CN108328574A - A kind of method of Adsorption of Phenol enhancing reformation hydrogen production - Google Patents

A kind of method of Adsorption of Phenol enhancing reformation hydrogen production Download PDF

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CN108328574A
CN108328574A CN201810099030.0A CN201810099030A CN108328574A CN 108328574 A CN108328574 A CN 108328574A CN 201810099030 A CN201810099030 A CN 201810099030A CN 108328574 A CN108328574 A CN 108328574A
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phenol
catalyst
method described
calcium
hydrogen
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CN108328574B (en
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余皓
吴世杰
王红娟
曹永海
彭峰
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • 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
    • B01J23/78—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 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Separation Of Gases By Adsorption (AREA)

Abstract

The invention discloses a kind of methods that Adsorption of Phenol enhances reformation hydrogen production.This method loads with catalysis in fixed bed reactors and absorbs CO2The Ni Ca Al O bifunctional catalysts of function, in the case where inert gas is as carrier gas, with weight (hourly) space velocity (WHSV) for 0.432 2.592h‑1It is passed through the phenol solution of a concentration of 0.0399 0.1594g/ml, reaction temperature is 400 700 DEG C；Work as CO2After adsorption saturation, 0.1 3h of catalyst regeneration is carried out for 500 1000 DEG C in an inert atmosphere.The hydrogen purity obtained in the present invention is up to 98% or more, and the conversion ratio of phenol is up to 99% or more, and the stability for being catalyzed and adsorbing is good.

Description

A kind of method of Adsorption of Phenol enhancing reformation hydrogen production
Technical field
The invention belongs to energy technology fields, and in particular to a kind of method of Adsorption of Phenol enhancing reformation hydrogen production.
Background technology
In recent years, it is increased rapidly with the demand of global energy, fossil energy is caused drastically to consume, while also resulted in tight The natural environment and climate problem of weight.Therefore, with find fossil feedstock substitute as the main purpose biomass resource be converted into the energy and The research of industrial chemicals causes the concern of many countries in the world.Hydrogen Energy is considered as 21 century most potential cleaning energy Source, since the 1970s, Hydrogen Energy research has just been carried out in many countries and regions extensively in the world.Although the original of current hydrogen manufacturing Most of material is all to use the fossil fuels such as methane, but consider environmental protection problem, and the technology of hydrogen manufacturing continues to develop so that system Hydrogen feedstock is gradually converted to the sustainable energies such as biomass direction.
Currently, two methods of biomass pyrolytic hydrogen manufacturing and biomass gasifying hydrogen making are broadly divided into using biomass hydrogen preparation, but Two kinds of hydrogen manufacturing means can all face the problems such as more serious coking in actual mechanical process, so as to cause density of hydrogen and hydrogen Gas yield is greatly lowered, and it is the higher aromatic compound of phosphorus content to form burnt main matter, and wherein phenols is exactly most Common one kind.Therefore, how to remove the coke in actual production is particularly important to improve the stability of biomass conversion.Perhaps More researchs, which all concentrate on to focus, carries out catalytic steam reforming, not only can be by the complicated burnt removal of composition, while can also generate The higher hydrogen of calorific value, therefore there is good application prospect.
Maite Artetxe et al. (Fuel, 2016,184:629-636) use Ni/Al2O3Catalyst Pyrogentisinic Acid steams Vapour is reformed, and the conversion ratio of phenol reaches 81%；Qingqing Peng et al. (ACS Sustainable Chemistry＆ Engineering.2017,5:2098-2108) Ni/Fe nanocatalyst Pyrogentisinic Acids is used to carry out steam reformation, can make benzene The conversion ratio of phenol reaches 87%, and the yield of hydrogen is up to 81%.Although Pyrogentisinic Acid's progress steam reformation can obtain relatively high Conversion ratio, but obtained hydrogen purity is relatively low, wherein containing a large amount of CO2, CO and CH4Equal by-products, need into one Step, which isolates and purifies, can just obtain the higher hydrogen of purity.And it adsorbs enhancing steam reforming process and is introduced compared to steam reforming process Adsorbent, can remove CO in situ2While this by-product, steam reacting condition can also be promoted so that reaction It balances and is moved to the direction for generating hydrogen, obtain the hydrogen of high-purity.Currently, the research about absorption enhancing steam reformation hydrogen production It is substantially and is used as raw material using the lower compound of some phosphorus content (such as methane, ethyl alcohol, acetic acid, glycerine etc.).Patent CN102070125A carries out absorption enhancing reformation hydrogen production to methane, and obtained density of hydrogen can reach 90%.Patent CN107098311A carries out absorption enhancing reformation hydrogen production using Ca-Co-O catalyst to glycerine, and the concentration of hydrogen can be made high Up to 95%.But using the higher substance of phosphorus content in coke, such as phenol, the research for adsorbing enhancing reformation hydrogen production then rarely has report Road.
Invention content
For overcome the deficiencies in the prior art, the present invention provides a kind of methods that Adsorption of Phenol enhances reformation hydrogen production.
A kind of method of Adsorption of Phenol enhancing reformation hydrogen production, includes the following steps：
(1) it is loaded in fixed bed reactors with catalysis and absorbs CO2The Ni-Ca-Al-O catalyst of function；
(2) in the case where inert gas is as carrier gas, phenol solution is injected in the fixed bed reactors and is reacted； The weight (hourly) space velocity (WHSV) of a concentration of 0.0399-0.1594g/ml of the phenol solution, phenol solution are 0.432-2.592h-1, The temperature of reaction is 400-700 DEG C.
Preferably, the Ni-Ca-Al-O catalyst described in step (1) is to contain nickel oxide (NiO), mayenite (Ca12Al14O33, Ca3Al2(OH)12) Ni-Ca-Al-O compounds, preparation method includes the following steps：By nickel salt, calcium salt and Aluminium salt is dissolved in the water, and calcines 1-10h after drying at 500-1000 DEG C, obtains Ni-Ca-Al-O catalyst.
It is further preferred that the nickel salt is nickel nitrate.
It is further preferred that the calcium salt is one or more of calcium nitrate, calcium chloride and calcium phosphate.
It is further preferred that the aluminium salt is one or more of aluminum nitrate, aluminum sulfate and aluminium chloride.
It is further preferred that the molar ratio of calcium and aluminium is (0.8-3.8) in the calcium salt and aluminium salt：1；The Ni-Ca- The content of Ni is 5wt%-20wt% in Al-O catalyst.
It is further preferred that the temperature of the calcining is 800-900 DEG C, the time of calcining is 4-6h.
Preferably, a concentration of 0.0598g/ml-0.0797g/ml of phenol solution described in step (2).
Preferably, the weight (hourly) space velocity (WHSV) of the phenol solution described in step (2) is 1.296h-1-1.944h-1。
Preferably, the temperature of step (2) described reaction is 500-650 DEG C.
Preferably, in step (2), as Ni-Ca-Al-O Catalyst Adsorptions CO2After reaching saturation, carried out in argon gas atmosphere Catalyst regeneration, regeneration temperature are 500-1000 DEG C, recovery time 0.1-3h.
It is further preferred that the regenerated temperature is 800-850 DEG C, the regenerated time is 0.5-1h.
Compared with prior art, the invention has the advantages that：
The present invention carries out absorption enhancing steam reformation using phenol, compared to steam reforming process so that the purity of hydrogen It greatly improves, up to 98%；The activity of Ni-Ca-Al-O catalyst used is high, and stability is good.
Description of the drawings
Fig. 1 is the X-ray diffractogram of 1 gained Ni-Ca-Al-O catalyst of embodiment.
Fig. 2 is that the TEM of 1 gained Ni-Ca-Al-O catalyst of embodiment schemes.
Specific implementation mode
The specific implementation of the present invention is further described with attached drawing below by way of example, but protection scope of the present invention It is not limited to following embodiment.
The concentration of hydrogen is measured by gas-chromatography (GC) analysis in the following example, and the computational methods of GC detections use Internal standard method.
Embodiment 1-5：
0.0043mol nickel nitrates are weighed, the aluminium salt in calcium salt and 0.023mol tables 1 in 0.064mol tables 1 is dissolved in In 50ml water, 120 DEG C of dryings, obtained product roasts 4h in Muffle furnace at 800 DEG C, obtains Ni-Ca-Al-O catalyst, Ni-Ca-Al-O catalyst is loaded in fixed bed, argon gas makees carrier gas, with 1.296h-1Weight (hourly) space velocity (WHSV) be passed through a concentration of 0.0797g/ The phenol solution of ml, reaction temperature are 550 DEG C, and the purity of hydrogen see the table below 1 in product after reaction 15min.1 gained of embodiment X-ray diffractogram, the TEM figures of Ni-Ca-Al-O catalyst are as shown in Figure 1 and Figure 2.
Table 1
Embodiment 1 2 3 4 5
Calcium salt Calcium nitrate Calcium nitrate Calcium nitrate Calcium phosphate Calcium chloride
Aluminium salt Aluminum nitrate Aluminum sulfate Aluminium chloride Cobalt chloride Cobaltous sulfate
The purity (%) of hydrogen 98.66 93.24 92.56 91.26 90.25
Embodiment 6-11：
0.0043mol nickel nitrates, 0.064mol calcium nitrate and 0.023mol aluminum nitrates are weighed, is dissolved in 50ml water, 120 DEG C drying, obtained product roast under conditions of table 2, obtain Ni-Ca-Al-O catalyst, Ni-Ca- is loaded in fixed bed Al-O catalyst, argon gas make carrier gas, with 1.296h-1Weight (hourly) space velocity (WHSV) be passed through the phenol solution of a concentration of 0.0797g/ml, instead It is 550 DEG C to answer temperature, and the purity of hydrogen see the table below 2 in product after reaction 15min.
Table 2
Embodiment 1 6 7 8 9 10 11
Calcination temperature (DEG C) 800 800 800 800 500 900 1000
Roasting time (h) 4 1 6 10 4 4 4
Hydrogen purity (%) 98.66 94.10 95.32 94.2 92.12 95.42 94.10
Embodiment 12-15：
Calcium nitrate shown in table 3 is weighed, aluminum nitrate and nickel nitrate are dissolved in 50ml water, 120 DEG C of dryings, obtained product 4h is roasted at 800 DEG C in Muffle furnace, obtains the Ni-Ca-Al-O catalyst of different Ni contents.Enhance steam weight in Adsorption of Phenol In whole reaction, Ni-Ca-Al-O catalyst is loaded in fixed bed reactors, argon gas makees carrier gas, with 1.296h-1Weight (hourly) space velocity (WHSV) It is passed through the phenol solution of a concentration of 0.0797g/ml, reaction temperature is 550 DEG C, reacts the purity of hydrogen in product after 15min 3 are see the table below with phenol conversion.
Table 3
Embodiment 12 1 13 14 15
Nickel nitrate (mol) - 0.0043 0.0086 0.0129 0.0172
Calcium nitrate (mol) 0.067 0.064 0.061 0.057 0.054
Aluminum nitrate (mol) 0.024 0.023 0.022 0.020 0.019
Hydrogen purity (%) 77.95 98.66 98.65 98.6 98.47
Phenol conversion (%) 51.52 100 100 100 100
Embodiment 16-18：
Calcium nitrate shown in table 4 is weighed, aluminum nitrate and nickel nitrate are dissolved in 50ml water, 120 DEG C of dryings, obtained product Roast 4h at 800 DEG C in Muffle furnace, obtain different calcium/aluminium than Ni-Ca-Al-O catalyst.Enhance steam in Adsorption of Phenol In reforming reaction, Ni-Ca-Al-O catalyst is loaded in fixed bed reactors, argon gas makees carrier gas, with 1.296h-1Heavy space-time Speed is passed through the phenol solution of a concentration of 0.0797g/ml, and reaction temperature is 550 DEG C, reacts after 15min the pure of hydrogen in product Degree and phenol conversion see the table below 4.
Table 4
Embodiment 1 16 17 18
Nickel nitrate (mol) 0.0043 0.0043 0.0043 0.0043
Calcium nitrate (mol) 0.064 0.040 0.056 0.068
Aluminum nitrate (mol) 0.023 0.050 0.031 0.018
Hydrogen purity (%) 98.66 94.12 98.67 97.80
Phenol conversion (%) 100 86.97 100 97.14
Embodiment 19-22
0.0043mol nickel nitrates, 0.064mol calcium nitrate and 0.023mol aluminum nitrates are weighed, is dissolved in 50ml water, 120 DEG C drying, obtained product roast 4h at 800 DEG C, obtain Ni-Ca-Al-O catalyst, Ni-Ca-Al- is loaded in fixed bed O catalyst, argon gas make carrier gas, and the phenol solution of a concentration of 0.0797g/ml is passed through with weight (hourly) space velocity (WHSV) shown in table 6, reaction The purity of hydrogen and the conversion ratio of phenol see the table below 6 in product after 15min.
Table 6
Embodiment 19 20 1 21 22
Weight (hourly) space velocity (WHSV) (h-1) 0.432 0.648 1.296 1.944 2.592
Density of hydrogen (%) 98.31 98.27 98.66 97.42 95.27
Embodiment 23-26
0.0043mol nickel nitrates, 0.064mol calcium nitrate and 0.023mol aluminum nitrates are weighed, is dissolved in 50ml water, 120 DEG C drying, obtained product roast 4h at 800 DEG C, obtain Ni-Ca-Al-O catalyst, Ni-Ca-Al- is loaded in fixed bed O catalyst, argon gas make carrier gas, with 1.296h-1Weight (hourly) space velocity (WHSV) to be passed through phenol solution concentration as shown in table 7, produced after reacting 15min The purity of hydrogen and the conversion ratio of phenol see the table below 7 in object.
Table 7
Embodiment 23 24 1 25 26
Phenol concentration (g/ml) 0.0399 0.0598 0.0797 0.1196 0.1594
Density of hydrogen (%) 98.64 98.45 98.66 97.96 96.51
Embodiment 27-31：
0.0043mol nickel nitrates, 0.064mol calcium nitrate and 0.023mol aluminum nitrates are weighed, is dissolved in 50ml water, 120 DEG C drying, obtained product roast 4h at 800 DEG C, obtain Ni-Ca-Al-O catalyst, Ni-Ca-Al- is loaded in fixed bed O catalyst, argon gas make carrier gas, with 1.296h-1Weight (hourly) space velocity (WHSV) be passed through the phenol solution of a concentration of 0.0797g/ml, reaction temperature Degree is as shown in table 5, and the purity of hydrogen and the conversion ratio of phenol see the table below 8 in product after reaction 15min.
Table 8
Embodiment 27 28 1 29 30 31
Temperature 400 500 550 600 650 700
Hydrogen purity (%) 70.1 99.71 98.66 96.22 86.48 83.01
Phenol conversion (%) 65.8 98.66 100 100 100 100
Embodiment 32-38
Circulation experiment：0.0043mol nickel nitrates, 0.064mol calcium nitrate and 0.023mol aluminum nitrates are weighed, is dissolved in In 50ml water, 120 DEG C of dryings, obtained product roasts 4h at 800 DEG C, Ni-Ca-Al-O catalyst is obtained, in fixed bed Ni-Ca-Al-O catalyst is loaded, argon gas makees carrier gas, with 1.296h-1Weight (hourly) space velocity (WHSV) be passed through the phenol of a concentration of 0.0797g/ml Aqueous solution, reaction temperature is 550 DEG C, reaction time 100min, as Ni-Ca-Al-O Catalyst Adsorptions CO2After reaching saturation, It is regenerated under the conditions of in argon gas atmosphere by table 6, cycle is three times.It is detected through GC, reacts the purity and benzene of hydrogen in product after 15min The conversion results of phenol are shown in Table 9.
Table 9
Embodiment 32 33 34 35 36 37 38
Regeneration temperature (DEG C) 800 800 800 800 500 700 1000
Recovery time (h) 0.1 0.5 1 3 1 1 1
1st circle hydrogen purity (%) 95.64 96.76 98.34 97.68 95.35 97.99 96.87
2nd circle hydrogen purity (%) 95.46 96.54 98.72 97.65 95.56 97.86 96.54
3rd circle hydrogen purity (%) 95.42 96.37 98.95 97.63 95.01 97.57 96.31
1st circle phenol conversion (%) 95.20 96.34 99.99 98.67 94.02 98.89 95.46
2nd circle phenol conversion (%) 95.24 96.45 99.99 98.65 94.01 98.56 95.62
3rd circle phenol conversion (%) 95.11 96.21 99.98 98.74 94.11 98.77 95.04
Embodiment 39
Stability experiment：Circulation experiment：Weigh 0.0043mol nickel nitrates, 0.064mol calcium nitrate and 0.023mol nitric acid Aluminium is dissolved in 50ml water, and 120 DEG C of dryings, obtained product roasts 4h at 800 DEG C, obtains Ni-Ca-Al-O catalyst, Ni-Ca-Al-O catalyst is loaded in fixed bed, argon gas makees carrier gas, with 1.296h-1Weight (hourly) space velocity (WHSV) be passed through a concentration of 0.0797g/ The phenol solution of ml, reaction temperature is 550 DEG C, reaction time 100min, as Ni-Ca-Al-O Catalyst Adsorptions CO2Reach After saturation, 800 DEG C of regeneration 1h, recycle 30 times in argon gas atmosphere.It is detected through GC, reacts the purity of hydrogen in product after 15min It is shown in Table 10 with the conversion results of phenol.
Table 10
Recycle the number of turns 1 5 10 20 30
Hydrogen purity (%) 98.75 98.82 98.69 98.69 98.97
Phenol conversion (%) 100 100 99.10 99.73 99.63
It can see from the result of table 10, in the above conditions, increased in absorption using Ni-Ca-Al-O catalyst Pyrogentisinic Acid Strong steam reformation shows extraordinary stability, and during cycle 30 is enclosed, the purity of hydrogen can reach 98% or more, The conversion ratio of phenol is also up to 99% or more simultaneously.
It must emphasize, above-described embodiment is not just for the sake of clearly demonstrating examples of the invention Complete restriction to embodiment.Those of ordinary skill in the art can also make on the basis of the above description it is other not With the variation of form, embodiment can not be provided without to all embodiments here, but thus amplify out aobvious and easy The variation seen is still in protection scope of the present invention.

Claims (10)

1. a kind of method of Adsorption of Phenol enhancing reformation hydrogen production, which is characterized in that include the following steps：
(1) Ni-Ca-Al-O catalyst is loaded in fixed bed reactors；
(2) in the case where inert gas is as carrier gas, phenol solution is injected in the fixed bed reactors and is reacted；It is described The weight (hourly) space velocity (WHSV) of a concentration of 0.0399-0.1594g/ml of phenol solution, phenol solution are 0.432-2.592h-1, reaction Temperature be 400-700 DEG C.
2. according to the method described in claim 1, it is characterized in that, step（1）The preparation of the Ni-Ca-Al-O catalyst Method includes the following steps：By nickel salt, calcium salt and aluminium salt are dissolved in the water, and calcine 1- after drying at 500-1000 DEG C 10h obtains Ni-Ca-Al-O catalyst.
3. according to the method described in claim 2, it is characterized in that, the nickel salt is nickel nitrate.
4. according to the method described in claim 2, the calcium salt is one or more of calcium nitrate, calcium chloride and calcium phosphate.
5. according to the method described in claim 2, the aluminium salt is one or more of aluminum nitrate, aluminum sulfate and aluminium chloride.
6. according to the method described in claim 2, it is characterized in that, the molar ratio of calcium and aluminium is in the calcium salt and aluminium salt （0.8-3.8）：1；The content of Ni is 5 wt %-20 wt % in the Ni-Ca-Al-O catalyst.
7. according to the method described in claim 2, it is characterized in that, the temperature of the calcining be 800-900 DEG C, the time of calcining For 4-6h.
8. according to the method described in claim 1, it is characterized in that, step（2）The temperature of the reaction is 500-650 DEG C.
9. according to the method described in claim 1, it is characterized in that, step（2）In, as Ni-Ca-Al-O Catalyst Adsorptions CO2It reaches To after saturation, catalyst regeneration is carried out in argon gas atmosphere, regeneration temperature is 500-1000 DEG C, recovery time 0.1-3h.
10. according to the method described in claim 9, it is characterized in that, the regenerated temperature is 800-850 DEG C, when regenerated Between be 0.5-1h.
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CN111330590A (en) * 2020-03-05 2020-06-26 宁波大学 Fly ash catalyst and preparation method and application thereof
CN111330590B (en) * 2020-03-05 2022-10-18 宁波大学 Fly ash catalyst and preparation method and application thereof
CN112221507A (en) * 2020-10-28 2021-01-15 华南理工大学 Organic acid intercalated Ni-CaO-Al2O3Bifunctional catalyst, preparation method and application thereof

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