CN102580768A - Novel catalyst for preparing ethylene by low-temperature oxidative dehydrogenation of ethane and using method thereof - Google Patents

Novel catalyst for preparing ethylene by low-temperature oxidative dehydrogenation of ethane and using method thereof Download PDF

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CN102580768A
CN102580768A CN2012100126547A CN201210012654A CN102580768A CN 102580768 A CN102580768 A CN 102580768A CN 2012100126547 A CN2012100126547 A CN 2012100126547A CN 201210012654 A CN201210012654 A CN 201210012654A CN 102580768 A CN102580768 A CN 102580768A
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ethane
catalyst
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oxidative dehydrogenation
tio
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CN102580768B (en
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胡瑞生
宋丽峰
秦丽婷
云振义
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Inner Mongolia University
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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
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Abstract

The invention aims at providing a novel catalyst for preparing ethylene by low-temperature oxidative dehydrogenation of ethane and a using method of the novel catalyst The catalyst takes HCl gas as a main active component and takes TiO2 as an auxiliary catalyzing component, the main active component (HCl gas) and reaction raw material gas (air and ethane) are mixed and then enter a reactor, and the reaction temperature is controlled to be 440-550 DEG C. The novel catalyst for preparing the ethylene by the low-temperature oxidative dehydrogenation of the ethane, disclosed by the invention, has the substantial advantages that the preparation method is simple in process, the reaction temperature is low, and the energy consumption is reduced; air is taken as a raw material gas, so that the cost is low; the prepared catalyst has good catalytic activity when used for preparing ethylene by low-temperature oxidative dehydrogenation of ethane, and the ethylene yield can reach 45-75%.

Description

A kind of catalyst of new type low temperature making ethylene from ethane oxidative dehydrogenation and method for using thereof
Technical field
The present invention relates to a kind of catalyst and method for using thereof of low temperature making ethylene from ethane oxidative dehydrogenation, refer in particular to a kind of have good conversion ratio and the good optionally method for using of catalyst.
Background technology
Ethane is the main component of casing-head gas, natural gas, refinery exhaust, how ethane is rationally utilized, and is the problem that domestic and international chemical boundary and petroleum chemical enterprise circle payes attention to.Especially still be in the research and development stage through the ethane dehydrogenation process of producing ethylene.At present, both at home and abroad with casing-head gas, the ethane in the refinery gas is produced ethene and is still adopted traditional steam pyrolysis system ethylene process process; Than under the condition, ethane conversion is not high at actual steam/alkane, secondly; The reaction time of cracking process is very short, and this brings difficulty with regard to the recycling of giving energy, moreover; More a large amount of low-boiling by-products such as hydrogen, methane etc. that cracking process produced make the separation of ethene and removal process complicated, and expensive.In addition, pyroreaction needs the reacting furnace or the agitated reactor of specific alloy, and equipment cost is improved greatly.
Comparatively speaking, it is a simple exothermic reaction that the ethane catalytic oxidative dehydrogenation is produced ethene, and it is possible reaching higher ethane conversion at a lower temperature, has so just reduced the energy consumption of process widely and has simplified lock out operation.The catalyst of oxidative dehydrogenation of ethane can be divided into low-temp reaction catalyst (about 500 ℃) on reaction temperature, high temperature reaction catalyst (＞800 ℃).Existing both at home and abroad institute carries out about low-temp reaction catalyst; U.S. Pat 4524236 and two patents of US4596787; Reported Mo-V-Nb-X class catalyst, wherein X can be down at least a in the column element: Li, Sc, Na, Be, Mg, Ca, Sr, Ba, Ti, Zr, Hf, Ta, Cr, Fe, Co, Ni, Ce, La, Zn, Cd, Hg, Al, Ti, Pb, As, Bi, Te, V and W, and this catalyst best result is at 450 ℃; Ethane conversion 50%, ethylene selectivity about 65%.The catalyst system of Chinese patent CN1121844A patent report is X-Y-Z-O or X-Y-Z-O/ carrier; Wherein X is that Li, Na, K, Rb, Cs are at least a; Y can be in some divalence, selects in trivalent or the variable valency metal element, can be at least a in these elements; These elements comprise La, Zr, Cr, Mo, Mn, Fe, Co, Ni, Pt, Pd, Cu, Zn, Cd, Al, Pb, Sn, Bi; Z is selected from the periodic table at least a in the alkaline-earth metal family in the formula, is selected from Be, Mg, Ca, Sr, Ba, and carrier is selected SiO for use 2, γ-Al 2O 3/ η-Al 2O 3, TiO 2, ZrO 2, wherein best catalyst system K-Mg-Zr-O is at 620 ℃ of ethane air speed 300h -1, ethane conversion is 58.45%, ethylene selectivity is 71.7%.
In the patent documentation of having reported; Mostly reaction raw materials gas is the gaseous mixture of ethane and oxygen,, and seldom has directly with air and the ethane report as reactor feed gas as carrier gas with inert gas; Can find out from existing report; The component of existing low temperature catalyst is comparatively complicated and not high to the conversion ratio of ethane, so this patent provides a kind of low temperature oxidative dehydrogenation of ethane catalyst, and this method for preparing catalyst is simple; As reactor feed gas, have higher ethane conversion and ethylene selectivity with air and ethane.
Summary of the invention
The technical problem that the present invention will solve provides a kind of catalyst and method for using thereof of low temperature making ethylene from ethane oxidative dehydrogenation; Prepared a kind of catalyst of low temperature making ethylene from ethane oxidative dehydrogenation of the HCl of containing gas; This catalyst applications is reacted in making ethylene from ethane oxidative dehydrogenation, have higher ethane conversion and ethylene selectivity.
Technical scheme of the present invention is following:
The catalyst of a kind of low temperature making ethylene from ethane oxidative dehydrogenation that content of the present invention relates to is main active component with HCl gas, with TiO 2For helping catalyst component.
The main active component HCl gas of the catalyst of described a kind of low temperature making ethylene from ethane oxidative dehydrogenation mixes the back and gets into reactor, flow of HCl gas (ml/min) and TiO with reactor feed gas (air and ethane) 2Quality (g) than being 1: 0-1: 3, the best is 1: 0.01-1: 2.
The HCl gas that uses in the catalyst of described a kind of low temperature making ethylene from ethane oxidative dehydrogenation is high-purity HCl gas.
The TiO that uses in the catalyst of described a kind of low temperature making ethylene from ethane oxidative dehydrogenation 2Make in order to the below method: butyl titanate splashes into deionized water and forms TiO with after absolute ethyl alcohol mixed in 1: 2 by volume under intense stirring condition 2Deposition, the volume of deionized water and the volume ratio of butyl titanate are 10: 1, normal temperature stirs down to be washed with deionized water after 4h filters deposition, washes with absolute ethyl alcohol then, washes washed TiO again with deionized water 280 ℃ of oven dry down, grinding evenly, back 600 ℃ of following roasting 4h can use; The TiO that uses in the catalyst of described a kind of low temperature making ethylene from ethane oxidative dehydrogenation 2Also can make in order to the below method: deionized water mixes with butyl titanate and absolute ethyl alcohol mixed liquor according to the above ratio, and normal temperature injects agitated reactor reaction 8h under 200 ℃ after stirring 1h down, will precipitate TiO then 2Leach, wash, wash with absolute ethyl alcohol then, wash with deionized water again, washed TiO with deionized water 2Can use 80 ℃ of following oven dry.
The catalyst applications of a kind of low temperature making ethylene from ethane oxidative dehydrogenation of the present invention's narration has obtained result preferably in the reaction of low temperature making ethylene from ethane oxidative dehydrogenation.Concrete experimental implementation: the activity of such catalysts evaluation experimental carries out C in the unstripped gas in internal diameter is the quartz fixed bed reactor of 15mm 2H 6(＞99%) and air mass flow ratio are 1: 5, and ethane gas is at first deviate from moisture through the drier that silica gel is housed, and hydrogen chloride gas is dry through 5A molecular sieve adsorption post; Before the reaction with moisture in the helium purge system and air, feed hydrogen chloride gas activation half an hour then after, lead to ethane gas again and react.Heating rate is 6 ℃/min, normal pressure, and 440 ℃-550 ℃ of reaction temperatures, reacted gas feeds sodium hydroxide solution and absorbs to remove hydrogen chloride gas, carries out the product gas composition analysis with online gas-chromatography.
The essential characteristics of the catalyst of low temperature making ethylene from ethane oxidative dehydrogenation provided by the invention is: method for preparing catalyst technology is simple; Reaction temperature is lower, has reduced energy resource consumption; , with low cost with air as unstripped gas; The catalyst of preparing has catalytic activity preferably as the catalyst of low temperature making ethylene from ethane oxidative dehydrogenation, and yield of ethene is at 45%-75%.
The specific embodiment
Embodiment 1: major catalyst HCl uses high-purity HCl (99.99%) flow 0ml/min, TiO 2Consumption is 0g, ethane flow 6ml/min, air mass flow 30ml/min, 440 ℃ of reaction temperatures.
Embodiment 2: major catalyst HCl uses high-purity HCl (99.99%) flow 0ml/min, TiO 2Consumption is 0g, ethane flow 6ml/min, air mass flow 30ml/min, 460 ℃ of reaction temperatures.
Embodiment 3: major catalyst HCl uses high-purity HCl (99.99%) flow 0ml/min, TiO 2Consumption is 0g, ethane flow 6ml/min, air mass flow 30ml/min, 480 ℃ of reaction temperatures.
Embodiment 4: major catalyst HCl uses high-purity HCl (99.99%) flow 0ml/min, TiO 2Consumption is 0g, ethane flow 6ml/min, air mass flow 30ml/min, 500 ℃ of reaction temperatures.
Embodiment 5: measure 10mlC with graduated cylinder 16H 36O 4Ti injects the 20ml absolute ethyl alcohol, and vigorous stirring splashes into the 100ml deionized water wherein simultaneously, and normal temperature stirs 4h down, filters the back to deposition and washes with deionized water, washes with absolute ethyl alcohol then, washes washed TiO again with deionized water 280 ℃ of oven dry down, grinding evenly, back 600 ℃ of following roasting 4h get co-catalyst TiO 2Major catalyst HCl uses high-purity HCl (99.99%) flow 0ml/min, TiO 2Consumption is 1g, ethane flow 6ml/min, air mass flow 30ml/min, 440 ℃ of reaction temperatures.
Embodiment 6:TiO 2Preparation is with embodiment 5, and major catalyst HCl uses high-purity HCl (99.99%) flow 0ml/min, TiO 2Consumption is 1g, ethane flow 6ml/min, air mass flow 30ml/min, 460 ℃ of reaction temperatures.
Embodiment 7:TiO 2Preparation is with embodiment 5, and major catalyst HCl uses high-purity HCl (99.99%) flow 0ml/min, TiO 2Consumption is 1g, ethane flow 6ml/min, air mass flow 30ml/min, 480 ℃ of reaction temperatures.
Embodiment 8:TiO 2Preparation is with embodiment 5, and major catalyst HCl uses high-purity HCl (99.99%) flow 0ml/min, TiO 2Consumption is 1g, ethane flow 6ml/min, air mass flow 30ml/min, 500 ℃ of reaction temperatures.
Embodiment 9: major catalyst HCl uses high-purity HCl (99.99%) flow 4ml/min, TiO 2Consumption is 0g, ethane flow 6ml/min, air mass flow 30ml/min, 500 ℃ of reaction temperatures.
Embodiment 10:TiO 2Preparation is with embodiment 5, and major catalyst HCl uses high-purity HCl (99.99%) flow 4ml/min, TiO 2Consumption is 0.5g, ethane flow 6ml/min, air mass flow 30ml/min, 500 ℃ of reaction temperatures.
Embodiment 11: major catalyst HCl uses high-purity HCl (99.99%) flow 8ml/min, TiO 2Consumption is 0g, ethane flow 10ml/min, air mass flow 50ml/min, 500 ℃ of reaction temperatures.
Embodiment 12:TiO 2Preparation is with embodiment 5, and major catalyst HCl uses high-purity HCl (99.99%) flow 8ml/min, TiO 2Consumption is 1g, ethane flow 10ml/min, air mass flow 50ml/min, 500 ℃ of reaction temperatures.
Embodiment 13: major catalyst HCl uses high-purity HCl (99.99%) flow 12ml/min, TiO 2Consumption is 0g, ethane flow 10ml/min, air mass flow 50ml/min, 440 ℃ of reaction temperatures.
Embodiment 14: major catalyst HCl uses high-purity HCl (99.99%) flow 12ml/min, TiO 2Consumption is 0g, ethane flow 10ml/min, air mass flow 50ml/min, 460 ℃ of reaction temperatures.
Embodiment 15: major catalyst HCl uses high-purity HCl (99.99%) flow 12ml/min, TiO 2Consumption is 0g, ethane flow 10ml/min, air mass flow 50ml/min, 480 ℃ of reaction temperatures.
Embodiment 16: major catalyst HCl uses high-purity HCl (99.99%) flow 12ml/min, TiO 2Consumption is 0g, ethane flow 10ml/min, air mass flow 50ml/min, 500 ℃ of reaction temperatures.
Embodiment 17:TiO 2Preparation is with embodiment 5, and major catalyst HCl uses high-purity HCl (99.99%) flow 12ml/min, TiO 2Consumption is 1g, ethane flow 10ml/min, air mass flow 50ml/min, 440 ℃ of reaction temperatures.
Embodiment 18:TiO 2Preparation is with embodiment 5, and major catalyst HCl uses high-purity HCl (99.99%) flow 12ml/min, TiO 2Consumption is 1g, ethane flow 10ml/min, air mass flow 50ml/min, 460 ℃ of reaction temperatures.
Embodiment 19:TiO 2Preparation is with embodiment 5, and major catalyst HCl uses high-purity HCl (99.99%) flow 12ml/min, TiO 2Consumption is 1g, ethane flow 10ml/min, air mass flow 50ml/min, 480 ℃ of reaction temperatures.
Embodiment 20:TiO 2Preparation is with embodiment 5, and major catalyst HCl uses high-purity HCl (99.99%) flow 12ml/min, TiO 2Consumption is 1g, ethane flow 10ml/min, air mass flow 50ml/min, 500 ℃ of reaction temperatures.
Embodiment 21:TiO 2Preparation is with embodiment 5, and major catalyst HCl uses high-purity HCl (99.99%) flow 12ml/min, TiO 2Consumption is 1g, ethane flow 15ml/min, air mass flow 75ml/min, 500 ℃ of reaction temperatures.
Embodiment 22: major catalyst HCl uses high-purity HCl (99.99%) flow 16ml/min, TiO 2Consumption is 0g, ethane flow 10ml/min, air mass flow 50ml/min, 500 ℃ of reaction temperatures.
Embodiment 23: measure 10mlC with graduated cylinder 16H 36O 4Ti injects the 20ml absolute ethyl alcohol, and vigorous stirring splashes into the 100ml deionized water wherein simultaneously, and normal temperature injects agitated reactor reaction 8h under 200 ℃ after stirring 1h down, will precipitate TiO then 2Leach, wash, wash with absolute ethyl alcohol then, wash with deionized water again, washed TiO with deionized water 2Oven dry obtains TiO2 under 80 ℃; Major catalyst HCl uses high-purity HCl (99.99%) flow 16ml/min, TiO 2Consumption is 1g, ethane flow 10ml/min, air mass flow 50ml/min, 500 ℃ of reaction temperatures.
Embodiment 24: major catalyst HCl uses high-purity HCl (99.99%) flow 18ml/min, TiO 2Consumption is 0g, ethane flow 10ml/min, air mass flow 50ml/min, 500 ℃ of reaction temperatures.
Embodiment 25:TiO 2Preparation is with embodiment 23, and major catalyst HCl uses high-purity HCl (99.99%) flow 18ml/min, TiO 2Consumption is 1g, ethane flow 10ml/min, air mass flow 50ml/min, 500 ℃ of reaction temperatures.
Catalyst activity is measured according to the methods below:
Be reflected in the quartz fixed bed reactor and carry out, heating rate is 6 ℃/min, and normal pressure, reacted gas feed sodium hydroxide solution and absorb to remove hydrogen chloride gas, carry out the product gas composition analysis with online gas-chromatography.The ethane conversion of the making ethylene from ethane oxidative dehydrogenation of the obtained catalyst of patent of the present invention and ethylene selectivity and yield of ethene see the following form.
Figure BSA00000658517000051

Claims (5)

1. the catalyst of a low temperature making ethylene from ethane oxidative dehydrogenation is characterized in that, this catalyst contains HCl gas and titanium dioxide.
2. the catalyst of a kind of low temperature making ethylene from ethane oxidative dehydrogenation according to claim 1 is characterized in that, this catalyst contains main catalytic component HCl gas and helps catalyst component titanium dioxide.
3. the catalyst of a kind of low temperature making ethylene from ethane oxidative dehydrogenation according to claim 1 is characterized in that, main active component HCl gas mixes the back and gets into reactor reaction with reactor feed gas (air and ethane).
4. the catalyst of a kind of low temperature making ethylene from ethane oxidative dehydrogenation according to claim 1 is characterized in that, the flow (ml/min) of described main catalytic component HCl gas and the quality (g) that helps catalyst component titanium dioxide are than being 1: 0-1: 3.
5. the catalyst of a kind of low temperature making ethylene from ethane oxidative dehydrogenation according to claim 1 is characterized in that, the flow (ml/min) of described main catalytic component HCl gas and the matter that helps catalyst component titanium dioxide (g) than being 1: 0.01-1: 2.
CN201210012654.7A 2012-01-17 2012-01-17 Novel catalyst for preparing ethylene by low-temperature oxidative dehydrogenation of ethane and using method thereof Expired - Fee Related CN102580768B (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN105080576A (en) * 2015-07-21 2015-11-25 清华大学 Method for activating MoVNbTeOx pure-phase M1 catalyst by utilizing plasma gas-solid phase method

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105080576A (en) * 2015-07-21 2015-11-25 清华大学 Method for activating MoVNbTeOx pure-phase M1 catalyst by utilizing plasma gas-solid phase method
CN105080576B (en) * 2015-07-21 2017-09-26 清华大学 A kind of method that utilization plasma gas solid method activates MoVNbTeOx pure phase M1 catalyst

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