CN116273053A - 一种整装铁基氨分解催化剂及其制备方法和应用 - Google Patents
一种整装铁基氨分解催化剂及其制备方法和应用 Download PDFInfo
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- CN116273053A CN116273053A CN202310296973.3A CN202310296973A CN116273053A CN 116273053 A CN116273053 A CN 116273053A CN 202310296973 A CN202310296973 A CN 202310296973A CN 116273053 A CN116273053 A CN 116273053A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 179
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 86
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 77
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 40
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- 239000006260 foam Substances 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
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- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000004323 potassium nitrate Substances 0.000 claims description 8
- 235000010333 potassium nitrate Nutrition 0.000 claims description 8
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 8
- 238000007306 functionalization reaction Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 238000004140 cleaning Methods 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
- 238000001816 cooling Methods 0.000 claims description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 2
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 claims description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 2
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims description 2
- JHOPGIQVBWUSNH-UHFFFAOYSA-N iron tungsten Chemical compound [Fe].[Fe].[W] JHOPGIQVBWUSNH-UHFFFAOYSA-N 0.000 claims description 2
- -1 iron-chromium-aluminum Chemical compound 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
- 239000002243 precursor Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000012546 transfer Methods 0.000 description 11
- 238000005470 impregnation Methods 0.000 description 9
- 239000006261 foam material Substances 0.000 description 8
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 3
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- 238000002156 mixing Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 2
- 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 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 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 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
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- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 1
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- 150000002505 iron Chemical class 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
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- 235000019355 sepiolite Nutrition 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
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Abstract
本发明公开了一种整装铁基氨分解催化剂及其制备方法和应用,制备得到的整装铁基氨分解催化剂,是先在骨架基体上生长一层非水溶性铁金属盐晶体层,经热分解和还原处理,制得未经改性的铁基催化剂,或在热分解和还原处理前先通过等体积浸渍法引入助剂改性,制得在金属载体上负载助剂改性的铁基催化剂。相较于其他方法制备的整体式催化剂,本发明提供的整装铁基氨分解催化剂具有制备过程可控性强、易于规模化生产和活性组分负载量高且结构稳定不易脱落等优势。这些特性赋予本发明的整装铁基氨分解催化剂在长时间运行中保持优异的稳定性。
Description
技术领域
本发明涉及氨分解催化剂的制备技术领域,具体涉及一种整装铁基氨分解催化剂及其制备方法和应用。
背景技术
燃烧化石燃料导致的环境污染和日益严重的能源危机激发了人们对清洁可持续能源的渴求。在所有替代能源中,氢能以优异的能量密度和环境友好性被公认为最有前景的“未来能源”。随着燃料电池技术的发展,进一步促使氢能成为清洁能源中的热点。然而,氢气输送成本高且安全系数低等因素严重阻碍了氢能的应用。相比之下,氨气液化条件温和,易于存储和运输,并且还具有安全性高(爆炸阈值为15.7%-27.4%)和体积能量密度(3kW/kg)大等优势(Energ.Fuel.2021,35,11693-11706)。因此,以氨气为储氢体进行储存和运输,再通过氨分解制取氢能的方式受到了广泛的关注和研究。
目前,氨分解制氢的方法主要是基于贵金属(如Ru、Ir和Pt等)和过渡金属(如Fe、Co和Ni等)催化剂的热催化过程。其中,贵金属Ru基催化剂的氨分解活性最好,低温活性佳,但其价格昂贵,制备成本高。大连化物所的陈萍等人报道了一种通过沉积沉淀法制备负载于MgO的K改性Ru催化剂,该催化剂在475℃,36000mL g-1h-1空速下,可得到近100%的氨气转化率。他们认为大表面的介孔MgO载体有利于Ru的分散以及对氨气的吸附,这使得该催化剂具有较好的低温性能(Appl.Catal.B,2017,211,167-175)。此外,过渡金属催化剂虽然价格低廉,但是氨分解温度较高(700-850℃)。东南大学肖睿等人报道一种以Al2O3为载体负载Co改性Ni催化剂,该催化剂在700℃,5000mL g-1h-1空速下,可得到近100%的氨气转化率。他们认为优异的催化性能得益于Co的引入可降低活性位的粒径和提高活性位的分散度(Fuel Process.Technol.,2021,221,106945)。迄今为止,氨分解催化剂的研究主要是以粉体型催化剂为主,该类催化剂在实际应用中为了减小压降,一般要进行成型操作。从反应器宏观角度上看,成型操作也将导致一系列传质问题如流体分布不均匀、湍流、返混和短路等。此外,该类粉体催化剂由于传热性能较差,在反应过程中还会存在反应温度不均匀,从而导致催化剂反应效率低和氨分解不完全等问题。
针对这一问题,也有研究者进行了一些探索。中国专利申请CN101147863A公开了一种整体式镍基氨分解催化剂,该催化剂的制备是将金属纤维、载体Al2O3颗粒以及粘结剂纤维素等加入打浆机打浆,接着进行成型制得载体,最后再浸渍活性组分Ni。该催化剂中含有开放结构的金属纤维,一定程度上可提高其传质和传热效率。在600℃和空速为17400h-1的反应条件下,CeO2改性的Ni催化剂可实现99%的氨气转化率。但是通过这种制备方法的整体式催化剂,其金属纤维和载体的粘结力较差结构强度低,在长时间的反应下极易脱落,从而堵塞反应器孔道,最终导致催化剂的传质/传热性能下降。
中国专利申请CN106693977A公开了一种以海泡石为载体的镍基催化剂,他们先将海泡石进行酸处理以提高其比表面积,从而有利于提高活性组分镍的分散度。Ni负载量为30%的催化剂在700℃的反应条件下,可实现近100%的氨气转化率。该类催化剂虽然活性较好,但是进一步放大应用时,同样面临着传质传热效率上的限制。
因此,开发一种兼具有良好反应性能和优异的传质传热性能的催化剂具有十分重要的意义。
发明内容
针对现有技术的不足,本发明旨在提供一种整装铁基氨分解催化剂及其制备方法和应用。
为了实现上述目的,本发明采用如下技术方案:
作为本发明的其中一种技术方案,一种整装铁基氨分解催化剂的制备方法,具体过程为:
S1、通过水热法在金属载体骨架上原位生长非水溶性铁盐晶体层,实现金属载体的原位催化功能化;
S2、将步骤S1制备得到的材料在空气气氛下于300-800℃焙烧0.5-12小时,最后在氢氮混合气气氛下于800℃还原0.5-6小时,即得整装铁基氨分解催化剂。
作为本发明的另一种技术方案,一种整装铁基氨分解催化剂的制备方法,具体过程为:
S1、通过水热法在金属载体骨架上原位生长非水溶性铁盐晶体层,实现金属载体的原位催化功能化;
S2、将步骤S1制备得到的材料浸渍于含助剂的水溶液中,在50-150℃下烘干2-24小时,制得整装铁基氨分解催化剂前驱体;
S3、将步骤S2制备得到的整装铁基氨分解催化剂前驱体在空气气氛下于300-800℃焙烧0.5-12小时,最后在氢氮混合气气氛下于200-900℃还原0.5-6小时,即得整装铁基氨分解催化剂。
进一步地,步骤S1的具体过程为:
S1.1、将金属载体置于丙酮溶液中超声,取出后用蒸馏水清洗并烘干备用;
S1.2、将步骤S1.1洗净的金属载体置于0.01-1摩尔每升的草酸溶液中,在50-250℃下于高压反应釜中反应2-48小时,冷却后取出用去离子水洗涤并烘干,从而得到草酸铁负载于金属载体的材料,完成金属载体的原位催化功能化。
进一步地,步骤S1中,所述金属载体骨架的材质为含铁合金。
更进一步地,所述含铁合金为铁、铁镍、铁铬铝、铁钨、铁硅、铁锰、铁钼中的任意一种。
进一步地,所述金属载体骨架的形态结构选自泡沫、纤维、纤维毡、丝网、圆管、圆片、颗粒中的任意一种。
进一步地,步骤S2中,所述助剂为钼酸铵、硝酸钴、硝酸钾、硝酸镍、硝酸铈、硝酸钌的任意一种或多种。
进一步地,所述整装铁基氨分解催化剂中,活性组分为铁,以质量百分比计,铁占催化剂的1~40%,助剂占催化剂的0~10%,余量为金属载体骨架。
本发明还提供一种上述制备方法制得的整装铁基氨分解催化剂。
一种上述制备方法制得的整装铁基氨分解催化剂可在氨分解反应中作为催化剂应用。
本发明的有益效果在于:
(1)本发明制备得到的整装铁基氨分解催化剂,是先在骨架基体上生长一层非水溶性铁金属盐晶体层,经热分解和还原处理,制得未经改性的铁基催化剂,或在热分解和还原处理前先通过等体积浸渍法引入助剂改性,制得在金属载体上负载助剂改性的铁基催化剂。相较于其他方法制备的整体式催化剂(如CN101147863A),本发明提供的整装铁基氨分解催化剂具有制备过程可控性强、易于规模化生产和活性组分负载量高且结构稳定不易脱落等优势。这些特性赋予本发明的整装铁基氨分解催化剂在长时间运行中保持优异的稳定性。
(2)本发明的整装铁基氨分解催化剂制作工艺简单,原料廉价易得,无需二次成型,传质传热性能好,适应高通量低压降的反应需求。相比于传统的粉末氨分解催化剂,本发明的整装铁基氨分解催化剂具有较好的导热性,使得催化剂床层温度分布更为均匀,较高的渗透率使得床层压降大大降低。此外,本发明提供的催化剂催化壳层较薄,可大幅度消除内扩散限制,从而提高活性组分的利用率。同时,本发明提供催化剂具有较高且规整的孔道结构,可避免在传统颗粒催化剂中普遍存在的流体分布不均匀、湍流、返混、沟流和气体短路等现象。因此,本发明提供的整装结构催化剂便于反应器的小型化和灵活设计,展现出了在氨分解制氢工业中的应用潜力。
附图说明
图1为本发明实施例1的Fe-foam和FeC2O4/Fe-foam的X射线衍射(XRD)图;
图2为本发明实施例1中Fe-foam和FeC2O4/Fe-foam的扫描电镜(SEM图),(a)和(b)为Fe-foam骨架基体的SEM图,(c)和(d)为FeC2O4/Fe-foam材料的SEM图;
图3为本发明实施例1中制备的FeC2O4/Fe-foam材料经过超声处理后的质量损失图;
图4为本发明实施例1中制备的FeC2O4/Fe-foam材料的吸脱附等温线和孔分布曲线图,(a)为吸脱附等温线,(b)为孔分布曲线图;
图5为本发明实施例8催化剂的稳定性测试图。
具体实施方式
以下将结合附图对本发明作进一步的描述,需要说明的是,本实施例以本技术方案为前提,给出了详细的实施方式和具体的操作过程,但本发明的保护范围并不限于本实施例。
实施例1
本实施例提供一种整装铁基氨分解催化剂的制备方法,具体过程为:
①将1克泡沫铁(孔隙度100PPI,表示为Fe-foam)在丙酮溶液中于80℃超声1小时,洗去表面油污和有机物,接着用蒸馏水洗净并烘干;
②将1.58克草酸(12.5毫摩尔)溶于50毫升的蒸馏水中(草酸摩尔浓度为0.25摩尔每升),并移入高压反应釜内,称取1克洗净后的泡沫铁浸入溶液中,于120℃下保持12小时,冷却后取出,并用去离子水洗涤后烘干,即可实现在金属载体骨架上原位生长草酸铁晶体层,表示为FeC2O4/Fe-foam;
③将所制备的FeC2O4/Fe-foam在空气气氛下于450℃焙烧2小时,最后在氢氮混合气气氛(氢气体积分数5%)下于800℃还原5小时,制得未改性的整装铁基氨分解催化剂;
在500-800℃下,采用流速为40mL min-1纯氨气体对该催化剂进行活性评价,催化剂装填0.2克,空速为12000mL g-1h-1,根据公式氨气转化率=(初始氨含量-尾气氨含量)/初始氨含量×100%,具体结果见表1。
图1是本实施例的Fe-foam和FeC2O4/Fe-foam的X射线衍射(XRD)图。这说明了通过水热法能成功在Fe-foam上生长出FeC2O4物相。图2是本实施例Fe-foam和FeC2O4/Fe-foam的扫描电镜(SEM图),其中,(a)和(b)为Fe-foam骨架基体的SEM图,(c)和(d)为FeC2O4/Fe-foam材料的SEM图。从图中可见,光滑的Fe骨架基底经过水热处理后原位生长出了FeC2O4晶体层。
图3是本实施例制备的FeC2O4/Fe-foam材料经过超声处理后的质量损失图。从图中可见,本实施例制备的FeC2O4/Fe-foam材料呈现出了较好的结构稳定性。
图4是本实施例制备的FeC2O4/Fe-foam材料的吸脱附等温线和孔分布曲线图。从图中可见,本实施例制备的FeC2O4/Fe-foam材料具有一定的介孔结构,孔径分布主要在6.2nm。
经过对焙烧后的整装铁基氨分解催化剂进行穆斯堡尔谱分析测定可得催化剂中氧化铁的含量,通过换算即可得由氧化铁经还原得到的活性铁物相含量。实验结果表明,在本实施例所制备的催化剂中,除骨架载体中的体相铁外,由氧化铁还原得到活性铁物相的质量含量为25%。
实施例2
本实施例提供一种整装铁基氨分解催化剂的制备方法,具体过程为:
①按照实施例1中步骤①和②的方法制备FeC2O4/Fe-foam;
②将0.247克的六水合硝酸钴溶于蒸馏水中,在室温下对1克所制备的FeC2O4/Fe-foam进行等体积浸渍,再于100℃进行烘干处理,在空气气氛下于450℃焙烧2小时,最后在氢氮混合气气氛(氢气体积分数5%)下于800℃还原5小时,制得整装铁基氨分解催化剂;
催化剂评价条件同实施例1,具体结果见表1。
同实施例1的方法,对本实施例中步骤②中所得的催化剂进行穆斯堡尔谱表征和电感耦合等离子体原子发射光谱(ICP)可测得活性组分和助剂的含量,在本实施例所制备的催化剂中,除骨架载体中的体相铁外,活性铁物种的质量含量为24.8%,助剂Co的质量含量为4.9%。
需要说明的是,步骤②中,六水合硝酸钴的用量可以是0.001-1克。
实施例3
本实施例提供一种整装铁基氨分解催化剂的制备方法,具体过程为:
①按照实施例1中的步骤①和②的方法制备FeC2O4/Fe-foam;
②将0.092克的四水合钼酸铵溶于蒸馏水中,在室温下对1克所制备的FeC2O4/Fe-foam进行等体积浸渍,再于100℃进行烘干处理,在空气气氛下于450℃焙烧2小时,最后在氢氮混合气气氛(氢气体积分数5%)下于800℃还原5小时,制得整装铁基氨分解催化剂;
催化剂评价条件同实施例1,具体结果见表1。
同实施例2的方法可测得,在本实施例所制备的催化剂中,除骨架载体中的体相铁外,活性铁物种的质量含量为24.9%,助剂Mo的质量含量为5.0%。
需要说明的是,步骤②中四水合钼酸铵可以是0.001-1克。
实施例4
本实施例提供一种整装铁基氨分解催化剂的制备方法,具体过程为:
①按照实施例1中的步骤①和②的方法制备FeC2O4/Fe-foam;
②将0.248克的六水合硝酸镍溶于蒸馏水中,在室温下对1克所制备的FeC2O4/Fe-foam进行等体积浸渍,再于100℃进行烘干处理,在空气气氛下于450℃焙烧2小时,最后在氢氮混合气气氛(氢气体积分数5%)下于800℃还原5小时,制得整装铁基氨分解催化剂;
催化剂评价条件同实施例1,具体结果见表1。
同实施例2的方法可测得,在本实施例所制备的催化剂中,除骨架载体中的体相铁外,活性铁物种的质量含量为24.9%,助剂Ni的质量含量为4.9%。
需要说明的是,步骤②中六水合硝酸镍可以是0.001-1克。
实施例5
本实施例提供一种整装铁基氨分解催化剂的制备方法,具体过程为:
①按照实施例1中的步骤①和②的方法制备FeC2O4/Fe-foam;
②将0.155克的六水合硝酸铈溶于蒸馏水中,在室温下对1克所制备的FeC2O4/Fe-foam进行等体积浸渍,再于100℃进行烘干处理,在空气气氛下于450℃焙烧2小时,最后在氢氮混合气气氛(氢气体积分数5%)下于800℃还原5小时,制得氨分解催化剂;
催化剂评价条件同实施例1,具体结果见表1。
同实施例2的方法可测得,在本实施例所制备的催化剂中,除骨架载体中的体相铁外,活性铁物种的质量含量为25.0%,助剂Ce的质量含量为5.0%。
需要说明的是,步骤②中六水合硝酸铈可以是0.001-1克。
实施例6
本实施例提供一种整装铁基氨分解催化剂的制备方法,具体过程为:
①按照实施例1中的步骤①和②的方法制备FeC2O4/Fe-foam;
②将0.026克的硝酸钾溶于蒸馏水中,在室温下对1克所制备的FeC2O4/Fe-foam进行等体积浸渍,再于100℃进行烘干处理,在空气气氛下于450℃焙烧2小时,最后在氢氮混合气气氛(氢气体积分数5%)下于800℃还原5小时,制得氨分解催化剂;
催化剂评价条件同实施例1,具体结果见表1。
同实施例2的方法可测得,在本实施例所制备的催化剂中,除骨架载体中的体相铁外,活性铁物种的质量含量为24.9%,助剂K的质量含量为1.0%。
需要说明的是,硝酸钾可以是0.001-1克。
实施例7
本实施例提供一种整装铁基氨分解催化剂的制备方法,具体过程为:
①同实施例1中的步骤①和②的方法制备FeC2O4/Fe-foam;
②称取0.0667克硝酸钌溶液(钌含量30%)溶于蒸馏水中,在室温下对1克所制备的FeC2O4/Fe-foam进行等体积浸渍,再于100℃进行烘干处理,在空气气氛下于450℃焙烧2小时,最后在氢氮混合气气氛(氢气体积分数5%)下于500℃还原5小时,制得氨分解催化剂;
在400-700℃下,采用流速为40mL min-1纯氨气体对该催化剂进行活性评价,催化剂装填0.2克,空速为12000mL g-1h-1,根据公式氨气转化率=(初始氨含量-尾气氨含量)/初始氨含量×100%,具体结果见表1。
同实施例2的方法可测得,在本实施例所制备的催化剂中,除骨架载体中的体相铁外,活性铁物种的质量含量为25.0%,活性组分Ru的质量含量为2.0%。
需要说明是,步骤②中硝酸钌溶液(钌含量30%)可以是0.001-1克。
实施例8
本实施例提供一种整装铁基氨分解催化剂的制备方法,具体过程为:
①按照实施例1中的步骤①和②的方法制备FeC2O4/Fe-foam;
②称取0.026克的硝酸钾和0.0667克硝酸钌溶液(钌含量30%)溶于蒸馏水中,在室温下对1克所制备的FeC2O4/Fe-foam进行等体积浸渍,再于100℃进行烘干处理,在空气气氛下于450℃焙烧2小时,最后在氢氮混合气气氛(氢气体积分数5%)下于500℃还原5小时,制得氨分解催化剂;
催化剂评价条件同实施例7,具体结果见表1。
同实施例2的方法可测得,在本实施例所制备的催化剂中,除骨架载体中的体相铁外,活性铁物种的质量含量为25.0%,活性组分Ru的质量含量为2.0%,助剂K的质量含量为0.9%。
需要说明的是,步骤②中的硝酸钾和硝酸钌溶液(钌含量30%)皆可以是0.001-1克。
对比例1
将0.026克的硝酸钾和0.0667克的硝酸钌溶于蒸馏水中,在室温下对1克的泡沫铁载体进行等体积浸渍,再于100℃进行烘干处理,在空气气氛下于450℃焙烧2小时,最后在氢氮混合气气氛(氢气体积分数5%)下于800℃还原5小时,制得对比例催化剂。
在400-700℃下,采用流速为40mL min-1纯氨气体对该催化剂进行活性评价,催化剂装填0.2克,空速为12000mL g-1h-1,根据公式氨气转化率=(初始氨含量-尾气氨含量)/初始氨含量×100%,具体结果见表1。
对比例2
将1.8克的九水合硝酸铁、0.026克的硝酸钾和0.0667克的硝酸钌溶于蒸馏水中,在室温下对1克的商用Al2O3载体进行等体积浸渍,再干燥处理,在空气气氛下于450℃焙烧2小时,最后在氢氮混合气气氛(氢气体积分数5%)下于800℃还原5小时,制得对比例催化剂。
在400-700℃下,采用流速为40mL min-1纯氨气体对该催化剂进行活性评价,催化剂装填0.2克且颗粒250-600μm,空速为12000mL g-1h-1,根据公式氨气转化率=(初始氨含量-尾气氨含量)/初始氨含量×100%,具体结果见表1。
对比例3
本对比例采用的催化剂为中国专利申请CN106693977A中实施例5的催化剂,在不同温度下,采用流速为40mL min-1纯氨气体对该催化剂进行活性评价,催化剂装填0.2克且剂颗粒250-600μm,反应温度为500-800℃,空速为12000mL g-1h-1,根据公式氨气转化率=(初始氨含量-尾气氨含量)/初始氨含量×100%,具体结果见表1。
表1
550℃ | 600℃ | 650℃ | 700℃ | |
实施例1 | 50.6 | 69.8 | 94.4 | / |
实施例2 | 53.4 | 74.1 | 97.2 | / |
实施例3 | 51.6 | 68.4 | 92.9 | 99.1 |
实施例4 | 63.6 | 84.3 | 99.6 | / |
实施例5 | 66.1 | 85.9 | 99.7 | / |
实施例6 | 60.7 | 80.9 | 99.7 | / |
实施例7 | 80.6 | 98.6 | 99.9 | / |
实施例8 | 84.1 | 99.5 | / | / |
对比例1 | 38.0 | 61.1 | 88.5 | 94.9 |
对比例2 | 48.6 | 66.9 | 92.9 | / |
对比例3 | 33.6 | 55.4 | 80.9 | 95.3 |
由表1可见:采用本发明实施例8所制备的催化剂在600℃时,氨气转化率接近平衡转化率(99.5%),该催化剂在50小时的稳定性测试中(图5),反应性能基本不变。通过对比实施例8和对比例1可得,在泡沫铁载体上生长草酸铁层能有效提高催化剂的反应性能。通过对比实施例8和对比例2可得,等负载量的粉末催化剂,整体式催化剂在不同温度下,氨分解活性皆要高于相应的粉末催化剂。通过对比实施例1-8和对比例2-3可得,整装催化剂性能要显著高于粉体催化剂。以上结果说明了,整装结构化设计,提高了传质和传热性能,从而对反应性能具有较好的促进作用,另外通过采取独特的金属载体表面催化功能化方法,进一步提高了催化剂的活性。
对于本领域的技术人员来说,可以根据以上的技术方案和构思,给出各种相应的改变和变形,而所有的这些改变和变形,都应该包括在本发明权利要求的保护范围之内。
Claims (10)
1.一种整装铁基氨分解催化剂的制备方法,其特征在于,具体过程为:
S1、通过水热法在金属载体骨架上原位生长非水溶性铁盐晶体层,实现金属载体的原位催化功能化;
S2、将步骤S1制备得到的材料在空气气氛下于300-800℃焙烧0.5-12小时,最后在氢氮混合气气氛下于800℃还原0.5-6小时,即得整装铁基氨分解催化剂。
2.一种整装铁基氨分解催化剂的制备方法,其特征在于,具体过程为:
S1、通过水热法在金属载体骨架上原位生长非水溶性铁盐晶体层,实现金属载体的原位催化功能化;
S2、将步骤S1制备得到的材料浸渍于含助剂的水溶液中,在50-150℃下烘干2-24小时,制得整装铁基氨分解催化剂前驱体;
S3、将步骤S2制备得到的整装铁基氨分解催化剂前驱体在空气气氛下于300-800℃焙烧0.5-12小时,最后在氢氮混合气气氛下于200-900℃还原0.5-6小时,即得整装铁基氨分解催化剂。
3.根据权利要求1或2所述的制备方法,其特征在于,步骤S1的具体过程为:
S1.1、将金属载体置于丙酮溶液中超声,取出后用蒸馏水清洗并烘干备用;
S1.2、将步骤S1.1洗净的金属载体置于0.01-1摩尔每升的草酸溶液中,在50-250℃下于高压反应釜中反应2-48小时,冷却后取出用去离子水洗涤并烘干,从而得到草酸铁负载于金属载体的材料,完成金属载体的原位催化功能化。
4.根据权利要求1或2所述的制备方法,其特征在于,步骤S1中,所述金属载体骨架的材质为含铁合金。
5.根据权利要求4所述的制备方法,其特征在于,所述含铁合金为铁、铁镍、铁铬铝、铁钨、铁硅、铁锰、铁钼中的任意一种。
6.根据权利要求1或2所述的制备方法,其特征在于,所述金属载体骨架的形态结构选自泡沫、纤维、纤维毡、丝网、圆管、圆片、颗粒中的任意一种。
7.根据权利要求2所述的制备方法,其特征在于,步骤S2中,所述助剂为钼酸铵、硝酸钴、硝酸钾、硝酸镍、硝酸铈、硝酸钌的任意一种或多种。
8.根据权利要求1或2所述的制备方法,其特征在于,所述整装铁基氨分解催化剂中,活性组分为铁,以质量百分比计,铁占催化剂的1~40%,助剂占催化剂的0~10%,余量为金属载体骨架。
9.一种权利要求1-8任一所述制备方法制得的整装铁基氨分解催化剂。
10.一种权利要求1-8任一所述制备方法制得的整装铁基氨分解催化剂在氨分解反应中的应用。
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