CN109718785A - The derivative cobalt-base catalyst of hydrocalumite for acetic acid self-heating reforming hydrogen manufacturing - Google Patents
The derivative cobalt-base catalyst of hydrocalumite for acetic acid self-heating reforming hydrogen manufacturing Download PDFInfo
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Abstract
The present invention relates to a kind of derivative cobalt-base catalysts of the hydrocalumite of acetic acid self-heating recapitalization hydrogen making.The present invention is directed to existing the catalyst variation of catalyst structure and oxidation of active component and sintering in acetic acid autothermal reforming reaction, the problem of leading to catalyst inactivation, provides a kind of stable structure, resistance to sintering, resistance to oxidation, anti-carbon deposit, activity high new catalyst.A mole composition for catalyst of the invention is (CaO)a(CoO)b(AlO1.5)c, wherein a is 1.66-5.19, b 0.34-0.81, c 1.0.The present invention is prepared for the presoma of Ca-Al hydrocalumite structure using coprecipitation, is fired to have obtained Ca-Co-Al-O mesoporous composite oxides, which contains cobalt aluminate object phase and a small amount of Ca using calcium oxide as skeleton12Al14O33, it is suppressed that the acidity of catalyst improves the coking resistivity and anti-caking power of catalyst, improves acetic acid self-heating reforming hydrogen manufacturing activity.
Description
Technical field
The present invention relates to a kind of cobalt-base catalysts of acetic acid self-heating reforming hydrogen manufacturing, more particularly to one kind with hydrocalumite knot
Structure is the cobalt-base catalyst and preparation method thereof of presoma, belongs to the field of acetic acid self-heating recapitalization hydrogen making.
Background technique
Current emerging energy mainly has Hydrogen Energy, solar energy, wind energy, geothermal energy, ocean energy and nuclear energy, wherein Hydrogen Energy conduct
It is a kind of efficiently, cleaning, the sustainable energy, have that energy density is high, from a wealth of sources, storage and transportation is convenient and utilizes various informative etc. excellent
Gesture has worldwide obtained common concern, therefore, how to produce and preferably has become the heat studied at present using Hydrogen Energy
Point.
Traditional hydrogen manufacturing mode is divided into following several: water electrolysis hydrogen production, petroleum hydrogen production from catalytic pyrolysis, natural gas catalytic reforming
Hydrogen manufacturing.Water electrolysis hydrogen production higher cost, and petroleum and methane hydrogen manufacturing need to consume a large amount of fossil feedstocks, it is unfavorable to bring to environment
It influences.Biomass is a kind of renewable energy, can reduce the pollution to environment, while reduction pair using it as raw material for preparing hydrogen
The dependence of fossil fuel.But since biomass energy metric density is low, so usually will be low-quality, solid phase in a manner of fast pyrogenation
Biomass pyrolytic then by catalytic reforming process converts hydrogen for bio-oil at the bio-oil of high-quality, liquid phase.Biology
The ingredient of matter oil is sufficiently complex, and acetic acid is one of main component of bio-oil, usually using acetic acid as the typical case of bio-oil
Compound is applied to hydrogen production process.
Acetic acid can be by vapor reforming hydrogen production, but this process is the heat absorption for needing extraneous persistently offer amount of heat
Reaction.And acetate moiety oxidation hydrogen manufacturing is an exothermic reaction, under certain reaction temperature, does not need external lasting heat supply,
But the yield of the reaction hydrogen is lower.For these problems, acetic acid self-heating reforming hydrogen manufacturing (CH can be used3COOH+1.44H2O+
0.28O2→2CO2+3.44H2), i.e., a small amount of O is introduced in steam reforming reaction2, utilize reaction raw materials or the oxygen of product
Change heat release and provides required heat for reforming reaction.This reaction bonded advantage of partial oxidation and steam reforming respectively,
Reaction is set to reach thermal balance by adjusting the additional proportion of oxygen, to realize the self-heating recapitalization of acetic acid.
In the reaction of acetic acid self-heating reforming hydrogen manufacturing, efficient reforming catalyst seems extremely important.Currently, common reformation
Catalysts mainly include noble metal catalyst and transition-metal catalyst.The reformation of noble metal catalyst such as Pt, Rh and Pd
Catalytic performance and anti-carbon deposition ability are all preferable, but it is expensive, using being subject to certain restrictions；Some transition metal such as Ni,
Co, Cu and Fe etc. also have the catalytic action similar with noble metal catalyst to the reaction of acetic acid catalysis reformation hydrogen production, study table
Bright, Co base catalyst is conducive to the fracture of C-C key and c h bond, reforms activity with higher and hydrogen yield for acetic acid.
However, because of the introducing of oxygen during acetic acid self-heating recapitalization, catalyst bed front end local temperature may be up to 1000
DEG C, cause catalyst activity component aggregation to become larger, number of active center is reduced；Active component is also easily oxidized in oxidizing atmosphere；
Meanwhile molecular acid, through decarboxylic reaction and dehydration, generates the intermediate species such as ketenes, hair after catalyst surface activation
Raw polycondensation reaction forms carbon deposit, is deposited on catalyst surface isolation catalyst and reactant, oxidation, sintering and carbon deposit then occurs
The problems such as, lead to catalyst activity reduction.Therefore, when designing acetic acid autothermal reforming reaction catalyst, it is suitable to need to select
Auxiliary agent, carrier and structure etc. improve thermal stability, the anti-sintering, anti-carbon deposit and oxidation resistance of catalyst.
The present invention acetic acid self-heating recapitalization conversion process catalyst there are aiming at the problem that, introduce Al and Ca component: urging
In agent, Al2O3Large specific surface area, porosity is high, is conducive to reactant acetic acid, O2With product CO/CO2Transmitting and diffusion, mention
High catalytic activity；And Al2O3Stable CoAl is formed in conjunction with CoO2O4Spinelle improves the anti-caking power of catalyst.
Meanwhile alkali metal Ca is introduced, CaO facilitates to H2The absorption and dissociation activation of O, the intermediate species such as formation * OH and * O, and *
Reforming reaction is participated on OH species dispersal to Co metallic, to improve the activity of catalyst；And the thermal stability of CaO compared with
It is good, the anti-caking power of catalyst can be improved；In addition, CaO has the ability of stronger absorption carbon dioxide, in reforming reaction
In the process and CO2Reaction generates CaCO3, CaCO3The * C carbon deposit forerunner's precursor reactant that can be generated in the process with acetic acid self-heating recapitalization,
Be conducive to the gasification and reduction of surface carbon deposit；On the other hand, alkaline calcium oxide helps to neutralize Al2O3Acidic site, inhibit to urge
Change cracking reaction, to reduce the generation of carbon deposit；Calcium oxide also has stronger electron donation, is conducive to improve active component
The reproducibility and inoxidizability of cobalt.
Catalyst structure also has a certain impact to catalyst performance.Houghite belongs to natural crystal catalyst, also known as
For layered double-hydroxide (LDHs), there are some excellent performances in terms of for catalysis, therefore hydrotalcite-like compound is one
A preferable selection.Hydrocalumite is one kind of houghite, has unique structure and property, and general structure isWherein An-Represent interlayer anion.Coprecipitation is commonly used for preparing high porosity
LDHs material, Ca-Al-LDHs obtained by this method has good layer structure.
Therefore, the present invention is prepared for the presoma of Ca-Al hydrocalumite structure using coprecipitation, passes through active component Co
The part of Ca is replaced, the laminate position of hydrocalumite structure is made it into, improves the dispersion degree of cobalt, increase catalyst
Number of active center, to improve the activity of catalyst.The Ca-Co- with open flourishing cellular structure is obtained after being fired
Al-O composite oxides, the catalyst contain cobalt aluminate object phase and a small amount of Ca using calcium oxide as skeleton12Al14O33, oxygen
The better heat stability for changing calcium skeleton can inhibit the aggregation growth of active component cobalt, improve the anti-caking power of catalyst；It is formed
Meso-hole structure be conducive to the transmitting and diffusion of reactant acetic acid and product molecule, improve catalytic activity；And meso-hole structure has
" confinement effect " plays the role of dispersion barrier to active component Co in reaction process, can effective inhibitory activity component Co
Migration and aggregation, polycondensation carbon deposit of the ethene suppressing ketone equivalance carbon precursor in duct further increase the anti-burning of catalyst
Knot and anti-carbon deposition ability.
Innovation on catalyst component of the present invention and structure improves heat of the catalyst in acetic acid autothermal reforming reaction
Stability, anti-carbon deposit, anti-oxidant and anti-caking power, and show excellent activity, selectivity and stability.
Summary of the invention
The technical problem to be solved by the present invention is to, for existing catalyst in acetic acid autothermal reforming reaction catalyst knot
The variation of structure, the oxidation of active component and sintering, carbon deposit, the problem of leading to the inactivation of catalyst, provide a kind of stable structure, anti-
Carbon deposit, resistance to sintering, anti-oxidant, activity stabilized new catalyst.
The present invention is introduced Ca, Al component, is prepared for Ca-Al hydrocalumite knot with coprecipitation using Co as active component
The presoma of structure has obtained Ca-Co-Al-O mesoporous composite oxides catalyst after being fired, the catalyst is using calcium oxide as bone
Frame contains cobalt aluminate object phase and a small amount of Ca12Al14O33.Catalyst of the present invention is used for the reaction of acetic acid self-heating reforming hydrogen manufacturing
In, in the case where reaction temperature is 700 DEG C, acetic acid (HAc) conversion ratio close to 100%, stablize in 2.80mol- by hydrogen yield
H2/ mol-HAc or so.
Technical solution of the present invention:
The present invention is directed to the characteristics of acetic acid self-heating recapitalization, and the forerunner of Ca-Al hydrocalumite structure is prepared for coprecipitation
Body has obtained Ca-Co-Al-O mesoporous composite oxides after being fired, the catalyst is brilliant containing cobalt aluminium point using calcium oxide as skeleton
Stone object phase and a small amount of Ca12Al14O33, improve the activity and stability of acetic acid self-heating recapitalization.Mole group of catalyst of the present invention
As (CaO)a(CoO)b(AlO1.5)c, wherein a is 1.66-5.19, b 0.34-0.81, c 1.0, according to weight percent group
Become: calcium oxide 53.2-71.6%, cobalt oxide 14.1-15.7%, aluminium oxide 14.3-31.1%.Of the invention is preferred
Catalyst is (CaO)3.43(CoO)0.57(AlO1.5)1.0, weight percent composition are as follows: calcium oxide 67.3%, cobalt oxide are
14.9%, aluminium oxide 17.8%.
The step of specific preparation method, is as follows:
1) according to catalyst chemical composition, a certain amount of cobalt nitrate, nitric acid the mixed solution of preparing metal nitrate: are weighed
Calcium, aluminum nitrate, are configured to nitrate mixed solution；
2) it prepares precipitating reagent: being 1:16 according to carbonate and molar ratio hydroxy, according to metal cation Ca, Co, Al
Charge summation and molar ratio hydroxy be 1:8, weigh a certain amount of sodium carbonate and sodium hydroxide be added distilled water prepare it is heavy
Shallow lake agent；
3) at 60-70 DEG C, the mixed solution of nitrate and precipitating reagent are subjected to coprecipitation reaction, by controlling precipitating reagent
Addition speed, control the pH value of reaction solution 10.5 ± 0.5 or so, and maintain stirring be put in aging 18- in 65 DEG C of water-baths
20h；Gained mixture washs sediment to neutrality through filtering, and is placed in 105 DEG C of baking ovens dry 12h；Obtain hydrocalumite
Presoma based on structure contains a small amount of CaCO3With Al (OH)3, typical phase structure such as X-ray diffractogram (attached drawing 1)
It is shown；
4) by the presoma after drying with the heating rate of 10 DEG C/min, and in 600-800 DEG C of roasting temperature 3-5h,
The Ca-Co-Al-O mesoporous composite oxides beaded catalyst of 20-40 mesh is obtained through tabletting, screening, which is with calcium oxide
Skeleton contains cobalt aluminate object phase and a small amount of Ca12Al14O33, exemplary x-ray diffraction pattern is as shown in Fig. 2, the hole BJH
Diameter distribution map is as shown in Fig. 3；
5) catalyst obtained by step 4) (50-300mg) is packed into fixed bed reactors, is first 20mL/min's in flow
H2It is restored 1 hour in atmosphere in 600-800 DEG C, is activated, is then purged through nitrogen, be finally passed through rubbing after vaporizing
You are reacted than the mixed gas for being acetic acid/water/oxygen=1.0/ (2.5-5.0)/(0.2-0.4) by catalyst bed,
Reaction temperature is 500 DEG C -700 DEG C.
Beneficial effects of the present invention:
1) presoma that catalyst of the present invention uses coprecipitation to prepare based on Ca-Al hydrocalumite structure,
Replaced by part of the active component Co to Ca, makes it into the laminate position of hydrocalumite structure；Ca- has been obtained after being fired
Co-Al-O mesoporous composite oxides, the catalyst contain cobalt aluminate object phase and a small amount of using calcium oxide as skeleton
Ca12Al14O33, the better heat stability of calcium oxide skeleton improves the anti-caking power of catalyst.
2) catalyst of the present invention forms meso-hole structure, is conducive to the transmitting and diffusion of reactants and products molecule, improves
Catalytic activity；And meso-hole structure has " confinement effect ", plays the work of dispersion barrier to active component Co in reaction process
With, the migration and aggregation of the effective inhibitory activity component Co of energy, and polycondensation of the ethene suppressing ketone equivalance carbon precursor in duct
Carbon deposit further increases anti-sintering and the anti-carbon deposition ability of catalyst.
3) catalyst of the present invention introduces alkali metal Ca, and CaO facilitates to H2The absorption and dissociation activation of O, forms * OH
It, can be with * CH with the intermediate species such as * Ox(x=0-3) etc. the reaction of species containing charcoal promotes catalyst surface removing carbon, improves
The anti-carbon deposition ability of cobalt-base catalyst；In addition, CaO has the ability of stronger absorption carbon dioxide, during reforming reaction
And CO2Reaction generatesCaCO3It can be with the * C product of generation during acetic acid self-heating recapitalization
Carbon precursor reactionBe conducive to the gasification and reduction of surface carbon deposit；And the thermal stability of CaO
Preferably, the anti-caking power of catalyst can be improved；Simultaneous oxidation calcium also has stronger electron donation, is conducive to improve and live
The reproducibility and inoxidizability of property component cobalt.
4) catalyst of the present invention introduces Al element, Al2O3Large specific surface area, porosity are high, be conducive to reactant acetic acid,
O2With product CO/CO2Transmitting and diffusion, improve catalytic activity；Co doping enters in the lattice of Al after catalyst roasting,
Form the lesser CoAl of partial size2O4Spinelle helps to improve the anti-sintering property of catalyst.
5) through acetic acid autothermal reforming reaction the result shows that, the composite mesoporous oxygen of Ca-Co-Al-O that catalyst of the invention is formed
Compound, each component have synergistic effect, have resistance to sintering, anti-carbon deposit, resistance to oxidation, activity stabilized and hydrogen during the reaction
The features such as yield is high.
Detailed description of the invention
Fig. 1: the X-ray diffraction spectrogram of catalyst precursor of the present invention
Fig. 2: the X-ray diffraction spectrogram of catalyst oxide of the present invention
Fig. 3: the BJH graph of pore diameter distribution of catalyst of the present invention
Specific embodiment
Reference example 1
Weigh the Ca (NO of 8.945g3)2·4H2O, the Co (NO of 2.487g3)2·6H2Al (the NO of O and 9.095g3)3·
9H2O is added in the deionized water of 70.7mL, is configured to mixed solution #1.Accurately weigh respectively 22.611g NaOH and
4.689g Na2CO3, it is added in the deionized water of 150.2mL, is configured to solution #2.At 65 DEG C, pH value of solution is 10.5 ± 0.5
Under conditions of, solution #1 and #2 is slowly added drop-wise in the beaker of 250mL simultaneously and carries out coprecipitation reaction, and maintains this temperature
Stir aging 18h.After mixed liquor is filtered, be washed with deionized 3 times, by gained sediment in 105 DEG C of dryings
Case dries 12h, obtains the presoma based on hydrocalumite structure, contains a small amount of CaCO3With Al (OH)3, sample after drying
Through 800 DEG C of roasting 4h, catalyst CDUT-CCA-101 is obtained, the weight percent of the catalyst is composition: calcium oxide is
53.2%, cobalt oxide 15.7.0%, aluminium oxide 31.1%.
Acetic acid autothermal reforming reaction activity rating carries out in continuous fixed bed reactor, raw material include oxygen and
The mixed solution of acetic acid and water.It by catalyst grinding, tabletting, is crushed, then screening is the particle of 20-40 mesh, is packed into reaction tube
In, at 600-800 DEG C, the H of 20-40mL/min2Reduction 1h is carried out in stream.By the mixed solution high voltage and constant current of acetic acid and water
After pump introduces vaporizer vaporization, mixture of oxygen, and using nitrogen as internal standard gas, forming mole group becomes CH3COOH/H2O/O2=
1/4/0.28 reactor feed gas, and by this unstripped gas be passed through reaction bed carry out autothermal reforming reaction, reaction condition be normal pressure,
Air speed 11000-30000mL/ (g-catalysth), reaction product use gas chromatograph on-line analysis.
Catalyst CDUT-CCA-101 is investigated through acetic acid self-heating recapitalization activity, and reaction pressure is normal pressure, air speed
15000mL/ (g-catalysth), reaction temperature are 700 DEG C, charge ratio CH3COOH/H2O/O2=1/4.0/0.28.It should
The initial acetic acid conversion of catalyst is 98.2%, hydrogen yield 2.2mol-H2/mol-HAc.In 10h reaction, with reaction
The progress of time, the conversion ratio of acetic acid drop to 87.9%, and carbon dioxide selectivity is finally increased to by initial 44.6%
48.9%, carbon monoxide selective maintains 27.5% or so, and the selectivity of methane is finally reduced to from initial 22.6%
17.6%, the selectivity of acetone is maintained at 5.8% or so, and crystal aerugo glycosylation reaction is not effectively suppressed, and activity is poor.
Embodiment 1
Weigh the Ca (NO of 11.329g3)2·4H2O, the Co (NO of 2.320g3)2·6H2Al (the NO of O and 5.246g3)3·
9H2The deionized water of 69.9mL is added in O, is configured to solution #1；Weigh NaOH the and 3.705g anhydrous Na of 22.374g2CO3, add
The deionized water for entering 148.6mL is configured to solution #2；Subsequent step obtains the forerunner based on hydrocalumite structure with reference example 1
Body contains a small amount of CaCO3With Al (OH)3, typical structure is as shown in Fig. 1；It is mesoporous that Ca-Co-Al-O has been obtained after being fired
Composite oxides, the catalyst contain cobalt aluminate object phase and a small amount of Ca using calcium oxide as skeleton12Al14O33, typical
Structure is as shown in Fig. 2, i.e. acquisition CDUT-CCA-102 catalyst；The weight percent of the catalyst forms are as follows: calcium oxide is
67.3%, cobalt oxide 14.9%, aluminium oxide 17.8%.
The CDUT-CCA-102 catalyst carries out active investigation through acetic acid autothermal reforming reaction, reaction condition be normal pressure,
15000mL/ (g-catalysth), 700 DEG C, charge ratio CH3COOH/H2O/O2=1/4.0/0.28.The catalyst is in second
Preferable catalytic activity and stability are shown in sour autothermal reforming reaction, acetic acid is totally converted in reaction process, and conversion ratio is
100%, hydrogen yield is also stabilized in 2.80mol-H2/ mol-HAc, meanwhile, the selectivity of carbon dioxide, carbon monoxide and methane
It is stable 68.7%, 29.0% and 2.0% or so respectively, by-product acetone (CH3COCH3) be not detected.Experimental result table
Bright, which has effective inhibitory effect, hydrogen high yield attribution to acetic acid methanation reaction and ketonization reaction respectively
In the low selectivity of by-product.Nitrogen low-temperature physics absorption representation is carried out to CDUT-CCA-102 catalyst, obtaining specific surface area is
75.7m2/ g, pore volume 0.29cm3/ g, average pore size 13.1nm.By active testing result as it can be seen that catalyst of the invention
In acetic acid autothermal reforming reaction, acetic acid conversion close to 100%, stablize in 2.80mol-H by preferred catalyst hydrogen yield2/
Mol-HAc or so.It is characterized in conjunction with XRD, TPR, TG etc., discovery active component cobalt is effectively dispersed, and does not assemble sintering, without obvious product
Charcoal shows that catalyst good thermal stability, resistance to sintering, anti-carbon deposit, hydrogen yield are high.
Embodiment 2
Weigh the Ca (NO of 13.113g3)2·4H2O, the Co (NO of 2.190g3)2·6H2Al (the NO of O and 4.122g3)3·
9H2The deionized water of 69.8mL is added in O, is configured to solution #1；Weigh NaOH the and 3.699g anhydrous Na of 22.335g2CO3, add
The deionized water for entering 148.3mL is configured to solution #2；Subsequent step obtains the presoma of hydrocalumite structure with reference example 1,
Contain a small amount of CaCO3With Al (OH)3, typical structure is as shown in Fig. 1, and it is mesoporous multiple that Ca-Co-Al-O has been obtained after being fired
Oxide is closed, which contains cobalt aluminate object phase and a small amount of Ca using calcium oxide as skeleton12Al14O33, typical case's knot
Structure is as shown in Fig. 2, i.e. acquisition CDUT-CCA-103 catalyst；The weight percent of the catalyst forms are as follows: calcium oxide is
71.6%, cobalt oxide 14.1%, aluminium oxide 14.3%.
The CDUT-CCA-103 catalyst carries out active investigation through acetic acid autothermal reforming reaction, reaction condition be normal pressure,
15000mL/ (g-catalysth), 700 DEG C, charge ratio CH3COOH/H2O/O2=1/4.0/0.28.When reacting starting
Acetic acid conversion is 93.7%, hydrogen yield 2.56mol-H2/mol-HAc.With the progress of reaction, hydrogen yield keeps steady
Fixed, acetic acid conversion gradually rises to 99.3%.The selectivity of carbon dioxide gradually rises from initial 60.7% to 66.6%,
The selectivity of methane and the selectivity of acetone are respectively maintained at 4.0%, 0.2% or so in entire reaction.To CDUT-CCA-
103 catalyst carry out nitrogen low-temperature physics absorption representation, as a result are as follows: specific surface area 52.8m2/ g, pore volume 0.17cm3/ g, it puts down
Equal aperture is 11.8nm.It is characterized in conjunction with XRD, TPR, TG etc., catalyst structure is stablized, without inactivations such as significant sintering, oxidation, carbon deposits
Situation.
Claims (4)
1. application of the derivative cobalt-base catalyst of hydrocalumite during acetic acid self-heating reforming hydrogen manufacturing, 50-300mg catalyst is existed
In 600-800 DEG C, the H of 20-40ml/min before acetic acid autothermal reforming reaction2It restores 1 hour, is activated in atmosphere；Then
It is passed through acetic acid/water/oxygen molar ratio=1.0/ (2.5-5.0)/(0.2-0.4) mixed gas, is carried out in catalyst bed
Reaction, reaction temperature are 500-700 DEG C.It is characterized by: preparing the mixed solution #1 of calcium, cobalt, aluminium gold genus nitrobacter；Configuration is heavy
Shallow lake agent: the mixed solution #2 of sodium carbonate and sodium hydroxide is prepared；At 60 DEG C~70 DEG C, #1 solution and #2 solution are added drop-wise to burning
It is stirred continuously carry out coprecipitation reaction in cup, by the addition speed of control precipitating reagent, controls pH value of solution 10.5 ± 0.5, and
Stirring aging 18h is maintained, and gained mixture is filtered, washed, and dry 12h is placed in 105 DEG C of baking ovens and obtains Ca-Al hydrocalumite knot
The presoma of structure；Roast 3-5h at 600-800 DEG C and obtain Ca-Co-Al-O mesoporous composite oxides catalyst, the catalyst with
Calcium oxide is skeleton, contains cobalt aluminate object phase and a small amount of Ca12Al14O33, mole group is as (CaO)a(CoO)b
(AlO1.5)c, wherein a is 1.66-5.19, and b 0.34-0.81, c 1.0 form according to weight percent are as follows: calcium oxide is
53.2-71.6%, cobalt oxide 14.1-15.7%, aluminium oxide 14.3-31.1%；The catalyst is used for acetic acid self-heating recapitalization
Hydrogen production process.
2. the cobalt-base catalyst of acetic acid self-heating reforming hydrogen manufacturing according to claim 1, it is characterised in that: the catalyst with
The weight percent of oxide forms are as follows: calcium oxide 53.2%, cobalt oxide 15.7%, aluminium oxide 31.1%.
3. the cobalt-base catalyst of acetic acid self-heating reforming hydrogen manufacturing according to claim 1, it is characterised in that: the catalyst with
The weight percent of oxide forms are as follows: calcium oxide 67.3%, cobalt oxide 14.9%, aluminium oxide 17.8%.
4. the cobalt-base catalyst of acetic acid self-heating reforming hydrogen manufacturing according to claim 1, it is characterised in that: the catalyst with
The weight percent of oxide forms are as follows: calcium oxide 71.6%, cobalt oxide 14.1%, aluminium oxide 14.3%.
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| CN112916018A (en) * | 2021-01-27 | 2021-06-08 | 成都理工大学 | Praseodymium-zirconium composite oxide cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
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| CN112742412A (en) * | 2021-01-20 | 2021-05-04 | 成都理工大学 | Mullite loaded W-promoted Co-based catalyst for autothermal reforming of acetic acid |
| CN112916018A (en) * | 2021-01-27 | 2021-06-08 | 成都理工大学 | Praseodymium-zirconium composite oxide cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN112916018B (en) * | 2021-01-27 | 2022-06-28 | 成都理工大学 | Praseodymium-zirconium composite oxide cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN112973700A (en) * | 2021-02-24 | 2021-06-18 | 清华大学 | Nickel-hydrocalumite-based derivative catalyst |
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