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CN1583273A - Preparing method for loaded metal oxide catalyst - Google Patents

Preparing method for loaded metal oxide catalyst Download PDF

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CN1583273A
CN1583273A CN 200410027561 CN200410027561A CN1583273A CN 1583273 A CN1583273 A CN 1583273A CN 200410027561 CN200410027561 CN 200410027561 CN 200410027561 A CN200410027561 A CN 200410027561A CN 1583273 A CN1583273 A CN 1583273A
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microwave
metal oxide
preparation
oxide catalyst
supported metal
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沈培康
田植群
徐常威
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Sun Yat Sen University
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Sun Yat Sen University
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Abstract

本发明公开了一种负载型金属氧化物催化剂的制备方法。该方法包括以下步骤：(1)先将载体、催化剂活性组分的前驱物充分混合至糊状物；(2)将糊状物放入微波系统中，选择微波敏感材料，进行微波处理，处理时间为1～20分钟，使之干燥；(3)经微波干燥的载体与活性材料前驱物的混合物，在微波系统中，进一步进行微波处理，处理的时间为1～120分钟，使活性材料前驱物最终热分解成相应的氧化物。本发明具有快速、节能、多相体系不偏析、成品自然成粉末状等特点。

The invention discloses a preparation method of a supported metal oxide catalyst. The method comprises the following steps: (1) fully mixing the carrier and the precursor of the catalyst active component into the paste; (2) putting the paste into a microwave system, selecting microwave-sensitive materials, and performing microwave treatment. The time is 1 to 20 minutes to make it dry; (3) the mixture of the microwave-dried carrier and the active material precursor is further subjected to microwave treatment in a microwave system, and the treatment time is 1 to 120 minutes to make the active material precursor The substances are finally thermally decomposed into the corresponding oxides. The invention has the characteristics of rapidity, energy saving, no segregation of the multi-phase system, and the natural powdery finished product.

Description

Load metal oxide Preparation of catalysts method
Technical field
The present invention relates to a kind of Preparation of catalysts method, specifically relate to a kind of method for preparing the load metal oxide catalyst.
Background technology
Metal oxide is at metallurgy, and petrochemical industry has purposes widely in function ceramics and the glass industry, especially in catalytic field, but the reaction such as the H of the multiple micromolecular compound of its catalysis 2, CO, O 2, NO XDeng, play an important role in the catalytic cracking of the control of vehicle exhaust, water treatment, oil, reformation etc.In this external electro-catalysis field, metal oxide such as MnO 2Oxygen is had good reduction, in fuel cell, be used as cathod catalyst.Co 2O 3Deng can catalytic oxidation of glucose as anode catalyst etc. little organic molecule.In order to improve the utilization rate of catalyst, increase the contact area of reactant and catalyst, adopt the load metal oxide catalyst usually, carrier is Al 2O 3, SiO 2, active carbon etc.
The preparation method of preparation load metal oxide has multiple, mainly can be divided into following several:
(1) precipitation heat decomposition method:
The precipitation heat decomposition method is under stirring state the metallic salt material fully to be mixed with carrier, drips alkaline precipitating agent, generates the hydroxide or the carbonate of metal, and after the oven dry, elevated temperature heat resolves into metal oxide in inert gas or air.People such as Yanhui Li utilize this method with CeO 2Preparation is on CNT (CNTs), and they are at first with CeCl 3Slowly adding in the dispersion liquid of CNTs, after fully stirring, is 9 at Dropwise 5 %NaOH until pH, and again with after the suspension oven dry, under 450 ℃ of conditions, heating is 20 minutes in the air, and making the CeOH thermal decomposition is CeO 2[Yanhui Li et al.Materials ResearchBulletin, 37 (2002) 313-318].
(2) heat of immersion decomposition method:
The metal precursor (nitrate, ammonium salt, formates, oxalates, acetate, organo-metallic compound etc.) that at first will be easy to thermal decomposition is fully mixed with carrier, dipping, after the oven dry, again in inert gas or air under the high temperature, thermal decomposition becomes metal oxide to make [A.F.P é rez-Cadenas et al, Journal ofCatalysis, 217 (2003) 30-37; Hui-Hsin Tseng, et al, Carbon, 41 (2003) 1079-1085].
(3) colloid method:
The colloidal particle for preparing metal oxide in advance, then by dip loading on carrier; Perhaps preparing metallic colloid carries out simultaneously with dipping.People such as J.Vondra ' k utilize this method successfully to prepare highly active MnO x/ C catalyst, they at first disperse the 4g carbon dust and the MnSO that contains 10mmol 4The aqueous solution is poured the KMnO that contains 33mmol subsequently into 4Be dissolved in 95 ℃ of 300ml water and react tens of seconds, purple solution until high manganese ion disappears, be cooled to room temperature, stirred for several hour to solution by the isabelline lark that becomes, filter, after the washing, make [J.Vondra ' k after 110 ℃ of oven dry, et al, J.NewMater.Electrochem.Syst., 1 (1998) 25; Petr Bezdicka, et al, Electrochimica Acta, 45 (1999) 913-920].
From the above method for preparing the load metal oxide catalyst commonly used, we can recognize, precipitation heat decomposition method and heat of immersion decomposition method are methods the most commonly used, and it is convenient, simple, can prepare most metal oxide catalyst, but this method need be carried out roasting under hot conditions, and this just exists serious energy consumption issues, because the roasting of high temperature has increased preparation time again, this just exists the tediously long problem of preparation process simultaneously; And colloid method, though it can prepare catalyst efficiently, course of reaction does not need high-temperature process, but needs strict control in the preparation process, process is very complicated.In above method, exist a common problem, the catalyst that is exactly gained all needs to carry out mechanical lapping at last, otherwise can not use.Therefore, particle is bigger.
Summary of the invention
The objective of the invention is to shortcoming, a kind of load metal oxide Preparation of catalysts method is provided at the prior art existence.Characteristics such as that the present invention has is quick, energy-conservation, not segregation of heterogeneous system, finished product are powdered naturally.
Load metal oxide Preparation of catalysts method of the present invention may further comprise the steps:
(1) elder generation is fully mixed to pastel with the predecessor of carrier, catalyst activity component;
Above-mentioned carrier is carbon black, titanium oxide, tungsten carbide, molybdenum carbide or CNT;
The predecessor of above-mentioned catalyst activity component is inorganic salts or other organo-metallic compound of iron, cobalt, nickel, copper, chromium, manganese, tin, lead, molybdenum, zirconium, vanadium, tungsten, scandium, titanium, niobium, tantalum; One or more mixtures of the inorganic salts of cerium, europium, samarium and organic compound;
The ratio of the predecessor of above-mentioned carrier and catalyst activity component is 99.9%: 0.1% to 5%: 90%;
(2) this pastel is put into microwave system, select microwave susceptor material, carry out microwave treatment, the processing time is that microwave treatment time is 1～20 minute, makes it dry;
Above-mentioned microwave susceptor material is carbon black, titanium carbide, tungsten carbide, molybdenum carbide, CNT; The addition of microwave susceptor material is 10～1000 times of pastel;
(3) through the carrier of microwave drying and the mixture of active material predecessor, in microwave system, further carry out microwave treatment, the time of processing is 1～120 minute, makes the final thermal decomposition of active material predecessor become corresponding oxide;
The microwave frequency band of the microwave treatment in above-mentioned (2) and (3) step is 0.896GHz～2.45GHz, and the power of microwave system is 500W～2000W, and temperature is controlled at 600 ℃-800 ℃.
(1) the employed mixed method of step is that ultrasonic wave or mechanical agitation are mixed.
As improvement of the technical scheme, the inorganic salts of the predecessor of catalyst activity component comprise carbonate, nitrate, perchlorate or ammonium salt in (1) step.
Another kind as technique scheme improves, and the organo-metallic compound of the predecessor of catalyst activity component is acetate, plain quinoline class, phthalocyanines, crown ether-like, schiff bases complex or carbonyls in (1) step.
(2) addition of microwave susceptor material is 50～800 times of pastel in the step, and optimum is 100～600 times.(2) time of microwave treatment is 3～6 minutes in the step.
As improvement, the time of microwave treatment is 2～30 minutes in (3) step.Optimum is 3～10 minutes.
As the further improvement to technique scheme, the microwave frequency band of microwave treatment is 0.915GHz～2.45GHz in (2) and (3) step.
Compared with the prior art, the present invention has following beneficial effect:
One, preparation speed is very fast.Heating using microwave is the body heating that material is caused by dielectric loss in electromagnetic field.In microwave field, the material molecule dipole polarization speed of response and microwave frequency are suitable, yet the dielectric dipole polarization that causes under microwave action often lags behind microwave frequency again, make the microwave field energy loss and are converted into heat energy.Therefore, the fuel factor of microwave is that the inside at medium takes place when microwave field applies, because this fuel factor is not to obtain indirectly through overheated conduction or thermal convection current from other media, but directly from the inside to the outside, self synchronous pyrogenicity, therefore, the heat conduction or the required time of thermal convection current process that do not have traditional heating.In the method, the time of microwave treatment is 1-120 minute, is generally 2-30 minute, is generally 3-10 minute, is significantly smaller than the required time of conventional method.Add all and mix the processing time that whole process of preparation is no more than 4 hours.This shows that adopt method of the present invention will need the time of tens hours even several days to be reduced to two hours with conventional method preparation, speed improves a lot.
Two, preparation process is energy-conservation.Because what we adopted is microwave treatment method, utilizes the dielectric heat effect of microwave to carrier, makes the temperature of carrier to reach higher temperature in tens of seconds, whole microwave process can be finished at short notice, and is very energy-conservation.And conventional method consumes the energy in a large number at the process need dozens of of heat drying, high-temperature process hour.
Three, not phase-splitting of multicomponent system.According to the mechanism of crystal growth, the salting liquid degree of super saturation is big more, and the nucleus of crystal generating rate is big more, and crystalline growth speed is less relatively, and crystallization as a result has little time growth, and the particle that obtains is less.Because microwave energy is evenly heated salting liquid in a short period of time, has eliminated the influence of thermograde greatly, makes precipitated phase sprout nucleation in moment, salt mixture has little time phase-splitting and separates out, thereby obtains uniform nano particle.And because nucleation rate is fast, and particle has little time to grow up, and the particle of formation is noncrystalline state to a great extent, there are a lot of defectives on the surface of particle, thereby has improved catalytic activity.
Four of advantage of the present invention is dried product nature powdereds, need not carry out mechanical crushing.Above-mentioned known, the dried product of conventional method needs further mechanical crushing, otherwise can not use.And be Powdered naturally with the material that this method is prepared into, do not need special pulverizing.When unusual high activity thing load capacity, the bonding The apparent phenomenon of part may appear after the drying, and still, handle shake gently or it is vibrated at once a little from powdered, do not need machining.
Description of drawings
Fig. 1 is 50%Co for the carrying capacity of embodiment 1 preparation 3O 4The XRD spectra of/C catalyst.
The specific embodiment
Embodiment 1
Get 1.0g carbon black (Vulcan XC-72, U.S. Cabot company produces) and place the 100ml reactor, (isopropyl alcohol: water=1: 3), ultrasonic agitation 10 minutes splashes into 12.46ml 1MCo (NO to add the 15ml isopropanol water solution 3) 3Ultrasonic subsequently all mixing to sample becomes pasty state, and it is that the volume of microwave susceptor material is in the big glass container of 250ml that the beaker that will contain sample is transferred to the tungsten carbide, above-mentioned reactor inserted (frequency is 2.45GHz in the micro-wave oven, power output is 850W, and temperature is 600 ℃).Adopt the intermittent type microwave heating schedule to make sample drying, heating schedule was controlled to be heating using microwave 15 seconds/stops carrying out repeatedly four times in 30 seconds.With the above-mentioned sample of drying, carry out following heating using microwave program again: heat 20 seconds/stop carrying out repeatedly six times in 60 seconds, after the reaction system cooling, sample.The X-ray diffraction analysis confirms that product is Co 3O 4/ C (see figure 1).
Embodiment 2
Get 1.0g carbon black (Vulcan XC-72, U.S. Cabot company produces) and place the 100ml reactor, (isopropyl alcohol: water=1: 3), ultrasonic agitation 10 minutes stirs and slowly splashes into 5.81ml 1MCeCl down to add the 15ml isopropanol water solution 3The aqueous solution drips K again 2CO 3Until pH is 9, become pasty state ultrasonic all mixing to sample subsequently, it is that the volume of microwave susceptor material is in the big glass container of 250ml that the beaker that will contain sample is transferred to the carbon black, above-mentioned reactor is inserted (frequency is 2.45GHz in the micro-wave oven, power output is 850W, and temperature is 750 ℃).Adopt the intermittent type microwave heating schedule to make sample drying, heating schedule was controlled to be heating using microwave 15 seconds/stops carrying out repeatedly four times in 30 seconds; With the above-mentioned sample of drying, carrying out following heating using microwave program: heat 20 seconds/stop carrying out repeatedly six times in 60 seconds, after the reaction system cooling, sample.The X-ray diffraction analysis confirms that product is CeO 2/ C.It has good catalytic oxidation performance to methyl alcohol and polyhydroxy-alcohol compounds to the electrochemistry experiment proof in alkaline solution.
Embodiment 3:
Get 1.0g nano-titanium oxide (Degusa P25 type, the U.S.) and place the 100ml reactor, (isopropyl alcohol: water=1: 3), ultrasonic agitation 10 minutes splashes into 13.11ml 1MMn (NO to add the 15ml isopropanol water solution 3) 3Ultrasonic subsequently all mixing to sample becomes pasty state, and it is that the volume of microwave susceptor material is in the big glass container of 250ml that the beaker that will contain sample is transferred to the molybdenum carbide, above-mentioned reactor inserted (frequency is 2.45GHz in the micro-wave oven, power output is 850W, and temperature is 800 ℃).Adopt the intermittent type microwave heating schedule to make sample drying, heating schedule was controlled to be heating using microwave 15 seconds/stops carrying out repeatedly four times in 30 seconds; With the above-mentioned sample of drying, carrying out following heating using microwave program: heat 20 seconds/stop carrying out repeatedly six times in 60 seconds, after the reaction system cooling, sample.The X-ray diffraction analysis confirms that product is Mn 3O 4/ C.

Claims (10)

1、一种负载型金属氧化物催化剂的制备方法，包括以下步骤：1. A method for preparing a supported metal oxide catalyst, comprising the following steps: (1)先将载体、催化剂活性组分的前驱物充分混合至糊状物；(1) fully mix the precursor of the carrier and the catalyst active component to the paste; 上述的载体为碳黑、氧化钛、碳化钨、碳化钼或碳纳米管；The above-mentioned carrier is carbon black, titanium oxide, tungsten carbide, molybdenum carbide or carbon nanotube; 上述的催化剂活性组分的前驱物为铁、钴、镍、铜、铬、锰、锡、铅、钼、锆、钒、钨、钪、钛、铌、钽的无机盐或其它有机金属化合物、铈、铕、钐的无机盐或有机化合物的一种或一种以上混合物；The precursors of the above catalyst active components are inorganic salts or other organometallic compounds of iron, cobalt, nickel, copper, chromium, manganese, tin, lead, molybdenum, zirconium, vanadium, tungsten, scandium, titanium, niobium, tantalum, One or more mixtures of inorganic salts or organic compounds of cerium, europium, samarium; 上述的载体与催化剂活性组分的前驱物的比例为99.9％∶0.1％～5％∶90％；The ratio of the above-mentioned carrier to the precursor of the catalyst active component is 99.9%: 0.1% to 5%: 90%; (2)将糊状物放入微波系统中，选择微波敏感材料，进行微波处理，处理时间为1～20分钟，使之干燥；(2) Put the paste into a microwave system, select microwave-sensitive materials, and carry out microwave treatment for 1 to 20 minutes to make it dry; 上述的微波敏感材料为碳黑、碳化钛、碳化钨、碳化钼、或碳纳米管；The above-mentioned microwave sensitive material is carbon black, titanium carbide, tungsten carbide, molybdenum carbide, or carbon nanotubes; 微波敏感材料的加入量是糊状物的10～1000倍；The amount of microwave-sensitive materials added is 10 to 1000 times that of the paste; (3)经微波干燥的载体与活性材料前驱物的混合物，在微波系统中，进一步进行微波处理，处理的时间为1～120分钟，使活性材料前驱物最终热分解成相应的氧化物；(3) The microwave-dried mixture of the carrier and the active material precursor is further subjected to microwave treatment in a microwave system, and the treatment time is 1 to 120 minutes, so that the active material precursor is finally thermally decomposed into corresponding oxides; 上述(2)、(3)步骤中的微波处理的微波频段是0.896GHz～2.45GHz，微波系统的功率为500W～2000W，温度控制在600℃-800℃。The microwave frequency band of the microwave treatment in the above (2) and (3) steps is 0.896GHz-2.45GHz, the power of the microwave system is 500W-2000W, and the temperature is controlled at 600°C-800°C. 2、根据权利要求1所述的一种负载型金属氧化物催化剂的制备方法，其特征在于(1)步骤所使用的混合方法为超声波或机械搅拌混合。2. The preparation method of a supported metal oxide catalyst according to claim 1, characterized in that the mixing method used in the (1) step is ultrasonic or mechanical mixing. 3、根据权利要求1或2所述的一种负载型金属氧化物催化剂的制备方法，其特征在于(1)步骤中催化剂活性组分的前驱物的无机盐是碳酸盐、硝酸盐、高氯酸盐或铵盐。3. The preparation method of a supported metal oxide catalyst according to claim 1 or 2, characterized in that the inorganic salt of the precursor of the catalyst active component in the step (1) is carbonate, nitrate, high chlorate or ammonium salt. 4、根据权利要求3所述的一种负载型金属氧化物催化剂的制备方法，其特征在于(1)步骤中催化剂活性组分的前驱物的有机金属化合物为醋酸盐、朴啉类、酞菁类、冠醚类、schiff碱类配合物或羰基化合物。4. The preparation method of a supported metal oxide catalyst according to claim 3, wherein the organometallic compound of the precursor of the catalyst active component in the step (1) is acetate, porphyrin, phthalate Cyanines, crown ethers, schiff base complexes or carbonyl compounds. 5、根据权利要求4所述的一种负载型金属氧化物催化剂的制备方法，其特征在于(2)步骤中微波敏感材料的加入量是糊状物的50～800倍。5. The preparation method of a supported metal oxide catalyst according to claim 4, characterized in that the amount of the microwave-sensitive material added in step (2) is 50-800 times that of the paste. 6、根据权利要求5所述的一种负载型金属氧化物催化剂的制备方法，其特征在于(2)步骤中微波敏感材料的加入量是糊状物的100～600倍。6. The preparation method of a supported metal oxide catalyst according to claim 5, characterized in that the amount of the microwave-sensitive material added in step (2) is 100-600 times that of the paste. 7、根据权利要求6所述的一种负载型金属氧化物催化剂的制备方法，其特征在于(2)步骤中微波处理的时间为3～6分钟。7. The preparation method of a supported metal oxide catalyst according to claim 6, characterized in that the microwave treatment time in step (2) is 3-6 minutes. 8、根据权利要求7所述的一种负载型金属氧化物催化剂的制备方法，其特征在于(3)步骤中微波处理的时间为2～30分钟。8. The preparation method of a supported metal oxide catalyst according to claim 7, characterized in that the microwave treatment time in step (3) is 2-30 minutes. 9、根据权利要求8所述的一种负载型金属氧化物催化剂的制备方法，其特征在于(3)步骤中微波处理的时间为3～10分钟。9. The preparation method of a supported metal oxide catalyst according to claim 8, characterized in that the microwave treatment time in step (3) is 3-10 minutes. 10、根据权利要求9所述的一种负载型金属氧化物催化剂的制备方法，其特征在于(2)、(3)步骤中微波处理的微波频段是0.915GHz～2.45GHz。10. The preparation method of a supported metal oxide catalyst according to claim 9, characterized in that the microwave frequency range of the microwave treatment in steps (2) and (3) is 0.915GHz-2.45GHz.
CN 200410027561 2004-06-11 2004-06-11 Preparing method for loaded metal oxide catalyst Pending CN1583273A (en)

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CN100353599C (en) * 2005-05-19 2007-12-05 中山大学 Carbon carried Pd/oxide composite electric catalyst and preparing process thereof
CN100467125C (en) * 2005-11-07 2009-03-11 中山大学 Preparation method of carbon-supported nano-tungsten carbide enhanced oxygen reduction electrocatalyst
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CN100569366C (en) * 2008-04-28 2009-12-16 中国矿业大学 Preparation method of sulfur-resistant molybdenum-based catalyst by all-microwave method
CN102728348B (en) * 2012-06-21 2014-06-25 华北电力大学 MnO2-TiO2 graphene-porous inorganic ceramic membrane low-temperature denitrification catalyst and preparation method thereof
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CN103102593A (en) * 2013-02-20 2013-05-15 四川大学 Supported metal oxide catalytic synergistic inorganic flame retardant polypropylene composite material and preparation method thereof
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CN108325514A (en) * 2018-05-10 2018-07-27 北京工业大学 A kind of preparation method improving cerium base SCR catalyst low temperature active
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