CN107406252A - 无铬的水煤气变换催化剂及其制备方法 - Google Patents
无铬的水煤气变换催化剂及其制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052796 boron Inorganic materials 0.000 claims abstract description 79
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 239000010949 copper Substances 0.000 claims abstract description 49
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004411 aluminium Substances 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- DOVLHZIEMGDZIW-UHFFFAOYSA-N [Cu+3].[O-]B([O-])[O-] Chemical compound [Cu+3].[O-]B([O-])[O-] DOVLHZIEMGDZIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 3
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 3
- DDSZSJDMRGXEKQ-UHFFFAOYSA-N iron(3+);borate Chemical compound [Fe+3].[O-]B([O-])[O-] DDSZSJDMRGXEKQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- FZQBLSFKFKIKJI-UHFFFAOYSA-N boron copper Chemical compound [B].[Cu] FZQBLSFKFKIKJI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims 2
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 claims 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims 1
- 229910010277 boron hydride Inorganic materials 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000011651 chromium Substances 0.000 abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052804 chromium Inorganic materials 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000013049 sediment Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- MAJZZCVHPGUSPM-UHFFFAOYSA-N nitric acid nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.O[N+]([O-])=O MAJZZCVHPGUSPM-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
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- 238000000975 co-precipitation Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001960 metal nitrate Inorganic materials 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910018182 Al—Cu Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical class O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005749 Copper compound Substances 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
- 241000220010 Rhode Species 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
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- 230000002779 inactivation Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000004690 nonahydrates Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001991 steam methane reforming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
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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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Abstract
一种无铬的水煤气变换催化剂。与工业标准的包括铬的水煤气催化剂相比,利用铁、硼、铜、铝及其混合物制备无铬的水煤气变换催化剂。该改进的催化剂提供了增强的热稳定性且避免潜在危险的铬。公开了包括铁和硼的无铬的水煤气催化剂的各种实施方式,其中一些包括铜、或包括铝和铜。硼可以大体上存在于催化剂的表面。在另一系列的实施方式中,无铬的水煤气催化剂可以包括硼和铜,并且这些实施方式还可以包括铝或铁。
Description
相关申请的交叉引用
本申请要求2016年3月9日递交的序列号为15/064,823的美国非临时专利申请的权益,该非临时专利申请要求2015年3月10日递交的第62/130,649号美国临时专利申请的权益。
关于由联邦资助的研究或开发的声明
本发明是由政府支持在国家科学基金(National Science Foundation)合同号1230320下作出的。政府可以在本发明中享有一定的权利。
技术领域
本发明总体涉及一种用于制备无铬的水煤气变换催化剂的方法。
背景技术
水煤气变换(WGS)反应是由碳氢化合物和/或合成气体(合成气)流生产氢的重要步骤。传统的高温水煤气变换催化剂是基于铁-铬组合物。铬被用于在操作期间减慢基于铁的活性位点的烧结。当前,由于六价铬的致癌性质,工业上努力去除基于铬的水煤气变换催化剂。本发明涉及无铬催化剂配方。具体地,我们公开了数种用于制备具有稳定的水煤气变换性能的催化剂的方法和无铬组合物。下面描述的催化剂将发现用在许多需要水煤气变换反应器的应用中。在下面描述该催化剂应用以及用于制备这些催化剂的方法的细节。
水煤气变换(WGS)反应是由碳氢化合物生产氢的重要步骤。下面所示的正向WGS反应在较低温度(其中,温度低于350℃,要求在典型的流组合物中>99%的转化率)下是热力学有利的:
(WGS反应)
在众多工艺中(例如用于合成氨的蒸汽甲烷转化至氢,用于燃料电池的燃料重整,和用于将煤、天然气或生物质转化成液体燃料或氢的工艺),可以找到水煤气变换催化反应器。由于热力学所需的较低的反应温度,催化剂对于增加WGS反应的速率是重要的。由于氢通常是来自反应的所期望的产物,故在较低温度下运行该反应对于提高工艺效率具有直接效果。
存在多种类型的市售的水煤气变换催化剂,包括低温铜基催化剂、高温Fe/Cr催化剂、中温非自燃性贵金属催化剂、和Co/Mo基酸气变换催化剂。表1概括了各种类型的WGS催化剂通常所用的工艺条件。
发明内容
公开了包括铁和硼的无铬的水煤气催化剂的各个实施方式,其中一些催化剂包括铜、或者包括铝和铜。硼可以大体上存在于催化剂的表面。在另一系列的实施方式中,无铬的水煤气催化剂可以包括硼和铜,并且这些实施方式还可以包括铝或铁。
用于制备具有改善的热稳定性的催化剂的方法可以包括以下步骤:将催化剂前体和硼源混合以形成第一混合物;然后在等于或大于300℃的温度处或者在其它实施方式中在等于或大于450℃的温度处,煅烧该第一混合物以形成催化剂。在一些不同的实施方式中,硼前体可以包括包含硼酸、氧化硼、碱金属硼酸盐、氮化硼、碱金属硼氢化物、硼烷氨、有机硼化合物、硼化铁、硼化铝、硼化铜、硼酸铁、硼酸铝、硼酸铜、及其混合物的硼源。在一些实施方式中,催化剂前体可以包括相对于催化剂具有等于或大于0.01%且等于或小于0.5%的硼重量的硼源。在多个实施方式中,催化剂前体可以包括铁的氢氧化物,铜的氢氧化物,铝的氢氧化物,上述氢氧化物的混合物,铁的碳酸盐,铜的碳酸盐,铝的碳酸盐,上述碳酸盐的混合物,以及铁的氢氧化物、铜的氢氧化物、铝的氢氧化物、上述氢氧化物的混合物、铁的碳酸盐、铜的碳酸盐、和铝的碳酸盐的混合物,以及硼源。
附图说明
在不限制如本文所公开的无铬的水煤气变换催化剂的范围的情况下,现在参照附图和数据:
图1示出商业化Fe/Cr催化剂在400psi下进行热循环的性能,示出了在该加速降解试验期间通常对于稳定性的工业标准;
图2示出无铬的掺硼的催化剂样品Fe2O3-Al0.40Cu0.10B0.10Ox(在700℃煅烧)在400psi下进行热循环的性能,示出了优异的催化耐久性;
图3示出无铬的催化剂样品Fe2O3-Al0.40Cu0.10Ox(在700℃煅烧)在400psi下进行热循环的性能,示出了差的耐久性;和
图4示出针对Fe2O3-Al0.40Cu0.10B0.10Ox(在700℃煅烧)的后续试验XRD分析,示出了主要的磁铁矿相。
根据下面的更加详细的描述,提供这些示图以帮助理解无铬的水煤气变换催化剂的配方及其制备方法的示例性实施方式,并且这些示图不应该被理解为不适当地限制说明书。特别地,在附图中所示的各个元素的相对间隔、定位、尺寸和大小可以不按比例绘制且可以扩大、缩小或出于提高清晰度的目的而被修改。本领域的普通技术人员也将理解到一些替选结构已被简单地省略以改善清晰度和减少附图的数量。
具体实施方式
实施例
制备多种组合物且检测其WGS性能,如在100psi下进行测试的表2和在400psi下进行测试的表3中所列出的。在这些催化剂中,诸如铜的促进剂和诸如硼和/或铝的表面积稳定剂被发现增加表面积和/或活性,其中最初的WGS性能大于商业化的铁-铬高温WGS催化剂。为了制备铁基催化剂,采用共沉淀方法。将金属硝酸盐溶解在蒸馏水中,例如Fe(III)硝酸盐九水合物(80%至90%)、Al(III)硝酸盐九水合物(8%至15%)、Cu(II)硝酸盐水合物-2.5-H2O(2%至5%),其中硼(优选来自硼酸或硼酸钠前体)的比例的最佳范围为0.5重量%至2重量%。随后将该酸式盐溶液加入到预热的(70℃)优选NaOH、KOH和/或NH4OH(所检测的摩尔范围为0.1摩尔至1摩尔)的碱溶液中(使用过量的碱)。在沉淀之后,在母液中将沉淀物老化给定的时间段、优选2小时至72小时,然后用蒸馏水多次清洗固体沉淀物以去除大部分溶解的离子,在70℃干燥,随后煅烧以形成催化剂。表2和表3中所列的组成为目标组成(基于所用的前体比例),而不是测量组成。通常,对于共沉淀过程,催化剂中的实际的硼浓度被认为是低于目标,这是因为不是所有的硼都沉淀。对于初湿含浸法(IW)过程,硼应该全部保留在催化剂中,这是因为在硼添加之后没有清洗前体。
以12500hr-1的空速,在8%的CO、5%的CO2、35%的H2、15%的N2和37%的H2O(按摩尔计)中测试所有样品。在装载到不锈钢微反应器中之前,将催化剂压成小球,然后粒化并通过15至80筛孔尺寸进行筛选。在每次测试中使用大约0.5克的催化剂。在每次测试中,在335℃和50psi处还原16小时后,将压力升至所报道的压力(100psi或400psi),且温度升至350℃保持24小时,然后在550℃和350℃之间进行24小时循环以加速降解。在100psi的测试中,铝和/或硼的添加对在热循环之前和之后的CO转化具有积极的效果(参见表2)。最好的样品Fe2O3-Al0.4Cu0.10B0.10Ox采用硼和铝的结合。与含有钴的样品不同,硼和铝促进的样品在升高的压力下不产生任何可检测出的甲烷。
当在700℃的煅烧温度处理1小时时,发现了硼稳定剂的更加显著的效果。在400psi时,发现在700℃煅烧的Fe2O3-Al0.40Cu0.10B0.10Ox样品展现比商业化的铁-铬催化剂更好的热稳定性。分别在图1和图2中示出了商业化的Fe/Cr和新型催化剂(在700℃煅烧的Fe2O3-Al0.40Cu0.10B0.10Ox)在400psi时的热稳定性能。在550℃,对于商业化的催化剂,甲烷化的程度最初是较高的;然而,在350℃,对于两种催化剂,通过气相色谱仪都没有检测出甲烷化。当比较图2和图3时,硼的有益效果是特别明显的。图3示出在没有硼的情况下与图2具有相同的Fe:Cu:Al比率发生的热降解。通过添加硼来抑制热降解证明了这些组合物是对于铬基高温变换(HTS)催化剂的可行的替代品。先前的研究已经表明硼加入到传统的Fe/Cr水煤气变换催化剂中破坏催化性能[Rhodes;Catalysis Communications,3(2002):381-84]。基于那些先前的报道,不会有动机向Fe基WGS催化剂加入硼。然而,基于所公开的结果,利用恰当的组成和/或处理过程,我们证明可以使用硼作为性能稳定剂,而基本上不影响最初的催化性能。虽然本领域技术人员会认识到会存在许多可能性来解释该效果,但可能的是硼酸盐相会形成,随后抑制催化剂的晶界的生长和铜和/或铁的烧结。硼化合物的低毒性和低成本可以能够被催化剂终端用户和制造商广泛采用。还应该注意到,具有铜的商业化催化剂遭受自燃性。添加硼和形成金属硼酸盐也可以阻止在含氧/湿气的周围环境中的可燃性/反应性。在600℃至700℃之间煅烧的样品的表面积近似商业化的HTS催化剂。
通过X射线光电子能谱(XPS)和电感耦合等离子体原子发射光谱(ICP-AES)进一步表征Fe2O3-Al0.40Cu0.10B0.10Ox催化剂。通过XPS检测三种催化剂变型:在500℃煅烧、在700℃煅烧、和在700℃煅烧的样品的后WGS测试(400psi)。XPS为一种表面灵敏的技术,故该分析确定在表面(通常为前几纳米)上的元素的相对比例。正如表4中所见,样品均在表面上包含Cu、Fe、B和Al。表面比例不匹配目标组成;因此,很可能催化剂的表面富含一些物质,例如Cu、B和Al。
对在700℃煅烧的样品进行ICP-AES分析以确定催化剂的主要组成。催化剂中Fe:Cu的比例和Fe:Al的比例类似于在沉淀过程中所用的目标组成。硼的组成低于目标组成,且比表面组成低得多。基于该结果,仅有小部分硼随着催化剂沉淀析出,并且在催化剂中的硼集中在表面处。硼集中在Fe、Al或Cu的晶界处是可以的。另外,关于理论基础没有任何限制,如果这样,这种Fe-B、Al-B或Cu-B相可以防止催化剂烧结和失活。也将预期到这样的相允许催化剂在煅烧之后维持高的表面积。
通过X射线衍射(XRD)进行测试后催化剂的进一步表征。XRD可被用于确定物质的结晶度。图4示出在700℃煅烧和在400℃耐久性测试之后的Fe2O3-Al0.40Cu0.10B0.10Ox催化剂的XRD图谱。XRD图谱表明该催化剂主要具有磁铁矿晶体结构。在煅烧后,将预期材料具有赤铁矿结构,故一旦催化剂被还原,该磁铁矿相很可能形成。由于WGS反应被认为通过氧化还原机制进行,因此在操作期间很可能多种氧化态和晶体结构会存在于表面上。XRD图谱的意义在于,没有观察到铝相、铜相或硼相的单独的晶体结构。这表明在极大程度上杂原子被密切地混合且包含在与铁相同的晶体结构中。也可以说,杂原子与铁氧化物一起形成了固溶体。
表4.催化剂样品的XPS分析
表5.催化剂样品的ICP-AES分析
实施例1.热碱共沉淀
为了制备铁-铝-铜-硼催化剂(Fe2O3-Al0.40Cu0.10B0.10Ox),采用共沉淀方法。将金属硝酸盐和硼酸溶解在250mL蒸馏水中,具体为Fe(III)硝酸盐九水合物(16.165克)、Al(III)硝酸盐九水合物(3.010克)、Cu(II)硝酸盐水合物-2.5-H2O(0.470克)、连同0.130克硼酸。然后,制备600mL的0.5M的NaOH并加热至70℃。将该酸式盐溶液快速地与已加热的碱混合,导致形成固体沉淀。在沉淀之后,将混合物搅拌2小时,在母液中将沉淀物老化70小时。然后,在搅拌混合物的同时,逐滴加入额外的0.5M的NaOH,直到混合物的pH为10,然后将混合物再老化2小时。最后,利用过滤法或离心法用蒸馏水多次清洗固体沉淀物以去除大部分溶解的离子,在70℃干燥,随后在空气中500℃煅烧1小时以形成催化剂。
实施例2.硼的初湿含浸法
为了制备铁-铝-铜-硼催化剂(Fe2O3-Al0.40Cu0.10B0.10Ox-IW),采用共沉淀法结合初湿含浸法。将金属硝酸盐溶解在250mL蒸馏水中,具体为Fe(III)硝酸盐九水合物(16.165克)、Al(III)硝酸盐九水合物(3.010克)、和Cu(II)硝酸盐水合物-2.5-H2O(0.470克)。然后,制备600mL的0.5M的NaOH并加热至70℃。将该酸式盐溶液快速地与已加热的碱混合,导致形成固体沉淀。在沉淀之后,将混合物搅拌2小时。然后,在搅拌混合物的同时,逐滴加入额外的0.5M的NaOH,直到混合物的pH为10,然后将混合物再老化2小时。最后,利用过滤法或离心法用蒸馏水多次清洗固体沉淀物以去除大部分溶解的离子,然后在70℃干燥。然后,将0.003g至0.120g、优选0.014g的硼酸(或者其它的可溶的硼前体)溶解在5mL蒸馏水中。然后在搅拌的同时向干燥的沉淀物逐滴加入硼酸溶液。然后再次在70℃干燥湿的沉淀物。最后,在300℃至700℃煅烧样品以形成催化剂。
因此,所要求保护的是包括铁和硼的无铬的水煤气催化剂的各个实施方式,铁可以包括多种铁氧化物。在一些实施方式中,催化剂可以包括铝,然而在其它实施方式中,催化剂可以包括铜、或者包括铝和铜。仅仅作为举例而不是限制性地,在各个实施方式中,催化剂可以被制备成具有至少30m2/g、至少60m2/g的表面积、至少90m2/g的表面积和至少120m2/g的表面积。
硼可以以不同的量存在于催化剂的表面上。在一个实施方式中,催化剂可以具有按摩尔计大于0.5%的硼且小于3.0%的硼的颗粒表面组成,然而在其它实施方式中,催化剂可以具有按摩尔计大于0.5%的硼且小于2%的硼的颗粒表面组成。类似地,在其它实施方式中,硼可以以不同的总组成存在于催化剂中。在一个实施方式中,催化剂可以具有按质量计大于.001%的硼且小于或等于2%的硼的总组成,然而在另一个实施方式中,催化剂可以具有大于0.01%的硼且小于或等于0.5%的硼的总组成。
在另一系列的实施方式中,无铬的水煤气催化剂可以包括硼和铜,并且这些实施方式还可以包括铝或铁。在一个特定的实施方式中,催化剂包括所有四种:铁、硼、铝和铜。
本领域技术人员将认识到一种用于制备具有改善的热稳定性的催化剂的方法,该方法包括以下步骤:将催化剂前体和硼源混合以形成第一混合物,然后在等于或大于300℃的温度处煅烧该第一混合物以形成催化剂。在一些不同的实施方式中,硼源可以包括由硼酸、碱金属硼酸盐、氮化硼、碱金属硼氢化物、硼烷氨、有机硼化合物、硼化铁、硼化铝、硼化铜、硼酸铁、硼酸铝、硼酸铜、及其混合物构成的硼源。在一些实施方式中,催化剂前体可以包括相对于催化剂具有等于或大于0.01%且等于或小于0.5%的重量的硼源。在各个实施方式中,催化剂前体可以包括铁的氢氧化物,铜的氢氧化物,铝的氢氧化物,上述氢氧化物的混合物,铁的碳酸盐,铜的碳酸盐,铝的碳酸盐,上述碳酸盐的混合物,以及铁的氢氧化物、铜的氢氧化物、铝的氢氧化物、上述氢氧化物的混合物、铁的碳酸盐、铜的碳酸盐、和铝的碳酸盐的混合物,以及硼源。本领域技术人员将能够认识到硼和催化剂前体的其它可能的来源。
本领域技术人员也将能够认识到针对煅烧硼和催化剂前体的第一混合物的步骤的宽的温度范围。在一个实施方式中,煅烧第一混合物的步骤实际上可以包括在等于或大于450℃时煅烧第一混合物的步骤。
Claims (22)
1.一种无铬的水煤气催化剂,包括:
铁,和
硼。
2.根据权利要求1所述的催化剂,还包括铝。
3.根据权利要求1所述的催化剂,还包括铜。
4.根据权利要求2所述的催化剂,还包括铜。
5.根据权利要求1所述的催化剂,具有至少30m2/g的表面积。
6.根据权利要求1所述的催化剂,具有至少60m2/g的表面积。
7.根据权利要求1所述的催化剂,具有至少90m2/g的表面积。
8.根据权利要求1所述的催化剂,具有至少120m2/g的表面积。
9.根据权利要求1所述的催化剂,其中,所述催化剂具有按摩尔计大于0.5%的硼且小于3.0%的硼的颗粒表面组成。
10.根据权利要求1所述的催化剂,其中,所述催化剂具有按质量计大于0.001%的硼且小于或等于2%的硼的总组成。
11.根据权利要求1所述的催化剂,其中,所述催化剂具有按摩尔计大于0.5%且小于2%的硼的颗粒表面组成。
12.根据权利要求1所述的催化剂,其中,所述催化剂具有大于0.01%的硼且小于或等于0.5%的硼的总组成。
13.根据权利要求1所述的催化剂,其中,所述铁还包括多种铁氧化物。
14.一种无铬的水煤气催化剂,包括:
硼,和
铜。
15.根据权利要求14所述的催化剂,还包括铝。
16.根据权利要求14所述的催化剂,还包括铁。
17.一种无铬的水煤气变换催化剂,包括:
铁;
硼;
铝;和
铜。
18.一种用于制备具有改善的热稳定性的催化剂的方法,所述方法包括以下步骤:
a.将催化剂前体和硼源混合以形成第一混合物;和
b.在等于或大于300℃的温度处煅烧所述第一混合物以形成所述催化剂。
19.根据权利要求18所述的方法,其中,将催化剂前体与硼源混合的步骤包括将催化剂前体与选自由以下构成的硼源的硼源混合:硼酸、氧化硼、碱金属硼酸盐、氮化硼、碱金属硼氢化物、硼烷氨、有机硼化合物、硼化铁、硼化铝、硼化铜、硼酸铁、硼酸铝、硼酸铜、及其混合物。
20.根据权利要求18所述的方法,其中,将催化剂前体与硼源混合的步骤包括将催化剂前体与相对于所述催化剂具有等于或大于0.01%且等于或小于0.5%的重量的硼源混合。
21.根据权利要求18所述的方法,其中,将催化剂前体与硼源混合的步骤包括将选自由以下构成的催化剂前体的组的催化剂前体与硼源混合:铁的氢氧化物,铜的氢氧化物,铝的氢氧化物,上述氢氧化物的混合物,铁的碳酸盐,铜的碳酸盐,铝的碳酸盐,上述碳酸盐的混合物,以及铁的氢氧化物、铜的氢氧化物、铝的氢氧化物、上述氢氧化物的混合物、铁的碳酸盐、铜的碳酸盐、和铝的碳酸盐的混合物。
22.根据权利要求18所述的方法,其中,在等于或大于300℃的温度处煅烧所述第一混合物的步骤还包括在等于或大于450℃的温度处煅烧所述第一混合物的步骤。
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