CN1199652A - RE oxide/zinc oxide catalyst for selective oxidation of ethane with carbon dioxide to produce ethylene - Google Patents
RE oxide/zinc oxide catalyst for selective oxidation of ethane with carbon dioxide to produce ethylene Download PDFInfo
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- CN1199652A CN1199652A CN 97111019 CN97111019A CN1199652A CN 1199652 A CN1199652 A CN 1199652A CN 97111019 CN97111019 CN 97111019 CN 97111019 A CN97111019 A CN 97111019A CN 1199652 A CN1199652 A CN 1199652A
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- Prior art keywords
- catalyst
- oxide
- ethane
- rare earth
- zno
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Abstract
The catalyst has ZnO as carrier and RE oxide as active component; the ZnO is superfine nanometer particles with average size of 5-80 nm; and the RE oxide used is one or several oxides of La, Ce, Sm and Pr and has content of 10-80 wt%. By using the catalyst, ethane can be transformed into ethylene through reaction with CO2 at high selectivity; the transform rate of ethane and the selectivity of ethylene may reach 60% and 90% separately; and the reaction can eliminate CO2 resulting in green-house effect.
Description
The invention provides a kind of CO of being used for
2Rare earth oxide/ZnO catalyst that selective oxidation ethane is ethylene reaction produced and preparation method thereof.
Produce ethene with carbon dioxide as a kind of selective oxidation agent catalyzed conversion ethane, can provide important raw material of industry ethene on the one hand, can eliminate the carbon dioxide that causes greenhouse effects again simultaneously.This is a catalytic reaction that prospects for commercial application is arranged.People such as Krylov (1.New Developmentsin Selective Oxidation II, (1994) 159; 2.Industrial ﹠amp; EngineeringChemistry Research 34 (1995) 474; 3.Catalysis Today, 24 (1995) 371) find on the transition metal oxide that supports, as contain on the oxide of manganese and chromium and can realize ethane and CO
2The selectivity catalyzed conversion, but ethane is not high enough to the directed selectivity that transforms of ethene.
The purpose of this invention is to provide a kind of CO of being used for
2The highly selective ethyl oxide is produced the Catalysts and its preparation method of ethene, utilizes this catalyst, ethane and CO
2But react the ethene that is converted into of high selectivity, ethane conversion can reach 60%, and selectivity of ethylene can reach 90%.
The CO that is used for of the present invention
2The highly selective ethyl oxide is produced the catalyst of ethene, with ZnO is that the supported carrier rare earth oxide is as active component, it is characterized in that carrier ZnO is the superfine nano particle, particle mean size is 5～80nm, used rare earth oxide is one or more mixed oxides of La, Ce, Sm or Pr rare earth element, wherein to contain La
2O
3Catalyst activity and selectivity the highest, the weight content of rare earth oxide is 10～80% of a catalyst.
Preparation of catalysts of the present invention can be used infusion process, and with nanoscale ZnO dipping rare earth nitrate aqueous solution, and technology is carried out drying and calcination process can make catalyst routinely.Above-mentioned roasting can be carried out 5～8 hours under 800～900 ℃ of air atmospheres, to obtain higher activity and stable.
On the rare earth oxide catalyst that nano level superfine ZnO of the present invention supports, with CO
2For the ethane oxidation conversion of oxidant is produced in the ethylene reaction, but the ethane highly selective is converted into ethene.Below by embodiment technology of the present invention is given to illustrate further.
Embodiment 1
With the ZnO dipping lanthanum nitrate aqueous solution method preparation of 10～50nm, and in 850 ℃ of air, handled 5～8 hours, make the catalyst of different lanthanum content.Ethane and CO
2Catalytic conversion reaction (carry out in the internal diameter 6～8mm), catalyst was swept 0.5～1.0 hour with the He air-blowing at 850 ℃, reduced to 800 ℃ then, logical reaction gas (C at the continuous feed fixed-bed quartz reactor
2H
6/ CO
2=1/2 mol ratio) begins reaction.Product is through online gas chromatographic analysis.Different L a
2O
3Reaction result is listed in table 1 on the catalyst of content.
Table 1. Different L a
2O
3The La of content
2O
3The last C of/ZnO
2H
6-CO
2Reaction result
Catalyst conversion ratio (%) ethylene selectivity yield of ethene (La
2O
3Contain weight %) C
2H
6CO
2(%) (%)
20％ 53.6 25.1 87.3 46.8
25％ 60.0 27.0 90.4 54.2
30％ 62.0 30.1 90.7 56.2
50％
* 62.5 31.0 91.0 56.9
GHSV=1200ml/gh, 800 ℃, atmospheric pressure, 2 hours reaction results
* be 780 ℃ of reaction results
Embodiment 2
Utilize embodiment 1 described method to prepare different rare earth oxides or mixed rare-earth oxide/ZnO catalyst, and be used for C
2H
6+ CO
2Reaction, it the results are shown in table 2.
C on the different rare earth oxides that table 2.ZnO supports
2H
6+ CO
2Reaction result is catalyst conversion ratio (%) ethylene selectivity (%) yield of ethene (%) relatively
C
2H
6CO220%Sm
2O
3/ ZnO 52.3 26.1 86.3 42.030La
2O
3/ ZnO 62.0 30.1 90.7 56.25%Pr
2O
3-20%La
2O
3/ ZnO 54.0 28.0 83.7 45.25%CeO
2-20%La
2O
3/ ZnO 51.4 25.2 90.0 46.2GHSV=1200ml/gh, 800 ℃, atmospheric pressure, 2 hours reaction result comparative examples 1
C on some catalyst that the present invention is used and document 1,2,3 catalyst system therefors
2H
6+ CO
2Reaction result relatively is shown in table 3.
Table 3
Catalyst ethylene selectivity (%)
30％La
2O
3AnO
(a) 90.7
5％Pr
2O
3-20％La
2O
3/ZnO
(a) 83.7
5％CeO
2-20％La
2O
3/AnO
(a) 90.0
17％MnO/SiO
2 (b) 61.0
1.5％K-5.5％Cr-17％MnO/SiO
2 (b) 76.8
(a), be the used catalyst of the present invention, (b) be document 1,2,3 catalyst system therefors.
This shows that ZnO of the present invention supports rare earth oxide catalyst, CO
2The ethane highly selective can be converted into ethene.While CO
2Be one of pernicious gas that causes the atmosphere greenhouse effects, utilize it to come the selective oxidation lower carbon number hydrocarbons significant.
Claims (3)
1. selective oxidation of ethane with carbon dioxide to produce ethylene RE oxide/zinc oxide catalyst, it is characterized in that carrier ZnO is the superfine nano particle, particle mean size is 5～80nm, used rare earth oxide is one or more mixed oxides of La, Ce, Sm or Pr rare earth element, and the weight content of rare earth oxide is 10～80% of a catalyst.
2. by the described catalyst of claim 1, it is characterized in that the active component rare earth oxide is La
2O
3
3. described Preparation of catalysts method of claim 1, be to adopt infusion process that rare-earth salts is supported on carrier, be carried out at dry and calcination process again, it is characterized in that it being that roasting was carried out 5～8 hours with nanoscale ZnO dipping rare earth nitrate aqueous solution under 800～900 ℃ of air atmospheres.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111019A CN1084223C (en) | 1997-05-17 | 1997-05-17 | RE oxide/zinc oxide catalyst for selective oxidation of ethane with carbon dioxide to produce ethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111019A CN1084223C (en) | 1997-05-17 | 1997-05-17 | RE oxide/zinc oxide catalyst for selective oxidation of ethane with carbon dioxide to produce ethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1199652A true CN1199652A (en) | 1998-11-25 |
| CN1084223C CN1084223C (en) | 2002-05-08 |
Family
ID=5171601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97111019A Expired - Fee Related CN1084223C (en) | 1997-05-17 | 1997-05-17 | RE oxide/zinc oxide catalyst for selective oxidation of ethane with carbon dioxide to produce ethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1084223C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2025660A3 (en) * | 2007-08-14 | 2009-03-04 | Rohm and Haas Company | Processes for producing ethylene and carbon monoxide mixtures from ethane |
| US10662127B2 (en) | 2017-08-28 | 2020-05-26 | 8 Rivers Capital, Llc | Oxidative dehydrogenation of ethane using carbon dioxide |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB203716A (en) * | 1922-09-11 | 1924-03-14 | Horace Garfield Waite | Improvements in radio receiving sets |
| US4450443A (en) * | 1982-03-18 | 1984-05-22 | The Garrett Corporation | Position transducer for digital systems |
-
1997
- 1997-05-17 CN CN97111019A patent/CN1084223C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2025660A3 (en) * | 2007-08-14 | 2009-03-04 | Rohm and Haas Company | Processes for producing ethylene and carbon monoxide mixtures from ethane |
| US7906699B2 (en) | 2007-08-14 | 2011-03-15 | Rohm And Haas Company | Processes for producing ethylene and carbon monoxide mixtures from ethane |
| US10662127B2 (en) | 2017-08-28 | 2020-05-26 | 8 Rivers Capital, Llc | Oxidative dehydrogenation of ethane using carbon dioxide |
| US11174208B2 (en) | 2017-08-28 | 2021-11-16 | 8 Rivers Capital, Llc | Oxidative dehydrogenation of ethane using carbon dioxide |
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| Publication number | Publication date |
|---|---|
| CN1084223C (en) | 2002-05-08 |
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