CN110115995A - A kind of iron sodium/molybdenum composite metal oxide catalyst and its preparation method and application - Google Patents
A kind of iron sodium/molybdenum composite metal oxide catalyst and its preparation method and application Download PDFInfo
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- CN110115995A CN110115995A CN201810112390.XA CN201810112390A CN110115995A CN 110115995 A CN110115995 A CN 110115995A CN 201810112390 A CN201810112390 A CN 201810112390A CN 110115995 A CN110115995 A CN 110115995A
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Abstract
The present invention discloses a kind of iron sodium/molybdenum composite metal oxide catalyst and its preparation method and application, the presoma of different amounts of iron oxide and molybdenum oxide is impregnated on alumina support jointly, 1MoxFeAl catalyst is obtained after drying, roasting, tabletting screening, wherein the load capacity of iron is 3-40%, x represents the molar ratio of iron and molybdenum, molar ratio range 3-15.The catalyst can be realized simultaneously propane high conversion and propylene it is highly selective, while in catalyst Lattice Oxygen introducing, broken thermodynamical equilibrium, improved the efficiency of catalyst.Propane passes through after catalyst bed, and the metal oxide of high-valence state is reduced, and is lost Lattice Oxygen and is become lower valency, loses catalytic activity.By N2After purifying, at the reaction temperatures, it is passed through air, by reoxidized time high-valence state of post catalyst reaction, supplements Lattice Oxygen, have the ability of oxidative dehydrogenation of propane again.
Description
Technical field
The present invention relates to a kind of metal composite oxide dehydrogenations, specifically include the oxidation of loading type iron sodium/molybdenum composite metal
The preparation of object catalyst and its application during chemical chain dehydrogenating propane.
Background technique
Propylene is a kind of important industrial chemicals, mainly for the production of the production of the chemical industry such as polypropylene, acrylonitrile, propylene oxide
Product, at this stage, the production capacity of propylene increase rapidly, but main source or light oil pyrolysis and mink cell focus catalytic cracking
By-product in technique.It is rich in a large amount of low-carbon alkanes in shale gas, is rationally produced using low value saturated alkane as a kind of
The effective way of the corresponding alkene of high added value, dehydrating alkanes recent years have obtained extensive concern.
By taking propane direct dehydrogenation (PDH) as an example, industrial catalyst mainly includes supported Pt catalysts and Cr2O3Catalyst,
Using Pt series catalysts, cost of investment is high, although the cost that Cr series catalysts, which have dropped low, to be produced, it makes and uses process
The Cr of middle generation6+Huge harm can be generated to human body and environment.On the other hand, PDH is strong endothermic reaction, in stage of reaction energy
Consumption is higher, simultaneously because being limited by thermodynamical equilibrium, the conversion per pass of propane is limited.Because C-C bond energy is than c h bond energy
It is low, so there are more side reaction (cracking, carbon distributions etc.) in certain embodiments, selectivity and regenerability requirement to catalyst
It is higher.Oxidative dehydrogenation (ODH) is that the production technology of another propane propylene is broken although ODH is a kind of exothermic reaction
The thermodynamics limitation of reaction, and reaction temperature is lower, decrease influence of the carbon distribution to catalyst, but in molecular oxygen
Under effect, propylene tends to the fracture of further occurrence C-C, and complete oxidation occurs and generates oxycarbide, and the selectivity of propylene is low,
And alkane and oxygen are mixed security risk, increase industrialized difficulty.In view of limitation existing for PDH and ODH,
There is an urgent need to develop the techniques of new dehydrogenating propane production propylene.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of iron sodium/molybdenum composite metal oxide catalyst and
Preparation method and application, in the reaction for chemical chain dehydrogenating propane, to break thermodynamics limitation, highly selective preparation third
Alkene.Using the c h bond of the lattice oxygen activation propane in iron sodium/molybdenum composite metal oxide in the present invention, driving a reaction is to generating propylene
Direction carry out, compared to simple iron oxide oxygen carrier, the doping of molybdenum improves the activity of Lattice Oxygen, promote propane turn
Change.
Technical purpose of the invention is achieved by following technical proposals:
Iron sodium/molybdenum composite metal oxide catalyst is made of carrier and iron sodium/molybdenum composite metal oxide, and carrier is carrier
Al2O3, the two-phase of iron sodium/molybdenum composite metal oxide is iron oxide and molybdenum oxide, and iron oxide and molybdenum oxide form solid solution on carrier
The molar ratio of body, iron and molybdenum is 3-30；Relative to carrier, the load capacity of iron oxide is 4-60%, and the load capacity of molybdenum oxide is 2-
30%.
In above-mentioned iron sodium/molybdenum composite metal oxide catalyst, the molar ratio of iron and molybdenum is 3-15
In above-mentioned iron sodium/molybdenum composite metal oxide catalyst, iron oxide is di-iron trioxide, and molybdenum oxide is molybdenum trioxide.
In above-mentioned iron sodium/molybdenum composite metal oxide catalyst, the load capacity of iron oxide is 40-60%, i.e. oxidation irony
Amount/(quality sum of iron oxide and carrier).
In above-mentioned iron sodium/molybdenum composite metal oxide catalyst, the load capacity of molybdenum oxide is 5-20%, i.e., molybdenum oxide quality/
(quality sum of molybdenum oxide and carrier).
In above-mentioned iron sodium/molybdenum composite metal oxide catalyst, the lanthanoid metal of metallic iron molal quantity 0.1-2% is added, it is excellent
Select 0.5-1% lanthanoid metal.
The preparation method of iron sodium/molybdenum composite metal oxide catalyst carries out as steps described below:
Step 1, the soluble-salt containing metallic iron and the soluble-salt containing metal molybdenum are evenly spread into deionized water
In, form homogeneous transparent solution；
Step 2, according to the method for incipient impregnation, by carrier Al2O3It is impregnated in the solution of step 1；
Step 3, the carrier after impregnating stands 8-12h under 20-25 degrees Celsius of room temperature, is then transferred into 80-100
DEG C environment in dry 8-12h, finally the compound gold of iron molybdenum can be obtained in 3-8 hours in 500-600 DEG C of roastings in air atmosphere
Belong to oxide catalyst, is marked in the present invention and specific embodiment with 1MoxFeAl catalyst, wherein x represents metallic iron
With the molar ratio of metal molybdenum.
In the above preparation method, the soluble-salt containing metallic iron is nine water ferric nitrates, iron chloride or ferric sulfate.
In the above preparation method, the soluble-salt containing metal molybdenum is ammonium molybdate.
In the above preparation method, in step 1, the soluble-salt containing lanthanoid metal is added, so that lanthanoid metal is impregnated into
On carrier, addition of the lanthanoid metal to catalyst is realized, the soluble-salt containing lanthanoid metal is lanthanum nitrate hexahydrate, lanthanum chloride or sulphur
Sour lanthanum, the additive amount of lanthanoid metal are 0.1-the 2% of metallic iron molal quantity, preferably 0.5-1%.
In the above preparation method, in step 3, the carrier after dipping stands 10-under 20-25 degrees Celsius of room temperature
12h is then transferred into 80-90 DEG C of environment dry 10-12h, roasts 4-6 hours for 550-600 DEG C in air atmosphere.
Iron sodium/molybdenum composite metal oxide catalyst of the invention is carrying out in use, catalyst is uniformly mixed with quartz sand
It is placed in reaction bed, is passed through nitrogen purging bed, be passed through reaction gas later, reaction gas and nitrogen total flow are 20-
50ml/min, reaction gas percentage by volume are 10-30%.The mass ratio of catalyst and quartz sand is (0.2-1): 1, preferably
(0.5-0.8): 1, the temperature of reaction is 550-600 degrees Celsius, preferably 560-580 DEG C.
It is carrying out in use, being sieved into 20-40 after by iron sodium/molybdenum composite metal oxide catalyst (powder) compression molding
The pellet type catalyst of mesh size.
It is a kind of advanced fuel transformation technology that chemical chain technology (chemical looping), which is used in the present invention, benefit
Reinforce the activation to reaction gas (such as propane) c h bond, highly selective production propylene with the Lattice Oxygen in metal oxide.Such as
Shown in Fig. 1, chemical chain dehydrogenating propane process is divided into two processes of reduction and oxidation, restores in bed, hydrogen in product or in
Between product hydrogen by the lattice oxygen consumption in oxygen carrier, broken the limitation of thermodynamical equilibrium, promoted reaction to the side for generating propylene
To progress.The oxidability of Lattice Oxygen is weaker simultaneously, avoids propylene by deep oxidation into oxycarbide.On the other hand, oxygen carrier
Intracorporal Lattice Oxygen also inhibits the generation of carbon distribution to a certain extent, has delayed the inactivation of catalyst.Specific reaction is as follows:
CnH2n+2+MOx=CnH2n+MOx-1+H2O
In oxidation bed, the metal oxide being reduced with air reaction, realizes oxidation regeneration at the reaction temperatures, by low
Valence state is re-converted to the high-valence state with high activity.In regenerative process, the recycle heat of oxidation reaction and carbon distribution burning generation
Into reduction bed, the self-heating operation of oxidation-reduction process is realized, also, chemical chain technique avoids oxygen and fuel gas
It directly contacts, without separating to air, has saved cost.
With the progress of reaction, the Lattice Oxygen in catalyst is consumed, and needs to regenerate catalyst, to guarantee to be catalyzed
The high activity of agent.The propane in nitrogen exclusion reaction bed is passed first into, is then passed through air, the load of lower valency at the reaction temperatures
Oxysome is oxidized back high-valence state again, carries out dehydrogenation reaction again after nitrogen purging.Chemical chain dehydrogenation is in nothing point
The oxidative dehydrogenation occurred under conditions of sub- oxygen, the Lattice Oxygen in higher valence metal oxide is as oxygen source, (such as with reaction gas
Propane) in hydrogen combine and generate water, driving a reaction is carried out to the direction for generating corresponding alkene (such as propylene).
Preferred alkane includes the straight chain alkane of 2-6 carbon atom in carrying out low-carbon alkanes (i.e. reaction gas) certain embodiments
Hydrocarbon, wherein most preferred alkane is propane.
Individual efficiency of metal oxide during chemical chain reaction is lower, main reason is that, the work of Lattice Oxygen
Property is lower, therefore, in catalyst of the invention, Al2O3In addition to maintain active component dispersity other than, also with active component
Synergistic effect, ensure that higher propane conversion per pass and Propylene Selectivity.
Compared with prior art, advantage of the present invention is as follows:
(1) loading type iron sodium/molybdenum composite metal oxide shows different lattices compared to single metal oxide
The transmission capacity of oxygen improves the conversion per pass of propane and the selectivity of propylene.It, can be with by adjusting the molar ratio of iron and molybdenum
The conversion ratio and selectivity of effective regulation reaction, to reach optimum value.
(2) using iron oxide as oxygen carrier in the present invention, cheap, nontoxic, there are no pollution to the environment, and fusing point is high,
Not easy-sintering in oxidation-reduction process, meanwhile, iron oxide will pass through ferroso-ferric oxide in reduction process, after ferrous oxide
It can become the iron of metallic state, more Lattice Oxygens can be provided.
(3) Pt and high toxicity metal Cr without precious metal in iron sodium/molybdenum composite metal oxide catalyst prepared by the present invention,
The alkane dehydrogenating catalyst for also not needing the low environmental protection such as introducing vulcanizing agent equally, is still able to maintain higher activity and selectivity.
(4) catalyst is prepared by simple dipping method in the present invention, and operation is simple, and catalyst passes through tabletting,
It can be reacted in fixed bed after screening, not need that other binder is added.
(5) catalyst is after by multiple redox regeneration cycles, and performance is relatively stable, conversion ratio and selectivity
It is basically unchanged.
(6) catalyst being reduced is passed through air under desorption temperature, and the metal oxide of lower valency supplements Lattice Oxygen, weight
It newly is oxidized to high-valence state metal oxide, saves the high expense of air separation, simultaneous oxidation reaction and carbon distribution burning generate
Heat feedback to reduction bed, provide heat for dehydrogenation reaction, reduce the energy consumption of system.
(7) present invention introduces chemical chain technology in the reaction of dehydrogenating propane, improves the conversion per pass of propane, and
The selectivity of product propylene reduces the energy consumption of reaction, the discharge of exhaust gas and cost, meanwhile, avoid connecing for propane and oxygen
Touching, reduces risk.
Detailed description of the invention
Fig. 1 is chemical chain preparing propylene by dehydrogenating propane process schematic representation in the present invention.
Fig. 2 is chemical chain dehydrogenating propane schematic device used in the present invention.
Fig. 3 is Fe in the present invention2O3/Al2O3With 1MoxFeAl catalyst chemical chain dehydrogenating propane active testing result figure.
Fig. 4 is Fe in the present invention2O3/Al2O3With the scanning electron microscope result and 1Mo9FeAl catalyst of 1Mo9FeAl catalyst
Elemental redistribution result figure.
Fig. 5 is 1MoxFeAl fresh catalyst H2- TPR test result spectrogram.
Fig. 6 is the XRD test result spectrogram of 1MoxFeAl fresh catalyst.
Fig. 7 is the regeneration cycle stability test result figure of 1Mo9FeAl catalyst.
Fig. 8 is that 1Mo9FeAl is fresh and regenerated catalyst XRD test result spectrogram
Fig. 9 is 1% La doped 1Mo9FeAl catalyst regeneration cycle stability test result figure.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.The compound gold of loading type iron molybdenum is carried out first
Belong to the preparation of oxide catalyst, while preparing the single metal oxides catalyst of iron and molybdenum, as a comparison, three kinds of metal oxidations
Object catalyst selects identical preparation technology parameter to carry out during the preparation process.Three kinds of catalyst carry out third at identical conditions
Alkane dehydrogenation reaction protrudes the superiority of 1MoxFeAl catalyst by the selectivity of the conversion ratio and propylene that compare propane.
Embodiment 1
Step 1, according to the molar ratio of iron and molybdenum, the ammonium molybdate ((NH of certain mass is added in 2ml deionized water4)6Mo7O24.4H2O), after wait be completely dissolved, nine water ferric nitrate (Fe (NO of 3.4g is added3)3.9H2), O formation uniformly mixes molten
Liquid, by the Al of 1.0g2O3It is impregnated into above-mentioned solution.
Step 2, glutinous slurry step 1 obtained is placed 12 hours at room temperature, then 12 hours dry at 80 DEG C, will be obtained
Blocks of solid grinding after, roast 6 hours at 600 DEG C in air, loading type iron sodium/molybdenum composite metal oxide can be obtained and urge
Agent, molecular formula 1MoxFeAl, wherein x=3,6,9,12,15, represent the molar ratio of iron and molybdenum.
Step 3, it sieves 1MoxFeAl solid powder tabletting to obtain the catalyst granules of 20-40 mesh.
Embodiment 2
Step 1, nine water ferric nitrate (Fe (NO of 3.4g is taken3)3.9H2O it) is added in 2ml deionized water, obtains clear solution
Afterwards, the Al of 1.0g is added2O3It is impregnated.
Step 2, by step 1 products therefrom respectively under the conditions of room temperature and 80 DEG C after drying 12 hours, grinding uniformly, is shifted
It is roasted 6 hours to 600 DEG C, obtains Fe2O3/Al2O3Catalyst.
Step 3, gained catalyst fines tabletting is sieved to obtain 20-40 mesh catalyst granules.
Embodiment 3
Step 1,0.36g ammonium molybdate ((NH is weighed4)6Mo7O24﹒ 4H2O it) is dissolved into 4ml deionized water, by 2.0gAl2O3
It is impregnated in the solution
Step 2, step 1 products therefrom is 12 hours dry under the conditions of room temperature and 80 DEG C respectively, and obtained solid is ground
Grinds roast 6 hours for 600 DEG C in air atmosphere, obtain MoO3/Al2O3Catalyst
Step 3, by gained MoO3/Al2O3Catalyst tabletting screening, takes 20-40 mesh catalyst granules.
Embodiment 4
The preparation of catalyst is carried out according to the method for embodiment 1, and the main distinction is, in dipping ammonium molybdate ((NH4)6Mo7O24﹒ 4H2O) He Jiushui ferric nitrate (Fe (NO3)3.9H2O the lanthanum (six of 1% (mole relative to iron) is added on the basis of)
Water lanthanum nitrate La (NO3)3·6H2O 0.0361g), obtain the 1MoxFeAl catalyst of La doped.
Embodiment 5
Weigh 1MoxFeAl, Fe obtained by 0.25g-0.8g2O3/Al2O3, MoO3/Al2O3Catalyst granules and 2ml quartz sand
(SiC), it is uniformly mixed, is placed into fixed bed reaction pipe, is passed through N2, reaction bed is purged, while temperature is raised to 560 DEG C, it
It is passed through the gaseous mixture of propane and nitrogen afterwards, wherein the total flow of propane and nitrogen is 21ml/min, and propane volume fraction is 20%.
After reaction 5 minutes, the tail gas flowed out in reaction tube is passed through in gas-chromatography, product composition is detected.Propane conversion
Rate is calculated by following formula:
Wherein:
--- conversion of propane, %
--- Reactor inlet propane molar flow, mol/min
--- reactor outlet propane molar flow, mol/min
Product gas phase selectivity is calculated by following formula:
Wherein:
SProduct A--- the selectivity of gas-phase product A, %
nProduct A--- the yield of gas-phase product A, mol
∑nProduct--- the sum of the amount of all product materials of gas phase, mol
xProduct A--- content of the gas-phase product A in all gas-phase products
Gas-phase product A includes: C3H6, COx(oxycarbide, i.e. carbon monoxide, carbon dioxide), CH4, C2H6, C2H4, target
Product is propylene, and raw material is propane.
As shown in figure 3, conversion of propane and Propylene Selectivity is shown in histogram, the doping of Mo is greatly improved
The conversion ratio of propane, but the selectivity of propylene does not change significantly, the conversion per pass of propane may be implemented in 1Mo9FeAl
Reach 48%.Fe2O3/Al2O3Catalyst activity it is lower main reason is that body phase oxygen transmitting rate it is lower, cannot be fine
Promote surface reaction progress；MoO3/Al2O3Oxygen of the catalyst on the initial stage surface of reaction is just reacted away rapidly, together
When the Mo that is exposed of surface promote the fracture of C-C key, therefore the selectivity of methane is greatly improved.And iron molybdenum
Bimetallic catalyst can effectively adjust the delivery rate of Lattice Oxygen in body phase, the effective conversion ratio for improving propane, still
The addition of excessive molybdenum, the conversion ratio that will lead to propane reduce, and the selectivity of propylene is also slightly decreased, so optimal support type
Iron sodium/molybdenum composite metal oxide catalyst is 1Mo9FeAl.
It can be seen that the doping of molybdenum to Fe from the scanning electron microscope result of Fig. 42O3/Al2O3The pattern of catalyst does not generate
Apparent to influence, the influence this eliminates catalyst morphology to performance can be seen according to the Elemental redistribution result of 1Mo9FeAl
Out, 4 kinds of elements have all obtained good dispersion in catalyst, and the formation for iron molybdenum solid solution provides strong evidence
H is carried out to the fresh catalyst of preparation2- TPR test, according to Fig. 5's as a result, iron oxide is main during reduction
It to include two characteristic peaks.It is change from di-iron trioxide to ferroso-ferric oxide that wherein the lower characteristic peak of reduction temperature is corresponding
Change, higher characteristic peak is then the transformation from ferroso-ferric oxide to metallic iron.The doping of molybdenum improves iron oxide and four oxygen simultaneously
The reduction temperature for changing three-iron reduces by-product CO so that iron oxide is more stable2Yield, illustrate the doping of molybdenum
The activity for effectively having regulated and controled the Lattice Oxygen of catalyst surface and body phase is conducive to react the direction progress towards production propylene.
Fig. 6 is the XRD of the fresh catalyst of different molybdenum contents as a result, the Fe just prepared2O3/Al2O3The characteristic peak and α-of catalyst
Fe2O3It matches, illustrates Fe2O3/Al2O3Iron oxide in catalyst mainly exists in the form of α phase, with mixing for Mo
It is miscellaneous, Fe2O3Characteristic peak have occurred different degrees of reduction, especially iron and molybdenum molar ratio be 6,9,12 three samples, say
The doping that molybdenum is illustrated improves the dispersion of iron oxide well, and with the addition of molybdenum, the characteristic peak offset of iron oxide is also
It is more and more obvious, illustrates the addition of molybdenum so that the lattice of iron oxide is distorted, caused the variation of lattice constant, from another
On the one hand the formation of iron molybdenum solid solution is illustrated.
As propane passes through reaction bed, the Lattice Oxygen of iron oxide is gradually consumed, and the activity of catalyst gradually decreases, and is needed
Catalyst is regenerated, after nitrogen purges reaction system, be passed through air, supplement low-valent metal oxidation at the reaction temperatures
The Lattice Oxygen of object is allowed to be restored to high-valence state, and the catalyst after regeneration, which continues to be passed through propane in the reactor, to be reacted,
Complete new certain embodiments.Chemical chain dehydrogenating propane cyclical stability is shown in attached drawing 7, is conversion ratio for raw material propane, for it
His gas is selectivity, with emphasis on the selectivity of target product propylene, the results showed that, by redox process
1Mo9FeAl catalyst performance is slowly reducing.Fig. 8 is the XRD of the carrier of oxygen after 9 circulations as a result, can from the comparison of XRD
To find out, the main reason for catalyst inactivation is that phase transformation has occurred in iron oxide, becomes magnetic iron oxide.To improve catalyst
Cyclical stability, is doped with 1% lanthanum in iron-molybdic catalyst, and catalyst still may be used after reaction-regenerated circulation
To be maintained at metastable performance (Fig. 9), i.e., conversion ratio and selectivity give relatively stable.
Content carries out the adjustment of technological parameter according to the present invention, and the preparation of catalyst can be achieved, show after tested
The almost the same performance with embodiment, illustrate catalyst system of the invention be suitable for catalyst crystal lattice oxygen to low-carbon alkanes into
Row Dehydroepiandrosterone derivative.Illustrative description has been done to the present invention above, it should explanation, in the feelings for not departing from core of the invention
Under condition, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work
Each fall within protection scope of the present invention.
Claims (10)
1. iron sodium/molybdenum composite metal oxide catalyst, which is characterized in that be made of carrier and iron sodium/molybdenum composite metal oxide, carrier
It is carrier Al2O3, the two-phase of iron sodium/molybdenum composite metal oxide is iron oxide and molybdenum oxide, iron oxide and the molybdenum oxide shape on carrier
At solid solution, the molar ratio of iron and molybdenum is 3-30；Relative to carrier, the load capacity of iron oxide is 4-60%, the load of molybdenum oxide
Amount is 2-30%.
2. iron sodium/molybdenum composite metal oxide catalyst according to claim 1, which is characterized in that iron oxide is three oxidations two
Iron, molybdenum oxide are molybdenum trioxide.
3. iron sodium/molybdenum composite metal oxide catalyst according to claim 1 or 2, which is characterized in that iron and molybdenum rub
You are than being 3-15, and the load capacity of iron oxide is 40-60%, and the load capacity of molybdenum oxide is 5-20%.
4. iron sodium/molybdenum composite metal oxide catalyst according to claim 1 or 2, which is characterized in that addition metallic iron
The lanthanoid metal of molal quantity 0.1-2%, preferably 0.5-1% lanthanoid metal.
5. the preparation method of iron sodium/molybdenum composite metal oxide catalyst, which is characterized in that carry out as steps described below:
Step 1, the soluble-salt containing metallic iron and the soluble-salt containing metal molybdenum are evenly spread in deionized water, shape
At homogeneous transparent solution；
Step 2, according to the method for incipient impregnation, by carrier Al2O3It is impregnated in the solution of step 1；
Step 3, the carrier after impregnating stands 8-12h under 20-25 degrees Celsius of room temperature, is then transferred into 80-100 DEG C
Dry 8-12h in environment, finally iron sodium/molybdenum composite metal oxygen can be obtained in 3-8 hours in 500-600 DEG C of roastings in air atmosphere
Compound catalyst.
6. the preparation method of iron sodium/molybdenum composite metal oxide catalyst according to claim 5, which is characterized in that contain gold
The soluble-salt for belonging to iron is nine water ferric nitrates, iron chloride or ferric sulfate；Soluble-salt containing metal molybdenum is ammonium molybdate.
7. the preparation method of iron sodium/molybdenum composite metal oxide catalyst according to claim 5, which is characterized in that in step
In 1, the soluble-salt containing lanthanoid metal is added, so that lanthanoid metal is impregnated on carrier, realizes addition of the lanthanoid metal to catalyst,
Soluble-salt containing lanthanoid metal is lanthanum nitrate hexahydrate, lanthanum chloride or lanthanum sulfate, and the additive amount of lanthanoid metal is metallic iron mole
Several 0.1-2%, preferably 0.5-1%.
8. the preparation method of iron sodium/molybdenum composite metal oxide catalyst according to claim 5, which is characterized in that in step
In 3, the carrier after dipping stands 10-12h under 20-25 degrees Celsius of room temperature, is then transferred into 80-90 DEG C of environment dry
10-12h are roasted 4-6 hours for 550-600 DEG C in air atmosphere.
9. iron sodium/molybdenum composite metal oxide catalyst as described in claim 1 or 2 with catalyst crystal lattice oxygen to lower alkanes
Hydrocarbon carries out the application in Dehydroepiandrosterone derivative, which is characterized in that low-carbon alkanes are the linear paraffin of 2-6 carbon atom, preferably propane.
10. application according to claim 9, which is characterized in that catalyst is uniformly mixed with quartz sand and is placed in reaction bed,
It is passed through nitrogen purging bed, is passed through reaction gas later, reaction gas and nitrogen total flow are 20-50ml/min, reaction gas
Percentage by volume is 10-30%.The mass ratio of catalyst and quartz sand is (0.2-1): 1, preferably (0.5-0.8): 1, reaction
Temperature be 550-600 degrees Celsius, preferably 560-580 DEG C；With the progress of reaction, the Lattice Oxygen in catalyst is consumed,
It needs to regenerate catalyst, to guarantee the high activity of catalyst；The reaction gas in nitrogen exclusion reaction bed is passed first into,
Then it is passed through air at the reaction temperatures, the oxygen carrier of lower valency is oxidized back high-valence state again, after nitrogen purging again
Re-start dehydrogenation reaction.
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| CN113318750A (en) * | 2021-06-22 | 2021-08-31 | 吉林大学 | Lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen through mobile phase and preparation method thereof |
| CN113398953A (en) * | 2021-06-08 | 2021-09-17 | 大连理工大学 | Plasma-assisted catalyst desulfurization and storage bit thermal regeneration method and application |
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| CN113398953A (en) * | 2021-06-08 | 2021-09-17 | 大连理工大学 | Plasma-assisted catalyst desulfurization and storage bit thermal regeneration method and application |
| CN113318750A (en) * | 2021-06-22 | 2021-08-31 | 吉林大学 | Lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen through mobile phase and preparation method thereof |
| CN113318750B (en) * | 2021-06-22 | 2022-04-26 | 吉林大学 | Lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen through mobile phase and preparation method thereof |
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| CN114797884B (en) * | 2022-05-19 | 2023-05-09 | 四川鸿鹏新材料有限公司 | Catalyst for producing vinylene carbonate, preparation method and application |
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