CN114260016A - 一种将Pd/ZnFexAl2-xO4催化剂用于甲醇重整制氢的方法 - Google Patents
一种将Pd/ZnFexAl2-xO4催化剂用于甲醇重整制氢的方法 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 62
- 239000001257 hydrogen Substances 0.000 title claims abstract description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002407 reforming Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 16
- 239000011029 spinel Substances 0.000 claims abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 6
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 238000003980 solgel method Methods 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000446 fuel Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
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- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- -1 hydrocarbon alcohols Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 229910001676 gahnite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B01J37/02—Impregnation, coating or precipitation
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- B01J37/18—Reducing with gases containing free hydrogen
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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Abstract
本发明公开了一种将Pd/ZnFexAl2‑xO4催化剂用于甲醇蒸汽重整制氢的方法，属于甲醇制氢领域。该方法包括以下步骤：1)将锌盐、掺杂金属离子盐和铝盐加入到异丙醇中进行水热反应制得ZnMxAl2‑xO4尖晶石载体；2)通过浸渍法或溶胶凝胶法等方法将贵金属Pd盐负载到ZnMxAl2‑xO4载体上；3)将PdZn/ZnMxAl2‑xO4催化剂在H2气氛中进行还原处理；4)将H2处理过的催化剂加入到甲醇水溶液中进行制氢反应，反应温度为150～300℃，反应压力为常压。结果表明：采用Pd含量较低(小于0.5wt％)的Pd/ZnFexAl2‑xO4催化剂即可实现甲醇重整制氢，且副产物CO的选择性与其它Pd含量高(>5％)的传统PdZn/ZnO、PdZn/ZnO/Al2O3基催化剂相一致，这样可极大节约生产成本，极具经济效益。此外，本发明的制氢方法还具有操作简单，可实现便携式制氢等优点。
Description
技术领域
本发明属于甲醇制氢领域，具体涉及一种将Pd/ZnFexAl2-xO4催化剂用于甲醇重整制氢的方法。
背景技术
氢燃料由于其高能量密度和低排放等优势被认为是解决日益严重的能源危机和环境污染的新一代清洁能源[1-4]。氢气可广泛应用于化工、冶金和电力等行业，还看用作还原气体、原料气体和燃料电池燃料等。特别是在燃料电池中的应用，近些年来受到越来越多的关注[5-8]。燃料电池具有能量转化效率高、排放低等优点，在交通运输及固定式发电等行业极具应用前景，也是目前学术界和产业界的研究热点和发展方向之一。作为燃料电池的一种能量载体，氢的热值高，反应速度快，并且水是它燃烧的唯一产物，非常清洁高效。然而，不同于其它燃料，氢气不能直接在自然界中获取。当前氢气制取方法主要有工业化制氢、副产氢气以及太阳能制氢系统等方法[9]。在我们所研究的工业化制氢法中又可以细分为煤的焦化和汽化制氢、烃醇类重整制氢以及电解水制氢等；其中烃醇类的重整制氢是当前工业上制氢的主要方法[10-11]。烃类主要以甲烷蒸汽重整为主，该工艺较为复杂，需要对甲烷进行脱硫、重整、水汽变换和甲烷脱除等步骤，存在能耗大，排放多等问题。相比之下醇类蒸汽重整，如甲醇重整制氢在相对较温和的条件下即可原位产氢，在解决了能耗高等问题的同时，也成功解决了氢气在提取和运输等方面存在的问题[12-15]。实际上，利用液体燃料作为氢载体是氢运输和储氢的有效选择方式之一，而甲醇由于其较温和的反应条件通常被认为是一种很有前途的液体燃料制氢载体。与其它的醇类相比，甲醇是最简单的醇类原料，它只含有一个碳原子，作为反应原料不涉及C-C键的解离，可以显著的减少反应副产物的数量。此外，甲醇还具有可与水混溶，常温下为液态，易运输，碳氢比例高等优点。甲醇重整制氢反应(MSR)在较低的温度下即可进行(200-350℃)，而其它醇类重整制氢，如乙醇重整的温度通常在400-500℃，甘油重整的温度则在500℃以上[16-18]。目前MSR的催化剂主要为Cu基催化剂，虽然Cu基催化剂在具有高CO2以及高经济效益等优点，但是Cu自身存在固有缺陷，如易自燃以及高温易失活等缺点。PdZn基催化剂不仅具有类铜的反应特性，还具备优异的化学和热稳定性，可适用于诸多反应领域，比如逆水汽反应、甲醇部分氧化、甲醇蒸气重整、一氧化碳/二氧化碳加氢反应等。
参考文献：
[1]Zhang S,Wang X,Xu X,et al.Hydrogen production via catalyticautothermal reforming of desulfurized Jet-A fuel[J].International Journal ofHydrogen Energy,2017,42(4):1932-1941.
[2]Cacciola G,Antonucci V,Freni S.Technology up date and newstrategies on fuel cells[J].Journal of Power Sources,2001,100(1-2):67-79.
[3]Ramirez D,Beites L,Blazquez F,et al.Distributed generation systemwith PEM fuel cell for electrical power quality improvement[J].InternationalJournal of Hydrogen Energy,2008,33(16):4433-4443.
[4]Won J,Kang Y S.Proton-conducting polymer membranes for directmethanol fuel cells[J].Macromolecular Symposia,2003,204(1):79-92.
[5]Ahmed S,Krumpelt M.Hydrogen from hydrocarbon fuels for fuel cells[J].International Journal of Hydrogen Energy,2001,26(4):291-301.
[6]Damle A S.Hydrogen production by reforming of liquid hydrocarbonsin a membrane reactor for portable power generation—Experimental studies[J].Journal of Power Sources,2009,186(1):167-177.
[7]Hoang D L,Chan S H,Ding O L.Hydrogen production for fuel cells byautothermal reforming of methane over sulfide nickel catalyst on a gammaalumina support[J].Journal of Power Sources,2006,159(2):1248-1257.
[8]Aicher T,Lenz B,Gschnell F,et al.Fuel processors for fuel cell APUapplications[J].Journal of Power Sources,2006,154(2):503-508.
[9]张伟,李世安,刘聪敏,等.车载甲醇重整微型反应器研究进展[J].现代化工,2019,39(7):27-32
[10]贾同国,王银山,李志伟.氢能源发展研究现状[J].节能技术,2011,3(29):264-267.
[11]杜彬.甲醇制氢研究进展[J].辽宁化工,2011,40(12):1252-1254.
[12]张菊香,史鹏飞,张新荣,等.燃料电池甲醇重整制氢研究进展[J].电池,2004,34(5):359-361.
[13]Xu X,Zhang S,Li P.Autothermal reforming of n-dodecane anddesulfurized Jet-A fuel for producing hydrogen-rich syngas[J].InternationalJournal of Hydrogen Energy,2014,39(34):19593-19602.
[14]Choudhury A,Chandra H,Arora A.Application of solid oxide fuelcell technology for power generation—A review[J].Renewable and SustainableEnergy Reviews,2013,20:430-442.
[15]Xu X,Zhang S,Wang X,et al.Fuel adaptability study of a lab-scale2.5kWth autothermal reformer[J].International Journal of Hydrogen Energy,2015,40(21):6798-6808.
[16]John C,Jesse K,and Srinivas P.Miniaturized Methanol Reformer forFuel Cell Powered Mobile Applications[J].International Journal of ChemicalReactor Engineering,2008,6(1):77-90.
[17]Zhang X,Hu H,Zhu Y,et al.Methanol Steam Reforming to Hydrogen ina Carbon Membrane Reactor System[J].Industrial&Engineering ChemistryResearch,2006,45(24):7997-8001.
[18]Basile A,Parmaliana A,Tosti S,et al.Hydrogen production bymethanol steam reforming carried out in membrane reactor on Cu/Zn/Mg-basedcatalyst[J].Catalysis Today,2008,137(1):17-22.
发明内容
针对上述现有技术存在的不足之处，本发明目的在于提供一种将PdZn/ZnFexAl2- xO4催化剂用于甲醇蒸汽重整制氢的方法。
为了达成上述目的，本发明的解决方案是：
一种将Pd/ZnMxAl2-xO4催化剂用于甲醇蒸汽重整制氢的方法，包括如下步骤：
1)将锌盐、掺杂金属离子盐和铝盐加入到异丙醇中进行水热反应，将所得固体焙烧后制得金属离子掺杂的ZnMxAl2-xO4尖晶石载体，其中，x＝0.05-0.2，掺杂金属离子M为Fe，Co，Ni，Cu或Mn中的一种；
2)通过浸渍法或溶胶凝胶法等方法将贵金属Pd盐负载到步骤1)中制得的金属离子掺杂的ZnMxAl2-xO4载体上，所得固体经干燥和焙烧后制得PdZn/ZnMxAl2-xO4催化剂；
3)将步骤2)中制得的PdZn/ZnMxAl2-xO4催化剂在H2气氛中进行还原处理；
4)将步骤3)中制得的H2处理过的PdZn/ZnMxAl2-xO4催化剂加入到甲醇水溶液中进行制氢反应，反应温度为150～300℃，反应压力为常压。
优选地，步骤1)中所述的锌盐为硝酸锌，硫酸锌，醋酸锌或氯化锌中的一种；所述的掺杂金属离子盐为硝酸铁，氯化铁，硫酸铁，醋酸铁，硝酸钴，氯化钴，硫酸钴，醋酸钴，硝酸镍，氯化镍，硫酸镍，醋酸镍，硝酸锰，氯化锰，醋酸锰或硫酸锰中的一种。
优选地，步骤1)中所述的水热反应为在180-200℃下水热6-10h；所述的焙烧条件为在600-800℃下焙烧4-6h。
优选地，步骤2)中所述的PdZn/ZnFexAl2-xO4催化剂中Pd的质量分数为0.1～0.5％，PdZn合金以β相存在。
优选地，步骤2)中所述的贵金属Pd盐为硝酸钯或醋酸钯中的一种。
优选地，步骤3)中所述的H2气氛中进行还原处理的温度为350-500℃，时间为1-3h。
优选地，步骤4)中所述的甲醇水溶液中甲醇和水的摩尔比为1:1.0～1：1.5。
本发明的设计原理如下：
本发明首先通过水热反应制得金属离子掺杂的ZnMxAl2-xO4尖晶石载体，然后将含贵金属Pd的前驱体溶液负载到ZnFexAl2-xO4上制备得到PdZn/ZnFexAl2-xO4催化剂；所制备的催化剂在用于催化甲醇蒸汽重整制氢反应前需经过H2还原，还原温度在300-400℃。对PdZn/ZnFexAl2-xO4催化剂进行XRD和TEM表征，结果表明其活性成分PdZn合金以β相存在；催化甲醇蒸汽重整制氢的实验研究结果表明在PdZn/ZnFexAl2-xO4催化剂中Pd含量越低，贵金属的利用率就越高，当Pd含量低至0.1wt％时，产物CO2和H2的选择性仍能达到较高水平，并且平均反应速率和贵金属Pd的利用率处于最优水平。
在锌铝尖晶石合成的时候掺杂第三种金属(例如三价铁离子)，可以在PdZn合金的界面上形成第二个活性位来促进水的活化，这样可以提高甲醇重整制氢的效率。
本发明以具有高比表面积和高稳定性的ZnAl2O4尖晶石为基础，在其基础上引入新的活性金属氧化物来替代体相中的Al，从而构建新型的改性尖晶石载体。尖晶石一般结构为AB2O4，其中A2+占据尖晶石的四面体位点八分之一，B3+占据八面体位点的二分之一。研究表明，并不是所有的物质均可以替代Al留在尖晶石体相中，替代Al需要具备以下两个条件：首先要有相同的原子半径，其次要能够在八面体位点稳定存在。本发明以ZnFexAl2-xO4为载体时，在低Pd负载量下即可有效形成PdZn合金，不仅考察了贵金属和载体间的相互作用，还探究了不同Pd负载量在其表面形成PdZn合金的规律，并从原子层面设计和构建多功能密切协同的PdZn复合催化体系。
本发明的制备方法具有以下有益效果：
1)采用Pd含量较低(0.1wt％)的PdZn/ZnFexAl2-xO4催化剂即可实现高效甲醇重整制氢，且副产物CO的选择性较低，这样可极大节约制氢的经济成本。
2)本发明所提供的制氢方法简单，可实现便携式制氢。
附图说明
图1为载体和催化剂的XRD谱图；其中，a为不同Fe掺杂量的载体的XRD谱图；b为催化剂反应前后的XRD谱图。
图2为还原态的2.5wt.％PdZn/ZnFexAl2-xO4(x＝0.05-0.2)催化剂的TEM图；其中：a为Fe掺杂量为0.05wt％催化剂的TEM图，b为Fe掺杂量为0.1wt％催化剂的TEM图，c为Fe掺杂量为0.2wt％催化剂的TEM图。
具体实施方式
下面进一步结合附图和实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，示例中具体的质量、反应时间和温度、工艺参数等也仅是合适范围中的一个示例，本领域的技术人员根据本发明的上述内容做出的一些非本质的改进和调整均属于本发明的保护范围。实施例中未注明具体技术或条件者，均为按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市场购买的常规产品。
催化剂的XRD分析表征采用的是RIGAKU理学公司的型号为Ultima-IV的多晶X射线粉末衍射仪进行，以Cu Kɑ(λ＝0.15406nm)为X射线的辐射源，测试条件为扫描速度10°/min，测试角度范围为10°-90°,光管电压为40kV，管电流为30mA。
催化剂的TEM表征是在JEOL JEM 2100F场发射透射电子显微镜上进行。测试前取少量样品分散在无水乙醇中，超声30min，然后将溶液滴于铜网上，晾干后备用。
实施例1
Pd质量分数为0.1wt.％的PdZn/ZnFe0.05Al1.95O4催化剂催化甲醇蒸汽重整制氢的具体方法如下：
1)将5.95g硝酸锌、0.4g硝酸铁和13.5g三氯化铝加入到100ml异丙醇中在180℃下水热反应10h，将所得固体在800℃焙烧4h后制得金属铁离子掺杂的ZnFe0.05Al1.95O4尖晶石载体；
2)取0.0025g Pd(NO3)2·2H2O前驱体于5mL样品管中，并用体积比1:3的硝酸水溶液(0.4mL)将其溶解制得Pd(NO3)2溶液；然后称取1g ZnFe0.05Al1.95O4载体至100mL烧杯中，室温下将其等量浸渍至Pd(NO3)2溶液中，过滤后将所得固体放置于100℃的烘箱中干燥一夜，最后将干燥后的固体在400℃下焙烧3h即可制备得到Pd的质量分数为0.1wt.％的PdZn/ZnFe0.05Al1.95O4催化剂；
3)将步骤2)中制得的Pd的质量分数为0.1wt.％的PdZn/ZnFe0.05Al1.95O4催化剂在H2气氛中进行还原处理，还原条件为：以H2为还原气，还原温度为350℃，还原时间为3h；
4)将0.3g步骤3)中制得的H2处理过的Pd的质量分数为0.1wt.％的PdZnFe0.05Al1.95O4催化剂加入到甲醇水溶液中进行制氢反应：反应压力为常压，反应温度为250℃，甲醇水溶液中水和甲醇按摩尔比为1.1:1，甲醇水溶液的质量空速为10h-1，反应结果见表1；甲醇转化率为23.9％，而副产物CO选择性则为2.8％。
实施例2
Pd质量分数为0.1wt.％的PdZn/ZnFe0.1Al1.9O4催化剂催化甲醇蒸汽重整制氢的具体方法参考实施例1，不同之处在于：步骤1)中硝酸铁的用量变为0.8g；其余步骤均同实施例1；反应结果见表1：甲醇转化率为36.25％，而副产物CO选择性则为2.38％。
实施例3
Pd质量分数为0.1wt.％的PdZn/ZnFe0.2Al1.8O4催化剂催化甲醇蒸汽重整制氢的具体方法参考实施例1，不同之处在于：步骤1)中硝酸铁的用量变为1.6g；其余步骤均同实施例1；反应结果见表1：甲醇转化率为25.67％，而副产物CO选择性则为2.17％。
实施例4
Pd质量分数为0.5wt.％的PdZn/ZnFe0.1Al1.9O4的催化剂催化甲醇蒸汽重整制氢的具体方法参考实施例2，不同之处在于：步骤2)中Pd(NO3)2·2H2O的用量变为0.0125g；其余步骤均同实施例2；反应结果见表1：甲醇转化率为88.5％，而副产物CO选择性则为1.4％。
实施例5
Pd质量分数为1.0wt.％的PdZn/ZnFe0.1Al1.9O4的催化剂催化甲醇蒸汽重整制氢的具体方法参考实施例2，不同之处在于：步骤2)中Pd(NO3)2·2H2O的用量变为0.025g；其余步骤均同实施例2；反应结果见表1：甲醇转化率为97.5％，而副产物CO选择性则为2.1％。
实施例6
Pd质量分数为2.5wt.％的PdZn/ZnFe0.1Al1.9O4的催化剂催化甲醇蒸汽重整制氢的具体方法参考实施例2，不同之处在于：步骤2)中Pd(NO3)2·2H2O的用量变为0.0625g；其余步骤均同实施例2；反应结果见表1：甲醇转化率为100％，而副产物CO选择性则为3.2％。
表1.实施例1～6甲醇蒸汽重整制氢结果
反应条件：催化剂量：300mg，载气N2：30ml/min。
如表1所示为PdZn/ZnFexAl2-xO4催化剂催化甲醇蒸汽重整制氢的结果：由实施例1-3可以发现催化剂的催化性能随着Fe含量的变化呈现明显的变化，Fe的掺杂量在0.1的时候展现出最优的催化性能。从实施例4-6中可以看到：从低Pd到高Pd含量，PdZn/ZnFe0.1Al1.9O4催化剂均有一个较高的CO2选择性，并且活性随着Pd的负载量的提高逐渐提升。
对所制备的催化剂进行表征，XRD表征谱图如图1所示，其中，图1a为不同Fe掺杂量的载体的XRD谱图；从图1a中可以看出：Fe的加入并没有改变尖晶石的衍射峰，说明Fe成功的进入尖晶石体相代替Al，Fe掺杂后的尖晶石的峰相比于ZnAl2O4尖晶石发生了偏移，并且随着Fe掺杂量的增加，尖晶石的衍射峰逐渐向ZnFe2O4偏移。此外，为了探究改性前后催化剂的稳定性是否与预期的相似，还分别对焙烧后的催化剂(2.5Pd-ZnFe0.1Al1.9O4-Cal)、还原后的催化剂(2.5Pd-ZnFe0.1Al1.9O4-Re)以及反应后的催化剂(2.5Pd-ZnFe0.1Al1.9O4-Spent)进行了XRD表征，结果如图1b所示：催化剂经过350℃还原后能够稳定的存在，不会发生分解；此外，可以明显的看到在衍射角2θ为41.2°处出现了衍射峰，通过标准PDF卡片(PDF#65-9523)比对，该峰对应的是β相的PdZn合金的(111)晶面；从图1b中还可以看出反应后的催化剂不管是载体还是PdZn合金相均没有发生明显变化，这说明改性后催化剂的稳定性有了很大的提高，这有利于反应的催化性能的改善。
还原态的2.5wt.％PdZn/ZnFexAl2-xO4(x＝0.05-0.2)TEM结果如图2a～2c所示：根据所得的衍射斑点图，可以测得不同样品中分别存在晶格间距为0.219nm和0.205nm的晶格条纹，其分别对应的是PdZn合金的(111)和(200)晶面(PDF#06-0620)，这更直接的验证了在载体表面能够很好的形成PdZn合金。
Claims (7)
1.一种将Pd/ZnMxAl2-xO4催化剂用于甲醇蒸汽重整制氢的方法，其特征在于包括如下步骤：
1)将锌盐、掺杂金属离子盐和铝盐加入到异丙醇中进行水热反应，将所得固体焙烧后制得金属离子掺杂的ZnMxAl2-xO4尖晶石载体，其中，x＝0.05-0.2，掺杂金属离子M为Fe，Co，Ni，Cu或Mn中的一种；
2)通过浸渍法或溶胶凝胶法等方法将贵金属Pd盐负载到步骤1)中制得的金属离子掺杂的ZnMxAl2-xO4载体上，所得固体经干燥和焙烧后制得PdZn/ZnMxAl2-xO4催化剂；
3)将步骤2)中制得的PdZn/ZnMxAl2-xO4催化剂在H2气氛中进行还原处理；
4)将步骤3)中制得的H2处理过的PdZn/ZnMxAl2-xO4催化剂加入到甲醇水溶液中进行制氢反应，反应温度为150～300℃，反应压力为常压。
2.根据权利要求1所述的将PdZn/ZnMxAl2-xO催化剂用于甲醇蒸汽重整制氢的方法，其特征在于步骤1)中所述的锌盐为硝酸锌，硫酸锌，醋酸锌或氯化锌中的一种；所述的掺杂金属离子盐为硝酸铁，氯化铁，硫酸铁，醋酸铁，硝酸钴，氯化钴，硫酸钴，醋酸钴，硝酸镍，氯化镍，硫酸镍，醋酸镍，硝酸锰，氯化锰，醋酸锰或硫酸锰中的一种。
3.根据权利要求1所述的将PdZn/ZnMxAl2-xO催化剂用于甲醇蒸汽重整制氢的方法，其特征在于步骤1)中所述的水热反应为在180-200℃下水热6-10h；所述的焙烧条件为在600-800℃下焙烧4-6h。
4.根据权利要求1所述的将PdZn/ZnMxAl2-xO催化剂用于甲醇蒸汽重整制氢的方法，其特征在于步骤2)中所述的PdZn/ZnFexAl2-xO4催化剂中Pd的质量分数为0.1～0.5％，PdZn合金以β相存在。
5.根据权利要求1所述的将PdZn/ZnMxAl2-xO催化剂用于甲醇蒸汽重整制氢的方法，其特征在于步骤2)中所述的贵金属Pd盐为硝酸钯或醋酸钯中的一种。
6.根据权利要求1所述的将PdZn/ZnMxAl2-xO4催化剂用于甲醇蒸汽重整制氢的方法，其特征在于步骤3)中所述的H2气氛中进行还原处理的温度为350-500℃，时间为1-3h。
7.根据权利要求1所述的将PdZn/ZnFexAl2-xO4催化剂用于甲醇蒸汽重整制氢的方法，其特征在于步骤4)中所述的甲醇水溶液中甲醇和水的摩尔比为1:1.0～1：1.5。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785513A (zh) * | 2005-09-30 | 2006-06-14 | 复旦大学 | 一种用于甲醇水蒸气重整制氢的纳米铜基催化剂及其制备方法 |
| US20080058202A1 (en) * | 2003-07-29 | 2008-03-06 | Japan Science And Technology Agency | Catalyst for Use in Reforming Methanol with Steam and Method for Preparation Thereof |
| CN108855065A (zh) * | 2018-05-24 | 2018-11-23 | 厦门大学 | 一种将Pd/ZnAl2O4催化剂用于甲醇蒸汽重整制氢的方法 |
| CN109718806A (zh) * | 2017-10-30 | 2019-05-07 | 中国科学院大连化学物理研究所 | 一种贵金属单原子催化剂及其制备方法和应用 |
| CN110013842A (zh) * | 2019-04-15 | 2019-07-16 | 厦门大学 | 一种原位生成尖晶石基纳米催化剂及其合成方法 |
| CN113198471A (zh) * | 2021-05-21 | 2021-08-03 | 晋中学院 | 一种甲醇重整制氢的铜铝尖晶石催化剂及其制法和应用 |
-
2021
- 2021-08-11 CN CN202110917324.1A patent/CN113477263A/zh not_active Withdrawn
- 2021-12-27 CN CN202111611277.4A patent/CN114260016A/zh active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080058202A1 (en) * | 2003-07-29 | 2008-03-06 | Japan Science And Technology Agency | Catalyst for Use in Reforming Methanol with Steam and Method for Preparation Thereof |
| CN1785513A (zh) * | 2005-09-30 | 2006-06-14 | 复旦大学 | 一种用于甲醇水蒸气重整制氢的纳米铜基催化剂及其制备方法 |
| CN109718806A (zh) * | 2017-10-30 | 2019-05-07 | 中国科学院大连化学物理研究所 | 一种贵金属单原子催化剂及其制备方法和应用 |
| CN108855065A (zh) * | 2018-05-24 | 2018-11-23 | 厦门大学 | 一种将Pd/ZnAl2O4催化剂用于甲醇蒸汽重整制氢的方法 |
| CN110013842A (zh) * | 2019-04-15 | 2019-07-16 | 厦门大学 | 一种原位生成尖晶石基纳米催化剂及其合成方法 |
| CN113198471A (zh) * | 2021-05-21 | 2021-08-03 | 晋中学院 | 一种甲醇重整制氢的铜铝尖晶石催化剂及其制法和应用 |
Non-Patent Citations (3)
| Title |
|---|
| FANGYUAN CHEN等: "Catalytic steam reforming of volatiles released via pyrolysis of wood sawdust for hydrogen-rich gas production on Fe–Zn/Al2O3 nanocatalysts", 《FUEL》 * |
| LIU YA-JIE等: "Cu-Ni-Al spinel catalyzed methanol steam reforming for hydrogen production: Effect of Al content", 《JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGY》 * |
| WIKTORIA WALERCZYK等: "Solvothermal Synthesis and Catalytic Properties of Nanocrystalline ZnFe2-xAlxO4 (x=0, 1, 2) Spinels in Aniline Methylation", 《CATALYSIS LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414931A (zh) * | 2022-08-31 | 2022-12-02 | 北京工业大学 | 一种用于甲醇蒸汽重整制氢的Pd/ZnO催化剂的制备方法 |
| CN115414931B (zh) * | 2022-08-31 | 2024-01-05 | 北京工业大学 | 一种用于甲醇蒸汽重整制氢的Pd/ZnO催化剂的制备方法 |
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