CN110833833A - Non-noble metal composite oxide honeycomb catalyst for catalytic combustion of low-carbon hydrocarbons - Google Patents

Non-noble metal composite oxide honeycomb catalyst for catalytic combustion of low-carbon hydrocarbons Download PDF

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CN110833833A
CN110833833A CN201911113364.XA CN201911113364A CN110833833A CN 110833833 A CN110833833 A CN 110833833A CN 201911113364 A CN201911113364 A CN 201911113364A CN 110833833 A CN110833833 A CN 110833833A
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composite oxide
catalyst
cumn
coating
honeycomb
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金晓东
曾利辉
李霖
李小虎
曾永康
张之翔
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Kaili Catalyst New Materials Co Ltd
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Kaili Catalyst New Materials Co Ltd
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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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The invention discloses a non-noble metal composite oxide honeycomb catalyst for low-carbon hydrocarbon catalytic combustion, which takes cordierite honeycomb ceramic as a substrate and is coated with CuMn2CexOδThe composite oxide coating is characterized in that x is 1-5, and CuMn2CexOδThe composite oxide coating accounts for 5-15% of the mass of the catalyst; the active component CuMn in the catalyst2CexOδThe composite oxide is prepared by a hydrothermal method by using ethylenediamine as a hydrothermal guiding precipitator, and then CuMn is added2CexOδThe composite oxide is prepared into the composite oxide honeycomb catalyst by pulping, dip-coating, drying and roasting. The catalyst has the advantages of simple preparation method, easily obtained raw materials, low cost and good catalytic combustion activity on low-carbon hydrocarbons such as methane, ethane, propane, ethylene, propylene, normal hexane and the likeAnd the catalyst can replace a noble metal catalyst and has better practical value.

Description

Non-noble metal composite oxide honeycomb catalyst for catalytic combustion of low-carbon hydrocarbons
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a non-noble metal composite oxide honeycomb catalyst for catalytic combustion of low-carbon hydrocarbons.
Background
The low-carbon alkane is an organic compound with simple structure and small molecular weight, is often discharged in large quantity as a byproduct in petrochemical industry, is an extremely strong source for causing greenhouse effect and ozone layer destruction, has great purification difficulty, seriously influences the atmospheric quality and ecological environment in China, and becomes one of waste gas problems to be solved urgently.
The catalytic combustion is an advanced and mature technology for purifying Volatile Organic Compounds (VOCs) at present, and the technology realizes low-temperature oxidation of the organic compounds by means of catalytic activity of a catalyst and decomposes the organic compounds into harmless water and carbon dioxide, so that the effect of purifying waste gas is achieved. The core of catalytic combustion is a catalyst, and a noble metal catalyst is a catalyst which is widely applied and technically mature in catalytic combustion at present, but as noble metals are rare and expensive, the cost is high, and the recovery is difficult, a non-noble metal catalyst with equivalent activity and lower cost is urgently needed to replace the noble metal catalyst.
Non-noble metal composite oxide catalysts are used as low-cost substitutes of noble metal catalysts, and in recent years, relevant research has made great progress, some transition metal oxides with strong oxidizability show higher activity in the oxidation process of low-carbon alkane such as methane and carbon monoxide, the perovskite, hexaaluminate, spinel and other composite oxides have better catalytic performance on most low-carbon organic compounds, and the active components of the catalysts are cheap and abundant in reserves, so the catalysts are optional for replacing the noble metal catalysts.
Disclosure of Invention
The invention aims to provide a non-noble metal composite oxide honeycomb catalyst which is used for low-carbon hydrocarbon catalytic combustion and has good low-temperature activity and strong stability, aiming at the problems that the active phase of a composite oxide is difficult to form, the active phase of a coating is not uniformly distributed, and the bonding force between the composite oxide and a carrier is weak in the prior art.
Aiming at the purposes, the non-noble metal composite oxide honeycomb catalyst adopted by the invention takes honeycomb ceramics as a substrate and is coated with CuMn2CexOδThe composite oxide coating is characterized in that x is 1-5, and CuMn2CexOδThe composite oxide coating accounts for 5-15% of the mass of the catalyst; the catalyst is prepared by preparing a composite oxide by a hydrothermal method, pulping the composite oxide, and uniformly dispersing and coating the composite oxide on a honeycomb substrate, and comprises the following specific steps:
1. pretreatment of honeycomb ceramics
And (3) placing the honeycomb ceramic in a muffle furnace, and roasting for 4-8 h at 300-500 ℃ to obtain the pretreated honeycomb ceramic.
2. Preparation of CuMn2CexOδComposite oxide
Adding Cu (NO)3)2·3H2O、50％Mn(NO3)2Solution, Ce (NO)3)3·6H2Dissolving O in water according to a molar ratio of 1:2: 1-5 to prepare an aqueous solution with a total metal ion concentration of 0.1-0.5 mol/L, adding a precipitation guiding agent with the total metal ion molar amount of 1-5 times, vigorously stirring, transferring to a hydrothermal kettle, crystallizing at 100-300 ℃ for 12-24 hours, filtering the precipitate, washing to be neutral, drying at 80-120 ℃, roasting at 500-800 ℃ to obtain CuMn2CexOδA composite oxide; the precipitation directing agent is one or more of urea, ammonium carbonate and ethylenediamine.
3. Preparation of coating solution
Mixing CuMn2CexOδMixing the composite oxide, pseudo-boehmite, an organic adhesive, water and ethanol, highly dispersing the mixture by a planetary ball mill to ensure that the granularity of the mixture is 5-15 mu m, and then using HNO3Adjusting the pH value to 3-4 to make the viscosity of the coating liquid be 200-300 mPa & s, and preparing a coating liquid; wherein, CuMn2CexOδThe composite oxide and the pseudo-boehmite totally occupy the coating liquid15-35% of the amount of CuMn2CexOδThe mass ratio of the composite oxide to the pseudo-boehmite is 7: 3-9: 1; the organic adhesive accounts for 1-5% of the mass of the coating liquid, the ethanol accounts for 1-5% of the mass of the coating liquid, and the balance is water.
4. Coating of honeycomb ceramics
And (2) immersing the honeycomb ceramic pretreated in the step (1) into the coating liquid for 5-15 min, taking out, blowing by using high-pressure air, after no residual liquid exists in the pore channel, ventilating and drying at room temperature for 6-12 h, ventilating and drying at 50-70 ℃ for 6-12 h, ventilating and drying at 90-110 ℃ for 12-24 h, transferring to a muffle furnace, roasting at 400-600 ℃ for 6-12 h, cooling, and repeating the operation until the loading capacity of the coating is 10% -15%, thus obtaining the catalyst.
Among the above catalysts, CuMn is preferred2CexOδThe composite oxide coating accounts for 10-15% of the mass of the catalyst.
In the preparation method of the catalyst, in step 1, the honeycomb ceramic is any one of cordierite and mullite.
In step 2 of the above-mentioned method for producing a catalyst, Cu (NO) is preferably used3)2·3H2O、50％Mn(NO3)2Solution, Ce (NO)3)3·6H2Metering O according to the molar ratio of metal ions of 1:2: 1-5, dissolving the O in water to prepare an aqueous solution with the total concentration of the metal ions of 0.4-0.5 mol/L, adding a precipitation guiding agent with the total molar amount of the metal ions of 1-3 times, violently stirring for 0.5-1 h, transferring to a hydrothermal kettle, crystallizing at 100-200 ℃ for 12-24 h, filtering the precipitate, washing to be neutral, drying at 100-120 ℃, roasting at 550-650 ℃ to obtain CuMn2CexOδA composite oxide.
In step 3 of the above-mentioned method for producing a catalyst, CuMn is preferred2CexOδThe composite oxide and the pseudo-boehmite account for 25-30% of the coating liquid in total, and CuMn2CexOδThe mass ratio of the composite oxide to the pseudo-boehmite is 8: 2; the organic adhesive accounts for 1.5-2% of the mass of the coating liquid, the ethanol accounts for 4-5% of the mass of the coating liquid, and the balance is water.
The organic adhesive is one or more of polyethylene glycol-4000, polyvinyl alcohol-1788, polyvinylpyrrolidone-K30, and carboxymethyl cellulose.
In the step 4 of the preparation method of the catalyst, the honeycomb ceramic pretreated in the step 1 is preferably immersed in the coating liquid for 10min, taken out and blown by high-pressure air, after no residual liquid exists in the pore channel, the honeycomb ceramic is subjected to room-temperature ventilation drying for 6-8 h, 60-DEG C ventilation drying for 6-8 h, 100-DEG C ventilation drying for 6-8 h, transferred to a muffle furnace and roasted at 500-DEG C for 6-12 h, and the operation is repeated after cooling until the loading capacity of the coating is 10% -15%, so that the catalyst is obtained.
The composite oxide honeycomb catalyst can be applied to the gas-solid reaction of catalytic combustion of low-carbon hydrocarbon, wherein the low-carbon hydrocarbon is one or more of methane, ethane, propane, ethylene, propylene, n-hexane and the like. More specifically, the catalyst is applied to a gas-solid reaction device for evaluation, the low-carbon hydrocarbon of the raw material gas is one or more of listed gases, the concentration is 1000-5000 mg/m3, and the reaction space velocity is 10000-30000/h.
The invention has the following beneficial effects:
1. the active components of the catalyst are mainly transition metals and rare earth metals, are cheap and easily available, are prepared by a hydrothermal method, and are simple to operate, and the microstructure is uniform and regular.
2. The catalyst has the advantages of simple preparation method, easily obtained raw materials, low cost and better substitution of noble metal catalysts, and therefore, the catalyst has better practical value.
3. The catalyst has uniform and firm coating, excellent catalytic performance in the gas-solid reaction of catalytic combustion of low-carbon hydrocarbons such as methane, ethane, propane, ethylene, propylene, normal hexane and the like, and good catalytic activity and stability.
Drawings
FIG. 1 shows the stability evaluation results of the catalyst prepared in example 7.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
1. Pretreatment of honeycomb ceramics
And placing the cordierite honeycomb ceramic into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain the pretreated cordierite honeycomb ceramic.
2. Preparation of CuMn2CeOδComposite oxide
24.16g (0.10mol) of Cu (NO)3)2·3H2O、71.58g(0.20mol)50％Mn(NO3)2Solution, 43.41g (0.10mol) Ce (NO)3)3·6H2Dissolving O in water, diluting to 800mL to prepare a solution with the total metal ion concentration of 0.5mol/L, adding 72g (1.20mol) of urea, vigorously stirring for 1h, transferring to a hydrothermal kettle, crystallizing at 180 ℃ for 12h, filtering precipitates in the kettle, washing to neutrality, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain CuMn2CeOδA composite oxide.
3. Preparation of coating solution
24g of CuMn2CeOδMixing the composite oxide, 6g of pseudo-boehmite, 2g of PEG-4000, 53g of water and 5g of ethanol, highly dispersing for 2 hours by a planetary ball mill to ensure that the particle size is 5-15 mu m, and then using HNO3The pH was adjusted to 3.83 to obtain a viscosity of 258mPa · s, thereby obtaining a coating solution.
4. Coating of honeycomb ceramics
And (3) immersing the cordierite honeycomb ceramic pretreated in the step (1) into the coating liquid in the step (3) for 10min, taking out, blowing the pore channels by using high-pressure air, after no residual liquid exists in the pore channels, carrying out ventilation drying at room temperature for 6h, carrying out ventilation drying at 60 ℃ for 6h, carrying out ventilation drying at 100 ℃ for 12h, transferring to a muffle furnace, roasting at 500 ℃ for 6h, cooling, and repeating the operation until the load of the oxide coating is 11.8%, thus obtaining the catalyst.
Example 2
1. Pretreatment of honeycomb ceramics
And placing the cordierite honeycomb ceramic into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain the pretreated cordierite honeycomb ceramic.
2. Preparation of CuMn2Ce2OδComposite oxidationArticle (A)
19.33g (0.08mol) of Cu (NO)3)2·3H2O、57.26g(0.16mol)50％Mn(NO3)2Solution 69.47g (0.16mol) Ce (NO)3)3·6H2Dissolving O in water, diluting to 800mL to prepare a solution with the total metal ion concentration of 0.5mol/L, adding 72.07g (1.20mol) of urea, vigorously stirring for 1h, transferring to a hydrothermal kettle, crystallizing at 180 ℃ for 12h, filtering precipitates in the kettle, washing to neutrality, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain CuMn2Ce2OδA composite oxide.
3. Preparation of coating solution
24g of CuMn2Ce2OδMixing the composite oxide, 6g of pseudo-boehmite, 2g of PEG-4000, 53g of water and 5g of ethanol, highly dispersing for 2 hours by a planetary ball mill to ensure that the particle size is 5-15 mu m, and then using HNO3The pH was adjusted to 3.65 to obtain a coating solution having a viscosity of 256mPa · s.
4. Coating of honeycomb ceramics
And (3) immersing the cordierite honeycomb ceramic pretreated in the step (1) into the coating liquid in the step (3) for 10min, taking out, blowing the pore channels by using high-pressure air, after no residual liquid exists in the pore channels, carrying out ventilation drying at room temperature for 6h, carrying out ventilation drying at 60 ℃ for 6h, carrying out ventilation drying at 100 ℃ for 12h, transferring to a muffle furnace, roasting at 500 ℃ for 6h, cooling, and repeating the operation until the load of the oxide coating is 10.9%, thus obtaining the catalyst.
Example 3
1. Pretreatment of honeycomb ceramics
And placing the cordierite honeycomb ceramic into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain the pretreated cordierite honeycomb ceramic.
2. Preparation of CuMn2Ce3OδComposite oxide
16.91g (0.07mol) of Cu (NO)3)2·3H2O、50.11g(0.14mol)50％Mn(NO3)2Solution 91.19g (0.21mol) Ce (NO)3)3·6H2O was dissolved in water and diluted to 840mL to prepare a solution with a total metal ion concentration of 0.5mol/L, and 75.68g (1) was added26mol) urea, stirring vigorously for 1h, transferring to a hydrothermal kettle, crystallizing at 180 ℃ for 12h, filtering the precipitate in the kettle, washing to neutrality, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain CuMn2Ce3OδA composite oxide.
3. Preparation of coating solution
24g of CuMn2Ce3OδMixing the composite oxide, 6g of pseudo-boehmite, 2g of PEG-4000, 53g of water and 5g of ethanol, highly dispersing for 2 hours by a planetary ball mill to ensure that the particle size is 5-15 mu m, and then using HNO3The pH was adjusted to 3.79 to 266mPa · s to obtain a coating solution.
4. Coating of honeycomb ceramics
And (3) immersing the cordierite honeycomb ceramic pretreated in the step (1) into the coating liquid in the step (3) for 10min, taking out, blowing the pore channels by using high-pressure air, after no residual liquid exists in the pore channels, carrying out ventilation drying at room temperature for 6h, carrying out ventilation drying at 60 ℃ for 6h, carrying out ventilation drying at 100 ℃ for 12h, transferring to a muffle furnace, roasting at 500 ℃ for 6h, cooling, and repeating the operation until the load of the oxide coating is 10.6%, thus obtaining the catalyst.
Example 4
1. Pretreatment of honeycomb ceramics
And placing the cordierite honeycomb ceramic into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain the pretreated cordierite honeycomb ceramic.
2. Preparation of CuMn2Ce4OδComposite oxide
14.50g (0.06mol) of Cu (NO)3)2·3H2O、42.95g(0.12mol)50％Mn(NO3)2Solution 104.21g (0.24mol) Ce (NO)3)3·6H2Dissolving O in water, diluting to 840mL to prepare a solution with the total metal ion concentration of 0.5mol/L, adding 75.68g (1.26mol) of urea, vigorously stirring for 1h, transferring to a hydrothermal kettle, crystallizing at 180 ℃ for 12h, filtering precipitates in the kettle, washing to neutrality, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain CuMn2Ce4OδA composite oxide.
3. Preparation of coating solution
24g of CuMn2Ce4OδMixing the composite oxide, 6g of pseudo-boehmite, 2g of PEG-4000, 53g of water and 5g of ethanol, highly dispersing for 2 hours by a planetary ball mill to ensure that the particle size is 5-15 mu m, and then using HNO3The pH was adjusted to 3.81 to obtain a coating solution having a viscosity of 258mPa · s.
4. Coating of honeycomb ceramics
And (3) immersing the cordierite honeycomb ceramic pretreated in the step (1) into the coating liquid in the step (3) for 10min, taking out, blowing the pore channels by using high-pressure air, after no residual liquid exists in the pore channels, carrying out ventilation drying at room temperature for 6h, carrying out ventilation drying at 60 ℃ for 6h, carrying out ventilation drying at 100 ℃ for 12h, transferring to a muffle furnace, roasting at 500 ℃ for 6h, cooling, and repeating the operation until the loading capacity of the oxide coating is 11.4%, thus obtaining the catalyst.
Example 5
1. Pretreatment of honeycomb ceramics
And placing the cordierite honeycomb ceramic into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain the pretreated cordierite honeycomb ceramic.
2. Preparation of CuMn2Ce5OδComposite oxide
12.08g (0.05mol) of Cu (NO)3)2·3H2O、35.79g(0.10mol)50％Mn(NO3)2Solution, 108.56g (0.25mol) Ce (NO)3)3·6H2Dissolving O in water, diluting to 800mL to prepare a solution with the total metal ion concentration of 0.5mol/L, adding 72.07g (1.2mol) of urea, vigorously stirring for 1h, transferring to a hydrothermal kettle, crystallizing at 180 ℃ for 12h, filtering precipitates in the kettle, washing to neutrality, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain CuMn2Ce5OδA composite oxide.
3. Preparation of coating solution
24g of CuMn2Ce5OδMixing the composite oxide, 6g of pseudo-boehmite, 2g of PEG-4000, 53g of water and 5g of ethanol, highly dispersing for 2 hours by a planetary ball mill to ensure that the particle size is 5-15 mu m, and then using HNO3The pH was adjusted to 3.79 to make the viscosity 262mPa · s, thereby obtaining a coating solution.
4. Coating of honeycomb ceramics
And (3) immersing the cordierite honeycomb ceramic pretreated in the step (1) into the coating liquid in the step (3) for 10min, taking out, blowing the pore channels by using high-pressure air, after no residual liquid exists in the pore channels, carrying out ventilation drying at room temperature for 6h, carrying out ventilation drying at 60 ℃ for 6h, carrying out ventilation drying at 100 ℃ for 12h, transferring to a muffle furnace, roasting at 500 ℃ for 6h, cooling, and repeating the operation until the loading capacity of the oxide coating is 11.6%, thus obtaining the catalyst.
Example 6
1. Pretreatment of honeycomb ceramics
And placing the cordierite honeycomb ceramic into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain the pretreated cordierite honeycomb ceramic.
2. Preparation of CuMn2Ce2OδComposite oxide
19.33g (0.08mol) of Cu (NO)3)2·3H2O、57.26g(0.16mol)50％Mn(NO3)2Solution 69.47g (0.16mol) Ce (NO)3)3·6H2Dissolving O in water, diluting to 800mL to prepare a solution with the total metal ion concentration of 0.5mol/L, adding 115.31g (1.20mol) of ammonium carbonate, vigorously stirring for 1h, transferring to a hydrothermal kettle, crystallizing at 100 ℃ for 12h, filtering precipitates in the kettle, washing to neutrality, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain CuMn2Ce2OδA composite oxide.
3. Preparation of coating solution
24g of CuMn2Ce2OδMixing the composite oxide, 6g of pseudo-boehmite, 2g of PEG-4000, 53g of water and 5g of ethanol, highly dispersing for 2 hours by a planetary ball mill to ensure that the particle size is 5-15 mu m, and then using HNO3The pH was adjusted to 3.71 to make the viscosity 260mPa · s, thereby obtaining a coating solution.
4. Coating of honeycomb ceramics
And (3) immersing the cordierite honeycomb ceramic pretreated in the step (1) into the coating liquid in the step (3) for 10min, taking out, blowing the pore channels by using high-pressure air, after no residual liquid exists in the pore channels, carrying out ventilation drying at room temperature for 6h, carrying out ventilation drying at 60 ℃ for 6h, carrying out ventilation drying at 100 ℃ for 12h, transferring to a muffle furnace, roasting at 500 ℃ for 6h, cooling, and repeating the operation until the loading capacity of the oxide coating is 11.4%, thus obtaining the catalyst.
Example 7
1. Pretreatment of honeycomb ceramics
And placing the cordierite honeycomb ceramic into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain the pretreated cordierite honeycomb ceramic.
2. Preparation of CuMn2Ce2OδComposite oxide
19.33g (0.08mol) of Cu (NO)3)2·3H2O、57.26g(0.16mol)50％Mn(NO3)2Solution 69.47g (0.16mol) Ce (NO)3)3·6H2Dissolving O in water, diluting to 800mL to prepare a solution with the total metal ion concentration of 0.5mol/L, adding 72.12g (1.20mol) of ethylenediamine, vigorously stirring for 1h, transferring to a hydrothermal kettle, crystallizing at 200 ℃ for 12h, filtering the precipitate in the kettle, washing to neutrality, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain CuMn2Ce2OδA composite oxide.
3. Preparation of coating solution
24g of CuMn2Ce2OδMixing the composite oxide, 6g of pseudo-boehmite, 2g of PEG-4000, 53g of water and 5g of ethanol, highly dispersing for 2 hours by a planetary ball mill to ensure that the particle size is 5-15 mu m, and then using HNO3The pH was adjusted to 3.75 to 268mPa · s to obtain a coating solution.
4. Coating of honeycomb ceramics
And (3) immersing the cordierite honeycomb ceramic pretreated in the step (1) into the coating liquid in the step (3) for 10min, taking out, blowing the pore channels by using high-pressure air, after no residual liquid exists in the pore channels, carrying out ventilation drying at room temperature for 6h, carrying out ventilation drying at 60 ℃ for 6h, carrying out ventilation drying at 100 ℃ for 12h, transferring to a muffle furnace, roasting at 500 ℃ for 6h, cooling, and repeating the operation until the loading capacity of the oxide coating is 12.3%, thus obtaining the catalyst.
Example 8
1. Pretreatment of honeycomb ceramics
And placing the cordierite honeycomb ceramic into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain the pretreated cordierite honeycomb ceramic.
2. Preparation of CuMn2Ce2OδComposite oxide
19.33g (0.08mol) of Cu (NO)3)2·3H2O、57.26g(0.16mol)50％Mn(NO3)2Solution 69.47g (0.16mol) Ce (NO)3)3·6H2Dissolving O in water, diluting to 800mL to prepare a solution with the total metal ion concentration of 0.5mol/L, adding 48.08g (0.80mol) of ethylenediamine, vigorously stirring for 1h, transferring to a hydrothermal kettle, crystallizing at 200 ℃ for 12h, filtering the precipitate in the kettle, washing to neutrality, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain CuMn2Ce2OδA composite oxide.
3. Preparation of coating solution
24g of CuMn2Ce2OδMixing the composite oxide, 6g of pseudo-boehmite, 2g of PVA-1788, 53g of water and 5g of ethanol, highly dispersing for 2 hours by a planetary ball mill to ensure that the particle size is 5-15 mu m, and then using HNO3The pH was adjusted to 3.79 to achieve a viscosity of 285mPa · s, thereby obtaining a coating solution.
4. Coating of honeycomb ceramics
And (3) immersing the cordierite honeycomb ceramic pretreated in the step (1) into the coating liquid in the step (3) for 10min, taking out, blowing the pore channels by using high-pressure air, after no residual liquid exists in the pore channels, carrying out ventilation drying at room temperature for 6h, carrying out ventilation drying at 60 ℃ for 6h, carrying out ventilation drying at 100 ℃ for 12h, transferring to a muffle furnace, roasting at 500 ℃ for 6h, cooling, and repeating the operation until the loading capacity of the oxide coating is 14.3%, thus obtaining the catalyst.
Example 9
1. Pretreatment of honeycomb ceramics
And placing the cordierite honeycomb ceramic into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain the pretreated cordierite honeycomb ceramic.
2. Preparation of CuMn2Ce2OδComposite oxide
19.33g (0.08mol) of Cu (NO)3)2·3H2O、57.26g(0.16mol)50％Mn(NO3)2Solution 69.47g (0.16mol) Ce (NO)3)3·6H2Dissolving O in water and diluting to 800mL to prepare metal ionsAdding 24.04g (0.40mol) of ethylenediamine into the solution with the total concentration of 0.5mol/L, vigorously stirring for 1h, transferring to a hydrothermal kettle, crystallizing at 200 ℃ for 12h, filtering the precipitate in the kettle, washing to neutrality, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain CuMn2Ce2OδA composite oxide.
3. Preparation of coating solution
24g of CuMn2Ce2OδMixing the composite oxide, 6g of pseudo-boehmite, 2g of PVP-K30, 53g of water and 5g of ethanol, highly dispersing for 2 hours by a planetary ball mill to ensure that the particle size is 5-15 mu m, and then using HNO3The pH was adjusted to 3.74 to give a viscosity of 275mPa · s, thereby obtaining a coating solution.
4. Coating of honeycomb ceramics
And (3) immersing the cordierite honeycomb ceramic pretreated in the step (1) into the coating liquid in the step (3) for 10min, taking out, blowing the pore channels by using high-pressure air, after no residual liquid exists in the pore channels, carrying out ventilation drying at room temperature for 6h, carrying out ventilation drying at 60 ℃ for 6h, carrying out ventilation drying at 100 ℃ for 12h, transferring to a muffle furnace, roasting at 500 ℃ for 6h, cooling, and repeating the operation until the load capacity of the oxide coating is 13.8%, thus obtaining the catalyst.
Example 10
1. Pretreatment of honeycomb ceramics
And placing the cordierite honeycomb ceramic into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain the pretreated cordierite honeycomb ceramic.
2. Preparation of CuMn2Ce2OδComposite oxide
19.33g (0.08mol) of Cu (NO)3)2·3H2O、57.26g(0.16mol)50％Mn(NO3)2Solution 69.47g (0.16mol) Ce (NO)3)3·6H2Dissolving O in water, diluting to 800mL to prepare a solution with the total metal ion concentration of 0.5mol/L, adding 72.12g (1.20mol) of ethylenediamine, vigorously stirring for 1h, transferring to a hydrothermal kettle, crystallizing at 200 ℃ for 12h, filtering the precipitate in the kettle, washing to neutrality, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain CuMn2Ce2OδA composite oxide.
3. Preparation of coating solution
16g of CuMn2Ce2OδThe composite oxide, 4g of pseudo-boehmite, 1g of CMC, 74g of water and 5g of ethanol were blended, highly dispersed for 2 hours by a planetary ball mill to have a particle size of 5 to 15 μm, and then adjusted to pH 3.66 by nitric acid to have a viscosity of 280mPa · s, to prepare a coating liquid.
4. Coating of honeycomb ceramics
And (3) immersing the cordierite honeycomb ceramic pretreated in the step (1) into the coating liquid in the step (3) for 10min, taking out, blowing the pore channels by using high-pressure air, after no residual liquid exists in the pore channels, carrying out ventilation drying at room temperature for 6h, carrying out ventilation drying at 60 ℃ for 6h, carrying out ventilation drying at 100 ℃ for 12h, transferring to a muffle furnace, roasting at 500 ℃ for 6h, cooling, and repeating the operation until the loading capacity of the oxide coating is 14.1%, thus obtaining the catalyst.
The catalyst prepared in the embodiment 1-7 is prepared at an airspeed of 10000/h, and the reaction gas comprises the following components: and testing and evaluating on a fixed bed reactor with 1 thousandth of methane, 2 thousandth of ethane, 2 thousandth of propane, 1 thousandth of propylene, 1 thousandth of normal hexane and the balance of air. The results of activity evaluation are shown in Table 1.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
T50 410℃ 390℃ 390℃ 385℃ 380℃ 380℃ 375℃
T95 545℃ 520℃ 525℃ 525℃ 530℃ 510℃ 505℃
As can be seen from table 1, the catalyst of the present invention has a good catalytic oxidation effect on low carbon hydrocarbons, and when the same conversion rate of mixed low carbon hydrocarbons is achieved, the ignition temperature and the conversion temperature of the catalyst prepared in examples 1 to 5 decrease as the Ce content increases; in the catalysts prepared in examples 5 to 7, the catalysts prepared in example 7 have the lowest light-off temperature and the lowest conversion temperature.
The catalyst prepared in example 7 was further prepared at a space velocity of 10000/h and a temperature of 505 ℃ with a reaction gas composition of: and testing and evaluating on a fixed bed reactor with 1 thousandth of methane, 2 thousandth of ethane, 2 thousandth of propane, 1 thousandth of propylene, 1 thousandth of normal hexane and the balance of air. The stability evaluation results are shown in FIG. 1. As can be seen from the results of FIG. 1, the catalyst of the present invention has good catalytic oxidation stability for low carbon hydrocarbons, and the conversion rate of the mixed low carbon hydrocarbons is maintained at 95% without significant attenuation when the catalyst is operated for 580 hours.
The results in table 1 and fig. 1 show that the catalyst of the present invention has good catalytic oxidation activity and stability for low carbon hydrocarbons. The catalyst has the advantages of simple preparation method, easily obtained raw materials, low cost and better substitution of noble metal catalysts, and therefore, the catalyst has better practical value.

Claims (7)

1. A non-noble metal composite oxide honeycomb catalyst for catalytic combustion of low-carbon hydrocarbons is characterized in that: the catalyst takes honeycomb ceramics as a matrix and is coated with CuMn2CexOδThe composite oxide coating is characterized in that x is 1-5, and CuMn2CexOδThe composite oxide coating accounts for 5-15% of the mass of the catalyst; the catalyst is prepared by the following method:
(1) pretreatment of honeycomb ceramics
Placing the honeycomb ceramic in a muffle furnace, and roasting for 4-8 hours at 300-500 ℃ to obtain pretreated honeycomb ceramic;
(2) preparation of CuMn2CexOδComposite oxide
Adding Cu (NO)3)2·3H2O、50％Mn(NO3)2Solution, Ce (NO)3)3·6H2Dissolving O in water according to a molar ratio of 1:2: 1-5 to prepare an aqueous solution with a total metal ion concentration of 0.1-0.5 mol/L, adding a precipitation guiding agent with the total metal ion molar amount of 1-5 times, vigorously stirring, transferring to a hydrothermal kettle, crystallizing at 100-300 ℃ for 12-24 hours, filtering the precipitate, washing to be neutral, drying at 80-120 ℃, roasting at 500-800 ℃ to obtain CuMn2CexOδA composite oxide; wherein the precipitation directing agent is one or more of urea, ammonium carbonate and ethylenediamine;
(3) preparation of coating solution
Mixing CuMn2CexOδComposite oxide, pseudo-boehmite, organic adhesive, water and ethanolBlending, highly dispersing by a planetary ball mill to ensure that the particle size is 5-15 mu m, and then using HNO3Adjusting the pH value to 3-4 to make the viscosity of the coating liquid be 200-300 mPa & s, and preparing a coating liquid; wherein, CuMn2CexOδThe composite oxide and the pseudo-boehmite account for 15-35 percent of the coating liquid in total, and CuMn2CexOδThe mass ratio of the composite oxide to the pseudo-boehmite is 7: 3-9: 1; the organic adhesive accounts for 1-5% of the mass of the coating liquid, the ethanol accounts for 1-5% of the mass of the coating liquid, and the balance is water;
(4) coating of honeycomb ceramics
Immersing the honeycomb ceramic pretreated in the step (1) into a coating liquid for 5-15 min, taking out, blowing by using high-pressure air, after no residual liquid exists in a pore channel, ventilating and drying at room temperature for 6-12 h, ventilating and drying at 50-70 ℃ for 6-12 h, ventilating and drying at 90-110 ℃ for 12-24 h, transferring to a muffle furnace, roasting at 400-600 ℃ for 6-12 h, cooling, and repeating the operation until the loading capacity of the coating is 10% -15% to obtain the catalyst.
2. The non-noble metal composite oxide honeycomb catalyst according to claim 1, characterized in that: in the catalyst, CuMn2CexOδThe composite oxide coating accounts for 10-15% of the mass of the catalyst.
3. The non-noble metal composite oxide honeycomb catalyst according to claim 1, characterized in that: in the step (1), the honeycomb ceramic is any one of cordierite and mullite.
4. The non-noble metal composite oxide honeycomb catalyst according to claim 1, characterized in that: in the step (2), Cu (NO) is added3)2·3H2O、50％Mn(NO3)2Solution, Ce (NO)3)3·6H2O is measured according to the molar ratio of metal ions of 1:2: 1-5 and dissolved in water to prepare an aqueous solution with the total concentration of the metal ions of 0.4-0.5 mol/L, then a precipitation guiding agent with the total molar weight of the metal ions of 1-3 times is added, the mixture is stirred vigorously for 0.5-1 h, and the reaction is carried out until the reaction temperature is reachedCrystallizing in a hydrothermal kettle at 100-200 ℃ for 12-24 h, filtering the precipitate, washing to be neutral, drying at 100-120 ℃, and roasting at 550-650 ℃ to obtain CuMn2CexOδA composite oxide.
5. The non-noble metal composite oxide honeycomb catalyst according to claim 1, characterized in that: in step (3), CuMn2CexOδThe composite oxide and the pseudo-boehmite account for 25-30% of the coating liquid in total, and CuMn2CexOδThe mass ratio of the composite oxide to the pseudo-boehmite is 8: 2; the organic adhesive accounts for 1.5-2% of the mass of the coating liquid, the ethanol accounts for 4-5% of the mass of the coating liquid, and the balance is water.
6. The non-noble metal composite oxide honeycomb catalyst according to claim 1 or 5, characterized in that: the organic adhesive is one or more of polyethylene glycol-4000, polyvinyl alcohol-1788, polyvinylpyrrolidone-K30 and carboxymethyl cellulose.
7. The non-noble metal composite oxide honeycomb catalyst according to claim 1, characterized in that: in the step (4), the honeycomb ceramic pretreated in the step (1) is immersed in the coating liquid for 10min, taken out and blown by high-pressure air, after no residual liquid exists in the pore channel, the honeycomb ceramic is subjected to room-temperature ventilation drying for 6-8 h, 60-DEG C ventilation drying for 6-8 h, 100-DEG C ventilation drying for 6-8 h, transferred to a muffle furnace and roasted at 500-DEG C for 6-12 h, and the operation is repeated after cooling until the loading capacity of the coating is 10% -15%, so that the catalyst is obtained.
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