CN112108191A - 一种用于1,2-二氯乙烷低温催化燃烧的负载钌钴合金纳米催化剂 - Google Patents
一种用于1,2-二氯乙烷低温催化燃烧的负载钌钴合金纳米催化剂 Download PDFInfo
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- CN112108191A CN112108191A CN202010958711.5A CN202010958711A CN112108191A CN 112108191 A CN112108191 A CN 112108191A CN 202010958711 A CN202010958711 A CN 202010958711A CN 112108191 A CN112108191 A CN 112108191A
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 16
- VLWBWEUXNYUQKJ-UHFFFAOYSA-N cobalt ruthenium Chemical compound [Co].[Ru] VLWBWEUXNYUQKJ-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 title claims description 19
- 239000000956 alloy Substances 0.000 title claims description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 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 11
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 10
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000000969 carrier Substances 0.000 claims abstract description 7
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- PVYPHUYXKVVURH-UHFFFAOYSA-N boron;2-methylpropan-2-amine Chemical compound [B].CC(C)(C)N PVYPHUYXKVVURH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000460 chlorine Substances 0.000 abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 abstract description 9
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 4
- 239000012855 volatile organic compound Substances 0.000 abstract description 4
- 239000002808 molecular sieve Substances 0.000 abstract description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000010718 Oxidation Activity Effects 0.000 abstract description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 18
- 239000000395 magnesium oxide Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Abstract
一种用于1,2‑二氯乙烷低温催化燃烧的负载钌钴合金纳米催化剂，属于纳米科学和催化燃烧环保术领域。将RuCo双金属纳米粒子负载到载体上，经过焙烧后形成RuCo/meso‑MgO、RuCo/meso‑Al2O3和RuCo/HZSM‑5催化剂。制备方法为：以乙酰丙酮钌、乙酰丙酮钴、异丙醇铝、ZSM‑5分子筛等为原料，采用软模版‑溶剂热法和离子交换法制备出不同酸碱性多孔载体，然后通过油相一步法制备出RuCo双金属纳米粒子，然后采用吸附法将其负载到介孔载体上。该催化剂的制备工艺简单、成本低、纳米粒子形貌规整可控，对含氯及非含氯VOCs均具有良好的低温催化氧化活性和稳定性，有着良好的应用前景。
Description
技术领域
本发明涉及一种用于1,2-二氯乙烷高效低温催化消除的不同酸碱性多孔载体(MgO、Al2O3或HZSM-5)负载RuCo合金纳米粒子催化剂及其制备方法，并提供了一种用于催化消除环境中含氯挥发性有机物的方法。属于纳米科学和催化燃烧技术领域。
背景技术
含氯挥发性有机化合物(CVOCs)属于高毒性的、致癌的、对生物系统会造成持久的、积累性影响的有机污染。多数含氯有机化合物具有良好的稳定性和热稳定性，不易被分解或生物降解,对环境造成持久性的污染。其中1,2-二氯乙烷是一种典型的非芳香脂肪烃类氯化物，产生于氯碱工业、制革、洗涤、制药等行业,其通过排放或泄漏可进入大气环境。由于这些排放过程都是关乎国计民生的工业过程，大量CVOCs的排放不可避免。因此，从源头上消除污染尚不具备可能性，而采用后处理的方法消除1,2-二氯乙烷所带来的污染成为唯一可行的途径。
在所有CVOCs消除技术中，催化燃烧由于其操作温度低(250～550℃)、无二次污染、消除污染物浓度宽、产物(CO2、HCl、H2O)选择性高等特点而成为目前广泛使用的方法之一。用于含氯有机化合物低温催化燃烧的常用催化剂可分为负载贵金属、固体酸、过渡金属氧化物等。贵金属催化剂存在价格相对昂贵、氯代反应活性高，在高温区易因为贵金属的流失而导致失活，使得贵金属催化剂的应用受到限制，而过渡金属氧化物和固体酸催化剂，具有适宜的酸性质、良好的热稳定性和低廉的价格等优点，但是容易积碳和低温活性较差。因此，在贵金属中掺杂一种过渡金属形成双金属纳米粒子并将其负载于具有介孔结构的不同酸碱性的载体上，有利于活性相的高分散，从而提高催化活性，降低贵金属用量、提高热稳定性和抗氯中毒性能的一种有效方法。本课题组已成功制备了PtxCo/meso-MnO2和mPt-nMnOx/meso-CeO2催化剂，分别用于甲醇和甲苯的催化燃烧(J.Yang,et al.,Catal.Today2019,332:168-176；X.H.Fu,et al.,Appl.Catal.A 2020,595:117509)。据我们所知，目前尚无RuCo合金纳米粒子负载于不同酸碱性多孔载体(MgO、Al2O3或HZSM-5)的催化剂的制备及其对1,2-二氯乙烷低温催化消除的报道。
发明内容
本发明的目的在于先利用油相一步法制备尺寸均匀的RuCo合金粒子(直径为2.0nm左右)，然后采用物理吸附法将其均匀分散负载到多孔结构的碱性载体MgO(采用水热-软模板法制备)、两性载体Al2O3(采用软模板焙烧法制备)或酸性载体HZSM-5(采用水热-离子交换法制备)表面，经过焙烧形成RuCo/meso-MgO、RuCo/meso-Al2O3和RuCo/HZSM-5催化剂，最终达到对1,2-二氯乙烷的高效低温催化氧化。RuCo双金属纳米粒子具有形貌规整的球状结构。RuCo双金属的负载量为0.8-1.5wt％。
本发明的目的在于提供一种低温催化燃烧活性高、催化寿命长且可有效抑制氯代反应发生、抗氯中毒能力强的可用于CVOCs低温燃烧的催化剂。
上述的负载钌钴合金纳米催化剂的制备方法，其特征在于，主要包括以下几个步骤：
(1)RuCo合金纳米粒子的制备：配制A液：称取双十二烷基胺和三正辛基膦加入到十八烯中，在氮气气氛中，加热搅拌1h，混合均匀，其中每0.5g双十二烷基胺对应0.1g三正辛基膦、10-15mL十八烯；配制B液：乙酰丙酮钌、乙酰丙酮钴、油胺和十八烯混合，加热搅拌30min，混合均匀，其中每50mg乙酰丙酮钌对应1-3mL油胺和5-10mL十八烯，Ru与Co的摩尔比为2.8～3.0∶1；先将A液升温到250℃，快速注入B液，搅拌10min,然后加入硼烷叔丁胺并保持10min，最后升温到300℃并保持40min；经过乙醇和环己烷混合洗涤、离心得到RuCo合金纳米粒子(平均粒径为2.0nm左右)，并将其分散到环己烷中；AB混合时，每0.5g双十二烷基胺对应每400mg-60mg乙酰丙酮钌、0.2g硼烷叔丁胺。
(2)采用物理吸附法，按照一定负载量计算出所需要的含有RuCo双金属溶液的量(优选采用环己烷溶剂)，将一定量的不同酸碱性多孔载体加入到含有双金属纳米粒子的环己烷溶液，持续搅拌吸附过夜，离心后放置于烘箱中干燥，将得到的催化剂在管式炉中以1℃/min的速率在空气气氛中升至350℃-450℃焙烧2h，最终得到RuCo/meso-MgO、RuCo/meso-Al2O3和RuCo/HZSM-5催化剂。
不同酸碱性多孔载体选自meso-MgO、meso-Al2O3或HZSM-5。
在1,2-二氯乙烷浓度为1000ppm、1,2-二氯乙烷/氧气摩尔比为1/200和空速为20000mL/(g h)的反应条件下，RuCo/moso-HZSM-5催化剂的T50％(1,2-二氯乙烷转化率达到50％时所需反应温度)和T90％(1,2-二氯乙烷转化率达到90％时所需反应温度)分别为238℃和281℃。同时，RuCo/moso-HZSM-5催化剂在温度为230℃和270℃的条件下连续反应24小时，其催化活性没有变化；在270℃时向反应气中通入体积含量5％的水蒸汽后，其催化活性也没有明显变化。
本发明具有制备工艺简单，原料价格便宜，低温活性优异和产物(CO2、HCl、H2O)选择性高等特点，在1,2-二氯乙烷催化氧化领域具有良好的应用前景。
研究结果表明，采用本发明的方法所制得的催化剂均具有较好的结晶度，RuCo合金纳米粒子形貌规整，负载双金属催化剂对1,2-二氯乙烷的催化氧化活性明显优于负载纯钌催化剂的。
本发明所制得催化剂具有优异的低温催化性能和高的CO2、HCl、H2O选择性，在低温下可将废气中含氯挥发性有机化合物氧化生成二氧化碳、氯化氢、水，不造成二次污染，完全燃烧尾气可采用稀碱溶液吸收后放空。同时反应条件比较温和。
附图说明
图1为所制得催化剂的XRD谱图。图中依次为(a)RuCo/meso-MgO、(b)RuCo/meso-Al2O3、(c)RuCo/HZSM-5、(d)Ru/HZSM-5和(e)Co/HZSM-5。
图2为所制得催化剂的TEM照片。图中依次为(a,b)RuCo/meso-MgO、(c,d)RuCo/meso-Al2O3和(e,f)RuCo/HZSM-5催化剂的TEM照片。
图3中(A)图为所制得催化剂对1,2-二氯乙烷催化氧化反应的催化活性；(a)RuCo/meso-MgO、(b)RuCo/meso-Al2O3、(c)RuCo/HZSM-5、(d)Ru/HZSM-5和(e)Co/HZSM-5催化剂对于1,2-二氯乙烷氧化的活性图；
(B)图为RuCo/HZSM-5催化剂对1,2-二氯乙烷在不同温度下的热稳定性。反应条件为:1000ppm 1,2-二氯乙烷，空速＝20000mL/(g h)。
具体实施方式
为了进一步阐述本发明，下面以实施例作详细说明，并给出附图描述本发明得到的各催化剂。
实施例1：采用水热-P123模板法制备介孔MgO。具体过程为：首先将0.8g氧化镁和P123加入到80mL去离子水中，充分搅拌。然后将所得液体转移至体积为100mL自压釜中，放入烘箱于240℃水热处理72h。待水热过程结束后，将自压釜冷却至室温，取出水热产物，进行抽滤，并以去离子水多次洗涤后，在80℃干燥10h后，放入马弗炉中并程序升温(5℃/min)至500℃灼烧5h，得到介孔氧化镁载体。
采用软模板法制备介孔Al2O3。具体过程为：首先将3.2g F127、0.4g柠檬酸和1.6g盐酸(37wt％)加入到20mL无水乙醇中，充分搅拌。然后加入3.26g异丙醇铝，接着在40℃水浴中搅拌24h，最后将溶液放入烘箱于60℃干燥48h。将得到的产物放入马弗炉中，程序升温(5℃/min)至500℃灼烧5h，得到介孔氧化铝。
采用离子交换法制备HZSM-5分子筛。具体过程为：首先将配制1mol/L的硝酸铵水溶液，边搅拌边加热至80℃，放入ZSM-5分子筛，持续搅拌5h，进行离子交换，相同步骤重复3次，然后通过离心水洗三次，在80℃烘干12h，最后在马弗炉中程序升温(5℃/min)至550℃灼烧6h，得到HZSM-5载体。
采用油相一步法制备RuCo合金纳米粒子。具体步骤如下：首先配制A液：称取0.5g双十二烷基胺和0.1g三正辛基膦加入到15mL十八烯中，在氮气气氛中，120℃加热搅拌1h；然后配制B液：50mg乙酰丙酮钌、15mg乙酰丙酮钴、2mL油胺和5mL十八烯混合，120℃加热搅拌30min；最后先将A液升温到250℃，快速注入B液，搅拌10min,然后加入0.2g硼烷叔丁胺并保持10min，进而升温到300℃并保持40min。降温后，经过乙醇和环己烷混合液洗涤、离心得到RuCo合金纳米粒子(平均粒径为2.0nm左右)，并将其分散于环己烷中。
采用物理吸附法负载RuCo合金纳米粒子：按照一定负载量计算出所需要的含有RuCo合金纳米粒子溶液的量，将一定量的不同酸碱性多孔载体(meso-MgO、meso-Al2O3或HZSM-5)加入到含有双金属纳米粒子的环己烷溶液，室温下搅拌吸附10h，然后离心，放置于烘箱中干燥过夜，将得到的催化剂在管式炉中以1℃/min的速率在空气气氛中升至400℃焙烧2h，得到RuCo/meso-MgO、RuCo/meso-Al2O3和RuCo/HZSM-5催化剂，所得催化剂RuCo的负载量为1wt％。
本发明制备得到的RuCo/HZSM-5催化剂对1,2-二氯乙烷氧化反应表现出优异的低温催化燃烧性能、良好的热稳定性、高的选择性以及抗氯中毒性能。
Claims (6)
1.一种用于1,2-二氯乙烷低温催化燃烧的负载钌钴合金纳米催化剂，其特征在于，先利用油相一步法制备尺寸均匀的RuCo合金粒子，然后采用物理吸附法将其均匀分散负载到多孔结构的碱性载体MgO、两性载体Al2O3或酸性载体HZSM-5表面，经过焙烧形成RuCo/meso-MgO、RuCo/meso-Al2O3和RuCo/HZSM-5催化剂。
2.按照权利要求1所述的一种用于1,2-二氯乙烷低温催化燃烧的负载钌钴合金纳米催化剂，其特征在于，RuCo双金属纳米粒子具有形貌规整的球状结构。
3.按照权利要求1所述的一种用于1,2-二氯乙烷低温催化燃烧的负载钌钴合金纳米催化剂，其特征在于，RuCo双金属的负载量为0.8-1.5wt％。
4.制备权利要求1-3任一项所述的一种用于1,2-二氯乙烷低温催化燃烧的负载钌钴合金纳米催化剂的方法，其特征在于，包括以下步骤：
(1)RuCo合金纳米粒子的制备：配制A液：称取双十二烷基胺和三正辛基膦加入到十八烯中，在氮气气氛中，加热搅拌1h，混合均匀，其中每0.5g双十二烷基胺对应0.1g三正辛基膦、10-15mL十八烯；配制B液：乙酰丙酮钌、乙酰丙酮钴、油胺和十八烯混合，加热搅拌30min，混合均匀，其中每50mg乙酰丙酮钌对应1-3mL油胺和5-10mL十八烯，Ru与Co的摩尔比为2.8～3.0：1；先将A液升温到250℃，快速注入B液，搅拌10min,然后加入硼烷叔丁胺并保持10min，最后升温到300℃并保持40min；经过乙醇和环己烷混合洗涤、离心得到RuCo合金纳米粒子，并将其分散到环己烷中；AB混合时，每0.5g双十二烷基胺对应每400mg-60mg乙酰丙酮钌、0.2g硼烷叔丁胺。
(2)采用物理吸附法，按照一定负载量计算出所需要的含有RuCo双金属溶液的量，将一定量的不同酸碱性多孔载体加入到含有双金属纳米粒子的环己烷溶液，持续搅拌吸附过夜，离心后放置于烘箱中干燥，将得到的催化剂在管式炉中以1℃/min的速率在空气气氛中升至350℃-450℃焙烧2h，最终得到RuCo/meso-MgO、RuCo/meso-Al2O3和RuCo/HZSM-5催化剂。
5.权利要求1-3任一项所述的一种用于1,2-二氯乙烷低温催化燃烧的负载钌钴合金纳米催化剂的应用，用于1,2-二氯乙烷低温催化燃烧。
6.按照权利要求5的应用，在1,2-二氯乙烷浓度为1000ppm、1,2-二氯乙烷/氧气摩尔比为1/200和空速为20000mL/(g h)的反应条件下，RuCo/moso-HZSM-5催化剂的T50％(1,2-二氯乙烷转化率达到50％时所需反应温度)和T90％(1,2-二氯乙烷转化率达到90％时所需反应温度)分别为238℃和281℃。同时，RuCo/moso-HZSM-5催化剂在温度为230℃和270℃的条件下连续反应24小时，其催化活性没有变化；在270℃时向反应气中通入体积含量5％的水蒸汽后，其催化活性也没有明显变化。
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| CN116726915A (zh) * | 2023-06-28 | 2023-09-12 | 中国科学院兰州化学物理研究所 | 一种低贵金属含量高热稳定性VOCs催化燃烧催化剂的制备和应用 |
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