CN102580768B - 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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Publication number
CN102580768B
CN102580768B CN201210012654.7A CN201210012654A CN102580768B CN 102580768 B CN102580768 B CN 102580768B CN 201210012654 A CN201210012654 A CN 201210012654A CN 102580768 B CN102580768 B CN 102580768B
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ethane
catalyst
flow
tio
hcl
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CN102580768A (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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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
    • 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

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 low temperature making ethylene from ethane oxidative dehydrogenation and using method thereof
Technical field
The present invention relates to a kind of catalyst and using method thereof of low temperature making ethylene from ethane oxidative dehydrogenation, refer in particular to a kind of using method with the catalyst of good conversion ratio and good selectivity.
Background technology
Ethane is the main component of casing-head gas, natural gas, refinery exhaust, how by ethane Appropriate application, is the problem that domestic and international region of chemistry and petroleum chemical enterprise circle pay attention to.The research and development stage is still in particularly by ethane dehydrogenation to ethene process.At present, both at home and abroad with casing-head gas, the ethane in refinery gas is produced ethene and is still adopted traditional steam pyrolysis ethylene process process, at actual steam/alkane than under condition, ethane conversion is not high, secondly, the reaction time of cracking process is very short, and this brings difficulty with regard to giving the recycling of energy, moreover, the relatively large low-boiling by-products that cracking process produces, as hydrogen, methane etc., makes separation and the removal process complexity of ethene, and somewhat expensive.In addition, pyroreaction needs reacting furnace or the reactor of specific alloy, also makes equipment cost greatly improve.
Comparatively speaking, it is a simple exothermic reaction that ethane catalytic oxidative dehydrogenation produces ethene, and it is possible for reaching higher ethane conversion at a lower temperature, so just greatly reduces the energy consumption of process and simplifies lock out operation.The catalyst of oxidative dehydrogenation of ethane can be divided into low-temp reaction catalyst (about 500 DEG C) reaction temperature, high temperature reaction catalyst (> 800 DEG C).Carried out about low-temp reaction catalyst is existing both at home and abroad, US Patent No. 4524236 and US4596787 two patents, report Mo-V-Nb-X class catalyst, wherein X can be at least one in following elements: 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, this catalyst best result is at 450 DEG C, ethane conversion 50%, ethylene selectivity about 65%.The caltalyst of Chinese patent CN1121844A patent report is X-Y-Z-O or X-Y-Z-O/ carrier, wherein X is Li, Na, K, Rb, Cs at least one, Y can in some divalence, select in trivalent or variable valency metal element, can be at least one in these elements, these elements comprise La, Zr, Cr, Mo, Mn, Fe, Co, Ni, Pt, Pd, Cu, Zn, Cd, Al, Pb, Sn, Bi, in formula, Z is selected from least one in periodic table in alkaline-earth metal race, be selected from Be, Mg, Ca, Sr, Ba, carrier selects SiO 2, γ-Al 2o 3/ η-Al 2o 3, TiO 2, ZrO 2, wherein best catalyst system K-Mg-Zr-O is at 620 DEG C of ethane air speed 300h -1, ethane conversion is 58.45%, and ethylene selectivity is 71.7%.
In the patent document reported, reaction raw materials gas mostly is the gaseous mixture of ethane and oxygen, with inert gas as carrier gas, and seldom have directly using air and ethane as the report of reactor feed gas, as can be seen from existing report, the component of existing low temperature catalyst is comparatively complicated and not high to the conversion ratio of ethane, therefore this patent provides a kind of low temperature oxidative dehydrogenation of ethane catalyst, this method for preparing catalyst is simple, using air and ethane as reactor feed gas, there is higher ethane conversion and ethylene selectivity.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst and using method thereof of low temperature making ethylene from ethane oxidative dehydrogenation, prepare a kind of catalyst of the low temperature making ethylene from ethane oxidative dehydrogenation containing HCl gas, this catalyst application is reacted in making ethylene from ethane oxidative dehydrogenation, there is higher ethane conversion and ethylene selectivity.
Technical scheme of the present invention is as follows:
The catalyst of a kind of low temperature making ethylene from ethane oxidative dehydrogenation that content of the present invention relates to HCl gas for main active component, with TiO 2for co catalysis component.
Reactor is entered, the flow (ml/min) of HCl gas and TiO after the main active component HCl gas of the catalyst of described a kind of low temperature making ethylene from ethane oxidative dehydrogenation mixes 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 used in the catalyst of described a kind of low temperature making ethylene from ethane oxidative dehydrogenation is high-purity HCl gas.
The TiO used in the catalyst of described a kind of low temperature making ethylene from ethane oxidative dehydrogenation 2in order to below method obtain: butyl titanate and absolute ethyl alcohol by volume 1: 2 mix after, instill under the condition of vigorous stirring deionized water formation TiO 2precipitation, the volume of deionized water and the volume ratio of butyl titanate are 10: 1, stir after 4h filters precipitation and wash by deionized water, then wash with absolute ethyl alcohol, then wash by deionized water under normal temperature, washed TiO 2dry at 80 DEG C, grinding evenly at latter 600 DEG C roasting 4h can use; The TiO used in the catalyst of described a kind of low temperature making ethylene from ethane oxidative dehydrogenation 2also can obtain in order to below method: deionized water mixes according to the above ratio with butyl titanate and absolute ethyl alcohol mixed liquor, injects reactor and react 8h at 200 DEG C, then will precipitate TiO under normal temperature after stirring 1h 2leach, wash by deionized water, then wash with absolute ethyl alcohol, then wash by deionized water, washed TiO 2dry at 80 DEG C and can use.
The catalyst application of a kind of low temperature making ethylene from ethane oxidative dehydrogenation that the present invention describes, in the reaction of low temperature making ethylene from ethane oxidative dehydrogenation, obtains good result.Specific experiment operates: the active appraisal experiment of catalyst carries out in the quartz fixed bed reactor that internal diameter is 15mm, C in unstripped gas 2h 6(> 99%) and air mass flow ratio are 1: 5, and first ethane gas deviates from moisture by the drier that silica gel is housed, and hydrogen chloride gas is dry through 5A molecular sieve adsorption post; With the moisture in helium purge system and air before reaction, after then passing into hydrogen chloride gas activation half an hour, more logical ethane gas reacts.Heating rate is 6 DEG C/min, normal pressure, reaction temperature 440 DEG C-550 DEG C, and reacted gas passes into sodium hydroxide solution to carry out absorbing to remove hydrogen chloride gas, carries out product gas composition analysis by 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 technique is simple; Reaction temperature is lower, reduces energy resource consumption; With air as unstripped gas, with low cost; The catalyst prepared has good catalytic activity as the catalyst of low temperature making ethylene from ethane oxidative dehydrogenation, and yield of ethene is at 45%-75%.
Detailed description of the invention
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, reaction temperature 440 DEG C.
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, reaction temperature 460 DEG C.
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, reaction temperature 480 DEG C.
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, reaction temperature 500 DEG C.
Embodiment 5: measure 10mlC with graduated cylinder 16h 36o 4ti injects 20ml absolute ethyl alcohol, and vigorous stirring by the instillation of 100ml deionized water wherein, stirs 4h under normal temperature, washes after precipitation is filtered by deionized water, then wash with absolute ethyl alcohol, then wash by deionized water simultaneously, washed TiO 2dry at 80 DEG C, grinding evenly at latter 600 DEG C roasting 4h obtain co-catalyst TiO 2; 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, reaction temperature 440 DEG C.
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, reaction temperature 460 DEG C.
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, reaction temperature 480 DEG C.
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, reaction temperature 500 DEG C.
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, reaction temperature 500 DEG C.
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, reaction temperature 500 DEG C.
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, reaction temperature 500 DEG C.
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, reaction temperature 500 DEG C.
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, reaction temperature 440 DEG C.
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, reaction temperature 460 DEG C.
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, reaction temperature 480 DEG C.
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, reaction temperature 500 DEG C.
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, reaction temperature 440 DEG C.
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, reaction temperature 460 DEG C.
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, reaction temperature 480 DEG C.
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, reaction temperature 500 DEG C.
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, reaction temperature 500 DEG C.
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, reaction temperature 500 DEG C.
Embodiment 23: measure 10mlC with graduated cylinder 16h 36o 4ti injects 20ml absolute ethyl alcohol, and vigorous stirring by the instillation of 100ml deionized water wherein, is injected reactor and react 8h at 200 DEG C, then will precipitate TiO under normal temperature simultaneously after stirring 1h 2leach, wash by deionized water, then wash with absolute ethyl alcohol, then wash by deionized water, washed TiO 2dry at 80 DEG C and obtain TiO 2; 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, reaction temperature 500 DEG C.
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, reaction temperature 500 DEG C.
Embodiment 25:TiO 2preparation is with embodiment 23, and major catalyst HCl uses high-purity HCl (99.99%) flow 18ml/min, TiO 2consumption is lg, ethane flow 10ml/min, air mass flow 50ml/min, reaction temperature 500 DEG C.
Catalyst activity measures according to the methods below:
Reaction is carried out in quartz fixed bed reactor, and heating rate is 6 DEG C/min, normal pressure, and reacted gas passes into sodium hydroxide solution to carry out absorbing to remove hydrogen chloride gas, carries out product gas composition analysis by online gas-chromatography.The ethane conversion of the making ethylene from ethane oxidative dehydrogenation of catalyst obtained by patent of the present invention and ethylene selectivity and yield of ethene see the following form.

Claims (2)

1. a catalyst for low temperature making ethylene from ethane oxidative dehydrogenation, is characterized in that, catalyst with HCl gas for main active component, with TiO 2for co catalysis component, with air and ethane for reactor feed gas, enter reactor reaction after main active component HCl gas mixes with reactor feed gas, the flow (ml/min) of HCl gas and TiO 2quality (g) than being 1: 0.01-1: 3.
2. the catalyst of a kind of low temperature making ethylene from ethane oxidative dehydrogenation according to claim 1, it is characterized in that, the flow (ml/min) of described main catalytic component HCl gas is 1: 0.01-1: 2 with the best ratio of the quality (g) of co catalysis component titanium dioxide.
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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CN1391545A (en) * 1999-11-22 2003-01-15 陶氏化学公司 Process for vinyl chloride manufacture from ethane and ethylene with secondary reactive consumption of reactor effluent HCI

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* Cited by examiner, † Cited by third party
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CN1391545A (en) * 1999-11-22 2003-01-15 陶氏化学公司 Process for vinyl chloride manufacture from ethane and ethylene with secondary reactive consumption of reactor effluent HCI

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* Cited by examiner, † Cited by third party
Title
"湿天然气中乙烷氧化脱氢的研究II.过渡金属催化剂的研究";卢萍等;《石油与天然气化工》;19981231;第27卷(第1期);第4页及表1 *
"脂肪族化合物的工业合成";周鼎;《化学文摘》;19661231(第1期);第6.1.63节 *

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