 ° C (263K).
  • Example 11 The finished catalyst prepared in Example 9, placed in the presence of a desiccant in the air a year or more, as the feed gas composition: CO: 1%; 0 2 : 12%; N 2: 87% (Volume percentage), when the gas volumetric space velocity is 1.5 X 10 4 h, the minimum total conversion temperature of CO can still reach-15 ° C (258K), and its catalytic activity is the same as that of fresh catalyst.
  • Example 12 Example 9 Preparation of the finished catalyst was then placed in the air for six months or even longer, as the feed gas composition: CO: 1%; 0 2 : 12%; N 2: 87% (volume percent), In the case of a gas volumetric space velocity of 1.5 ⁇ 10 4 !! ⁇ 1 , the minimum full conversion temperature of CO can still reach -15 ° C (258K), and its catalytic activity is the same as that of fresh catalyst.
  • Example 13 After the catalyst used in the test in Example 3 was left in the air for 6 months, 60 ml (half the amount of the catalyst used in Example 3) was taken and tested using the CO protective performance test device described in Example 3.
  • the composition is: CO: 0.25%; air is equilibrium gas, air temperature is 25 ° C, relative humidity is 97%, specific speed is: 0.75L / cm 2 .min, continuous reaction for 60 minutes, CO permeation concentration is lower than 10ppm, 85L Inhalation resistance after test is 330 Pa (standard requirement: 880Pa).

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Abstract

La présente invention concerne un catalyseur en or sur support pour l'oxydation catalytique de CO à basse température. Ledit catalyseur présente une activité hautement catalytique à basse température et il ne peut pas subir un empoisonnement en présence d'humidité ou de gaz composite contenant du soufre. Ledit catalyseur peut conserver son activité catalytique après un long stockage et il peut être réutilisé. Selon la présente invention, le composant actif est Au et le support est Al2O3 (ou bien Co3O4, TiO2, TiO2/oxyde d'un métal qui n'est pas un métal de transition). Le catalyseur selon l'invention peut être utilisé pour l'oxydation catalytique de CO à la température ambiante et dans des conditions d'humidité ambiantes. Etant donné que la concentration de CO dans le gaz d'alimentation est de 1,0 %, la concentration de perméation du CO est inférieure à 94 ppm après passage du gaz d'alimentation à travers ledit catalyseur pendant 300 min. Ledit catalyseur peut être utilisé dans des dispositifs servant à l'élimination du CO tels qu'un masque à gaz, ou bien servant à purger l'air d'une pièce. Les procédés de traitement dudit catalyseur sont également différents des procédés de traitement concernés par les brevets antérieurs, et le catalyseur obtenu selon les procédés de la présente invention offre des propriétés améliorées.
PCT/CN2001/001582 2001-11-23 2001-11-23 Catalyseur en or sur support pour l'oxydation catalytique de co a basse temperature WO2003043732A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2002221503A AU2002221503A1 (en) 2001-11-23 2001-11-23 Supported gold catalyst useful for catalytic oxidation of co at low temperature
PCT/CN2001/001582 WO2003043732A1 (fr) 2001-11-23 2001-11-23 Catalyseur en or sur support pour l'oxydation catalytique de co a basse temperature

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006003450A1 (fr) * 2004-07-06 2006-01-12 University College Cardiff Consultants Limited Catalyseurs a l'or supportes
CN107715872A (zh) * 2017-10-31 2018-02-23 中国石油大学(华东) 一种超高比表面介孔氧化铝负载金纳米催化剂（Au/γ‑Al2O3）的合成方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62155937A (ja) * 1985-08-30 1987-07-10 Agency Of Ind Science & Technol 金および金系複合酸化物を担持した触媒体を製造する方法
US4839327A (en) * 1987-04-08 1989-06-13 Agency Of Industrial Science & Technology Method for the production of ultra-fine gold particles immobilized on a metal oxide
US5068217A (en) * 1989-04-29 1991-11-26 Gutec Carrier catalysts for oxidizing carbon monoxide and process for their production
JPH078797A (ja) * 1994-03-10 1995-01-13 Agency Of Ind Science & Technol 金超微粒子固定化チタン系金属酸化物からなる酸化触媒、還元触媒、可燃性ガスセンサ素子および電極用触媒
JPH0796187A (ja) * 1993-09-28 1995-04-11 Agency Of Ind Science & Technol 窒素酸化物除去用触媒及び窒素酸化物除去方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62155937A (ja) * 1985-08-30 1987-07-10 Agency Of Ind Science & Technol 金および金系複合酸化物を担持した触媒体を製造する方法
US4839327A (en) * 1987-04-08 1989-06-13 Agency Of Industrial Science & Technology Method for the production of ultra-fine gold particles immobilized on a metal oxide
US5068217A (en) * 1989-04-29 1991-11-26 Gutec Carrier catalysts for oxidizing carbon monoxide and process for their production
JPH0796187A (ja) * 1993-09-28 1995-04-11 Agency Of Ind Science & Technol 窒素酸化物除去用触媒及び窒素酸化物除去方法
JPH078797A (ja) * 1994-03-10 1995-01-13 Agency Of Ind Science & Technol 金超微粒子固定化チタン系金属酸化物からなる酸化触媒、還元触媒、可燃性ガスセンサ素子および電極用触媒

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006003450A1 (fr) * 2004-07-06 2006-01-12 University College Cardiff Consultants Limited Catalyseurs a l'or supportes
CN107715872A (zh) * 2017-10-31 2018-02-23 中国石油大学(华东) 一种超高比表面介孔氧化铝负载金纳米催化剂（Au/γ‑Al2O3）的合成方法

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