CN1303739A - Catalyst for reducing nitrogen monoxide with carbon monoxide - Google Patents
Catalyst for reducing nitrogen monoxide with carbon monoxide Download PDFInfo
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- CN1303739A CN1303739A CN 99124914 CN99124914A CN1303739A CN 1303739 A CN1303739 A CN 1303739A CN 99124914 CN99124914 CN 99124914 CN 99124914 A CN99124914 A CN 99124914A CN 1303739 A CN1303739 A CN 1303739A
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Abstract
The invented catalyst consists of active component CoMMgAl and component ptRh/CoMMgAl, in which M=Cu,Cr and Ni, and is prepared by adopting the coprecipitation process. Said catalyst possesses relatively high activity for eliminating NO at low temp., can obtain 100% of NO conversion at 100-700 deg.C, and N2 selectivity can be up to 100% at above 200 deg.C.
Description
The invention relates to a catalyst for a reaction of reducing nitric oxide by carbon monoxide, which can simultaneously eliminate carbon monoxide and nitric oxide in automobile exhaust.
CO and NO are two major pollutants in automobile exhaust, and their harm to human body and its environment is very serious. CO can cause people to have chronic poisoning and can cause people to be poisoned and dead in severe cases; NO is more toxic than carbon monoxide and is a carcinogen, and besides, the harm to the environment is mainly reflected in four environmental problems caused by NO, such as photochemical smog, acid rain, greenhouse effect, ozone layer cavity effect and the like. At present, the environmental pollution caused by automobile exhaust is very serious, and how to thoroughly and effectively eliminate the automobile exhaust becomes one of the very serious andurgent problems faced by countries in the world.
From the present situation, the actual commercialized catalyst is limited to noble metal catalyst (main active components are Pt, Pd, Rh), and Al is commonly used as carrier2O3And the like. These catalysts generally have a high temperature activity, with the disadvantage of a low activity at low temperatures (less than 200 ℃). The R.C.Rijkeboer writes that the exhaust emission of the automobile in the cold start process is very serious, and the temperature of the automobile exhaust emission is very low and large at this timeThe catalyst has a very low NO conversion in the temperature range of about 100 to 150 ℃. In order to improve the low-temperature activity of the catalyst for eliminating NO, a plurality of scholars at home and abroad research the activity, and the current main research results are as follows: reported as TiO by Ravindancatathan Thampi, K et al (J Catal,1990,126:572)2(P25) a supported Ru catalyst that is also limited to fixed source emission exhaust abatement; ZrQ2(Catal Taday,1997,3671) and TiO reported by Yasuaki Qkamoto et al2The Cu catalyst loaded by the (Appl Surface Sci, 1997121/122: 509) has a large gap from practical application; CoCuAl (7: 1) hydrotalcite-like compounds reported by Wangchong et al (catalytic journal 1997,18(6):443), although reported to have very high low temperature activity (lowest temperature for complete conversion of NO)The degree can reach 120 ℃), but high-temperature activity is not reported.
The invention aims to provide a catalyst which has high low-temperature activity of NO conversion and high-temperature activity of NO conversion in a CO + NO reaction, can ensure that NO can be completely converted at 100-700 ℃, and has good repeatability and thermal stability.
The purpose ofthe invention is realized by the following technical scheme.
The catalyst of the invention is a catalyst consisting of an active component A, CoMMgAl and a component B, PtRh/CoMMgAl (wherein the active components are Pt and Rh, and the carrier is CoMMgAl), and can effectively catalyze And (3) carrying out the reaction. M in the catalyst is Cu, Cr and Ni, Co/Al = 1-9, M/Al = 1-2 and Mg/Al = 0-2 (molar ratio); in the component B, active components Pt and Rh respectively account for 0.10-1.0 (mass)% and 0.01-0.20 (mass)% of the whole component B, and the balance is a carrier consisting of CoMMgAl. The mass ratio of the component A to the component B is 20: 1-50: 1.
The catalyst adopted by the invention is CoMMgAl [ active component A]]+ PtRh/CoMMgAl [ components B, Pt and Rh as active components]M is Cu, Cr and Ni, the active component A is prepared by coprecipitation method, the precipitant is K2CO3And KOH; the component B is prepared by an impregnation method, and the carrierIs a precursor of the active component A. The preparation method comprises the following steps: weighing a certain amount of nitrates of Co, M, Mg and Al according to the mole fractions of Co, M, Mg and Al in the catalyst, dissolving the nitrates in a proper amount of distilled water, and adding CO according to the mole fractions of Co, M, Mg and Al3 2-/(Co + M + Mg + Al) = 0.5-1.5 (molar ratio) weighing a certain amount of K2CO3Dissolving the two solutions in a proper amount of distilled water, then simultaneously dropwise adding the two solutions into the stirred distilled water, and after dropwise adding, adjusting the pH value of the mixture to 10.0 by using a KOH solution. Then aging for 10-15 hours under the condition of continuous stirring, then filtering, and washing until the pH of the filtrate is = 7.0. And finally drying at 100-150 ℃ toprepare a catalyst precursor, wherein the catalyst precursor is used for preparing the component A and the component B of the catalyst. Preparation of component A: weighing a certain amount of the precursor according to the dosage, and roasting the precursor in a muffle furnace at 400-500 ℃ for 10-15 hours; preparation of component B: weighing a certain amount of H according to the mass fraction of Pt and Rh in the catalyst in the component B2PtCl6.6H2O andRhCl3.H2dissolving O in 0.01-0.03 mol/L HCl solution, then pouring a certain amount of the prepared precursor, drying at 100-150 ℃, roasting at 400-500 ℃ for 10-15 hours, and then roasting at 5-15% H2/N2And (5) carrying out medium reduction for 3-5 hours. And finally, weighing a certain amount of the component A and the component B according to the mass fraction of the component A and the component B in the catalyst, placing the component A and the component B in a mortar, uniformly grinding, tabletting and crushing into a certain mesh number.
All the catalysts are carried out under the conditions that the ratio of NO to CO is 1-2 and the reaction temperature is 50-700 ℃, and the NO and the CO can be efficiently converted.
A small reaction evaluation device is adopted in the experiment, the reactor is a quartz tube with the inner diameter of 7 mm, the loading of the catalyst is 0.1-1.5 g, and reactants and products are analyzed by an SC-6 gas chromatograph.
The CoMMgAl + PtRh/CoMMgAl catalyst adopted by the invention only contains trace precious metals, can completely convert NO within the temperature range of 100-700 ℃, and N2The selectivity is 100% at 200-700 ℃, and the conversion rate of CO is 100% at more than 150 ℃.
To further illustrate the present invention, the following examples are provided. It is apparent that the embodiments of the present invention are not limited to the following examples.
Example 1:
first 23 g of Co (NO) are weighed3)2.6H2O,3 g Cu (NO)3)2.3H2O and 4 g Al (NO)3)3.9H2O, and dissolving in a beaker filled with 100 ml of distilled water at 80 ℃; further 14 g of K are weighed2CO3Dissolved in another beaker containing 100 ml of distilled water at 80 ℃. Then, the two solutions were simultaneously added dropwise to distilled water while stirring, and after the addition was completed, the pH of the mixture was adjusted to 10.0 with KOH solution. Then aged for 15 hours with continued stirring and filtered and washed until the filtrate had PH = 7.0. Finally dried at 120 ℃ to obtain a precursor of the catalyst, which is used for preparing component A and component B of the catalyst. Preparation of component A: weighing 7 g of precursor, and roasting in a muffle furnace at 450 ℃ for 12 hours; preparation of component B: 0.13 g of H is weighed out separately2PtCl6.6H2O and 0.01 g RhCl3.H2O, simultaneously dissolved in 30 ml of 0.0168 mol/l HCl solution, 10 g of precursor are poured in with constant stirring, the water is evaporated to dryness at 120 ℃ and the mixture is transferred intoMuffle furnace, roasting at 450 deg.C for 12 hr, then at 10% H2/N2And reducing for 4 hours. And finally, weighing 5 g of the component A and 0.17 g of the component B, placing the components in a mortar, uniformly grinding, and then tabletting and crushing the components into 0.4-0.6 micron particles for later use.
0.2 g of catalyst is put into a quartz reactor, and the raw material gas comprises the following components: 1.0% NO + 1.0% CO, He equilibrium, volume space velocity of 5000 hours-1And the reaction temperature is 50-700 ℃, and reactants and products are analyzed by an SC-6 gas chromatograph. The conversion rate of NO at 100-700 ℃ is 100%, and N2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Example 2:
first 22 g Co (NO) are weighed3)2.6H2O,3 g Cu (NO)3)2.3H2O and 4.7 g Al (NO)3)3.9H2O, dissolved simultaneously in a beaker containing 100 ml of distilled water at 80 ℃ and the rest of the preparation of the catalyst is as in example 1.
The activity evaluation method of the catalyst is the same as that of example 1, the conversion rate of NO at 100-700 ℃ is 100%, and N is2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Example 3:
first 21 g of Co (NO) are weighed3)2.6H2O,3.5 g Cu (NO)3)2.3H2O and 5.4 g Al (NO)3)3.9H2O, dissolved simultaneously in a beaker containing 100 ml of distilled water at 80 ℃ and the rest of the preparation of the catalyst is as in example 1.
The activity evaluation method of the catalyst is the same as that of example 1, the conversion rate of NO at 100-700 ℃ is 100%, and N is2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Example 4:
first 21 g of Co (NO) are weighed3)2.6H2O,3 g Cu (NO)3)2.9H2O,3 g Mg (NO)3)26H2O and 4 g Al (NO)33.9H2O, dissolved in water at 80 deg.C and 100 mlThe restof the preparation of the catalyst in a beaker of distilled water was the same as in example 1.
The activity evaluation method of the catalyst is the same as that of example 1, the conversion rate of NO at 100-700 ℃ is 100%, and N is2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Example 5:
18 g of Co (NO) are first weighed3)2.6H2O,3 g Cu (NO)3)2.9H2O, 3.2 g Mg (NO)3)2.6H2O and 5 g Al (NO)3)3.9H2O, dissolved simultaneously in a beaker containing 100 ml of distilled water at 80 ℃ and the rest of the preparation of the catalyst is as in example 1.
The activity evaluation method of the catalyst is the same as that of example 1, the conversion rate of NO at 100-700 ℃ is 100%, and N is2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Example 6:
first, 24 g of Co (NO) is weighed3)2.6H2O, 4 g Cr (NO)3)3.9H2O and 3 g Al (NO)3)3.9H2O, while being dissolved in a beaker containing 100 ml of distilled water at 80 ℃ was subjected to the same procedure as in example 1 to obtain a catalyst precursor. Then 0.13 g of H is weighed2PtCl6.6H2O and 0.01 g RhCl3.H2O, dissolved in 30 ml of 0.0168 mol/l HCl solution, 10 g of the precursor are poured in with constant stirring, the water is evaporated to dryness at 120 ℃, the mixture is transferred into a muffle furnace, calcined at 450 ℃ for 12 hours and then treated with 10% H2/N2And reducing for 4 hours. Finally, 5 g of the component A prepared in example 1 and 0.17 g of the component B prepared above are weighed, placed in a mortar, ground uniformly, and then tableted and crushed into particles of 0.4-0.6 microns for later use.
The activity evaluation method of the catalyst is the same as that of example 1, the conversion rate of NO at 100-700 ℃ is 100%, and N is2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Example 7:
first 21 g of Co (NO) are weighed3)2.6H2O, 4 g Ni (NO)3)2.6H2O and 5 gAl(NO3)3.9H2O, was dissolved in a beaker containing 100 ml of distilled water at 80 ℃ and the remaining catalyst was prepared in the same manner as in example 6.
The activity evaluation method of the catalyst is the same as that of example 1, the conversion rate of NO at 100-700 ℃ is 100%, and N is2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Example 8:
preparation of component A As in example 1, preparation of component B, 0.26 g of H was weighed out separately2PtCl6.6H2O and 0.04 g RhCl3.H2O, simultaneously dissolved in 30 ml of 0.0168 mol/l HCl solution, the rest of the catalyst was prepared as in example 1.
The activity evaluation method of the catalyst is the same as that of example 1, the conversion rate of NO at 100-700 ℃ is 100%, and N is2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Example 9:
component a was prepared as in example 1; preparation of component B, 0.06 g of H are weighed out separately2PtCl6.6H2O and 0.004 g of RhCl3.H2O, simultaneously dissolved in 30 ml of 0.0168 mol/l HCl solution, the rest of the catalyst was prepared as in example 1.
The activity evaluation method of the catalyst is the same as that of example 1, the conversion rate of NO at 100-700 ℃ is 100%, and N is2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Example 10:
component a was prepared as in example 1; preparation of component B, 0.24 g of H are weighed out separately2PtCl6.6H2O and 0.02 g RhCl3.H2O, simultaneously dissolved in 30 ml of 0.0168 mol/l HCl solution, the rest of the catalyst was prepared as in example 1.
The activity evaluation method of the catalyst is the same as that of the catalyst in the example I, the conversion rate of NO at 100-700 ℃ is 100 percent, and N2The selectivity is 100% at 200-700 ℃. CO at more than 150 DEG CThe conversion of (a) was 100%.
Example 11:
the preparation method of the component A and the component B is the same as that of the embodiment 1, 5 g of the component A and 0.25 g of the component B are weighed and placed in a mortar for even grinding, and then the components are tableted and crushed into 0.4-0.6 micron particles for later use.
The activity evaluation method of the catalyst is the same as that of example 1, the conversion rate of NO at 100-700 ℃ is 100%, and N is2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Example 12:
the preparation method of the component A and the component B is the same as that of the embodiment 1, 5 g of the component A and 0.13 g of the component B are weighed and placed in a mortar for even grinding, and then the components are tableted and crushed into 0.4-0.6 micron particles for later use.
The activity evaluation method of the catalyst is the same as that of example 1, the conversion rate of NO at 100-700 ℃ is 100%, and N is2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Example 13:
the preparation method of the component A and the component B is the same as that of the embodiment 4, 5 g of the component A and 0.1 g of the component B are weighed and placed in a mortar for even grinding, and then the components are tableted and crushed into 0.4-0.6 micron particles for later use.
The activity evaluation method of the catalyst is the same as that of example 1, the conversion rate of NO at 100-700 ℃ is 100%, and N is2The selectivity is 100% at 200-700 ℃. The conversion of CO at>150 ℃ was 100%.
Claims (2)
1. A catalyst for reducing nitric oxide by carbon monoxide is characterized by consisting of CoMMgAl of an active component A and PtRh/CoMMgAl of a component B, wherein the active component in the component B is Pt and Rh, and a carrier is CoMMgAl; m is Cu, Cr and Ni, Co/Al = 1-9, M/Al = 1-2 and Mg/Al = 0-2 (molar ratio); the active components Pt and Rh account for 0.10-1.0 (mass)% and 0.01-0.20 (mass)% of the whole component B respectively; the mass ratio of the component A to the component B is 20: 1-50: 1.
2. A process for preparing a catalyst as claimed in claim 1, which comprises: weighing nitrates of Co, M, Mg and Al according to the molar ratio of Co/Al = 1-9, M/Al = 1-2 and Mg/Al = 0-2, dissolving the nitrates in distilled water, and adding CO according to the proportion3 2-Weighing K according to the molar ratio of Co + M + Mg + Al of 0.5-1.52CO3Dissolving the two solutions in distilled water, dropwise adding the two solutions in distilled water, adjusting the pH value of the two solutions to 10.0 by using KOH, aging for 10-15 hours, filtering and washing until the pH value of the filtrate is =7.0, and drying at 100-150 ℃ to obtain a catalyst precursor; part of the catalyst precursor is inRoasting at 400-500 ℃ for 10-15 hours to obtain the CoMMgAl of the catalyst active component A; h is weighed according to the active components Pt and Rh accounting for 0.1-1.0 (mass)% and 0.01-0.20 (mass)% of the whole component B respectively2PtCl6.6H2O and RhCl3.H2Dissolving O in 0.01-0.03 mol/L HCl solution, adding a catalyst precursor, drying at 100-150 ℃, roasting at 400-500 ℃, and then roasting at 5-15% H2/N2Reducing for 3-5 hours to obtain PtRh/CoMMgAl of the component B; the component A and the component B are mixed according to the mass ratio of 20: 1-50: 1 to prepare the catalyst.
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| CN99124914A CN1091650C (en) | 1999-11-30 | 1999-11-30 | Catalyst for reducing nitrogen monoxide with carbon monoxide |
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| CN99124914A CN1091650C (en) | 1999-11-30 | 1999-11-30 | Catalyst for reducing nitrogen monoxide with carbon monoxide |
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| CN1091650C CN1091650C (en) | 2002-10-02 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979138A (en) * | 2010-11-11 | 2011-02-23 | 中国科学院山西煤炭化学研究所 | Cobalt-copper Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN106466609A (en) * | 2015-08-20 | 2017-03-01 | 中国石油化工股份有限公司 | The catalyst of carbon monoxide under low temperature catalysis reduction removing nitrogen oxides |
| CN106824208A (en) * | 2017-03-22 | 2017-06-13 | 中国人民大学 | A kind of catalyst with core-casing structure for denitration demercuration decarburization simultaneously and preparation method thereof |
| CN107570004A (en) * | 2017-06-23 | 2018-01-12 | 清华大学 | A kind of method that NO is discharged in reduction boiler smoke |
| CN112138665A (en) * | 2020-10-21 | 2020-12-29 | 石河子大学 | CO-SCR low-temperature high-efficiency non-noble metal oxide catalyst and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4001484A1 (en) * | 1990-01-19 | 1991-08-01 | Bayer Ag | METHOD FOR PRODUCING POWDER-FORMAL ALUMINUM ALLOYS |
| CA2156464C (en) * | 1994-09-30 | 1999-07-20 | Raghu K. Menon | Reduction of emissions from fcc regenerators |
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1999
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979138A (en) * | 2010-11-11 | 2011-02-23 | 中国科学院山西煤炭化学研究所 | Cobalt-copper Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN101979138B (en) * | 2010-11-11 | 2012-07-25 | 中国科学院山西煤炭化学研究所 | Cobalt-copper Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN106466609A (en) * | 2015-08-20 | 2017-03-01 | 中国石油化工股份有限公司 | The catalyst of carbon monoxide under low temperature catalysis reduction removing nitrogen oxides |
| CN106824208A (en) * | 2017-03-22 | 2017-06-13 | 中国人民大学 | A kind of catalyst with core-casing structure for denitration demercuration decarburization simultaneously and preparation method thereof |
| CN106824208B (en) * | 2017-03-22 | 2019-04-23 | 中国人民大学 | A kind of catalyst with core-casing structure and preparation method thereof for denitration demercuration decarburization simultaneously |
| CN107570004A (en) * | 2017-06-23 | 2018-01-12 | 清华大学 | A kind of method that NO is discharged in reduction boiler smoke |
| CN112138665A (en) * | 2020-10-21 | 2020-12-29 | 石河子大学 | CO-SCR low-temperature high-efficiency non-noble metal oxide catalyst and preparation method thereof |
| CN112138665B (en) * | 2020-10-21 | 2022-10-28 | 石河子大学 | CO-SCR low-temperature high-efficiency non-noble metal oxide catalyst and preparation method thereof |
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