CN1308268C - Preparation of formaldehyde and ethylene by carbon monoxide electrocatalytic hydrogenation reduction - Google Patents
Preparation of formaldehyde and ethylene by carbon monoxide electrocatalytic hydrogenation reduction Download PDFInfo
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- CN1308268C CN1308268C CNB200510122240XA CN200510122240A CN1308268C CN 1308268 C CN1308268 C CN 1308268C CN B200510122240X A CNB200510122240X A CN B200510122240XA CN 200510122240 A CN200510122240 A CN 200510122240A CN 1308268 C CN1308268 C CN 1308268C
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- carbon monoxide
- formaldehyde
- hydrogenation reduction
- purity
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000005977 Ethylene Substances 0.000 title abstract 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 229920001971 elastomer Polymers 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 23
- 238000006722 reduction reaction Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000004458 analytical method Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- 239000007784 solid electrolyte Substances 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract 3
- -1 polytetrafluoroethylene Polymers 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 1
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 4
- 239000010416 ion conductor Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本发明以α-Zr(HPO4)2H2O(ZrP)为固体质子电解质，Cu、Fe作为阴极，铂网(100目)作为阳极，电极、电解质在模具中压成圆形压片，压片上下层分别为Cu、Fe阴极电极层和Pt阳极电极层，中间为ZrP电解质层。压片通过橡胶O形圈和螺栓与两个聚四氟乙烯帽盖紧密连接，形成阴极室和阳极室，电解采用恒电流模式，在常温常压下进行，电解反应的流程是阴极室通入计量高纯一氧化碳，阳极室通入经去离子水鼓泡的高纯氢气，阴极室得到产物甲醛和乙烯。In the present invention, α-Zr(HPO 4 ) 2 H 2 O(ZrP) is used as the solid proton electrolyte, Cu and Fe are used as the cathode, platinum mesh (100 mesh) is used as the anode, and the electrodes and the electrolyte are pressed into a circular tablet in a mold. The upper and lower layers of the pressed tablet are Cu, Fe cathode electrode layer and Pt anode electrode layer respectively, and the middle is ZrP electrolyte layer. The tablet is tightly connected with two polytetrafluoroethylene caps through rubber O-rings and bolts to form a cathode chamber and an anode chamber. The electrolysis adopts constant current mode and is carried out at normal temperature and pressure. The process of electrolysis reaction is that the cathode chamber High-purity carbon monoxide is measured, high-purity hydrogen bubbled by deionized water is introduced into the anode chamber, and the products formaldehyde and ethylene are obtained in the cathode chamber.
Description
Technical field
The present invention relates to C
1Carbon monoxide electrocatalytic hydrogenation reduction prepared in reaction chemical basic product technical field in the chemistry.
Background technology
The economic Sustainable development and the coordinated development of human society and physical environment, large-scale development and use along with petroleum resources, become urgent day by day studying a question of being significant with coal etc. once more as the chemical raw material, developed country comes at recent two decades as the new technology deposit, carried out new technology basis and applied research, the research electricity of domestic one-carbon chemical has been obtained obvious improvement.The reaction of carbon monoxide reduction catalysts is one of one-carbon chemical most important, for co hydrogenation Fischer-Tropsch Synthesis reduction reactions such as (F-T), in recent years research concentrates on aspects such as homogeneous phase coordination compound catalyzer, heterogeneous metal screening of catalyst and technological process both at home and abroad, seldom relates to the research of carbon monoxide electrocatalytic reduction reaction.It is to meet the new technology that Green Chemistry requires that electrocatalysis prepares chemical products, along with the diversity of chemically modified electrode, optionally development and the going deep into of solid state ionic conductor investigation of materials, uses solid state ionic conductor to develop electrocatalysis and prepare chemical products and develop rapidly as ionogen.Abroad be the catalytic oxidation research of ionogen carbon monoxide room-temperature normal pressure and High Temperature High Pressure at present to solid state ionic conductor; more bibliographical information is still arranged; mainly relate to the exploitation of new fuel cell and be that the electrocatalysis of object vehicle tail gas transforms with the environment protection, and relevant patent is not seen in the research of solid electrolyte electrolyzer carbon monoxide electrocatalytic reduction reaction.Therefore, at the energy structure of China's rich coal oil starvation weak breath, the research and development carbon monoxide is that the new technology of raw material production chemical basic product is significant.Under the subsidy of Tianjin State Scientific and Technological Commission nature fund (No.023606411) and Ministry of Education of the state's emphasis fund (No.03009), design to solid electrolyte electrolyzer carbon monoxide electrocatalytic reduction reaction electrolyzer, proton is in the migration of solid electrolyte, electrode materials is selected, reactant at the electrode table and kinetics such as absorption further investigate, realized the new reaction and the new technology of carbon monoxide room-temperature normal pressure electrocatalytic hydrogenation reduction prepared in reaction formaldehyde and ethene.
Summary of the invention
The present invention is with α-Zr (HPO
4)
2H
2O (ZrP) is the solid proton ionogen, and Cu, Fe are the electrode design electrolyzer, realizes carbon monoxide room-temperature normal pressure electrocatalytic hydrogenation reduction prepared in reaction formaldehyde and ethene.
The technological line that adopts is with α-Zr (HPO
4)
2H
2O (ZrP) is the solid proton ionogen, and Cu, Fe be as negative electrode, and platinum guaze (100 order) is as anode, electrode, ionogen compressing tablet in mould, 500-600MPa/cm
-2, preparation diameter 13mm, the round tablet of thickness 1.2-1.5mm, the compressing tablet levels is respectively Cu, Fe negative electrode layer and Pt anode electrode layer, and the centre is the ZrP dielectric substrate.Compressing tablet closely is connected with two tetrafluoroethylene caps with bolt by rubber o-ring, form cathode compartment and anolyte compartment, the volume of cathode compartment and anolyte compartment is respectively 20mL, constant current mode is adopted in electrolysis, carries out at normal temperatures and pressures, and the flow process of electrolytic reaction is that cathode compartment feeds the metering high-purity CO, flow velocity 10mL/min, the anolyte compartment feeds the high-purity hydrogen through the deionized water bubbling, and flow velocity 10mL/min, cathode compartment product are formaldehyde and ethene.
The preparation of Cu electrode: the Cu electrode is made up of Cu metal-powder (purity 99.0%, 10 μ m) and ZrP, and weight ratio is: 7: 3, the Cu metal-powder with preceding through pickling deoxidation layer, ultrasonic cleaning and drying.
The preparation of Fe electrode: the Fe electrode is made up of with ZrP exsiccant Fe wire netting (purity 99.0%, 325 order) and Fe powder (purity 99.9%, 10 μ m), and weight ratio is: 7: 3.
Product analysis: the different current density cathode compartment of gas-chromatography silica-coating capillary column on-line analysis product obtains faraday (faradaic) current efficiency of product formaldehyde and ethene.
The ZrP preparation: the present invention adopts complexing decomplexing method to prepare ZrP: a certain amount of ZrOCl
28H
2The O aqueous solution, agitation and dropping HF-H
3PO
4(ratio/mol:2: 1) solution, ZrOCl
28H
2O/HF-H
3PO
4Mol ratio be 1: 2, be warmed to 50 ℃ and kept 48 hours, precipitate and separate is washed to no Cl
-, F
-Detect, 48 hours .ZrP of 110 ℃ of constant temperature carry out XRD material phase analysis (Cu-K
α, 2 θ: 5-80 °), result such as table 1.
The XRD material phase analysis of table 1 ZrP
| 2θ | Inten | d-vslue | F-whm |
| 11.802 | 28159 | 7.491 | 0.3410 |
| 19.671 | 2112 | 4.508 | 0.420 |
| 24.829 | 4237 | 3.583 | 0.440 |
| 27.973 | 418 | 3.187 | 0.600 |
| 33.859 | 1823 | 2.645 | 0.480 |
| 36.075 | 658 | 2.487 | 0.480 |
| 37.388 | 475 | 2.403 | 0.320 |
| 38.293 | 430 | 2.348 | 0.420 |
| 41.475 | 375 | 2.161 | 0.320 |
| 42.688 | 391 | 2.116 | 0.340 |
| 2θ | Inten | d-vslue | F-whm |
| 44.253 | 459 | 2.044 | 0.321 |
| 48.224 | 608 | 1.885 | 0.240 |
| 48.865 | 757 | 1.862 | 0.480 |
| 51.100 | 451 | 1.786 | 0.540 |
| 51.815 | 361 | 1.763 | 0.260 |
| 52.864 | 431 | 1.730 | 0.340 |
| 55.864 | 431 | 1.730 | 0.340 |
| 55.156 | 470 | 1.663 | 0.500 |
| 60.635 | 576 | 1.525 | 0.540 |
| 62.269 | 560 | 1.489 | 0.380 |
The spacer of ZrP sample is P2
1/ n, Z=8 by 2 θ=11 ° diffracted ray, calculates interplanar distance d
001=0.75nm, the interlamellar spacing of corresponding ZrP laminate structure is 0.75nm, α-Zr (HPO
4)
2H
2O and Zr (HPO
4)
2Weight ratio be 87: 13 (%).
ZrP is with 500-600MPa/cm
-2Compressing tablet, diameter 13mm, thickness 1-2mm, both sides are coated with sliver-powder conducting glue and copper sheet is bonding as potential electrode, and after placing a week under the room temperature water saturated vapor pressure condition, frequency analyzer is measured its specific conductivity, and frequency 5HZ-1MHZ. specific conductivity is 3.01e
-6S/cm.
Cu is the negative electrode of electrolyzer, current density 20-100mAcm
-2, product is formaldehyde and ethene.
Fe is the negative electrode of electrolyzer, current density 30-100mAcm
-2, product is ethene and formaldehyde.
The invention has the beneficial effects as follows and realized carbon monoxide electrocatalytic hydrogenation reduction prepared in reaction formaldehyde and ethene under the normal temperature and pressure conditions.
Description of drawings
No accompanying drawing
Embodiment
With α-Zr (HPO
4)
2H
2O (ZrP) is the solid proton ionogen, and Cu, Fe be as negative electrode, and platinum guaze (100 order) is as anode, electrode, ionogen compressing tablet in mould, 500-600MPa/cm
-2, preparation diameter 13mm, the round tablet of thickness 1.2-1.5mm, the compressing tablet levels is respectively Cu, Fe negative electrode layer and Pt anode electrode layer, and the centre is the ZrP dielectric substrate.Compressing tablet closely is connected with two tetrafluoroethylene caps with bolt by rubber o-ring, form cathode compartment and anolyte compartment, the volume of cathode compartment and anolyte compartment is respectively 20mL, constant current mode is adopted in electrolysis, carry out at normal temperatures and pressures, the flow process of electrolytic reaction is that cathode compartment feeds the metering high-purity CO, flow velocity 10mL/min, the anolyte compartment feeds the high-purity hydrogen through the deionized water bubbling, flow velocity 10mL/min, the different current density cathode compartment of gas-chromatography silica-coating capillary column on-line analysis product.Reaction calculated faraday (faradaic) current efficiency of product formaldehyde and ethene in 1 hour.
Embodiment 1
Cu is the negative electrode of electrolyzer, current density 20mAcm
-2, product is formaldehyde and ethene, and the faradaic current efficiency (%) of formaldehyde is 12.0, and the faradaic current efficiency (%) of ethene is 6.0.
Embodiment 2
Cu is the negative electrode of electrolyzer, current density 75mAcm
-2, product is formaldehyde and ethene, and the faradaic current efficiency (%) of formaldehyde is 24.0, and the faradaic current efficiency (%) of ethene is 3.0.
Embodiment 3
Cu is the negative electrode of electrolyzer, current density 100mAcm
-2, product is formaldehyde and ethene, and the faradaic current efficiency (%) of formaldehyde is 29.0, and the faradaic current efficiency (%) of ethene is 2.1.
Embodiment 4
Fe is the negative electrode of electrolyzer, current density 30mAcm
-2, product is ethene and formaldehyde, and the faradaic current efficiency (%) of ethene is 3.0, and the faradaic current efficiency (%) of formaldehyde is 0.0.
Embodiment 5
Fe is the negative electrode of electrolyzer, current density 50mAcm
-2, product is ethene and formaldehyde, and the faradaic current efficiency (%) of ethene is 7.0, and the faradaic current efficiency (%) of formaldehyde is 0.0.
Embodiment 6
Fe is the negative electrode of electrolyzer, current density 100mAcm
-2, product is ethene and formaldehyde, and the faradaic current efficiency (%) of ethene is 15.0, and the faradaic current efficiency (%) of formaldehyde is 1.5.
Claims (6)
- The reaction of 1 carbon monoxide electrocatalytic hydrogenation reduction is characterized in that: the reaction of carbon monoxide solid electrolyte electrocatalytic hydrogenation reduction, and with α-Zr (HPO 4) 2H 2O is the solid proton ionogen, α-Zr (HPO 4) 2H 2O is abbreviated as ZrP, and Cu, Fe be as negative electrode, and 100 order platinum guazes are as anode, electrode, ionogen compressing tablet in mould, 500-600MPa/cm -2Preparation diameter 13mm, the round tablet of thickness 1.2-1.5mm, the compressing tablet levels is respectively Cu, Fe negative electrode layer and Pt anode electrode layer, the centre is the ZrP dielectric substrate, compressing tablet closely is connected with two tetrafluoroethylene caps with bolt by rubber o-ring, form cathode compartment and anolyte compartment, the volume of cathode compartment and anolyte compartment is respectively 20mL, and constant current mode is adopted in electrolysis, carry out at normal temperatures and pressures, the flow process of electrolytic reaction is that cathode compartment feeds the metering high-purity CO, flow velocity 10mL/min, and the anolyte compartment feeds the high-purity hydrogen through the deionized water bubbling, flow velocity 10mL/min, cathode compartment product are formaldehyde and ethene.
- 2 carbon monoxide electrocatalytic hydrogenation reduction reactions according to claim 1, it is characterized in that: the Cu electrode is by the Cu metal-powder, and purity 99.0%, 10 μ m and ZrP form, weight ratio is: 7: 3, the Cu metal-powder with preceding through pickling deoxidation layer, ultrasonic cleaning and drying; The Fe electrode is by exsiccant Fe wire netting, purity 99.0%, 325 order and Fe powder, and purity 99.9%, 10 μ m and ZrP form, and weight ratio is: 7: 3.
- 3 carbon monoxide electrocatalytic hydrogenation reduction reactions according to claim 1 is characterized in that: adopt complexing decomplexing method to prepare ZrP: a certain amount of ZrOCl 28H 2The O aqueous solution, agitation and dropping HF-H 3PO 4Solution, HF/H 3PO 4Mol ratio be: 2: 1; ZrOCl 28H 2O/HF-H 3PO 4Mol ratio be 1: 2, be warmed to 50 ℃ and kept 48 hours, precipitate and separate is washed to no Cl -, F -Detect 110 ℃ of constant temperature 48 hours; ZrP carries out the XRD material phase analysis, and the spacer of ZrP is P2 1/ n, interplanar distance d 001=0.75nm, interlamellar spacing is 0.75nm, α-Zr (HPO 4) 2H 2O and Zr (HPO 4) 2Weight ratio be 87: 13, frequency analyzer is measured its specific conductivity, frequency 5H Z-1MH Z, specific conductivity is 3.01e -6S/cm.
- 4 carbon monoxide electrocatalytic hydrogenation reduction reactions according to claim 1 is characterized in that: adopt the different current density cathode compartment of gas-chromatography silica-coating capillary column on-line analysis product, obtain the faradaic current efficient of product.
- 5 carbon monoxide electrocatalytic hydrogenation reduction reactions according to claim 1, it is characterized in that: Cu is the negative electrode of electrolyzer, current density 20-100mAcm -2, product is formaldehyde and ethene.
- 6 carbon monoxide electrocatalytic hydrogenation reduction reactions according to claim 1, it is characterized in that: Fe is the negative electrode of electrolyzer, current density 30-100mAcm -2, product is ethene and formaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510122240XA CN1308268C (en) | 2005-12-08 | 2005-12-08 | Preparation of formaldehyde and ethylene by carbon monoxide electrocatalytic hydrogenation reduction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510122240XA CN1308268C (en) | 2005-12-08 | 2005-12-08 | Preparation of formaldehyde and ethylene by carbon monoxide electrocatalytic hydrogenation reduction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1775713A CN1775713A (en) | 2006-05-24 |
| CN1308268C true CN1308268C (en) | 2007-04-04 |
Family
ID=36765456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510122240XA Expired - Fee Related CN1308268C (en) | 2005-12-08 | 2005-12-08 | Preparation of formaldehyde and ethylene by carbon monoxide electrocatalytic hydrogenation reduction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1308268C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113041773A (en) * | 2019-12-27 | 2021-06-29 | 苏州五蕴明泰科技有限公司 | Method, apparatus and medium for utilization of emitted carbon monoxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299744B1 (en) * | 1997-09-10 | 2001-10-09 | California Institute Of Technology | Hydrogen generation by electrolysis of aqueous organic solutions |
| WO2004000453A2 (en) * | 2002-06-25 | 2003-12-31 | Alicja Zaluska | New type of catalytic materials based on active metal-hydrogen-electronegative element complexes for hydrogen transfer |
| JP2004068127A (en) * | 2002-08-09 | 2004-03-04 | Permelec Electrode Ltd | Electrode for electrolysis, method for manufacturing the same, and electrolytic cell having this electrode for electrolysis |
-
2005
- 2005-12-08 CN CNB200510122240XA patent/CN1308268C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299744B1 (en) * | 1997-09-10 | 2001-10-09 | California Institute Of Technology | Hydrogen generation by electrolysis of aqueous organic solutions |
| WO2004000453A2 (en) * | 2002-06-25 | 2003-12-31 | Alicja Zaluska | New type of catalytic materials based on active metal-hydrogen-electronegative element complexes for hydrogen transfer |
| JP2004068127A (en) * | 2002-08-09 | 2004-03-04 | Permelec Electrode Ltd | Electrode for electrolysis, method for manufacturing the same, and electrolytic cell having this electrode for electrolysis |
Non-Patent Citations (6)
| Title |
|---|
| RH-4/Al-2O-3上CO歧化表面羰基氢化物与CO加氢反应机理 陈耀强 陈豫 张堰黎，催化学报，第6期 1991 * |
| RH-4/Al-2O-3上CO歧化表面羰基氢化物与CO加氢反应机理 陈耀强 陈豫 张堰黎，催化学报，第6期 1991;ZRO 2 /R-Al 2 O-3体系中氧化物间的相互作用及其时催化性能的影响 苏桂琴 张文忠 杨华，催化学报，第2期 1995;国外碳一化学技术进展 化工部然气化工信息站，天然气化工(C1化学与化工)，第4期 1995;绿色化学和一氧化碳的综合利用 翟林峰 史铁钧，化工科技市场，第7期 2003;一氧化碳均相加加氢合成低碳烃的催化剂新体系 高国华 元骐 金道森，分子催化，第2期 1993 * |
| ZRO 2 /R-Al 2 O-3体系中氧化物间的相互作用及其时催化性能的影响 苏桂琴 张文忠 杨华，催化学报，第2期 1995 * |
| 一氧化碳均相加加氢合成低碳烃的催化剂新体系 高国华 元骐 金道森，分子催化，第2期 1993 * |
| 国外碳一化学技术进展 化工部然气化工信息站，天然气化工(C1化学与化工)，第4期 1995 * |
| 绿色化学和一氧化碳的综合利用 翟林峰 史铁钧，化工科技市场，第7期 2003 * |
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| Publication number | Publication date |
|---|---|
| CN1775713A (en) | 2006-05-24 |
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