CN111185179A - 一种甲烷裂解催化剂及其制备方法 - Google Patents
一种甲烷裂解催化剂及其制备方法 Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000005336 cracking Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000006104 solid solution Substances 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 17
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 nickel-copper-aluminum Chemical compound 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 239000011780 sodium chloride Substances 0.000 claims abstract description 4
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 239000012752 auxiliary agent Substances 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
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- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 14
- PTXYJEHHENKNLZ-UHFFFAOYSA-N [O-2].[Al+3].[Cu]=O.[Ni]=O.[O-2].[O-2].[Al+3] Chemical compound [O-2].[Al+3].[Cu]=O.[Ni]=O.[O-2].[O-2].[Al+3] PTXYJEHHENKNLZ-UHFFFAOYSA-N 0.000 claims description 8
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 claims description 2
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- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
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- 239000012018 catalyst precursor Substances 0.000 abstract description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 abstract description 2
- 235000017491 Bambusa tulda Nutrition 0.000 abstract description 2
- 241001330002 Bambuseae Species 0.000 abstract description 2
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- 239000011425 bamboo Substances 0.000 abstract description 2
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- LDSIKPHVUGHOOI-UHFFFAOYSA-N copper;oxonickel Chemical compound [Ni].[Cu]=O LDSIKPHVUGHOOI-UHFFFAOYSA-N 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 17
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- 230000000052 comparative effect Effects 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- 239000012716 precipitator Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
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- 238000001228 spectrum Methods 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- 229910018054 Ni-Cu Inorganic materials 0.000 description 3
- 229910018481 Ni—Cu Inorganic materials 0.000 description 3
- 230000004913 activation Effects 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
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- 239000003345 natural gas Substances 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- ZPCFDBGVDLCXSO-UHFFFAOYSA-N aluminum nickel(2+) pentanitrate Chemical compound [N+](=O)([O-])[O-].[Ni+2].[Al+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] ZPCFDBGVDLCXSO-UHFFFAOYSA-N 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
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- 238000002309 gasification Methods 0.000 description 1
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- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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Abstract
本发明公开了一种甲烷裂解催化剂及其制备方法,属于甲烷裂解催化剂制备技术领域。本发明催化剂以镍铜合金纳米粒子为活性相、氧化铝为结构助剂,首先采用共沉淀法合成镍铜铝层状复合氢氧化物作为催化剂前驱体,经500℃焙烧分解形成岩盐型氧化镍‑氧化铜‑氧化铝固溶体,然后经800℃氢气还原处理原位生成高分散镍铜合金纳米粒子。本发明催化剂的镍铜合金平均晶粒尺寸为9~10 nm,具有组成均匀和组成可调的特点,对高温甲烷裂解反应表现出良好的催化性能,反应温度650℃时的碳产率可达70 克每克催化剂,可获得竹节型结构的碳纳米管。
Description
技术领域
本发明属于甲烷裂解催化剂制备技术领域,具体涉及一种甲烷裂解催化剂及其制备方法。
技术背景
氢气是一种优质清洁燃料,可通过各种方式转化为电能和其他低污染的能源形式,不会产生环境问题。由于氢气在自然界的含量极低,工业上大规模制氢主要通过煤气化、石脑油水蒸汽重整、部分氧化或天然气水蒸气重整、自热重整或醇水蒸气重整等途径。与其他化石燃料相比,天然气是生产氢气最好的原料,其主要成分是甲烷,氢碳比含量最高。甲烷水蒸汽重整是目前世界上规模最大、最经济的制氢技术,约占世界氢气产量的50%。然而,该过程会产生大量CO、CO2副产物。CO易使燃料电池Pt电极中毒失活,而CO2是主要的温室气体之一。甲烷催化裂解是制取纯氢的一种简单、有效的方法,不仅没有CO x 副产物,而且生成的碳如碳纳米管(CNTs)、碳纳米纤维(CNFs)是一种良好的纳米材料,具有优异的光电性能、机械强度和表面积高等特点,有广泛的应用前景。
CH4分子具有高度稳定的四面体结构,C–H键键能高达434kJ/mol。因此,C–H键断裂需要很高的活化能,是甲烷裂解最为关键的一步。为降低反应活化能,使用催化剂是最有效的方法。大量研究表明,第VIII族过渡金属如Ni、Co、Fe对甲烷分解具有较高的活性。Ni催化剂和Co催化剂在500~800℃温度范围内对甲烷裂解反应就有足够的活性,而Fe催化剂的活化温度一般在800℃以上。相同反应条件下,Ni催化剂比Co催化剂具有更高的活性和稳定性。Ni催化剂在较低温度就具有活性,其活性组分单位质量氢气的产率比较高。甲烷裂解是一个吸热反应,升高反应温度有利于提高甲烷裂解速率,但是Ni催化剂在高温条件下很容易失活。因此,必须研发一种具有良好高温催化性能的甲烷裂解催化剂。
发明内容
本发明的目的在于针对现有技术不足,提供一种甲烷裂解催化剂及其制备方法。本发明采用层状复合氢氧化物作为催化剂前驱体,经过焙烧和还原处理,制备高分散、组成均匀的镍铜合金甲烷裂解催化剂。
为实现上述目的,本发明采用如下技术方案:
采用共沉淀法合成以镍、铜、铝金属阳离子的氢氧化物为主体层板、以碳酸根离子为插层的层状复合氢氧化物前驱体,经焙烧分解形成岩盐型氧化镍-氧化铜-氧化铝固溶体,再经氢气程序升温还原得到镍铜合金纳米粒子,所述催化剂中摩尔比(Ni+Cu):Al = 3:1、Ni:Cu = 90:10~70:30。
上述镍铜合金甲烷裂解催化剂的制备方法,其具体步骤如下:
a、镍铜铝层状复合氢氧化物的合成:采用共沉淀法合成镍铜铝层状复合氢氧化物,在转速800转/分钟搅拌下,将100ml Ni(NO3)2·6H2O、Cu(NO3)2·3H2O、Al(NO3)3·9H2O混合溶液用滴液漏斗以30滴/分钟的速度逐滴加入到Na2CO3溶液,同时将沉淀剂NaOH溶液以35滴/分钟的速度缓慢滴入Na2CO3溶液;整个沉淀过程在室温下进行,维持pH=10±0.5;滴加完毕后继续搅拌1 h,然后静置24h,过滤并用去离子水洗涤至 pH=7±0.2,于100℃烘干12h,得到层状复合氢氧化物驱体;
b、焙烧和还原处理:将a步骤所得层状复合氢氧化物前驱体置于马弗炉,于空气气氛500℃焙烧得到混合氧化物;将混合氧化物在H2气氛中程序升温至800℃进行还原处理,得到镍铜合金催化剂。
进一步,所述a步骤中Na2CO3溶液的Na2CO3摩尔数为Al(NO3)3·9H2O摩尔数的1:2。
进一步,所述a步骤中沉淀剂NaOH溶液的浓度为2 mol/L,NaOH摩尔用量与Ni(NO3)2·6H2O、Cu(NO3)2·3H2O、Al(NO3)3·9H2O摩尔用量总和的比值为2:1。
进一步,所述b步骤中的焙烧处理条件为:焙烧气氛为空气,焙烧温度500 ℃,升温速率3 ℃/min,在500℃保持5 h。
进一步,所述b步骤中的还原处理条件为:H2流速30 mL/min,还原温度800 ℃,升温速率10 ℃/min,在800 ℃保持30min。
本发明的有益效果在于:
(1)本发明采用镍铜铝层状复合氢氧化物作为催化剂前驱体,经由氧化镍-氧化铜-氧化铝固溶体,使得催化剂组分保持高度、均匀分散,避免发生团聚、不均匀等现象,有利于准确控制合金组成;
(2)本发明的镍铜合金平均晶粒尺寸为9~10 nm,分散度高,且每个合金粒子的组成相似,具有组成均匀和组成可调的特点;
(3)本发明的镍铜合金催化剂对高温甲烷裂解反应表现出良好的催化性能,可获得较高产率的碳纳米材料。
附图说明
图1为本发明实施例1催化剂的X射线粉末衍射谱图;
图2为本发明实施例2催化剂的X射线粉末衍射谱图;
图3为本发明实施例3催化剂的X射线粉末衍射谱图;
图4为本发明实施例3催化剂的扫描透射电镜X射线能谱分析结果;
图5为本发明实施例3催化剂的X射线能谱点分析谱图;
图6为本发明实施例3催化剂的X射线能谱线分析谱图;
图7为本发明实施例3催化剂催化甲烷裂解生成碳纳米材料的透射电镜图;
图8为本发明实施例1和对比例催化剂在600℃的甲烷裂解测试结果;
图9为本发明实施例1~3催化剂在650℃的甲烷裂解测试结果。
具体实施方式
以下结合具体实施例对本发明做进一步说明,但本发明不仅仅限于这些实施例。
实施例1:
称取20g NaOH固体,溶于250 mL去离子水,搅拌10 min,配成2 mol/L的NaOH水溶液。按摩尔比(Ni2++Cu2+):Al3+ = 75:25、Ni2+:Cu2+ = 90:10,分别称取7.8513g Ni(NO3)2·6H2O、0.7248g Cu(NO3)2·3H2O、3.7513g Al(NO3)3·9H2O溶于100 mL去离子水,搅拌10 min,使硝酸盐完全溶解,得到混合溶液。按Na2CO3摩尔量为Al(NO3)3·9H2O摩尔量的一半称取0.5300gNa2CO3,溶于100 mL去离子水,作为底液。将镍铜铝硝酸盐混合溶液用滴液漏斗以30滴/分钟的速度逐滴滴入含有Na2CO3溶液的烧杯中,并不断搅拌。同时用蠕动泵将沉淀剂NaOH溶液以35滴/分钟的速度缓慢滴入烧杯中,维持沉淀pH = 10 ± 0.5,滴加完毕后继续搅拌1 h,然后静置24 h,过滤并用去离子水洗涤至pH = 7 ± 0.2,接着在100 ℃干燥12 h,得到镍铜铝层状复合氢氧化物前驱体。将前驱体置于马弗炉,以3 ℃/min升至500 ℃焙烧5 h,得到氧化镍-氧化铜-氧化铝固溶体。将氧化物固溶体置于石英管,在30 mL/min H2气流中以10℃/min升至800 ℃并保持30 min,然后冷却至室温,得到镍铜合金催化剂。
用X射线粉末衍射对上述样品进行物相分析,如图1所示,位于2θ = 52.08º、60.87º、91.64º衍射峰对应于Ni-Cu合金的(111)、(200)、(220)晶面,通过谢乐公式计算合金平均晶粒尺寸为9.6 nm,通过布拉格法则计算合金组成为Cu/(Ni+Cu) = 9%(摩尔比),与催化剂本体组成基本一致。
实施例2:
称取20g NaOH固体,溶于250 mL去离子水,搅拌10 min,配成2 mol/L的NaOH水溶液。按摩尔比(Ni2++Cu2+):Al3+= 75:25、Ni2+:Cu2+ = 80:20,分别称取6.9790g Ni(NO3)2·6H2O、1.4496g Cu(NO3)2·3H2O、3.7513g Al(NO3)3·9H2O溶于100 mL去离子水,搅拌10 min,使硝酸盐完全溶解,得到混合溶液。按Na2CO3摩尔量为Al(NO3)3·9H2O摩尔量的一半称取0.5300gNa2CO3,溶于100 mL去离子水,作为底液。将镍铜铝硝酸盐混合溶液用滴液漏斗以30滴/分钟的速度逐滴滴入含有Na2CO3溶液的烧杯中,并不断搅拌。同时用蠕动泵将沉淀剂NaOH溶液以35滴/分钟的速度缓慢滴入烧杯中,维持沉淀pH = 10 ± 0.5,滴加完毕后继续搅拌1 h,然后静置24 h,过滤并用去离子水洗涤至pH = 7 ± 0.2,接着在100 ℃干燥12 h,得到镍铜铝层状复合氢氧化物前驱体。将前驱体置于马弗炉,以3 ℃/min升至500 ℃焙烧5 h,得到氧化镍-氧化铜-氧化铝固溶体。将氧化物固溶体置于石英管,在30 mL/min H2气流中以10℃/min升至800 ℃并保持30 min,然后冷却至室温,得到镍铜合金催化剂。
用X射线粉末衍射对上述样品进行物相分析,如图2所示,位于2θ = 51.95º、60.74º、91.37º衍射峰对应于Ni-Cu合金的(111)、(200)、(220)晶面,通过谢乐公式计算合金平均晶粒尺寸为9.5 nm,通过布拉格法则计算合金组成为Cu/(Ni+Cu) = 22%(摩尔比),与催化剂本体组成基本一致。
实施例3:
称取20g NaOH固体,溶于250 mL去离子水,搅拌10 min,配成2 mol/L的NaOH水溶液。按摩尔比(Ni2++Cu2+):Al3+ = 75:25、Ni2+:Cu2+ = 70:30,分别称取6.1066g Ni(NO3)2·6H2O、2.1744g Cu(NO3)2·3H2O、3.7513g Al(NO3)3·9H2O溶于100 mL去离子水,搅拌10 min,使硝酸盐完全溶解,得到混合溶液。按Na2CO3摩尔量为Al(NO3)3·9H2O摩尔量的一半称取0.5300gNa2CO3,溶于100 mL去离子水,作为底液。将镍铜铝硝酸盐混合溶液用滴液漏斗以30滴/分钟的速度逐滴滴入含有Na2CO3溶液的烧杯中,并不断搅拌。同时用蠕动泵将沉淀剂NaOH溶液以35滴/分钟的速度缓慢滴入烧杯中,维持沉淀pH = 10 ± 0.5,滴加完毕后继续搅拌1 h,然后静置24 h,过滤并用去离子水洗涤至pH = 7 ± 0.2,接着在100 ℃干燥12 h,得到镍铜铝层状复合氢氧化物前驱体。将前驱体置于马弗炉,以3 ℃/min升至500 ℃焙烧5 h,得到氧化镍-氧化铜-氧化铝固溶体。将氧化物固溶体置于石英管,在30 mL/min H2气流中以10℃/min升至800 ℃并保持30 min,然后冷却至室温,得到镍铜合金催化剂。
用X射线粉末衍射对上述催化剂进行物相分析,如图3所示,位于2θ = 51.78º、60.54º、91.03º衍射峰对应于Ni-Cu合金的(111)、(200)、(220)晶面,通过谢乐公式计算合金平均晶粒尺寸为9.8nm,通过布拉格法则计算合金组成为Ni0:Cu0= 68:32(摩尔比),与催化剂本体组成基本一致。
用扫描透射电镜X射线能谱分析合金组成,如图4所示,1~3号合金粒子的组成分别为Ni0:Cu0 = 71:29、72:28、73:27,说明合金组成均匀。
1号合金粒子的X射线能谱点分析结果如图5所示,根据峰面积计算出合金组成Ni0:Cu0 = 71:29。
用X射线能谱线分析合金元素分布,如图6所示,Ni和Cu均匀分布在粒子表面和体相,说明形成了均匀合金。
用透射电镜分析上述催化剂在650℃甲烷裂解反应后生成的碳的形貌,如图7所示,可得到竹节型结构的碳纳米管。
对比例1:
取20g NaOH固体,溶于250mL去离子水中,搅拌10min,配成2 mol/L的NaOH水溶液。按Ni2+/Al3+摩尔比为3,分别称取8.7237g Ni(NO3)2·6H2O 和3.7513g Al(NO3)3·9H2O溶于100 mL去离子水,搅拌10 min,使硝酸盐完全溶解,得到混合溶液。按Na2CO3摩尔量为Al(NO3)3·9H2O摩尔量的一半称取0.5300g Na2CO3,溶于100 mL去离子水,作为底液。将镍铝硝酸盐混合溶液用滴液漏斗以30滴/分钟的速度逐滴滴入含有Na2CO3溶液的烧杯中,并不断搅拌。同时用蠕动泵将沉淀剂NaOH溶液以35滴/分钟的速度缓慢滴入烧杯中,维持沉淀pH =10 ± 0.5,滴加完毕后继续搅拌1 h,然后静置24 h,过滤并用去离子水洗涤至pH = 7 ±0.2,接着在100 ℃干燥12 h,得到镍铝层状复合氢氧化物前驱体。将前驱体置于马弗炉,以3 ℃/min升至500 ℃焙烧5 h,得到氧化镍-氧化铝固溶体。将氧化物固溶体置于石英管,在30 mL/min H2气流中以10 ℃/min升至800 ℃并保持30 min,然后冷却至室温,得到镍催化剂。
对比例2:
称取20g NaOH固体,溶于250 mL去离子水,搅拌10 min,配成2 mol/L的NaOH水溶液。按摩尔比(Ni2++Co2+):Al3+ = 75:25、Ni2+:Co2+ = 90:10,分别称取7.8513g Ni(NO3)2·6H2O、0.8731g Co(NO3)2·6H2O、3.7513g Al(NO3)3·9H2O溶于100 mL去离子水,搅拌10 min,使硝酸盐完全溶解,得到混合溶液。按Na2CO3摩尔量为Al(NO3)3·9H2O摩尔量的一半称取0.5300gNa2CO3,溶于100 mL去离子水,作为底液。将镍钴铝硝酸盐混合溶液用滴液漏斗以30滴/分钟的速度逐滴滴入含有Na2CO3溶液的烧杯中,并不断搅拌。同时用蠕动泵将沉淀剂NaOH溶液以35滴/分钟的速度缓慢滴入烧杯中,维持沉淀pH = 10 ± 0.5,滴加完毕后继续搅拌1 h,然后静置24 h,过滤并用去离子水洗涤至pH = 7 ± 0.2,接着在100 ℃干燥12 h,得到镍钴铝层状复合氢氧化物前驱体。将前驱体置于马弗炉,以3 ℃/min升至500 ℃焙烧5 h,得到氧化镍-氧化钴-氧化铝固溶体。将氧化物固溶体置于石英管,在30 mL/min H2气流中以10℃/min升至800 ℃并保持30 min,然后冷却至室温,得到镍钴合金催化剂。
对比例3:
称取20g NaOH固体,溶于250 mL去离子水,搅拌10 min,配成2 mol/L的NaOH水溶液。按摩尔比Ni2+/(Fe3++Al3+) = 75:25、Ni2+:Fe3+ = 90:10,分别称取7.8513g Ni(NO3)2·6H2O、1.2120g Fe(NO3)3·9H2O、3.7513g Al(NO3)3·9H2O溶于100 mL去离子水,搅拌10 min,使硝酸盐完全溶解,得到混合溶液。按Na2CO3摩尔量为Al(NO3)3·9H2O摩尔量的一半称取0.5300gNa2CO3,溶于100 mL去离子水,作为底液。将镍钴铝硝酸盐混合溶液用滴液漏斗以30滴/分钟的速度逐滴滴入含有Na2CO3溶液的烧杯中,并不断搅拌。同时用蠕动泵将沉淀剂NaOH溶液以35滴/分钟的速度缓慢滴入烧杯中,维持沉淀pH = 10 ± 0.5,滴加完毕后继续搅拌1 h,然后静置24 h,过滤并用去离子水洗涤至pH = 7 ± 0.2,接着在100 ℃干燥12 h,得到镍铁铝层状复合氢氧化物前驱体。将前驱体置于马弗炉,以3 ℃/min升至500 ℃焙烧5 h,得到氧化镍-氧化铁-氧化铝固溶体。将氧化物固溶体置于石英管,在30 mL/min H2气流中以10℃/min升至800 ℃并保持30 min,然后冷却至室温,得到镍铁合金催化剂。
上述催化剂的甲烷裂解反应性能评价在法国Setram公司Setsys Evolution同步热分析仪进行。首先将50 mg催化剂在固定床反应器于800℃用H2还原30min,之后在25 mL/min N2气流下降至室温,然后称取1 mg还原催化剂置于氧化铝坩埚,在5mL/minN2气流下升温至600℃或650℃,之后通入5mL/min CH4,反应结果如图8、9所示。图8是实施例1催化剂和对比例1~3催化剂在600℃的反应结果。可以看到,催化剂的催化稳定性和碳产率为实施例1>> 对比例3 > 对比例2 > 对比例1(碳产率分别为66.3、24.1、20.0、11.5克碳/克催化剂),即镍铜合金 >> 镍铁合金 > 镍钴合金 > 镍,说明铜的添加效果显著优于铁和钴。图9是实施例1~3催化剂和对比例1催化剂在650℃的反应结果。可以看到,对比例1催化剂很快发生失活,碳产率仅1.4克碳/克催化剂,而本发明实施例1~3催化剂显示了很高的催化稳定性,碳产率分别达到了23.2、43.5、70.0克碳/克催化剂,是对比例1催化剂的16、31、50倍。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (8)
1.一种甲烷裂解催化剂,其特征在于:所述催化剂是以镍铜合金纳米粒子为活性相、Al2O3为结构助剂,其中(Ni+Cu):Al摩尔比为3:1,Ni:Cu摩尔比为90:10~70:30。
2.一种如权利要求1所述的甲烷裂解催化剂的制备方法,其特征在于:采用共沉淀法合成镍铜铝层状复合氢氧化物前驱体,经焙烧分解形成岩盐型氧化镍-氧化铜-氧化铝固溶体,再经氢气程序升温还原生成镍铜合金纳米粒子,即得到甲烷裂解催化剂。
3.根据权利要求2所述的制备方法,其特征在于:具体包括以下步骤:
a、镍铜铝层状复合氢氧化物的合成:在转速为800转/分钟搅拌下,将Ni(NO3)2·6H2O、Cu(NO3)2·3H2O、Al(NO3)3·9H2O混合溶液用滴液漏斗以30滴/分钟的速度逐滴加入到Na2CO3溶液,同时将沉淀剂NaOH溶液以30滴/分钟的速度缓慢滴入Na2CO3溶液;整个沉淀过程在室温下进行,维持pH = 10 ± 0.5;滴加完毕后继续搅拌1 h,然后静置24 h,过滤并用去离子水洗涤至 pH = 7 ± 0.2,于100 ℃烘干12 h,得到以镍铜铝氢氧化物为主体层板、碳酸根离子为插层的层状复合氢氧化物;
b、焙烧和氢气程序升温还原:将a步骤所得层状复合氢氧化物置于马弗炉,经过焙烧分解生成氧化镍-氧化铜-氧化铝固溶体;将氧化物固溶体还原,得到高分散、组成均匀的镍铜合金纳米粒子,即得到甲烷裂解催化剂。
4.根据权利要求3所述的制备方法,其特征在于:所述a步骤中(Ni2++Cu2+):Al3+摩尔比为3:1,Ni2+:Cu2+摩尔比为90:10~70:30。
5.根据权利要求3所述的制备方法,其特征在于:所述a步骤中Na2CO3溶液的Na2CO3与Al(NO3)3·9H2O的摩尔比为1:2。
6.根据权利要求3所述的制备方法,其特征在于:所述a步骤中NaOH溶液浓度为2 mol/L,NaOH摩尔用量与Ni(NO3)2·6H2O、Cu(NO3)2·6H2O、Al(NO3)3·9H2O摩尔用量总和的比值为2:1。
7.根据权利要求3所述的制备方法,其特征在于:所述b步骤的焙烧条件为:焙烧气氛为空气,焙烧温度500 ℃,升温速率3 ℃/min,在500℃保持5 h。
8.根据权利要求3所述的制备方法,其特征在于:所述b步骤的还原条件为:H2流速30mL/min,还原温度从室温到800 ℃,升温速率10 ℃/min,在800℃保持30 min。
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