CN109794250A - Hydrogen synthesis catalyst and preparation method thereof - Google Patents
Hydrogen synthesis catalyst and preparation method thereof Download PDFInfo
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- CN109794250A CN109794250A CN201811647577.6A CN201811647577A CN109794250A CN 109794250 A CN109794250 A CN 109794250A CN 201811647577 A CN201811647577 A CN 201811647577A CN 109794250 A CN109794250 A CN 109794250A
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- synthesis catalyst
- hydrogen synthesis
- hydrogen
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000001257 hydrogen Substances 0.000 title claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract 16
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 32
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims abstract description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 230000010355 oscillation Effects 0.000 claims abstract 5
- 239000002244 precipitate Substances 0.000 claims abstract 5
- 238000005406 washing Methods 0.000 claims abstract 4
- 239000002245 particle Substances 0.000 claims abstract 3
- 230000032683 aging Effects 0.000 claims abstract 2
- 238000001354 calcination Methods 0.000 claims description 5
- 230000035939 shock Effects 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 26
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229940116318 copper carbonate Drugs 0.000 abstract description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000009514 concussion Effects 0.000 description 5
- 230000029087 digestion Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 206010068150 Acoustic shock Diseases 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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Abstract
The invention relates to the technical field of methanol hydrogen production, in particular to a hydrogen synthesis catalyst and a preparation method thereof, and the hydrogen synthesis catalyst comprises the following steps: (1) adding copper nitrate and basic zinc carbonate into deionized water, gradually adding a sodium carbonate solution under ultrasonic oscillation, adjusting the pH value, ending the oscillation, aging, and filtering to obtain a precipitate; (2) and washing the precipitate, adding lanthanum oxide, performing ball milling dispersion, and then washing, drying and roasting to obtain the hydrogen synthesis catalyst. By combining the one-step reverse precipitation method and the ultrasonic oscillation technology, copper carbonate precipitates with smaller particle size and larger specific surface area can be generated in the ultrasonic oscillation process and are easy to attach to basic zinc carbonate, and compared with a common one-step precipitation method or a two-step precipitation method, the prepared catalyst has higher specific surface area and Cu dispersity; in addition, lanthanum oxide is mixed in the precipitate, so that the stability of the catalyst and the hydrogen production rate can be improved.
Description
Technical field
The present invention relates to Technology for Production Hydrogen from Methanol fields, and in particular to a kind of hydrogen synthetic catalyst and preparation method thereof.
Background technique
Hydrogen is as ideal chemical fuel, energy carrier and energy storage tool, rich reserves on earth, combustion heat value
Height, and do not generate any pollution after burning, is conducive to environmental protection, therefore is counted as 21 century ideal clean new energy.
In all too many levels of hydrogen manufacturing key technology it may first have to solve the Discussion On Development of effective catalyst.No matter from technology
Maturity or from existing infrastructure using from the point of view of degree, with fossil fuel (including methanol, natural gas, vapour
Oil, diesel oil etc.) hydrogen manufacturing is the important channel for solving small-scale distributing hydrogen source at this stage.Liquid fuel carbinol is due to hydrogen manufacturing
The features such as conversion condition (temperature, pressure, volume, quality) is relatively mild, sulfur-bearing, low toxicity, hydrogen production process are not realized relatively easily
As the first choice in these hydrogen-rich fuels.
Currently, the report that copper-based catalysts are applied to methanol steam reforming reaction is more, number of patent application is
201810320327.5 patent of invention discloses the catalyst of CuO/ZnO/ScO a kind of, which has methanol conversion high
The characteristics of, but have no and illustrate for the stability and hydrogen yield of catalyst.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of methanol conversions
High, stable and high hydrogen yield hydrogen synthetic catalyst and preparation method thereof.
The purpose of the invention is achieved by the following technical solution:
A kind of preparation method of hydrogen synthetic catalyst, includes the following steps:
(1) basic zinc carbonate of the copper nitrate and 36-40 parts by weight that take 3-6 parts by weight is added to 100 parts by weight deionizations
In water, under ultrasonic vibration, it is gradually added into sodium carbonate liquor, adjusting pH value is 7.5-8.5, terminates concussion, is aged, and filtering obtains
To precipitating；
(2) precipitating is washed, 0.5-1 parts by weight lanthana is added and carries out ball milling dispersion, then washed, done
It is dry, roasting to get arrive the hydrogen synthetic catalyst.
The present invention utilizes the combination of a step reverse-precipitation and ultrasonic vibration technique, during ultrasonic vibration, can be generated
The bigger copper carbonate precipitating of partial size more small specific surface product, and be easy to be attached on basic zinc carbonate, relative to a common step
The precipitation method or two precipitation method, catalyst obtained have higher specific surface area and Cu dispersion degree；In addition, the present invention is also heavy
It is mixed into lanthana in shallow lake, the stability and hydrogen-producing speed of catalyst can be promoted.
Wherein, the ultrasonic frequency of the ultrasonic vibration is 20-40kHz, ultrasonic power 20-30W.Ultrasonic wave generates
Cavitation effect can promote the uniform generation of the evenly dispersed of basic zinc carbonate and precipitating, but supersonic frequency or power mistake
Height, cavitation effect excessively can acutely make precipitating be not easy to be attached on basic zinc carbonate instead, reduce the dispersion degree of Cu, thus super
The ultrasonic frequency that acoustic shock is swung is 20-40kHz, ultrasonic power 20-30W.
Wherein, in the step (1), it is 60-70 DEG C that the temperature of solution is kept while ultrasonic vibration.Keep suitable temperature
Degree is conducive to improve the specific surface area of catalyst, and when temperature is 50 DEG C or 80 DEG C, the specific surface area of catalyst is not achieved
46.5m2/g。
Wherein, the digestion time is 40-80min.By control digestion time, sediment recurring structure is promoted to reset,
The catalyst prepared by has higher specific surface area and catalytic activity.
Wherein, the partial size of the basic zinc carbonate is 120-180nm, and the partial size of lanthana is 200-300nm.Basic carbonate
When the partial size of zinc is lower than 120nm, it can still find that part is reunited under the ultrasound condition of 20-40kHz and 20-30W of the invention
Phenomenon, partial size are higher than 180nm, are unfavorable for being deposited in the uniform attachment on basic zinc carbonate；And pass through the partial size of control lanthana
Its dispersibility can be promoted.
Wherein, the concentration of the sodium carbonate liquor is 1.0-2.0mol/L.The concentration of sodium carbonate liquor lower than 1mol/L or
Higher than 2mol/L, it is unfavorable for the control of pH, and is easy residual sodium ion in catalyst, reduces the catalytic activity of catalyst and steady
It is qualitative.
Wherein, the temperature of the drying is 80-120 DEG C.
Wherein, the maturing temperature is 340-360 DEG C, calcining time 2-3h.When by control maturing temperature and roasting
Between the catalyst of available large specific surface area and uniform component distribution, enhance copper zinc between interaction, promoted hydrogen produce
Rate.
The hydrogen synthetic catalyst specific surface area as made from method as above is 81.3-89.6m2The dispersion degree of/g, Cu is
12.1-13.8%.
The beneficial effects of the present invention are: the present invention utilizes the combination of a step reverse-precipitation and ultrasonic vibration technique, surpasses
During acoustic shock is swung, the bigger copper carbonate precipitating of partial size more small specific surface product can be generated, and be easy to be attached to basic carbonate
On zinc, relative to common a step precipitation method or two precipitation method, catalyst obtained has higher specific surface area and Cu points
Divergence；In addition, the present invention is also mixed into lanthana in precipitating, the stability and hydrogen-producing speed of catalyst can be promoted.
Detailed description of the invention
Fig. 1 be the hydrogen synthetic catalyst of embodiment 1 for hydrogen from methyl alcohol when methanol conversion-temperature profile.
Specific embodiment
For the ease of the understanding of those skilled in the art, make below with reference to 1 couple of present invention of examples and drawings further
Illustrate, the content that embodiment refers to not is limitation of the invention.
Embodiment 1
A kind of preparation method of hydrogen synthetic catalyst, includes the following steps:
(1) basic zinc carbonate of the copper nitrate and 38g that take 4.5g is added into 100g deionized water, under ultrasonic vibration,
It is gradually added into sodium carbonate liquor, adjusting pH value is 8, terminates concussion, is aged, and filtering is precipitated；
(2) precipitating is washed, 0.7g lanthana is added and carries out ball milling dispersion, is then washed, dried, roasted,
Obtain the hydrogen synthetic catalyst.
Wherein, the ultrasonic frequency of the ultrasonic vibration is 30kHz, ultrasonic power 25W
Wherein, in the step (1), it is 65 DEG C that the temperature of solution is kept while ultrasonic vibration.
Wherein, the digestion time is 60min.
Wherein, the partial size of the basic zinc carbonate is 150nm, and the partial size of lanthana is 250nm.
Wherein, the concentration of the sodium carbonate liquor is 1.5mol/L.
Wherein, the temperature of the drying is 100 DEG C.
Wherein, the maturing temperature is 350 DEG C, calcining time 2.5h.
The hydrogen synthetic catalyst specific surface area as made from method as above is 89.6m2The dispersion degree of/g, Cu are 13.8%.
Catalyst is crushed, after taking 8-10 mesh 2.5g to be packed into reactor, (30ml/min) is risen in a nitrogen atmosphere
Reaction temperature after temperature arrives, starts charging and reacts, the methanol conversion (result is as shown in Figure 1) of test reaction, at 350 DEG C,
Alcohol conversion reaches 98.6%, and measuring the hydrogen content produced in gas is 75.8%.
Embodiment 2
A kind of preparation method of hydrogen synthetic catalyst, includes the following steps:
(1) basic zinc carbonate of the copper nitrate and 36g that take 3g is added into 100g deionized water, under ultrasonic vibration, by
Sodium carbonate liquor is gradually added, adjusting pH value is 7.5, terminates concussion, is aged, and filtering is precipitated；
(2) precipitating is washed, 0.5g lanthana is added and carries out ball milling dispersion, is then washed, dried, roasted,
Obtain the hydrogen synthetic catalyst.
Wherein, the ultrasonic frequency of the ultrasonic vibration is 20kHz, ultrasonic power 20W
Wherein, in the step (1), it is 60 DEG C that the temperature of solution is kept while ultrasonic vibration.
Wherein, the digestion time is 40min.
Wherein, the partial size of the basic zinc carbonate is 120nm, and the partial size of lanthana is 200nm.
Wherein, the concentration of the sodium carbonate liquor is 1.0mol/L.
Wherein, the temperature of the drying is 80 DEG C.
Wherein, the maturing temperature is 340 DEG C, calcining time 2h.
The hydrogen synthetic catalyst specific surface area as made from method as above is 81.3m2The dispersion degree of/g, Cu are 12.1%.
Embodiment 3
A kind of preparation method of hydrogen synthetic catalyst, includes the following steps:
(1) basic zinc carbonate of the copper nitrate and 40g that take 6g is added into 100g deionized water, under ultrasonic vibration, by
Sodium carbonate liquor is gradually added, adjusting pH value is 8.5, terminates concussion, is aged, and filtering is precipitated；
(2) precipitating is washed, 1g lanthana is added and carries out ball milling dispersion, is then washed, dried, roasted, i.e.,
Obtain the hydrogen synthetic catalyst.
Wherein, the ultrasonic frequency of the ultrasonic vibration is 40kHz, ultrasonic power 30W
Wherein, in the step (1), it is 70 DEG C that the temperature of solution is kept while ultrasonic vibration.
Wherein, the digestion time is 80min.
Wherein, the partial size of the basic zinc carbonate is 180nm, and the partial size of lanthana is 300nm.
Wherein, the concentration of the sodium carbonate liquor is 2.0mol/L.
Wherein, the temperature of the drying is 120 DEG C.
Wherein, the maturing temperature is 360 DEG C, calcining time 3h.
The hydrogen synthetic catalyst specific surface area as made from method as above is 84.4m2The dispersion degree of/g, Cu are 12.8%.
Comparative example 1
This comparative example the difference from embodiment 1 is that: the preparation method of catalyst includes the following steps:
(1) zinc nitrate of the copper nitrate and 16g that take 4.5g is added into 100g deionized water, under ultrasonic vibration, gradually
Sodium carbonate liquor is added, adjusting pH value is 8, terminates concussion, is aged, and filtering is precipitated；
(2) precipitating is washed, 0.7g lanthana is added and carries out ball milling dispersion, is then washed, dried, roasted,
Obtain the catalyst.
The hydrogen synthetic catalyst specific surface area as made from method as above is 45.3m2The dispersion degree of/g, Cu are 7.4%.
Comparative example 2
This comparative example the difference from embodiment 1 is that: in step (1) without use ultrasonic vibration.
The hydrogen synthetic catalyst specific surface area as made from method as above is 48.1m2The dispersion degree of/g, Cu are 9.1%.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0724320A (en) * | 1993-07-07 | 1995-01-27 | Agency Of Ind Science & Technol | Production of catalyst for steam reforming of methanol |
| CN1672789A (en) * | 2004-03-25 | 2005-09-28 | 中国科学院大连化学物理研究所 | Catalyst for autothermal reformation of methanol to prepared hydrogen and its prepn process and application |
| US20080045400A1 (en) * | 2006-08-15 | 2008-02-21 | Battelle Energy Alliance, Llc | Precursor of a catalytic structure, a catalytic structure, a method of fabricating the same, and a system and a method for using the same |
| CN101850253A (en) * | 2010-05-11 | 2010-10-06 | 大唐国际化工技术研究院有限公司 | Copper-based catalyst containing inorganic pore-enlarging agent and preparation method thereof |
| CN103223343A (en) * | 2013-04-15 | 2013-07-31 | 天津大学 | Alkali metal modified copper-based catalyst for hydrogen production by dimethyl ether steam reforming and preparation method |
| CN103831110A (en) * | 2013-12-03 | 2014-06-04 | 中国科学院过程工程研究所 | Preparation method of ZnO assistant-containing copper catalyst for synthesis of methylchlorosilane |
| CN106423175A (en) * | 2016-11-02 | 2017-02-22 | 复旦大学 | Method for preparing copper-based catalyst for catalyzing carbon dioxide hydrogenation reduction |
| CN106540701A (en) * | 2015-09-18 | 2017-03-29 | 中国石油天然气股份有限公司 | A kind of oxalate hydrogenation catalyst and preparation method thereof |
| CN106622253A (en) * | 2016-12-23 | 2017-05-10 | 温州大学 | CuO/ZnO composite nano-catalyst, and preparation method and application thereof |
| CN108404925A (en) * | 2018-04-11 | 2018-08-17 | 厦门大学 | A kind of preparing hydrogen by reforming methanol catalyst and preparation method thereof |
-
2018
- 2018-12-29 CN CN201811647577.6A patent/CN109794250A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0724320A (en) * | 1993-07-07 | 1995-01-27 | Agency Of Ind Science & Technol | Production of catalyst for steam reforming of methanol |
| CN1672789A (en) * | 2004-03-25 | 2005-09-28 | 中国科学院大连化学物理研究所 | Catalyst for autothermal reformation of methanol to prepared hydrogen and its prepn process and application |
| US20080045400A1 (en) * | 2006-08-15 | 2008-02-21 | Battelle Energy Alliance, Llc | Precursor of a catalytic structure, a catalytic structure, a method of fabricating the same, and a system and a method for using the same |
| CN101850253A (en) * | 2010-05-11 | 2010-10-06 | 大唐国际化工技术研究院有限公司 | Copper-based catalyst containing inorganic pore-enlarging agent and preparation method thereof |
| CN103223343A (en) * | 2013-04-15 | 2013-07-31 | 天津大学 | Alkali metal modified copper-based catalyst for hydrogen production by dimethyl ether steam reforming and preparation method |
| CN103831110A (en) * | 2013-12-03 | 2014-06-04 | 中国科学院过程工程研究所 | Preparation method of ZnO assistant-containing copper catalyst for synthesis of methylchlorosilane |
| CN106540701A (en) * | 2015-09-18 | 2017-03-29 | 中国石油天然气股份有限公司 | A kind of oxalate hydrogenation catalyst and preparation method thereof |
| CN106423175A (en) * | 2016-11-02 | 2017-02-22 | 复旦大学 | Method for preparing copper-based catalyst for catalyzing carbon dioxide hydrogenation reduction |
| CN106622253A (en) * | 2016-12-23 | 2017-05-10 | 温州大学 | CuO/ZnO composite nano-catalyst, and preparation method and application thereof |
| CN108404925A (en) * | 2018-04-11 | 2018-08-17 | 厦门大学 | A kind of preparing hydrogen by reforming methanol catalyst and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| MING-CHUNG TSAI ET AL.: ""Promotion of a copper–zinc catalyst with rare earth for the steam reforming of methanol at low temperatures"", 《JOURNAL OF CATALYSIS》 * |
| SAN XIAOGUANG ET AL.: ""Synthesis of Cu/ZnO Flower-like Hierarchical Porous Structures and Investigation of Their Catalytic Performance for Dimethyl Oxalate Hydrogenation"", 《CHINA PETROLEUM PROCESSING AND PETROCHEMICAL TECHNOLOGY》 * |
| 李淑莲等: ""甲醇自热重整制氢用Cu-ZnO/Al2O3催化剂的研究"", 《催化学报》 * |
| 蔡迎春等: ""La 助剂对甲醇水蒸气转化制氢CuO-ZnO/Al2O3催化剂性能的影响"", 《石油化工》 * |
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