CN101618319A - Efficient CrOx/mesoporous CaO catalyst for preparing isobutene by oxidative dehydrogenation of iso-butane and preparation method thereof - Google Patents
Efficient CrOx/mesoporous CaO catalyst for preparing isobutene by oxidative dehydrogenation of iso-butane and preparation method thereof Download PDFInfo
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- CN101618319A CN101618319A CN200810116139A CN200810116139A CN101618319A CN 101618319 A CN101618319 A CN 101618319A CN 200810116139 A CN200810116139 A CN 200810116139A CN 200810116139 A CN200810116139 A CN 200810116139A CN 101618319 A CN101618319 A CN 101618319A
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Abstract
The invention discloses an efficient CrOx/mesoporous CaO catalyst for preparing isobutene by oxidative dehydrogenation of iso-butane and a preparation method thereof, and belongs to the field of catalysis. The prior catalyst for preparing the isobutene by the oxidative dehydrogenation of the iso-butane has the problems of low isobutene selectivity and the like. The catalyst provided by the invention uses mesoporous CaO as a carrier and uses CrOx as an active component, wherein x is 1 to 3; and the loading capacity of the CrOx active component is 4 to 12 percent in percentage by mass of Cr2O3. The preparation method comprises the following steps: dissolving soluble chromium salt into anhydrous ethanol, then adding the solution into the mesoporous CaO carrier, stirring the mixture evenly, and drying the mixture for 12 hours at 120 DEG C to obtain white solid powder; and heating the white solid powder to 550 DEG C at the rate of 1 DEG C per minute in air atmosphere in a muffle furnace, and firing the heated white solid powder for 3 hours at constant temperature to obtain the CrOx/mesoporous CaO catalyst. The CrOx/mesoporous CaO catalyst prepared by the method has high isobutene selectivity and high activity, and the preparation method has low cost and simple and convenient operation.
Description
Technical field
The invention belongs to catalytic field, be specifically related to a kind of CrO of efficient producing isobutene from oxidative dehydrogenation of isobutane
x/ mesoporous CaO Catalysts and its preparation method.
Background technology
Isobutene is an important chemical material, the method for traditional preparing isobutene through dehydrogenation of iso-butane because of reaction temperature high and catalyst surface easily tie problem such as carbon and cause the low and easy inactivation of catalyst of its target product selectivity.Low-carbon alkanes oxidative dehydrogenation is a kind of exothermic reaction, can carry out at a lower temperature, again because the introducing of oxygen can be eliminated the knot carbon phenomenon of catalyst surface, thereby makes the strategy of producing isobutene from oxidative dehydrogenation of isobutane receive much concern.Yet under the oxygen existence condition, the deep oxidation reaction easily takes place in the target product (alkene) of isobutene for oxo-dehydrogenation reaction and raw material iso-butane, causes problems such as the selectivity of the waste of raw material and target product (alkene) is low.Therefore, it is significant to research and develop the catalyst of producing isobutene from oxidative dehydrogenation of isobutane of a kind of high conversion and high selectivity.Studies show that reaction has higher activity to the support type chromium oxide catalyst for isobutene for oxo-dehydrogenation.For example, Al-Zahrani etc. by the research iso-butane at CrO
x/ Al
2O
3Observe during oxidative dehydrogenation on the catalyst, when iso-butane/when the oxygen mol ratio is 4/1, at 10%CrO
x/ Al
2O
3In the time of 350 ℃, can obtain 5.8% isobutene yield on the catalyst, but selective isobutene is only up to 57.0%, the iso-butane conversion ratio be 10.1% (S.M.Al-Zahrani, et al., J.Mol.Catal.A, 2004,218:179-186).Hakuli etc. are at 11%CrO
x/ SiO
2In the time of 540 ℃, obtained higher isobutene yield (18%) on (in the mass fraction of Cr) catalyst, but selective isobutene lower (72%), and there is serious knot carbon phenomenon (mainly being) because due to the acid carrier silica, cause catalysqt deactivation (A.Hakuli, et al., J.Catal., 1999,184:349-356).
Basic supports is unfavorable for the absorption (promptly helping its desorption) of unsaturated hydrocarbons, thereby helps the raising of target product olefine selective.CaO is a kind of super base, and its alkalescence is far above MgO.Both at home and abroad catalyst has carried out certain research to being carrier with no hole body phase CaO.For example, methane and ethane are at La
2O
3/ CaO and SrO-La
2O
3The last catalytic oxidation of/CaO (L.Yu, et al., Appl.Catal.A, 1998,175:173-179), methane and ethane are at Na
+Last oxidative coupling of/CaO and oxidative dehydrogenation (A.Machocki, A.Denis, Chem.Eng.J., 2002,90:165-172), dimethyl ether is at SnO
2The last catalytic oxidation of/CaO produce corresponding hydrocarbon (L.Yu, et al., J.Natural Gas Chem., 2007,16:200-203), etc.And mesoporous CaO is except having superpower alkalescence, also has high-specific surface area, flourishing pore passage structure and than characteristics such as large pore volumes, helps active component and form the high degree of dispersion state on its surface, thereby improve the catalytic activity to oxidative dehydrogenation of hydrocarbons.But up to now, still there is not the report that relevant meso-pore calcium oxide is the chromium oxide catalyst of carrier.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, and a kind of CrO of efficient producing isobutene from oxidative dehydrogenation of isobutane is provided
x/ mesoporous CaO catalyst.
The CrO of efficient producing isobutene from oxidative dehydrogenation of isobutane provided by the present invention
x/ mesoporous CaO catalyst is to be carrier with the mesoporous CaO, with CrO
xBe active component, x is 1-3; In the catalyst, active component CrO
xLoad capacity with Cr
2O
3The quality percentage composition count 4-12%.
The present invention adopts immersion process for preparing CrO
x/ mesoporous CaO, concrete steps are as follows:
1) adopts the auxiliary synthesising mesoporous CaO carrier of hydro-thermal method of polyethylene glycol, promptly prepare mesoporous CaO (meso-CaO) carrier with reference to disclosed method among the CN101187055;
2) the solubility chromic salts is dissolved in the absolute ethyl alcohol suitable with the mesoporous CaO carrier bulk, wherein, the consumption of solubility chromic salts is (with Cr
2O
3Quality percentage composition meter) 4-12% of solubility chromic salts and mesoporous CaO carrier quality sum;
3) with step 2) in the solution of preparation add in the mesoporous CaO carrier for preparing in the step 1), after stirring,, obtain the white solid powder in 120 ℃ of dryings 12 hours;
4) with the white solid powder transfer to Muffle furnace, under air atmosphere, be warming up to 550 ℃ and constant temperature calcination 3 hours with the speed of 1 ℃/min, obtain CrO
x/ mesoporous CaO catalyst.
Compare with existing butane oxidation dehydrogenation preparing isobutene catalyst, the present invention has following beneficial effect:
The prepared catalyst of the present invention has meso-hole structure, and the aperture is 9.3-17.6nm, and catalyst surface contains the chromium (Cr that is high dispersion state
6+) species, have OR performance preferably; Air speed be 30000mL/ (gh), iso-butane/oxygen mol ratio be 1/2 and temperature be not higher than under 340 ℃ the reaction condition, selective isobutene is all more than 90%, and do not contain suitable-butylene, anti--butylene and 1,3-butadiene in the product mixtures; When reaction temperature is 500 ℃, 10%CrO
xSelective isobutene is 81% on the/mesoporous CaO catalyst, and the iso-butane conversion ratio is 10%, and corresponding isobutene yield is 8%.
Description of drawings
Fig. 1, prepared mesoporous CaO and the CrO of the present invention
xThe wide-angle XRD spectra of/mesoporous CaO catalyst; Wherein, (a) being the wide-angle XRD spectra of mesoporous CaO, (b) is the CrO of embodiment 1 preparation
xThe wide-angle XRD spectra of/mesoporous CaO catalyst (c) is the CrO of embodiment 2 preparations
xThe wide-angle XRD spectra of/mesoporous CaO catalyst (d) is the CrO of embodiment 3 preparations
xThe wide-angle XRD spectra of/mesoporous CaO catalyst.
Fig. 2, prepared mesoporous CaO and the CrO of the present invention
xThe SEM of/mesoporous CaO catalyst, TEM photo and SAED pattern; Wherein, (a) being the SEM photo of mesoporous CaO, (b) is the TEM photo and the SAED pattern (the built-in figure of Fig. 2 (b)) thereof of mesoporous CaO, (c) is the CrO of embodiment 2 preparations
xThe SEM photo of/mesoporous CaO catalyst (d) is the CrO of embodiment 2 preparations
xThe TEM photo of/mesoporous CaO catalyst and SAED pattern thereof (the built-in figure of Fig. 2 (d)).
Fig. 3, the prepared CrO of the present invention
xThe adsorption desorption curve and the graph of pore diameter distribution of/mesoporous CaO catalyst wherein, (A) are CrO
xThe adsorption desorption curve map of/mesoporous CaO catalyst; (B) be CrO
xThe graph of pore diameter distribution of/mesoporous CaO catalyst; (a) CrO of corresponding embodiment 1 preparation
x/ mesoporous CaO catalyst; (b) CrO of corresponding embodiment 2 preparations
x/ mesoporous CaO catalyst; (c) CrO of corresponding embodiment 3 preparations
x/ mesoporous CaO catalyst.
Fig. 4, the prepared CrO of the present invention
x/ mesoporous CaO catalyst is that 30000mL/ (gh) and iso-butane/oxygen mol ratio are under 1/2 the reaction condition in air speed, to the catalytic activity figure of isobutene for oxo-dehydrogenation reaction; Wherein, (A) be graph of a relation between selective isobutene and the reaction temperature; (B) be graph of a relation between iso-butane conversion ratio and the reaction temperature; (C) be graph of a relation between isobutene yield and the reaction temperature; (D) be C
1-C
3Graph of a relation between accessory substance selectivity and the reaction temperature; (E) be CO
xRelation between selectivity and the reaction temperature; The CrO of corresponding embodiment 1 preparation of curve (a)
x/ mesoporous CaO catalyst; (b) CrO of corresponding embodiment 2 preparations
x/ mesoporous CaO catalyst; (c) CrO of corresponding embodiment 3 preparations
x/ mesoporous CaO catalyst.
The invention will be further described below in conjunction with the drawings and specific embodiments.
The specific embodiment
With catalyst X-ray diffraction (XRD), the N for preparing among the following embodiment
2Adsorption-desorption (BET), SEM (SEM), transmission electron microscope (TEM) and SEAD technology such as (SAED) characterize, and the catalytic activity that adopts quartzy microreactor of fixed bed and gas chromatograph for determination catalyst that producing isobutene from oxidative dehydrogenation of isobutane is reacted.
1) prepares the mesoporous CaO carrier with reference to disclosed method among the CN101187055: the 3.1g polyethylene glycol is dissolved in the 120mL deionized water, add 2.24g CaO powder, transfer to after stirring under the room temperature from pressing in the still and placing baking oven, in 240 ℃ of hydrothermal treatment consists 72 hours, take out product and naturally cool to room temperature, through suction filtration, washing, dry, get white powder, white powder is put into Muffle furnace, rose to 600 ℃ and calcination 5 hours with the speed of 2 ℃/min from room temperature, obtain the CaO monocrystal particle of burrow-shaped mesopores cubic crystal structure, i.e. mesoporous CaO carrier, and in 100 ℃ of dryings 1 hour;
2) take by weighing the 0.4386g chromic nitrate, be dissolved in the absolute ethyl alcohol that equates with 2.0000g mesoporous CaO volume;
3) with step 2) in the solution of preparation add in the 2.0000g step 1) in the dried mesoporous CaO powder, after fully stirring, in 120 ℃ of dryings 12 hours, be transferred in the Muffle furnace after grinding the gained powder evenly, speed with 1 ℃/min under air atmosphere is warming up to 550 ℃ of constant temperature calcinations 3 hours, makes CrO
x/ mesoporous CaO catalyst, wherein, active component CrO
xLoad capacity with Cr
2O
3The quality percentage composition count 4%.
1) with embodiment 1 step 1);
2) take by weighing the 1.1700g chromic nitrate, be dissolved in the absolute ethyl alcohol that equates with 2.0000g mesoporous CaO volume;
3) with step 2) in the solution of preparation add in the 2.0000g step 1) in the dried mesoporous CaO powder, after fully stirring, in 120 ℃ of dryings 12 hours, be transferred in the Muffle furnace after grinding the gained powder evenly, speed with 1 ℃/min under air atmosphere is warming up to 550 ℃ of constant temperature calcinations 3 hours, makes CrO
x/ mesoporous CaO catalyst, wherein, active component CrO
xLoad capacity with Cr
2O
3The quality percentage composition count 10%.
1) with embodiment 1 step 1);
2) take by weighing the 1.4354g chromic nitrate, be dissolved in the absolute ethyl alcohol that equates with 2.0000g mesoporous CaO volume;
3) with step 2) in the solution of preparation add in the 2.0000g step 1) in the dried mesoporous CaO powder, after fully stirring, in 120 ℃ of dryings 12 hours, be transferred in the Muffle furnace after grinding the gained powder evenly, speed with 1 ℃/min under air atmosphere is warming up to 550 ℃ of constant temperature calcinations 3 hours, makes CrO
x/ mesoporous CaO catalyst, wherein, active component CrO
xLoad capacity with Cr
2O
3The quality percentage composition count 12%.
| Catalyst | Specific area (m 2/g) | Average pore size (nm) | Pore volume (cm 3/g) |
| Mesoporous CaO | ??79.1 | ??9.3 | ??0.20 |
| ??4％CrO x/ mesoporous CaO | ??35.9 | ??11.8 | ??0.11 |
| ??10％CrO x/ mesoporous CaO | ??34.3 | ??11.3 | ??0.10 |
| ??12％CrO x/ mesoporous CaO | ??13.8 | ??17.6 | ??0.06 |
Mesoporous CaO that table 1 the present invention is prepared and CrO
xThe specific area of/mesoporous CaO, average pore size and pore volume.
Claims (2)
1, a kind of CrO of efficient producing isobutene from oxidative dehydrogenation of isobutane
x/ mesoporous-CaO catalyst is characterized in that, described catalyst is to be carrier with the mesoporous CaO, with CrO
xBe active component, x is 1-3; In the catalyst, active component CrO
xLoad capacity with Cr
2O
3The quality percentage composition count 4-12%.
2, the CrO of efficient producing isobutene from oxidative dehydrogenation of isobutane according to claim 1
x/ mesoporous-CaO Preparation of catalysts method is characterized in that, may further comprise the steps:
1) adopts the auxiliary synthesising mesoporous CaO carrier of hydro-thermal method of polyethylene glycol;
2) the solubility chromic salts is dissolved in the absolute ethyl alcohol suitable with the mesoporous CaO carrier bulk, wherein, the consumption of solubility chromic salts is with Cr
2O
3The quality percentage composition count the 4-12% of solubility chromic salts and mesoporous CaO carrier quality sum;
3) with step 2) in the solution of preparation add in the mesoporous CaO carrier for preparing in the step 1), after stirring,, obtain the white solid powder in 120 ℃ of dryings 12 hours;
4) with the white solid powder transfer to Muffle furnace, under air atmosphere, be warming up to 550 ℃ and constant temperature calcination 3 hours with the speed of 1 ℃/min, obtain CrO
x/ mesoporous CaO catalyst.
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| CN2008101161397A CN101618319B (en) | 2008-07-04 | 2008-07-04 | Efficient CrOx/mesoporous CaO catalyst for preparing isobutene by oxidative dehydrogenation of iso-butane and preparation method thereof |
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|---|---|---|---|
| CN2008101161397A CN101618319B (en) | 2008-07-04 | 2008-07-04 | Efficient CrOx/mesoporous CaO catalyst for preparing isobutene by oxidative dehydrogenation of iso-butane and preparation method thereof |
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| CN101618319A true CN101618319A (en) | 2010-01-06 |
| CN101618319B CN101618319B (en) | 2012-05-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102794167A (en) * | 2012-06-15 | 2012-11-28 | 北京石油化工学院 | Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method for catalyst |
| CN103420768A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing isobutene from isobutane |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101138717A (en) * | 2007-09-07 | 2008-03-12 | 北京工业大学 | High activity Crox/mesoporous Ce0.6Zr0.35Y0.05O2 catalysts preparing method |
| CN100564613C (en) * | 2007-09-07 | 2009-12-02 | 北京工业大学 | A kind of preparation method of high specific surface area single-crystal meso-pore calcium oxide particle |
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2008
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420768A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing isobutene from isobutane |
| CN103420768B (en) * | 2012-05-16 | 2016-01-13 | 中国石油化工股份有限公司 | The method of Trimethylmethane preparing isobutene |
| CN102794167A (en) * | 2012-06-15 | 2012-11-28 | 北京石油化工学院 | Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method for catalyst |
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