CN116651460A - 一种低负载量Ni–Mo基催化剂的制备方法与应用 - Google Patents
一种低负载量Ni–Mo基催化剂的制备方法与应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 229910003296 Ni-Mo Inorganic materials 0.000 title claims abstract description 22
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012266 salt solution Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 13
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims abstract description 12
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims abstract description 12
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 43
- 238000011068 loading method Methods 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 35
- 230000000694 effects Effects 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/16—Reducing
- 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
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- 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
一种低负载量Ni–Mo基催化剂的制备方法及应用,该方法包括以下步骤:将六水合硝酸镍和四水合钼酸铵分别溶于去离子水中得到混合盐溶液,再将活性γ‑氧化铝载体浸渍到混合盐溶液中搅拌,调节pH值至8~10,继续搅拌并加热蒸干溶剂得到浸渍有Ni和Mo的催化剂前驱体;将催化剂前驱体干燥后煅烧得到负载镍氧化物和钼氧化物的未还原催化剂;将未还原催化剂置于氧化铝瓷舟中后,放入管式炉,在还原气氛下还原得到低负载量Ni–Mo基催化剂。该制备工艺简单,易于放大制备和工业生产;所制备得到的Ni‑Mo基催化剂耐高温、催化活性高、抗积碳性能良好,将其应用于POM反应或低浓度瓦斯部分氧化中,可提高CH4转化率和CO选择性。
Description
技术领域
本发明属于催化剂制备技术领域,具体涉及一种低负载量Ni–Mo基催化剂的制备方法与应用。
背景技术
矿井瓦斯是一种非常重要的非常规天然气,与常规天然气的热值相近,被认为是一种潜在的清洁能源。在采煤过程中,由于矿井瓦斯不可避免地与空气混合,导致产生主要由CH4、O2和N2组成的混合气体,根据CH4浓度的不同,矿井瓦斯可分为高浓度瓦斯(CH4浓度大于30%)和低浓度瓦斯(CH4浓度小于30%)两类。高浓度瓦斯可直接用作家庭和工业燃料,也可用于发电。但是,低浓度瓦斯直接利用困难,需要经过除氧、脱硫、脱氮等复杂的净化工艺。由于热值低、成本高、利用效率低以及一些技术限制,低浓度瓦斯的利用受限,目前低浓度瓦斯的主要利用方式有瓦斯提纯、内燃机燃烧发电、催化燃烧等,利用效率较低。因此,目前我国煤矿矿井开采过程中仍有大量的低浓度瓦斯由于没有合适的利用方式而被直接排放到大气中,造成巨大的能源浪费。由于甲烷的温室效应是CO2的25倍,其对大气环境的影响不容忽视,因此开发高效、低污染地利用低浓度瓦斯的方法是十分必要的。
合成气(H2和CO的混合气)是费托合成生产高附加值化学品的重要原料,可以通过甲烷的重整进行生产。目前生产合成气的一个重要的工业途径是甲烷蒸汽重整(SMR),这是一种最经济的大规模生产工艺。但是,甲烷蒸汽重整是一个能源密集型、投资成本高的反应,在反应过程中为了避免碳沉积,需要引入H2O/CH4摩尔比略高于化学计量值的过热蒸汽。甲烷部分氧化重整(POM)反应(公式1)是一个有吸引力的替代方案,因为它是一个微放热反应,避免了对大量过热蒸汽的需求,并且反应过程更快速。事实上,由于低浓度瓦斯中的甲烷浓度低,且含有一定浓度的氧气,这种特殊的气体组成使得低浓度瓦斯非常适合通过部分氧化重整的方式生产合成气。
CH4+1/2O2→CO+2H2ΔH 298=-36 kJ/mol (1)
POM反应可将煤矿开采过程中的低浓度瓦斯废气(CH4浓度小于30%)转化为增值合成气(CO和H2),是实现碳中和的重要途径之一。设计高活性、高稳定性和抗积碳催化剂是实现高效POM反应的一大挑战。目前,低浓度瓦斯部分氧化的催化剂主要有Ru、Rh、Pt、Ir贵金属催化剂和Ni、Co、Cu过渡金属催化剂。虽然贵金属催化剂有良好的活性,但昂贵的价格限制了它的工业应用,且贵金属在耐高温、抗积碳、耐硫中毒等方面具有一定的缺陷。非贵金属催化剂中镍催化剂的活性高、成本低,是低浓度瓦斯部分氧化反应的良好选择,但其仍然容易受到高温和积碳的影响。含镍催化剂的活性也与镍金属颗粒大小、载体结构的热稳定性、第二金属元素和助剂的选择添加等因素相关。因此,筛选出活性高、抗积碳能力强、同时耐硫中毒的非贵金属催化剂对高效利用低浓度瓦斯具有非常重要的意义。
发明内容
本发明的目的在于提供一种低负载量Ni–Mo基催化剂的制备方法与应用,该制备工艺简单,易于放大制备和工业生产;所制备得到的Ni-Mo基催化剂耐高温、催化活性高、抗积碳性能良好,将其应用于POM反应或低浓度瓦斯部分氧化中,可提高CH4转化率和CO选择性。
为实现上述目的,本发明提供一种低负载量Ni–Mo基催化剂的制备方法,包括以下步骤:
(1)将六水合硝酸镍和四水合钼酸铵分别溶于去离子水中得到混合盐溶液,再将活性γ-氧化铝载体浸渍到混合盐溶液中搅拌,调节pH值至8~10,继续搅拌并加热蒸干溶剂得到浸渍有Ni和Mo的催化剂前驱体;
(2)将步骤(1)制得的浸渍有Ni和Mo的催化剂前驱体干燥后放入马弗炉中煅烧得到负载镍氧化物和钼氧化物的未还原催化剂;
(3)将步骤(2)制得的未还原催化剂置于氧化铝瓷舟中后,放入管式炉,在还原气氛下还原,由室温升温至还原温度后保温一段时间,最后自然降温得到低负载量Ni–Mo基催化剂。
进一步的,步骤(1)中,活性γ-氧化铝载体通过氧化镧修饰改性。
优选的,步骤(1)中,采用一次浸渍或多次浸渍或等体积浸渍来将活性γ-氧化铝载体浸渍到混合盐溶液中;
当采用一次浸渍时,所述六水合硝酸镍和四水合钼酸铵分别在混合盐溶液中的浓度为199-248g/L、19-92g/L,每10mL混合盐溶液中加入10g活性γ-氧化铝载体;
当采用多次浸渍时,所述六水合硝酸镍和四水合钼酸铵分别在混合盐溶液中的浓度为199-248g/L、19-92g/L,每10mL混合盐溶液中加入10g活性γ-氧化铝载体;
当采用等体积浸渍时,所述六水合硝酸镍和四水合钼酸铵分别在混合盐溶液中的浓度为398-496g/L、38-184g/L,每5mL混合盐溶液中加入10g活性γ-氧化铝载体。
优选的,步骤(2)中,所述浸渍有Ni和Mo的催化剂前驱体在80℃~120℃下干燥4-12h。
优选的,步骤(2)中,所述煅烧温度为450~800℃,所述保温时间为4~5h。
优选的,步骤(3)中,所述还原气氛为氢气或氢气-氮气,所述管式炉的升温速率为5℃/min,所述还原温度为450~650℃,还原保温时间为2~4h。
优选的,步骤(3)中,所述低负载量Ni–Mo基催化剂中,Ni的负载量低于5wt%,Mo的负载量低于5wt%。
为实现上述目的,本发明还提供了上述制备方法得到的低负载量Ni-Mo基催化剂在POM反应或低浓度瓦斯部分氧化中的应用。
本发明根据催化剂在低浓度瓦斯部分氧化(POM)反应中的使用条件,采用优化后的浸渍法制备了一种催化活性高、抗积碳性能良好、耐高温的低负载量Ni-Mo基催化剂。本发明采用活性高的金属镍颗粒作为甲烷分解的活性中心,以活性氧化铝为载体提供大比表面积和一定的机械强度,并添加三氧化钼促进Ni金属颗粒高度分散、抑制Ni氧化和抗积碳。该制备工艺简单,易于放大制备和工业生产。
本发明利用Mo对Ni基催化剂在甲烷部分氧化(POM)反应过程中抗积碳性能的促进作用,实现催化剂在750℃以上的CH4转化率达到99%,CO选择性达到96%以上,800℃时CO选择性达到99%,产生的合成气氢碳比维持在较理想的2.1左右,在800℃下稳定运行100小时后无衰减。通过Mo改性提供了MoOx和MoOxCy之间的氧化还原循环动态变化,促进了POM反应过程中的高效脱碳。Mo的引入使Ni0的催化活性提高并始终保持在较高的水平。由Mo修饰的Ni/Al2O3驱动产生的甲酸盐等中间体可以更有效地抑制POM反应过程中的结焦,同时提高了传统Ni催化剂的活性和抗结焦性。
附图说明
图1为实施例一所制备得到的催化剂C1的SEM图。
具体实施方式
以下结合实施例对本发明作进一步详细说明。
实施例一
一种低负载量Ni–Mo基催化剂的制备方法,包括以下步骤:
(1)采用一次浸渍法,配制六水合硝酸镍浓度为248g/L、四水合钼酸铵浓度为92g/L的混合盐溶液10mL,再将10g活性γ-氧化铝载体浸渍到10mL混合盐溶液中加热至95℃搅拌,悬浊液蒸发至湿润状态时,加入少量氨水调节pH值至8~10,继续搅拌蒸干溶剂得到浸渍有Ni和Mo的催化剂前驱体;
(2)将浸渍有Ni和Mo的催化剂前驱体在120℃干燥12h,然后放入马弗炉中550℃煅烧5h,得到负载镍氧化物和钼氧化物的未还原的催化剂。
(3)将0.5g未还原催化剂置于氧化铝瓷舟中后,放入管式炉,在氢气气氛下以5℃/min的升温速率由室温升温至650℃保温2h,最后自然降温得到还原后的负载5wt%Ni和5wt%Mo的低负载量Ni–Mo基催化剂C1。
从图1中可以看出,本实施例所制备得到的催化剂C1表面颗粒尺寸分布较分散,表面颗粒呈微米级至纳米级尺寸的块状,以较无序的状态堆叠在一起,催化剂表面具有一定的微观孔隙结构,可以给金属活性位点提供一定的支撑表面,并有较大的孔隙使气体在活性位点充分吸附和快速脱附。
实施例二
一种低负载量Ni–Mo基催化剂的制备方法,包括以下步骤:
(1)采用多次浸渍法,配制六水合硝酸镍浓度为248g/L、四水合钼酸铵浓度为55g/L的混合盐溶液20mL,将10g改性后的催化剂载体浸渍到混合盐溶液中,静止10min后捞出载体,记录载体吸收混合盐溶液的体积,将浸渍后的催化剂120℃干燥2h以上,然后重复浸渍步骤至载体吸收混合盐溶液总体积为10mL;
所述改性后的催化剂载体为活性γ-氧化铝载体通过氧化镧修饰改性得到,具体改性过程为:将0.66g六水合硝酸镧溶于10mL去离子水中,将10g干燥后的γ-氧化铝载体浸渍到溶液中,然后在95℃的条件下加热混合物至溶剂蒸干,将所得固体在550℃下煅烧5h得到氧化镧改性后的催化剂载体;
(2)将浸渍有Ni和Mo的催化剂前驱体在120℃干燥12h,然后放入马弗炉中550℃煅烧5h,得到负载镍氧化物和钼氧化物的未还原的催化剂;
(3)将0.5g未还原催化剂置于氧化铝瓷舟中后,放入管式炉,在氢气气氛下以5℃/min的升温速率由室温升温至650℃保温2h,最后自然降温得到还原后的负载5wt%Ni和3wt%Mo的催化剂C2。
实施例三
一种低负载量Ni–Mo基催化剂的制备方法,包括以下步骤:
(1)采用等体积浸渍法,配制六水合硝酸镍浓度为398g/L、四水合钼酸铵浓度为38g/L的混合盐溶液5mL,再将混合盐溶液滴至装有10g活性γ-氧化铝载体的烧杯中至催化剂整体呈湿润状态,此时搅拌并加入少量氨水调节pH值至8~10,继续搅拌并加热至50℃蒸干溶剂得到浸渍有Ni和Mo的催化剂前驱体;
(2)将浸渍有Ni和Mo的催化剂前驱体在120℃干燥12h,然后放入马弗炉中550℃煅烧5h,得到负载镍氧化物和钼氧化物的未还原的催化剂;
(3)将0.5g未还原催化剂置于氧化铝瓷舟中后,放入管式炉,在氢气气氛下以5℃/min的升温速率由室温升温至550℃保温2小时,最后自然降温得到还原后的负载4wt%Ni和1wt%Mo的催化剂C3。
对比例1:以活性γ-氧化铝为载体,制备Ni负载量为5wt%的镍基催化剂,制备方法与实施例1相同。
对比例2:选用公开号为CN105642288B的专利中效果最好的实施例10,即以氢型ZSM-5负载20wt%Ni、5wt%Mg的催化剂。
对比例3:是按照文献(PANTALEO G,LA PAROLA V,DEGANELLO F,et al.Synthesisand support composition effects on CH4 partial oxidation over Ni-CeLa oxides[J].Applied Catalysis B-Environmental,2015,164:135-43.)所述方法制备的催化剂Ni-CeLa(WI)。
对比例4:是按照文献(CHEEPHAT C,DAORATTANACHAI P,DEVAHASTIN S,etal.Partial oxidation of methane over monometallic and bimetallic Ni-,Rh-,Re-based catalysts:Effects of Re addition,co-fed reactants and catalyst support[J].APPLIED CATALYSIS A-GENERAL,2018,563:1-8.)所述方法制备的贵金属Rh负载量为1wt%的Pt-Al2O3催化剂。
催化剂性能评价在常压连续流动固定催化反应床上进行,将0.5g催化剂装填在内径8mm的石英管内,反应气体组成为8%甲烷、4%氧气、88%氮气,反应气体过水,过水后气体含水量约为3%。反应前,反应炉在氮气气氛下升温至650℃,然后切换为反应气,由650℃分别升温至700℃、750℃、800℃、850℃,在每个温度点保温20min,温度稳定15min后色谱开始测试反应气出口处尾气中的甲烷、CO、CO2、H2的浓度,由尾气中甲烷、CO、CO2、H2的浓度计算甲烷转化率、CO选择性和产物中H2和CO的摩尔浓度比值,计算公式如下:
甲烷转化率=(反应器出口气体中CO2摩尔分数+反应器出口气体中CO摩尔分数)/(反应器出口气体中甲烷摩尔分数+反应器出口气体中CO2摩尔分数+反应器出口气体中CO摩尔分数)×100%;
CO选择性=反应器出口气体中CO摩尔分数/(反应器出口气体中CO2摩尔分数+反应器出口气体中CO摩尔分数)×100%;
n(H2)/n(CO)=反应器出口气体中H2摩尔分数/反应器出口气体中CO摩尔分数。实施例一至三和对比例一至四分别所制备得到的催化剂的评价结果见下表1。
表1催化剂在800℃的反应性能
从上表1中可以看出,本发明所制备得到的催化剂具有较高的CH4转化率、高CO选择性和良好的高温稳定性。
Claims (8)
1.一种低负载量Ni–Mo基催化剂的制备方法,其特征在于,包括以下步骤:
(1)将六水合硝酸镍和四水合钼酸铵分别溶于去离子水中得到混合盐溶液,再将活性γ-氧化铝载体浸渍到混合盐溶液中搅拌,调节pH值至8~10,继续搅拌并加热蒸干溶剂得到浸渍有Ni和Mo的催化剂前驱体;
(2)将步骤(1)制得的浸渍有Ni和Mo的催化剂前驱体干燥后放入马弗炉中煅烧得到负载镍氧化物和钼氧化物的未还原催化剂;
(3)将步骤(2)制得的未还原催化剂置于氧化铝瓷舟中后,放入管式炉,在还原气氛下还原,由室温升温至还原温度后保温一段时间,最后自然降温得到低负载量Ni–Mo基催化剂。
2.根据权利要求1所述的一种低负载量Ni–Mo基催化剂的制备方法,其特征在于,步骤(1)中,活性γ-氧化铝载体通过氧化镧修饰改性。
3.根据权利要求1或2所述的一种低负载量Ni–Mo基催化剂的制备方法,其特征在于,步骤(1)中,采用一次浸渍或多次浸渍或等体积浸渍来将活性γ-氧化铝载体浸渍到混合盐溶液中;
当采用一次浸渍时,所述六水合硝酸镍和四水合钼酸铵分别在混合盐溶液中的浓度为199-248g/L、19-92g/L,每10mL混合盐溶液中加入10g活性γ-氧化铝载体;
当采用多次浸渍时,所述六水合硝酸镍和四水合钼酸铵分别在混合盐溶液中的浓度为199-248g/L、19-92g/L,每10mL混合盐溶液中加入10g活性γ-氧化铝载体;
当采用等体积浸渍时,所述六水合硝酸镍和四水合钼酸铵分别在混合盐溶液中的浓度为398-496g/L、38-184g/L,每5mL混合盐溶液中加入10g活性γ-氧化铝载体。
4.根据权利要求1或2所述的一种低负载量Ni–Mo基催化剂的制备方法,其特征在于,步骤(2)中,所述浸渍有Ni和Mo的催化剂前驱体在80℃~120℃下干燥4-12h。
5.根据权利要求1或2所述的一种低负载量Ni–Mo基催化剂的制备方法,其特征在于,步骤(2)中,所述煅烧温度为450~800℃,所述保温时间为4~5h。
6.根据权利要求1或2所述的一种低负载量Ni–Mo基催化剂的制备方法,其特征在于,步骤(3)中,所述还原气氛为氢气或氢气-氮气,所述管式炉的升温速率为5℃/min,所述还原温度为450~650℃,还原保温时间为2~4h。
7.根据权利要求1或2所述的一种低负载量Ni–Mo基催化剂的制备方法,其特征在于,步骤(3)中,所述低负载量Ni–Mo基催化剂中,Ni的负载量低于5wt%,Mo的负载量低于5wt%。
8.根据权利要求1~7任意一项所述的低负载量Ni-Mo基催化剂的制备方法得到的低负载量Ni-Mo基催化剂在POM反应或低浓度瓦斯部分氧化中的应用。
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