CN1044789C - Catalyst for preparing carbon dihydrocarbon - Google Patents
Catalyst for preparing carbon dihydrocarbon Download PDFInfo
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- CN1044789C CN1044789C CN94107757A CN94107757A CN1044789C CN 1044789 C CN1044789 C CN 1044789C CN 94107757 A CN94107757 A CN 94107757A CN 94107757 A CN94107757 A CN 94107757A CN 1044789 C CN1044789 C CN 1044789C
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- Prior art keywords
- catalyst
- earth metal
- oxyfluoride
- rare earth
- dihydrocarbon
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a catalyst for preparing carbon dihydrocarbon by methane oxidation coupling reaction, which comprises an alkaline earth metal compound and rare earth metal oxyfluoride, wherein the content of the rare earth metal oxyfluoride is from 95% to 5%. Rare earth metal fluoride and rare earth metal oxide are mixed and are uniformly ground according to the proportion of 1: 1 of the molar ratio of fluorine to oxygen, the fluoride and the oxide are mixed into paste by de-ionized water, and the fluoride and the oxide are made into the oxyfluoride after a pressing process and a roasting process. The measuring rare earth metal oxyfluoride and the measuring alkaline earth metal compound are mixed and are uniformly ground, and the oxyfluoride and the compound are formed by pressing and are made into the catalyst of 40 to 80 meshes after a roasting process. The catalyst for preparing carbon dihydrocarbon by methane oxidation coupling reaction can be used for preparing the carbon dihydrocarbon by the methane oxidation coupling reaction under low temperature, in reaction products, the selectivity of ethylene is higher than that of ethane, and the catalyst for preparing carbon dihydrocarbon by methane oxidation coupling reaction has the advantages of stable performance and long life time.
Description
The present invention relates to a kind of catalyst for preparing carbon dihydrocarbon.
The main component of natural gas is methane (content 90%～100%).In the world, explored gas reserves is greater than reserves; Compare with coal, the hydrogen-carbon ratio height of natural gas pollutes for a short time, is a kind of energy of cleaning.But the most attractive potential application approach of natural gas (or first a heatable brick bed) is by preparing carbon dihydrocarbon, especially produces ethene.
Be used for catalyst for preparing carbon dihydrocarbon, AU-8554352 and US4777313 patent disclosure the single or mixed metal oxide catalyst that promotes of a kind of alkali metal; AU-A-42806/89 and EP418971 patent disclosure the metal oxide catalyst that promotes of a kind of alkali metal or alkaline earth metal chloride; US4914252, patent disclosures such as AU8652925 and EP418971 a kind of metal halide load on Al
2O
3, SiO
2, the catalyst on the inert carrier such as float stone, wherein the disclosed LiCl-Silicotitanate catalyst of US4914252 patent is at CH
4: O
2: dil=2.5: under 1: 46 the condition, methane conversion reaches 50%, and the C 2 hydrocarbon overall selectivity reaches 79%, is best catalyst in reporting at present.But it is little that above-mentioned catalyst exists such as air speed more, uses Macrodilution gas, and problem such as poor stability.The CN1068052A patent application discloses a kind of catalyst based on fluoride, is not using carrier gas, and air speed is 15000h
-1Condition under, can obtain 20% C 2 hydrocarbon yield.
Purpose of the present invention aims to provide a kind of catalyst of the preparing carbon dihydrocarbon based on oxyfluoride.
The said catalyst of the present invention contains more than one (containing a kind of) alkaline earth metal compounds; Also contain the oxyfluoride that more than one (containing a kind of) rare earth metals are formed, the content of oxyfluoride in catalyst is 95%～5%, with 92.5%～40% for well, be preferably 90%～50%, the oxyfluoride of said rare earth metal mainly is La, Sm, the oxyfluoride of Y.
Said alkaline earth metal compound is meant the oxide of alkaline-earth metal, and fluoride or oxyfluoride, said alkaline-earth metal are Mg, Ca, Sr, Ba.
Said rare earth metal oxyfluoride is even in 1: 1 ratio mixed grinding of fluorine oxygen mol ratio the oxide of the fluoride of rare earth metal and rare earth metal, uses deionized water furnishing pasty state again, in 100 ℃ of oven dry down, 200～400Kg/cm
2Pressure under compression moulding, at roasting temperature 2～8h of 600～950 ℃, firing temperature is 700～900 ℃ preferably, is preferably between 800～850 ℃ and fires, the firing time is 6～8h preferably; Said oxyfluoride also can be that the nitrate solution of rare earth metal adds HF or NH by 50% amount of nitrate anion molal quantity
4The aqueous solution of F stirs, in 100 ℃ of down oven dry, and compression moulding and to fire condition the same.
Fluoride (rare earth and alkali earth metal fluoride) can be by the soluble salt of rare earth or alkaline-earth metal respectively with HF or NH
4The aqueous solution precipitation preparation of F also can be the fluoride of commercial grade.
Said catalyst is even the alkaline earth metal compound mixed grinding of the oxyfluoride of rare earth metal of metering and metering, compression moulding and fire the condition of condition with oxyfluoride, and the catalytic materials of making screening 40～80 orders are standby.
The evaluation of catalyst under normal pressure, is used CH in fixed bed reactors
4: O
2=3: 1 unstripped gas is not using any carrier gas, and air speed is 15000h
-1Condition under carry out.550～850 ℃ of reaction temperatures, yield can reach 20.6%.
Catalyst of the present invention can be used for preparing carbon dihydrocarbon under lower temperature, the selectivity height of C 2 hydrocarbon in the product, particularly selectivity of ethylene is higher than the selectivity of ethane, do not use any carrier gas, be easy to carry out separating of unstripped gas and product, and can under high-speed, react, the stable performance of catalyst, long service life, in the life experiment of 240h, performance is not seen tangible change.
The present invention is further illustrated by embodiment below.
Embodiment 1:
With La
2O
39.78g with L
2F
35.88g mix, grind evenly, mix well with deionized water, in 100 ℃ of oven dry, 200Kg/cm
2Pressure under be pressed into sheet, in 800 ℃ of following roasting 6h, make L again
2OF is standby, with the BaF of 1.05g
2Even with the above-mentioned LaOF mixed grinding of making of 10.44g, in 200Kg/cm
2Pressure under be pressed into sheet, in 800 ℃ of following roasting 5h, make BaF again
2/ LaOF catalyst, screening 40～80 orders carry out oxidative coupling of methane.Use the catalyst of 0.5ml, with CH
4: O
2=3: 1 gaseous mixture is a reactor feed gas, and in fixed bed reactors, under normal pressure, the reaction gas air speed is 15000h
-1, reaction temperature is that methane conversion is 33.08% under 780 ℃ the condition, generating selectivity of ethylene is 34.85%, generates ethane selectivity 27.62%, the overall selectivity 62.47% of C 2 hydrocarbon, the yield 20.66% of C 2 hydrocarbon.At CH
4: O
2=9: 1,750 ℃ of temperature are under the same reaction condition of all the other conditions, methane conversion 16.64% generates selectivity of ethylene 23.48%, and the selectivity that generates ethane is 61.07%, generate the overall selectivity 84.55% of C 2 hydrocarbon, the yield of C 2 hydrocarbon is 14.07%.
Embodiment 2:
With 10.37gSmF
3With 16.29gLa
2O
3Mixed grinding is even, and the method for preparing LaOF by embodiment 1 is prepared Sm
1/3La
2/3OF is with 1.06gBaF
2With the above-mentioned Sm that makes of 20.26g
1/3La
2/3The OF mixed grinding is even, presses embodiment 1 preparation BaF
2/ La
2O
3Method prepare BaF
2/ Sm
1/3La
2/3The OF catalyst, screening 40～80 orders carry out oxidative coupling of methane.Under normal pressure, in the fixed bed reactors, reaction gas is formed CH
4: O
2=3: 1, air speed 15000h
-1, under the condition that reaction temperature is 600 ℃, methane conversion is 33.77%, and generating selectivity of ethylene is 29.63%, and the selectivity that generates ethane is 26.60%, and the overall selectivity that generates C 2 hydrocarbon is 56.13%, the yield 18.96% of C 2 hydrocarbon.
Embodiment 3:
With 4.08gCaF
2Even with 10.44gLaOF (preparation method is with embodiment 1) mixed grinding.Press embodiment 1 preparation BaF
2The method of/LaOF prepares CaF
2/ LaOF catalyst is at 790 ℃, under the reaction condition of all the other conditions with embodiment 2, methane conversion is 32.74%, and generating selectivity of ethylene is 37.91%, and the selectivity that generates ethane is 22.09%, the overall selectivity that generates C 2 hydrocarbon is 60.00%, the yield 19.64% of C 2 hydrocarbon.
Embodiment 4:
6.774gY
2O
3(A.P.) and 5.877gLeF
3, levigate mixing is in 200Kg/cm
2Pressure under be pressed into sheet, in 850 ℃ of following roasting 4h, make YLaOF, again with 0.3507gBaF
2(A.P.) with the above-mentioned YLaOP2.53g that makes, mixed grinding is even, prepares BaF by the method for preparing YLaOF
2/ YLaOF catalyst, screening 40～80 orders carry out oxidative coupling of methane.At CH
4: O
2=3.5: 1, air speed is 15000h
-1, reaction temperature is under 820 ℃ the condition, and methane conversion 32.71% generates selectivity of ethylene 40.72%, and the selectivity that generates ethane is 21.02%, generates the selectivity 61.75% of C 2 hydrocarbon, and the yield of C 2 hydrocarbon is 17.14%.
Embodiment 5:
6.974g Sm
2O
3SmF with 4.147g
3, mixed grinding is even, in 200Kg/cm
2Pressure under be pressed into sheet, in 850 ℃ of following roasting 4h, make SmOF, again with 0.282gBaF
2(A.R.) even with the above-mentioned SmOF2.686g mixed grinding of making, prepare BaF by the method for the above-mentioned SmOF of preparation
2/ SmOF catalyst, screening 40～80 orders carry out oxidative coupling of methane.At CH
4: O
2=3.4: 1, air speed is 15000h
-1, reaction temperature is under 780 ℃ the condition, and methane conversion 30.2% generates selectivity of ethylene 28.73%, and the selectivity that generates ethane is 31.02%, generates the selectivity 59.76% of C 2 hydrocarbon, and the yield of C 2 hydrocarbon is 18.05%.
Embodiment 6:
4.516gY
2O
3(A.R.) and 2.925gYF
3(A.R.), levigate mixing is in 200Kg/cm
2Pressure under be pressed into sheet, in 850 ℃ of following roasting 4h, make YOF, again with 0.4172gBaF
2(A.R.) even with the above-mentioned YOF2.453g mixed grinding of making, by the above-mentioned method for preparing YOF, prepare BaF
2/ YOF catalyst, screening 40～80 orders carry out oxidative coupling of methane.At CH
4: O
2=3.7: 1, air speed is 15000h
-1, reaction temperature is under 780 ℃ the condition, and methane conversion 29.44% generates selectivity of ethylene 29.99%, and the selectivity that generates ethane is 28.08%, generates the selectivity 58.07% of C 2 hydrocarbon, and the yield of C 2 hydrocarbon is 17.10%.
Embodiment 7:
BaO (A.R.) and BaF
2(A.R.) etc. the mole mixed grinding is even, in 200Kg/cm
2Pressure under be pressed into sheet, in 850 ℃ of following roastings, make BaO
1/2F is with 0.3287gBaO
1/2The levigate mixing of F and 1.57LaOF (preparation method is with embodiment 1) is pressed embodiment 1 preparation BaF
2The method of/LaOF is prepared BaO
1/2F/LaOF, screening 40～80 orders carry out oxidative coupling of methane.At CH
4: O
2=3: 1, air speed is 15000h
-1, under the condition that reaction temperature is 840 ℃, methane conversion 32.60% generates selectivity of ethylene 44.50%, and the selectivity that generates ethane is 13.69%, generates the selectivity 58.50% of C 2 hydrocarbon, and the yield of C 2 hydrocarbon is 19.10%.
Embodiment 8:
BaO (A.R.) 0.3647g and YOF (preparation method is with embodiment 6) 2.453g, levigate mixing is prepared BaO/YOF by the method for embodiment 6, and screening 40～80 orders are used for oxidative coupling of methane.At CH
4: O
2=3.7: 1, air speed is 15000h
-1, reaction temperature is under 780 ℃ the condition, and methane conversion 33.02% generates selectivity of ethylene 32.20%, and the selectivity that generates ethane is 23.05%, generates the selectivity 55.25% of C 2 hydrocarbon, and the yield of C 2 hydrocarbon is 18.24%.
Embodiment 9:
Take by weighing La (NO
3)
33.79g and NH
4F0.56g is dissolved in respectively in the deionized water of heat, with NH
4The aqueous solution of F is added dropwise to La (NO while stirring
3)
3The aqueous solution in, then with resulting emulsion in 100 ℃ of following evaporating water, in 200Kg/cm
2Pressure under compression moulding, in 850 ℃ of following roasting 6h, make LaOF again.Take by weighing 1.256gSrF
2And the above-mentioned LaOF that makes of 1.74g, mixed grinding is even, and in 200Kg/cm
2Pressure under compression moulding, in 850 ℃ of following roasting 6h, make SrF
2/ YOF catalyst, screening 40～80 orders carry out the methane oxidation coupling experiment.At CH
4: O
2=3: 1, air speed is 15000h
-1, under the condition that reaction temperature is 830 ℃, methane conversion 28.46% generates selectivity of ethylene 40.67%, and the selectivity that generates ethane is 20.33%, generates the selectivity 61.00% of C 2 hydrocarbon, and the yield of C 2 hydrocarbon is 17.37%.
Claims (6)
1. catalyst for preparing carbon dihydrocarbon, contain one or more alkaline earth metal compounds, it is characterized in that also containing the oxyfluoride that one or more rare earth metals are formed, the weight percentage of oxyfluoride in catalyst is 5%～95%, said alkaline earth metal compound is the oxide of Mg, Ca, Sr, Ba, fluoride, oxyfluoride;
Said rare earth metal oxyfluoride is even in 1: 1 ratio mixed grinding of fluorine oxygen mol ratio the fluoride of rare earth metal and oxide, uses deionized water furnishing pasty state again, in 100 ℃ of oven dry down, 200～400Kg/cm
2Pressure under compression moulding, at roasting temperature 2～8h of 600～950 ℃; The nitrate solution that also can be rare earth metal adds HF or NH by 50% amount of nitrate anion molal quantity
4The aqueous solution of F stirs, and in 100 ℃ of down oven dry, compression moulding is with to fire condition identical;
Said catalyst is even the alkaline earth metal compound mixed grinding of the oxyfluoride of the rare earth metal of metering and metering, with deionized water furnishing pasty state, in 100 ℃ of oven dry down, 200～400Kg/cm
2Pressure under compression moulding, catalyst screening 40～80 orders of making.
2. a kind of catalyst for preparing carbon dihydrocarbon as claimed in claim 1, the oxyfluoride that it is characterized in that said rare earth metal is La, Sm, the oxyfluoride of Y.
3. a kind of catalyst for preparing carbon dihydrocarbon as claimed in claim 1 is characterized in that the weight percentage of rare earth metal oxyfluoride in catalyst is 40%～92.5%.
4. a kind of catalyst for preparing carbon dihydrocarbon as claimed in claim 3 is characterized in that the weight percentage of rare earth metal oxyfluoride in catalyst is 50%～90%.
5. a kind of catalyst for preparing carbon dihydrocarbon as claimed in claim 1, the firing temperature that it is characterized in that oxyfluoride is 700～900 ℃, the firing time is 6～8h.
6. a kind of catalyst for preparing carbon dihydrocarbon as claimed in claim 5, the firing temperature that it is characterized in that oxyfluoride is 800～850 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94107757A CN1044789C (en) | 1994-06-25 | 1994-06-25 | Catalyst for preparing carbon dihydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94107757A CN1044789C (en) | 1994-06-25 | 1994-06-25 | Catalyst for preparing carbon dihydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1100669A CN1100669A (en) | 1995-03-29 |
| CN1044789C true CN1044789C (en) | 1999-08-25 |
Family
ID=5033198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94107757A Expired - Fee Related CN1044789C (en) | 1994-06-25 | 1994-06-25 | Catalyst for preparing carbon dihydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1044789C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112012030016B8 (en) | 2010-05-24 | 2021-05-18 | Siluria Technologies Inc | process for preparing ethylene from methane and method for preparing an ethylene downstream product |
| WO2012162526A2 (en) * | 2011-05-24 | 2012-11-29 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
| EP2785458A2 (en) | 2011-11-29 | 2014-10-08 | Siluria Technologies, Inc. | Nanowire catalysts and methods for their use and preparation |
| EP2855011A2 (en) | 2012-05-24 | 2015-04-08 | Siluria Technologies, Inc. | Catalytic forms and formulations |
| EP2969184A4 (en) | 2013-03-15 | 2016-12-21 | Siluria Technologies Inc | Catalysts for petrochemical catalysis |
| CA2947483C (en) | 2014-05-02 | 2023-08-01 | Siluria Technologies, Inc. | Heterogeneous catalysts |
| CA2960555A1 (en) | 2014-09-17 | 2016-03-24 | Siluria Technologies, Inc. | Catalysts for oxidative coupling of methane and oxidative dehydrogenation of ethane |
| CN109499588B (en) * | 2018-12-18 | 2021-05-11 | 浙江工业大学 | Carbon-spaced barium lanthanum fluoride composite catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068052A (en) * | 1992-06-25 | 1993-01-20 | 厦门大学 | Methane oxidation coupling system carbon two above hydrocarbon catalysts |
| CN1069907A (en) * | 1992-08-21 | 1993-03-17 | 厦门大学 | Catalyst for making ethylene from ethane oxidative dehydrogenation |
| CN1074391A (en) * | 1992-01-17 | 1993-07-21 | 厦门大学 | Thorotrast-calcium oxide-barium carbonate methane oxidation coupling catalyst for making ethylene |
-
1994
- 1994-06-25 CN CN94107757A patent/CN1044789C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074391A (en) * | 1992-01-17 | 1993-07-21 | 厦门大学 | Thorotrast-calcium oxide-barium carbonate methane oxidation coupling catalyst for making ethylene |
| CN1068052A (en) * | 1992-06-25 | 1993-01-20 | 厦门大学 | Methane oxidation coupling system carbon two above hydrocarbon catalysts |
| CN1069907A (en) * | 1992-08-21 | 1993-03-17 | 厦门大学 | Catalyst for making ethylene from ethane oxidative dehydrogenation |
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| Publication number | Publication date |
|---|---|
| CN1100669A (en) | 1995-03-29 |
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