CN1835797A - 催化还原和氧化方法 - Google Patents
催化还原和氧化方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title claims abstract description 10
- 238000010531 catalytic reduction reaction Methods 0.000 title description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 46
- 229910052709 silver Inorganic materials 0.000 claims abstract description 39
- 239000004332 silver Substances 0.000 claims abstract description 34
- 239000010931 gold Substances 0.000 claims abstract description 21
- 229910052737 gold Inorganic materials 0.000 claims abstract description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
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- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 5
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- -1 magnesium aluminate Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000007868 Raney catalyst Substances 0.000 description 21
- 229910000564 Raney nickel Inorganic materials 0.000 description 21
- 230000000694 effects Effects 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 229910020068 MgAl Inorganic materials 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000006424 Flood reaction Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 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 2
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 230000010718 Oxidation Activity Effects 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940043430 calcium compound Drugs 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 238000005137 deposition process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J23/892—Nickel and noble metals
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Abstract
用于有机和无机化合物的氧化或还原的催化方法,包括在氧化或还原条件下使该化合物与载体催化剂相接触,该载体催化剂由银或金助催化的镍作为活性催化组分组成,基于催化剂中镍的含量计算,银或金的含量在0.001wt%-30wt%之间。
Description
技术领域
本发明涉及催化还原和氧化方法,以及一种用于该方法的催化剂。特别是,该方法涉及用于不同的催化还原和氧化反应的由银或金助催化(promote)的镍催化剂。
背景技术
镍是一种可用于许多反应的众所周知的催化剂。这些反应中的几个的主要问题在于镍的高反应活性。对于烃反应来说,这会在特定条件下导致含碳物质在表面上沉积而破坏活性[J.R.Rostrup-Nielsen,Steam Reforming Catalysts,Danish Technical Press Inc.,Copenhagen1975],而且对于氧化反应来说经常形成氧化镍。人们还发现镍催化剂在某些情况下会形成过多的副产品,也就是说,与诸如镍相比其选择性低。
当被镍催化剂催化时存在问题而当存在诸如贵金属基催化剂时问题较少的还原和氧化反应的例子是:
氢化和脱氢反应:
选择性氧化,例如,在不同时发生氢的氧化的情况下CO在氢气氛中选择性氧化:
SO2的氧化:
用CO还原NO:
CO甲烷化(methanisation):
乙烷的氢解:
在像这样的情况下的常用备选方案是使用例如铂或钯的贵金属基催化剂。这些物质的活性较低,因此在表面污染方面存在的问题较少。然而,铂和钯比镍昂贵得相当多,因此非常希望能够改变镍的表面性质以使其表现出与例如铂或钯相近的活性。换句话说,希望镍显示更“贵重(noble)”的行为。这将有可能为许多反应开发出更便宜的催化剂。
已知对于其它目的,用银对镍催化剂进行助催化并且由此希望其表现出某些“贵重”的行为,参见例如美国专利第4,060,498号。
发明内容
本发明的目的是对镍催化剂进行改性以改变其活性,并且为其提供更“贵重”的行为,从而使该催化剂与纯的镍催化剂相比更适用于许多氧化和还原反应。
因此,提供了一种由银或金助催化的镍作为活性催化组分组成的催化剂,基于催化剂中镍的含量计算,银或金的含量在0.001wt%-30wt%之间,该催化剂用于有机和无机化合物的氧化或还原的催化方法。
基于以上陈述,本发明的一个广泛的实施方式涉及一种对镍催化剂进行改性的方法,该方法通过用银或金助催化,从而改变它的催化性质,以使其行为变得更加“贵重”,并且具有可与例如铂相比的性质。
在某些还原和氧化反应中,需要比用纯镍所获得的更高的转化率或选择性,而在其它反应中,希望获得当与纯镍相比时有所降低的转化率或选择性。
使用根据本发明的银或金助催化的镍催化剂可以实现这一点。根据反应的类型,活性可以显示出升高或降低。这是因为存在的助催化剂原子阻塞了催化剂上特定类型的活性位点这一事实。并非所有的活性位点均被阻塞。其它体系中也可以观察到这一现象,例如用金修饰的钌(S.Dahl等人,Phys.Rev.Letters,83(1999)1814)。对于中毒很重要的反应和条件来说,阻断有毒的副反应将会提高活性。对于这种副反应的重要性较低的反应或条件来说,由于助催化剂原子的沉积导致较少的活性位点可用,将会观察到活性的降低。铂的特征在于在所涉及的反应中几乎不会发生副反应,因此助催化的镍催化剂将显示出可与铂相比的性质。
催化剂中含有的银或金的量取决于镍的边缘表面积。可以通过载体物质与含有可溶性镍盐和银或金助催化剂的盐的溶液的共浸渍或顺序浸渍制备银或金助催化的镍催化剂。
为了用银或金改变镍的性质,银或金必须位于镍的表面。在某些情况下,可以通过载体与同时含有镍和银前体的溶液的共浸渍实现这一点,如例如美国专利第4,060,498号所提及。然而,该专利仅仅包括了蒸汽重整的催化剂。
实现镍表面部分覆盖的另一种方式是通过顺序浸渍,在这里载体首先与镍前体一起浸渍、煅烧和还原,然后与银前体一起浸渍。然后通过被镍表面原子还原或者借助于沉积过程中加入的还原剂将银置于镍的表面。J.Margitfalvi,S.Szabo,F.Nagy在Supported BimetallicCatalysts prepared by Controlled Surface Reactions(通过可控反应制备的载体双金属催化剂),Studies in Surface Science and Catalysis,第27卷,第11章,Elsevier 1986中对这样的方法进行了进一步描述。金的沉积应当以类似的方式进行,如美国专利第5,997,835号中所提及,然而,这一专利也仅仅包括蒸汽重整。
合适的前体是包括盐酸盐、硝酸盐、碳酸盐、醋酸盐或草酸盐的盐类。
另外一种确保银或金在镍表面上沉积的方式是使用银或金在还原的镍催化剂上的化学汽相沉积。合适的前体包括对于银的银(I)-(β-二酮基)络合物和对于金的金(III)-(β-二酮基)络合物。
载体物质通常选自碳、氧化铝、氧化镁、二氧化钛、二氧化硅、氧化锆、氧化铍、二氧化钍、氧化镧(lanthania)、氧化钙及其化合物或混合物。优选的物质包括氧化铝、二氧化钛和镁铝尖晶石。
由此获得的助催化的Ni催化剂可以用于不同的催化反应中,如以上提到的和下文中作为例子的,从而代替了更昂贵的铂催化剂。
具体实施方式
以下实施例中将进一步对本发明加以说明。镍和银或金在催化剂中的所有浓度均以重量百分比给出(wt%)。
实施例1
苯的氢化
通过将MgAl2O4尖晶石载体与硝酸镍,然后与硝酸银一起进行顺序浸渍,制备由17wt%的镍和0.3wt%的银组成的银助催化的镍催化剂。在与银前体一起进行浸渍之前,使硝酸镍分解。干燥后,将催化剂颗粒装填在反应器中,并通过在大气压下在流动的氢气中加热至500℃进行活化。在下列条件下测定将苯转化为环己烷时产生的副产品的量:
催化剂尺寸,μm :150-300
催化剂量,g :0.1
惰性物质尺寸,μm :150-300
惰性物质量,g :0.1
温度,℃ :300
压力,巴 :11
进料气体组成,Nl/h
H2 :6
气体苯 :0.6
基于碳计算的苯的转化率和副产品的产率如表所示。
表1
催化剂 | 载体 | 苯的转化率 | 副产品的产率 |
17wt%镍 | MgAl2O4 | 96.3% | 4.0% |
17wt%镍/0.3wt%银 | MgAl2O4 | 97.3% | 2.1% |
该表中所示结果显示,银助催化的镍催化剂使副产品的形成明显减少,并且转化率更高。
实施例2
CO优先的氧化
如实施例1,制备由17wt%的镍和2.455wt%的银组成的银助催化的镍催化剂样品。干燥后,将催化剂颗粒装填到反应器中,并通过在大气压下在流动的氢气中加热至570℃进行活化。在下列条件下测定对于CO和H2的活性:
催化剂尺寸,μm :150-300
催化剂量,mg :50
温度,℃ :60
总流速,Nl/h :1.8
进料气体组成,体积%:
CO :0.5
O2 :0.5
H2 :4.4
Ar :94.6
纯的镍催化剂和Ag助催化的镍催化剂的CO2和H2O转化率如表2所示。
表2
催化剂 | 载体 | 转化率 | |
CO+O2→CO2 | H2+O2→H2O | ||
17wt%Ni | MgAl2O4 | <0.1% | 0 |
17wt%Ni/2.455wt%Ag | MgAl2O4 | 2.23% | <0.4% |
由表2可以看出,镍催化剂对于CO氧化几乎没有活性,而对H2氧化没有活性。根据本发明用银对镍催化剂进行改性增强了活性,并且能够使CO优先氧化为CO2。
例如,该催化剂可以用于作为PEM燃料电池燃料使用的重整气体的清理。
实施例3
SO2的氧化
如实施例1,通过二氧化钛(TiO2)载体的顺序浸渍制备由4wt%的镍和0.2wt%的银组成的银助催化的镍催化剂样品。如实施例1,使用[Au(NH3)4](NO3)3作为金前体制备尖晶石载体上的由17wt%的镍和0.3wt%的金组成的金助催化的镍催化剂样品。干燥后,将催化剂颗粒装填入反应器中,在下列条件下在大气压下测量SO2氧化的活性:
催化剂尺寸,mm×mm :以TiO2为载体,9×3
:以MgAl2O4为载体,4.5×4.5
催化剂量,g :1.66-4.75
温度,℃ :380
进料气体组成,Nl/h:
SO2 :0.7
O2 :7
N2 :92.3
活性如表3所示。
表3
催化剂 | 载体 | 相对活性 |
4wt%Ni | TiO2 | 100 |
4wt%Ni/0.2wt%Ag | TiO2 | 700 |
16wt%Ni | MgAl2O4 | 100 |
16wt%Ni/0.3wt%Au | MgAl2O4 | 200 |
从该表中可以看出,根据本发明,与纯的镍催化剂相比,银助催化的镍催化剂和金助催化的镍催化剂在氧化活性上均有明显改进。
实施例4
NO的还原
如实施例1,制备含有16wt%的镍和0.577wt%的银的银助催化的镍催化剂样品。干燥后,将催化剂颗粒装填在反应器中,并通过在大气压下在流动的氢气中加热至500℃进行活化。在下列条件下测定用CO还原NO的活性:
催化剂尺寸,μm :150-300
催化剂量,g :0.5
温度,℃ :200
总流速 :2.4Nl/h
进料气体组成,vol ppm :
CO :2850vol ppm
NO :2850vol ppm
平衡气 :He
各催化剂的NO转化率如表4所示。
表4
催化剂 | 载体 | 相对转化率 |
16wt%Ni/ | MgAl2O4 | 100 |
16wt%Ni/0.577wt%Ag | MgAl2O4 | 150 |
从表4中可以看出,根据本发明,通过用银助催化,镍催化剂的活性得以明显改进。这可以例如作为汽油废弃催化剂使用。
实施例5
CO甲烷化
如实施例1,制备由17wt%的镍和3wt%的银组成的银助催化的镍催化剂样品。干燥后,将催化剂颗粒装填到反应器中,并通过在大气压下在流动的氢气中加热至500℃进行活化。在下列条件下测定CO甲烷化活性:
催化剂尺寸,μm :150-300
催化剂量,g :0.1
温度,℃ :250
进料气体组成,Nl/h :
CO :0.13
H2 :13.0
活性如表5所示。
表5
催化剂 | 载体 | 相对活性 |
16wt%Ni | MgAl2O4 | 100 |
16wt%Ni/3wt%Ag | MgAl2O4 | 50 |
由表5明显可见,根据本发明用银对含镍催化剂进行改性使CO转化为CH4的活性得以大大降低。
该催化剂可以用于不希望发生CO甲烷化的反应中,例如,在甲醇合成反应和水煤气变换反应中。
实施例6
乙烷氢解
通过将尖晶石载体上的硝酸镍和硝酸银与含镍催化剂(1wt%)进行共浸渍,制备由0.9wt%的镍和0.1wt%的银组成的银助催化的镍催化剂样品。干燥后,将催化剂颗粒装填在反应器中,并通过在大气压下在流动的氢气中加热至500℃进行活化。在下列条件下在大气压下测定乙烷氢解的活性:
催化剂尺寸,μm :150-300
催化剂量,g :0.1
温度,℃ :325
进料气体组成,Nl/h :
C2H6 :0.12-0.21
H2 :0.90-1.80
He :4.0-4.1
发现下列动力学表达式为实验结果给出了极好的描述:反应速率=k·P(乙烷)·(P(氢))-0.5,其中P(x)是组分x的压力。速率常数表示的活性如表6所示。
表6
催化剂 | 载体 | 速率常数μmol/(g·s·(bar)0.5) |
1wt%Ni | MgAl2O4 | 133 |
0.9wt%Ni/0.1wt%Ag | MgAl2O4 | 12 |
从表6中明显可见,根据本发明,用银对含镍催化剂进行改性使C2H6转化为CH4的活性得以大大降低。
该催化剂可以用于不希望发生C-C键氢解的反应中,例如,在实施例1所述的氢化反应中。
Claims (8)
1.一种用于有机和无机化合物的氧化或还原的催化方法,其包括使所述的有机或无机化合物在氧化或还原条件下与由用银或金助催化的镍作为活性催化组分组成的载体催化剂相接触,所述银或金的含量基于催化剂中镍的含量计算在0.001wt%-30wt%之间。
2.根据权利要求1所述的方法,其中所述的催化方法是脱氢。
3.根据权利要求1所述的方法,其中所述的催化方法是SO2氧化。
4.根据权利要求1所述的方法,其中所述的催化方法是用CO还原NO。
5.根据权利要求1所述的方法,其中所述的催化方法是CO甲烷化。
6.根据权利要求1所述的方法,其中所述的催化方法是氢化。
7.根据权利要求1所述的方法,其中所述的催化方法是乙烷氢解。
8.根据权利要求1所述的方法,其中所述的载体是氧化铝、二氧化钛或镁铝尖晶石。
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CN109046380A (zh) * | 2018-09-03 | 2018-12-21 | 厦门大学 | 一种甲烷化催化剂及其制备方法和应用 |
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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 |
KR101614816B1 (ko) | 2011-05-24 | 2016-04-22 | 도요타 지도샤(주) | 배기 정화 시스템 |
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CN103534024A (zh) * | 2011-07-07 | 2014-01-22 | 丰田自动车株式会社 | Nox净化催化剂及其制备方法 |
US9132419B2 (en) | 2011-07-07 | 2015-09-15 | Toyota Jidosha Kabushiki Kaisha | NOx purification catalyst and method of producing the same |
CN103534024B (zh) * | 2011-07-07 | 2016-03-30 | 丰田自动车株式会社 | Nox净化催化剂及其制备方法 |
CN109046380A (zh) * | 2018-09-03 | 2018-12-21 | 厦门大学 | 一种甲烷化催化剂及其制备方法和应用 |
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