CN106964392A - Oxidative dehydrogenation of propane catalyst and application thereof - Google Patents
Oxidative dehydrogenation of propane catalyst and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
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Abstract
The present invention relates to a kind of oxidative dehydrogenation of propane catalyst and application thereof, the problem of dehydrogenation conversion ratio that mainly prepared by solution prior art is relatively low.The present invention is by using in terms of parts by weight, including following components：A) 1~20 part of Cr element or its oxide；B) 0.1~5 part of B element and its oxide；C) 0~5 part of alkali metal or its oxide；D) technical scheme of 70~99 parts of MFI molecular sieves preferably solves the problem, has the advantages that technique is simple, activity is high, stability is good, the industrialized production available for propane and carbon dioxide preparing propene by oxidative dehydrogenation.
Description
Technical field
The present invention relates to a kind of oxidative dehydrogenation of propane catalyst and application thereof.
Background technology
Propylene is the Organic Ingredients that petrochemical industry is only second to ethene, mainly for the production of polypropylene,
Sorted according to consumption figure, propylene is additionally operable to production acrylonitrile, phenol, octyl alconyl, expoxy propane, third
The important chemical products such as olefin(e) acid.At present, propylene is still derived mainly from ethene coproduction and refinery's by-product, China
Technology for Increasing Propylene Yield is synchronous with world level, particularly FCC Technologies For Increasing Propylenes, in the world
Leading position.In addition with the development of coal chemical technology, particularly MTO technology commercializations, propylene
Yield is quickly increased.But the demand of propylene downstream product is more vigorous in recent years, according to China's throwing
Provide the Chinese propylene industry analysis report of consulting network's issue, prediction coming 10 years China propylene consumption figure
More than propylene supply, propylene imbalance between supply and demand is very prominent.Although propane direct dehydrogenation propylene can be solved
Certainly a part of problem, but be one because direct dehydrogenation reaction is a thermodynamical equilibrium limit procedure
Strong endothermic reaction, must can just obtain comparatively ideal olefin yields under low pressure, hot conditions, and too high
Reaction temperature will make alkane cracking reaction and deep dehydrogenation aggravation, easily occur polymerization, cyclisation, charing
Deng side reaction, make the quick carbon distribution of catalyst surface, inactivation, cause catalyst performance variation, selectivity
Relatively low the problems such as.
Oxidative dehydrogenation of propane technology is introducing small amounts agent, such as oxygen, dioxy in reaction raw materials
Change carbon, nitrogen dioxide etc., carry out dehydrogenation reaction, reaction temperature can not only be reduced, enable reaction not by
Thermodynamical equilibrium is limited, and improves conversion of propane and Propylene Selectivity, and catalyst not easy in inactivation,
Stability is improved.Therefore, in recent years preparing propene by oxidative dehydrogenation of propane by domestic and international researcher
Greatly concern.At present, catalyst for preparing propene by oxidative dehydrogenation of propane system mainly has two aspects, i.e. vanadium
Base catalyst and non-catalytic component based on vanadium, catalytic component based on vanadium can generally be divided into VMgO catalyst and
Supported vanadium-based catalyst；Non- catalytic component based on vanadium includes molybdenum oxide catalyst, rare earth catalyst, phosphorus
Barbiturates catalyst and transition metal-type catalyst etc..In catalytic component based on vanadium, VMgO catalyst performances
It is relatively preferable, and Propylene Selectivity is relatively low on support type vanadium oxide catalyst.Chinese patent CN
1396146A discloses one kind using mesoporous molecular sieve SBA-15 as carrier, using V as active component
Loaded catalyst, the conversion of propane at 600 DEG C is 50%, and Propylene Selectivity is 72%, is received
Rate is 36%.Nickel molybdate is more effective to dehydrogenating low-carbon alkane in molybdic acid saline catalyst, and particularly third
The preparing propene by oxidative dehydrogenation of alkane has preferable catalytic performance.Phosphoric acid salt catalyst is generally divided into pyrophosphoric acid
Salt, the vanadium aluminum phosphate and molybdophosphate of substitution, Chinese patent CN 101219389A disclose one kind
Phosphato-molybdic heteropolyacid alkali metal salt-nickel oxide composite material catalyst, in 450 DEG C, catalyst amount 0.5
Gram, air speed is 6000 milliliters of hours- 1Gram- 1When, conversion of propane is 23.6%, Propylene Selectivity
For 48.7%.Rare-earth-based oxyfluoride has preferable catalytic to the selective oxidation of low-carbon alkanes
Can, in the reaction of the preparing propene by oxidative dehydrogenation of propane, when best result is 500 DEG C,
3%Cs2O/2CeO2/CeF3Upper conversion of propane is 53.4%, Propylene Selectivity about 67.5%, propylene
Yield about 36% [H.L.Wan, X.P.Zhou, W.Z.Weng, R.Q.Long, Z.S.Chao, W.
D.Zhang, M.S.Chen, J.Z.Luo, S.Q.Zhou, Catal Today, 1999,51：161],
But the catalyst easy in inactivation.In addition to above-mentioned catalyst system, also there are more new oxidative dehydrogenation of propane to urge
Agent system is developed and reported that United States Patent (USP) US20110045969A reports a kind of Pt bases
Oxidative dehydrogenation of propane catalyst, conversion of propane 25.7%, Propylene Selectivity 68.0% during 500 DEG C of reactions.
Chinese patent CN 1686085A disclose one kind using gallium oxide as active component, with high silica alumina ratio
HZSM-5 zeolites are reaction, propene yield 25.7%, third at the catalyst system of carrier, 600 DEG C
Alkene selectivity 57.3%.Chinese patent CN102294251A discloses one kind with nickel oxide or four oxygen
Change three cobalts for active component, metal sulfate is the nano-oxide catalyst of modification component, and it is third
Alkane/oxygen/nitrogen=1.2/1/8, air speed is 30000 milliliters of hours- 1Gram- 1, catalyst amount 0.1
Gram, during 400 DEG C of reaction temperature, conversion of propane is 25.8%, and Propylene Selectivity is 46.8%.Generation
Boundary patent WO 0048971 discloses a kind of Ni or the compound as catalyst containing Ni, by lower alkanes
Hydrocarbon (such as ethane, propane, iso-butane, normal butane), which is passed through together with oxygen in reactor, to react,
The conversion ratio of ethane is more than 10% under the conditions of 250~350 DEG C, and ethylene selectivity is higher than 70%, uses
In the conversion ratio also only 20% of oxidative dehydrogenation of propane, selectivity 70%.Above-mentioned oxidative dehydrogenation of propane catalysis
Agent system, catalyst activity is relatively low, less stable, therefore seeks high activity, has good stability
Oxydehydrogenation catalyst is one of focus of the current repercussion study.
Although oxidative dehydrogenation of propane catalyst has been achieved with greater advance at present, catalyst work is still suffered from
The problem of in terms of the relatively low, less stable of property.Cr is direct in propane as transition metal
Dehydrogenation field is widely used, and when modified with alkali metal promoter and other nonmetalloids, can be improved
Cr catalyst surface characteristics, contribute to active component Cr in stable react, therefore with preferably application
Prospect.
The content of the invention
One of technical problems to be solved by the invention are oxidative dehydrogenation of propane catalyst in the prior art
There is provided a kind of new oxidative dehydrogenation of propane catalyst for the problem of activity is relatively low.The invention solves the problems that skill
The two of art problem are to provide a kind of purposes of the catalyst.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of propane oxygen
Fluidized dehydrogenation catalyst, in terms of parts by weight, including following components：
A) 1~20 part of Cr elements or its oxide；
B) 0.1~5 part of B element or its oxide；
C) 0~5 part of alkali metal or its oxide；
D) 70~99 parts of MFI carriers.
In above-mentioned technical proposal, in terms of oxidative dehydrogenation of propane catalyst weight number, chromium or its oxide
Number be 3~10 parts.
In above-mentioned technical proposal, in terms of oxidative dehydrogenation of propane catalyst weight number, B or its oxide
Number be 0.5~2 part.
In above-mentioned technical proposal, in terms of oxidative dehydrogenation of propane catalyst weight number, alkali metal or its oxygen
0.1~1 part of compound.
In above-mentioned technical proposal, with Cr in molar ratio computing catalyst:B is 3~50：1.
In above-mentioned technical proposal, with Cr in molar ratio computing catalyst:Alkali metal B is 0.1~10：1.
In above-mentioned technical proposal, the silica alumina ratio of MFI molecular sieves is 10~1000, preferably 60~500.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：By the catalysis
Agent is used for oxidative dehydrogenation of propane, and oxidant is CO2、NO2, air or wherein any two gaseous mixture,
Reaction condition is：Reaction pressure be 0~1MPa, temperature be 500~650 DEG C, mass space velocity be
0.1~10h-1；Reaction raw materials, oxidant obtain propylene with the catalyst haptoreaction.
The preparation method of heretofore described catalyst comprises the following steps：
A) by the tabletting of MFI molecular sieves, screening, choose the carrier after 40~60 mesh sieves point 400~
Calcination process 0.5~12 hour under the conditions of 600 DEG C, obtains catalyst carrier I；
B) by carrier I and soluble solution of the aequum containing Cr, the soluble compound containing B,
Soluble solution mixing resulting mixture I containing the alkali metal such as K or Li, Na, Rb, Cs, with inorganic
Ammonia or inorganic ammonium salt solution is under the conditions of 10~80 DEG C in temperature, regulation mixture I pH value for 1~
7, obtain mixture II；
C) said mixture II is impregnated 0.5~8 hour under the conditions of temperature is 10~100 DEG C, then
Filtered, dried, 300~800 DEG C are calcined 0.5~12 hour, obtain required oxidative dehydrogenation of propane
Catalyst.
In above-mentioned technical proposal, inorganic ammonia or inorganic ammonium salt preferred scheme are selected from ammoniacal liquor, ammonium carbonate or carbon
Sour hydrogen ammonium, the pH value preferred scope of solution is 1~7, and more preferably scope is 1~3；Dipping temperature
Preferred scope is 50~80 DEG C, and dip time preferred scope is 1~3 hour, catalyst sintering temperature
Preferred scope is 400~600 DEG C, and roasting time preferred scope is 4~8 hours.
Obtained catalyst carries out activity rating in isotherm formula fixed bed reactors as stated above, right
For preparing propene by oxidative dehydrogenation of propane system appraisal, summary process is as follows：
The gases such as propane, carbon dioxide and nitrogen are adjusted into flow by mass flowmenter (wherein to aoxidize
Property gas can contain oxygen), mixed into pre-add hot-zone, subsequently into reaction zone, reactor
Pre-add hot-zone and reaction zone use electric-heating-wire-heating, make up to predetermined temperature, reactor it is interior
Footpath is Ф 9mm- Ф 6mm stainless steel sleeve pipe, is about 400mm.Reacted gas passes through condensation
After tank, into its composition of gas chromatographic analysis.
Evaluating catalyst condition is as follows in isotherm formula fixed bed reactors：By 0.5 gram or so of catalyst
It is fitted into the isothermal reactor that internal diameter is Ф 9mm- Ф 6mm (catalyst bed layer height about 17mm),
Reaction pressure is normal pressure, gas space velocity 600 hours-1, 560 DEG C of reaction temperature.
Conversion of propane and Propylene Selectivity are calculated as follows：
During oxidative dehydrogenation of propane, simple Cr2O3/ HZSM-5 catalyst due to surface acidity compared with
By force, the easy carbon distribution of catalyst surface and accelerate deactivation rate.To slow down catalyst inactivation speed, typically
Need to add alkali metal reduction catalyst surface acidity, catalyst performance is improved, while can also drop
Low reaction temperatures mitigate catalyst surface carbon distribution.Nonmetalloid B easily replaces Al in molecular sieve, shape
Into B occupy-places；When active component Cr is added, can be replaced by Cr, increase active sites content and
The distribution of catalyst surface, so as to improve catalyst performance.Using above-mentioned appreciation condition by the present invention's
Catalyst be used for oxidative dehydrogenation of propane reaction in, its Activity evaluation shows, the catalyst have compared with
High conversion of propane, compared with low reaction temperatures reachable 43%, while there is higher olefine selective,
More than 73%, preferable technique effect is achieved.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
3 grams of Si/Al=20 of weighing MFI molecular sieves, 0.47 gram of nine water chromic nitrate, 0.053 gram of boric acid,
In 0.03 gram of potassium nitrate, the deionized water for being added to 10 milliliters, pH value of solution is adjusted with 2.5% ammoniacal liquor
Value is to 3.5, after then being impregnated 1 hour in 80 DEG C of water-baths, takes out sample and is filtered, at 100 DEG C
Dried 8 hours in baking oven, then sample be put into Muffle furnace roasting 4 hours under the conditions of 550 DEG C,
Obtain required catalyst.Propane, carbon dioxide, nitrogen mixed gas are adjusted by mass flowmenter
Amount of restriction, is mixed into pre-add hot-zone, subsequently into reaction zone, the pre-add hot-zone of reactor and
Reaction zone uses electric-heating-wire-heating, makes up to predetermined temperature, the internal diameter of reactor is
Ф 10mm- Ф 7mm quartz ampoule, is about 450mm.After reacted gas is by drainer, enter
Entering gas chromatographic analysis, it is constituted.
Evaluating catalyst condition is as follows in isotherm formula fixed bed reactors：1.0 grams of catalyst are loaded
(catalyst bed layer height 18mm) is stated in isothermal fixed bed reactors, reaction pressure is normal pressure, mixed
The volume flow ratio for closing propane, carbon dioxide and nitrogen in gas is 1:2:2.7, gas space velocity 750 hours-1, 560 DEG C of reaction temperature.It the results are shown in Table 1.
【Embodiment 2】
Weigh 3 grams of Si/Al=1000 MFI molecular sieves, 0.47 gram of nine water chromic nitrate, 0.053 gram of boron
Acid, 0.03 gram of potassium nitrate, in the deionized water for being added to 10 milliliters, adjusted with 2.5% ammoniacal liquor
Solution ph is to 3.5, after then being impregnated 1 hour in 80 DEG C of water-baths, takes out sample and is filtered,
Dried 8 hours in 100 DEG C of baking ovens, then sample is put into Muffle furnace the roasting under the conditions of 550 DEG C
4 hours, obtain required catalyst.Examination condition be the same as Example 1, the results are shown in Table 1.
【Embodiment 3】
3 grams of Si/Al=60 of weighing MFI molecular sieves, 0.47 gram of nine water chromic nitrate, 0.053 gram of boric acid,
In 0.03 gram of potassium nitrate, the deionized water for being added to 10 milliliters, pH value of solution is adjusted with 2.5% ammoniacal liquor
Value is to 3.5, after then being impregnated 1 hour in 80 DEG C of water-baths, takes out sample and is filtered, at 100 DEG C
Dried 8 hours in baking oven, then sample be put into Muffle furnace roasting 4 hours under the conditions of 550 DEG C,
Obtain required catalyst.Examination condition be the same as Example 1, the results are shown in Table 1.
【Embodiment 4】
Weigh 3 grams of Si/Al=150 MFI molecular sieves, 0.47 gram of nine water chromic nitrate, 0.265 gram of boron
In acid, 0.03 gram of potassium nitrate, the deionized water for being added to 10 milliliters, 87 grams of carrying aluminas are added
Body, adjusts solution ph to 3.5 with 2.5% ammoniacal liquor, is then impregnated 1 hour in 80 DEG C of water-baths
Afterwards, take out sample to be filtered, dried 8 hours in 100 DEG C of baking ovens, then sample is put into Muffle
It is calcined 4 hours under the conditions of 550 DEG C in stove, obtains required catalyst.Examination condition be the same as Example
1, it the results are shown in Table 1.
【Embodiment 5】
Weigh 3 grams of Si/Al=300 MFI molecular sieves, 0.47 gram of nine water chromic nitrate, 0.053 gram of boron
In acid, 0.13 gram of sodium nitrate, the deionized water for being added to 10 milliliters, 87.498 grams of oxidations are added
Alumina supporter, adjusts solution ph to 3.5 with 2.5% ammoniacal liquor, then impregnates 1 in 80 DEG C of water-baths
After hour, take out sample and filtered, dried 8 hours in 100 DEG C of baking ovens, then sample is put into
It is calcined 4 hours under the conditions of 550 DEG C in Muffle furnace, obtains required catalyst.Examination condition is with real
Example 1 is applied, 1 is the results are shown in Table.
【Embodiment 6】
Weigh 3 grams of Si/Al=500 MFI molecular sieves, 0.47 gram of nine water chromic nitrate, 0.053 gram of boron
It is molten with 2.5% ammoniacal liquor regulation in acid, 0.03 gram of lithium nitrate, the deionized water for being added to 10 milliliters
Liquid pH value is to 7, after then being impregnated 1 hour in 80 DEG C of water-baths, takes out sample and is filtered,
Dried 8 hours in 100 DEG C of baking ovens, then sample is put into Muffle furnace is calcined 4 under the conditions of 550 DEG C
Hour, obtain required catalyst.Examination condition be the same as Example 1, the results are shown in Table 1.
【Embodiment 7】
3 grams of Si/Al=800 of weighing MFI molecular sieves, 0.47 gram of chromic nitrate, 0.053 gram of boric acid,
In 0.047 gram of rubidium nitrate, the deionized water for being added to 10 milliliters, solution is adjusted with 2.5% ammoniacal liquor
PH value is to 1, after then being impregnated 1 hour in 80 DEG C of water-baths, takes out sample and is filtered, at 120 DEG C
Dried 8 hours in baking oven, then sample be put into Muffle furnace roasting 4 hours under the conditions of 550 DEG C,
Obtain required catalyst.Examination condition be the same as Example 1, the results are shown in Table 1.
【Embodiment 8】
Weigh 3 grams of Si/Al=60 MFI molecular sieves, 1.56 grams of chromic nitrates, 0.027 gram of boric acid, 0.06
In gram potassium nitrate, the deionized water for being added to 10 milliliters, solution ph is adjusted with 2.5% ammoniacal liquor
To 5, after then being impregnated 1 hour in 80 DEG C of water-baths, take out sample and filtered, in 120 DEG C of bakings
Dried 8 hours in case, then sample is put into Muffle furnace roasting 4 hours under the conditions of 550 DEG C, obtained
To required catalyst.The catalyst of preparation is fitted into fixed bed reactors, under the conditions of 550 DEG C
Activity rating is carried out, 1 is the results are shown in Table.
【Embodiment 9】
Weigh 3 grams of Si/Al=60 MFI molecular sieves, 0.16 gram of chromic nitrate, 0.106 gram of boric acid, 0.006
In gram potassium nitrate, the deionized water for being added to 10 milliliters, solution ph is adjusted with 2.5% ammoniacal liquor
To 3, after then being impregnated 1 hour in 80 DEG C of water-baths, take out sample and filtered, in 120 DEG C of bakings
Dried 8 hours in case, then sample is put into Muffle furnace roasting 4 hours under the conditions of 550 DEG C, obtained
To required catalyst.Examination condition be the same as Example 1, the results are shown in Table 1.
【Embodiment 10】
Weigh 3 grams of Si/Al=60 MFI molecular sieves, 3.13 grams of chromic nitrates, 0.053 gram of boric acid, 0.3
In gram potassium nitrate, the deionized water for being added to 10 milliliters, adjust solution ph with 2.5% ammoniacal liquor
To 3.5, after then being impregnated 1 hour in 50 DEG C of water-baths, take out sample and filtered, at 120 DEG C
Dried 8 hours in baking oven, then sample be put into Muffle furnace roasting 4 hours under the conditions of 550 DEG C,
Obtain required catalyst.Examination condition be the same as Example 1, the results are shown in Table 1.
【Embodiment 11】
Weigh 3 grams of Si/Al=60 MFI molecular sieves, 0.78 gram of chromic nitrate, 0.053 gram of boric acid, 0.12
In gram potassium nitrate, the deionized water for being added to 10 milliliters, solution ph is adjusted with 2.5% ammoniacal liquor
To 3.5, after then being impregnated 1 hour in 50 DEG C of water-baths, take out sample and filtered, at 100 DEG C
Dried 8 hours in baking oven, then sample be put into Muffle furnace roasting 4 hours under the conditions of 550 DEG C,
Obtain required catalyst.Examination condition be the same as Example 1, the results are shown in Table 1.
【Embodiment 12】
Weigh 3 grams of Si/Al=60 MFI molecular sieves, 0.78 gram of chromic nitrate, 0.053 gram of boric acid, 0.3
In gram potassium nitrate, the deionized water for being added to 10 milliliters, solution ph is adjusted with 2.5% ammoniacal liquor
To 3.5, after then being impregnated 1 hour in 50 DEG C of water-baths, take out sample and filtered, at 100 DEG C
Dried 8 hours in baking oven, then sample be put into Muffle furnace roasting 4 hours under the conditions of 550 DEG C,
Obtain required catalyst.Examination condition be the same as Example 1, the results are shown in Table 1.
【Comparative example 1】
3 grams of Si/Al=150 of weighing MFI molecular sieves, 0.47 gram of chromic nitrate, 0.027 gram of boric acid,
In the deionized water for being added to 10 milliliters, solution ph is adjusted to 4 with 3.0% ammoniacal liquor, then
After being impregnated 1 hour in 70 DEG C of water-baths, take out sample and filtered, 8 are dried in 100 DEG C of baking ovens
Hour, then sample is put into Muffle furnace roasting 4 hours under the conditions of 550 DEG C, urging needed for obtaining
Agent.Examination condition be the same as Example 1, the results are shown in Table 1.
【Comparative example 2】
3 grams of Si/Al=10 of weighing MFI molecular sieves, 0.47 gram of chromic nitrate, 0.03 gram of potassium nitrate,
In the deionized water for being added to 10 milliliters, solution ph is adjusted to 4 with 3.0% ammoniacal liquor, then
After being impregnated 1 hour in 70 DEG C of water-baths, take out sample and filtered, 8 are dried in 110 DEG C of baking ovens
Hour, then sample is put into Muffle furnace roasting 4 hours under the conditions of 550 DEG C, urging needed for obtaining
Agent.Examination condition be the same as Example 1, the results are shown in Table 1.
【Comparative example 3】
3 grams of Si/Al=100 MFI molecular sieves are weighed, 0.47 gram of chromic nitrate is added to 10 milliliters
In deionized water, solution ph is adjusted to 1.5 with 3.0% ammoniacal liquor, is then soaked in 70 DEG C of water-baths
After stain 1 hour, take out sample and filtered, drying 8 hours in 110 DEG C of baking ovens, then by sample
It is put into Muffle furnace and is calcined 4 hours under the conditions of 550 DEG C, obtains required catalyst.Examination condition
Be the same as Example 1, the results are shown in Table 1.
Table 1
【Embodiment 13~15】
Will【Embodiment 1】The catalyst prepared is used for oxidative dehydrogenation of propane, and reaction raw materials are third
Alkane, carbon dioxide, nitrogen mixture (nitrogen makees Balance Air), reaction raw materials under certain condition with
Catalyst haptoreaction obtains propylene；Reaction condition and evaluation result are shown in Table 2.
Table 2
Claims (9)
1. a kind of oxidative dehydrogenation of propane catalyst, in terms of catalyst weight number, including following components：
A) 1~20 part of Cr element or its oxide；
B) 0.1~5 part of B element and its oxide；
C) 0~5 part of alkali metal or its oxide；
D) 70~99 parts of MFI molecular sieves.
2. oxidative dehydrogenation of propane catalyst according to claim 1, it is characterised in that with propane oxygen
The number of fluidized dehydrogenation catalyst weight number meter, chromium or its oxide is 3~10 parts.
3. oxidative dehydrogenation of propane catalyst according to claim 1, it is characterised in that with propane oxygen
The number of fluidized dehydrogenation catalyst weight number meter, B or its oxide is 0.5~2 part.
4. oxidative dehydrogenation of propane catalyst according to claim 1, it is characterised in that with propane oxygen
0.1~1 part of fluidized dehydrogenation catalyst weight number meter, alkali metal or its oxide.
5. oxidative dehydrogenation of propane catalyst according to claim 1, it is characterised in that with mol ratio
Count Cr in catalyst:B is 3~50：1.
6. oxidative dehydrogenation of propane catalyst according to claim 1, it is characterised in that with mol ratio
Count Cr in catalyst:Alkali metal B is 0.1~10：1.
7. oxidative dehydrogenation of propane catalyst according to claim 1, it is characterised in that MFI molecules
The silica alumina ratio of sieve is 10~1000.
8. oxidative dehydrogenation of propane catalyst according to claim 7, it is characterised in that MFI molecules
It is 60~500 to sieve silica alumina ratio.
9. any one of claim 1~8 catalyst is used for into oxidative dehydrogenation of propane, oxidant is
CO2、NO2, air or wherein any two gaseous mixture, reaction condition is：Reaction pressure be 0~1MPa,
Temperature is 500~650 DEG C, mass space velocity is 0.1~10h-1；Reaction raw materials, oxidant and the catalysis
Agent haptoreaction obtains propylene.
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| CN109289908A (en) * | 2018-10-18 | 2019-02-01 | 南京大学连云港高新技术研究院 | A kind of preparation method for the high initial activity catalyst of preparing propylene by dehydrogenating propane |
| CN112536072A (en) * | 2019-09-20 | 2021-03-23 | 中国石油化工股份有限公司 | Impregnation liquid and preparation method thereof, catalyst and preparation method and application thereof, and alkane dehydrogenation method |
| CN114522703A (en) * | 2022-02-23 | 2022-05-24 | 浙江浙能技术研究院有限公司 | Preparation method and application of NiO-X catalyst based on anionic surface modification |
| CN114713266A (en) * | 2022-05-05 | 2022-07-08 | 内蒙古师范大学 | Ammonium modified silicon oxide loaded boron oxide for propane oxidative dehydrogenation and preparation method thereof |
| CN115501905A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Catalyst with dehydrogenation function, preparation method and application thereof, and method for preparing small-molecule olefin |
| CN115501904A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Shaped support, shaped dehydrogenation catalyst, method for the production thereof and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109289908A (en) * | 2018-10-18 | 2019-02-01 | 南京大学连云港高新技术研究院 | A kind of preparation method for the high initial activity catalyst of preparing propylene by dehydrogenating propane |
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| CN112536072B (en) * | 2019-09-20 | 2023-09-29 | 中国石油化工股份有限公司 | Impregnating solution and preparation method thereof, catalyst and preparation method and application thereof, and alkane dehydrogenation method |
| CN115501905A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Catalyst with dehydrogenation function, preparation method and application thereof, and method for preparing small-molecule olefin |
| CN115501904A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Shaped support, shaped dehydrogenation catalyst, method for the production thereof and use thereof |
| CN114522703A (en) * | 2022-02-23 | 2022-05-24 | 浙江浙能技术研究院有限公司 | Preparation method and application of NiO-X catalyst based on anionic surface modification |
| CN114713266A (en) * | 2022-05-05 | 2022-07-08 | 内蒙古师范大学 | Ammonium modified silicon oxide loaded boron oxide for propane oxidative dehydrogenation and preparation method thereof |
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