CN105080596A - Isobutane oxidation dehydrogenation catalyst and preparation method and application method thereof - Google Patents
Isobutane oxidation dehydrogenation catalyst and preparation method and application method thereof Download PDFInfo
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Abstract
The invention relates to an isobutane oxidation dehydrogenation catalyst and a preparation method thereof, and mainly solves the problems of low activity and rapid inactivation of catalysts in the prior art in isobutane oxidation dehydrogenation. The isobutane oxidation dehydrogenation catalyst includes the following components by weight: a) 1-20% of Cr element or an oxide thereof; b) 0.1-12% of Li, Na, K, Rb, Cs elements or oxides thereof; c) 0.1-8% of Be, Mg, Ca element or oxides thereof; and d) ZSM-5 zeolite with the silica alumina ratio of 20-1000, and by the technical scheme, the problem is better solved.
Description
Technical field
The present invention relates to a kind of for isobutene for oxo-dehydrogenation Catalysts and its preparation method and use thereof.
Background technology
Low-carbon alkanes prepares by catalytic dehydrogenation process the focus of attention that corresponding alkene was stone chemical industry in the last few years always, has become one of the center of gravity and forward position of petrochemical industry research field.Isobutene is a kind of important Organic Chemicals, mainly for the preparation of methyl tertiary butyl ether (MTBE), butyl rubber, isoprene rubber, polyisobutene.In addition, it also can be used to various Organic Ingredients and the fine chemicals such as synthesizing methylmethacrylate (MMA), isoprene, BDO, tert-butylamine, tertiary butyl phenol, ABS resin.In traditional handicraft, the main source of isobutene is the accessory substance tert-butyl alcohol (TAB) in the by-product C 4 fraction of naphtha steam cracking ethylene unit, the by-product C 4 fraction of refinery's fluid catalytic cracking (FCC) device and the synthesis of Halcon method expoxy propane.Along with the exploitation of isobutene downstream product, the contradiction of global isobutene inadequate resource.The isobutene of traditional source can not satisfy the demands.Therefore, expand the source of isobutene, increase the output of isobutene, become the task of top priority of Global Oil development of chemical industry.Iso-butane is the accessory substance of oil plant, and mainly for the production of the cold-producing medium of replacement fluorine Leon, added value of product is low.After iso-butane is converted into isobutene, can value-added content of product be improved, increase the purposes of product.Therefore, the new technology of Development and Production isobutene becomes focus, utilizes abundance, to prepare isobutene be one of most promising method to cheap dehydrogenation of isobutane.The dehydrogenation of iso-butane alkane is a strong endothermic reaction, only under low pressure, hot conditions, just can obtain comparatively ideal olefin yields.Due to reasons such as reaction temperature is high, energy consumption is large, the easy coking and deactivations of catalyst, it is made to be very limited in the industrial production.Compared with iso-butane direct dehydrogenation preparing isobutene, the CO of iso-butane
2preparing isobutene by oxidative dehydrogenation thermodynamically advantageously.Adopt CO
2participate in reaction as mild oxidizer, not only can improve the selective of alkene, greenhouse gases CO can also be reduced
2discharge, realizes the trans-utilization of carbon resource;
Although relevant producing isobutene from oxidative dehydrogenation of isobutane research is more at present, the catalyst exploratory stage is still in for alkanes oxidative dehydrogenation reaction, realizes large-scale industrialization and still have any problem.Isobutene for oxo-dehydrogenation catalyst system mainly contains two classes: a class is vanadium base or catalyst with base of molybdenum, mainly V oxide or Mo oxide carried on carrier or they itself between and with the mixing of other oxides; An other class is chromium base catalyst system and catalyzing, mainly different additive modification or the Cr after adulterating
2o
3loaded catalyst.Compared with catalytic component based on vanadium, Cr
2o
3loaded catalyst activity is high, and stability is strong, lower to the requirement of the impurity in raw material, therefore causes more concern.CN101618319 once reported a kind of CrOx/ mesoporous CaO Catalysts and its preparation method of efficient producing isobutene from oxidative dehydrogenation of isobutane, catalyst take mesoporous CaO as carrier, take CrOx as active component (x is 1-3), iso-butane conversion ratio is only 10%, and conversion ratio is poor.According to current paper, Sun Guosong etc. at " catalysis journal " 2011, " the catalyst based catalysis CO of Cr of different carriers load delivered on 32 (8)
2oxidation preparing isobutene through dehydrogenation of iso-butane " in have studied isobutene for oxo-dehydrogenation process under carbon dioxide atmosphere on different carriers; investigated various factors affect catalyst performance; wherein on CrOx/MSU-1 catalyst; the maximum conversion of iso-butane and the yield of the highest isobutene are respectively 59.2% and 39.5%; but inactivation is rapidly, catalyst activity is poor.According to above-mentioned literature method self-control Cr/MSU-1 catalyst, the present inventor verify its selective only 51%.
Summary of the invention
One of technical problem to be solved by this invention is poor, the active lower problem of isobutene for oxo-dehydrogenation catalyst stability in prior art, provides a kind of catalyst for isobutene for oxo-dehydrogenation newly.The technical problem to be solved in the present invention two, is to provide a kind of method for preparing catalyst corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of isobutene for oxo-dehydrogenation catalyst, by weight percentage, comprises following component:
A) 1 ~ 20% Cr element or its oxide;
B) at least one be selected from Li, K, Na, Rb, Cs element or its oxide of 0.1 ~ 12%;
C) at least one be selected from Be, Mg, Ca element or its oxide of 0.1 ~ 8%;
D) silica alumina ratio is the molecular sieve of the ZSM-5 of 20 ~ 1000.
In technique scheme, by weight percentage, the preferable range of Cr element is 3 ~ 15%, the preferable range of Li, K, Na, Rb, Cs element is 0.5 ~ 10%, the preferable range of Be, Mg, Ca element is 0.5 ~ 5%, the silica alumina ratio preferable range of ZSM-5 is 100 ~ 400, and more preferably scope is 150 ~ 200.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of be used for isobutene for oxo-dehydrogenation Catalysts and its preparation method, comprises the following steps:
A) by ZSM-5 molecular sieve carrier compressing tablet, screening, choose 40 ~ 60 mesh sieves divide after carrier calcination process 0.5 ~ 12 hour under 400 ~ 600 DEG C of conditions, obtain ZSM-5 molecular sieve carrier I;
B) by carrier I and the aequum solubility solution containing Cr, the solubility solution containing Li, Na, K, Rb, Cs at least one element, be mixed into mixture I containing the solubility solution of Be, Mg, Ca at least one element, with inorganic ammonia or inorganic ammonium salt solution under temperature is 15 ~ 80 DEG C of conditions, the pH value regulating mixture I is 1 ~ 7, obtains mixture II;
C) under temperature is 15 ~ 100 DEG C of conditions, said mixture II is flooded 0.5 ~ 12 hour, then carry out filtering, dry, 300 ~ 800 DEG C of roastings 0.5 ~ 12 hour, obtain required isobutene for oxo-dehydrogenation catalyst.
In technique scheme, inorganic ammonia or inorganic ammonium salt preferred version are selected from ammoniacal liquor, ammonium carbonate or carbonic hydroammonium, and the pH value preferable range of solution is 1 ~ 7, and more preferably scope is 2 ~ 5; Dipping temperature preferable range is 50 ~ 80 DEG C, and dip time preferable range is 1 ~ 3 hour, and catalyst sintering temperature preferable range is 400 ~ 650 DEG C, and roasting time preferable range is 3 ~ 8 hours.
When isobutene for oxo-dehydrogenation catalyst is used for isobutene for oxo-dehydrogenation reaction, reaction temperature 500 ~ 600 DEG C, reaction pressure be 1 ~ 5 atmospheric pressure, gas space velocity is 10 ~ 2000 hours
-1condition under, isobutene for oxo-dehydrogenation is obtained by reacting isobutene.
Catalyst obtained as stated above carries out activity rating in isotherm formula fixed bed reactors, and for the evaluation of isobutene for oxo-dehydrogenation olefinic system, summary process is as follows:
Isobutene for oxo-dehydrogenation, for 80% carbon dioxide and 20% iso-butane gaseous mixture, by unstrpped gas by mass flowmenter adjust flux, enter pre-add hot-zone to mix, then enter reaction zone, the pre-add hot-zone of reactor and reaction zone all adopt electric-heating-wire-heating, make it to reach predetermined temperature, the internal diameter of reactor is the quartz ampoule of Ф 10mm-Ф 7mm, is about 450mm.Reacted gas, by after drainer, enters its composition of gas chromatographic analysis.
In isotherm formula fixed bed reactors, evaluating catalyst condition is as follows: it is (catalyst bed layer height is about 18mm) in the isothermal reactor of Ф 10mm-Ф 7mm that the catalyst of about 0.5 gram is loaded internal diameter, and reaction pressure is normal pressure, gas space velocity 870 hours
-1, reaction temperature 560 DEG C.
Iso-butane conversion ratio and selective isobutene calculate as follows:
Isobutene for oxo-dehydrogenation reacting phase is than the reaction of iso-butane direct dehydrogenation because its reaction raw materials is different, and reaction mechanism is also not quite similar, and is two diverse reaction systems, and isobutene for oxo-dehydrogenation reaction has more excellent stability.
In isobutene for oxo-dehydrogenation process, iso-butane can generate isobutene product, and isobutene is more active than iso-butane chemical property, further reaction easily occurs and loses, and carbon distribution reaction easily occurs on a catalyst, causing catalysqt deactivation.Therefore require that catalyst has fine dehydrogenation activity and stability.Simple Cr
2o
3/ ZSM-5 catalyst surface has comparatively highly acid, easily causes catalyst carbon deposition and deactivation rate is accelerated.Generally, along with the reduction of silica alumina ratio, sour bit density can increase, and therefore each sour position acid strength will reduce.When silica alumina ratio is 150 ~ 200, on ZSM-5 carrier, the acid strength of sour bit density and each sour position reaches optimal value, is conducive to the generation suppressing side reaction.For slowing down catalysqt deactivation speed, also improve catalyst performance by adding other auxiliary agent, also can reduce reaction temperature alleviates catalyst surface carbon distribution simultaneously.Adding of alkali and alkaline earth metal ions element can reduce its surface acidity, thus improves Cr series catalysts carbon accumulation resisting ability, improves catalyst performance.For the carbon dioxide oxidative dehydrogenation of raw material iso-butane, components b is worked as in catalyst) be K element or its oxide, simultaneously amount of component b) for Mg element or its oxide time, catalyst has optimum catalytic effect, reaction result display achieves good technique effect, its olefine selective reaches as high as 65%, achieves unforeseeable technique effect.Above-mentioned appreciation condition is adopted to be used for by catalyst of the present invention in isobutene for oxo-dehydrogenation reaction, its Activity evaluation shows, this catalyst has higher alkane conversion, comparatively can reach 66% under low reaction temperatures, there is higher olefine selective simultaneously, be greater than 60%, achieve good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 20, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, 0.03 gram of KNO
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.By normal butane, carbon dioxide, nitrogen mixed gas by mass flowmenter adjust flux, enter pre-add hot-zone to mix, then reaction zone is entered, the pre-add hot-zone of reactor and reaction zone all adopt electric-heating-wire-heating, make it to reach predetermined temperature, the internal diameter of reactor is the quartz ampoule of Ф 10mm-Ф 7mm, is about 450mm.Reacted gas, by after condenser, enters its composition of gas chromatographic analysis.
In isotherm formula fixed bed reactors, evaluating catalyst condition is as follows: loaded by 1 gram of catalyst (catalyst bed layer height 18mm) in above-mentioned isothermal fixed bed reactors, reaction pressure is normal pressure, reaction gas iso-butane, feed carbon dioxide volume flow ratio are 1:3, gas space velocity 750 hours
-1, reaction temperature 560 DEG C.It the results are shown in Table 1.
[embodiment 2]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 1000, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, 0.03 gram of KNO
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 2 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 3]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 100, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, 0.03 gram of KNO
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 4]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 400, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, 0.03 gram of KNO
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 5]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 150, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, 0.03 gram of KNO
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 6]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 200, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, 0.03 gram of KNO
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 7 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 7]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 100, add 5 ml deionized water, add 0.16 gram of Cr (NO
3)
3, 0.006 gram of KNO
3with 0.019 gram of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 8]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 100, add 5 ml deionized water, add 0.16 gram of Cr (NO
3)
3, 0.014 gram of LiNO
3with 0.019 gram of Mg (NO
3)
2, regulate solution ph to 5.5 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 9]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 150, add 10 ml deionized water, add 0.16 gram of Cr (NO
3)
3, 0.6 gram of KNO
3with 0.95 gram of Mg (NO
3)
2, regulate solution ph to 3.5 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 10]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 150, add 5 ml deionized water, add 0.16 gram of Cr (NO
3)
3, 1.3 grams of NaNO
3with 0.95 gram of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 50 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 11]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 200, add 10 ml deionized water, add 1.6 grams of Cr (NO
3)
3, 1.56 grams of NaNO
3with 1.52 grams of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 8 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 12]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 200, add 5 ml deionized water, add 1.6 grams of Cr (NO
3)
3, 0.72 gram of KNO
3with 0.72 gram of Ca (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 420 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 13]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 400, add 5 ml deionized water, add 2.37 grams of Cr (NO
3)
3, 0.03 gram of KNO
3with 0.09 gram of Ca (NO
3)
2, regulate solution ph to 4 with the sal volatile of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 14]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 400, add 10 ml deionized water, add 2.37 grams of Cr (NO
3)
3, 0.02 gram of CsNO
3with 0.08 gram of Be (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 8 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 15]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 1000, add 10 ml deionized water, add 3.16 grams of Cr (NO
3)
3, 0.3 gram of KNO
3with 0.57 gram of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 1 hour in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 8 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 16]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 1000, add 10 ml deionized water, add 3.16 grams of Cr (NO
3)
3, 0.18 gram of KNO
3with 0.95 gram of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 1 hour in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 8 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 17]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 20, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, 0.02 gram of CsNO
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 1 hour in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 8 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 18]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 20, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, 0.015 gram of KNO
3, 0.01 gram of CsNO
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 1 hour in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 8 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 19]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 20, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, 0.03 gram of KNO
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 2 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition is as follows: loaded in isothermal fixed bed reactors by 2 grams of catalyst, reaction pressure is normal pressure, and reaction gas iso-butane, feed carbon dioxide volume flow ratio are 1:3, gas space velocity 1500 hours
-1, reaction temperature 530 DEG C.It the results are shown in Table 2.
[embodiment 20]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 20, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, 0.03 gram of KNO
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 2 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition is as follows: loaded in isothermal fixed bed reactors by 0.5 gram of catalyst, reaction pressure is 0.3MPa, and reaction gas iso-butane, feed carbon dioxide volume flow ratio are 1:4, gas space velocity 375 hours
-1, reaction temperature 580 DEG C.It the results are shown in Table 2.
[embodiment 21]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 20, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, 0.03 gram of KNO
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 2 with the ammoniacal liquor of 3.0w.t.%, then flood after 2 hours in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition is as follows: loaded in isothermal fixed bed reactors by 1.5 grams of catalyst, reaction pressure is 0.5MPa, and reaction gas iso-butane, feed carbon dioxide volume flow ratio are 1:5, gas space velocity 1125 hours
-1, reaction temperature 600 DEG C.It the results are shown in Table 2.
[comparative example 1]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 150, add 0.47 gram of Cr (NO
3)
3with 0.095 gram of Mg (NO
3)
2, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 1 hour in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[comparative example 2]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 20, add 0.47 gram of Cr (NO
3)
3with 0.03 gram of KNO
3, regulate solution ph to 4 with the ammoniacal liquor of 3.0w.t.%, then flood after 1 hour in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
[comparative example 3]
Weigh the ZSM-5 carrier that 3 grams of silica alumina ratios are 100, add 5 ml deionized water, add 0.47 gram of Cr (NO
3)
3, regulate solution ph to 1.5 with the ammoniacal liquor of 3.0w.t.%, then flood after 1 hour in 70 DEG C of water-baths, take out sample to filter, in 110 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
Table 1
Table 2
Note: catalyst is Cr3%, K0.5%; Mg0.5%.
Claims (10)
1. for a catalyst for isobutene for oxo-dehydrogenation, by weight percentage, comprise following component:
A) 1 ~ 20% Cr or its oxide;
B) at least one be selected from Li, Na, K, Rb, Cs element or its oxide of 0.1 ~ 12%;
C) at least one be selected from Be, Mg, Ca element or its oxide of 0.1 ~ 8%;
D) 60 ~ 98.8% silica alumina ratios are the molecular sieve of the ZSM-5 of 20 ~ 1000.
2. according to claim 1 for isobutene for oxo-dehydrogenation catalyst, it is characterized in that by weight percentage, the content of chromium or its oxide accounts for 3 ~ 15%.
3. according to claim 1 for the catalyst of isobutene for oxo-dehydrogenation, it is characterized in that by weight percentage, the content of Li, Na, K, Rb, Cs element or its oxide accounts for 0.5 ~ 10%.
4. according to claim 1 for the catalyst of isobutene for oxo-dehydrogenation, it is characterized in that weight percent meter, the content of Be, Mg, Ca element or its oxide accounts for 0.5 ~ 5%.
5., according to claim 1 for the catalyst of isobutene for oxo-dehydrogenation, it is characterized in that the silica alumina ratio of ZSM-5 is 100 ~ 400.
6., according to claim 5 for the catalyst of isobutene for oxo-dehydrogenation, it is characterized in that the silica alumina ratio of ZSM-5 is 150 ~ 200.
7. described in claim 1 for the preparation method of isobutene for oxo-dehydrogenation catalyst, comprise the following steps successively:
A) by ZSM-5 molecular sieve carrier calcination process 0.5 ~ 12 hour under 400 ~ 650 DEG C of conditions, ZSM-5 carrier I is obtained;
B) by carrier I and the aequum solubility solution containing Cr, the solubility solution containing Li, Na, K, Rb, Cs at least one element, be mixed into mixture I containing the solubility solution of Be, Mg, Ca at least one element, with inorganic ammonia or inorganic ammonium salt solution under temperature is 15 ~ 80 DEG C of conditions, the pH value regulating mixture I is 1 ~ 7, obtains mixture II;
C) under temperature is 15 ~ 100 DEG C of conditions, said mixture II is flooded 0.5 ~ 12 hour, then carry out suction filtration, drying, 300 ~ 800 DEG C of roastings 0.5 ~ 12 hour, obtain required isobutene for oxo-dehydrogenation catalyst.
8. the preparation method of isobutene for oxo-dehydrogenation catalyst according to claim 7, it is characterized in that the solubility solution of Cr is selected from chromic nitrate, chromium acetate, chromic acid one or more; The solubility solution of K be selected from potassium nitrate, potash, potassium chloride one or more; The solubility solution of Mg to be selected from magnesium nitrate, magnesium chloride one or more.
9. the method for an isobutene for oxo-dehydrogenation, take iso-butane as raw material, one in oxygen, carbon dioxide, carbon monoxide is oxidant, under nitrogen carrier gas, enter reactor, and reaction temperature 500 ~ 600 DEG C, reaction pressure are 1 ~ 5 atmospheric pressure, volume space velocity is 10 ~ 2000 hours
-1, raw material obtains isobutene with oxidant reaction under catalyst action described in any one of claim 1-6.
10. the method for isobutene for oxo-dehydrogenation according to claim 9, is characterized in that the volume ratio of iso-butane and oxidant is 1:3 ~ 1:5.
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