CN1178719A - Catalyst for preparing ethane and ethylene by selective oxidizing of methylene with carbon dioxide - Google Patents
Catalyst for preparing ethane and ethylene by selective oxidizing of methylene with carbon dioxide Download PDFInfo
- Publication number
- CN1178719A CN1178719A CN96119470A CN96119470A CN1178719A CN 1178719 A CN1178719 A CN 1178719A CN 96119470 A CN96119470 A CN 96119470A CN 96119470 A CN96119470 A CN 96119470A CN 1178719 A CN1178719 A CN 1178719A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- catalyst
- hydrocarbon
- reaction
- zno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 title claims description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 title claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title description 7
- 239000005977 Ethylene Substances 0.000 title description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 2
- 239000001569 carbon dioxide Substances 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 15
- 239000004480 active ingredient Substances 0.000 claims description 4
- 239000012495 reaction gas Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 4
- 239000011787 zinc oxide Substances 0.000 abstract 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical group O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 229910052746 lanthanum Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910007650 ZnO(a) Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- -1 rare earth nitrate Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
In the said RE oxide/zinc oxide catalyst, the carrier is nm-level ZnO particles with size of 5-100 nm and RE oxide as active component is preferably La2O3 and amounts 1-50% of catalyst. At 800-850 deg. c, the said catalyst enables CO2 and CH4 to convert into C2 hydrocarbon with reaction selectivity as high as 90% and methylane conversion rate higher than 3%. The said method provides one industrial path for the utilization of methylane resource.
Description
The invention provides a kind of CO of can be used for
2Rare earth oxide/the ZnO catalyst of selective oxidizing of methylene system ethane and ethene and this building-up reactions.
Methane is converted into C
2Hydrocarbon, especially ethene are one of effective ways of gas utilization.The directly oxidizing methane that with oxygen is oxygenant is converted into C
2Hydrocarbon is because the high reaction activity of oxygen under temperature of reaction causes C
2The further deep oxidation of hydrocarbon is inevitable, and makes C
2The selectivity of hydrocarbon is not high.Recently, people such as Kryliv [Newdevelopments in Selective Oxidation II, 159 (1994)] find CO
2Can be used as a kind of effective as selective oxygenant oxidation hydrocarbons, but be used for methane and CO
2Optionally obtain synthetic gas (CO+H through catalyzed conversion
2).People such as Asami [Appl.catal.A, 126,245 (1995)] find on some single component rare earth oxide catalysts, methane and CO
2Reaction be converted into C
2The selectivity of hydrocarbon about 30%, C
2The yield of hydrocarbon is lower than 1.5%.
The purpose of this invention is to provide a kind of CO of being used for
2The catalyzer of selective oxidizing of methylene system ethane and ethene utilizes this catalyzer, methane and CO
2But at high temperature react the C that is converted into of highly selective
2Hydrocarbon, methane conversion can be greater than 3%, C
2The selectivity of hydrocarbon is greater than 90%.
The CO that is used for of the present invention
2Selective oxidizing of methylene system C
2The catalyzer of hydrocarbon be with ZnO be the supported carrier rare earth oxide as active ingredient, it is characterized in that carrier ZnO is the superfine nano_scale particle, mean particle size is 5～100nm.Used rare earth oxide is one or more the mixed oxide compounds in La, Ce, Sm, Pr or the Yb rare earth element, wherein with La
2O
3Catalytic activity the highest.The weight content of rare earth oxide is 1～50%, and it is preferably 5～30%.
Preparation of catalysts of the present invention can adopt pickling process, and with nano_scale particle ZnO dipping rare earth nitrate aqueous solution, and technology is carried out drying and calcination process can make finished catalyst routinely.Above-mentioned roasting can be carried out under 700～850 ℃ 1～5 hour, to obtain higher activity and stable.
Use catalyzer of the present invention to carry out CH
4With CO
2Also should use inert gas, for example He or N down before the reaction at 800～850 ℃
2Oxygen purged 0.5～3 hour, can lead to reaction gas (CH then under this temperature
4+ CO
2) react.
Below by example technology of the present invention is given to illustrate further.
Embodiment 1
With the ZnO proofing lanthanum nitrate aqueous solution method preparation of 5～100nm, and in 800 ℃ of air, handled 3～5 hours, make catalyzer.Methane and CO
2Catalytic conversion reaction (carry out in the internal diameter 6～8mm) at the continuously feeding fixed-bed quartz reactor.Catalyzer was swept 0.5～1.5 hour with the He air-blowing at 850 ℃, logical then reaction gas (CH
4+ CO
2) begin to react.Reaction product is through online gas chromatographic analysis.Supposition CO during calculating
2In carbon only change CO into, the carbon in the methane changes C into
2Hydrocarbon and CO.Its Different L a
2O
3Reaction result is listed in table 1 on the catalyzer of content.
Table 1 Different L a
2O
3The La of content
2O
3The last CH of/ZnO
4-CO
2Reaction result catalyzer transformation efficiency (%) C
2Hydrocarbon-selective (%) ethylene/ethane (La
2O
3Contain weight %) CH
4CO
21％ 2.0 3.1 96.0 0.510％ 2.1 3.7 96.9 0.520％ 3.1 5.4 90.6 0.730％ 2.9 5.5 91.2 0.750％ 2.5 5.3 90.7 0.6
GHSV=1800ml/gh, 850 ℃, normal atmosphere, CH
4/ CO
2=2 (mol ratios), 4 hours reaction results.
Embodiment 2
Utilize example 1 described method to prepare and contain 20%La
2O
3Catalyzer, and utilize the reaction unit of example 1 to carry out CH
4+ CO
2Reaction, the mol ratio of its reaction pressure and feeding gas is at 20%La
2O
3The last CH of/ZnO
4-CO
2React the table 2 that the results are shown in of influence.
The reaction result of table 2 reaction pressure and feeding gas mol ratio
Transformation efficiency (%) C
2Hydrocarbon-selective (%) ethylene/ethane
CH
4CO
2A 3.1 5.4 90.6 0.7b 3.2 9.0 97.0 2.2c 3.0 2.4 92.5 0.7d 3.8 5.0 90.8 1.9GHSV=1800ml/gh, 850 ℃, 4 hours reaction result a:CH
4/ CO
2=2 (mol/mol), normal atmosphere b:CH
4/ CO
2=2 (mol/mol), 0.1MPac:CH
4/ CO
2=1 (mol/mol), normal atmosphere d:CH
4/ CO
2=1 (mol/mol), 0.1MPa embodiment 3
Utilize example 1 described method to prepare different rare earth oxide/ZnO catalysts, its CH
4-CO
2Reaction result is listed in table 3.
CH on the different rare earth oxides that table 3 ZnO supports
4-CO
2Reaction result is catalyzer transformation efficiency (%) C relatively
2Hydrocarbon-selective (%)
CH
4 CO
220％Al
2O
3/ZnO 3.1 5.4 90.620％Yb
2O
3/ZnO 5.6 6.8 62.920％Sm
2O
3/ZmO 5.3 6.0 73.6
GHSV=1800ml/gh, 850 ℃, normal atmosphere, CH
4/ CO
2=2 (mol ratios), 4 hours reaction results
Comparative example 1
Press example 1 described reaction method and device, CH
4/ CO
2At single component La
2O
3, common ZnO supports 20%La
2O
3, ZnO of the present invention supports 20%La
2O
3And different oxide compounds support 20%La
2O
3On reaction result relatively be shown in table 4.
Table 4 CH
4+ CO
2The 20%La that supports at different oxide compounds
2O
3Reaction result compares catalyzer transformation efficiency (%) C on the catalyzer
2Hydrocarbon-selective (%) ethylene/ethane
CH
4 CO
2La
2O
3 1.4 4.4 40.5 0.3La
2O
3/ZnO(a) 2.5 7.8 59.6 0.6La
2O
3/ZnO(b) 3.1 5.4 90.6 0.7La
2O
3/SnO
2 4.5 12.7 10.4 0.3La
2O
3/Cr
2O
3 12.5 47.7 0.0 ---La
2O
3/TiO
2 8.0 32.5 1.4 ---La
2O
3/CaO 2.4 6.8 42.0 0.4
Reaction conditions: GHSV=1800ml/g h; 850 ℃; Normal atmosphere.
(a) common ZnO supports 20%La
2O
3(b) ZnO of the present invention supports 20%La
2O
3
Result by above-mentioned example and comparative example can see that the rare earth that ZnO of the present invention supports is La particularly
2O
3Utilize CO on the catalyzer
2But highly selective is C with methane conversion
2Hydrocarbon.This is significant for utilizing methane resource to develop feasible course of industrialization.
Claims (5)
1. one kind is used for CO
2Selective oxidizing of methylene system C
2The rare earth metal oxide catalyst of hydrocarbon is characterized in that carrier is the nano level ZnO particle, and active ingredient is a rare earth oxide, and the weight content of rare earth oxide is 1～50%.
2. according to the described rare earth oxide catalyst of claim 1, it is characterized in that ZnO is that granularity is the particulate of 5～100nm.
3. according to the described rare earth metal oxide catalyst of claim 1, it is characterized in that active ingredient is La
2O
3
4. according to claim 1,2,3 described rare earth metal oxide catalysts, the content that it is characterized in that the active ingredient rare earth oxide is 5～30%.
5. one kind is utilized the described rare earth metal oxide catalyst of claim 1 to carry out CO
2With CH
4Reaction system C
2The reaction process of hydrocarbon is characterized in that catalyzer, feeds reaction gas again and reacts after 0.5～3 hour with inert gas purge down in 800～850 ℃ before use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96119470A CN1085116C (en) | 1996-10-09 | 1996-10-09 | Catalyst for preparing ethane and ethylene by selective oxidizing of methylene with carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96119470A CN1085116C (en) | 1996-10-09 | 1996-10-09 | Catalyst for preparing ethane and ethylene by selective oxidizing of methylene with carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1178719A true CN1178719A (en) | 1998-04-15 |
| CN1085116C CN1085116C (en) | 2002-05-22 |
Family
ID=5125723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96119470A Expired - Fee Related CN1085116C (en) | 1996-10-09 | 1996-10-09 | Catalyst for preparing ethane and ethylene by selective oxidizing of methylene with carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1085116C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10662127B2 (en) | 2017-08-28 | 2020-05-26 | 8 Rivers Capital, Llc | Oxidative dehydrogenation of ethane using carbon dioxide |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1353768A1 (en) * | 1985-11-18 | 1987-11-23 | Томский государственный университет им.В.В.Куйбышева | Method of producing ethylene |
| FR2623797B2 (en) * | 1987-08-05 | 1990-05-04 | Inst Francais Du Petrole | PROCESS FOR THE CONVERSION OF METHANE INTO HIGHER HYDROCARBONS |
| EP0582004B1 (en) * | 1992-07-29 | 1997-01-29 | Council of Scientific and Industrial Research | Novel composite catalysts and their use in a process for the oxidative conversion of methane or natural gas to synthesis gas |
| IT1255945B (en) * | 1992-10-30 | 1995-11-17 | Eniricerche Spa | PROCEDURE AND CATALYST FOR THE TRANSFORMATION OF METHANE INTO HIGHER HYDROCARBON PRODUCTS. |
| CN1045198C (en) * | 1992-11-20 | 1999-09-22 | 中国石油化工总公司 | Low temp. catalyst for methane oxidative coupling |
-
1996
- 1996-10-09 CN CN96119470A patent/CN1085116C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1085116C (en) | 2002-05-22 |
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| C14 | Grant of patent or utility model | ||
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| CF01 | Termination of patent right due to non-payment of annual fee |