CN1067831A - Methane conversion is become the catalyst and the process of higher hydrocarbon - Google Patents
Methane conversion is become the catalyst and the process of higher hydrocarbon Download PDFInfo
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- CN1067831A CN1067831A CN 91104243 CN91104243A CN1067831A CN 1067831 A CN1067831 A CN 1067831A CN 91104243 CN91104243 CN 91104243 CN 91104243 A CN91104243 A CN 91104243A CN 1067831 A CN1067831 A CN 1067831A
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- catalyst
- metal oxide
- compound
- become
- higher hydrocarbon
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Abstract
Methane conversion is become the catalyst and the process of higher hydrocarbon, relate to the catalyst and the process of the hydrocarbon conversion.Catalyst of the present invention is with SiO
2Or Al
2O
3Be carrier, contain the compound of alkali metal, alkaline-earth metal or ammonium of at least a tungstenic or phosphorus and at least a manganese, lanthanum, titanium, zirconium, vanadium or the like metal oxide.With catalyst of the present invention the gas of methane and molecule-containing keto is introduced reaction system and in 750~850 ℃ of reactions down, can be obtained considerable ethene and ethane.
Description
The present invention relates generally to methane conversion is become the catalyst of higher hydrocarbon (particularly ethene) and the method for preparation thereof.It also further relates to methane conversion is the particularly process of ethene and ethane of higher hydrocarbon.
Chinese scholars had been developed and much had been applicable to methane oxidation coupling system higher hydrocarbon catalyst for reaction in recent years, the patent of large quantities of these class catalyst occurred.Catalytic activity and higher hydrocarbon (mainly are C to have found to have oxide, halide except alkali, alkaline earth, rare earth and variable valency metal preferably
2Hydrocarbon) outside the selectivity, oxysalt and compound class Study of Catalyst also come into one's own gradually, show the research tendency that becomes increasingly active, the catalyst that has has also reached catalytic performance index preferably, and for example United States Patent (USP) the 4th, introduced 15%Mn5%Na 544, No. 784
4P
2O
7/ SiO
2Application of Catalyst, but its use operation needs employing intermittent feeding mode, and suitable methane air speed is also lower.United States Patent (USP) the 4th, 665 has been introduced 5%Na No. 261
2WO
4/ NaMnO
4Catalyst, the higher hydrocarbon selectivity of this catalyst is very high, reaches 96%, but its methane conversion is very low, only has about 2.5%.Other most this class catalyst is from present visible patent report, or the catalytic performance of catalyst itself is not good, or exists the harsh requirement to reaction condition, constantly doses problems such as chloride in course of reaction as needs.
The objective of the invention is to overcome outside the deficiency of prior art, propose a kind of methane oxidation coupling system higher hydrocarbon particularly catalyst and the process of ethene.
Purpose of the present invention can realize by following measure:
Of the present invention with containing (a) 3-20%(weight in the catalyst prepared) at least a tungstenic or the compound of alkali metal, alkaline-earth metal or the ammonium of phosphorus; (b) 0-10%(weight) but at least aly methane conversion can be become the metal oxide of higher hydrocarbon or the metallic compound that thermal decomposition becomes above-mentioned metal oxide; (c) and surplus be SiO
2Or Al
2O
3Bead is as carrier; Perhaps the catalyst with Slurry mixing preparation contains (a) 5-40%(weight) at least a tungstenic or the compound of alkali metal, alkaline-earth metal or the ammonium of phosphorus; (b) 0-10%(weight) but at least aly methane conversion can be become the metal oxide of higher hydrocarbon or the metallic compound that thermal decomposition becomes above-mentioned metal oxide; (c) and surplus be that the gel of silicon or aluminium is as carrier.
The method that the present invention preferentially selects for use with the immersion process for preparing catalyst comprises the following steps:
(A) choose the SiO that suitable specific area and particle diameter are arranged
2Or Al
2O
3Bead toasted about 3 hours in the baking oven about 100 ℃ earlier.
(B) with the alkali metal oxysalt of tungstenic or phosphorus with an amount of water-soluble separating, but again thermal decomposition is become can make the soluble metal compound of metal oxide that methane conversion becomes higher hydrocarbon with an amount of water-soluble separating, divide to soak or be immersed in altogether and dried by the fire on the carrier of getting well.
(C) macerate that obtains in the drying steps (B).
(D) the dry macerate that obtains in the calcination steps (C).
The present invention prepares the method that catalyst selects for use with Slurry mixing and may further comprise the steps:
(a) gel of preparation silicon or aluminium
(b) but with the alkali metal of tungstenic or phosphorus or alkaline earth metal compound and at least a metallic compound that can make metal oxide that methane conversion becomes higher hydrocarbon or thermal decomposition become above-mentioned metal oxide, add an amount of water and mix with the gel that step (a) makes.
(c) grind the gel mixture that makes in the step (b) with ball mill.
(d) gel mixture that makes in the drying steps (c).
(e) gel mixture that makes in the calcination steps (d).
Catalyst of the present invention can also be realized by following measure:
Of the present invention with containing (a) 5-10%(weight in the catalyst prepared) at least a tungstenic or the compound of alkali metal, alkaline-earth metal or the ammonium of phosphorus; (b) 0.1-0.5%(weight) but at least aly methane conversion can be become the metal oxide of higher hydrocarbon or the metallic compound that thermal decomposition becomes above-mentioned metal oxide; (c) and surplus be SiO
2Or Al
2O
3Bead is as carrier; Perhaps, the catalyst with Slurry mixing preparation comprises (a) 10-20%(weight) at least a tungstenic or the compound of alkali metal, alkaline-earth metal or the ammonium of phosphorus; (b) 0.5-3%(weight) but at least aly methane conversion can be become the metal oxide of higher hydrocarbon or the metallic compound that thermal decomposition becomes above-mentioned metal oxide; (c) and surplus be that the gel of silicon or aluminium is as carrier.
The alkali metal of tungsten or alkaline earth metal compound are advisable with sodium tungstate, potassium tungstate, ammonium tungstate and artificial schellite, are best with sodium tungstate wherein.
The alkali metal compound of phosphorus is advisable with sodium pyrophosphate, potassium pyrophosphate, is best with sodium pyrophosphate wherein.
Methane conversion can be become the metal oxide of higher hydrocarbon to be preferably at least a of metal oxides such as manganese, lanthanum, titanium, zirconium, vanadium, chromium, molybdenum, iron, cobalt, nickel, copper, cerium, praseodymium, samarium, lead, tin, wherein preferred metal oxide is a manganese oxide, but thermal decomposition becomes in the metallic compound of above-mentioned metal oxide preferably nitrate, carbonate and acetate.
Above-mentioned SiO
2And Al
2O
3Carrier can be selected the product of various commercial sizes.
Dry run generally needs 4-16 hour, is advisable with 8-12 hour.Baking temperature generally is controlled at 60-150 ℃, is advisable with 100-110 ℃.
Roasting process generally needs 2-6 hour, is advisable with 2-4 hour, and sintering temperature generally is controlled at 780-850 ℃, is advisable with 800-820 ℃.
The catalyst that the present invention preferentially selects for use constitutes Na
2WO
4MnxOy/SiO
2Or Na
2WO
4MnxOyP
2O
5/ SiO
2Here x and y are respectively the valence state of manganese and oxygen in the Mn oxide.
Reaction medium is the gas of methane and molecular oxygen.Methane can be used pure substantially methane, also can be the methane that is mixed with other alkane (for example ethane, propane etc.), and also available if desired inert dilution gas is as nitrogen, helium or water vapour.The gas of molecule-containing keto can be air or pure substantially oxygen, and methane can contact with catalyst continuously with the mist of oxygen and react.The mist of methane and oxygen suitable composition under atmospheric pressure, general methane to the mol ratio of oxygen in the 2-20 scope.
Operating temperature range is 650-900 ℃, is preferably 750-850 ℃; Pressure limit is preferably the 0.1-3 MPa, by under standard temperature and pressure (STP), calculate gas space velocity be preferably 5,000-100, at 000 o'clock
-1, be preferably 10,000-40, at 000 o'clock
-1
Catalyst is applicable to fixed bed, fluid bed or other form.
Now catalyst of the present invention is described further with embodiment.
Embodiment 1:
Impregnated catalyst Na
2WO
4MnxOy/SiO
2Preparation
To contain 5wt% Na
2WO
4, 0.32wt%Mn manganese nitrate aqueous solution be immersed in a certain amount of SiO equably
2(specific area 100-200m on the bead carrier
2/ g, particle size range 20-60 order), at room temperature placed 2-10 hour, put then in the baking oven and in about 110 ℃, dried by the fire 8-12 hour, in 400 ℃ of following roastings 1 hour, be warming up to 820 ℃ of roastings 2 hours at air atmosphere then.
The catalyst that the application present embodiment makes changes into C in the methane oxygenation
2The experiment of hydrocarbon.
Getting 20 milliliters of catalyst internal diameter of packing into is in 28 millimeters the quartz ampoule fluid bed, reaction condition with the results are shown in table 1.
Table 1:
Reaction temperature ℃ | During methane air speed GHSV -1 | CH 4:O 2:H 2O (mol ratio) | Methane conversion (% | C 2Hydrocarbon-selective (% | C 2Hydrocarbon yield (% | Ethylene/ethane |
820 | 12500 | 3.2:1:0 | 29.8 | 58.0 | 17.3 | 3.4 |
820 | 12500 | 4.2:1:0 | 24.2 | 63.6 | 16.2 | 2.9 |
840 | 12500 | 3.7:1:1 | 26.3 | 66.6 | 17.5 | 3.2 |
Embodiment 2:
Mix slurry catalyst Na
2WO
4MnxOyP
2O
5/ SiO
2Preparation
At first prepare the silicon gel, measure its water content, will contain 15wt%(NH then
4)
2WO
4, 10wt%MnO
2, 15wt%Na
4P
2O
7SiO with 60wt%
2Mix, inserted in the ball mill ball milling 6-8 hour, the baking oven that the good glue of taking-up mill is put into inherent 100-110 ℃ of enamel tray toasted 8-12 hour, jello after will drying is then put into the high temperature furnace roasting, sintering temperature be 400 ℃ following 1 hour, 820 ℃ following 2 hours, at last that roasting is good catalyst is pulverized, screening.In the above-mentioned preparation process, if any the grit blast former, glue that can ball milling is good becomes bead through the shot-blasting machine spray, and then handles through identical drying, roasting condition.
The catalyst that the application present embodiment makes changes into C in the methane oxygenation
2The experiment of hydrocarbon.
Getting 0.2 milliliter of catalyst, to put into internal diameter be 8 millimeters quartz tube reactor, and the beds place outer temperature of pipe is 800 ℃, and the mist air speed is 40,000 o'clock
-1, gained the results are shown in table 2.
Table 2:
CH 4:O 2:N 2(mol ratio) | Methane conversion (% | C 2Hydrocarbon-selective (% | C 2Hydrocarbon yield (% | Ethylene/ethane |
2.5:1:2.5 | 39.5 | 63.8 | 25.2 | 3.1 |
4.5:1:0 | 24.5 | 74.9 | 18.4 | 2.0 |
Above-mentioned experiment remains on T=800 ℃, GHSV=40,000
-1, CH
4: O
2: N
2=3: under 1: 2.5 the condition, catalyst continued operation 33 hours, gained the results are shown in table 3.
Table 3:
Operating time (time) | Methane conversion (% | C 2Hydrocarbon-selective (% | C 2Hydrocarbon yield (%) | Ethylene/ethane |
0-11 | 36.1 | 63.8 | 23.0 | 2.6 |
12-22 | 36.2 | 65.0 | 23.5 | 2.6 |
23-33 | 36.3 | 65.2 | 23.7 | 2.6 |
Embodiment 3:
Mix slurry catalyst MnxOyK
2WO
4/ SiO
2Preparation.
Preparation method and step are with embodiment 2, and catalyst contains 5wt%K
2WO
4And contain and be equivalent to 3wt%MnO
2Mn(NO
3)
26H
2The O aqueous solution and 92wt%SiO
2Gel.
Embodiment 4:
Impregnated catalyst MnxOyNa
2WO
4/ Al
2O
3Preparation.
Preparation method and step are with embodiment 1, and catalyst contains 5wt%Na
2WO
4And contain and be equivalent to 3wt%MnO
2Mn(NO
3)
26H
2The O aqueous solution and 92wt%Al
2O
3Bead.
Embodiment 5:
Impregnated catalyst CaONa
2WO
4/ SiO
2Preparation.
Preparation method and step are with embodiment 1.Catalyst contains 7wt%Na
2WO
4And contain nitrate aqueous solution and the 88wt%SiO that is equivalent to 5wt%CaO
2Bead.
Embodiment 6:
Impregnated catalyst Bi
2O
3Na
2WO
4/ SiO
2Preparation.
Preparation method and step are with embodiment 1, and catalyst contains 5wt%Na
2WO
4And contain and be equivalent to 3wt%Bi
2O
3Nitrate aqueous solution and 92wt%SiO
2Bead.
Embodiment 7:
Impregnated catalyst CoONa
2WO
4/ SiO
2Preparation.
Preparation method and step are with embodiment 1, and catalyst contains 3wt%Na
2WO
4And contain nitrate aqueous solution and the 94wt%SiO that is equivalent to 3wt%CoO
2Bead.
Embodiment 8:
Impregnated catalyst ZrO
2Na
2WO
4/ SiO
2Preparation.
Preparation method and step are with embodiment 1, and catalyst contains 5wt%Na
2WO
4And contain and be equivalent to 3wt%ZrO
2Nitrate aqueous solution and the SiO of 92wt%
2Bead.
Embodiment 9:
Impregnated catalyst CdONa
2WO
4/ SiO
2Preparation.
Preparation method and step are with embodiment 1, and catalyst contains 10wt%Na
2WO
4And contain nitrate aqueous solution and the 87wt%SiO that is equivalent to 3wt%CdO
2Bead.
Embodiment 10:
Impregnated catalyst La
2O
3Na
2WO
4/ SiO
2Preparation.
Preparation method and step are with embodiment 1, and catalyst contains 5wt%Na
2WO
4And contain and be equivalent to 3wt%La
2O
3Nitrate aqueous solution and 92wt%SiO
2Bead.
Embodiment 11:
Preparation method and step are with embodiment 1, and catalyst contains 5wt%Na
2WO
4, 3wt%MnO
2With nitrate aqueous solution that contains 3wt%ZnO and 89wt%SiO
2Bead, dipping carries out in two steps, and the first step is soaked Na
2WO
4The aqueous solution, second goes on foot, and soaks the mixed solution of manganese nitrate and zinc nitrate.
The catalyst that the foregoing description 3-11 is prepared, at reaction temperature T=800 ℃, CH
4: O
2: N
2=3: 1: 2.5(gas mole ratio); Mist air speed GHSV=43,200 o'clock
-1Under reaction condition, 0.1 gram catalyst is that reaction result in 8 millimeters the fixed-bed quartz reactor is listed in table 4 at internal diameter.
Table 4:
Embodiment number | Catalyst | Methane conversion (%) | C 2Hydrocarbon yield (%) | C 2Hydrocarbon-selective (%) | Ethylene/ethane |
3 | A | 33.2 | 21.5 | 64.7 | 2.1 |
4 | B | 30.6 | 10.8 | 35.2 | 1.7 |
5 | C | 25.1 | 16.1 | 64.2 | 1.2 |
6 | D | 27.3 | 15.9 | 58.4 | 1.5 |
7 | E | 26.2 | 14.8 | 56.6 | 0.8 |
8 | F | 30.3 | 17.6 | 58.1 | 1.7 |
9 | G | 28.8 | 17.0 | 59.1 | 1.6 |
10 | H | 26.2 | 16.3 | 62.1 | 0.9 |
11 | I | 32.7 | 22.0 | 67.4 | 1.8 |
A:MnxOy·K
2WO
4/SiO
2B:MnxOy·Na
2WO
4/Al
2O
3
C:CaO·Na
2WO
4/SiO
2D:Bi
2O
3·Na
2WO
4/SiO
2
E:CoO·Na
2WO
4/SiO
2F:ZrO
2·Na
2WO
4/SiO
2
G:CaO·Na
2WO
4/SiO
2H:La
2O
3·Na
2WO
4/SiO
2
I:ZnO-MnxOy·N
2WO
4/SiO
2
Claims (12)
1, a kind ofly be used for the catalyst that methane oxidation is converted into higher hydrocarbon (particularly ethene and ethane), it is characterized in that, comprise with catalyst prepared:
The compound of at least a tungstenic of a, 3-10% (weight) or alkali metal, alkaline-earth metal or the ammonium of phosphorus;
B, 0-10% (weight) but at least aly methane conversion can be become the metal oxide of higher hydrocarbon or the metallic compound that thermal decomposition becomes above-mentioned metal oxide;
C, and surplus be SiO
2Or Al
2O
3Bead is as carrier;
Perhaps, the catalyst with the Slurry mixing preparation comprises:
The compound of at least a tungstenic of a, 5-40% (weight) or alkali metal, alkaline-earth metal or the ammonium of phosphorus;
B, 0-15% (weight) but at least aly methane conversion can be become the metal oxide of higher hydrocarbon or the metallic compound that thermal decomposition becomes above-mentioned metal oxide;
C, and surplus be that the gel of silicon or aluminium is as carrier.
2, catalyst as claimed in claim 1 is characterized in that, comprises with catalyst prepared:
A, 3-7%(weight) at least a tungstenic or the compound of alkali metal, alkaline-earth metal or the ammonium of phosphorus;
B, 0.1-0.5%(weight) but at least aly methane conversion can be become the metal oxide of higher hydrocarbon or the metallic compound that thermal decomposition becomes above-mentioned metal oxide;
C, and surplus be SiO
2Or Al
2O
3Bead is as carrier;
Perhaps, the catalyst with the Slurry mixing preparation comprises:
A, 10-20%(weight) at least a tungstenic or the compound of alkali metal, alkaline-earth metal or the ammonium of phosphorus;
B, 0.5-3%(weight) but at least aly methane conversion can be become the metal oxide of higher hydrocarbon or the metallic compound that thermal decomposition becomes above-mentioned metal oxide;
C, and surplus be that the gel of silicon or aluminium is as carrier.
3, catalyst as claimed in claim 1 or 2 is characterized in that the alkali metal of tungstenic or phosphorus or alkaline earth metal compound are sodium tungstate, potassium tungstate, artificial schellite or sodium pyrophosphate, potassium pyrophosphate.
4, catalyst as claimed in claim 3, the alkali metal compound that it is characterized in that tungstenic is a sodium tungstate.
5, catalyst as claimed in claim 1 or 2 is characterized in that methane conversion can be become the metal oxide of higher hydrocarbon is at least a of oxides such as manganese, lanthanum, titanium, zirconium, vanadium, chromium, molybdenum, iron, cobalt, nickel, copper, cerium, praseodymium, samarium, lead, tin; The metallic compound that can be decomposed into above-mentioned metal oxide is its nitrate, carbonate and acetate.
6, catalyst as claimed in claim 5 is characterized in that metal oxide is a manganese oxide.
7, Preparation of catalysts method as claimed in claim 1 or 2 is characterized in that comprising the steps:
A: choose SiO
2Or Al
2O
3Bead, baking is 3 hours under the temperature about 100 ℃; Or the gel of preparation silicon or aluminium.
B: the soluble compound of alkali metal, alkaline-earth metal or the ammonium of tungstenic or phosphorus is added an amount of water-soluble separating, again but thermal decomposition is become to make methane conversion become the soluble metal compound of the metal oxide of higher hydrocarbon to be dissolved in water, respectively with above-mentioned solution impregnation or soak altogether and dried by the fire in the carrier of getting well; Or the metal oxide that methane conversion can be become higher hydrocarbon or its corresponding compounds of mentioning in the alkali metal of tungstenic or phosphorus or alkaline earth metal compound and the claim 1 added in the gel that makes in the step (A).
The macerate or the gel that obtain in C, the drying steps (B).
The macerate or the gel that obtain in D, the calcination steps (C).
8, the preparation method described in claim 7 is characterized in that baking temperature is 60-150 ℃, and be 4-16 hour drying time.
9, the Preparation of catalysts method described in claim 7 is characterized in that dry preferred temperature is 100-110 ℃, and be to be advisable in 8-12 hour drying time.
10, the method for preparing catalyst described in claim 7 is characterized in that sintering temperature is 780-850 ℃, roasting time 2-6 hour.
11, the Preparation of catalysts method described in claim 10 is characterized in that the preferred temperature of roasting is 800-820 ℃, and roasting time was advisable with 2-4 hour.
12, a kind of process that methane conversion is become higher hydrocarbon (particularly ethene and ethane), it is characterized in that the gas of methane and molecule-containing keto is introduced into reaction system respectively in this process, and under 750-850 ℃ of temperature, contact with the catalyst that makes of arbitrary described method among the claim 1-11.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 91104243 CN1044094C (en) | 1991-06-20 | 1991-06-20 | Catalyst and process for changing methone intor high-level hydrocarbon |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 91104243 CN1044094C (en) | 1991-06-20 | 1991-06-20 | Catalyst and process for changing methone intor high-level hydrocarbon |
Publications (2)
Publication Number | Publication Date |
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CN1067831A true CN1067831A (en) | 1993-01-13 |
CN1044094C CN1044094C (en) | 1999-07-14 |
Family
ID=4906509
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CN 91104243 Expired - Fee Related CN1044094C (en) | 1991-06-20 | 1991-06-20 | Catalyst and process for changing methone intor high-level hydrocarbon |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1059609C (en) * | 1998-04-15 | 2000-12-20 | 浙江大学 | Catalyst for oxidation and coupling of sulfur-bearing methane to produce higher hydrocarbon and its preparation |
CN100431692C (en) * | 2004-09-06 | 2008-11-12 | 石油工业研究院 | Improved catalyst for direct conversion of methane to ethane and ethylene and conversion method |
CN102471181A (en) * | 2009-06-29 | 2012-05-23 | 弗纳技术股份有限公司 | Process for the oxidative coupling of methane |
WO2015101345A1 (en) * | 2014-01-02 | 2015-07-09 | 易高环保能源研究院有限公司 | Oxidative coupling of methane catalyst and preparation method for same |
CN103657640B (en) * | 2012-09-10 | 2015-09-16 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and methane oxidation coupling producing light olefins |
CN105170138A (en) * | 2014-05-29 | 2015-12-23 | 中国石油化工股份有限公司 | Methane oxidative coupling reaction catalyst and preparation method thereof |
CN114401788A (en) * | 2019-09-16 | 2022-04-26 | 切弗朗菲利浦化学公司 | Chromium-based catalysts and processes for converting alkanes to higher and lower aliphatic hydrocarbons |
CN115591563A (en) * | 2022-10-08 | 2023-01-13 | 华东师范大学(Cn) | Catalyst suitable for fluidized bed to perform methane oxidation coupling reaction and preparation method and application thereof |
Families Citing this family (1)
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KR101039604B1 (en) | 2009-06-04 | 2011-06-09 | 한국과학기술연구원 | Catalysts for Oxidative Coupling of Methane and Conversion Method of Methane using the Same Catalysts |
-
1991
- 1991-06-20 CN CN 91104243 patent/CN1044094C/en not_active Expired - Fee Related
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1059609C (en) * | 1998-04-15 | 2000-12-20 | 浙江大学 | Catalyst for oxidation and coupling of sulfur-bearing methane to produce higher hydrocarbon and its preparation |
CN100431692C (en) * | 2004-09-06 | 2008-11-12 | 石油工业研究院 | Improved catalyst for direct conversion of methane to ethane and ethylene and conversion method |
CN102471181A (en) * | 2009-06-29 | 2012-05-23 | 弗纳技术股份有限公司 | Process for the oxidative coupling of methane |
CN103657640B (en) * | 2012-09-10 | 2015-09-16 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and methane oxidation coupling producing light olefins |
WO2015101345A1 (en) * | 2014-01-02 | 2015-07-09 | 易高环保能源研究院有限公司 | Oxidative coupling of methane catalyst and preparation method for same |
CN105170138A (en) * | 2014-05-29 | 2015-12-23 | 中国石油化工股份有限公司 | Methane oxidative coupling reaction catalyst and preparation method thereof |
CN114401788A (en) * | 2019-09-16 | 2022-04-26 | 切弗朗菲利浦化学公司 | Chromium-based catalysts and processes for converting alkanes to higher and lower aliphatic hydrocarbons |
CN114401788B (en) * | 2019-09-16 | 2024-03-08 | 切弗朗菲利浦化学公司 | Chromium-based catalyst and process for converting alkanes to higher and lower aliphatic hydrocarbons |
CN115591563A (en) * | 2022-10-08 | 2023-01-13 | 华东师范大学(Cn) | Catalyst suitable for fluidized bed to perform methane oxidation coupling reaction and preparation method and application thereof |
CN115591563B (en) * | 2022-10-08 | 2024-04-23 | 华东师范大学 | Catalyst suitable for fluidized bed methane oxidative coupling reaction and preparation method and application thereof |
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