CN1130305C - 蒸汽转化烃的方法 - Google Patents
蒸汽转化烃的方法 Download PDFInfo
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- 238000000629 steam reforming Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000008569 process Effects 0.000 title claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 title description 13
- 150000002430 hydrocarbons Chemical class 0.000 title description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 239000010931 gold Substances 0.000 claims abstract description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052737 gold Inorganic materials 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 3
- 230000005764 inhibitory process Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000009826 distribution Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100189378 Caenorhabditis elegans pat-3 gene Proteins 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101100232929 Caenorhabditis elegans pat-4 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DFCVQVFZSSOGOG-UHFFFAOYSA-N N.[Au] Chemical compound N.[Au] DFCVQVFZSSOGOG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
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- 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
- C01B3/34—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 by reaction of hydrocarbons with gasifying agents
- C01B3/38—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 by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—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 by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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Abstract
没有任何积碳的催化蒸汽转化含碳原料的方法，其中将原料与一种还含有0.01wt%～30wt%(以在催化剂中镍重量计)的金的载体上的镍催化剂接触进行。
Description
本发明涉及通过蒸汽转化烃生产富含氢气和/或一氧化碳气体。具体地说，本发明涉及用于蒸汽转化烃原料的含金的镍转化催化剂。
在已知的富含氢气和/或一氧化碳气体的生产方法中，烃和蒸汽和/或二氧化碳混合气在高温和高压下通过装填有催化剂的反应器，催化剂主要由作为活性催化成分的镍构成。
适于蒸汽转化的烃原料是例如天然气、炼油厂气、丙烷、石脑油和液化石油气。以甲烷为例，发生的反应可以用以下方程代表：
(1)
(2)
(3)
除了转化反应(1)和(2)之外，某些碳生成反应可以按以下方式发生：
(4)
(5)
由此形成的碳在几个方面有害处。它通过堵塞活性部位减低催化剂的活性。积碳可以进一步引起催化剂颗粒的散裂和粉碎，导致催化床上的压力降增大从而由于反应器的堵塞而使转化操作不能连续进行。
通过增加在反应气体里蒸汽对烃的比例或通过降低原料的分子量以减少碳的形成潜力来阻止积碳是公知的。
然而，增加蒸汽对烃的比例，由于更多的一氧化碳向二氧化碳转移，会导致CO产率降低。这样，为了将CO/H2生产维持在要求的产率上，要求更大量的催化剂和原料，这会降低这种转化过程的经济性。
已经做出了各种尝试以克服积碳而不影响最佳的蒸汽对烃的比例。
在英国专利GB 2 015 027中提出了制备具有高还原潜力的还原气体的转化过程中防止积碳的一种方法。采用这种公开的方法，在原料中，在2~10ppm(体积)硫或硫化物存在下将富含甲烷的原料气在载体上的镍催化剂上进行转化。因此，硫的存在抑制积碳的形成，从而保证满意的催化剂转化活性，以形成一氧化碳和氢气。
此外，过去也曾提出了几种减少积碳的催化剂。一般说来，这些现有的具有积碳抑制作用的催化剂主要由带有碱金属促进剂的镍构成的。碱金属促进的催化剂的缺点是低活性和碱金属的流动性，在催化剂运行期间它们引起碱金属促进剂的迁移和蒸发。
在美国专利US 3 926 583中提出没有碱金属的催化剂，其中镍、铁或钴转化催化剂是通过将具有一种镁铝尖晶石与混合固相的镍、铁或钴氧化物的紧密混合物的前体进行还原来制备，在美国专利US 3 791 993中公开了一种镍、铁或钴、镁氧化物的转化催化剂。在本技术领域中还提出了其它促进剂。美国专利US 4 060 498中提出了一种用在耐热氧化物载体上的银促进的镍催化剂的蒸汽转化方法。此外，欧洲专利EP 470 626描述了IVa和Va族金属抑制积碳形成的效果。在这种含镍的催化剂中，锗、锡、铅、砷、锑和铋的量为0.1~30wt％，以金属镍量为基计。
在这个专利里不包括Ib族的元素，在这个文献里指明，金的加入既没有对积碳的形成起作用也没有对转化活性起作用(用于蒸汽转化的单和双-金属催化剂，Ph.D.Thesis by Isar-Ul Haque，University of New South Wales，1990)。
近来SIM研究(L.P.Nielsen等人，Phys.Rev.Lett.71(1993)754)表明，金可以在镍单晶体的表面形成一种合金，虽然这二种元素在松散态(in the bulk)是不溶混的。另外，使用密度函数理论计算预计，加入少量的金会改变相邻镍原子的反应性(P.Kratzer等人，J.Chem.Phys.105(13)(1996)5595)。以少量的金促进的镍单晶体的分子束研究证实了这一点(P.M.Holmblad等人，J.Chem.Phys.104(1996)7289)。
因此，本发明的主要目的是在烃的蒸汽转化中防止碳沉积。
我们现在观察到，把少量金加入含镍催化剂中提供了一种具有在烃的蒸汽转化期间抑制碳沉积的催化剂。虽然金减低了镍催化剂的催化活性，但这种催化剂仍然提供了足够的蒸汽转化的活性。EXAFS证明金位于镍的表面(AnnualReport from HASYLAB，1996)。
基于以上观察，本发明的主要实施例以不形成积碳催化蒸汽转化含碳原料的方法为目的，其中发生在蒸汽转化期间的碳生成反应通过将原料与载体上的镍催化剂接触显著减少，这种载体上的镍催化剂还含有，以在催化剂里镍的重量计，0.01％～30％的金。载体上的镍催化剂可含有按催化剂总重量计0.001-10％的金。
在催化剂中金的加入量取决于镍表面积。
含金的镍催化剂可以通过含有镍盐溶液和金盐促进剂的溶液与载体材料的共浸渍或顺序浸渍来制备。适用的盐包括氯化物、硝酸盐、碳酸盐、醋酸盐或草酸盐。
载体材料一般选自氧化铝、氧化镁、二氧化钛、二氧化硅、氧化锆、氧化铍、氧化钍、氧化镧、氧化钙和它们的化合物或混合物。优选的材料包括氧化铝、钙的铝酸盐和镁铝尖晶石。这样获得的促进的催化剂可以用于蒸汽转化甲烷或更高级的烃生产富含氢气和/或一氧化碳的气体。
所得到的富含氢气和/或一氧化碳的气体可以用于很多过程中。氢气在精练厂中广泛使用，而氢气与一氧化碳的混合气用于例如氧化烃的合成以及合成燃料的合成。富含氢气体的一个重要应用是制备氨和甲醇。
镍-金催化剂一般设置成在顶部供料的管式转化反应器里的固定床。根据处理的条件，碳形成的可能性通常在管子的顶层最高。因此，将镍-金催化剂设置为传统的镍蒸汽转化催化剂固定床上部的一层就足够了。其中，镍-金催化剂层优选构成催化剂床的5％～50％。本发明将用下列实施例进一步描述。
实施例1
蒸汽转化活性
通过将尖晶石载体用硝酸镍和硝酸四氨金[Au(NH3)4](NO3)3顺序浸渍，制备一系列含有17wt％镍和具有不同金含量的镍-金催化剂。在用金前体浸渍前，硝酸镍被分解。干燥后，将催化剂颗粒装入一反应器内并在大气压下在氢气流中加热到350℃激活。
在下列条件下测定蒸汽转化活性：
催化剂尺寸， mm 4×4
催化剂的量 g 0.2
温度 ℃ 400～650℃
原料气体组成， Nl/h
CH4 4.0
H2O 16.0
H2 1.6在550℃获得的活性示于表1中。表1 在550℃蒸汽转化的活性
| 100·Au/Ni 重量/重量 | 相对活性 |
| 催化剂1 0.00 | 100 |
| 催化剂2 1.85 | 65 |
从表1中明显看出，与纯的镍催化剂相比较，含金的镍催化剂的蒸汽转化活性有较少降低。
表2 TGA测量
在丁烷的蒸汽转化期间实施例1中制备的转化催化剂上的积碳速率用重力分析法在450℃~550℃温度之间的各段值测定。温度以0.5℃/min增加。使用传统的试验装置用于这个测定，试验装置包括一个与在线微量天平(on-linemicrobalace)连结的加热的反应器管。一种催化剂颗粒(0.1g)放在微量天平的一个臂的悬吊篮里。流过这个催化剂颗粒的供入蒸汽的总流量和浓度如下：
总流量 ＝ 21.82Nl/h
丁烷 ＝ 3.76vol％
蒸汽 ＝ 22.91vol％
氢气 ＝ 4.58vol％
氮气 ＝ 68.74vol％
在上述条件下积碳的速率描绘在图1中，图1示出在不同温度(℃·1000)沉积在催化剂2上的碳的量(μg碳/g催化剂·100)，与传统的镍转化催化剂的比较，催化剂2按实施例1的条件制备；传统的镍转化催化剂也按实施例1的条件制备。
从图中明显看出，根据本发明的催化剂具有大大提高的在蒸汽转化期间防止碳生成的能力。
Claims (4)
1、具有高的抑制碳生成能力的含碳原料的催化蒸汽转化的方法，通过将原料与一种还含有按催化剂中镍的重量计0.01wt％～30wt％的金的在载体上的镍催化剂接触进行，金的存在抑制了固体碳的形成。
2、权利要求1的方法，其中金的重量在0.001％～10％之间，以催化剂总重量计。
3、权利要求1的方法，其中含金的镍催化剂设置为传统的镍蒸汽转化催化剂固定床的最上层。
4、权利要求3的方法，其中最上层构成全部催化剂床的5％～50％。
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| DK199700683A DK174077B1 (da) | 1997-06-10 | 1997-06-10 | Fremgangsmåde til carbonhydriddampreformering under anvendelse af en guldholdig nikkeldampreformingkatalysator |
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| DK173897B1 (da) * | 1998-09-25 | 2002-02-04 | Topsoe Haldor As | Fremgangsmåde til autotermisk reforming af et carbonhydridfødemateriale indeholdende højere carbonhydrider |
| EP1209121A1 (en) | 2000-11-22 | 2002-05-29 | Haldor Topsoe A/S | Process for the catalytic oxidation of carbon monoxide and/or methanol |
| JP4098508B2 (ja) * | 2001-08-20 | 2008-06-11 | 財団法人 ひろしま産業振興機構 | 炭化水素と水蒸気とを反応させるための触媒の製造方法および当該触媒を使用した炭化水素から水素を製造する方法 |
| DE10219723B4 (de) | 2002-05-02 | 2005-06-09 | Uhde Gmbh | Verfahren zur Herstellung ungesättigter halogenhaltiger Kohlenwasserstoffe sowie dafür geeignete Vorrichung |
| US6911161B2 (en) * | 2002-07-02 | 2005-06-28 | Conocophillips Company | Stabilized nickel-containing catalysts and process for production of syngas |
| JP2006511431A (ja) | 2002-12-20 | 2006-04-06 | 本田技研工業株式会社 | 白金−ルテニウムを含有する水素生成用触媒配合物 |
| JP2006511331A (ja) * | 2002-12-20 | 2006-04-06 | 本田技研工業株式会社 | 水素生成用触媒の製造方法 |
| AU2003299785A1 (en) * | 2002-12-20 | 2004-07-22 | Honda Giken Kogyo Kabushiki Kaisha | Catalyst formulations for hydrogen generation |
| CN1729141B (zh) | 2002-12-20 | 2010-04-28 | 本田技研工业株式会社 | 用于氢产生的铂-碱金属/碱土金属催化剂配方 |
| CN1729140B (zh) * | 2002-12-20 | 2010-04-21 | 本田技研工业株式会社 | 用于氢产生的不含铂的钌-钴催化剂配方 |
| US7687051B2 (en) * | 2002-12-20 | 2010-03-30 | Honda Giken Koygo Kabushiki Kaisha | Platinum and rhodium and/or iron containing catalyst formulations for hydrogen generation |
| JP4648004B2 (ja) * | 2002-12-20 | 2011-03-09 | 本田技研工業株式会社 | 水素生成用の貴金属を含まないニッケル触媒配合物 |
| US7682598B2 (en) * | 2002-12-20 | 2010-03-23 | Honda Giken Kogyo Kabushiki Kaisha | Alkali-containing catalyst formulations for low and medium temperature hydrogen generation |
| DE10319811A1 (de) | 2003-04-30 | 2004-11-18 | Uhde Gmbh | Vorrichtung zum Einkoppeln von elektromagnetischer Strahlung in einen Reaktor sowie Reaktor enthaltend diese Vorrichtung |
| ATE378435T1 (de) * | 2003-06-12 | 2007-11-15 | Topsoe Fuel Cell As | Brennstoffzelle und anode |
| US7829035B2 (en) | 2006-01-19 | 2010-11-09 | Massachusetts Institute Of Technology | Oxidation catalyst |
| US20100068130A1 (en) * | 2008-09-17 | 2010-03-18 | Frederick Carl Wilhelm | Process for the Production of Hydrogen Gas Employing a Thermally Stable Catalyst |
| US20100147749A1 (en) * | 2008-12-11 | 2010-06-17 | American Air Liquide, Inc. | Multi-Metallic Catalysts For Pre-Reforming Reactions |
| FR2949077B1 (fr) | 2009-08-17 | 2011-07-22 | Inst Francais Du Petrole | Procede de preparation d'un catalyseur supporte a base de ni et d'un metal du groupe ib pour l'hydrogenation selective d'hydrocarbures polyinsatures |
| FR2949078B1 (fr) | 2009-08-17 | 2011-07-22 | Inst Francais Du Petrole | Procede de preparation d'un catalyseur supporte ni/sn pour l'hydrogenation selective d'hydrocarbures polyinsatures |
| US9079167B2 (en) * | 2011-02-07 | 2015-07-14 | Toyota Jidosha Kabushiki Kaisha | NOx purification catalyst |
| CN106486682B (zh) * | 2016-09-27 | 2020-07-14 | 上海交通大学 | 球形核壳状PdxNi1-x@Pt/C催化剂及其制备 |
| CN114308061B (zh) * | 2020-09-29 | 2023-08-22 | 中国科学院大连化学物理研究所 | NiAu双金属合金纳米催化剂及其合成与应用 |
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| GB1032754A (en) * | 1962-12-17 | 1966-06-15 | Ici Ltd | Improvements in or relating to the steam reforming of hydrocarbons and catalysts therefor |
| GB1182829A (en) * | 1967-06-12 | 1970-03-04 | Haldor Frederik Axel Topsoe | Improvements in or relating to Nickel Catalysts. |
| US3926583A (en) * | 1967-06-12 | 1975-12-16 | Haldor Topsoe As | Process for the catalytic steam reforming of hydrocarbons |
| US3666412A (en) * | 1968-10-21 | 1972-05-30 | Du Pont | Dispersed phase activated and stabilized metal catalysts |
| US4060498A (en) * | 1972-06-02 | 1977-11-29 | Hitachi, Ltd. | Process for steam reforming of hydrocarbons |
| GB2015027B (en) * | 1978-02-03 | 1982-06-23 | Haldor Topsoe As | Reforming process |
| DK166995B1 (da) * | 1990-08-09 | 1993-08-16 | Topsoe Haldor As | Katalysator til dampreforming af carbonhydrider og anvendelse ved fremstilling af hydrogen- og/eller carbonmonoxidrige gasser |
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| CN1211560A (zh) | 1999-03-24 |
| AU6998098A (en) | 1998-12-17 |
| KR100508792B1 (ko) | 2005-11-25 |
| JP4233633B2 (ja) | 2009-03-04 |
| KR19990006806A (ko) | 1999-01-25 |
| EP0884274A1 (en) | 1998-12-16 |
| NO982649D0 (no) | 1998-06-09 |
| NZ330609A (en) | 1999-10-28 |
| US5997835A (en) | 1999-12-07 |
| CA2239843C (en) | 2008-01-15 |
| MX9804630A (es) | 1998-12-31 |
| ES2209002T3 (es) | 2004-06-16 |
| NO321201B1 (no) | 2006-04-03 |
| EP0884274B1 (en) | 2003-10-08 |
| DE69818748T2 (de) | 2004-08-05 |
| DK68397A (da) | 1998-12-11 |
| JPH1179704A (ja) | 1999-03-23 |
| DE69818748D1 (de) | 2003-11-13 |
| NO982649L (no) | 1998-12-11 |
| AU738898B2 (en) | 2001-09-27 |
| DK174077B1 (da) | 2002-05-21 |
| CA2239843A1 (en) | 1998-12-10 |
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