CN103418424A - Preparation method of composite oxide catalyst with CeO2-Cr2O3 loaded on molecular sieve - Google Patents
Preparation method of composite oxide catalyst with CeO2-Cr2O3 loaded on molecular sieve Download PDFInfo
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- CN103418424A CN103418424A CN2013102379889A CN201310237988A CN103418424A CN 103418424 A CN103418424 A CN 103418424A CN 2013102379889 A CN2013102379889 A CN 2013102379889A CN 201310237988 A CN201310237988 A CN 201310237988A CN 103418424 A CN103418424 A CN 103418424A
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Abstract
The invention relates to a preparation method of high-performance chlorinated organic waste gas combustion catalyst, in particular to a preparation method of a composite oxide catalyst with CeO2-Cr2O3 loaded on a molecular sieve. According to the preparation method of the composite oxide catalyst, chromic nitrate, cerous nitrate and an H-shaped molecular sieve are adopted as raw materials, the composite oxide catalyst is prepared according to a precipitation-deposition method, wherein the molar ratio of Ce/Cr is 4:1, the mass ratio of Cr2O3+CeO2/molecular sieve ranges from (4:1) to (1:4). The composite oxide catalyst adopting cheap chromic nitrate and cerous nitrate as well as the industrially produced molecular sieve as the raw materials and adopting the precipitation-deposition method is simple in preparation process, and low in cost, thereby being the high-performance chlorinated organic waste gas combustion catalyst. The composite oxide catalyst has favorable catalytic degradation activity and stability for chlorinated organic compounds such as DCM, DCE, TCE and chlorobenzene.
Description
Technical field
The present invention relates to a kind of preparation method of high performance chloride organic exhaust gas combustion catalyst, particularly relate to molecular sieve carried CeO
2-Cr
2O
3The preparation method of composite oxide catalysts.
Background technology
At present, China's environment is except reality such as sulfur dioxide, discharged nitrous oxides, pellet (PM10, PM2.5) controls and, stubborn problem, also be faced with the severe challenge from volatile organic contaminant (VOCs).Chloride volatile organic matter (CVOCs) is that a class has the compound of very big harm to environment and human health, common are carrene (DCM), chloroform (CF), dichloroethanes (DCE), trichloro-ethylene (TCE), carbon tetrachloride (CT), chlorobenzene (PhCl) etc., they are as a kind of organic solvent commonly used and the semi-finished product in chemical process and be widely used.For the removal of CVOCs, the main method of flame combustion that adopts is carried out post processing at present.With the heat treatment phase ratio, catalytic combustion and advantage economically technical due to it, be process important of VOCs pollutant purification and one of effective means very, same, in the application aspect elimination CVOCs, also more and more receives people's concern.Great majority all concentrate on following four class catalyst about the research report of CVOCs catalyst for catalytic combustion: noble metal, transition metal oxide, rare earth and composite oxides thereof and molecular sieve.Reaction is eliminated in catalysis for chlorinated hydrocarbon, and noble metal catalyst is vulnerable to chlorinated compound and decomposes the Cl produced in course of reaction
2With the HCl poisoning effect; Easily generate the oxychlorination compound in high-temperature region and inactivation; Very high and produce many chloro organic cpds to Deacon reaction and chlorination activity, especially the processing for chlorinated aromatic hydrocarbons tends to produce many chlorine aromatic hydrocarbons and the dioxin compounds that toxicity is larger.In general, the activity of non-noble metal oxide (VB, II B) is lower than noble metal, but anti-hetero atom is as slightly strong as Cl, Br, S poisoning capability; Although in the catalytic oxidation of chlorinated aromatic hydrocarbons, titania oxide supported V oxide catalyst shows high activity and high stability, and the toxicity because of V does not obtain practical application eventually.Complex rare-earth oxidate containing valuable metal, the problem existed as perovskite is that high, the easy inactivation of reaction temperature or metal oxide run off; CeO
2There is good oxygen storage capacity and oxygen mobility with the Ce-Zr composite oxides, in the reaction of catalysis elimination CVOCs, show good oxidation susceptibility, also caused people's extensive concern.The solid acid catalyst of rising in recent years faces active low, can not reach complete oxidation and causes secondary pollution problems, also easily because of the carbon distribution inactivation.Therefore, developing efficient, stable chloride organic exhaust gas combustion catalyst has great importance for the extensive use of catalytic combustion technology.
Summary of the invention
The purpose of this invention is to provide a kind of high performance chloride organic exhaust gas combustion catalyst, specifically refer to molecular sieve carried CeO
2-Cr
2O
3The preparation method of composite oxide catalysts.
The specific solution of the present invention is as follows:
The present invention is a kind of molecular sieve carried CeO
2-Cr
2O
3The preparation method of composite oxide catalysts, take chromic nitrate, cerous nitrate and H type molecular sieve is raw material, adopts precipitation-sedimentation to prepare molecular sieve carried CeO
2-Cr
2O
3Composite oxide catalysts, in catalyst, the mol ratio of Ce/Cr is 4:1, Cr
2O
3+ CeO
2The mass ratio of/molecular sieve is 4:1 ~ 1:4; Concrete preparation process is: by described Cr
2O
3+ CeO
2The mass ratio of/molecular sieve, at the cerous nitrate [Ce (NO that sets concentration
3)
36H
2O] and chromic nitrate [Cr (NO
3)
39H
2O] add the molecular sieve powder of set amount in mixed solution, drip (the NH that sets concentration after stirring under high degree of agitation
4)
2CO
3Precipitating reagent, drop to pH and reach 9.2 ~ 9.4 rear room temperatures placement ageing 12 hours, and then filtration, deionized water are washed repeatedly to filtrate neutrality, and under 110 ℃, drying is 2 hours, and 500 ℃ of lower roastings are processed in 2 hours, make molecular sieve carried CeO
2-Cr
2O
3Composite oxide catalysts.
As further improvement, H type molecular sieve of the present invention is the H-ZSM-5 molecular sieve, SiO
2/ Al
2O
3Than being 22 ~ 100.
As further improvement, Cr of the present invention
2O
3And CeO
2Optimum content be respectively 2.0% ~ 8.0% and 18.0 % ~ 72.0 %.
As further improvement, cerous nitrate of the present invention [Ce (NO
3)
36H
2O] and chromic nitrate [Cr (NO
3)
39H
2O] concentration C of mixed solution
Ce+CrBe 0.25 mol/L.
As further improvement, described (NH of the present invention
4)
2CO
3The concentration of precipitating reagent is 0.5 mol/L.
A kind of molecular sieve carried CeO provided by the present invention
2-Cr
2O
3The preparation method of composite oxide catalysts, have a beneficial effect as follows: the molecular sieve that adopts cheap cerous nitrate, chromic nitrate and suitability for industrialized production is raw material, adopts precipitation-sedimentation to make molecular sieve carried CeO
2-Cr
2O
3Composite oxide catalysts, preparation technology is simple, and the catalyst cost is low, is a kind of high performance chloride organic exhaust gas combustion catalyst.This catalyst has good catalytic degradation activity and stability, CO to chlorine-containing organic compounds such as carrene (DCM), dichloroethanes (DCE), trichloro-ethylene (TCE) and chlorobenzenes
2Selective high and produce without accessory substances such as polychlorocarbons with HCl, the extensive use of catalytic combustion technology is had great importance.
The specific embodiment:
Below by specific embodiment, technical scheme of the present invention is described further: embodiment 1
3.6g chromic nitrate and 15.6g cerous nitrate are dissolved in 280ml water, add 27.5g molecular sieve (H-ZSM-5, SiO after stirring
2/ Al
2O
3Than being 25) powder.Drip (NH under high degree of agitation
4)
2CO
3Precipitating reagent, drop to pH and reach 9.2 ~ 9.4 rear room temperatures placement ageing 12 hours, and then filtration, deionized water are washed repeatedly to filtrate neutrality, and under 110 ℃, drying is 2 hours, and 500 ℃ of lower roastings are processed in 2 hours, make molecular sieve carried CeO
2-Cr
2O
3Composite oxide catalysts.Cr in this catalyst
2O
3And CeO
2Content be respectively 2.0% and 18.0%.
Embodiment 2
The identical operation with embodiment 1, difference is: change the consumption of molecular sieve into 6.9g, Cr in this catalyst
2O
3And CeO
2Content be respectively 5.0% and 45.0%.
Embodiment 3
The identical operation with embodiment 1, difference is: change the consumption of molecular sieve into 1.7g, Cr in this catalyst
2O
3And CeO
2Content be respectively 8.0% and 72.0%.
Embodiment 4
The identical operation with embodiment 1, difference is: change the consumption of chromic nitrate into 6.0g, the consumption of cerous nitrate changes 26.0g into, is dissolved in 300ml water, does not add molecular sieve.Cr in this catalyst
2O
3And CeO
2Content be respectively 10.0% and 90.0%.
In 1 ~ 4 example, catalyst is as shown in the table to the catalytic degradation activity of chlorinated organics:
Annotate: 0.3ml, particle diameter are 40-60 purpose catalyst, and air speed is 15000h
-1.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (5)
1. a molecular sieve carried CeO
2-Cr
2O
3The preparation method of composite oxide catalysts, is characterized in that, take chromic nitrate, cerous nitrate and H type molecular sieve is raw material, adopts precipitation-sedimentation to prepare molecular sieve carried CeO
2-Cr
2O
3Composite oxide catalysts, in catalyst, the mol ratio of Ce/Cr is 4:1, Cr
2O
3+ CeO
2The mass ratio of/molecular sieve is 4:1 ~ 1:4; Concrete preparation process is: by described Cr
2O
3+ CeO
2The mass ratio of/molecular sieve, at the cerous nitrate [Ce (NO that sets concentration
3)
36H
2O] and chromic nitrate [Cr (NO
3)
39H
2O] add the molecular sieve powder of set amount in mixed solution, drip (the NH that sets concentration after stirring under high degree of agitation
4)
2CO
3Precipitating reagent, drop to pH and reach 9.2 ~ 9.4 rear room temperatures placement ageing 12 hours, and then filtration, deionized water are washed repeatedly to filtrate neutrality, and under 110 ℃, drying is 2 hours, and 500 ℃ of lower roastings are processed in 2 hours, make molecular sieve carried CeO
2-Cr
2O
3Composite oxide catalysts.
2. molecular sieve carried CeO according to claim 1
2-Cr
2O
3The preparation method of composite oxide catalysts is characterized in that: described H type molecular sieve is the H-ZSM-5 molecular sieve, SiO
2/ Al
2O
3Than being 22 ~ 100.
3. molecular sieve carried CeO according to claim 1
2-Cr
2O
3The preparation method of composite oxide catalysts is characterized in that: described Cr
2O
3And CeO
2Optimum content be respectively 2.0% ~ 8.0% and 18.0 % ~ 72.0 %.
4. molecular sieve carried CeO according to claim 1
2-Cr
2O
3The preparation method of composite oxide catalysts is characterized in that: described cerous nitrate [Ce (NO
3)
36H
2O] and chromic nitrate [Cr (NO
3)
39H
2O] concentration C of mixed solution
Ce+CrBe 0.25 mol/L.
5. molecular sieve carried CeO according to claim 1
2-Cr
2O
3The preparation method of composite oxide catalysts is characterized in that: described (NH
4)
2CO
3The concentration of precipitating reagent is 0.5 mol/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251476A (en) * | 2015-10-10 | 2016-01-20 | 浙江大学 | Preparation method of CeO2-Cr2O3-Nb2O5 compound oxide catalyst |
| CN109126290A (en) * | 2018-09-20 | 2019-01-04 | 俞小峰 | A kind of high-strength anti-flaming air filting material and preparation method thereof |
| CN115845912A (en) * | 2022-11-01 | 2023-03-28 | 四川省生态环境科学研究院 | Composite transition metal molecular sieve catalyst, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050081998A1 (en) * | 1997-02-24 | 2005-04-21 | Hampden-Smith Mark J. | Chemical-mechanical planarization slurries and powders and methods for using same |
| CN102133541A (en) * | 2011-01-10 | 2011-07-27 | 浙江大学 | Preparation method of Cr-Ce composite molecular sieve based catalyst |
-
2013
- 2013-06-13 CN CN201310237988.9A patent/CN103418424B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050081998A1 (en) * | 1997-02-24 | 2005-04-21 | Hampden-Smith Mark J. | Chemical-mechanical planarization slurries and powders and methods for using same |
| CN102133541A (en) * | 2011-01-10 | 2011-07-27 | 浙江大学 | Preparation method of Cr-Ce composite molecular sieve based catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 孟中华 等: "铈铬比例对CeO2-CrOX复合氧化物催化剂上1,2-二氯乙烷催化氧化性能的影响", 《物理化学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251476A (en) * | 2015-10-10 | 2016-01-20 | 浙江大学 | Preparation method of CeO2-Cr2O3-Nb2O5 compound oxide catalyst |
| CN105251476B (en) * | 2015-10-10 | 2018-01-05 | 浙江大学 | A kind of CeO2‑Cr2O3‑Nb2O5The preparation method of composite oxide catalysts |
| CN109126290A (en) * | 2018-09-20 | 2019-01-04 | 俞小峰 | A kind of high-strength anti-flaming air filting material and preparation method thereof |
| CN115845912A (en) * | 2022-11-01 | 2023-03-28 | 四川省生态环境科学研究院 | Composite transition metal molecular sieve catalyst, and preparation method and application thereof |
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|---|---|
| CN103418424B (en) | 2015-09-16 |
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