CN103028400B - Selective oxidation catalyst and preparation method thereof - Google Patents
Selective oxidation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN103028400B CN103028400B CN201110300940.9A CN201110300940A CN103028400B CN 103028400 B CN103028400 B CN 103028400B CN 201110300940 A CN201110300940 A CN 201110300940A CN 103028400 B CN103028400 B CN 103028400B
- Authority
- CN
- China
- Prior art keywords
- solution
- catalyst
- selective oxidation
- hydrogen
- nanometer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
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 exceedes ethene 1 times.In the output of propylene, 59% produces the byproduct of ethene from steam cracking device, 33% produces the byproduct of gasoline and diesel oil from refinery catalytic cracking unit, 3% from dehydrogenating propane technique, 5% is obtained by additive method, and Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane technology occupies more and more critical role in the above-mentioned methods.The method take propane as raw material, target product propylene is obtained under dehydrogenation effect, obtain by-product hydrogen simultaneously, due to dehydrogenating propane be a by force heat absorption, the reaction that increases of reversible, molecular number, chemical reaction, by the impact of balanced reaction, exists that propane conversion per pass is lower, energy consumption is higher in course of reaction, adds the carbon-collecting problem that in course of reaction, cracking causes, so catalyst needs frequent regeneration, constrain its economic competitiveness and further genralrlization application.If the byproduct hydrogen gas of dehydrogenating propane is carried out selective catalyst combustion, not only can provide heat for 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 finds efficient hydrogen selective oxidation catalyst, makes it only react with the hydrogen in component, and do not affect the wherein low-carbon (LC) such as propane, propylene hydro carbons.The catalyst system and catalyzing reported at present mainly contains two kinds: (1) Pt based catalyst system, as PtSn/SiO
2catalyst under certain condition, when 500 DEG C to hydrogen catalytic combustion have 90% selective, but its to there is activity lower, the problems such as less stable; (2) metal oxide catalyst systems, as In
2o
3/ SiO
2catalyst energy selective catalyst combustion hydrogen, its selective about 90%, but the subject matter existed is less stable, actively after circulation ten circle reduces about 32%.Nano oxidized aluminium particle size is little, be evenly distributed, and its specific surface is higher, excellent adsorption, has resistant to elevated temperatures inertia simultaneously, active high, belongs to activated alumina, widely applies at petrochemical industry.According to current paper, Shinji Kaneko (careful gold) is at " Applied Catalysis A:General " (applied catalysis A: introduction) 2009,356, " Dehydrogenation of propane combined withselective hydrogen combustion over Pt-Sn bimetallic catalysts " (in dehydrogenating propane process research of PtSn bimetallic catalyst selective oxidation hydrogen) that 80-87 delivers, the document have studied PtSn/Al
2o
3with the selective oxidation performance of PtSn/Zn-Al-O catalyst to hydrogen, but result shows oxygen conversion lower (about 92%) in reaction, and the hydrocarbon proportion of goods damageds are higher, and testing according to the present inventor proves that its proportion of goods damageds reach 2%.
Summary of the invention
There is OTR in one of technical problem to be solved by this invention prior art lower, hydrocarbon consumes more problem, provide a kind of newly for hydrogen during propane dehydrogenation catalyst for selective oxidation.This catalyst has the advantages that OTR is high, the hydrocarbon proportion of goods damageds are low.The technical problem to be solved in the present invention two, is to provide a kind of method for preparing catalyst corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of for hydrogen during propane dehydrogenation catalyst for selective oxidation, by weight percentage, comprises following component:
A) at least one be selected from Pt, Pd, Ag, Au, Ir element or its oxide of 0.1 ~ 10%;
B) at least one be selected from Sn, Sb, Zn, Fe, Co, Ni element or its oxide of 0.25 ~ 10%;
C) at least one be selected from Ce, La, Zr element or its oxide of 0.1 ~ 10%;
D) particle diameter of 80 ~ 99% is the Al of 2 ~ 200 nanometers
2o
3.
In technique scheme, with the preferable range of molar ratio computing Sn: Pt for 0.1 ~ 10: 1, more preferably scope is 0.5 ~ 5: 1, and the preferable range of ratio Ce: Pt is 0.1 ~ 10: 1, and more preferably scope is 0.5 ~ 5: 1, nanometer Al used
2o
3granular size preferable range be 2 ~ 200 nanometers, the preferable range of specific area is 30 ~ 200 meters
2/ gram, 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 be used for hydrogen during propane dehydrogenation catalyst for selective oxidation and preparation method thereof, comprises the following steps:
A) by nanometer Al
2o
3carrier compressing tablet, screening, choose 40 ~ 60 mesh sieves divide after carrier calcination process 0.5 ~ 12 hour under 400 ~ 600 DEG C of conditions, obtain nanometer Al
2o
3carrier I;
B) by carrier I and the aequum solubility solution containing Pt, Pd, Ag, Au, Ir at least one element, the solubility solution containing Sn, Sb, Zn, Fe, Co, Ni at least one element, be mixed into mixture I containing the solubility Solutions Solution of Ce, La, Zr at least one element, with inorganic ammonia or inorganic ammonium salt solution under temperature is 10 ~ 80 DEG C of conditions, the pH value regulating mixture I is 1 ~ 7, obtains mixtures II;
C) under temperature is 10 ~ 100 DEG C of conditions, said mixture II is flooded 0.5 ~ 8 hour, then carry out filtering, dry, 300 ~ 800 DEG C of roastings 0.5 ~ 12 hour, obtain required hydrogen selective oxidation catalyst.
In technique scheme, inorganic ammonia or inorganic ammonium salt preferred version are selected from ammoniacal liquor, ammonium carbonate or carbonic hydroammonium, and the pH value preferable range of solution is 1 ~ 7, and more preferably scope is 1 ~ 3; Dipping temperature preferable range is 50 ~ 80 DEG C, and dip time preferable range is 1 ~ 3 hour, and catalyst sintering temperature preferable range is 400 ~ 00 DEG C, and roasting time preferable range is 4 ~ 8 hours.
Catalyst obtained as stated above carries out activity rating in isotherm formula fixed bed reactors, and for preparing propylene by dehydrogenating propane-oxidation of hydrogen system appraisal, summary process is as follows:
By gas components such as propane, propylene, hydrogen and oxygen by mass flowmenter adjust flux, enter pre-add hot-zone to mix, then reaction zone is entered, the pre-add hot-zone of reactor and reaction zone all adopt electric-heating-wire-heating, make it to reach predetermined temperature, the internal diameter of reactor is the stainless steel sleeve pipe of Φ 9mm-Φ 6mm, is about 400mm.Reacted gas, by after condensation, gas-liquid separation, enters its composition of gas chromatographic analysis.
In isotherm formula fixed bed reactors, evaluating catalyst condition is as follows: it is (catalyst bed layer height is about 17mm) in the isothermal reactor of Φ 9mm-Φ 6mm that the catalyst of about 0.3 gram is loaded internal diameter, and reaction pressure is normal pressure, gas space velocity 600 hours
-1, reaction temperature 550 DEG C.
Selective and the oxygen conversion of oxidation of hydrogen, the proportion of goods damageds of hydrocarbon calculate as follows:
In hydrogen during propane dehydrogenation selective oxidation reaction process, catalyst be made to have good selective, catalyst just must be made only to play oxidation to hydrogen, and can not to the propane in reaction component, propylene component generation effect.As the Al with stronger surface acidity
2o
3material, adding of rare earth element ce can improve carrier surface properties, and Ce can improve the anti-caking power of catalyst Pt metal, stop the formation of Pt-Sn alloy, therefore effectively catalyst performance can be improved, improve conversion ratio and the hydrogen selective oxidation of oxygen in reaction, reach the object reducing hydrocarbon loss.Adopt catalyst of the present invention in dehydrogenating propane-hydrogen Selective Oxidation, its Activity evaluation shows, this catalyst has higher oxygen conversion, can 98% be reached, have the lower hydro carbons proportion of goods damageds, be less than 1%, the selective oxidizing of hydrogen is higher simultaneously, be greater than 70%, achieve good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Al
2o
3the preparation of carrier see patent (number of patent application: 201010146868.4), lower with.
Weighing 2 grams of granular sizes is 10 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 0.18 milliliter of mass concentration is 0.004 grams per milliliter respectively
2ptCl
6solution and 1.44 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.022 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 70%, and the conversion ratio of oxygen is 98.0%, and the proportion of goods damageds of hydrocarbon are 1.0%.
[embodiment 2]
Weighing 2 grams of granular sizes is 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 0.88 milliliter of mass concentration is 0.004 grams per milliliter respectively
2ptCl
6solution and 7.2 milliliters of mass concentrations are the La (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.0439 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 1, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 76%, and the conversion ratio of oxygen is 98.4%, and the proportion of goods damageds of hydrocarbon are 0.8%.
[embodiment 3]
Weighing 2 grams of granular sizes is 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 0.88 milliliter of mass concentration is 0.004 grams per milliliter respectively
2ptCl
6solution and 7.2 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.3295 gram of Fe (NO
3)
3solution, the ammoniacal liquor with 2.5% regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 69%, and the conversion ratio of oxygen is 98.2%, and the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 4]
Weighing 2 grams of granular sizes is 35 nanometers, and specific surface is 100 meters
2/ gram, the nanometer Al of aperture 20 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 0.88 milliliter of mass concentration is 0.004 grams per milliliter respectively
2ptCl
6solution and 28.8 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.2195 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 73%, and the conversion ratio of oxygen is 98.1%, and the proportion of goods damageds of hydrocarbon are 0.7%.
[embodiment 5]
Weighing 2 grams of granular sizes is 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 1.77 milliliters of mass concentrations are 0.004 grams per milliliter respectively
2pdCl
6solution and 2.88 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.2195 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 70%, and the conversion ratio of oxygen is 98.3%, and the proportion of goods damageds of hydrocarbon are 0.8%.
[embodiment 6]
Weighing 2 grams of granular sizes is 80 nanometers, and specific surface is 40 meters
2/ gram, the nanometer Al of aperture 35 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 1.77 milliliters of mass concentrations are 0.004 grams per milliliter respectively
2ptCl
6solution and 14.4 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.2195 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 7, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 79%, and the conversion ratio of oxygen is 98.5%, and the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 7]
Weighing 2 grams of granular sizes is 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 1.77 milliliters of mass concentrations are 0.004 grams per milliliter respectively
2ptCl
6solution and 28.8 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.2865 gram of Zn (NO
3)
2solution, the ammoniacal liquor with 2.5% regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 80%, and the conversion ratio of oxygen is 98.5%, and the proportion of goods damageds of hydrocarbon are 1.0%.
[embodiment 8]
Weighing 2 grams of granular sizes is 10 nanometers, and specific surface is 180 meters
2/ gram, the nanometer Al of aperture 16 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 8.84 milliliters of mass concentrations are 0.004 grams per milliliter respectively
2ptCl
6solution and 14.4 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.4389 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 78%, and the conversion ratio of oxygen is 98.4%, and the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 9]
Weighing 2 grams of granular sizes is 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 8.84 milliliters of mass concentrations are 0.004 grams per milliliter respectively
2ptCl
6solution and 14.4 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.4389 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 3, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 71%, and the conversion ratio of oxygen is 98.2%, and the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 10]
Weighing 2 grams of granular sizes is 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 8.84 milliliters of mass concentrations are 0.004 grams per milliliter respectively
2ptCl
6solution and 14.4 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.4389 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 3.5, then floods after 1 hour in 50 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 73%, and the conversion ratio of oxygen is 98.3%, and the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 11]
Weighing 2 grams of granular sizes is 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 8.84 milliliters of mass concentrations are 0.004 grams per milliliter respectively
2ptCl
6solution and 14.4 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.4389 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 3.5, then floods after 8 hours in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 75%, and the conversion ratio of oxygen is 98.5%, and the proportion of goods damageds of hydrocarbon are 0.8%.
[embodiment 12]
Weighing 2 grams of granular sizes is 35 nanometers, and specific surface is 100 meters
2/ gram, the nanometer Al of aperture 20 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 8.84 milliliters of mass concentrations are 0.004 grams per milliliter respectively
2ptCl
6solution and 14.4 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.4389 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 400 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 70%, and the conversion ratio of oxygen is 98.2%, and the proportion of goods damageds of hydrocarbon are 1.0%.
[embodiment 13]
Weighing 2 grams of granular sizes is 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 8.84 milliliters of mass concentrations are 0.004 grams per milliliter respectively
2ptCl
6solution and 14.4 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.4389 gram of SnCl
4solution, the sal volatile with 2.5% regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 76%, and the conversion ratio of oxygen is 98.1%, and the proportion of goods damageds of hydrocarbon are 0.8%.
[embodiment 14]
Weighing 2 grams of granular sizes is 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 8.84 milliliters of mass concentrations are 0.004 grams per milliliter respectively
2ptCl
6solution and 14.4 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.4389 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 8 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 75%, and the conversion ratio of oxygen is 98.5%, and the proportion of goods damageds of hydrocarbon are 0.9%.
[embodiment 15]
Weighing 2 grams of granular sizes is 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 8.84 milliliters of mass concentrations are 0.004 grams per milliliter respectively
2ptCl
6solution and 14.4 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.4389 gram of SnCl
4solution, add 0.5 gram of NaCl again, ammoniacal liquor with 2.5% regulates solution ph to 3.5, then flood in 80 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 8 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 69%, and the conversion ratio of oxygen is 98.01%, and the proportion of goods damageds of hydrocarbon are 1.3%.
[comparative example 1]
Weighing 2 grams of specific surfaces is 5 meters
2/ gram, granular size is the Al of 200 nanometers
2o
3carrier, pipettes the H that 0.88 milliliter of mass concentration is 0.004 grams per milliliter
2ptCl
6solution, drips 0.2195 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 66%, and the conversion ratio of oxygen is 96.8%, and the proportion of goods damageds of hydrocarbon are 1.7%.
[comparative example 2]
Weighing 2 grams of granular sizes is 60 nanometers, and specific surface is 50 meters
2/ gram, the nanometer Al of aperture 29 nanometer
2o
3carrier, pipettes the H that 0.88 milliliter of mass concentration is 0.004 grams per milliliter
2ptCl
6solution, drips 0.2195 gram of SnCl
4solution, the ammoniacal liquor with 2.5% regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 76%, and the conversion ratio of oxygen is 97.8%, and the proportion of goods damageds of hydrocarbon are 0.9%.
[comparative example 3]
Weighing 2 grams of specific surfaces is 10 meters
2/ gram, the nanometer Al of aperture 200 nanometer
2o
3carrier, adds 10 ml deionized water, pipettes the H that 0.88 milliliter of mass concentration is 0.004 grams per milliliter
2ptCl
6solution and 14.4 milliliters of mass concentrations are the Ce (NO of 0.0012 grams per milliliter
3)
4solution, drips 0.2195 gram of SnCl
4solution and 0.12 gram of NaNO
3solution, the ammoniacal liquor with 2.5% regulates solution ph to 1.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Loaded in fixed bed reactors by the catalyst of preparation, under 550 DEG C of conditions, carry out activity rating, result is as follows: in this process, the selective of hydrogen is 53%, and the conversion ratio of oxygen is 97.5%, and the proportion of goods damageds of hydrocarbon are 2%.
Claims (4)
1., for a hydrogen during propane dehydrogenation catalyst for selective oxidation, in catalyst weight percent, comprise following component:
A) at least one be selected from Pt, Pd, Ag, Au, Ir element or its oxide of 0.1 ~ 10%;
B) at least one be selected from Sn, Sb, Zn, Fe, Co, Ni element or its oxide of 0.25 ~ 10%;
C) at least one be selected from Ce, La, Zr element or its oxide of 0.1 ~ 10%;
D) particle diameter of 80 ~ 99% is the Al of 2 ~ 100 nanometers
2o
3;
Described nanometer Al
2o
3specific area be 30 ~ 200 meters
2/ gram, aperture is 15 ~ 45 nanometers.
2. described in claim 1 for the preparation method of hydrogen during propane dehydrogenation catalyst for selective oxidation, comprise following step:
A) by nanometer Al
2o
3carrier compressing tablet, screening, choose 40 ~ 60 mesh sieves divide after carrier calcination process 0.5 ~ 12 hour under 400 ~ 600 DEG C of conditions, obtain nanometer Al
2o
3carrier I;
B) by carrier I and the aequum solubility solution containing Pt, Pd, Ag, Au, Ir at least one element, the solubility solution containing Sn, Sb, Zn, Fe, Co, Ni at least one element, be mixed into mixture I containing the solubility Solutions Solution of Ce, La, Zr at least one element, with inorganic ammonia or inorganic ammonium salt solution under temperature is 10 ~ 80 DEG C of conditions, the pH value regulating mixture I is 1 ~ 7, obtains mixture II;
C) under temperature is 10 ~ 100 DEG C of conditions, said mixture II is flooded 0.5 ~ 8 hour, then carry out filtering, dry, 300 ~ 800 DEG C of roastings 0.5 ~ 12 hour, obtain required hydrogen selective oxidation catalyst.
3. according to claim 2 for the preparation method of hydrogen during propane dehydrogenation catalyst for selective oxidation, it is characterized in that inorganic ammonia is selected from ammoniacal liquor, inorganic ammonium salt is selected from ammonium carbonate or carbonic hydroammonium at least one.
4., according to claim 2 for the preparation method of hydrogen during propane dehydrogenation catalyst for selective oxidation, it is characterized in that the solubility solution of Pt is selected from H
2ptCl
6; The solubility solution of Sn is selected from SnCl
4; The solubility solution of Ce is selected from Ce (NO
3)
4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110300940.9A CN103028400B (en) | 2011-09-30 | 2011-09-30 | Selective oxidation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110300940.9A CN103028400B (en) | 2011-09-30 | 2011-09-30 | Selective oxidation catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103028400A CN103028400A (en) | 2013-04-10 |
| CN103028400B true CN103028400B (en) | 2015-06-10 |
Family
ID=48016093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110300940.9A Active CN103028400B (en) | 2011-09-30 | 2011-09-30 | Selective oxidation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103028400B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105582918B (en) * | 2014-10-24 | 2019-01-01 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of low-carbon paraffin and application thereof |
| CN104998667A (en) * | 2015-06-26 | 2015-10-28 | 王敏 | Propane dehydrogenation catalyst and preparation method thereof |
| CN105396586B (en) * | 2015-11-05 | 2018-09-04 | 中国海洋石油集团有限公司 | A kind of quaternary platinum base catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof |
| CN108722469B (en) | 2017-04-22 | 2021-11-05 | 天津大学 | Supported high-selectivity core-shell structure bimetallic catalyst and preparation method and application thereof |
| CN115055182B (en) * | 2022-07-01 | 2023-09-15 | 中国科学院生态环境研究中心 | Propane oxidative dehydrogenation catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1466558A (en) * | 2000-09-26 | 2004-01-07 | �����ɷ� | Method for the dehydrogenation of hydrocarbons |
| CN101015802A (en) * | 2007-02-09 | 2007-08-15 | 东南大学 | Catalyst for preparing propylene by propane dehydrogenation and its prepn. |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101411978A (en) * | 2008-11-28 | 2009-04-22 | 南开大学 | Catalyst for preparing propylene by propane dehydrogenation as well as preparation and application thereof |
-
2011
- 2011-09-30 CN CN201110300940.9A patent/CN103028400B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1466558A (en) * | 2000-09-26 | 2004-01-07 | �����ɷ� | Method for the dehydrogenation of hydrocarbons |
| CN101015802A (en) * | 2007-02-09 | 2007-08-15 | 东南大学 | Catalyst for preparing propylene by propane dehydrogenation and its prepn. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103028400A (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103028400B (en) | Selective oxidation catalyst and preparation method thereof | |
| CN105457653B (en) | A kind of surface strengthened palladium-based catalyst and preparation method thereof for low-concentration methane catalysis burning | |
| CN103894201B (en) | Catalyst for dehydrogenation of low-carbon paraffin, preparation method and its usage | |
| NO323722B1 (en) | Process for oxidation of ammonia | |
| CN104588023B (en) | Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN104107712B (en) | Mix C3/C4 alkane dehydrogenating catalysts and preparation method thereof | |
| Ai et al. | Effect of surface and bulk palladium doping on the catalytic activity of La 2 Sn 2 O 7 pyrochlore oxides for diesel soot oxidation | |
| CN109701547B (en) | Preparation method of manganese cerium catalyst with high methane catalytic activity and product | |
| CN104549248A (en) | Preparation method for catalyst for dehydrogenation of low-carbon alkane | |
| CN104549245B (en) | A kind of preparation method of dehydrogenation | |
| WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
| CN111790381A (en) | Metal catalyst for dehydrogenation of low-carbon alkane | |
| CN101249437B (en) | Ternary catalyst of magnalium composite oxides adulterating metallic and manufacture method thereof | |
| CN105646153B (en) | A kind of support type Au/C3N4The method of the nanocatalyst catalytic oxidation of cyclohexane of@SBA 15 | |
| CN106732539A (en) | Compound non-noble metal oxide catalyst for catalysis burning toluene and its preparation method and application | |
| CN104588033A (en) | Slurry bed Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN103846110A (en) | Activation method and application of Fischer-Tropsch synthesis catalyst | |
| CN108067228B (en) | Propane dehydrogenation catalyst and preparation method thereof | |
| CN102218314B (en) | Hydrogen selective oxidation catalyst used in the propane dehydrogenation process and preparation method thereof | |
| CN102864008B (en) | Composite oxide oxygen carrier and preparation method and application thereof | |
| CN110548521B (en) | High-performance low-temperature NH3-SCR catalyst and its preparation method and use | |
| CN105582920A (en) | Dehydrogenation catalyst for light alkanes and application of dehydrogenation catalyst | |
| CN112892569B (en) | Silicon carbide loaded cerium oxide catalyst and method for preparing sulfur by hydrogen sulfide selective oxidation under medium-high temperature condition by adopting same | |
| CN103030496B (en) | Method of selective oxidation of hydrogen in propane dehydrogenation process | |
| CN103769150A (en) | Low water ratio ethylbenzene dehydrogenation catalyst and method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |