CN104707623A - Method for preparing catalyst for catalytic combustion of methane - Google Patents
Method for preparing catalyst for catalytic combustion of methane Download PDFInfo
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- CN104707623A CN104707623A CN201310682164.2A CN201310682164A CN104707623A CN 104707623 A CN104707623 A CN 104707623A CN 201310682164 A CN201310682164 A CN 201310682164A CN 104707623 A CN104707623 A CN 104707623A
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Abstract
The present invention relates to a method for preparing a catalyst for catalytic combustion of methane, and belongs to the field of inorganic material preparation, particularly to a method for co-preparation of a catalyst for catalytic combustion of methane through a hydrothermal method and an impregnating method. The method is characterized in that the catalyst carrier is cerium-iron-cobalt composite oxide, wherein the cerium content is 90-96%, the iron content is 3-7%, the cobalt content is 3-5%, and the active component is palladium and accounts for 0.5-2% of the total catalyst. The catalyst preparation method comprises: (1) preparing a cerium oxide/ferric oxide/cobalt oxide (CeO2/Fe2O3/Co2O3) carrier through a hydrothermal method, and (2) preparing a palladium nitrate (Pd(NO3)2) solution, impregnating the catalyst carrier prepared in the step (1) in the palladium nitrate solution, standing, drying, and calcining to prepare the catalyst finished product. The catalyst has advantages of short preparation period, high methane catalysis efficiency, low catalysis temperature, good aging resistance, and the like.
Description
Invention field
The present invention relates to a kind of method preparing methane catalytic combustion catalyst, particularly a kind of hydro-thermal method and infusion process prepare the method for methane catalytic combustion catalyst jointly.
Background technology
Coal bed gas is commonly called as " gas ", and main component is methane, and with coal association, calorific value is 2 ~ 5 times of coal, and very clean after burning, produces waste gas hardly, can be widely used in industry and resident living etc.If be not used to coal bed gas, be directly discharged in air, the greenhouse effects caused are about CO
221 times, serious have impact on ecological environment, runs counter to " energy-saving and emission-reduction ".Therefore, coal bed gas is made full use of most important.
But, traditional methane flame burned flame adiabatic temperature more than 2000 DEG C, the N at this temperature in air
2and O
2can react, cause a large amount of NO_x formation; Meanwhile, combustion apparatus can not bear high temperature like this.By contrast, methane catalytic combustion can reduce methyl hydride combustion temperature, thus reduces the infringement to equipment, also reduces the pollution to environment simultaneously.But select any methane catalytic combustion catalyst more effective, become the research emphasis of people.General methane catalytic combustion catalyst is made up of carrier and active component.Noble metal has good low-temperature catalyzed performance and ageing resistace, is therefore widely used as the active component of methane catalytic combustion catalyst.Catalyst carrier kind is varied, comprises aluminium oxide, molecular sieve and metal oxide etc.
Patent CN103203233A discloses a kind of preparation method of palladium-based catalyst, and using palladium as active component, meso-porous alumina, as carrier, shows good catalytic performance, but this catalyst preparing cycle is long.
Patent CN103131489A discloses a kind of method that co-precipitation-infusion process prepares sosoloid catalyst of methyl alkyl catalyzing burned, and with iron cerium composite oxides for carrier, take silver as active component, this catalyst low-temperature activity is higher, and low temperature conversion rate is higher.
Learnt by above patent, develop a kind of manufacturing cycle short, the methane catalytic combustion catalyst that low temperature conversion rate is high has very important application prospect.
In the majority with solid solution catalyst in methane catalytic combustion catalyst, the method preparing solid solution catalyst has coprecipitation, sol-gel process, microemulsion method and high-energy ball milling method etc.This patent adopts a kind of hydro-thermal and infusion process jointly to prepare the method for methane catalytic combustion catalyst, and manufacturing cycle is short, and catalytic activity is high, the initiation temperature of methane is lower than 270 DEG C, and combustion temperature is lower than 390 DEG C eventually, and ageing-resistant performance is good, low temperature conversion rate is high, and 450 DEG C just can reach more than 95%.
Summary of the invention
The object of the invention is to solve the current methane catalytic combustion catalyst preparing cycle long, the defects such as catalytic efficiency is low, and catalytic temperature is higher, loss of properties on aging, obtain the more effective methane catalytic combustion catalyst of one.A kind of method preparing Catalytic methane oxidation catalyst of exploitation, namely under the common conditions of hydro-thermal and dipping, obtains the method for methane catalytic combustion catalyst.
Compared with prior art, the invention is characterized in that the manufacturing cycle of methane is short, catalytic activity is high, and the initiation temperature of methane is lower than 270 DEG C, and combustion temperature is lower than 390 DEG C eventually.Catalyst is after 1200 DEG C of high temperature ageings, and catalytic activity is good.Catalyst composition and percentage are: carrier is ferrocerium cobalt composite oxide, and wherein cerium content is 90% ~ 96%, and iron content is 3% ~ 7%, and cobalt content is 3% ~ 5%; Active component is palladium, and it accounts for 0.5% ~ 2% of total catalyst percentage composition.
The invention provides a kind of method preparing methane catalytic combustion catalyst, its step is as follows:
(1) hydro-thermal method prepares cerium oxide/di-iron trioxide/cobalt oxide (CeO
2/ Fe
2o
3/ Co
2o
3) carrier: cerous nitrate, ferric nitrate and cobalt nitrate are dissolved in the distilled water of certain volume, and stir, obtain solution A and add precipitating reagent urea or ammonium carbonate in solution A, regulate PH to be greater than 7, then join in autoclave, sealing, puts into baking oven.After having reacted, take out precipitation, and wash, dry, the then obtained catalyst carrier of calcining.
(2) palladium nitrate solution is configured, by above-mentioned obtained impregnation of catalyst carriers in palladium nitrate solution, after leaving standstill a period of time, the obtained finished catalyst of calcining.
(3) described in step (1), cerium content is 90% ~ 96%, and iron content is 3% ~ 7%, and cobalt content is 3% ~ 5%.
(4) in step (1), reaction temperature is generally 60 DEG C ~ 140 DEG C, and the reaction time is generally 3 ~ 6h.
(5) step (2) described palladium accounts for 0.5% ~ 2% of catalyst total amount.
(6) dipping described in step (2) is incipient impregnation.
(7) described in step (2), time of repose is 2 ~ 3h.
(8) above-mentioned steps calcining heat is generally 300 ~ 500 DEG C, and calcination time is generally 2h.
Fixed-bed micro-reactor is verified the catalytic combustion activity to methane, air inlet consists of V (methane): V (air)=1: 99, the gas of front and back is answered in negate respectively, by gas-chromatography, quantitative analysis is carried out to it, thus the catalytic activity of this catalyst is evaluated.
Detailed description of the invention
Embodiment 1:
(1) hydro-thermal method prepares cerium oxide/di-iron trioxide/cobalt oxide (CeO
2/ Fe
2o
3/ Co
2o
3) carrier:
Weigh cerous nitrate, ferric nitrate and cobalt nitrate respectively and be respectively 20 ~ 32g, 2.5 ~ 3.49g, 0.5 ~ 1.44g, join in 150ml distilled water, stir, obtain mixing salt solution A, then in solution, 6 ~ 10g urea (wherein urea is excessive) is added, react in closed system, temperature is 60 DEG C ~ 140 DEG C, and the reaction time is 3 ~ 6h.After reaction terminates, question response still naturally cools to room temperature, takes out precipitation, and through washing, 105 DEG C of dry 3h, then 450 DEG C of calcining 2h, obtain Multimetal oxide mixed catalytic agent carrier.
(2) palladium the equipment of dipping liquid
Preparation molar concentration is the Pd (NO of 0.05 ~ 0.1mol/L
3)
2solution, gets 0.5mlPd (NO
3)
2solution, adds distilled water to 3 ~ 6ml, stirs.
(3) load of active component
By catalyst carrier grinding obtained for step (1), weighing 6g impregnated in the solution in step (2), and room temperature immersion 3h is put in 105 DEG C of dry 3h in baking oven after dipping terminates, afterwards 450 DEG C of calcining 2h.The finished catalyst of gained is used for evaluating catalyst.Wherein palladium accounts for 0.89% of catalyst content.
This catalyst is when air/methane (volume ratio)=99, and the total air speed of gas is 18000h
-1, catalyst amount is that under the condition of 1.5g, catalytic perfomance is as follows:
Embodiment 2:
(1) hydro-thermal method prepares cerium oxide/di-iron trioxide/cobalt oxide (CeO
2/ Fe
2o
3/ Co
2o
3) carrier:
Weigh cerous nitrate, ferric nitrate and cobalt nitrate respectively and be respectively 20 ~ 32g, 2.5 ~ 3.49g, 0.5 ~ 1.44g, join in 150ml distilled water, stir, obtain mixing salt solution A, then in solution, 10g urea (wherein urea is excessive) is added, react in closed system, temperature is 60 DEG C ~ 140 DEG C, and the reaction time is 3 ~ 6h.After reaction terminates, question response still naturally cools to room temperature, takes out precipitation, and through washing, 105 DEG C of dry 3h, then 450 DEG C of calcining 2h, obtain Multimetal oxide mixed catalytic agent carrier.Wherein CeO
2, Fe
2o
3and Co
2o
3content be respectively 90%, 6%, 4%.
(2) palladium the equipment of dipping liquid
Preparation molar concentration is the Pd (NO of 0.1mol/L
3)
2solution, gets 0.5mlPd (NO
3)
2solution, adds distilled water to 6ml, stirs.
(3) load of active component
By catalyst carrier grinding obtained for step (1), weighing 6g impregnated in the solution in step (2), and room temperature immersion 3h is put in 105 DEG C of dry 3h in baking oven after dipping terminates, afterwards 450 DEG C of calcining 2h.The finished catalyst of gained is used for evaluating catalyst.Wherein palladium accounts for 0.89% of catalyst content.
This catalyst is when air/methane (volume ratio)=99, and the total air speed of gas is 18000h
-1, catalyst amount is that under the condition of 1.5g, catalytic perfomance is as follows:
Embodiment 3:
(1) hydro-thermal method prepares cerium oxide/di-iron trioxide/cobalt oxide (CeO
2/ Fe
2o
3/ Co
2o
3) carrier:
Weigh cerous nitrate, ferric nitrate and cobalt nitrate respectively and be respectively 32g, 3.49g, 1.44g, join in 150ml distilled water, stir, obtain mixing salt solution A, then in solution, 10g urea (wherein urea is excessive) is added, react in closed system, temperature is 60 DEG C ~ 140 DEG C, and the reaction time is 3 ~ 6h.After reaction terminates, question response still naturally cools to room temperature, takes out precipitation, and through washing, 105 DEG C of dry 3h, then 450 DEG C of calcining 2h, obtain Multimetal oxide mixed catalytic agent carrier.Wherein CeO
2, Fe
2o
3and Co
2o
3content be respectively 92%, 5%, 3%.
(2) palladium the equipment of dipping liquid
Preparation molar concentration is the Pd (NO of 0.1mol/L
3)
2solution, gets 1mlPd (NO
3)
2solution, adds distilled water to 6ml, stirs.
(3) load of active component
By catalyst carrier grinding obtained for step (1), weighing 6g impregnated in the solution in step (2), and room temperature immersion 3h is put in 105 DEG C of dry 3h in baking oven after dipping terminates, afterwards 450 DEG C of calcining 2h.The finished catalyst of gained is used for evaluating catalyst.Wherein palladium accounts for 1.37% of catalyst content.
This catalyst is when air/methane (volume ratio)=99, and the total air speed of gas is 18000h
-1, catalyst amount is that under the condition of 1.5g, catalytic perfomance is as follows:
Claims (5)
1. prepare a method for methane catalytic combustion catalyst, it is characterized in that catalyst carrier is iron cerium cobalt complex oxides, wherein cerium content is 90% ~ 96%, and iron content is 3% ~ 7%, and cobalt content is 3% ~ 5%; Active component is palladium, and it accounts for 0.5% ~ 2% of total catalyst percentage composition.Concrete implementation step is as follows:
(1) hydro-thermal method prepares cerium oxide/di-iron trioxide/cobalt oxide (CeO
2/ Fe
2o
3/ Co
2o
3) carrier
Cerous nitrate, ferric nitrate and cobalt nitrate are dissolved in the distilled water of certain volume by a, and stir, and obtain solution A;
B adds precipitating reagent urea or ammonium carbonate in solution A;
C seals, and makes reaction system become closed system;
D is warmed up to assigned temperature T, and arranges the reaction time at the reaction temperatures; General reactions temperature range is 60 DEG C ~ 140 DEG C; The General reactions time is 3 ~ 6h;
After e reaction terminates, question response still drops to room temperature, suction filtration drying obtains catalyst carrier.
(2) palladium the equipment of dipping liquid
Prepare the Pd (NO of certain molar concentration
3)
2solution, gets a certain amount of Pd (NO
3)
2solution, adds distilled water diluting to certain volume, stirs.
(3) load of active component
By catalyst carrier grinding obtained for step (1), weigh the solution of a certain amount of catalyst soakage in step (2), room temperature immersion 2 ~ 3h, be put in baking oven dry after dipping terminates, calcine subsequently.Finally the finished catalyst of gained is used for evaluating catalyst.
2., according to claim 1, it is characterized in that reaction raw materials is the nitrate compound of cerium, iron, cobalt and palladium.
3., according to claim 1, it is characterized in that in catalyst carrier, cerium content is 90% ~ 96%, iron content is 3% ~ 7%, and cobalt content is 3% ~ 5%.
4., according to claim 1, it is characterized in that palladium accounts for 0.5% ~ 2% of total catalyst content.
5., according to claim 1, it is characterized in that dipping is incipient impregnation.
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|---|---|---|---|
| CN201310682164.2A CN104707623A (en) | 2013-12-16 | 2013-12-16 | Method for preparing catalyst for catalytic combustion of methane |
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|---|---|---|---|
| CN201310682164.2A CN104707623A (en) | 2013-12-16 | 2013-12-16 | Method for preparing catalyst for catalytic combustion of methane |
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Family
ID=53407646
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105772027A (en) * | 2016-04-28 | 2016-07-20 | 中国科学院上海高等研究院 | Supported cobaltosic oxide catalyst and preparation method and application thereof |
| CN108906078A (en) * | 2018-07-20 | 2018-11-30 | 上海理工大学 | A kind of efficient Pd/Co3O4The preparation method of monolith catalysts |
| CN111151247A (en) * | 2018-11-08 | 2020-05-15 | 中国科学院大连化学物理研究所 | Supported catalyst and preparation method and application thereof |
| CN115318303A (en) * | 2022-08-25 | 2022-11-11 | 上海净舒汽车技术服务中心 | Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof |
| CN116726948A (en) * | 2023-06-13 | 2023-09-12 | 华东理工大学 | Catalyst for low-temperature catalytic combustion elimination of light alkane and preparation method and application thereof |
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| US6458334B1 (en) * | 2000-03-02 | 2002-10-01 | The Boc Group, Inc. | Catalytic partial oxidation of hydrocarbons |
| CN1631522A (en) * | 2004-11-19 | 2005-06-29 | 清华大学 | Binary composite mesopore oxide material making cerium as base and its preparation |
| CN101767012A (en) * | 2009-12-25 | 2010-07-07 | 昆明理工大学 | Low-temperature combustion catalyst for eliminating diesel engine carbon black |
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2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55155739A (en) * | 1979-05-23 | 1980-12-04 | Toyota Central Res & Dev Lab Inc | Exhaust gas purifying catalyzer |
| US6458334B1 (en) * | 2000-03-02 | 2002-10-01 | The Boc Group, Inc. | Catalytic partial oxidation of hydrocarbons |
| CN1631522A (en) * | 2004-11-19 | 2005-06-29 | 清华大学 | Binary composite mesopore oxide material making cerium as base and its preparation |
| CN101767012A (en) * | 2009-12-25 | 2010-07-07 | 昆明理工大学 | Low-temperature combustion catalyst for eliminating diesel engine carbon black |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105772027A (en) * | 2016-04-28 | 2016-07-20 | 中国科学院上海高等研究院 | Supported cobaltosic oxide catalyst and preparation method and application thereof |
| CN105772027B (en) * | 2016-04-28 | 2018-09-25 | 中国科学院上海高等研究院 | A kind of support type cobaltosic oxide catalyst and its preparation method and application |
| CN108906078A (en) * | 2018-07-20 | 2018-11-30 | 上海理工大学 | A kind of efficient Pd/Co3O4The preparation method of monolith catalysts |
| CN108906078B (en) * | 2018-07-20 | 2021-05-11 | 上海理工大学 | High-efficiency Pd/Co3O4Process for preparing block catalyst |
| CN111151247A (en) * | 2018-11-08 | 2020-05-15 | 中国科学院大连化学物理研究所 | Supported catalyst and preparation method and application thereof |
| CN115318303A (en) * | 2022-08-25 | 2022-11-11 | 上海净舒汽车技术服务中心 | Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof |
| CN115318303B (en) * | 2022-08-25 | 2024-03-01 | 上海净舒汽车技术服务中心 | Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof |
| CN116726948A (en) * | 2023-06-13 | 2023-09-12 | 华东理工大学 | Catalyst for low-temperature catalytic combustion elimination of light alkane and preparation method and application thereof |
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Application publication date: 20150617 |