CN113181955B - 一种高活性Ru/S-HZSM-5催化剂及其制备方法与应用 - Google Patents
一种高活性Ru/S-HZSM-5催化剂及其制备方法与应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 230000000694 effects Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 10
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 9
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002474 experimental method Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004817 gas chromatography Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract description 15
- OCDXZFSOHJRGIL-UHFFFAOYSA-N cyclohexyloxycyclohexane Chemical compound C1CCCCC1OC1CCCCC1 OCDXZFSOHJRGIL-UHFFFAOYSA-N 0.000 abstract description 11
- 229920005610 lignin Polymers 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 10
- 125000002619 bicyclic group Chemical group 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- AGPKZVBTJJNPAG-UHFFFAOYSA-N Isoleucine Chemical compound CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000012075 bio-oil Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- SJUYAEJVZYZLMQ-UHFFFAOYSA-N 5-(1,4-dimethylcyclohexa-2,4-dien-1-yl)oxy-2,5-dimethylcyclohexa-1,3-diene Chemical compound C1=CC(C)=CCC1(C)OC1(C)C=CC(C)=CC1 SJUYAEJVZYZLMQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 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
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
本发明公开了一种高活性Ru/S‑HZSM‑5催化剂及其制备方法与应用,首先通过水热合成法制备载体S‑HZSM‑5,再通过浸渍法负载金属钌,得到高活性的Ru/S‑HZSM‑5催化剂。该催化剂能够在极其温和的条件下对木质素模型化合物进行加氢脱氧,与目前报道的催化剂相比,该催化剂活性和选择性更高。尤其在二苯醚的转化过程中,反应路径与已报道的存在较大差异。Ru/S‑HZSM‑5催化剂具有极高的加氢性能,可快速将二苯醚双环加氢生产二环己基醚,随后断裂C‑O键快速生成唯一产物环己烷。
Description
技术领域
本发明涉及催化剂制备技术领域,具体涉及一种高活性Ru/S-HZSM-5催化剂及其制备方法与应用。
背景技术
如今,能源短缺和环境污染已成为世界范围内的两个主要问题,探索低NOx和SOx排放的新型可再生能源非常迫切。木质纤维素由于其丰富的来源、高的能量含量和低廉的价格而引起了极大的关注。热处理后,木质纤维素可以转化为生物油。在温和条件下,木质素裂解产生较多的含氧化学品,例如酚类、醚类等,含氧化合物存在大量的C-O键,包括4-O-5键、α-O-4键和β-O-4键,而高的氧含量将降低生物油的质量,并且需要通过脱氧方法以获得具有高能量密度的烷烃燃料。通过去除多余的氧原子来提质生物油最为重要,并且仍然具有挑战性。加氢脱氧是一种去除氧原子并将木质素转化为高能产物(例如环烷烃)的有效技术。在这个过程中,催化剂发挥关键作用。
镍、硫化镍、磷化镍和镍或钴与钼或钨结合用作加氢脱氧工艺中的催化剂。然而,这类催化剂的本身活性相当低,并且加氢脱氧工艺需要高温条件,而且,来自硫化物催化剂的硫对产物的污染是要考虑的严重问题。具有高芳香族氢化活性的贵金属是加氢脱氧催化剂的替代选择。不同载体上如活性炭、金属氧化物和沸石负载不同贵金属如钯、铂、铑和钌在加氢脱氧过程中进行了评估。具有酸性的沸石载体负载金属展现出优异的加氢脱氧性能,在贵金属当中,钌金属价格最低。尽管目前在木质素衍生化合物的加氢脱氧方面取得了成就,但是在温和条件下工作的催化剂仍然具有挑战性。
发明内容
本发明的目的之一是提供一种高活性Ru/S-HZSM-5催化剂的制备方法,步骤简单。
本发明的目的之二是提供采用上述制备方法制得的高活性Ru/S-HZSM-5催化剂,能在温和条件下对木质素模型化合物进行加氢脱氧。
本发明的目的之三是提供上述高活性Ru/S-HZSM-5催化剂在加氢脱氧催化反应中的应用。
为实现上述目的,本发明采用的技术方案如下:
本发明的一个方面,提供了一种高活性Ru/S-HZSM-5催化剂的制备方法,包括如下步骤:
(1)根据合成分子筛的摩尔比,氧化硅:氧化铝:四丙基氢氧化铵:氢氧化铵:水=100:1:25:14:2500,将一定量异丙醇铝加入到一定量的含四丙基氢氧化铵的溶液中,搅拌20-40min,称取一定量正硅酸四乙酯在搅拌和室温下逐滴加入上述混合溶液中,并且调节pH值为11;在40℃下搅拌12h后,将所得混合物转移至水热釜中,在150-180℃下烘箱中晶化24-72h;晶化完成之后离心,洗涤,干燥;最后将获得的白色固体置于马弗炉中,通入空气于500-600℃下煅烧5h,以除去模板剂和杂质,获得的分子筛载体标记为S-HZSM-5;
(2)将步骤(1)制得的S-HZSM-5载体加入到三氯化钌水溶液中,超声15-30min,然后将混合溶液在真空干燥箱中浸渍24h;浸渍完成之后,将混合物烘干,之后在惰性气氛中,于300℃煅烧2h,然后在300℃的氢气气氛中还原2h;煅烧还原之后,再切换成惰性气氛冷却至室温,获得Ru/S-HZSM-5催化剂。
本发明的另一个方面,提供了一种高活性Ru/S-HZSM-5催化剂,采用上述的制备方法制得。
优选的,所述Ru/S-HZSM-5催化剂中钌的负载量为5wt.%。
本发明的另一个方面,提供了上述高活性Ru/S-HZSM-5催化剂在加氢脱氧催化反应中的应用。
具体的应用步骤包括:将底物、Ru/S-HZSM-5催化剂和正己烷放入反应器中,密封后,通过通入氢气排除残留的空气;随后,在室温温度下用氢气将反应器加压至期望的压力(0.5-1.0MPa),然后将温度升至所需的反应温度(120-150℃),并剧烈搅拌30-120min。实验结束后,将反应系统自然冷却至室温并释放压力。过滤反应混合物以除去催化剂,并通过气质联用仪(GC-MS)和气相(GC)分析获得的有机相。
优选的,所述底物为环己醇、苯酚、二苯醚、4-苯氧基苯酚、二环苯基醚、苯甲醚、苯乙醚、对二甲苯基醚中的一种。
优选的,所述搅拌的转速为800-900rpm。
优选的,所述Ru/S-HZSM-5催化剂的用量为所述底物质量的15%-20%。
与现有技术相比,本发明具有如下有益效果:
1.本发明通过简单的方法合成了Ru/S-HZSM-5催化剂,该催化剂能够在极其温和的条件下对木质素模型化合物进行加氢脱氧,与目前报道的催化剂相比,该催化剂活性和选择性更高。尤其在二苯醚的转化过程中,催化反应的条件更温和,但二苯醚的转化率可达到100%,产物的选择性为100%,最佳反应条件为1MPa H2,150℃和2h。在其它木质素模型化合物加氢脱氧反应中也能达到100%转化率和100%产物选择性。
2.本发明制得的Ru/S-HZSM-5催化剂在二苯醚的转化过程中,反应路径与已报道的存在较大差异。Ru/S-HZSM-5催化剂具有极高的加氢性能,可快速将二苯醚双环加氢生产二环己基醚,随后断裂C-O键快速生成唯一产物环己烷。
附图说明
图1是本发明实施例1制得的催化剂Ru/S-HZSM-5的XRD图;
图2是本发明实施例1制得的催化剂Ru/S-HZSM-5的SEM图;
图3是本发明实施例1制得的催化剂Ru/S-HZSM-5的TEM图;
图4是本发明实施例1制得的催化剂Ru/S-HZSM-5中金属钌粒径分布图;
图5是反应温度对二苯醚转化的影响(0min);
图6是反应温度对二苯醚转化的影响(120min);
图7是氢气压力对二苯醚转化的影响;
图8是反应时间对二苯醚转化的影响;
图9是Ru/S-HZSM-5催化剂催化二苯醚转化的路径图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明。
实施例1:催化剂Ru/S-HZSM-5的制备
一、水热合成法制备载体S-HZSM-5
首先,根据合成分子筛的摩尔比,氧化硅:氧化铝:四丙基氢氧化铵:氢氧化铵:水=100:1:25:14:2500。将一定量异丙醇铝(25wt.%Al2O3)加入到一定量的含四丙基氢氧化铵的溶液中,搅拌30min,称取一定量正硅酸四乙酯在搅拌和室温下逐滴加入上述烧杯中,并且添加氨水调节pH值为11。在40℃下搅拌12h后,将所得混合物转移至水热釜中,在170℃下烘箱中晶化48h。完成之后,离心分离沉淀物,用去离子水洗涤,在110℃下烘箱中干燥12h。最后,将获得的白色固体在马弗炉中通入空气于550℃下煅烧5h,以除去模板剂和杂质,获得的分子筛载体标记为S-HZSM-5。
二、浸渍法制备Ru/S-HZSM-5催化剂
将0.228g的钌前躯体三氯化钌水合物放入烧杯中,加入适量去离子水溶解。搅拌5-15min后,将1g S-HZSM-5载体加入到水溶液中,并超声15-30min。然后,将混合溶液在真空干燥箱中浸渍24h。浸渍完成之后,将混合物在110℃的干燥箱中干燥10h,在70mL/min的氩气流量下于300℃煅烧2h,然后在300℃的氢气下以相同的流量还原2h,煅烧和还原的升温速率保持在15℃/min。煅烧还原之后,再切换成氩气冷却至室温,获得Ru/S-HZSM-5催化剂。负载量为5wt.%。
图1是实施例1制得的催化剂Ru/S-HZSM-5的XRD图;由图1可知,Ru/S-HZSM-5催化剂中金属钌的特征衍射峰出现在2θ值为38.4°、44.2°和69.4°处,分别属于钌的(100)、(101)和(110)晶格面,各个特征峰的强度较弱,说明钌在S-HZSM-5载体表面均匀分布。
图2是实施例1制得的催化剂Ru/S-HZSM-5的SEM图;由图2可知,Ru/S-HZSM-5催化剂颗粒大小分布均匀,颗粒尺寸大约为300nm。
图3是实施例1制得的催化剂Ru/S-HZSM-5的TEM图;由图3可知,金属钌在Ru/S-HZSM-5催化剂中分布均匀,无团聚现象。
图4是实施例1制得的催化剂Ru/S-HZSM-5中金属钌粒径分布图;由图4可知,Ru/S-HZSM-5催化剂中金属钌的平均颗粒尺寸为3.57nm,均匀分布而尺寸较小,催化活性较高。
实施例2:二苯醚的脱氧加氢应用
所有催化反应均在100mL不锈钢高压釜中进行。在典型的实验中,将底物(100mg)、催化剂(15mg)和正己烷(20mL)放入反应器中。密封后,通过通入氢气3次排除残留的空气。随后,在室温温度下用氢气将反应器加压至期望的压力(0.5-1.0MPa)。然后将温度升至所需的反应温度(120-150℃),并在800rpm的剧烈搅拌速度下保持一定时间(0-120min)。实验结束后,将反应系统自然冷却至室温并释放压力。过滤反应混合物以除去催化剂,并通过气质联用仪(GC-MS)和气相(GC)分析获得的有机相。
表1不同催化剂对二苯醚的加氢催化性能
[1]Highly Stable Nb2O5-Al2O3 Composites Supported Pt CatalystsforHydrodeoxygenation of Diphenyl Ether.Ind.Eng.Chem.Res.,2017,56,14034-14042.
[2]Hydrodeoxygenation of lignin model compounds to alkanes over Pd-Ni/HZSM-5 catalysts.J.Energy Inst.,2020,93(3),899-910.
[3]Selective Hydrodeoxygenation of Lignin-Derived Phenolic MonomersandDimers to Cycloalkanes on Pd/C and HZSM-5Catalysts.ChemCatChem,2012,4,64-68.
[4]Hydrodeoxygenation of Lignin-Derived Phenolic Monomers andDimersto Alkane Fuels over Bifunctional Zeolite-Supported MetalCatalysts.ACSSustainable Chem.Eng.,2014,2,683-691.
[5]Hydrodeoxygenation of lignin-derived phenolic compounds overbi-functional Ru/H-Beta under mild conditions.Fuel,2015,150,175-183.
由表1可知,本实施例1制备的Ru/S-HZSM-5催化剂在1MPa H2,120℃和2h的条件下,可100%转化二苯醚;在1MPa H2,150℃和0h的条件下,二苯醚的转化率为78.9%;在0.5MPa H2,150℃和2h的条件下,也可100%转化二苯醚。此时,二苯醚转化率较高,但产物的分布较广。调整反应条件之后,Ru/S-HZSM-5催化剂在1MPa H2,150℃和2h的条件下,既可100%转化二苯醚,且得到的产物只存在环己烷,选择性为100%。与文献(1,2,3,4,5)报道的催化剂催二苯醚的条件相比,Ru/S-HZSM-5催化剂的反应温度显著降低,反应压力显著降低和反应时间显著减少,显著优化了反应条件。Ru/S-HZSM-5催化剂在1MPa H2,150℃和2h的条件下,得到100%的二苯醚转化率和100%的环己烷,选择性催化活性极高。
实施例3:反应温度对二苯醚转化的影响
反应步骤同实施例2,不同的是反应条件:100mg二苯醚,20mL正己烷,15mg Ru/S-HZSM-5催化剂,1MPa H2,0min;
反应步骤同实施例2,不同的是反应条件:100mg二苯醚,20mL正己烷,15mg Ru/S-HZSM-5催化剂,1MPa H2,120min。
由图5-图6可以看出,在0min时,Ru/S-HZSM-5催化剂催化二苯醚转化的转化率随着反应温度的升高逐渐增加,仅仅在160℃时,转化率达到最大值100%。在较短的时间内,虽然二苯醚可被完全转化,但产物分布较广。调整反应条件后,在120min时,Ru/S-HZSM-5催化剂催化二苯醚转化的转化率在反应温度为120-160℃内保持100%,且仅在150℃时,产物环己烷的选择性达到最大值100%。在较低的反应温度下,产物中只存在两种化合物,环己烷和二环己基醚,随着温度的升高,产物中环己烷的选择性逐渐增加,在150℃时,达到最大值100%;产物中二环己基醚的选择性逐渐减少,在150℃时完全消失。
实施例4:氢气压力对二苯醚转化的影响
反应步骤同实施例2,不同的是反应条件:100mg二苯醚,20mL正己烷,15mg Ru/S-HZSM-5催化剂,150℃,2h。
由图7可知,Ru/S-HZSM-5催化剂催化二苯醚转化的转化率随着氢气压力增加迅速增加,仅在0.5MPa时,达到最大值100%,随后保持不变。产物中环己烷的选择性随着氢气压力的增加而逐渐增加,在1MPa时,可获得100%选择性的环己烷。
实施例5:反应时间对二苯醚转化的影响
反应步骤同实施例2,不同的是反应条件:100mg二苯醚,20mL正己烷,15mg Ru/S-HZSM-5催化剂,150℃,1MPa。
由图8可知,Ru/S-HZSM-5催化剂催化二苯醚转化的转化率随着氢气压力增加迅速增加,仅在15min时,达到最大值100%,随后保持不变。产物中环己烷的选择性随着反应时间的增加逐渐增加,最终在120min时达到最大值100%;产物中二环己基醚的选择性先随反应时间的增加逐渐增加,在15min时,达到最大值,然后随反应时间的增加逐渐减少,最终在120min时完全消失;其它产物如环己醇和环己基苯基醚的选择性均较低,在30min时,均完全消失,在30-120min之间,只存在两种产物环己烷和二环己基醚。
通过分析可知,二苯醚的反应路径如图9所示,二苯醚主要路径是先被直接加氢生成二环己基醚,然后二环己基醚直接裂解生成两个环己烷;次要路径是先直接裂解C-O键,随后进一步转化为环己烷,或者先单环加氢生成环己基苯基醚,随后进一步转化为环己烷。相对于目前文献2和5中报道的路径,报道的催化剂主要表现为较低的加氢性能,反应过程中能检测到苯和苯酚。而本发明中的Ru/S-HZSM-5催化剂加氢性能更强,可直接快速的将二苯醚转化为二环己基醚,随后能直接转化为环己烷,而无法检测到苯和苯酚,尤其是在150℃下,反应时间为30min时,其它产物如环己醇和环己基苯基醚均完全消失,在30-120min之间,只存在两种产物环己烷和二环己基醚。反应路径上很大不同,相比之下,Ru/S-HZSM-5催化剂催化性能更高。
实施例6:不同木质素模型化合物在Ru/S-HZSM-5催化剂上的加氢脱氧
所有催化反应均在100mL不锈钢高压釜中进行。反应步骤同实施例2,不同的是反应条件:100mg反应物,15mg Ru/S-HZSM-5,150℃,20mL正己烷,1MPa H2,2h。
表2不同木质素模型化合物在Ru/S-HZSM-5催化剂上的加氢脱氧
由表2可知,Ru/S-HZSM-5催化剂对环己醇、苯酚、二苯醚、4-苯氧基苯酚、二环苯基醚、苯甲醚、苯乙醚和对二甲苯基醚均具有催化作用,能够有效裂解C-O键,对产物进行加氢脱氧生成无氧的环烷烃,转化率均为100%,产物选择性大部分为100%。
Claims (5)
1.一种高活性Ru/S-HZSM-5催化剂在二苯醚加氢脱氧催化反应中的应用,其特征在于,所述高活性Ru/S-HZSM-5催化剂通过如下步骤制备得到:
(1)根据合成分子筛的摩尔比,氧化硅:氧化铝:四丙基氢氧化铵:氢氧化铵:水=100:1:25:14:2500,将一定量异丙醇铝加入到一定量的含四丙基氢氧化铵的溶液中,搅拌20-40min,称取一定量正硅酸四乙酯在搅拌和室温下逐滴加入上述混合溶液中,并且调节pH值为11;在40 oC下搅拌12 h后,将所得混合物转移至水热釜中,在150-180 oC的烘箱中晶化24-72 h;晶化完成之后离心,洗涤,干燥;最后将获得的白色固体置于马弗炉中,通入空气于500-600 oC下煅烧5 h,以除去模板剂和杂质,获得的分子筛载体标记为S-HZSM-5;
(2)将步骤(1)制得的S-HZSM-5载体加入到三氯化钌水溶液中,超声15-30 min,然后将混合溶液在真空干燥箱中浸渍24 h;浸渍完成之后,将混合物烘干,之后在惰性气氛中,于300 oC煅烧2 h,然后在300 oC的氢气气氛中还原2 h;煅烧还原之后,再切换成惰性气氛冷却至室温,获得Ru/S-HZSM-5催化剂。
2.根据权利要求1所述的应用,其特征在于,所述Ru/S-HZSM-5催化剂中钌的负载量为5wt.%。
3.根据权利要求1所述的应用,其特征在于,具体的应用步骤包括:将底物二苯醚、Ru/S-HZSM-5催化剂和正己烷放入反应器中,密封后,通过通入氢气排除残留的空气;随后,在室温温度下用氢气将反应器加压至0.5-1.0 MPa,然后将温度升至所需的反应温度120-150oC,并剧烈搅拌30-120 min;实验结束后,将反应系统自然冷却至室温并释放压力;过滤反应混合物以除去催化剂,并通过气质联用仪和气相分析获得的有机相。
4.根据权利要求1所述的应用,其特征在于,所述搅拌的转速为800-900 rpm。
5.根据权利要求1所述的应用,其特征在于,所述Ru/S-HZSM-5催化剂的用量为所述底物质量的15%-20%。
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