CN102294251B - Nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof - Google Patents
Nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof Download PDFInfo
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- CN102294251B CN102294251B CN2011101476187A CN201110147618A CN102294251B CN 102294251 B CN102294251 B CN 102294251B CN 2011101476187 A CN2011101476187 A CN 2011101476187A CN 201110147618 A CN201110147618 A CN 201110147618A CN 102294251 B CN102294251 B CN 102294251B
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Abstract
A nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and a preparation method thereof. The invention relates to an oxide catalyst. The nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane is composed of an active component, an essential modification component and a non-essential modification component, wherein the active component contains nickel oxide or cobaltosic oxide and the like; the essential modification component contains a metal sulfate; and the non-essential modification component contains one selected from the group consisting of alkaline earth oxide, rare-earth oxide, niobium oxide, zirconia, molybdena and the like. The preparation method provided by the invention comprises the following steps of: dissolving nicdel nitrate or cobalt nitrate into water, adding ammonium sulfate or nickel sulfate after dissolving so as to obtain a mixed solution; dissolving citric acid into water to obtain a citric acid solution, adding the mixed solution into the citric acid solution, stirring until the solution becomes a gel, drying, roasting, and granulating to obtain the nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane. According to the invention, the reaction condition is mild, the catalytic performance of the product is good, and the cost is low.
Description
Technical field
The present invention relates to a kind of oxide catalyst, especially relate to a kind of nano-oxide catalyst and preparation method of preparing propene by oxidative dehydrogenation of propane.
Background technology
Propylene is the very important petrochemical industry basic material that is only second to ethene, is widely used in producing the serial important chemical products such as polypropylene, acrylonitrile, phenol, oxo alcohol, expoxy propane and acrylic acid.At present, the supply of propylene mainly comes from the byproduct of naphtha pyrolysis ethene processed and catalytic cracking process, and the critical shortage of petrochemical industry resource is so that this technique is difficult to satisfy growing demand; Thermodynamics is limited, operating temperature is high, the shortcoming of the easy inactivation of catalyst and exist by the dehydrogenating propane preparing propone.If in the dehydrogenating propane raw material, introduce a small amount of oxygen (oxidative dehydrogenation), can not only reduce reaction temperature, and catalyst is difficult for inactivation, so preparing propene by oxidative dehydrogenation of propane obtains domestic and international researcher's very big concern in recent years.
The catalyst of existing preparing propene by oxidative dehydrogenation of propane is mainly vanadium base, molybdenum base, rare earth based and nickel-base catalyst.The conversion of propane of V/MCF catalyst in the time of 550 ℃ is 40.8%, and that propylene selectively is 68.5% ([1] Y.M.Liu, W.L.Feng, T.C.Li, H.Y.He at this moment, W.L.Dai, W.Huang, Y.Cao, K.N.Fan, J.Catal., 2006,239,125-136).The conversion of propane of Ni-Mo-O in the time of 500 ℃ is 22%, Propylene Selectivity be 63% ([2] O.Lezla, E.Bordes, P.Courtine, G.Hecquet, J.Catal., 1997,170,346-356).The catalyst with optimum performance of having reported is 3wt%Cs
2O/2CeO
2-CeF
3, the conversion of propane in the time of its 500 ℃ is 53.4%, Propylene Selectivity is 67.5% ([3] H.L.Wan, X.P.Zhou, W.Z.Weng, R.Q.Long, Z.S.Chao, W.D.Zhang, M.S.Chen, J.Z.Luo, S.Q.Zhou, Catal.Today, 1999,51-161).But above-mentioned catalyst all carries out under higher reaction temperature.
Nickel-base catalyst is the oxidative dehydrogenation of propane catalyst that the class reported in recent years has better low-temperature catalytic activity.Chinese patent CN 1557546A discloses the nano-composite catalyst of a kind of Ce of containing, Ni, and when reaction temperature was 300 ℃, conversion of propane was 52%, and Propylene Selectivity is 31.7%.Although this catalyst has higher low-temperature catalytic activity, its Propylene Selectivity is lower.Chinese patent CN 101543781A discloses a kind of oxidative dehydrogenation of propane nickel-base catalyst and preparation method thereof: take anion surfactant and non-ionic surface active agent as template, urea etc. are precipitating reagent, adopt hydrothermal synthesis method to prepare Ni-based composite oxides, wherein the Ni-Ce-O catalyst is when 450 ℃ of reactions, conversion of propane is 27.8%, and propene yield reaches 15.1%.But catalyst prepares that needed raw material is more, price is higher, and the preparation method is comparatively loaded down with trivial details.So far, the oxidative dehydrogenation of propane nickel-base catalyst generally is take NiO as main active component, add alkali metal, alkaline-earth metal, rare earth metal or other transition metal oxide and carry out modulation, but the research of relevant anion modulation NiO catalyst there is not yet report.
Summary of the invention
The object of the present invention is to provide that a kind of reaction condition is gentle, catalytic performance is better and nano-oxide catalyst and the preparation method of lower-cost preparing propene by oxidative dehydrogenation of propane.
The nano-oxide catalyst of described preparing propene by oxidative dehydrogenation of propane is comprised of a kind of active component, essential modification component and nonessential modification component, and described active component is nickel oxide or cobaltosic oxide etc.; Described essential modification component is metal sulfate; Described nonessential modification component is selected from a kind of in alkaline earth oxide, rare-earth oxide, niobium oxide, zirconia, the molybdenum oxide etc.; By mass percentage, essential modification component is 0.5%～35%, and nonessential modification component is 0～20%, and remaining is active component; Preferably by mass percentage, essential modification component is 0.5%～30%, and nonessential modification component is 0～15%, and remaining is active component;
The preparation method of the nano-oxide catalyst of described preparing propene by oxidative dehydrogenation of propane may further comprise the steps:
1) nickel nitrate or cobalt nitrate is soluble in water, add ammonium sulfate or nickelous sulfate after the dissolving, get mixed solution;
2) citric acid is soluble in water, get citric acid solution;
3) with step 1) mixed solution that makes joins step 2) in the gained citric acid solution, be stirred to gel after, drying, roasting, granulation gets the nano-oxide catalyst of preparing propene by oxidative dehydrogenation of propane.
In step 2) in, the mol ratio of the consumption of the consumption of described citric acid and nickel nitrate or cobalt nitrate can be 0.5～2.
In step 3) in, the temperature of described stirring can be 50～100 ℃; The temperature of described drying can be 70～110 ℃, and the dry time can be 15～30h; The temperature of described roasting can be 300～600 ℃, and heating rate is 1 ℃/min, and the time of roasting can be 1～6h.
Raw material of the present invention is cheap and easy to get, and preparation technology is simple, and catalytic performance is stable, is applicable to large-scale production.This catalyst can be used for preparing propene by oxidative dehydrogenation of propane at a lower temperature, and higher catalytic activity and Propylene Selectivity are arranged.
Description of drawings
Fig. 1 is the X-ray diffraction powder spectrogram of the embodiment of the invention 1 sample.In Fig. 1, abscissa is angle of diffraction 2Theta (degree), and ordinate is diffracted intensity Intensity (a.u.).
Fig. 2 is the FT-IR spectrogram of the embodiment of the invention 1 sample.In Fig. 2, abscissa is wavelength wavenumber (cm
-1), ordinate is light transmittance Transmittance (%).
The specific embodiment
The present invention is further illustrated in connection with accompanying drawing for following examples, but the present invention is not limited to these embodiment.
Catalyst preparation: at room temperature the 5.81g Nickelous nitrate hexahydrate is dissolved in the 20ml deionized water, adds 0.066g ammonium sulfate after the dissolving; The 4.2028g monohydrate potassium is dissolved in the 20ml deionized water; Under stirring the former is added dropwise among the latter, 70 ℃ are continued to be stirred to the solution gel, 110 ℃ of lower dry 24h, and the speed of 1 ℃/min is warmed up to 400 ℃, and then at 400 ℃ of lower roasting 4h, aftershaping to be lowered the temperature is 40～80 order particles.
Make the X-ray diffraction coatings of sample referring to Fig. 1, make the FT-IR figure of sample referring to Fig. 2.In Fig. 1, the crystalline phase diffraction maximum of nickel oxide has only appearred.In Fig. 2,548cm
-1The stretching vibration that the absworption peak correspondence at place the Ni-O key, 800-1200cm
-1Absworption peak in the wave band can belong to and Ni
2+Interactional O-S-O, O=S=O stretching vibration.Fig. 1 shows that the main phase of this catalyst is nickel oxide, and Fig. 2 shows that sulfur species exists with the form of sulfate radical in this catalyst.
The examination condition: carry out in atmospheric fixed bed quartz reactor, reaction gas forms C
3H
8: O
2: N
2=1.2: 1: 8, air speed was 30000ml.h
-1.g
-1, catalyst amount 0.1g, the catalyst volume ratio is 1: 1 quartz sand dilution, investigates the reactivity worth under the different temperatures.
The appraisal result of the catalyst performance under the differential responses temperature sees Table 1.
Catalyst performance under the table 1. differential responses temperature
The catalyst preparation is changed to 0.0264g ammonium sulfate with reference to embodiment 1 with the 0.066g ammonium sulfate in the first step, and all the other conditions are identical.The examination condition is with reference to embodiment 1, and when reaction temperature was 375 ℃, conversion of propane was 25.0%, and Propylene Selectivity is 45.5%, and propene yield is 11.4%.
Embodiment 3
The catalyst preparation is changed to 0.132g ammonium sulfate with reference to embodiment 1 with the 0.066g ammonium sulfate in the first step, and all the other conditions are identical.The examination condition is with reference to embodiment 1, and when reaction temperature was 400 ℃, conversion of propane was 25.2%, and Propylene Selectivity is 47.8%, and propene yield is 12.0%.
Embodiment 4
The catalyst preparation is changed to 0.198g ammonium sulfate with reference to embodiment 1 with the 0.066g ammonium sulfate in the first step, and all the other conditions are identical.The examination condition is with reference to embodiment 1, and when reaction temperature was 400 ℃, conversion of propane was 24.9%, and Propylene Selectivity is 47.0%, and propene yield is 11.7%.
Embodiment 5
Catalyst preparation: at room temperature the 5.81g Nickelous nitrate hexahydrate is dissolved in the 10ml deionized water, adds 0.066g ammonium sulfate after the dissolving; The 4.2028g monohydrate potassium is dissolved in the 15ml deionized water; Stir and lower the former to be added dropwise among the latter, continue to be stirred to the solution gel under 70 ℃, 110 ℃ of lower dry 24h, the speed of 1 ℃/min is warmed up to 400 ℃, and then at 400 ℃ of lower roasting 4h, aftershaping to be lowered the temperature is 40～80 order particles.
The examination condition is with reference to embodiment 1, and when reaction temperature was 375 ℃, conversion of propane was 25.0%, and Propylene Selectivity is 47.2%, and propene yield is 11.8%..
Embodiment 6
The catalyst preparation is changed to the 0.2630g nickelous sulfate with reference to embodiment 5 with the 0.066g ammonium sulfate in the first step, and all the other conditions are identical.The examination condition is with reference to embodiment 1, and when reaction temperature was 400 ℃, conversion of propane was 24.7%, and Propylene Selectivity is 47.0%, and propene yield is 11.6%.
Embodiment 7
Catalyst preparation: at room temperature the 5.81g Nickelous nitrate hexahydrate is dissolved in the 10ml deionized water, adds again 0.066g ammonium sulfate and 0.4342g cerous nitrate, stirring and dissolving; The 4.2028g monohydrate potassium is dissolved in the 15ml deionized water; Under stirring the former is added dropwise among the latter, 70 ℃ are continued to be stirred to the solution gel, 110 ℃ of lower dry 24h, and the speed of 1 ℃/min is warmed up to 400 ℃, and then at 400 ℃ of lower roasting 4h, aftershaping to be lowered the temperature is 40～80 order particles.
The examination condition is with reference to embodiment 1, and when reaction temperature was 350 ℃, conversion of propane was 24.8%, and Propylene Selectivity is 46.2%, and propene yield is 11.5%.
Embodiment 8
The catalyst preparation is changed to the 0.3030g ammonium niobium oxalate with reference to embodiment 7 with the 0.4342g cerous nitrate in the first step, and all the other conditions are identical.The examination condition is with reference to embodiment 1, and when reaction temperature was 375 ℃, conversion of propane was 24.2%, and Propylene Selectivity is 52.5%, and propene yield is 12.7%.
Embodiment 9
The catalyst preparation is changed to the 0.2564g magnesium nitrate with reference to embodiment 7 with the 0.4342g cerous nitrate in the first step, and all the other conditions are identical.The examination condition is with reference to embodiment 1, and when reaction temperature was 400 ℃, conversion of propane was 25.7%, and Propylene Selectivity is 47.8%, and propene yield is 12.3%.
The catalyst preparation is changed to the 0.2116g strontium nitrate with reference to embodiment 7 with the 0.4342g cerous nitrate in the first step, and all the other conditions are identical.The examination condition is with reference to embodiment 1, and when reaction temperature was 350 ℃, conversion of propane was 25.0%, and Propylene Selectivity is 44.9%, and propene yield is 11.2%.
Embodiment 11
The catalyst preparation is changed to the 0.420g zirconium nitrate with reference to embodiment 7 with the 0.4342g cerous nitrate in the first step, and all the other conditions are identical.The examination condition is with reference to embodiment 1, and when reaction temperature was 400 ℃, conversion of propane was 9.2%, and Propylene Selectivity is 70.3%, and propene yield is 6.5%.
Embodiment 12
The catalyst preparation is changed to the 0.0352g ammonium molybdate with reference to embodiment 7 with the 0.4342g cerous nitrate in the first step, and all the other conditions are identical.The examination condition is with reference to embodiment 1, and when reaction temperature was 400 ℃, conversion of propane was 26.3%, and Propylene Selectivity is 49.9%, and propene yield is 13.1%.
Embodiment 13
The catalyst preparation is changed to the 5.81g cobalt nitrate with reference to embodiment 1 with the 5.81g nickel nitrate in the first step, and all the other conditions are identical.The examination condition is with reference to embodiment 1, and when reaction temperature was 400 ℃, conversion of propane was 21.6%, and Propylene Selectivity is 33.1%, and propene yield is 7.2%.
Reference examples 1
Catalyst preparation: at room temperature the 5.81g Nickelous nitrate hexahydrate is dissolved in the 20ml deionized water; The 4.2028g monohydrate potassium is dissolved in the 20ml deionized water; Stir and lower the former to be added dropwise among the latter, continue to be stirred to the solution gel under 70 ℃, 110 ℃ of lower dry 24h, the speed of 1 ℃/min is warmed up to 400 ℃, and then at 400 ℃ of lower roasting 4h, aftershaping to be lowered the temperature is 40～80 order particles.
The examination condition is with reference to embodiment 1, sees Table 2 without the appraisal result of dressing agent nickel oxide catalyst different temperatures reactivity worth.
Table 2. is without dressing agent nickel oxide catalyst different temperatures reactivity worth
Reference examples 2
Catalyst preparation: at room temperature the 5.25g six hydration nickel sulfate is dissolved in the 20ml deionized water; The 4.2028g monohydrate potassium is dissolved in the 20ml deionized water; Stir and lower the former to be added dropwise among the latter, continue to be stirred to the solution gel under 70 ℃, 110 ℃ of lower dry 24h, the speed of 1 ℃/min is warmed up to 400 ℃, and then at 400 ℃ of lower roasting 4h, aftershaping to be lowered the temperature is 40～80 order particles.
The examination condition is with reference to embodiment 1, and the appraisal result of Catalyzed by Nickel Sulfate agent different temperatures reactivity worth sees Table 3.
Table 3. Catalyzed by Nickel Sulfate agent different temperatures reactivity worth
Reference examples 3
The catalyst preparation is changed to the 5.81g cobalt nitrate with reference to reference examples 1 with the 5.81g nickel nitrate in the first step, and all the other conditions are identical.The examination condition is with reference to embodiment 1, sees Table 4 without the appraisal result of dressing agent cobalt/cobalt oxide catalyst different temperatures reactivity worth.
Table 4. is without dressing agent cobalt/cobalt oxide catalyst different temperatures reactivity worth
Claims (6)
1. the nano-oxide catalyst of a preparing propene by oxidative dehydrogenation of propane is characterized in that being comprised of a kind of active component, essential modification component and nonessential modification component, and described active component is nickel oxide or cobaltosic oxide; Described essential modification component is metal sulfate; Described nonessential modification component is selected from a kind of in alkaline earth oxide, rare-earth oxide, niobium oxide, zirconia, the molybdenum oxide; By mass percentage, essential modification component is 0.5%～35%, and nonessential modification component is 0～20%, and remaining is active component.
2. the nano-oxide catalyst of a kind of preparing propene by oxidative dehydrogenation of propane as claimed in claim 1 is characterized in that by mass percentage, and essential modification component is 0.5%～30%, and nonessential modification component is 0～15%, and remaining is active component.
3. the preparation method of the nano-oxide catalyst of a kind of preparing propene by oxidative dehydrogenation of propane as claimed in claim 1 is characterized in that may further comprise the steps:
1) nickel nitrate or cobalt nitrate is soluble in water, add ammonium sulfate or nickelous sulfate after the dissolving, get mixed solution;
2) citric acid is soluble in water, get citric acid solution; The mol ratio of the consumption of the consumption of described citric acid and nickel nitrate or cobalt nitrate is 0.5～2;
3) mixed solution that step 1) is made joins step 2) in the gained citric acid solution, be stirred to gel after, drying, roasting, granulation gets the nano-oxide catalyst of preparing propene by oxidative dehydrogenation of propane.
4. the preparation method of the nano-oxide catalyst of a kind of preparing propene by oxidative dehydrogenation of propane as claimed in claim 3 is characterized in that in step 3), and the temperature of described stirring is 50～100 ℃.
5. the preparation method of the nano-oxide catalyst of a kind of preparing propene by oxidative dehydrogenation of propane as claimed in claim 3 is characterized in that in step 3), and the temperature of described drying is 70～110 ℃, and the dry time is 15～30h.
6. the preparation method of the nano-oxide catalyst of a kind of preparing propene by oxidative dehydrogenation of propane as claimed in claim 3 is characterized in that in step 3), and the temperature of described roasting is 300～600 ℃, and heating rate is 1 ℃/min, and the time of roasting is 1～6h.
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| CN105013488A (en) * | 2014-04-15 | 2015-11-04 | 中国石化扬子石油化工有限公司 | Mesoporous carbon loaded Co3O4 catalyst, preparation and applications thereof |
| CN110614116A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation |
| CN112808294B (en) * | 2021-01-05 | 2023-02-17 | 中国石油大学(华东) | Boron nitride/nickel oxide composite material and preparation method and application thereof |
| CN113955810B (en) * | 2021-10-20 | 2023-06-13 | 西安交通大学 | Self-assembled sea urchin-shaped cobaltosic oxide, and preparation method and application thereof |
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|---|---|---|---|---|
| CN1557546A (en) * | 2004-01-16 | 2004-12-29 | 复旦大学 | Composite oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof |
| US20070197378A1 (en) * | 1999-02-22 | 2007-08-23 | Yumin Liu | Ni catalysts and methods for alkane dehydrogenation |
| CN101219389A (en) * | 2007-12-26 | 2008-07-16 | 厦门大学 | Solid catalyst for propylene manufacture with propane oxo-dehydrogenation and method for producing the same |
| CN101543781A (en) * | 2009-05-04 | 2009-09-30 | 厦门大学 | Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof |
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Patent Citations (4)
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|---|---|---|---|---|
| US20070197378A1 (en) * | 1999-02-22 | 2007-08-23 | Yumin Liu | Ni catalysts and methods for alkane dehydrogenation |
| CN1557546A (en) * | 2004-01-16 | 2004-12-29 | 复旦大学 | Composite oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof |
| CN101219389A (en) * | 2007-12-26 | 2008-07-16 | 厦门大学 | Solid catalyst for propylene manufacture with propane oxo-dehydrogenation and method for producing the same |
| CN101543781A (en) * | 2009-05-04 | 2009-09-30 | 厦门大学 | Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof |
Non-Patent Citations (1)
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| Shaobin Wang et al..Selective oxidation of ethane and propane over sulfated zirconia-supported nickel oxide catalysts.《Journal of Chemical Technology and Biotechnology》.2001,第76卷第265-272页. * |
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