CN103028400A - Selective oxidation catalyst and preparation method thereof - Google Patents
Selective oxidation catalyst and preparation method thereof Download PDFInfo
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- CN103028400A CN103028400A CN2011103009409A CN201110300940A CN103028400A CN 103028400 A CN103028400 A CN 103028400A CN 2011103009409 A CN2011103009409 A CN 2011103009409A CN 201110300940 A CN201110300940 A CN 201110300940A CN 103028400 A CN103028400 A CN 103028400A
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Abstract
The invention relates to a hydrogen gas selective oxidation catalyst for a propane dehydrogenation process and a preparation method thereof, and the catalyst is mainly used for solving the problems of lower oxygen transfer rate and higher hydrocarbon loss rate of the hydrogen gas oxidation catalyst prepared in the prior art. The technical scheme adopted by the invention is as follows: the hydrogen gas selective oxidation catalyst for the propane dehydrogenation process comprises the following components in percentage by weight: a) 0.1-10% of Pt, Pd, Ag, Au and Ir elements or oxides thereof, b) 0.25-10% of Sn, Sb, Zn, Fe, Co and Ni elements or oxides thereof, c) 0.1-10% of Ce, La and Zr elements or oxides thereof, and d) 80-99% of Al2O3 with the particle size of 2-200nm, so that the problems in the prior art are well solved. The catalyst can be used in dehydrogenation-hydrogen selective oxidation industrial production.
Description
Technical field
The present invention relates to a kind of for catalyst for selective oxidation and preparation method thereof.
Background technology
Propylene is a kind of important Organic Chemicals, and its consumption is only second to ethene, and along with the development of World Economics, global propylene demand increases, and estimates will be increased to 86.0x10 in 2010
6T, its growth rate surpasses 1 times of ethene.In the output of propylene, 59% byproduct from steam cracking device production ethene, 33% byproduct from refinery catalytic cracking unit's production gasoline and diesel oil, 3% from dehydrogenating propane technique, 5% by the additive method acquisition, and the Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane technology occupies more and more critical role in said method.The method is take propane as raw material, under the dehydrogenation effect, obtain the target product propylene, obtain simultaneously by-product hydrogen, because dehydrogenating propane is a strong heat absorption, reversible, reaction that molecular number increases, chemical reaction is subjected to the impact of balanced reaction, has that the propane conversion per pass is lower, energy consumption is higher in the course of reaction, adds the carbon-collecting problem that cracking causes in the course of reaction, so catalyst needs frequent regeneration, restricted its economic competitiveness and further applied.If the accessory substance hydrogen of dehydrogenating propane is carried out selective catalyst combustion, not only can provide heat for the dehydrogenating propane process, reduce outside heat supply, reduce energy consumption, and can promote that molecular balance moves, improve conversion of propane and propene yield, therefore become the focus of preparing propylene by dehydrogenating propane technical research.
Realize dehydrogenating propane-hydrogen selective oxidation coupled reaction, the key of problem is to seek efficient hydrogen selective oxidation catalyst, make its only with component in hydrogen react, and do not affect the wherein low-carbon (LC) such as propane, propylene hydro carbons.The catalyst system and catalyzing of having reported at present mainly contains two kinds: (1) Pt based catalyst system, and such as PtSn/SiO
2Catalyst under certain condition, in the time of 500 ℃ to the hydrogen catalytic combustion have 90% selective, but it exists activity lower, the problems such as less stable; (2) metal oxide catalyst system is such as In
2O
3/ SiO
2Catalyst can selective catalyst combustion hydrogen, it is selective about 90%, but Main Problems is less stable, activity decreased about 32% behind circulation ten circles.Nano oxidized aluminium particle size is little, be evenly distributed, and its specific surface is higher, and excellent adsorption has resistant to elevated temperatures inertia simultaneously, and is active high, belongs to activated alumina, widely uses at petrochemical industry.According to current paper, Shinji Kaneko (careful gold) is at " Applied Catalysis A:General " (applied catalysis A: introduction) 2009,356, " the Dehydrogenation of propane combined with selective hydrogen combustion over Pt-Sn bimetallic catalysts " that delivers on the 80-87 (PtSn bimetallic catalyst selective oxidation hydrogen research in the dehydrogenating propane process), the document has been studied PtSn/Al
2O
3With the selective oxidation performance of PtSn/Zn-Al-O catalyst to hydrogen, but the result shows oxygen conversion lower (about 92%) in the reaction, and the hydrocarbon proportion of goods damageds are higher, reach 2% according to its proportion of goods damageds of inventor's evidence.
Summary of the invention
Exist OTR lower in one of technical problem to be solved by this invention prior art, hydrocarbon consumes more problem, and a kind of new hydrogen during propane dehydrogenation catalyst for selective oxidation that is used for is provided.This catalyst has OTR height, characteristics that the hydrocarbon proportion of goods damageds are low.Two of the technical problem to be solved in the present invention provides 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 for the hydrogen during propane dehydrogenation catalyst for selective oxidation, by weight percentage, comprise following component:
A) 0.1～10% be selected from least a in Pt, Pd, Ag, Au, Ir element or its oxide;
B) 0.25～10% be selected from least a in Sn, Sb, Zn, Fe, Co, Ni element or its oxide;
C) 0.1～10% be selected from least a in Ce, La, Zr element or its oxide;
D) 80～99% particle diameter is the Al of 2～200 nanometers
2O
3
In the technique scheme, take the preferable range of molar ratio computing Sn: Pt as 0.1～10: 1, more preferably scope is 0.5～5: 1, the preferable range of counting in molar ratio Ce: Pt is 0.1～10: 1, more preferably scope is 0.5～5: 1, used nanometer Al
2O
3The granular size preferable range be 2～200 nanometers, the preferable range of specific area is 30～200 meters
2/ gram, the aperture preferable range is 15～45 nanometers.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of for hydrogen during propane dehydrogenation catalyst for selective oxidation and preparation method thereof, may further comprise the steps:
A) with nanometer Al
2O
3Carrier after 40～60 mesh sieves divide calcination process 0.5～12 hour under 400～600 ℃ of conditions is chosen in carrier compressing tablet, screening, gets nanometer Al
2O
3Carrier I;
B) carrier I and aequum are contained the solubility solution of Pt, Pd, Ag, Au, at least a element of Ir, the solubility solution that contains Sn, Sb, Zn, Fe, Co, at least a element of Ni, the solubility solution solution that contains Ce, La, at least a element of Zr and be mixed into mixture I, be under 10～80 ℃ of conditions with inorganic ammonia or inorganic ammonium salt solution in temperature, the pH value of regulating mixture I is 1～7, gets mixtures II;
C) temperature be under 10～100 ℃ of conditions with said mixture II dipping 0.5～8 hour, filter again, drying, 300～800 ℃ of roastings 0.5～12 hour obtain required hydrogen selective oxidation catalyst.
In the 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 1～3; The dipping temperature preferable range is 50～80 ℃, and the dip time preferable range is 1～3 hour, and catalyst sintering temperature preferable range is 400～00 ℃, and the roasting time preferable range is 4～8 hours.
The catalyst that makes as stated above carries out activity rating in the isotherm formula fixed bed reactors, for preparing propylene by dehydrogenating propane-oxidation of hydrogen system evaluation, the summary process is as follows:
The gas components such as propane, propylene, hydrogen and oxygen are passed through the mass flowmenter adjust flux, enter to preheat to distinguish and mix, then enter reaction zone, reactor preheat the district and reaction zone all adopt electric-heating-wire-heating, make it to reach predetermined temperature, the internal diameter of reactor is the stainless steel sleeve pipe of Φ 9mm-Φ 6mm, is about 400mm.Reacted gas by condensation, gas-liquid separation after, enter its composition of gas chromatographic analysis.
The evaluating catalyst condition is as follows in the isotherm formula fixed bed reactors: be that reaction pressure is normal pressure, gas space velocity 600 hours in the isothermal reactor of Φ 9mm-Φ 6mm (the about 17mm of catalyst bed layer height) with the internal diameter of packing into of the catalyst about 0.3 gram
-1, 550 ℃ of reaction temperatures.
Selective and the oxygen conversion of oxidation of hydrogen, the proportion of goods damageds of hydrocarbon are calculated as follows:
In the hydrogen during propane dehydrogenation selective oxidation reaction process, it is good selective that catalyst will be had, and just must make catalyst only hydrogen be played oxidation, and can be to reacting propane, the propylene component generation effect in the component.As the Al with stronger surface acidity
2O
3Material, the adding of rare earth element ce can improve the carrier surface characteristic, and Ce can improve the anti-caking power of catalyst Pt metal, stop the formation of Pt-Sn alloy, therefore can effectively improve catalyst performance, improve conversion ratio and the hydrogen selective oxidation of oxygen in the reaction, reach the purpose that reduces the hydrocarbon loss.Adopt catalyst of the present invention to be used for dehydrogenating propane-hydrogen Selective Oxidation, its activity rating is the result show, this catalyst has higher oxygen conversion, can reach 98%, have the lower hydro carbons proportion of goods damageds, less than 1%, the selective oxidizing of hydrogen is higher simultaneously, greater than 70%, obtained preferably technique effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Al
2O
3Patent (number of patent application: 201010146868.4), lower same is seen in the preparation of carrier.
Weighing 2 gram granular sizes are 10 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 0.18 milliliter of mass concentration be 0.004 grams per milliliter
2PtCl
6Solution and 1.44 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.022 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 3.5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 70%, the conversion ratio of oxygen is 98.0%, the proportion of goods damageds of hydrocarbon are 1.0%.
[embodiment 2]
Weighing 2 gram granular sizes are 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 0.88 milliliter of mass concentration be 0.004 grams per milliliter
2PtCl
6Solution and 7.2 milliliters of La (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.0439 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 1 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 76%, the conversion ratio of oxygen is 98.4%, the proportion of goods damageds of hydrocarbon are 0.8%.
[embodiment 3]
Weighing 2 gram granular sizes are 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 0.88 milliliter of mass concentration be 0.004 grams per milliliter
2PtCl
6Solution and 7.2 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.3295 gram Fe (NO
3)
3Solution, then the ammoniacal liquor regulator solution pH value to 3.5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 69%, the conversion ratio of oxygen is 98.2%, the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 4]
Weighing 2 gram granular sizes are 35 nanometers, and specific surface is 100 meters
2/ gram, the nanometer Al of aperture 20 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 0.88 milliliter of mass concentration be 0.004 grams per milliliter
2PtCl
6Solution and 28.8 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.2195 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 3.5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 73%, the conversion ratio of oxygen is 98.1%, the proportion of goods damageds of hydrocarbon are 0.7%.
[embodiment 5]
Weighing 2 gram granular sizes are 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 1.77 milliliters of mass concentrations be 0.004 grams per milliliter
2PdCl
6Solution and 2.88 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.2195 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 3.5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 70%, the conversion ratio of oxygen is 98.3%, the proportion of goods damageds of hydrocarbon are 0.8%.
[embodiment 6]
Weighing 2 gram granular sizes are 80 nanometers, and specific surface is 40 meters
2/ gram, the nanometer Al of aperture 35 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 1.77 milliliters of mass concentrations be 0.004 grams per milliliter
2PtCl
6Solution and 14.4 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.2195 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 7 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 79%, the conversion ratio of oxygen is 98.5%, the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 7]
Weighing 2 gram granular sizes are 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 1.77 milliliters of mass concentrations be 0.004 grams per milliliter
2PtCl
6Solution and 28.8 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.2865 gram Zn (NO
3)
2Solution, then the ammoniacal liquor regulator solution pH value to 3.5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 80%, the conversion ratio of oxygen is 98.5%, the proportion of goods damageds of hydrocarbon are 1.0%.
[embodiment 8]
Weighing 2 gram granular sizes are 10 nanometers, and specific surface is 180 meters
2/ gram, the nanometer Al of aperture 16 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 8.84 milliliters of mass concentrations be 0.004 grams per milliliter
2PtCl
6Solution and 14.4 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.4389 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 78%, the conversion ratio of oxygen is 98.4%, the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 9]
Weighing 2 gram granular sizes are 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 8.84 milliliters of mass concentrations be 0.004 grams per milliliter
2PtCl
6Solution and 14.4 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.4389 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 3 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 71%, the conversion ratio of oxygen is 98.2%, the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 10]
Weighing 2 gram granular sizes are 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 8.84 milliliters of mass concentrations be 0.004 grams per milliliter
2PtCl
6Solution and 14.4 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.4389 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 3.5 with 2.5% floods after 1 hour in 50 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 73%, the conversion ratio of oxygen is 98.3%, the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 11]
Weighing 2 gram granular sizes are 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 8.84 milliliters of mass concentrations be 0.004 grams per milliliter
2PtCl
6Solution and 14.4 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.4389 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 3.5 with 2.5% floods after 8 hours in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 75%, the conversion ratio of oxygen is 98.5%, the proportion of goods damageds of hydrocarbon are 0.8%.
[embodiment 12]
Weighing 2 gram granular sizes are 35 nanometers, and specific surface is 100 meters
2/ gram, the nanometer Al of aperture 20 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 8.84 milliliters of mass concentrations be 0.004 grams per milliliter
2PtCl
6Solution and 14.4 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.4389 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 3.5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 400 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 70%, the conversion ratio of oxygen is 98.2%, the proportion of goods damageds of hydrocarbon are 1.0%.
[embodiment 13]
Weighing 2 gram granular sizes are 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 8.84 milliliters of mass concentrations be 0.004 grams per milliliter
2PtCl
6Solution and 14.4 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.4389 gram SnCl
4Solution, then the sal volatile regulator solution pH value to 3.5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 76%, the conversion ratio of oxygen is 98.1%, the proportion of goods damageds of hydrocarbon are 0.8%.
[embodiment 14]
Weighing 2 gram granular sizes are 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 8.84 milliliters of mass concentrations be 0.004 grams per milliliter
2PtCl
6Solution and 14.4 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.4389 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 3.5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 8 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 75%, the conversion ratio of oxygen is 98.5%, the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 15]
Weighing 2 gram granular sizes are 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette respectively 8.84 milliliters of mass concentrations be 0.004 grams per milliliter
2PtCl
6Solution and 14.4 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.4389 gram SnCl
4Solution, add again 0.5 gram NaCl, ammoniacal liquor regulator solution pH value to 3.5 with 2.5%, then in 80 ℃ of water-baths, flood after 1 hour, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 8 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 69%, the conversion ratio of oxygen is 98.01%, the proportion of goods damageds of hydrocarbon are 1.3%.
[comparative example 1]
Weighing 2 gram specific surfaces are 5 meters
2/ gram, granular size is the Al of 200 nanometers
2O
3Carrier, the H that to pipette 0.88 milliliter of mass concentration be 0.004 grams per milliliter
2PtCl
6Solution drips 0.2195 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 3.5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 66%, the conversion ratio of oxygen is 96.8%, the proportion of goods damageds of hydrocarbon are 1.7%.
[comparative example 2]
Weighing 2 gram granular sizes are 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometers
2O
3Carrier, the H that to pipette 0.88 milliliter of mass concentration be 0.004 grams per milliliter
2PtCl
6Solution drips 0.2195 gram SnCl
4Solution, then the ammoniacal liquor regulator solution pH value to 3.5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 76%, the conversion ratio of oxygen is 97.8%, the proportion of goods damageds of hydrocarbon are 0.9%.
[comparative example 3]
Weighing 2 gram specific surfaces are 10 meters
2/ gram, the nanometer Al of aperture 200 nanometers
2O
3Carrier adds 10 ml deionized water, the H that to pipette 0.88 milliliter of mass concentration be 0.004 grams per milliliter
2PtCl
6Solution and 14.4 milliliters of Ce (NO that mass concentration is 0.0012 grams per milliliter
3)
4Solution drips 0.2195 gram SnCl
4Solution and 0.12 gram NaNO
3Solution, then the ammoniacal liquor regulator solution pH value to 1.5 with 2.5% floods after 1 hour in 80 ℃ of water-baths, taking out sample filters, in 120 ℃ of baking ovens dry 8 hours, again sample is put into Muffle furnace roasting 4 hours under 550 ℃ of conditions, obtain required catalyst.The catalyst of preparation is packed in the fixed bed reactors, carry out activity rating under 550 ℃ of conditions, the result is as follows: this Hydrogen gas selectively be 53%, the conversion ratio of oxygen is 97.5%, the proportion of goods damageds of hydrocarbon are 2%.
Claims (5)
1. one kind is used for the hydrogen during propane dehydrogenation catalyst for selective oxidation, in catalyst weight percentage, comprises following component:
A) 0.1～10% be selected from least a in Pt, Pd, Ag, Au, Ir element or its oxide;
B) 0.25～10% be selected from least a in Sn, Sb, Zn, Fe, Co, Ni element or its oxide;
C) 0.1～10% be selected from least a in Ce, La, Zr element or its oxide;
D) 80～99% particle diameter is the Al of 2～200 nanometers
2O
3
2. described for the hydrogen during propane dehydrogenation catalyst for selective oxidation according to claim 1, it is characterized in that nanometer Al
2O
3Granular size be 2～100 nanometers, specific area is 30～200 meters
2/ gram, the aperture is 15～45 nanometers.
3. the described preparation method for the hydrogen during propane dehydrogenation catalyst for selective oxidation of claim 1 comprises following step:
A) with nanometer Al
2O
3Carrier after 40～60 mesh sieves divide calcination process 0.5～12 hour under 400～600 ℃ of conditions is chosen in carrier compressing tablet, screening, gets nanometer Al
2O
3Carrier I;
B) carrier I and aequum are contained the solubility solution of Pt, Pd, Ag, Au, at least a element of Ir, the solubility solution that contains Sn, Sb, Zn, Fe, Co, at least a element of Ni, the solubility solution solution that contains Ce, La, at least a element of Zr and be mixed into mixture I, be under 10～80 ℃ of conditions with inorganic ammonia or inorganic ammonium salt solution in temperature, the pH value of regulating mixture I is 1～7, gets mixtures II;
C) temperature be under 10～100 ℃ of conditions with said mixture II dipping 0.5～8 hour, filter again, drying, 300～800 ℃ of roastings 0.5～12 hour obtain required hydrogen selective oxidation catalyst.
4. described preparation method for the hydrogen during propane dehydrogenation catalyst for selective oxidation according to claim 3 is characterized in that inorganic ammonia is selected from ammoniacal liquor, and inorganic ammonium salt is selected from ammonium carbonate or carbonic hydroammonium is at least a.
5. described preparation method for the hydrogen during propane dehydrogenation catalyst for selective oxidation according to claim 3 is characterized in that the solubility solution of Pt is selected from H
2PtCl
6The solubility solution of Sn is selected from SnCl
4The solubility solution of Ce is selected from Ce (NO
3)
4
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