CN1305566C - 甲醇重整制氢整体式催化剂及其制备方法 - Google Patents
甲醇重整制氢整体式催化剂及其制备方法 Download PDFInfo
- Publication number
- CN1305566C CN1305566C CNB2004100538858A CN200410053885A CN1305566C CN 1305566 C CN1305566 C CN 1305566C CN B2004100538858 A CNB2004100538858 A CN B2004100538858A CN 200410053885 A CN200410053885 A CN 200410053885A CN 1305566 C CN1305566 C CN 1305566C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxide
- reaction
- hydrogen
- active component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 239000001257 hydrogen Substances 0.000 title claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000919 ceramic Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 13
- 238000002407 reforming Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 7
- 210000003850 cellular structure Anatomy 0.000 claims description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 3
- 239000011247 coating layer Substances 0.000 abstract 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000003618 dip coating Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Catalysts (AREA)
Abstract
本发明公开了一种甲醇氧化重整制氢整体式催化剂及其制备方法。本发明的甲醇氧化重整制氢整体式催化剂包括:蜂窝状陶瓷载体,负载在蜂窝状陶瓷载体外表面及微孔内表面上的底层,负载在底层上的活性组分和助催化剂涂层。本发明提供的催化剂应用于甲醇氧化重整制氢反应时,因其双功能性,可使得吸热和放热反应在同一催化剂床层进行,这种耦合的催化反应效果,不仅充分利用了反应热,节约了能量,而且放热和吸热的直接热传递会产生快速启动和出色的动态响应效果。本发明提供的甲醇重整氧化制氢整体式催化剂的低温活性好,氢气中一氧化碳浓度低,催化剂强度高,动态响应快,特别适合车载和小型现场供氢装置使用。
Description
技术领域
本发明涉及一种甲醇重整制氢催化剂及其制备方法,具体的说涉及一种用于甲醇重整制氢的铜锌基多组分催化剂及其制备方法。
背景技术
近年来随着燃料电池技术的日益成熟及其对环境保护的意义,采用燃料电池技术的燃料电池汽车得到迅速发展,甲醇车载制氢,成为较为理想的供氢方案之一。
甲醇水蒸气重整制氢,因其较高的产氢率,成熟的生产工艺,已在制氢工业中广为应用。但甲醇水蒸气重整为吸热反应,需外部提供大量的热量。热量发生和换热装置限制了制氢装置的小型化。此外,颗粒状的工业催化剂也易在车辆行驶过程的颠簸、震动中粉化。
因此开发一种能够在同一催化剂上以部分甲醇氧化产生的热量直接供水蒸汽重整的甲醇氧化重整工艺和整体式催化剂,成为众多科技人员十分关注的课题。
目前的甲醇重整或氧化重整催化剂基本上是通过共沉淀法制备的,这种制备方法对沉淀的pH值的控制有较高的要求,且沉淀液的洗涤需耗费大量的水,同时又产生大量的废水,既不经济也不环保,更重要的是这种制备方法难以制成整体式催化剂。
发明内容
本发明需要解决的技术问题是公开甲醇重整制氢整体式催化剂及其制备方法,以克服现有技术存在的上述缺陷,满足有关领域发展的需要。
本发明的甲醇重整制氢整体式催化剂包括:
蜂窝状陶瓷载体,负载在蜂窝状陶瓷载体外表面及微孔内表面上的底层,负载在底层上的活性组分和助催化剂涂层;
所说的底层为掺入了镧、铈、镨、钕、锆或钛的氧化物中的一种或一种以上的氧化铝,掺入的氧化物为氧化铝重量的2-50%;底层负载量为10-200克/升催化剂。
所说的活性组分和助催化剂涂层为含有活性组分和助催化剂的氧化铝,其中:
所说的活性组分为铜和锌;
所说的助催化剂为稀土金属氧化物或氧化锆中的一种或一种以上,其摩尔份数为:
铜1.0份 锌0.1-1.0份 氧化锆0-0.5份 稀土金属氧化物0-0.5份,稀土元素选自La、Ce、Pr、Nd、Y、Sc中的一种或一种以上;
活性组分和助催化剂涂层的负载量为50-500克/升催化剂。
本发明的甲醇重整制氢整体式催化剂的制备方法包括如下步骤:
(1)采用常规的方法进行载体预处理,可将蜂窝状陶瓷载体经去离子水洗涤、脱水后,在流动空气氛中,于120-200℃下,干燥4-10小时,自然冷却至室温;
(2)载体涂层
将上述载体在真空条件下,过量浸渍于掺有稀土元素镧、铈、镨、钕、锆或钛的硝酸盐、醋酸盐、氯化物、硫酸盐或氧化物中的一种或一种以上的氧化铝浆液,其中以金属氧化物掺入量为浆料中氧化铝重量的2-50%,浸涂5-60分钟后,除去载体孔道内的余浆,自然干燥4-24小时,在流动空气氛中,于80-150℃下,干燥4-10小时,在300-700℃下,焙烧2-10小时,获得具有底层的催化剂载体。
(3)在真空条件下,具有底层的催化剂载体浸渍于掺有铜、锌、锆及稀土元素的氧化铝浆液,掺入的元素包括硝酸盐、醋酸盐、氯化物、硫酸盐或氧化物中的任一形式,其中稀土元素选自镧、铈、镨、钕、钇或钪中的一种或一种以上,浸涂5-60分钟后,除去载体孔道内的余浆,自然干燥4-24小时,在流动空气氛中,于80-150℃下,干燥4-10小时,在250-600℃下,焙烧2-10小时,获得具有活性组分涂层的催化剂。
本发明的催化剂,可用于甲醇氧化重整制氢反应,使用时,需要进行催化剂活化,将上述催化剂,于氢气浓度为10-100%的流动气氛中,在100-500℃下,原位活化1-10小时,即可用于甲醇重整制氢过程。
本发明提供的铜、锌基多组分催化剂应用于甲醇氧化重整制氢反应时,因其双功能性,可使得吸热和放热反应在同一催化剂床层进行,这种耦合的催化反应效果,不仅充分利用了反应热,节约了能量,而且放热和吸热的直接热传递会产生快速启动和出色的动态响应效果。
本发明提供的甲醇重整制氢整体式催化剂的低温活性好,氢气中一氧化碳浓度低,催化剂强度高,动态响应快,特别适合车载和小型现场供氢装置使用。
具体实施方式
实施例1
取一个尺寸为Φ19×30、孔数为47孔/cm2的园柱形堇青石陶瓷蜂窝载体,将该载体经去离子水洗涤、脱水后,在流动空气氛中,于120℃下,干燥4小时,在500℃下,焙烧2小时,自然冷却至室温。
将经预处理的载体脱气、抽真空后,浸渍于添加了镧、铈和钛的固含量为25%的氧化铝浆料,浆料中各组分的重量百分组成(以氧化物计)如下:
γ-Al2O3 88%
La2O3(以硝酸镧溶于水后加入) 5%
CeO2(以硝酸铈溶于水后加入) 5%
TiO2(以偏钛酸加入) 2%
浸涂10分钟后,除去载体孔道内的余浆,自然干燥6小时,在流动空气氛中,于80℃下,干燥6小时,在500℃下,焙烧4小时,获得具有预涂层的催化剂载体。
将具有预涂层的催化剂载体经脱气、抽真空后,过量浸涂添加铜、锌、锆及镧的固含量为30%的氧化铝浆料,浆料中各组分的重量百分组成(以氧化物计)如下:
γ-Al2O3 72%
CuO(以硝酸铜溶于水后加入) 15%
ZnO(以硝酸锌溶于水后加入) 7%
ZrO2(以硝酸锆溶于水后加入) 3%
La2O3(以硝酸镧溶于水后加入) 3%
浸渍10分钟后,除去载体孔道内的余浆,自然干燥6小时,在流动空气氛中,于80℃下,干燥6小时,在450℃下,焙烧4小时,获得具有活性组分涂层的催化剂前体。
将上述具有活性组分涂层的催化剂前体,置于实施例5所述的反应器中,在氢气浓度为40%的流动气氛中,于350℃下,活化3小时,即制得本发明所述的活化态甲醇氧化重整整体式催化剂。
实施例2
甲醇氧化重整整体式催化剂采用与实施例1相同的制备方法,但活性涂层中氧化锆的含量增加一倍,即6%,γ-Al2O3的含量减为69%,而其它组分含量不变。
实施例3
甲醇氧化重整整体式催化剂采用与实施例1相同的制备方法,但活性涂层中氧化锆的含量为零,CeO2的含量为6%,而其它组分含量不变。
实施例4
甲醇氧化重整整体式催化剂采用与实施例1相同的制备方法,但活性涂层中各组分的重量百分组成(以氧化物计)如下:
γ-Al2O3 64%
CuO(以硝酸铜溶于水后加入) 22%
ZnO(以硝酸锌溶于水后加入) 10%
ZrO2(以硝酸锆溶于水后加入) 4%
实施例5
取实施例1制备的催化剂置于内径为20mm的不锈钢管式反应器进行活性评价。评价条件:反应物料的汽化温度维持在200℃,反应温度为200-250℃,常压,用微量泵通入甲醇和水的混合液,进料速率为0.25ml/min,水醇摩尔比为1∶1,用空气泵通入空气,使氧醇摩尔比为0.22。反应稳定后,取样分析。反应产物经冷凝后,气相产物用两个串联的气相色谱进行在线分析。首先经活性炭填充柱分离后,由带有热导检测器(TCD)的气相色谱检测氢气等的浓度。然后经带有甲烷化转化器及氢火焰检测器(FID)的气相色谱检测CO、CO2等的浓度。冷凝收集的液相产物中未反应甲醇的浓度由带有GDX-401填充柱和氢火焰检测器(FID)的气相色谱检测。评价结果见表1
反应温度(℃) | 甲醇转化率(%) | CO2选择性(%) | CO浓度(%) |
250 | 96 | 98.4 | 0.35 |
225 | 88 | 99.2 | 0.15 |
200 | 84 | 99.5 | 0.10 |
表1
实施例6
取实施例2制备的催化剂置于内径为20mm的不锈钢管式反应器进行活性评价,评价及分析条件同实施例5。评价结果见表2。
反应温度(℃) | 甲醇转化率(%) | CO2选择性(%) | CO浓度(%) |
250 | 99 | 98.9 | 0.20 |
225 | 87 | 99.5 | 0.16 |
200 | 80 | 99.8 | 0.09 |
表2
实施例7
取实施例3制备的催化剂置于内径为20mm的不锈钢管式反应器进行活性评价。评价条件:反应物料的汽化温度维持在200℃,反应温度为200-250℃,常压,用微量泵通入甲醇和水的混合液,进料速率为0.25ml/min,水醇摩尔比为3∶1。分析条件同实施例5。评价结果见表3。
反应温度(℃) | 甲醇转化率(%) | CO2选择性(%) | CO浓度(%) |
250 | 84 | 99.4 | 0.1 |
225 | 77 | 99.4 | 0.1 |
200 | 69 | 99.5 | 0.05 |
表3
实施例8
取实施例4制备的催化剂置于内径为20mm的不锈钢管式反应器进行活性评价,评价及分析条件同实施例5。评价结果见表4。
反应温度(℃) | 甲醇转化率(%) | CO2选择性(%) | CO浓度(%) |
250 | 96 | 98.7 | 0.28 |
225 | 93 | 99.7 | 0.16 |
200 | 70 | 99.1 | 0.09 |
表4
比较例
称取59克Cu(NO3)2·3H2O,31克Zn(NO3)2·6H2O,13克Zr(NO3)2·6H2O,45克Al(NO3)3·9H2O,分别溶解后,将4种溶液混合置于分液漏斗中,取Na2CO3溶液置于另一分液漏斗中,用共沉淀法制备催化剂。控制沉淀温度在65℃左右,并在不断搅拌下,将两者并流到三口烧瓶中,调节pH=7.6左右,搅拌老化2h,洗涤过滤至滤液为中性,110℃烘干得催化剂前驱体,焙烧、活化条件同实施例1,制得CuZnAlZr复合氧化物催化剂。将粉状催化剂在5-7MPa下压片成型,再破碎至0.45-0.9mm。量取9ml催化剂,在与实施例5相同的条件下考评催化剂。评价结果见表5。
反应温度(℃) | 甲醇转化率(%) | CO2选择性(%) | CO浓度(%) |
250 | 97 | 97.0 | 0.60 |
225 | 97 | 99.3 | 0.10 |
200 | 95 | 99.0 | 0.07 |
表5
Claims (5)
1.一种甲醇重整制氢整体式催化剂,其特征在于,由蜂窝状陶瓷载体、负载在蜂窝状陶瓷载体外表面及微孔内表面上的底层、负载在底层上的活性组分和助催化剂涂层构成;
所说的底层为掺入了镧、铈、镨、钕、锆或钛的氧化物中的一种或一种以上的氧化铝;
所说的活性组分和助催化剂涂层为含有活性组分和助催化剂的氧化铝,其中:
所说的活性组分为铜和锌;
所说的助催化剂为稀土金属氧化物或氧化锆中的一种或一种以上,其摩尔份数为:
铜1.0份,锌0.1-1.0份,氧化锆0-0.5份,稀土金属氧化物0-0.5份,稀土元素选自La、Ce、Pr、Nd、Y、Sc中的一种或一种以上;
底层掺入的氧化物为氧化铝重量的2-50%。
2.根据权利要求1所述的催化剂,其特征在于,活性组分和助催化剂涂层的负载量为50-500克/升催化剂。
3.根据权利要求1所述的催化剂,其特征在于,底层负载量为10-200克/升催化剂。
4.制备权利要求1、2或3所述的甲醇重整制氢整体式催化剂的方法,其特征在于,包括如下步骤:
(1)将蜂窝状陶瓷载体浸渍于掺有镧、铈、镨、钕、锆或钛的硝酸盐、醋酸盐、氯化物、硫酸盐或氧化物中的一种或一种以上的氧化铝浆料中,其中金属氧化物掺入量为浆料中氧化铝重量的2-50%,干燥后,在300-700℃下,焙烧2-10小时,获得具有底层的催化剂载体;
(2)将具有底层的催化剂载体浸渍于掺有铜、锌、锆及稀土元素的氧化铝浆料,干燥后,在250-600℃下,焙烧2-10小时。
5.根据权利要求4所述的方法,其特征在于,将具有底层的催化剂载体浸渍于掺有铜、锌、锆及稀土元素的氧化铝浆料,掺入的元素选自硝酸盐、醋酸盐、氯化物、硫酸盐或氧化物中的任一形式,其中稀土元素选自镧、铈、镨、钕、钇或钪中的一种或一种以上。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2004100538858A CN1305566C (zh) | 2004-08-20 | 2004-08-20 | 甲醇重整制氢整体式催化剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2004100538858A CN1305566C (zh) | 2004-08-20 | 2004-08-20 | 甲醇重整制氢整体式催化剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1597104A CN1597104A (zh) | 2005-03-23 |
CN1305566C true CN1305566C (zh) | 2007-03-21 |
Family
ID=34666126
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2004100538858A Expired - Lifetime CN1305566C (zh) | 2004-08-20 | 2004-08-20 | 甲醇重整制氢整体式催化剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1305566C (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102897712B (zh) * | 2012-09-13 | 2014-08-06 | 上海合既得动氢机器有限公司 | 一种甲醇水制氢系统及其制氢方法 |
CN102897713B (zh) * | 2012-09-13 | 2014-12-24 | 上海合既得动氢机器有限公司 | 一种甲醇水蒸气重整制氢设备及制氢方法 |
CN102872867B (zh) * | 2012-10-19 | 2014-05-07 | 厦门大学 | 一种用于甲醇水蒸气重整制氢的催化剂及其制备方法 |
CN105552414A (zh) * | 2016-01-28 | 2016-05-04 | 博源燃料电池(上海)有限公司 | 一种纯氢纯氧高温电池系统 |
CN111717890B (zh) * | 2019-01-24 | 2021-08-10 | 中氢新能技术有限公司 | 甲醇重整器 |
CN113318722B (zh) * | 2020-02-28 | 2023-08-01 | 中科粤能净(山东)新材料有限公司 | 一种光催化剂及其制备方法和应用 |
CN111760596A (zh) * | 2020-06-13 | 2020-10-13 | 华东理工大学 | 一种光固化制备结构化催化剂载体的方法 |
CN114538374B (zh) * | 2022-03-18 | 2023-06-30 | 中国科学院生态环境研究中心 | 一种车载生物乙醇重整制氢的装置系统及重整制氢的方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4552861A (en) * | 1984-03-02 | 1985-11-12 | Institut Francais Du Petrole | Process for manufacturing catalysts containing copper, zinc, aluminum and at least one metal from the group formed of rare earths and zirconium and the resultant catalysts for reactions involving a synthesis gas |
CN1042696A (zh) * | 1989-10-28 | 1990-06-06 | 齐鲁石油化工公司研究院 | 烃类水蒸汽转化催化剂及应用 |
CN1334141A (zh) * | 2000-07-18 | 2002-02-06 | 三井化学株式会社 | 甲醇蒸汽重整催化剂及用该催化剂制备氢气的方法 |
CN1397484A (zh) * | 2002-08-13 | 2003-02-19 | 上海燃料电池汽车动力系统有限公司 | 一种用于甲醇蒸汽重整制氢的催化剂 |
CN1502407A (zh) * | 2002-11-19 | 2004-06-09 | 南昌大学 | 汽车尾气净化催化剂及其制备方法 |
-
2004
- 2004-08-20 CN CNB2004100538858A patent/CN1305566C/zh not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4552861A (en) * | 1984-03-02 | 1985-11-12 | Institut Francais Du Petrole | Process for manufacturing catalysts containing copper, zinc, aluminum and at least one metal from the group formed of rare earths and zirconium and the resultant catalysts for reactions involving a synthesis gas |
CN1042696A (zh) * | 1989-10-28 | 1990-06-06 | 齐鲁石油化工公司研究院 | 烃类水蒸汽转化催化剂及应用 |
CN1334141A (zh) * | 2000-07-18 | 2002-02-06 | 三井化学株式会社 | 甲醇蒸汽重整催化剂及用该催化剂制备氢气的方法 |
CN1397484A (zh) * | 2002-08-13 | 2003-02-19 | 上海燃料电池汽车动力系统有限公司 | 一种用于甲醇蒸汽重整制氢的催化剂 |
CN1502407A (zh) * | 2002-11-19 | 2004-06-09 | 南昌大学 | 汽车尾气净化催化剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1597104A (zh) | 2005-03-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2586528B1 (en) | Catalyst having monolithic structure for manufacturing ethylene glycol by oxalate hydrogenation, preparation method and application thereof | |
Ye et al. | Recent progress in improving the stability of copper-based catalysts for hydrogenation of carbon–oxygen bonds | |
Chen et al. | Manganese oxide nanoarray-based monolithic catalysts: tunable morphology and high efficiency for CO oxidation | |
CA2341068C (en) | A method for catalytic conversion of carbon monoxide in a hydrogen-containing gas mixture with improved cold start behaviour and a catalyst therefor | |
CN1449361A (zh) | 产生富含氢的气体的方法 | |
CA2341056A1 (en) | A method for catalytic conversion of carbon monoxide in a hydrogen-containing gas mixture | |
CN109529821B (zh) | 一种用于热催化甲醛降解的钯基催化剂 | |
CN1772378A (zh) | 一种用于甲醇蒸汽重整制氢的铜锆催化剂及其制备方法 | |
CN107537480B (zh) | 复合物催化剂及其使用方法 | |
CN101053833A (zh) | 一种用于高温甲醇水蒸汽重整制氢贵金属催化剂 | |
CN1305567C (zh) | 一种甲醇自热重整制氢催化剂及制备方法和应用 | |
CN1830566A (zh) | FeCrAl载体上涂覆铜铈催化剂的制备方法 | |
Peng et al. | Alkali/alkaline-earth metal-modified MnOx supported on three-dimensionally ordered macroporous–mesoporous TixSi1-xO2 catalysts: Preparation and catalytic performance for soot combustion | |
CN1305566C (zh) | 甲醇重整制氢整体式催化剂及其制备方法 | |
US7919424B2 (en) | Platinum based catalyst for oxidation/reduction reaction and its use | |
CN101147863A (zh) | 一种整体式氨分解制氢催化剂 | |
CN1850331A (zh) | 一种CuZnAl复合氧化物催化剂、制备及其用途 | |
CN113070062A (zh) | 一种催化甲酸产氢的铈基纳米球型催化剂及其制备方法 | |
Liu et al. | Effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria: Soot-ceria contact and interfacial oxygen evolution | |
CN1586718A (zh) | 一种纳米碳材料改性的铜基催化剂及其制备方法 | |
Rostami et al. | A review study on methanol steam reforming catalysts: Evaluation of the catalytic performance, characterizations, and operational parameters | |
CN1093433C (zh) | 天然气自热氧化重整制合成气催化剂及其制备方法 | |
CN1190357C (zh) | 一种用于低温选择氧化氢气中co的催化剂及其制备方法和应用 | |
CN1788841A (zh) | 一种制氢催化剂、制备及其用途 | |
CN100429814C (zh) | 一种一氧化碳水汽变换催化剂及制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |