CN105195154A - Biomass depolymerized product reforming hydrogen production catalyst and preparation method thereof - Google Patents
Biomass depolymerized product reforming hydrogen production catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a biomass depolymerized product reforming hydrogen production catalyst and a preparation method thereof. The catalyst consists of Ni/Zn/Al type hydrotalcite of which the mole ratio of Ni to Zn is (0.25: 1)-(4: 1) or the mole ratio of (Ni+Zn) to Al is (2: 1)-(10: 1). Soluble metal salt ion Ni(NO3)2, Zn(NO3)2 and Al(NO3)3 and alkaline solutions NaOH and Na2CO3 are co-precipitated to generate the biomass depolymerized product water phase reforming hydrogen production Ni/Zn/Al type hydrotalcite catalyst. According to a method for realizing biomass depolymerized product water phase reforming hydrogen production by adopting the catalyst, the H2 selectivity is up to about 60-100 percent, the alkane selectivity is up to about 30-2 percent, and the ethylene glycol conversion rate is about 100 percent. The catalyst and the preparation process are simple, low in cost and convenient to operate.
Description
Technical field
The present invention relates to living beings aqueous phase reformation hydrogen production field, specifically comprise Ni/Zn/Al houghite Catalysts and its preparation method.
Background technology
Hydrogen Energy is paid close attention to by the mankind gradually as a kind of energy of high-efficiency cleaning, and according to statistics, the hydrogen of current 95% all comes from fossil energy.But fossil energy is in continuous exhaustion.Therefore, regenerative resource preparing hydrogen is utilized to become a kind of effective method, such as living beings or its depolymerization product.At present the research of vapor reforming hydrogen production is carried out comparatively extensively and profoundly to living beings or its depolymerization product, but the method needs higher reaction temperature (more than 450 DEG C) and pressure (more than 4.0MPa), and course of reaction is complicated.And aqueous phase reforming hydrogen production process course of reaction that is simple with it, low-temp low-pressure (250 DEG C, below 3.5MPa) gets the nod, the study hotspot of this reaction concentrates on exploitation for efficient, cheap catalyst and improvement.
At present for the catalyst of aqueous phase reforming hydrogen manufacturing, be mainly divided into two parts: with Pt be representative noble metal catalyst and with the non-precious metal catalyst of Ni for main metal active constituent.Pass through H
2the height of the results such as selective, methanation reaction is active judges the height of catalyst catalytic performance.Pt system noble metal catalyst has higher catalytic activity, but is difficult to realize industrialized development because its cost is higher; Cheap Ni series catalysts shows good C-C bond fission ability in aqueous phase reforming hydrogen production reaction, but there is H
2selective low, active high, the easy generation carbon deposit of methanation reaction and cause the problems such as catalysqt deactivation.The hydrogen-producing speed of the RaneyNi catalyst be widely studied is suitable with Pt series catalysts, but easily in atmosphere spontaneous combustion occurs, and chemical stability is poor.Based on the problems referred to above, need to develop a kind of H
2selective height, methanation reaction ability are low, the new catalyst that chemical stability is good.
Summary of the invention
Based on the problems of the prior art, the invention provides a kind of living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen and preparation method thereof, solve catalyst methane reactivity in prior art high, the problem of poor stability.
The present invention is achieved through the following technical solutions:
A kind of living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen, catalyst consists of the molar ratio 0.25:1 ~ 4:1 of Ni/Zn, and the molar ratio of (Ni+Zn)/Al is the Ni/Zn/Al houghite of 2:1 ~ 10:1.
Catalyst composition is preferably the molar ratio 1:1 of Ni/Zn, and the molar ratio of (Ni+Zn)/Al is the Ni/Zn/Al houghite of 6:1.
The preparation method of living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen of the present invention, with the ionizable metal salt Ni (NO of solubility
3)
2, Zn (NO
3)
2with Al (NO
3)
3, with aqueous slkali NaOH and Na
2cO
3co-precipitation, generates living beings depolymerization product aqueous phase reforming hydrogen manufacturing Ni/Zn/Al houghite catalyst.
Concrete steps are as follows:
(1) be that 2:1 ~ 10:1 takes Ni (NO with the molar ratio of the molar ratio 0.25:1 ~ 4:1 of Ni/Zn, (Ni+Zn)/Al
3)
26H
2o, Zn (NO
3)
26H
2o and Al (NO
3)
39H
2o, under magnetic stirring, is dissolved in deionized water, obtains a kind of green transparent solution A; NaOH and Na is taken again with the molar ratio of 63:100
2cO
3, under magnetic stirring, be dissolved in deionized water, obtained colourless transparent solution B;
(2) under agitation, dropped in colourless transparent solution B by green transparent solution A, until form blue cotton-shaped suspension, then at 60 ~ 85 DEG C, ageing 12h obtains blue jelly;
(3) utilize the deionized water being heated to 100 DEG C to wash blue jelly to pH=6-10, suction filtration gained solid is placed in baking oven, obtains blue-green solid after drying 12h at 100 DEG C;
(4) blue-green solid is placed in Muffle furnace, at 300 ~ 500 DEG C, obtains black solid after roasting 3-5h, ground after taking-up, pulverize, cross 20 ~ 40 mesh sieves, namely obtain Ni/Zn/Al houghite catalyst.
Utilize catalyst of the present invention to carry out the method for living beings depolymerization product aqueous phase reforming hydrogen manufacturing, in autoclave, splendid attire ethylene glycol solution, utilizes N
2regulating system pressure, reaction temperature is 210 ~ 240 DEG C, and reaction pressure is 1.95 ~ 3.4MPa, reaction time 3 ~ 18h; Ni/Zn/Al houghite catalyst input amount (g) is 2g/L.
Reaction result shows, utilizes the catalyst in the present invention that living beings depolymerization product (ethylene glycol) is carried out reformation hydrogen production, can make H
2selectively reach about 60 ~ 100%; Paraffin selectivity reaches about 30 ~ 2%; Ethylene glycol reforming rate reaches about 100%.
Beneficial effect of the present invention is: living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen prepared by the method has following advantage:
(1) in living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen preparation process, prepare with ZnO, NiO and ZnAl
2o
4for the composite catalyst of main body.Because the specific area of catalyst is large, particle diameter is little, makes its metal dispersion better.
(2) in living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen preparation process, catalyst defines hydrotalcite precursor before roasting, this presoma presents the serious asymmetric special layer structure of a kind of crystalline field, in the lattice of cation on laminate, the interlayer of anion outside lattice, and interlayer anion can exchange with other anion, high-valence anion is easy to exchange and enters interlayer, and anion is easy to be swapped out at a low price, so, the kind of interlayer anion can be adjusted by the kind and quantity changing its anion, to obtain required catalyst property
(3) in living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen preparation process, catalyst composite metal oxide of gained after roasting has higher heat endurance.
(4) in living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen preparation process, catalyst has higher hydrogen selective and lower paraffin selectivity.
Catalyst of the present invention and preparation process simple, with low cost, easy to operate.
Accompanying drawing explanation
Fig. 1 is the XRD figure of example 1-5 of the present invention;
Fig. 2 is the heat stabilization test result figure of example 1-5 of the present invention.
Detailed description of the invention
A kind of living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen, described catalyst can form houghite presoma, and wherein the molar ratio of Ni/Zn is 0.25:1 ~ 4:1, and the molar ratio of (Ni+Zn)/Al is 2:1 ~ 10:1.
As preferred proportioning, in catalyst, the molar ratio of Ni/Zn is 1:1, and the molar ratio of (Ni+Zn)/Al is 6:1.
A preparation method for living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen, is characterized in that, with the ionizable metal salt Ni (NO of solubility
3)
26H
2o, Zn (NO
3)
26H
2o and Al (NO
3)
39H
2o, with aqueous slkali NaOH and Na
2cO
3co-precipitation, generate a kind of living beings depolymerization product aqueous phase reforming hydrogen manufacturing Ni/Zn/Al houghite catalyst efficiently, the preparation method of this catalyst comprises the following steps:
(1) with the molar ratio of Ni/Zn for 0.25:1 ~ 4:1, the molar ratio of (Ni+Zn)/Al is that 2:1 ~ 10:1 takes Ni (NO
3)
26H
2o, Zn (NO
3)
26H
2o and Al (NO
3)
39H
2o, under magnetic stirring, is dissolved in deionized water, obtains a kind of green transparent solution A; NaOH and Na is taken again with the molar ratio of 63:100
2cO
3, under magnetic stirring, be dissolved in deionized water, obtained colourless transparent solution B;
(2) under strong agitation condition, gained green transparent solution A in step (1) is dropwise dropped in the middle gained colourless transparent solution B of step (1), until form blue cotton-shaped suspension, then at 60 ~ 85 DEG C, ageing 12h obtains blue jelly;
(3) utilize the deionized water being heated to 100 DEG C to wash blue for gained in step (2) jelly to pH=6-10, suction filtration gained solid after washing is placed in baking oven, dry 12h at 100 DEG C after, obtains blue-green solid;
(4) blue-green solid of gained in step (3) is placed in Muffle furnace, black solid is obtained after roasting 3-5h at 300 ~ 500 DEG C, ground after taking-up, pulverized, crossed 20 ~ 40 mesh sieves, namely obtained Ni/Zn/Al houghite catalyst.
Preferred method comprises the following steps:
(1) with the molar ratio of Ni/Zn for 1:1, the molar ratio of (Ni+Zn)/Al is that 6:1 takes Ni (NO
3)
26H
2o, Zn (NO
3)
26H
2o and Al (NO
3)
39H
2o, under magnetic stirring, is dissolved in deionized water, obtains a kind of green transparent solution A; NaOH and Na is taken with 63:100
2cO
3, under magnetic stirring, be dissolved in deionized water, obtained colourless transparent solution B;
(2) under strong agitation condition, gained green transparent solution A in step (1) is dropwise dropped in the middle gained colourless transparent solution B of step (1), until form blue cotton-shaped suspension, then at 60 DEG C, ageing 12h obtains blue jelly;
(3) utilize the deionized water being heated to 100 DEG C to wash blue for gained in step (2) jelly to pH=7, suction filtration gained solid after washing is placed in baking oven, dry 12h at 100 DEG C after, obtains blue-green solid; (4) blue-green solid obtained in step (3) is placed in Muffle furnace, at 500 DEG C, obtains black solid after roasting 3h, ground after taking-up, pulverize, cross 20 ~ 40 mesh sieves, namely obtain Ni/Zn/Al houghite catalyst.
Utilize catalyst of the present invention to carry out the hydrogen manufacturing of living beings depolymerization product aqueous phase reforming, this reaction is carried out in autoclave.In autoclave, splendid attire ethylene glycol solution, utilizes N
2regulating system pressure, reaction temperature is set between 210 ~ 240 DEG C, and reaction pressure is set between 1.95 ~ 3.4MPa, and the reaction time is set between 3 ~ 18h; Ni/Zn/Al houghite catalyst input amount (g) is 2g/L.
Below in conjunction with accompanying drawing, the present invention is elaborated:
The preparation method of living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen of the present invention, the method comprises the following steps:
(1) with the molar ratio of Ni/Zn for 0.25:1 ~ 4:1, the molar ratio of (Ni+Zn)/Al is
2:1 ~ 10:1 takes Ni (NO
3)
26H
2o, Zn (NO
3)
26H
2with Al (NO
3)
39H
2o, under magnetic stirring, is dissolved in and is equipped with in 50mL deionized water, obtains a kind of green transparent solution A; NaOH and Na is taken again with the molar ratio of 63:100
2cO
3, under magnetic stirring, be dissolved in and be equipped with in the deionized water of 50mL, obtained colourless transparent solution B;
(2) under strong agitation condition, gained green transparent solution A in step (1) is dropwise dropped in the middle gained colourless transparent solution B of step (1), until form blue cotton-shaped suspension, then at 60 ~ 85 DEG C, ageing 12h obtains blue jelly;
(3) utilize the deionized water being heated to 100 DEG C to wash blue for gained in step (2) jelly to pH=6-10, suction filtration gained solid after washing is placed in baking oven, dry 12h at 100 DEG C after, obtains blue-green solid;
(4) blue-green solid of gained in step (3) is placed in Muffle furnace, at 300-500 DEG C, obtains black solid after roasting 3-5h, ground after taking-up, pulverize, cross 20 ~ 40 mesh sieves, namely obtain Ni/Zn/Al houghite catalyst.
Catalyst Preparation Example:
Take Ni (NO respectively
3)
26H
2o, Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o is dissolved in 50mL deionized water and forms mixed solution A, then takes NaOH respectively, Na
2cO
3be dissolved in 50mL deionized water and form mixed solution B, Na
2cO
3with Al (NO
3)
39H
2the mol ratio of O is 0.375:1, NaOH and Al (NO
3)
39H
2the mol ratio of O is 6.30:10, and each component dosage is as shown in table 1.Solution A is dropwise added drop-wise to the B solution under strong agitation, this mixed solution is placed in 60 DEG C of oil bath pan constant temperature and places 12h, take out again and to pH=7, at 100 DEG C, dry 12h with 100 DEG C of deionized water washings, roasting 3h in 500 DEG C of Muffle furnaces, grinding, compressing tablet, pulverizing, excessively 20 ~ 40 mesh sieves, obtain different Ni/Zn/Al houghite catalyst.As shown in table 3, wherein embodiment 3 is the embodiments utilizing method for optimizing to prepare.
The Ni/Zn/Al dosage of table 1 different catalysts
The BET characterization result of table 2 different catalysts
From the XRD spectra of Fig. 1, the Ni/Zn/Al hydrotalcite catalyst prepared under this condition, mainly forms ZnO, NiO crystal formation, and Al is with spinelle ZnAl
2o
4form be present in catalyst.
From the BET characterization result of table 2, the Ni/Zn/Al hydrotalcite catalyst prepared under this condition, (high specific surface area can reach 37.4m to have larger specific area
2/ g), less nanoscale aperture.Therefore, the metal dispersion of catalyst can be made better.
Embodiment 6 takes Ni (NO with the molar ratio of 1:1:1
3)
26H
2o, Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o is dissolved in 50mL deionized water and forms mixed solution A, then takes NaOH respectively with the molar ratio of 63:100, Na
2cO
3be dissolved in 50mL deionized water and form mixed solution B.Solution A is dropwise added drop-wise to the B solution under strong agitation, this mixed solution is placed in 70 DEG C of oil bath pan constant temperature and places 12h, take out again and to pH=6, at 100 DEG C, dry 12h with 100 DEG C of deionized water washings, roasting 3h in 300 DEG C of Muffle furnaces, grinding, compressing tablet, pulverizing, excessively 20 ~ 40 mesh sieves, obtain NiZnAl houghite catalyst.
Embodiment 7 takes Ni (NO with the molar ratio of 2:2:1
3)
26H
2o, Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o is dissolved in 50mL deionized water and forms mixed solution A, then takes NaOH respectively with the molar ratio of 63:100, Na
2cO
3be dissolved in 50mL deionized water and form mixed solution B.Solution A is dropwise added drop-wise to the B solution under strong agitation, this mixed solution is placed in 75 DEG C of oil bath pan constant temperature and places 12h, take out again and to pH=8, at 100 DEG C, dry 12h with 100 DEG C of deionized water washings, roasting 3h in 400 DEG C of Muffle furnaces, grinding, compressing tablet, pulverizing, excessively 20 ~ 40 mesh sieves, obtain Ni
2zn
2al houghite catalyst.
Embodiment 8 takes Ni (NO with the molar ratio of 4:4:1
3)
26H
2o, Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o is dissolved in 50mL deionized water and forms mixed solution A, then takes NaOH respectively with the molar ratio of 63:100, Na
2cO
3be dissolved in 50mL deionized water and form mixed solution B.Solution A is dropwise added drop-wise to the B solution under strong agitation, this mixed solution is placed in 80 DEG C of oil bath pan constant temperature and places 12h, take out again and to pH=9, at 100 DEG C, dry 12h with 100 DEG C of deionized water washings, roasting 4h in 500 DEG C of Muffle furnaces, grinding, compressing tablet, pulverizing, excessively 20 ~ 40 mesh sieves, obtain Ni
4zn
4al houghite catalyst.
Embodiment 9 takes Ni (NO with the molar ratio of 5:5:1
3)
26H
2o, Zn (NO
3)
26H
2o, Al (NO
3)
39H
2o is dissolved in 50mL deionized water and forms mixed solution A, then takes NaOH respectively with the molar ratio of 63:100, Na
2cO
3be dissolved in 50mL deionized water and form mixed solution B.Solution A is dropwise added drop-wise to the B solution under strong agitation, this mixed solution is placed in 85 DEG C of oil bath pan constant temperature and places 12h, take out again and to pH=10, at 100 DEG C, dry 12h with 100 DEG C of deionized water washings, roasting 5h in 500 DEG C of Muffle furnaces, grinding, compressing tablet, pulverizing, excessively 20 ~ 40 mesh sieves, obtain Ni
5zn
5al houghite catalyst.
Catalyst is used for aqueous phase reforming hydrogen manufacturing and prepares embodiment:
The embodiment 1-5 catalyst of preparation is used for aqueous phase reforming hydrogen production reaction: as shown in table 3, wherein embodiment 10 utilizes above-described embodiment 1 to carry out the result of reacting, embodiment 11 utilizes above-described embodiment 2 to carry out the result of reacting, by that analogy, embodiment 12 ~ 14 is the results utilizing above-described embodiment 3 ~ 5 to react.
Biomass derivatives aqueous phase reforming hydrogen production reaction carries out in autoclave, and the volume of autoclave is 100mL.The ethylene glycol solution of splendid attire 20% concentration in autoclave, catalyst amounts is 0.2g, utilizes N
2regulating system pressure, reaction temperature 225 DEG C, reaction pressure 2.60MPa, reaction time 3.5h.Gas-phase product is analyzed online by a north point 3420a type gas-chromatography: H
2, CO, CH
4and CO
2be separated by 5A molecular sieve packed column, adopt TCD to detect; CH
4, C
2h
6, C
3h
8and C
4h
10be separated by Porapak packed column, adopt FID to detect.Result is as shown in table 3.
Table 3 catalyst is used for aqueous phase reforming hydrogen manufacturing experimental result
It can thus be appreciated that under same reaction conditions, different Ni/Zn mol ratio has a significant impact catalyst activity.Suitable increase Ni content, can make catalyst suppress the generation of alkane, improve catalyst activity; Ni content continues to increase, and causes catalyst member carbon distribution, and catalytic activity reduces.When Ni/Zn mol ratio is 1, hydrogen selective can improve nearly 20% compared with it is minimum, and paraffin selectivity can reduce nearly 16% compared with it is the highest.
Embodiment 15: the embodiment 3 of preparation be used for, in ethylene glycol aqueous phase reforming hydrogen production reaction, reacting and carrying out in autoclave, the volume of autoclave is 100mL.The ethylene glycol solution of splendid attire 20% concentration in autoclave, catalyst amounts is 0.2g, utilizes N
2regulating system pressure, reaction temperature 210 DEG C, reaction pressure 1.95MPa, reaction time 3.5h.The analysis of gas-phase product and liquid product is same as described above.Reaction result shows, its H
2selective about 60%, paraffin selectivity about 30%, ethylene glycol reforming rate about 95%.
Embodiment 16: the embodiment 3 of preparation be used for, in ethylene glycol aqueous phase reforming hydrogen production reaction, reacting and carrying out in autoclave, the volume of autoclave is 100mL.The ethylene glycol solution of splendid attire 20wt% concentration in autoclave, catalyst amounts is 0.2g, utilizes N
2regulating system pressure, reaction temperature 240 DEG C, reaction pressure 3.40MPa, reaction time 3.5h.The analysis of gas-phase product and liquid product is same as described above.Reaction result shows, its H
2selective about 75%, paraffin selectivity about 22%, ethylene glycol reforming rate about 98%.
Comparative example 1:
Ni
3zn
3the contrast of Al houghite biomass derivatives aqueous phase reforming catalyst for preparing hydrogen and conventional RaneyNi catalyst is applied, and reaction condition is identical.From reaction result, in ethylene glycol aqueous phase reforming hydrogen production reaction, catalyst activity is all higher than conventional RaneyNi catalyst, and hydrogen selective and the ethylene glycol reforming conversion ratio for gaseous product improve 51% and 53% respectively, and paraffin selectivity reduces by 16%.
Comparative example 2
For the stability of catalyst testing, by Ni in comparative example 1
3zn
3al houghite biomass derivatives aqueous phase reforming catalyst for preparing hydrogen carries out successive reaction experiment, and reaction condition is identical.In reaction 18h, Ni/Zn/Al catalyst does not show obvious catalysqt deactivation phenomenon, after 18h, still keeps its catalytic activity of 95%, higher than RaneyNi catalyst activity 45% under the same terms, as shown in Figure 2.
Claims (6)
1. a living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen, is characterized in that catalyst consists of the molar ratio 0.25:1 ~ 4:1 of Ni/Zn, and the molar ratio of (Ni+Zn)/Al is the Ni/Zn/Al houghite of 2:1 ~ 10:1.
2. catalyst as claimed in claim 1, it is characterized in that catalyst consists of the molar ratio 1:1 of Ni/Zn, the molar ratio of (Ni+Zn)/Al is the Ni/Zn/Al houghite of 6:1.
3. the preparation method of the living beings depolymerization product aqueous phase reforming catalyst for preparing hydrogen of claim 1, is characterized in that, with the ionizable metal salt Ni (NO of solubility
3)
2, Zn (NO
3)
2with Al (NO
3)
3, with aqueous slkali NaOH and Na
2cO
3co-precipitation, generates living beings depolymerization product aqueous phase reforming hydrogen manufacturing Ni/Zn/Al houghite catalyst.
4. method as claimed in claim 3, is characterized in that step is as follows:
(1) be that 2:1 ~ 10:1 takes Ni (NO with the molar ratio of the molar ratio 0.25:1 ~ 4:1 of Ni/Zn, (Ni+Zn)/Al
3)
26H
2o, Zn (NO
3)
26H
2o and Al (NO
3)
39H
2o, under magnetic stirring, is dissolved in deionized water, obtains a kind of green transparent solution A; NaOH and Na is taken again with the molar ratio of 63:100
2cO
3, under magnetic stirring, be dissolved in deionized water, obtained colourless transparent solution B;
(2) under agitation, dropped in colourless transparent solution B by green transparent solution A, until form blue cotton-shaped suspension, then at 60 ~ 85 DEG C, ageing 12h obtains blue jelly;
(3) utilize the deionized water being heated to 100 DEG C to wash blue jelly to pH=6-10, suction filtration gained solid is placed in baking oven, obtains blue-green solid after drying 12h at 100 DEG C;
(4) blue-green solid is placed in Muffle furnace, at 300 ~ 500 DEG C, obtains black solid after roasting 3-5h, ground after taking-up, pulverize, cross 20 ~ 40 mesh sieves, namely obtain Ni/Zn/Al houghite catalyst.
5. utilize the catalyst of claim 1 or 2 to carry out the method for living beings depolymerization product aqueous phase reforming hydrogen manufacturing, it is characterized in that splendid attire ethylene glycol solution in autoclave, utilize N
2regulating system pressure, reaction temperature is 210 ~ 240 DEG C, and reaction pressure is 1.95 ~ 3.4MPa, reaction time 3 ~ 18h.
6. method as claimed in claim 5, is characterized in that Ni/Zn/Al houghite catalyst input amount (g) is for 2g/L.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285128A (en) * | 2017-01-09 | 2018-07-17 | 天津大学（青岛）海洋工程研究院有限公司 | A kind of phenol aqueous phase reforming hydrogen production process |
| CN112341312A (en) * | 2020-11-13 | 2021-02-09 | 华南理工大学 | Method for preparing cyclohexanol and derivative thereof by selective hydrogenolysis of lignin |
| CN113663666A (en) * | 2021-08-26 | 2021-11-19 | 清华大学 | Preparation method and application of hydrocalumite-based derived ethanol reforming catalyst |
| CN115475629A (en) * | 2021-06-16 | 2022-12-16 | 南京工业大学 | Pt and Ru double-active-component dehydrogenation catalyst taking Ni/Zn/Al hydrotalcite as carrier, preparation method and application thereof |
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| JP2004345874A (en) * | 2003-05-20 | 2004-12-09 | Research Institute Of Innovative Technology For The Earth | Hydrogen production method, and hydrogen production system |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285128A (en) * | 2017-01-09 | 2018-07-17 | 天津大学（青岛）海洋工程研究院有限公司 | A kind of phenol aqueous phase reforming hydrogen production process |
| CN112341312A (en) * | 2020-11-13 | 2021-02-09 | 华南理工大学 | Method for preparing cyclohexanol and derivative thereof by selective hydrogenolysis of lignin |
| CN112341312B (en) * | 2020-11-13 | 2022-03-29 | 华南理工大学 | Method for preparing cyclohexanol and derivative thereof by selective hydrogenolysis of lignin |
| CN115475629A (en) * | 2021-06-16 | 2022-12-16 | 南京工业大学 | Pt and Ru double-active-component dehydrogenation catalyst taking Ni/Zn/Al hydrotalcite as carrier, preparation method and application thereof |
| CN115475629B (en) * | 2021-06-16 | 2023-12-22 | 南京工业大学 | Pt, ru double-active-component dehydrogenation catalyst taking Ni/Zn/Al hydrotalcite as carrier, and preparation method and application thereof |
| CN113663666A (en) * | 2021-08-26 | 2021-11-19 | 清华大学 | Preparation method and application of hydrocalumite-based derived ethanol reforming catalyst |
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