CN108927164A - A kind of nickel magnesium chromium composite oxide catalysts for acetic acid self-heating reforming hydrogen manufacturing - Google Patents
A kind of nickel magnesium chromium composite oxide catalysts for acetic acid self-heating reforming hydrogen manufacturing Download PDFInfo
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
The present invention relates to a kind of nickel magnesium chromium mesoporous composite oxides catalyst of acetic acid self-heating reforming hydrogen manufacturing.The present invention is directed to the oxidation and sintering of existing catalyst variation of catalyst structure and active component during acetic acid self-heating recapitalization, and the problem of leading to catalyst inactivation, provide a kind of stable structure, resistance to sintering, anti-carbon, resistance to oxidation, activity high new catalyst.A mole composition for catalyst of the present invention is (NiO)a(MgO)b(CrO1.5)c, wherein a is 0.08-0.12, b 0.55-0.92, c 0-0.33 is formed are as follows: nickel oxide content 12.0-20.0%, content of magnesia 40.0-88.0%, chromic oxide content 0-40.0% by weight percentage.The present invention is prepared for catalyst precursor using coprecipitation, wherein introduce chromium as auxiliary agent, is formed after being fired and stable contains MgCr2O4And NiCr2O4The mesoporous composite oxides catalyst of spinel structure and Mg-Ni-Cr-O solid solution, improves the reproducibility and stability of active component, while improving hydrogen yield, resistance to sintering and carbon accumulation resisting ability during acetic acid self-heating recapitalization.
Description
Technical field
The present invention relates to a kind of nickel magnesium chromium mesoporous composite oxides catalyst and its system for acetic acid self-heating reforming hydrogen manufacturing
Preparation Method belongs to the field of the hydrogen making of acetic acid self-heating recapitalization.
Background technique
Hydrogen is a kind of clean energy carrier.Compared with traditional non-renewable energy, there are calorific value height, rich reserves etc.
Advantage.Producing mainly with natural gas, alcohols, bio-oil etc. for raw material for hydrogen, it is anti-by steam reforming, partial oxidation
It should be made with approach such as self-heating recapitalizations.From the point of view of the principle, technique and production efficiency of existing all kinds of hydrogen producing technologies, in order to effectively control
The discharge of pollutant in hydrogen production process processed and cost is reduced, the main direction of development of hydrogen manufacturing is to utilize cleaning, cheap and easy to get
Renewable energy extensive produced with distribution.Since biomass has the characteristics that renewable and relatively inexpensive, biology
Matter hydrogen manufacturing has become one of the technology using biomass that the world today is concerned.Directly exist by raw material hydrogen manufacturing of biomass
Some problems, such as containing compared with juicy and volatile component, in addition its composition is sufficiently complex, reforming reaction mechanism is also more multiple
It is miscellaneous.The development of biomass fast pyrolysis technology can convert biomass into bio-oil, wherein containing a large amount of in water-phase product
The ingredients such as acetic acid, therefore cheap hydrogen can be obtained using the acetic acid from bio-oil as raw material.
Acetic acid can be through steam reforming process hydrogen making, but the process is the endothermic reaction；And acetic acid self-heating recapitalization mistake
Journey uses acetic acid, vapor and oxygen or air for raw material, and steam reforming and the exothermic partial oxidation for combining heat absorption are anti-
It answers, can adjust the thermal balance of reaction, there is significant advantage.During acetic acid self-heating recapitalization, in addition to techniques such as temperature, pressure
Outside condition, catalyst is a key factor: active component, auxiliary agent, carrier, structure of catalyst etc. will have a direct impact on catalyst
Catalytic performance, to influence reaction process stability.
At this stage, the catalyst for reforming process mainly has noble metal catalyst and non-precious metal catalyst.Your gold
Metal catalyst such as platinum, ruthenium, palladium etc. has higher catalytic activity, carbon accumulation resisting ability and hydrogen yield in acetic acid self-heating recapitalization,
But its application of its expensive price limit.Non-precious metal catalyst such as Co, Cu, Ni, Fe etc. are also used catalytically reforming hydrogen producing
Reaction, cost is slightly lower, and catalytic performance is preferable, has become one of primary study catalyst of acetic acid hydrogen manufacturing at present.Wherein, Ni base
Catalyst has the ability of stronger fracture C-C key and c h bond, so that gaseous product percentage increases in reaction product, and
The percentage of product liquid such as acetaldehyde, acetone etc. reduces, and then improves the selectivity and yield of hydrogen.Therefore, Ni base catalyst is
A preferable selection in acetic acid catalyst for autothermal reformation.However, due to introduce during self-heating recapitalization oxygen or
Person's air, the oxygen in raw material consume in reaction bed front end, so that local temperature is increased to 1000 degrees Celsius or more, cause to urge
Agent active component nickel crystallite increases, and sintering deactivation occurs；Meanwhile the oxidizing atmosphere during self-heating recapitalization, it is easy to make to live
Property component nickel metal occur oxidation and inactivate；Further, since in acetic acid conversion certain embodiments, through CH3COOH→*CH3COO→*
CH3CO→*CHxSpecies transitions such as (x=0-3), so formed carbon species * C deposition and aggregation growth, generate include graphitic carbon,
The carbon species such as fibrous carbon and amorphous carbon cause carbon distribution to cover and inactivate.
To solve sintering during self-heating recapitalization, oxidation and the problems such as carbon distribution, in Ni base catalyst, carrier and help
Therefore the selection and combination of agent becomes an important factor for optimization catalyst.The present invention is directed to the feature in acetic acid conversion process,
Carrier selection aspect, it is contemplated that MgO thermal stability with higher can form more stable Ni-Mg- when in conjunction with NiO
O solid solution.But at this point, nickel oxide is difficult to be reduced out in solid solution, it will lead to acetic acid self-heating reforming hydrogen manufacturing activity and hydrogen
The decline of gas yield.For this reason, it may be necessary to the lattice structure of regulating catalyst, as improved active group in Ni/MgO catalyst using auxiliary agent
Divide the reduction of Ni.In terms of auxiliary agent, the characteristics of for acetic acid self-heating recapitalization process, the Cr with high-fire resistance2O3Even if its
Also it is not susceptible to phase transformation under high temperature, the high-temperature stability and anti-sintering property of catalyst can be improved.Simultaneously as active component Ni
The 3d of atom has partial holes, these holes can receive the electronics of other atoms or ion, during reduction activation, because of Ni
Facilitation and H overflow effect, Cr3+It is easily reduced into the Cr ion of lower valency, this unstable reduction-state has very strong
Electron donation, easily by electronics transfer to Ni2+Ion makes Ni2+The electron density of ion increases, and therefore, improves the reduction of Ni
Property.In addition, chromium ion radius is 64pm, nickel ion radius is 69pm, magnesium ion radius is 72pm, since radius is not much different,
After Cr addition, a certain amount of Cr2O3MgCr can be formed with MgO and NiO2O4And NiCr2O4Spinelle largely reduces
The interaction of NiO and MgO, this not only further enhances the reducing property of catalyst, but also the spinel structure formed
Thermostabilization is good, and the anti-caking power of catalyst also can be improved, inhibit the oxidation of Ni, reduce the generation of carbon distribution.Meanwhile it reacting
Cheng Zhong inhibits the production of the by-products such as acetone, ethylene by promoting certain embodiments and oxidation process in the conversion of reactant acetic acid
It is raw, while promoting * CHxThe oxidation conversion process of the intermediate species such as (x=0-3), to improve catalytic activity and stability.
The structure and preparation method of catalyst are also an important factor for influencing catalyst activity.For the second of nickeliferous, magnesium, chromium
Sour self-heating recapitalization catalyst can obtain presoma using coprecipitation, and after being fired, obtaining has open flourishing duct
The mesoporous composite oxides of structure, uniform component distribution inhibit carbon deposit presoma such as ketone, alkene by the confinement effect in duct
The deposition of class and polymerization dehydrogenation and inhibit carbon deposit, obtain that specific surface area is high, reducing property is good, urging with high activity and stability
Change material；In this material, Cr is introduced, is replaced by part of the Cr to Mg and Ni in Ni-Mg-O solid solution, it is suppressed that
The strong interaction of MgO and NiO is conducive to the dispersion of catalytic active component, enhances the synergistic effect between active component and carrier,
It opens the transmitting and diffusion that flourishing cellular structure is also conducive to reactants and products molecule simultaneously, therefore catalyst of the present invention is answered
For acetic acid autothermal reforming reaction, and excellent activity, selectivity and stability are embodied in the reaction.
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, resistance to
Sintering, anti-carbon deposit, resistance to oxidation, activity stabilized new catalyst.
The present invention uses Ni as active component, introduces Mg, Cr, is formed stable containing MgCr2O4And NiCr2O4Spinelle and
The mesoporous composite oxides catalyst of Mg-Ni-Cr-O solid solution.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 °C, acetic acid conversion close to 100%, stablize in 2.85mol-H by hydrogen yield2/mol-
HAc。
Technical solution of the present invention:
The present invention is directed to the characteristics of acetic acid self-heating recapitalization, is prepared for catalyst precursor with coprecipitation, wherein introducing chromium conduct
Auxiliary agent is formed stable containing MgCr after being fired2O4And NiCr2O4Spinel structure and Mg-Ni-Cr-O solid solution it is mesoporous multiple
Oxide catalyst is closed, the activity and stability of acetic acid self-heating recapitalization are improved.A mole composition of the invention is (NiO)a(MgO)b
(CrO1.5)c, wherein a is 0.08-0.12, b 0.55-0.92, c 0-0.33 is formed are as follows: nickel oxide by weight percentage
Content is 12.0-20.0%, content of magnesia 40.0-88.0%, chromic oxide content 0-40.0%；Preferred catalytic of the invention
The weight percent of agent are as follows: nickel oxide 14.9%, magnesia 50.1%, chromium oxide 35.0%.
The step of specific preparation method, is as follows:
1) mixed solution of preparing metal nitrate: according to catalyst chemical composition, weigh a certain amount of nickel nitrate, chromic nitrate,
Magnesium nitrate is configured to nitrate mixed solution；
2) it prepares precipitating reagent: being 1:16 ~ 30 according to carbonate and molar ratio hydroxy, according to metal cation Ni, Mg, Cr
Charge summation and molar ratio hydroxy are 1:12 ~ 18, prepare the mixed solution of sodium carbonate and sodium hydroxide；
3) solution that the solution and step 2 prepared step 1) are prepared passes through control in 65 °C of -75 °C of progress coprecipitation reactions
The addition speed for the solution that step 2 is prepared, controls the pH value of reaction solution 10.5 ± 0.5 or so, and maintains stirring aging
18-20h；Gained sediment is through filtering, and by catalyst detergent to neutrality, is placed in 105 °C of baking ovens dry 12h；
4) sample after drying is roasted, under temperature programmed control, is heated up with the rate of 5 °C/min, and at 600-800 °C
At a temperature of keep 4 h of roasting to obtain the catalyst, shown in typical structure such as XRD spectra (attached drawing 1), BJH pore-size distribution is such as
Shown in attached drawing 2, for containing MgCr2O4And NiCr2O4The mesoporous composite oxides knot of spinel structure and Mg-Ni-Cr-O solid solution
Structure.This catalyst using it is preceding 600-800 °C at a temperature of in H2In carry out 1 h of reduction, purge, be passed through mole through nitrogen
Than the mixed gas for acetic acid/water/oxygen=1/ (1.3-5.0)/(0.21-0.35), reacted by catalyst bed, instead
Answering temperature is 500 °C -850 °C.
Beneficial effects of the present invention:
1) catalyst of the present invention introduces the components such as Mg, Cr with coprecipitation, forms stable Mg- using Ni as active component
The composite oxides of Ni-Cr-O solid solution improve the dispersion degree and thermal stability of catalyst activity component；Catalyst forms
Meso-hole structure opens flourishing cellular structure and is also conducive to the transmitting and diffusion of reactants and products molecule, while passing through duct
Confinement effect, it is suppressed that carbon deposit the presoma such as deposition of ketone, alkenes and polymerization and inhibit carbon deposit, improve catalytic activity.
2) MgCr formed in catalyst of the present invention2O4And NiCr2O4Spinel structure thermostabilization is good, improves catalyst
Anti- caking power.
3) catalyst of the present invention introduces suitable Cr2O3, due to the facilitation of Ni and the overflow effect of H, Cr3+Easily reduction
At the Cr ion of lower valency, this unstable reduction-state has very strong electron donation, easily by electronics transfer to Ni2+From
Son makes Ni2+The electron density of ion increases.This improves the reproducibilities of the Ni in reduction process, and inhibit Ni in self-heating
The oxidation of reforming process.
4) for catalyst of the present invention during self-heating recapitalization, what nickel, chromium, magnesium component in catalyst were formed contains MgCr2O4With
NiCr2O4The meso-hole structure of spinel structure and Mg-Ni-Cr-O solid solution effectively facilitates the dehydrogenation in the conversion of reactant acetic acid
Journey and oxidation process, inhibit the generation of the by-products such as acetone, ethylene, while promoting * CHxThe gas of the intermediate species such as (x=0-3)
Change conversion process, it is suppressed that carbon deposit generates.
5) show that catalyst of the invention has resistance to sintering, anti-carbon deposit, resistance to oxidation, work through acetic acid thermal reforming reaction result
The features such as stable and hydrogen yield of property is high.
Detailed description of the invention
Fig. 1: the X-ray diffraction spectrogram of catalyst of the present invention.
Fig. 2: the BJH graph of pore diameter distribution of catalyst of the present invention.
Fig. 3: the X-ray diffraction spectrogram of sample after catalyst reaction of the present invention.
Specific embodiment
Reference example 1
Weigh the Mg (NO of 21.635g3)2·6H2Ni (the NO of O and 2.331g3)2·6H2The deionized water of 92.30 ml is added in O
In, it is configured to solution #1；The Na of the NaOH and 1.958g of 11.826g are accurately weighed respectively2CO3, the deionized water of 250ml is added
In, it is configured to solution #2；By solution #1 and #2 pH be 10.5 ± 0.5 in the range of, co-precipitation behaviour is carried out under 70-75 °C
Make, and this temperature is maintained to stir aging 18-20h；Sediment is through filtering, deionized water washing, and in 110 °C of dry 16h；It is dry
Sample afterwards is through 700 °C of roasting 4h up to CUT-NM catalyst；The weight of the catalyst forms are as follows: nickel oxide content 14.9%,
Magnesia is 85.1%.
Acetic acid autothermal reforming reaction activity rating carries out in continuous fixed bed reactor.Catalyst is ground and pressed
Then piece is sieved into little particle, and the particle of 20-40 mesh is fitted into reactor, 700 °C at a temperature of in H 2Middle reduction
1 h；Then acetic acid-water mixed solution that molar ratio is 1:4 is injected into vaporizer after vaporizing with constant flow pump, 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 this is former
Material conductance enters reaction bed, and reaction condition is normal pressure, air speed 10000-30000 h-1, reaction end gas using gas chromatograph it is online
Analysis.
Catalyst CUT-NM is investigated through acetic acid self-heating recapitalization activity, is normal pressure, 30000 ml/ of air speed in reaction condition
(g-catalysth), when reaction temperature is 700 °C, unstripped gas acetic acid/water/oxygen=1/4.0/0.28, the catalyst
For initial acetic acid conversion 98.7%, the initial yield of hydrogen is 2.80mol-H2/ mol-HAc, CO2Selectivity is selected in 59% or so, CO
Selecting property is in 36% or so, CH4Selectivity between 1.0% to 3.2%, and have 7% or so by-product acetone.With reaction into
Row, reactivity decline, and after reaction time 10h, acetic acid conversion drops to 85%, and hydrogen yield is reduced to 2.38mol-H2/
mol-HAc.XRD characterization is the results show that since the catalyst group becomes Mg-Ni-O solid solution, the reducing degree of active component nickel
It is low, simultaneously because not containing chromium, not formed stable MgCr2O4And NiCr2O4Spinel structure is urged in autothermal reforming reaction
It is lower to change activity.
Embodiment 1
Weigh the Cr (NO of 8.903g3)3·9H2, 11.411g Mg (NO3)2·6H2Ni (the NO of O and 2.005g3)2.6H2O adds
In the deionized water for entering 73.60 ml, it is configured to solution #1.Accurately weigh the NaOH's and 1.610g of 9.427g respectively
Na2CO3, it is added in the deionized water of 250ml, is configured to solution #2.Subsequent step is obtained with typical structure such as with reference example 1
It is attached shown in FIG. 1 containing MgCr2O4And NiCr2O4Spinel structure and Mg-Ni-Cr-O solid solution, as shown in Fig. 2 aperture
It is distributed the mesoporous composite oxides CUT-NMC-201 catalyst being concentrated mainly within the scope of 10-20nm.The weight group of the catalyst
Become: nickel oxide content 14.9%, magnesia 55.1%, chromium oxide 30.0%.
Catalyst CUT-NMC-201 is investigated through acetic acid self-heating recapitalization activity, when reaction condition is normal pressure, air speed 30000
Ml/ (g-catalysth), reaction temperature are 700 °C, when unstripped gas acetic acid/water/oxygen=1/4.0/0.28, the catalyst
Acetic acid conversion stablize 100%, hydrogen yield 2.80mol-H2/ mol-HAc, carbon dioxide selectivity 55% or so,
44% or so, methane selectively is generated 1.2% or so without by-product acetone carbon monoxide selective.With reaction into
Row, catalyst activity keep stablizing.Nitrogen absorption under low temperature characterization is carried out to CUT-NMC-201 catalyst, as a result are as follows: specific surface area is
25.9m2/ g, pore volume 0.084cm3/ g, average pore size 12.9nm.Catalyst after reaction is characterized, such as attached drawing 3
XRD spectra shown in, catalyst structure is stablized, and active component nickel effectively disperses, do not assemble sintering, valence stability and not by
Oxidation, grain size do not have significant changes, do not find Carbon spices, show the active stabilization of catalyst of the present invention, hydrogen yield
The advantages that height, anti-carbon, anti-oxidant, stable structure.
Embodiment 2
Accurately weigh the Cr (NO of 8.566g3)3·9H2O, the Mg (NO of 12.484g3)2·6H2Ni (the NO of O and 2.336g3)2.6H2O is added in the deionized water of 75.00 ml, is configured to solution #1.The NaOH and 1.603g of 9.681g are accurately weighed respectively
Na2CO3, it is added in the deionized water of 225ml, is configured to solution #2.Subsequent step is obtained with reference example 1 with typical structure
It is as shown in Fig. 1 and attached shown in Fig. 2 containing MgCr2O4And NiCr2O4Spinel structure and Mg-Ni-Cr-O solid solution, aperture
Distribution concentrates on the mesoporous composite oxides catalyst CUT-MNC-301 within the scope of 10-20nm.The weight of the catalyst forms
Are as follows: nickel oxide content 14.9%, magnesia 50.1%, chromium oxide 35.0%.
Catalyst CUT-NMC-301 is investigated through acetic acid self-heating recapitalization activity, and reaction condition is normal pressure, air speed 30000
Ml/ (g-catalysth), reaction temperature are 700 °C, when unstripped gas acetic acid/water/oxygen=1/4.0/0.28, the catalyst
Acetic acid conversion stablize 100%, the initial yield of hydrogen is 2.85mol-H2/ mol-HAc, carbon dioxide selectivity is on 60% left side
The right side, carbon monoxide selective is 39% or so, and methane selectively is 0.8% or so, almost without by-product acetone, and 10h's
It keeps stablizing in test.Nitrogen absorption under low temperature characterization is carried out to CUT-NMC-301 catalyst, as a result are as follows: specific surface area 21.9m2/
G, pore volume is 0.090cm3/ g, average pore size 12.5nm.Catalyst after reaction is characterized, typical structure such as attached drawing
Shown in 3 XRD spectra, active component nickel is effectively dispersed, and does not assemble sintering and valence stability, and grain size does not become significantly
Change, shows the advantages that active stabilization of invention catalyst, hydrogen yield are high, without carbon distribution, stable structure.
By active testing result as it can be seen that catalyst of the invention is in acetic acid autothermal reforming reaction, acetic acid conversion reaches
100%, the hydrogen yield of preferred catalyst reaches 2.85mol-H2/ mol-HAc, and keep stable；Shown by characterizations such as XRD
This catalyst has the characteristics that stable structure, resistance to oxidation, anti-carbon, resistance to sintering.
Claims (4)
1. being used for the nickel magnesium chromium mesoporous composite oxides catalyst of acetic acid self-heating reforming hydrogen manufacturing, it is characterised in that: preparing metal nitre
The mixed solution of hydrochlorate: according to chemical composition prepare nickel, magnesium, chromium nitrate mixed solution；Prepare precipitating reagent: according to carbonic acid
Root and molar ratio hydroxy are 1:16 ~ 30, according to the charge summation and molar ratio hydroxy of metal cation Ni, Mg, Cr
For 1:12 ~ 18, the mixed solution of sodium carbonate and sodium hydroxide is prepared；By the mixed solution of metal nitrate and precipitating reagent at 65 °C
~ 75 °C of progress coprecipitation reactions control reacting solution pH value in the range of 10.5 ± 0.5, and maintain stirring aging 18-20h,
Gained sediment is filtered, washing, and the roasting temperature 4h after drying 12 hours at 600-800 °C obtains having containing MgCr2O4With
NiCr2O4The mesoporous composite oxides catalyst of spinelle and Mg-Ni-Cr-O solid solution, a mole composition is (NiOa)(MgO)b
(CrO1.5)c, wherein a is 0.08-0.12, b 0.55-0.92, c 0-0.33 is formed are as follows: nickel oxide by weight percentage
Content is 12.0-20.0%, content of magnesia 40.0-88.0%, chromic oxide content 0-40.0%；The catalyst is used for acetic acid
Self-heating reforming hydrogen manufacturing process.
2. the catalyst of acetic acid self-heating reforming hydrogen manufacturing according to claim 1, it is characterised in that: the catalyst is to aoxidize
The weight percent of object forms are as follows: nickel oxide 14.9%, magnesia 55.1%, chromium oxide 30.0%.
3. the catalyst of acetic acid self-heating reforming hydrogen manufacturing according to claim 1, it is characterised in that: the catalyst is to aoxidize
The weight percent of object forms are as follows: nickel oxide 14.9%, magnesia 50.1%, chromium oxide 35.0%.
4. the purposes that catalyst described in claim 1-3 is reacted in acetic acid self-heating reforming hydrogen manufacturing, it is characterised in that: take 0.05-
The told catalyst of any one of 0.30g claim 1-3 is with 600-800 °C in H2After middle reduction 1h, be passed through molar ratio be acetic acid/
Water/oxygen=1/ (1.3-5.0)/(0.21-0.35) mixed gas carries out acetic acid autothermal reforming reaction by catalyst bed,
Reaction temperature is 500-850 °C.
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| CN114272928A (en) * | 2022-01-05 | 2022-04-05 | 成都理工大学 | Magnesium-titanium perovskite nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
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| CN114272928A (en) * | 2022-01-05 | 2022-04-05 | 成都理工大学 | Magnesium-titanium perovskite nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN114272928B (en) * | 2022-01-05 | 2023-03-14 | 成都理工大学 | Magnesium-titanium perovskite nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
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