CN109847757B - The derivative nickel-base catalyst of lithium aluminum hydrotalcite for acetic acid self-heating reforming hydrogen manufacturing - Google Patents
The derivative nickel-base catalyst of lithium aluminum hydrotalcite for acetic acid self-heating reforming hydrogen manufacturing Download PDFInfo
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Abstract
The present invention relates to a kind of derivative nickel-base catalysts of the lithium aluminum hydrotalcite of acetic acid self-heating recapitalization hydrogen making.For the problem that the variation of existing catalyst catalyst structure present in acetic acid autothermal reforming reaction and the oxidation and sintering of active component, lead to the inactivation of catalyst, the new catalyst of a kind of stable structure, resistance to sintering, anti-carbon deposit, resistance to oxidation is provided.The chemical component of catalyst of the invention is (LiO0.5)a(NiO)b(AlO1.5)c, wherein a is 1.47-3.63, b 0.38-0.60, c 2.00-4.00.The present invention is prepared for the presoma of Li-Al carbonate form hydrotalcite structure using coprecipitation, the Li-Ni-Al-O composite oxide catalysts of the partially substituted nickel aluminate of lithium are obtained by roasting, the gasification for promoting carbon containing intermediate species improves thermal stability and catalytic activity of the catalyst in acetic acid autothermal reforming reaction.
Description
Technical field
The present invention relates to a kind of nickel-base catalysts for acetic acid self-heating reforming hydrogen manufacturing, more particularly to one kind with lithium aluminum water
Anatase structure is the nickel-base catalyst for acetic acid self-heating recapitalization hydrogen making of presoma, belongs to acetic acid self-heating recapitalization preparing hydrogen
The field of gas.
Background technique
Now, the mankind rely life, production main energy sources be still the fossil energies such as natural gas, petroleum；But resource is deficient
The ecological environment problems such as weary, greenhouse effects, atmosphere pollution increasingly highlight, and the development and utilization of clean energy resource are increasingly closed in various countries
Note.In recent years, Hydrogen Energy has become the hot spot that scientists from all over the world study, and is primarily due to its energy density height, heating conduction
It gets well, have good burning performance, storage form is various, from a wealth of sources.
Existing hydrogen production process includes water electrolysis hydrogen producing, petroleum hydrogen production from catalytic pyrolysis and natural gas catalytically reforming hydrogen producing.
But, water electrolysis hydrogen producing higher cost, the electric energy of consumption are already higher than energy caused by hydrogen burning itself；The fossils such as natural gas
Fuel vapour catalytically reforming hydrogen producing, is also limited by hydrogen feedstock.Biomass is a kind of ideal hydrogen source: resourceful and can
Regeneration, is a kind of environmental-friendly energy.But biomass distribution dispersion and energy density is low, can will be biological by high temperature pyrolysis process
Matter is converted to liquid, the higher bio-oil of energy density；The main component of bio-oil is acetic acid, therefore researcher often selects
Acetic acid is selected as research object, probes into the process that acetic acid catalysis reforms hydrogen making.
Acetic acid can obtain the hydrogen of higher degree by steam reforming process, and this method is normal in current reformation hydrogen production mode
One kind, but steam reforming process be the endothermic reaction, needed for heat by the external world provide.And self-heating recapitalization (CH3COOH
+xO2+yH2O→aCO+bCO2+cH2) it is the process for combining steam reformation with partial oxidative steam reforming, therefore heat may be implemented
The homeostasis of amount.
The selection of catalyst is particularly important for Efficient Conversion biology acetic acid hydrogen making during self-heating recapitalization.In existing rank
Section, the catalyst for self-heating recapitalization process mainly have noble metal catalyst and non-precious metal catalyst.Noble metal catalyst is such as
Pt, Ru, Pd etc. have higher catalytic activity and preferable carbon accumulation resisting ability, but expensive price limit in acetic acid self-heating recapitalization
Its industrial application is made.Non-precious metal catalyst such as Co, Cu, Ni, Fe etc. are also used catalytically reforming hydrogen producing process, and cost is more expensive
Metal is low.Wherein nickel-base catalyst activity with higher can promote the fracture of carbon-carbon bond and C-H bond in molecular acid, therefore
It is a preferable selection by the process that Ni base catalyst is used for acetic acid self-heating recapitalization.
Ni base catalyst can promote the activation of molecular acid, generate CH after acetic acid is activated3It is produced among COO*, CH3CO* etc.
Object further decomposes and generates hydrogen, CO, CO2Equal products；Meanwhile acetic acid also occurs that the side reactions such as dehydration and ketonization, generates
The intermediate products such as acetone, ketenes, acetone, ketenes, CHxCarbon distribution is formed Deng the polycondensation reaction of further occurrence containing carbon species, is covered
Ni active site is covered, reactivity is reduced.In addition, oxygen is in reactor front end due to being passed through oxygen during the reaction
It is consumed, so that reactor head temperature increases, agglomeration, generation are sintered and inactivate Ni particle at high temperature；Meanwhile oxygen
Can also oxidized metal Ni make its inactivation.With the progress of reaction, reactor leading portion is constantly mobile to catalytic bed rear end, finally leads
Cause entire catalytic bed that sintering, oxidation, loss of catalytic activity occurs.
In order to improve thermal stability, anti-caking power, carbon accumulation resisting ability and the oxidation resistance of Ni base catalyst, the present invention
Catalyst introduces Li, Al component, is prepared for [Li by coprecipitation1-x +Alx 3+(OH)2]m+[(CO3)m/2·yH2O] Li-Al
Carbonate form hydrotalcite-like compound catalyst precursor.In the preparation process of presoma, Ni is introduced2+, Ni2+Ion half
Diameter (69pm) and Li+Ionic radius (76pm) it is close, therefore Ni2+It can be to Li+Part substitution is carried out, Ni is made2+Into hydrotalcite knot
On structure laminate, the dispersion degree of active component Ni is improved.Presoma forms composite oxides Li-Ni-Al-O object after being fired
Phase.The composite oxides are using nickel aluminate as main component, and lithium replaces nickel aluminium ion part, and is highly dispersed at nickel aluminium
In spinelle skeleton.The partially substituted nickel aluminate thermostabilization is good, has peptizaiton to active component Ni, reduces Ni
Aggregation, improve the anti-caking power of catalyst.But for the nickel-base catalyst that aluminium oxide supports, nickel can promote oxycarbide
Methanation reaction；Meanwhile alumina support has acidity, can promote acetic acid pyrolytic reaction and assimilation polymerization reaction, aoxidize
Carbon distribution is formed on the surface of the opening of alumina supporter.To solve the above problems, catalyst of the present invention introduces auxiliary agent lithium.The lithium of alkalinity
The acidity of aluminium oxide can be neutralized, catalyst surface is improved to the adsorption strength of water, promotes catalyst surface active center to second
The adsorption activation of acid molecule especially induces the certain embodiments of acetic acid, forms CH3COO* promotes species among the methyl generated
CHxConversion, and inhibit assimilation polymerization reaction；Meanwhile also promoting reactant H2O and O2Dissociation activation, promote generate O*
Species and carbon containing intermediate species CHxGasification reaction, so that carbon distribution be inhibited to generate；Lithium also inhibits the C* species that CO is dissociated
Hydrogenation, so that methane be inhibited to generate.In addition, lithium further promotes the reduction of nickel oxide, increase the metallic nickel site of catalyst surface
Quantity, provide more for acetic acid conversion active site, improve catalytic activity.In addition, the catalyst passes through co-precipitation
Process forms meso-hole structure in structure, and porous structure is conducive to the transmitting and diffusion of reactant acetic acid and product molecule,
And the dispersion degree of active component nickel is improved, improve the catalytic activity of catalyst；And cellular structure can limit acetic acid self-heating recapitalization
The polymerization of carbon distribution presoma ketenes etc. in hydrogen production process inhibits carbon distribution, and improves to reaction product hydrogen and CO/CO2Choosing
Selecting property.
Innovation on catalyst component of the present invention and structure improves heat of the catalyst in acetic acid autothermal reforming reaction
Stability, anti-caking power, carbon accumulation resisting ability and oxidation resistance.The catalyst is applied to the activity of acetic acid autothermal reforming reaction
The catalyst that test result also shows invention has 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 activity it is low,
The problem of stability is poor, is easily oxidized and intolerant to sintering, leads to catalyst inactivation provides a kind of stable structure, resistance to sintering, antioxygen
Change, anti-carbon deposit, activity stabilized new catalyst.
The present invention uses Ni as active component, introduces Li, Al component, prepares Li-Al carbonate form water using coprecipitation
The presoma of anatase structure, the metalepsis by active component Ni to Li, improves the dispersion degree of Ni, after presoma is fired
Li-Ni-Al-O composite oxides are formed, main component is the partially substituted nickel aluminate structure of lithium, by Li and carrying
The acidity of body inhibits CO/CO2Methanation reaction, promote nickel oxide reduction, promote CHxEtc. carbon containing intermediate species gasification and
Inhibit the assimilation polymerization reaction during acetic acid self-heating recapitalization, to improve the carbon accumulation resisting ability and oxidation resistance of catalyst.
Catalyst of the present invention is used in the reaction of acetic acid self-heating reforming hydrogen manufacturing, in the case where reaction temperature is 650 DEG C, acetic acid (HAc)
Conversion ratio close to 100%, stablize in 2.7mol-H by hydrogen yield2/ mol-HAc or so.
Technical solution of the present invention:
The present invention is directed to the characteristics of acetic acid self-heating recapitalization, is prepared for Li-Al carbonate form hydrotalcite structure with coprecipitation
The Li-Ni-Al-O composite oxide catalysts of the partially substituted nickel aluminate of lithium derived from presoma, improve catalyst and exist
Activity and stability in acetic acid autothermal reforming reaction.A mole composition for catalyst of the present invention is (LiO0.5)a(NiO)b
(AlO1.5)c, wherein a is 1.47-3.63, b 0.38-0.60, c 2.00-4.00, corresponding weight percent composition are as follows: oxidation
Nickel (NiO) content 12.0%-18.0%, lithia (LiO0.5) content 8.0%-30.0%, aluminium oxide (AlO1.5) content
55.0%-77.0%.
Currently preferred catalyst is (LiO0.5)3.40(NiO)0.60(AlO1.5)4.00, weight percent are as follows: lithia is
17.0%, nickel oxide 15.0%, aluminium oxide 68.0%.
The step of specific preparation method, is as follows:
1) mixed solution of preparing metal nitrate: according to each group component mole fraction (LiO in catalyst0.5)a(NiO)b
(AlO1.5)c, wherein a is 1.47-3.63, and b 0.38-0.60, c 2.00-4.00 weighs a certain amount of lithium nitrate, nitric acid
Nickel, aluminum nitrate, addition deionized water, which stirs evenly, is configured to nitrate mixed solution；
2) prepare precipitating reagent: being 1:14~18 according to carbonate and molar ratio hydroxy, according to metal cation Li,
The charge summation and molar ratio hydroxy of Ni, Al are 1:12~18, weigh a certain amount of sodium carbonate and sodium hydroxide, addition is gone
Ionized water mixed preparing precipitating reagent；
3) solution that the solution and step 2) prepared step 1) are prepared passes through control in 40-60 DEG C of progress coprecipitation reaction
The addition speed for the solution that step 2) processed is prepared controls the pH value of reaction solution 8 ± 0.5, maintains stirring and aging after the completion
12h；Mixture is filtered after aging, then is repeatedly washed with deionized water to neutrality, filter cake is placed in 105 DEG C of dryings
The dry catalyst precursor for obtaining that there is Li-Al carbonate form hydrotalcite-like compound for 24 hours in case, typical phase structure such as X
Shown in x ray diffration pattern x (attached drawing 1)；
4) sample after drying is heated up with the heating rate of 10 DEG C/min, and in 600-800 DEG C of roasting temperature 3-
5h obtains catalyst, and shown in typical structure such as X-ray diffractogram (attached drawing 2), typical case's BJH pore-size distribution is as shown in Fig. 3,
Form the Li-Ni-Al-O composite oxide catalysts of the partially substituted nickel aluminate of lithium.This catalyst in reaction before
In H at a temperature of 600-800 DEG C2Middle reduction 1h；Reaction is carrier gas with nitrogen, and being passed through molar ratio is acetic acid/water/oxygen=1/
The mixed gas of (1.3-5.0)/(0.2-0.5), is reacted by catalyst bed, and reaction temperature is 600-800 DEG C.
Beneficial effects of the present invention:
1) catalyst of the present invention uses coprecipitation to prepare using nickel as active component with Li-Al carbonate form
Presoma based on hydrotalcite-like compound, active component Ni carries out part substitution to Li, so that active component Ni enters class water
The skeleton of anatase structure improves the dispersion degree of active component Ni.
2) catalyst of the present invention forms meso-hole structure, and BJH pore-size distribution is as shown in Fig. 3, porous structure benefit
In the transmitting and diffusion of reactant acetic acid and product molecule, be conducive to the dispersion of active component nickel, the catalysis for improving catalyst is living
Property；And cellular structure limits the polymerization of carbon deposit presoma ketenes etc. during acetic acid self-heating reforming hydrogen manufacturing, inhibits carbon deposit, and
It improves to reaction product hydrogen and CO/CO2Selectivity.
3) catalyst of the present invention introduces alumina catalyst support and it is partially substituted to form lithium after the presoma of formation is fired
Nickel aluminate structure, the spinel structure thermostabilization is good, has peptizaiton to active component Ni, reduces the aggregation of Ni,
Improve the anti-caking power of catalyst.
4) auxiliary agent lithium is introduced in catalyst of the present invention, alkaline lithium can neutralize the acidity of aluminium oxide, improve catalyst table
In face of the adsorption strength of water, promote catalyst surface active center to the adsorption activation of molecular acid, especially induction acetic acid
Certain embodiments form CH3COO* promotes species CH among the methyl generatedxConversion, and inhibit assimilation polymerization reaction；Meanwhile
Also promote reactant H2O and O2Dissociation activation, promote generate O* species and carbon containing intermediate species CHxDeng gasification reaction,
To inhibit carbon distribution to generate；The C* species hydrogenation that lithium also inhibits CO to dissociate, inhibits methane to generate.In addition, lithium further promotes
The reduction of nickel oxide increases the quantity in catalyst surface metallic nickel site, provides the active site more converted for acetic acid,
Improve catalytic activity.
5) through acetic acid autothermal reforming reaction the results show that catalyst of the present invention is in acetic acid conversion process, second can be induced
The Efficient Conversion of acid, the effectively generation of inhibition acetone, ketenes, the by-products such as methane, have anti-oxidant, resistance to sintering, anti-carbon,
The features such as activity stabilized.
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 of the present invention
Fig. 3: the BJH graph of pore diameter distribution of catalyst of the present invention
Specific embodiment
Reference example one
Weigh the Ni (NO of 2.322g3)2·6H2O, the Al (NO of 22.609g3)2·9H2The LiNO of O and 1.527g3, it is added
The deionized water of 90.3ml is configured to solution #1；Weigh the anhydrous Na of the NaOH and 4.791g of 28.930g2CO3, it is added
The deionized water of 200.8ml is configured to solution #2；Under conditions of 48 DEG C, pH value of solution are 8.0 ± 0.5, by solution #1 and molten
Liquid #2, which is added drop-wise in beaker, is stirred continuously carry out coprecipitation reaction, and continues to stir aging 12h；Mixture is taken out after aging
Filter, washing 3 times, gained sediment is 24 hours dry in 105 DEG C of drying boxes；Sediment obtains after roasting 4 hours at 750 DEG C
To CDUT-LNA-101 catalyst.The catalyst mole group becomes (LiO0.5)1.47(NiO)0.53(AlO1.5)4.00, weight percent
Composition are as follows: lithia 8.0%, nickel oxide 15.0%, aluminium oxide 77.0%.
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 weighed 0.1-0.2g and is fitted into reactor, at 600 DEG C -800 DEG C
At a temperature of in H2Middle reduction 1h；Then acetic acid-water mixed solution is injected into vaporizer after vaporizing with constant flow pump, mixes oxygen
Gas, and using nitrogen as internal standard gas, forming molar ratio is CH3COOH/H2O/O2=1/ (1.3-5.0)/(0.2-0.5) reaction
Unstripped gas, and this unstripped gas is imported into reaction bed, reaction condition is 600-800 DEG C, normal pressure, air speed 10000-35000ml/
(g-catalysth), reaction end gas uses gas chromatograph on-line analysis.
The CDUT-LNA-101 catalyst carries out active investigation through acetic acid autothermal reforming reaction, and reduction temperature is 700 DEG C, empty
Speed is 11000ml/ (g-catalysth), reaction temperature is 650 DEG C, raw materials components mole ratio CH3COOH/H2O/O2=1/4.0/
0.28.The catalyst acetic acid conversion ratio is lower, is 80.6%, hydrogen yield is in 2.2mol-H2/ mol-HAc or so, carbon dioxide
Selectivity is 63% or so, and carbon monoxide selective is 35% or so, and by-product acetone selectivity is 0.1% or so；To CDUT-
LNA-101 catalyst carries out nitrogen low-temperature physics absorption representation, as a result are as follows: specific surface area 96.64m2/ g, pore volume are
0.33cm3/ g, average pore size 10.91nm.
Embodiment one
Weigh the Ni (NO of 2.369g3)2·6H2O, the Al (NO of 16.299g3)2·9H2The LiNO of O and 5.250g3, it is added
The deionized water of 130.7ml is configured to solution #1；Weigh the anhydrous Na of the NaOH and 1.381g of 8.342g2CO3, it is added
The deionized water of 221.8ml is configured to solution #2；Subsequent step obtains the presoma of hydrotalcite-like compound with reference example one,
Typical structure is as shown in Fig. 1；The Li-Ni-Al-O combined oxidation of the partially substituted nickel aluminate of lithium is obtained after being fired
Object, typical structure are as shown in Fig. 2.Obtain CDUT-LNA-102 catalyst；The catalyst is mesoporous material, typical hole
Diameter distribution is as shown in Fig. 3.The catalyst mole group becomes (LiO0.5)3.63(NiO)0.38(AlO1.5)2.00, weight percent group
Become: lithia 17.0%, nickel oxide 15.0%, aluminium oxide 68.0%.
The CDUT-LNA-102 catalyst carries out active investigation through acetic acid autothermal reforming reaction, and reduction temperature is 700 DEG C, empty
Speed is 11000mL/ (g-catalysth), reaction temperature is 650 DEG C, raw materials components mole ratio CH3COOH/H2O/O2=1/4.0/
0.28.The catalyst acetic acid conversion ratio is stablized 99.9%, and hydrogen yield is in 2.7mol-H2/ mol-HAc or so, carbon dioxide
Selectivity is 66% or so, and carbon monoxide selective does not have by-product acetone 33% or so, and catalytic activity keeps stablizing, not
See inactivation；Nitrogen low-temperature physics absorption representation is carried out to CDUT-LNA-102 catalyst, as a result are as follows: specific surface area 131.74m2/
G, pore volume is 0.46cm3/ g, average pore size 9.07nm.Catalyst has carried out the characterization such as XRD, BET, TPR, urges as the result is shown
Agent keeps stable without significant carbon deposit, active component nickel, without sintering phenomenon.
Embodiment two
Weigh the Ni (NO of 2.330g3)2·6H2O, the Al (NO of 20.038g3)2·9H2The LiNO of O and 3.130g3, it is added
The deionized water of 160.3ml is configured to solution #1；Weigh the anhydrous Na of the NaOH and 5.661g of 34.187g2CO3, it is added
The deionized water of 200.7ml is configured to solution #2；Subsequent step obtains the presoma of hydrotalcite-like compound with reference example one,
Typical structure is as shown in Fig. 1, and the Li-Ni-Al-O combined oxidation of the partially substituted nickel aluminate of lithium is obtained after being fired
Object, typical structure is as shown in Fig. 2, i.e. acquisition CDUT-LNA-103 catalyst.The catalyst mole group becomes
(LiO0.5)3.40(NiO)0.60(AlO1.5)4.00, weight percent are as follows: lithia 30.0%, nickel oxide 15.0%, aluminium oxide
It is 55.0%.
The CDUT-LNA-103 catalyst carries out active investigation, 700 DEG C of reduction temperature, air speed through acetic acid autothermal reforming reaction
It is 650 DEG C for 11000mL/ (g-catalysth), reaction temperature, raw materials components mole ratio CH3COOH/H2O/O2=1/4.0/
0.28.The catalyst acetic acid conversion ratio is stablized near 96.7%, and hydrogen yield is in 2.5mol-H2/ mol-HAc or so, dioxy
Change carbon selectivity 61% or so, carbon monoxide selective has no that by-product acetone, catalyst activity keep steady 34% or so
It is fixed, have no inactivation；Nitrogen low-temperature physics absorption representation is carried out to CDUT-LNA-103 catalyst, as a result are as follows: specific surface area is
92.86m2/ g, pore volume 0.30cm3/ g, average pore size 8.24nm.
By active testing result as it can be seen that catalyst of the invention is in acetic acid autothermal reforming reaction, acetic acid conversion is close
100%, preferred catalyst hydrogen yield is stablized in 2.7mol-H2/ mol-HAc or so.It is found in conjunction with characterizations such as XRD, BET, TPR
The active component nickel of the catalyst is effectively dispersed, and sintering and valence stability are not assembled, and shows catalyst good thermal stability, resistance to
Sintering, activity stabilized, hydrogen yield is high, without obvious carbon distribution.
Claims (4)
1. application of the derivative nickel-base catalyst of lithium aluminum hydrotalcite during acetic acid self-heating reforming hydrogen manufacturing, it is characterised in that: will
0.1-0.2g catalyst is before acetic acid autothermal reforming reaction in 600-800 DEG C of H21h is restored in atmosphere, being passed through molar ratio is
CH3COOH/H2O/O2=1/ (1.3-5.0)/(0.2-0.5) mixed gas carries out acetic acid self-heating recapitalization by catalyst bed
Reaction, reaction temperature are 600 DEG C -800 DEG C；The preparation process of the derivative nickel-base catalyst of the lithium aluminum hydrotalcite are as follows: according to chemical group
At lithium nitrate, nickel nitrate and aluminum nitrate are dissolved in deionized water and are configured to metal salt solution (#1)；According to carbonate and hydroxyl
Molar ratio be 1:14-18 and the charge summation of metal cation Li, Ni, Al with molar ratio hydroxy are that 1:12-18 claims
A certain amount of natrium carbonicum calcinatum and sodium hydroxide are taken, deionized water is dissolved in and forms mixed solution (#2)；By #1 solution and #2 solution
It is added drop-wise in beaker and is stirred continuously carry out coprecipitation reaction, during dropwise addition, keep pH value of solution 8.0 ± 0.5, bath temperature
40-60 DEG C, aging 12h is filtered, is washed, and filter cake obtains for 24 hours in 105 DEG C of dryings with Li-Al carbonate form houghite afterwards
The catalyst precursor of structure；Catalyst precursor roasts 3-5h at 600-800 DEG C and obtains the partially substituted nickel aluminium point crystalline substance of lithium
The catalyst in the Li-Ni-Al-O composite oxides activated centre of stone, chemical component is (LiO0.5)a(NiO)b(AlO1.5)c,
Middle a is 1.47-3.63, and b 0.38-0.60, c 2.00-4.00 is formed are as follows: lithia 8.0%- according to weight percent
30.0%, nickel oxide 12.0%-18.0%, aluminium oxide 55.0-77.0%.
2. derivative nickel-base catalyst the answering during acetic acid self-heating reforming hydrogen manufacturing of lithium aluminum hydrotalcite according to claim 1
With, it is characterised in that: the catalyst is formed with the weight percent of oxide are as follows: lithia 8.0%, nickel oxide are
15.0%, aluminium oxide 77.0%.
3. derivative nickel-base catalyst the answering during acetic acid self-heating reforming hydrogen manufacturing of lithium aluminum hydrotalcite according to claim 1
With, it is characterised in that: the catalyst is formed with the weight percent of oxide are as follows: lithia 17.0%, nickel oxide are
15.0%, aluminium oxide 68.0%.
4. derivative nickel-base catalyst the answering during acetic acid self-heating reforming hydrogen manufacturing of lithium aluminum hydrotalcite according to claim 1
With, it is characterised in that: the catalyst is formed with the weight percent of oxide are as follows: lithia 30.0%, nickel oxide are
15.0%, aluminium oxide 55.0%.
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Non-Patent Citations (2)
| Title |
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| 不同金属改性的镁铝水滑石在酯交换反应中的研究;马士博等;《黑龙江大学自然科学学报》;20171231;第34卷(第6期);689-694 * |
| 乙酸自热重整制氢用类水滑石衍生Zn-Ni-Al-Fe-O催化剂研究;杨浩等;《燃料化学学报》;20181130;第46卷(第11期);1352-1358 * |
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