CN1068052A - Methane oxidation coupling system carbon two above hydrocarbon catalysts - Google Patents
Methane oxidation coupling system carbon two above hydrocarbon catalysts Download PDFInfo
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- CN1068052A CN1068052A CN 92105258 CN92105258A CN1068052A CN 1068052 A CN1068052 A CN 1068052A CN 92105258 CN92105258 CN 92105258 CN 92105258 A CN92105258 A CN 92105258A CN 1068052 A CN1068052 A CN 1068052A
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- fluoride
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- earth metal
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Abstract
A kind of is that main component is equipped with a small amount of alkaline earth or rare-earth oxide or ThO with alkaline earth or rare earth metal fluoride
2, ZrO
2Deng the catalyst of forming, between 450 ℃ to 650 ℃, air speed is 15000h
-1, under the no carrier gas situation to CH
4Selective Oxidation C
2 +Hydrocarbon has high activity and selectivity preferably.CH
4Conversion ratio between 27%-34%, selectivity between 44% to 62%, C
2 +The hydrocarbon yield is between 13% to 20%.Catalyst of the present invention is made simple, and good stability has practical prospect.
Description
The methane oxidation coupling system of the invention belongs to carbon two above hydrocarbon catalysis techniques.
Contain a large amount of methane in the natural gas, if can be that raw material is produced C with it
2And C
2Basic chemical industry raw materials such as above hydro carbons then can be saved the oil base hydro carbons.Satisfy demand to ethene.Worldwide carried out this research work over past ten years widely.
Changchun applied chemistry research institute in do one-carbon chemical that dragon etc. holds in Chengdu in September, 1991 can on reported a kind of Li-La
1-xM
N-xO
2-λCatalyst is used CH
4: O
2: N
2=2: 1: 7 gaseous mixture is a unstripped gas, is 15000h in air speed
-1, temperature is to obtain C under 750 ℃ the condition
+ 2Yield 22%.Xiamen University's Lamb, Gordon Clive etc. has been reported a kind of BaO-La in same meeting
2O
3Catalyst is used CH
4: O
2: N
2Be 4: 1: 9: 6 unstripped gas, in 60000h
-1, 750 ℃ down C
2Hydrocarbon yield 173%.The Takahito Nishiyama of Japan etc. 6(1991) have reported a kind of Li at Catalysis Today on the 391-397
2CO
3-Ca(OH)
2Catalyst is 1500h in air speed
-1, 800 ℃ with CH
4: O
2: (N
2+ He) be 2: 1: 683 gaseous mixture.In 72 hours, obtain C
2Yield 257%.
The objective of the invention is to develop a kind of practical prospect that has, based on the methane oxidation coupling system C of fluoride
2The hydrocarbon new catalyst.
Detailed description of the invention:
Catalyst of the present invention is a kind of catalyst of methane oxidation coupling system carbon two above hydrocarbon, and said catalyst contains a kind of oxide, and said oxide can be selected from the oxide of alkaline-earth metal, particularly Mg, Ca, Sr, Ba; Also can be the oxide of rare earth element, particularly Ce, La, Sm or be selected from thorium, Zirconium oxide.Said catalyst also contains fluoride.Said fluoride also can be the fluoride of rare earth metal, particularly Ce, La, Sm.Said fluoride can be the fluoride of single kind, also can be the mixture of multiple fluoride, and content of fluoride is 20% to 98%, 60% to 98% better, preferably 90%～96%.
Fluoride can be by the soluble salt of alkaline earth or rare earth element with NH
4The F or the HF aqueous solution precipitate corresponding soluble salt preparation, also can use the commercial grade fluoride.
Said catalyst is the salt that the fluoride of metering and the oxide of metering maybe can be decomposed into oxide to be mixed mill evenly, mixes well into pasty state with deionized water again, in 100 ℃ of oven dry 10 hours.Roasting is 2 to 6 hours between 500 ℃ to 1200 ℃, and firing temperature is 800 ℃ to 1000 ℃ preferably, preferably fires 4 to 6 hours at 850 ℃ to 900 ℃.Making the granularity that needs, generally is 40 to 80 orders.
Evaluating catalyst is in fixed bed reactors, under the normal pressure, uses CH
4: O
2Be 3: 1 unstripped gas, at no carrier gas, air speed is 15000h
-1Carry out under the condition.Reaction temperature can change in a big way, is generally between 550 ℃ to 700 ℃.C
+ 2The hydrocarbon yield is between 12% to 20%.
Catalyst of the present invention can be used for oxidative coupling of methane at a lower temperature.C 2 hydrocarbon content height in the reaction end gas, no carrier gas is easy to separate, and catalyst is made simple, and intensity is good, catalyst performance stabilised.
The invention will be further described by embodiment below.
Example 1:
1.8 gram BaF
2Add 2 gram LaF
3Add 125 gram ZrO
2Mill after the mixing, mix well with deionized water.Dried 10 hours down for 100 ℃, 900 ℃ were burnt 6 hours down, make 40～80 orders.With CH
4: O
2Be that 3: 1 gaseous mixtures are made raw material, under 640 ℃ of normal pressures, catalyst amount is 0.2ml, and air speed is 15000h
-1Reaction, ethylene contents is 5.64% in the tail gas, ethane content is 3.94%, C
3Content 0.8%, conversion ratio 3236% generates C 2 hydrocarbon selectivity 622%, yield 20%.
Example 2:
1 gram BaO adds 12 gram Ia
2O
3With HNO
3(50%) after the dissolving, adds the NH of a great deal of
4F(is can all generate BaF
2, IaF
3Be degree), add ThO
2132 grams are heated to driedly on electric furnace, fire 6 hours, and make 40～80 orders for 900 ℃.600 ℃ of reactions under the condition of embodiment 1, C in the tail gas
2H
44.37%, C
2H
6405%, carbon three hydrocarbon 072%, CH
4Conversion ratio 30%.Be total to carbon two above hydrocarbon-selectives 572%, yield 173%.
The catalyst of embodiment 3 to 12 is except that catalytic reaction temperature difference, and its preparation method appreciation condition is identical with embodiment 1.As shown in the table.
| Embodiment | Form (gram) | Temperature ℃ | Ethene % | Ethane % | Carbon three % | CH 4Conversion ratio % | C + 2Selectivity % | Yield % |
| 3 | 1.24MgF 20.66ThO 2 | 880 | 7.73 | 3.25 | ～ | 32.0 | 62.0 | 19.8 |
| 4 | 2 LaF 31.3ThO 2 | 550 | 3.61 | 3.45 | ～ | 29.6 | 44.5 | 13.2 |
| 5 | 2 LaF 30.66ThO 2 | 480 | 3.40 | 3.62 | ～ | 28.5 | 45.1 | 12.8 |
| 6 | 4?LaF 30.8LaO 3 | 550 | 4.17 | 3.72 | ～ | 30.4 | 48.2 | 14.7 |
| 7 | 2 LaF 30.88CeO 2 | 500 | 3.8 | 3.75 | ～ | 28.2 | 52.1 | 14.7 |
| 8 | 8?LaF 32.46ZrO 2 | 650 | 4.46 | 3.14 | ～ | 27.1 | 52.2 | 14.1 |
| 9 | 2.5MgF 22.4ZrO 2 | 700 | 5.1 | 2.52 | ～ | 30.8 | 46.0 | 14.2 |
| 10 | 7.0BaF 22.46ZrO 2 | 740 | 6.68 | 4.2 | ～ | 34.34 | 57.4 | 19.7 |
| 11 | 1.75BaF 21.75CeO 2 | 600 | 3.59 | 3.27 | 0.88 | 28.0 | 54.0 | 15.1 |
| 12 | CaF 2:CeO 2=4:1 | 650 | 4.40 | 3.52 | ～ | 29.84 | 48.4 | 14.0 |
Claims (4)
1, a kind of catalyst of methane oxidation coupling system carbon two above hydrocarbon, said catalyst contains a kind of oxide, said oxide can be selected from alkaline-earth metal, Mg particularly, Ca, Sr, the oxide of Ba, it also can be rare earth element, Ce particularly, La, the oxide of Sm or be selected from thorium, Zirconium oxide, feature of the present invention is that said catalyst also contains fluoride, said fluoride can be an alkaline-earth metal, Mg particularly, Ca, Sr, the fluoride of Ba, also can be rare earth metal, particularly Ce, La, the fluoride of Sm, said fluoride can be single kinds, it also can be the mixture of two kinds of fluorides, content of fluoride is 20% to 98%, 60% to 98% better in the catalyst, preferably 90%～96%; Said catalyst be will metering fluoride to add the oxide mill of metering even, mix well with deionized water, dried 10 hours for 100 ℃, 500 ℃ to 1200 ℃ roastings 2 to 6 hours, better be to fire 4 to 6 hours, preferably fire and made in 6 hours at 900 ℃ at 800 ℃ to 1000 ℃.
2, catalyst according to claim 1 is characterized in that said alkali earth metal fluoride is MgF, CaF, SrF, BaF.
3, catalyst according to claim 1 is characterized in that said rare earth metal fluoride is CeF, LaF.
4, catalytic materials according to claim 1 is characterized in that said content of fluoride is 60% to 98%, 90%～60% better.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92105258 CN1030136C (en) | 1992-06-25 | 1992-06-25 | C2-n hydrocarbon catalyst produced from methane by oxidation coupling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92105258 CN1030136C (en) | 1992-06-25 | 1992-06-25 | C2-n hydrocarbon catalyst produced from methane by oxidation coupling |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1068052A true CN1068052A (en) | 1993-01-20 |
| CN1030136C CN1030136C (en) | 1995-10-25 |
Family
ID=4941265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92105258 Expired - Fee Related CN1030136C (en) | 1992-06-25 | 1992-06-25 | C2-n hydrocarbon catalyst produced from methane by oxidation coupling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1030136C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044789C (en) * | 1994-06-25 | 1999-08-25 | 厦门大学 | Catalyst for preparing carbon dihydrocarbon |
| CN1044787C (en) * | 1993-12-29 | 1999-08-25 | 厦门大学 | Producing isobutene catalyst by oxidizing and dehydrogenating isobutane |
| CN103764276A (en) * | 2011-05-24 | 2014-04-30 | 希路瑞亚技术公司 | Catalysts for petrochemical catalysis |
| CN107646027A (en) * | 2015-06-08 | 2018-01-30 | 沙特基础全球技术有限公司 | The low entry temperature of methane oxidation coupling |
-
1992
- 1992-06-25 CN CN 92105258 patent/CN1030136C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044787C (en) * | 1993-12-29 | 1999-08-25 | 厦门大学 | Producing isobutene catalyst by oxidizing and dehydrogenating isobutane |
| CN1044789C (en) * | 1994-06-25 | 1999-08-25 | 厦门大学 | Catalyst for preparing carbon dihydrocarbon |
| CN103764276A (en) * | 2011-05-24 | 2014-04-30 | 希路瑞亚技术公司 | Catalysts for petrochemical catalysis |
| CN103764276B (en) * | 2011-05-24 | 2017-11-07 | 希路瑞亚技术公司 | Catalyst for methane oxidative coupling |
| CN107646027A (en) * | 2015-06-08 | 2018-01-30 | 沙特基础全球技术有限公司 | The low entry temperature of methane oxidation coupling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1030136C (en) | 1995-10-25 |
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