CN109718764A - It is a kind of for the noble metal catalyst of preparing propylene by dehydrogenating propane and its preparation and application - Google Patents
It is a kind of for the noble metal catalyst of preparing propylene by dehydrogenating propane and its preparation and application Download PDFInfo
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- CN109718764A CN109718764A CN201711020751.XA CN201711020751A CN109718764A CN 109718764 A CN109718764 A CN 109718764A CN 201711020751 A CN201711020751 A CN 201711020751A CN 109718764 A CN109718764 A CN 109718764A
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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
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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
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Abstract
The invention belongs to catalyst and its preparation field, it is related to a kind of magnesium gallium composite oxides supported precious metal catalyst and its preparation and application, it is specially a kind of for preparing propylene by dehydrogenating propane magnesium gallium composite oxides supported precious metal catalyst and preparation method thereof.The catalyst is by magnesium gallium composite oxides MgOxGa2O3The mass fraction of (0.5 < x < 2) and load is that the noble metal active component of 0.01-5wt% is constituted, and active component includes: any one of tri- kinds of noble metals of Rh, Ir and Pt and two or more.The catalyst shows very high Propylene Selectivity and high temperature sintering resistant performance to dehydrogenating propane reaction in 550-700 DEG C of fixed bed reactors, has high circulation charcoal regeneration stability advantage.
Description
Technical field
The present invention relates to a kind of for the highly selective anti-sintering noble metal catalyst and its system for generating propylene of dehydrogenating propane
Standby and application, and the method for the dehydrogenating propane highly-selective preparation of propylene using the catalyst.
Background technique
Propylene is basic chemical raw materials important in industry, is widely used in production polypropylene, acrylonitrile, acrylic acid, ring
The chemical products such as Ethylene Oxide, oxo-alcohols.The production of propylene at present mainly passes through three kinds of approach: naphtha pyrolysis ethylene by-product third
Alkene process, methanol-to-olefins (MTO) process and dehydrogenating propane (PDH) propylene process processed.Wherein with naphtha pyrolysis by-product third
Based on alkene, yield accounts for about the 80% of propylene total output, but the process is not the process to produce propylene as target product, because
, with the increase of propylene demand, which will be difficult to meet demand for this.Therefore, the generation propylene process of purpose will become and expand
One important channel in big propylene source.Propane is the important composition ingredient of natural gas, largely finding and opening with shale gas
It adopts, dehydrogenating propane, which directly generates propylene process, will become a significant process of production propylene.
Dehydrogenating propane reaction is a strong endothermic reaction.To obtain higher conversion of propane, which is generally required
It is carried out under 550 degree or more of hot conditions.But excessively high reaction temperature is easy to make propane that cracking reaction generation lower carbon number hydrocarbons occur,
Causing the selectivity of propylene reduces；Sintering and the area carbon inactivation of catalyst can also be caused under hot conditions simultaneously.Therefore third
The key of alkane De-hydrogen Technology is to prepare the catalyst with high Propylene Selectivity, high anti-sintering property and anti-carbon.
Current industrialized propane dehydrogenation catalyst is mainly platinum group and chromium-based catalysts, is adopted with the Oleflex technique of UOP
Sn, K or Li modified Pt/Al2O3The CrO used with the Catofin technique of ABB Lummus3/Al2O3To represent.Wherein,
Chromium-based catalysts are easy to that area carbon and rapid deactivation occurs in certain embodiments, need to carry out frequent charcoal regeneration, and chromium
All there is large effect to human health and environment, therefore the utilization of chromium-based catalysts will be limited；And platinum group catalyst
Because the advantages such as dehydrogenating propane activity with higher, low pollution become the hot spot of propane dehydrogenation catalyst.
However there is also more problems for Pt series catalysts, the Propylene Selectivity of predominantly list Pt catalyst is low and Pt receives
The sintering deactivation of rice grain.For improve propylene selectivity, currently used strategy be by addition Sn, Cu, Ga, Zn, Li, K,
The auxiliary agents such as V carry out modulation to the geometry and electronic property of Pt, such as CN101898130B discloses a kind of platinum group metal and is
Active component, tin are the propane dehydrogenation catalyst of auxiliary agent, and the addition of tin auxiliary agent significantly improves the selectivity of propylene and reacts steady
It is qualitative.(Angew.Chem.Int.Ed.2014,53,9251-9256.) such as Bert reports the Pt/ addition agent modified using Ga
Al2O3Catalyst, the addition of Ga auxiliary agent are remarkably improved the Pt/Al of extremely low Pt load capacity2O3The conversion of propane of catalyst and third
Alkene selectivity.Though this addition agent modified method is remarkably improved the Propylene Selectivity of platinum group catalyst, in pyroreaction item
Under part, it is easy to which the reduction that auxiliary agent occurs is precipitated, and then influences the performance of catalyst.CN101884922A discloses a kind of colloidal sol
Tin component is introduced Aluminum sol by gel method, impregnates active component platinum and other metal promoters again after drying and moulding, and then slow down
The reduction precipitation phenomenon of tin component, but the catalyst preparation process is complex, and it is limited to inhibit tin that effect is precipitated.Another party
Face passes through duct frequently with porous acid material as carrier to improve the anti-sintering property of dehydrogenating propane platinum group catalyst
The anti-sintering property of Pt is realized in confinement effect.CN106311311A discloses a kind of Group IIB metal or alkaline-earth metal as auxiliary agent
The mesoporous molecular sieve carried platinum group catalyst of modification, it is steady which shows good dehydrogenating propane to dehydrogenating propane reaction
It is qualitative, the Propylene Selectivity of good dehydrogenating propane conversion ratio and raising can be still kept after reaction in 100 hours.
As can be seen that existing technology mostly uses platinum as active component greatly, and auxiliary agent is added to the geometry knot of catalyst
Structure and electronic property carry out modulation, to obtain high Propylene Selectivity；High anti-burning is obtained as carrier using porous material
Tie performance.
Summary of the invention
The invention discloses the composite oxide supported anti-sintering noble metal catalysts of magnesium gallium to be used for dehydrogenating propane high selection
Property generate propylene reaction, solve existing dehydrogenating propane platinum group catalyst Propylene Selectivity under no auxiliary agent adding conditional it is low and
The high temperature sintering problem of noble metal.The preparation method for providing the catalyst and the catalyst are for the highly selective system of dehydrogenating propane
The method of standby propylene.
To achieve the above object, a kind of preparing propylene by dehydrogenating propane magnesium gallium composite oxides supported precious metal provided by the invention
Catalyst, which is characterized in that the carrier of the catalyst is magnesium gallium composite oxides MgOxGa2O3(0.5 < x < 2), active group
It is divided into any one of tri- kinds of noble metals of Rh, Ir and Pt and two or more, wherein the weight percentage of noble metal is 0.01-
5wt%, optimization weight percent are 0.1-1wt%.
The method for preparing catalyst are as follows:
1) magnesium gallium composite oxide carrier is prepared: by magnesium-containing metal salt precursor body and metal salt presoma containing gallium by Mg:
Ga molar ratio is that 1:2x (0.5 < x < 2) mixing is codissolved in water, and the presoma is the nitrate or acetate of magnesium or gallium, is formed
Appropriate ammonium hydroxide is added in 0.01-5mol/L solution, and adjusting pH value is 8-10, stirs 0.5-24 hours, filtering, by filter cake in 90-
150 DEG C are 2-24 hours dry, then through 400-600 DEG C roasting 2-12 hours, obtain magnesium gallium composite oxide carrier；
2) it prepares catalyst: magnesium gallium composite oxide carrier is immersed in the active component Rh's, Ir and Pt of certain content
In precursor solution, the presoma is chloride or nitrate of noble metal etc., is stirred 2-24 hours, be then filtered,
Washing, then in air atmosphere 400-600 DEG C roasting 2-12 hour 2-24 hours dry at 90-150 DEG C, then in 500-
Reductase 12-12 hours under 800 DEG C of hydrogen atmospheres, the weight percentage for obtaining noble metal is the catalyst of 0.01-5wt%, is lived
Property component particle size be it is monatomic to 3nm be distributed.Catalyst anti-sintering property with higher, 800 DEG C of air atmospheres
After roasting 24 hours, the particle size of active component still exists with monatomic to 3nm and form of nanoparticles below.
The present invention also provides a kind of methods of dehydrogenating propane highly-selective preparation of propylene.It specifically includes: being urged described in use
Agent, using fixed-bed reactor, using volume ratio for 1:1 propane and hydrogen as raw material, air speed 3000-50000h-1,
Pressure is 0.1-0.2Mpa, and reacting is 550-700 DEG C.The result shows that can be obtained using the above method close to equilibrium conversion
The Propylene Selectivity of conversion of propane and 90% or more, and the rear catalyst for repeatedly burning carbon cycle regeneration still shows high propane and turns
Rate and Propylene Selectivity.
Detailed description of the invention
Fig. 1 is the Rh/MgOGa prepared using the method for the invention embodiment 2,3 and 42O3(a), Ir/MgO
Ga2O3(b) and Pt/MgOGa2O3(c) electron microscopic picture of three kinds of catalyst.
Fig. 2 is the Rh/MgOGa prepared using the method for the invention embodiment 22O3Catalyst carries out the anti-of application examples 1
Answer conversion of propane obtained and Propylene Selectivity.
Fig. 3 is the Ir/MgOGa prepared using the method for the invention embodiment 32O3Catalyst carries out the anti-of application examples 1
Answer conversion of propane obtained and Propylene Selectivity.
Fig. 4 is the Pt/MgOGa prepared using the method for the invention embodiment 42O3Catalyst carries out the anti-of application examples 1
Answer conversion of propane obtained and Propylene Selectivity.
Fig. 5 is the Pt/Al prepared using the method for the invention comparative example 12O3The reaction institute of catalyst progress application examples 1
The conversion of propane and Propylene Selectivity of acquisition.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description, but the present invention is not limited to this.
Embodiment 1
Embodiment 1 uses method provided by the invention, prepares magnesium gallium composite oxides MgOxGa2O3(x=1).Specific step
It is rapid as follows: (1) to weigh 0.05 mole of magnesium nitrate hexahydrate respectively and 0.10 mole of nine water gallium nitrate is dissolved in 500mL water, stir molten
Solution, forms the magnesium nitrate of 0.10mol/L and the gallium nitrate solution of 0.20mol/L；(2) ammonium hydroxide of appropriate 10wt.% is then added,
Adjusting pH value is 9, is stirred 12 hours, filtering；(3) filter cake is 12 hours dry at 120 DEG C, then roasted 5 hours through 600 DEG C,
Obtain MgOGa2O3Magnesium gallium composite oxide carrier.
Embodiment 2
Embodiment 2 uses method provided by the invention, and the magnesium gallium composite oxides for using embodiment 1 to prepare is carrier preparations
The composite oxide supported high dispersive rhodium catalyst of magnesium gallium.The specific method is as follows: weighing 5.0g MgOGa2O3Carrier be added to
In the radium chloride aqueous solution of 150ml rhodium containing 0.05g, 2h is stirred at room temperature, filters, washing, obtained solid is placed in 150 DEG C of dryings 2
Hour, it is roasted 5 hours in 600 DEG C of air, 800 DEG C of reductase 12 h in pure hydrogen.Obtain the composite oxide supported high score of magnesium gallium
Rhodium catalyst is dissipated, Rh/MgOGa is denoted as2O3。
Embodiment 3
Embodiment 3 uses method provided by the invention, and the magnesium gallium composite oxides for using embodiment 1 to prepare is carrier preparations
The composite oxide supported high dispersive iridium catalyst of magnesium gallium.The specific method is as follows: weighing 5.0g MgOGa2O3Carrier be added to
In the aqueous solution of chloraurate of 150ml iridium containing 0.15g, it is stirred at room temperature for 24 hours, filters, washing, obtained solid is placed in 90 DEG C of dryings 24
Hour, it is roasted 12 hours in 400 DEG C of air, 600 DEG C of reduction 5h in pure hydrogen.Obtain the composite oxide supported high score of magnesium gallium
Iridium catalyst is dissipated, Ir/MgOGa is denoted as2O3。
Embodiment 4
Embodiment 4 uses method provided by the invention, and the magnesium gallium composite oxides for using embodiment 1 to prepare is carrier preparations
The composite oxide supported high dispersive platinum catalyst of magnesium gallium.The specific method is as follows: weighing 5.0g MgOGa2O3Carrier be added to
In the chloroplatinic acid aqueous solution of 150ml platinum containing 0.005g, 12h is stirred at room temperature, filters, washing, obtained solid is placed in 120 DEG C of dryings
It 12 hours, roasts 10 hours in 500 DEG C of air, 500 DEG C of reduction 12h in pure hydrogen.It is composite oxide supported to obtain magnesium gallium
High dispersive platinum catalyst, is denoted as Pt/MgOGa2O3。
Comparative example 1
Comparative example 1 uses common incipient impregnation method.It chooses specific surface area and is greater than 100m2Business γ-the Al of/g2O3
For carrier, the 5.0g γ-Al is weighed2O3It is added into the chloroplatinic acid aqueous solution containing 0.05g platinum prepared according to its water absorption,
Ultrasonic vibration, stirring 1 hour, drying at room temperature 12 hours, subsequent 80 DEG C of dryings 12 hours, obtain catalyst precarsor.The catalyst
Precursor roasts 5 hours using in 500 DEG C of air, 500 DEG C of reductase 12 h in pure hydrogen.Obtain γ-Al2O3The high dispersive platinum of load is urged
Agent is denoted as Pt/Al2O3。
Catalyst application examples 1
In fixed bed reactors, it is packed into Rh/MgOGa prepared by embodiment 22O3Catalyst 0.3g (20-40 mesh), warp
3.0g quartz sand (20-40 mesh) dilution.Above-mentioned catalyst first passes around pretreatment, i.e., 600 DEG C of reduction are warming up in pure hydrogen
Processing 2 hours.It is reacted after pretreatment, reaction condition are as follows: the mass space velocity for controlling propane feed is 12000h-1；Hydrogen is made
For carrier gas, and the volume ratio of hydrogen and propane is 1:1；580 DEG C of reaction temperature, reaction pressure 0.1Mpa.
Catalyst application examples 2-4
According to the method for application examples 1, the difference is that, by Rh/MgOGa2O3Catalyst replaces with Ir/MgOGa2O3、
Pt/MgO·Ga2O3And Pt/Al2O3, preparing propylene by dehydrogenating propane reaction is carried out respectively.
Claims (4)
1. a kind of noble metal catalyst for preparing propylene by dehydrogenating propane, which is characterized in that the carrier of the catalyst is magnesium gallium
Composite oxides MgOxGa2O3(0.5 < x < 2), any one of active component tri- kinds of noble metals of Rh, Ir and Pt and two kinds
More than, wherein the weight percentage of noble metal is 0.01-5wt%, and optimization weight percent is 0.1-1wt%.
2. a kind of preparation method of catalyst described in claim 1, it is characterised in that:
1) it prepares magnesium gallium composite oxide carrier: magnesium-containing metal salt precursor body and the metal salt presoma containing gallium is rubbed by Mg:Ga
, than being that 1:2x (0.5 < x < 2) mixing is codissolved in water, the presoma is one of nitrate or acetate of magnesium or gallium for you
Or it is two or more, 0.01-5mol/L solution is formed, appropriate ammonium hydroxide is added, adjusting pH value is 8-10, is stirred 0.5-24 hours, mistake
Filter, filter cake is 2-24 hours dry at 90-150 DEG C, then through 400-600 DEG C roasting 2-12 hours, obtain magnesium gallium combined oxidation
Object carrier；
2) it prepares catalyst: magnesium gallium composite oxide carrier being immersed in active component Rh, Ir and Pt mass concentration is 0.0001-
In the precursor solution of 50g/L, the presoma is the chloride or one or more of nitrate of above-mentioned noble metal,
Stirring 2-24 hours, is then filtered, washs, 2-24 hours dry at 90-150 DEG C, then 400-600 in air atmosphere
DEG C roasting 2-12 hours, then reductase 12-12 hours under 500-800 DEG C of hydrogen atmosphere, obtain the weight percentage of noble metal
For the catalyst of 0.01-5wt%.
3. a kind of application of catalyst described in claim 1, it is characterised in that: it is applied to preparing propylene by dehydrogenating propane and reacts, tool
Body includes: using the catalyst, and using fixed-bed reactor, propane and hydrogen using volume ratio for 1:1 are used as raw material, sky
Speed is 3000-50000h-1, reaction pressure 0.001-0.2Mpa, preferably reaction pressure are 0.1-0.2Mpa, and reaction temperature is
550-700℃。
4. the application of catalyst according to claim 3, it is characterised in that: catalyst first passes around pretreatment, i.e., pure
In hydrogen, reduction treatment is carried out at 500 DEG C~700 DEG C, reduction treatment is carried out at preferably 550 DEG C~600 DEG C, and the processing time is 2
~5h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112657492A (en) * | 2021-01-06 | 2021-04-16 | 华东理工大学 | Ir-GaOx-based propane dehydrogenation catalyst and preparation method and application thereof |
Citations (2)
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|---|---|---|---|---|
| CN104525196A (en) * | 2014-12-11 | 2015-04-22 | 天津大学 | Platinum-gallium catalyst loaded on double-oxide composite carrier as well as preparation method and application of platinum-gallium catalyst |
| CN106512994A (en) * | 2016-09-27 | 2017-03-22 | 大连理工大学 | Anti-carbon deposition platinum-based catalyst for preparing propylene through propane dehydrogenation and preparation method thereof |
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2017
- 2017-10-27 CN CN201711020751.XA patent/CN109718764B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525196A (en) * | 2014-12-11 | 2015-04-22 | 天津大学 | Platinum-gallium catalyst loaded on double-oxide composite carrier as well as preparation method and application of platinum-gallium catalyst |
| CN106512994A (en) * | 2016-09-27 | 2017-03-22 | 大连理工大学 | Anti-carbon deposition platinum-based catalyst for preparing propylene through propane dehydrogenation and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| M.A. ARAMENDI´A等: "Synthesis and characterization of Pt/MgO catalysts and their use in n-hexane conversion", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》 * |
| MARK R. WEIR等: "Effects of pH and Mg:Ga Ratio on the Synthesis of Gallium-Containing Layered Double Hydroxides and Their Polyoxometalate Anion Exchanged Products", 《CHEM. MATER.》 * |
| 刘艳: "丙烷在Ga2O3(100)表面脱氢反应机理的理论研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112657492A (en) * | 2021-01-06 | 2021-04-16 | 华东理工大学 | Ir-GaOx-based propane dehydrogenation catalyst and preparation method and application thereof |
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