CN101053832A - Magnenese-cerium composite oxide supported catalyst for purifying formaldehyde in the indoor air - Google Patents
Magnenese-cerium composite oxide supported catalyst for purifying formaldehyde in the indoor air Download PDFInfo
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- CN101053832A CN101053832A CN 200610011663 CN200610011663A CN101053832A CN 101053832 A CN101053832 A CN 101053832A CN 200610011663 CN200610011663 CN 200610011663 CN 200610011663 A CN200610011663 A CN 200610011663A CN 101053832 A CN101053832 A CN 101053832A
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- manganese
- catalyst
- composite oxide
- cerium
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Abstract
Disclosed is a load type manganese-cerium oxide catalyst, which active ingredients comprise silver, gold or platinum. The Mn/Ce mol ratio of the manganese-cerium composite oxide is 1.0 and active ingredient loading is 0.1-5% of the weight of the manganese-cerium oxide. The preparing method has main steps of: d) suspending the manganese-cerium composite oxide powder into water solution, adding a soluble solution of the silver, gold or platinum after agitating to form a manganese-cerium composite oxide powder suspension with the silver, gold or platinum; e) in supernatant liquid of the step d, adding KOH or K2CO3 solution, respectively, to make PH value to be 9-10, then precipitating and filtering; f) drying precipitate obtained from the step e at 80-120 DEG C, and calcining the same for 2-10 hours at 300-500 DEG C. to get the aim product. The catalyst of the invention has higher activity and stability for a complete oxidation reaction of formaldehyde existing in indoor air so as to oxidate the formaldehyde into carbon dioxide and water at room temperature.
Description
Technical field
The present invention relates to a kind of silver, gold, platinum catalyst of manganese-cerium composite oxide load.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to above-mentioned Application of Catalyst.
Background technology
Indoor and the closed system formaldehyde pollution problem that finishing, decoration cause has caused that various circles of society greatly pay close attention to.Formaldehyde is the higher material of toxicity, studies show that short term contact formaldehyde can stimulate eyes, nasal cavity and respiratory tract and causes allergic reaction, and long-term contact can increase the possibility of suffering from cancer.Formaldehyde is defined as carcinogenic and teratogenesis shape material by the World Health Organization.For this reason, " IAQ standard " the regulation formaldehyde in indoor air sanitary standard (maximum permissible concentration) of China's promulgation is 0.08mg/m
3, at room temperature be about 0.06ppm.Yet according to investigations, Chinese most city half family air content of formaldehyde exceeds standard, and adds that the modern has time of 80% to spend indoor approximately.Therefore, people have carried out various explorations to the improvement technology of formaldehyde in indoor air.
Improvement method to formaldehyde in indoor air mostly is absorption method greatly at present.Yet physical absorption still is that chemisorbed all can not obtain satisfied effect, because when absorption and desorption reached balance, adsorbent will lose efficacy maybe to be needed to regenerate.The formaldehyde that catalytic oxidation is removed in the room air is a kind of long-acting method, and characteristics are that it can utilize airborne oxygen that formaldehyde is completely oxidized to carbon dioxide and water, and catalyst can use for a long time.
U.S. Pat 5,585,083 has invented the method that a kind of catalytic oxidation is removed formaldehyde, is oxidant with airborne oxygen, and the platinum of 12wt.% is loaded on the tin oxide as catalyst, and the oxidation removal of PARA FORMALDEHYDE PRILLS(91,95) has good effect.The advantage of this catalyst is not need to add additional energy source in the reaction, promptly just can reach effect preferably in the time of-5-25 ℃, and shortcoming is: the content of platinum is too high, so catalyst costs an arm and a leg.Chinese patent CN 1698932A when the content of gold is 3wt.%, also can obtain effect preferably with the rare earth oxide or the rare-earth composite oxide catalyst of load gold under 80-100 ℃ of temperature.But shortcoming is to provide extra energy to catalyst, promptly could realize at a certain temperature formaldehyde complete oxidation and remove.
Summary of the invention
The object of the present invention is to provide a kind of silver, gold or platinum catalyst that is used for the manganese-cerium composite oxide load of formaldehyde in indoor air purification.
Another object of the present invention is to provide a kind of above-mentioned Preparation of catalysts method.
For achieving the above object, catalyst provided by the invention is silver, gold, the platinum catalyst in the manganese-cerium composite oxide load, in its manganese-cerium composite oxide, the mol ratio of Mn/Ce is 1.0, and silver, gold, platinum are 0.1-5wt% with respect to the loading of manganese cerium solid solution.
The method of the above-mentioned catalyst of preparation provided by the invention adopts wet impregnation technology and precipitation-deposition method, and its key step is:
A) with manganese, cerium oxide powder suspension in the aqueous solution, stir the solution that adds silver soluble, gold, platinum salt down, make the manganese cerium oxide powder suspension of silver, gold, platinum;
B) in the suspension of step a, add KOH or K respectively
2CO
3Solution makes it the pH value and equals 9-10, filters, precipitates;
C) sediment that step b is obtained is through 80-120 ℃ of drying, 300-500 ℃ roasting 2-10 hour, target product.
Preparation method's of the present invention advantage is: the strong interaction by silver, gold, platinum and manganese cerium oxide solid solution obtains a kind of highly active catalyst.
Catalyst provided by the invention can be removed airborne noxious pollutant-formaldehyde effectively, promptly at room temperature just oxidation of formaldehyde can be become carbon dioxide and water, does not need to add extra energy.The temperature 15-25 of catalyst layer ℃, the concentration 30-580ppm of formaldehyde, oxygen are 18vol.%, and gas space velocity is 30,000mL/ (g
-catH), CO
2Selectivity is 100%.Catalyst activity height provided by the invention, stability are good.
Description of drawings
Fig. 1 is the Pt/MnO of the present invention's preparation
x-CeO
2, Pt/MnO
x-CeO
2/ SiO
2And Pt/MnO
x-CeO
2The stability test of-Cl catalyst;
Test condition: 30ppm formaldehyde, 18%O
2/ He, air speed 21,000ml/g.h, room temperature.
The specific embodiment
Embodiment 1: the preparation of the manganese-cerium composite oxide that the present invention relates to
In the round-bottomed flask of 500mL, add the 100mL deionized water, with KMnO
4(0.63g4.0mmol) with (NH
4)
2Ce (NO
3)
6(5.48g 10.0mmol) adds wherein and stirring makes it dissolving; Get 50mL and contain Mn (NO
3)
26H
2(2.10g, aqueous solution 6.0mol) adds in the above-mentioned solution under condition of stirring O, and then adds 2mol/L KOH or K
2CO
3Solution makes the pH=10.5 of solution, and what obtain is deposited in 50-80 ℃ and stirs down ageing 6 hours; With the sedimentation and filtration of gained, spend deionised water three times, in 110 ℃ of dryings 12 hours; 500 ℃ of roastings 6 hours in Muffle furnace more promptly obtain the Mn/Ce mol ratio and are 1.0 catalyst.
Catalyst A g/MnO
x-CeO
2Preparation of catalysts:
Manganese-cerium composite oxide preparation: in the round-bottomed flask of 500mL, add the 100mL deionized water, with KMnO
4(0.63g 4.0mmol) and (NH
4)
2Ce (NO
3)
6(5.48g 10.0mmol) adds wherein and stirring makes it dissolving; Get 50mL and contain Mn (NO
3)
26H
2(2.10g, aqueous solution 6.0mol) adds in the above-mentioned solution under condition of stirring O, and then adds 2mol/L KOH or K
2CO
3Solution makes the pH=10.5 of solution, and what obtain is deposited in 50-80 ℃ and stirs down ageing 6 hours; With the sedimentation and filtration of gained, spend deionised water three times, in 110 ℃ of dryings 12 hours; 500 ℃ of roastings 6 hours in Muffle furnace more promptly obtain the Mn/Ce mol ratio and are 1.0 catalyst;
In the aqueous solution, stir adding AgNO down at the above-mentioned manganese cerium oxide powder suspension that makes
3Solution; Add pH that 0.25MKOH solution makes above-mentioned suspension then 9, ageing 2h filters, washing is after 120 ℃ of dry 7h, and 500 ℃ of roastings 2 hours obtain Ag/MnO like this
x-CeO
2Catalyst.
The performance test of catalyst is carried out on the fixed bed reactors of continuous-flow, and before the performance test of catalyst, catalyst is through preliminary treatment.Catalyst consumption is 0.2g, and particle diameter is 0.25-0.5mm.The generation of gaseous formaldehyde is as follows: (96%, the Acros) gas generator of packing into places gas generator one 20 ℃ constant temperature water bath device with the solid-state paraformaldehyde of 2.0g; Sweep the surface of paraformaldehyde with the He air-blowing of 10mL/min and take gaseous formaldehyde out of, gaseous formaldehyde of taking out of then and 20vol.%O
2/ He mixes and forms unstripped gas.Unstripped gas through catalyst layer consists of: formaldehyde 30ppm, and oxygen 18vol.%, balance gas are He; Gas space velocity (GHSV) is 30,000mL/ (g
-catH).Reactor outlet gas HP6890 type gas chromatograph on-line analysis.Chromatogram configuration TCD and fid detector, nickel converter of assembling before fid detector, its effect is in hydrogen atmosphere carbon dioxide to be converted into methane quantitatively, the minimum dfetectable quantity of carbon dioxide is 0.1ppm.At room temperature (15-25 ℃) tested, and the results are shown in Table 1.
Catalyst A u/MnO
x-CeO
2Preparation of catalysts: the manganese-cerium composite oxide powder suspension that makes among the embodiment 1 in the aqueous solution, is stirred the solution that adds gold chloride down; Add 0.25K then
2CO
3Solution makes the pH of above-mentioned suspension 11, and ageing 6h filters, washing is after 100 ℃ of dry 5h, and 400 ℃ of roastings 5 hours obtain Au/MnO like this
x-CeO
2Catalyst.
The performance test of catalyst is with embodiment 1.The results are shown in Table 1.
Embodiment 3
Catalyst Pt/MnO
x-CeO
2Preparation of catalysts: the manganese-cerium composite oxide powder suspension that makes among the embodiment 1 in the aqueous solution, is stirred the solution that adds the non-chlorine platinum salt of solubility down, be evaporated to driedly then, through 80 ℃ of dry 14h, 300 ℃ of roastings 10 hours obtain Pt/MnO
x-CeO
2Catalyst.
The performance test embodiment 1 of catalyst.The conversion ratio of formaldehyde and CO
2Selectivity all be 100%.The results are shown in Table 1 and Fig. 1.
Preparation of catalysts method and step are with the Pt/MnO among the embodiment 3
x-CeO
2Catalyst.The performance test of catalyst is with embodiment 1, and the temperature of regulating the constant temperature water bath device makes between the concentration 30-580ppm of the formaldehyde that obtains and changes, and other step is with embodiment 1.The results are shown in Table 2.
Removing the platinum source is H
2PtCl
6Outward, other data of Preparation of catalysts are with the Pt/MnO among the embodiment 3
x-CeO
2Catalyst, the catalyst that obtains like this is designated as Pt/MnO
x-CeO
2-Cl.The performance test of catalyst the results are shown in Figure 1 with embodiment 1.
MnO
x-CeO
2Preparation is with the MnO among the embodiment 1
x-CeO
2, difference is the silica gel of adding 30% before roasting, is extruded into the clavate MnO that the cross section is 1.5mm then
x-CeO
2/ SiO
2Platinum loads on above-mentioned clavate MnO
x-CeO
2/ SiO
2The preparation method of supported catalyst is with the Pt/MnO among the embodiment 1
x-CeO
2Catalyst, the catalyst that obtains is designated as Pt/MnO
x-CeO
2/ SiO
2In the performance test of catalyst with embodiment 1.The results are shown in Figure 1.
Table 1 Ag, Au, Pt/MnO
x-CeO
2Catalytic activity at ambient temperature
| Sample | Ag/MnO x-CeO 2 | Au/MnO x-CeO 2 | Pt/MnO x-CeO 2 |
| The room temperature conversion ratio of formaldehyde | 28.3 | 32.5 | 100 |
Table 2 concentration of formaldehyde is to Pt/MnO
x-CeO
2The influence of catalyst room temperature activity
| Sample | 30ppm | 100ppm | 200ppm | 580ppm |
| Pt/MnO
x- | 100 | 100 | 98.0 | 75.4 |
Claims (6)
1, a kind of support type manganese cerium oxide catalyst, its active component are silver, gold or platinum; The mol ratio of Mn/Ce is 1.0 in the manganese-cerium composite oxide, and the loading of active component is the 0.1-5% of manganese cerium oxide weight.
2, support type manganese cerium oxide catalyst as claimed in claim 1, the wherein SiO that has gross weight 30% in the manganese cerium oxide
2
3, prepare the method for catalyst according to claim 1, adopt precipitation-deposition method, its key step is:
A) with KMnO
4(NH
4)
2Ce (NO
3)
6Stirring and dissolving is made the aqueous solution;
B) with Mn (NO
3)
26H
2On the aqueous solution of O in the aqueous solution of step a, and then add KOH or K
2CO
3Solution makes the pH=9-11 of solution, and what obtain is deposited in 50-80 ℃ and stirs down ageing 2-6 hour, filters;
C) sediment of step b is in 80-120 ℃ of dry 8-12 hour, in 300-500 ℃ of roasting 2-10 hour, promptly obtains the Mn/Ce mol ratio and be 1.0 manganese-cerium composite oxide catalyst powder;
D) with the manganese-cerium composite oxide powder suspension in the aqueous solution, stir the solution that adds silver soluble, gold or platinum down, make the manganese cerium oxide powder suspension of silver, gold or platinum;
E) in the supernatant liquid of steps d, add KOH or K respectively
2CO
3Solution makes the pH value equal 9-10, precipitation, filtration;
F) sediment that step e is obtained is through 80-120 ℃ of drying, 300-500 ℃ roasting 2-10 hour, target product.
4, method as claimed in claim 3, wherein the sediment of step b adds silica gel, carries out step c again, must contain the manganese-cerium composite oxide solids of gross weight 30% silicon, adopts infusion process that silver, gold or platinum are loaded on the solids.
5, method as claimed in claim 3 wherein precipitates after ageing of solution 2-6 hour of step e preparation and filters.
6, claim 1 or the 2 described catalyst complete oxidation of formaldehyde that is used for purifying the air of a room.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100116639A CN100450610C (en) | 2006-04-13 | 2006-04-13 | Magnenese-cerium composite oxide supported catalyst for purifying formaldehyde in the indoor air |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100116639A CN100450610C (en) | 2006-04-13 | 2006-04-13 | Magnenese-cerium composite oxide supported catalyst for purifying formaldehyde in the indoor air |
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| CN100450610C CN100450610C (en) | 2009-01-14 |
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| CN102139234A (en) * | 2011-01-06 | 2011-08-03 | 梁耀彰 | Loaded reduced precious metal catalyst as well as preparation method and application thereof |
| CN102228790A (en) * | 2011-04-16 | 2011-11-02 | 大连理工大学 | Indoor air pollutant formaldehyde ''storage-oxidation'' cycle purification method |
| CN101497042B (en) * | 2009-03-11 | 2012-10-03 | 华东理工大学 | Catalyst for eliminating formaldehyde in air by low-temperature catalytic oxidation |
| CN103894194A (en) * | 2014-03-28 | 2014-07-02 | 武汉理工大学 | Loading type catalyst for removing formaldehyde under room temperature |
| CN104084191A (en) * | 2014-07-21 | 2014-10-08 | 贝谷科技股份有限公司 | Manganese-cerium solid solution monolithic catalyst for removing formaldehyde at room temperature and preparation method thereof |
| CN108940264A (en) * | 2018-06-30 | 2018-12-07 | 华南理工大学 | A kind of Mn/Ce base catalyst and preparation method thereof with room temperature decomposing formaldehyde performance |
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| CN110038566A (en) * | 2019-04-29 | 2019-07-23 | 南京融众环境工程研究院有限公司 | A kind of loaded nano Ag/MnCeOx/ Attapulgite Catalyst and preparation method thereof |
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| CN110496641A (en) * | 2018-05-18 | 2019-11-26 | 中国科学院大连化学物理研究所 | A kind of formaldehyde completely oxidizing catalyst and application at room temperature |
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| US5585083A (en) * | 1995-03-30 | 1996-12-17 | The United States As Represented By The Administrator Of The National Aeronautics And Space Administration | Catalytic process for formaldehyde oxidation |
| CN1321722C (en) * | 2005-04-21 | 2007-06-20 | 内蒙古大学 | Supported nano gold catalyst for clearing formaldehyde from indoor air and method for preparing the same |
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| CN102139234A (en) * | 2011-01-06 | 2011-08-03 | 梁耀彰 | Loaded reduced precious metal catalyst as well as preparation method and application thereof |
| CN102228790A (en) * | 2011-04-16 | 2011-11-02 | 大连理工大学 | Indoor air pollutant formaldehyde ''storage-oxidation'' cycle purification method |
| CN103894194A (en) * | 2014-03-28 | 2014-07-02 | 武汉理工大学 | Loading type catalyst for removing formaldehyde under room temperature |
| CN104084191A (en) * | 2014-07-21 | 2014-10-08 | 贝谷科技股份有限公司 | Manganese-cerium solid solution monolithic catalyst for removing formaldehyde at room temperature and preparation method thereof |
| CN110496528A (en) * | 2018-05-16 | 2019-11-26 | 天津工业大学 | A kind of method of normal temperature oxidation formaldehyde |
| CN110496641A (en) * | 2018-05-18 | 2019-11-26 | 中国科学院大连化学物理研究所 | A kind of formaldehyde completely oxidizing catalyst and application at room temperature |
| CN108940264A (en) * | 2018-06-30 | 2018-12-07 | 华南理工大学 | A kind of Mn/Ce base catalyst and preparation method thereof with room temperature decomposing formaldehyde performance |
| CN109337564A (en) * | 2018-09-12 | 2019-02-15 | 安徽康瑞高科新材料技术工程有限公司 | A kind of polyurethane water-proof paint and preparation method thereof |
| CN109486330A (en) * | 2018-09-12 | 2019-03-19 | 安徽康瑞高科新材料技术工程有限公司 | A kind of anti-methanal paint and preparation method thereof |
| CN110038566A (en) * | 2019-04-29 | 2019-07-23 | 南京融众环境工程研究院有限公司 | A kind of loaded nano Ag/MnCeOx/ Attapulgite Catalyst and preparation method thereof |
| WO2020220193A1 (en) * | 2019-04-29 | 2020-11-05 | 南京融众环境工程研究院有限公司 | Supported nano ag/mnceo x/attapulgite catalyst and preparation method therefor |
| CN110180533A (en) * | 2019-05-09 | 2019-08-30 | 华中科技大学 | One kind containing KxMn8O16Process for synthetic catalyst and application |
| CN110180533B (en) * | 2019-05-09 | 2020-09-11 | 华中科技大学 | KxMn-containing alloy8O16Catalyst synthesis method and application |
| CN114573450A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for preparing acetic acid by catalyzing levulinic acid with MnCeOx |
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