CN109550521B - 一种处理废胺液的催化剂、其制备方法及其应用 - Google Patents
一种处理废胺液的催化剂、其制备方法及其应用 Download PDFInfo
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- CN109550521B CN109550521B CN201710874149.6A CN201710874149A CN109550521B CN 109550521 B CN109550521 B CN 109550521B CN 201710874149 A CN201710874149 A CN 201710874149A CN 109550521 B CN109550521 B CN 109550521B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 150000001412 amines Chemical class 0.000 title claims abstract description 30
- 239000007788 liquid Substances 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000013207 UiO-66 Substances 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 239000004332 silver Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 150000003754 zirconium Chemical class 0.000 claims description 8
- 239000002798 polar solvent Substances 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
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- 238000007789 sealing Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 abstract description 16
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002351 wastewater Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
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- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
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- 230000002349 favourable effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
本发明公开了一种处理废胺液的催化剂、其制备方法及其应用。处理废胺液的催化剂，由90‑99％的载体和1‑10％的活性组分构成，其中，载体为具有多级孔结构的金属有机骨架材料UiO‑66，活性组分为铜、钴、镍、铁、银、铬、钼或锰中的至少一种，活性组分的存在形式为金属单质、金属硫化物或金属氧化物，所述百分比为质量百分比。本发明催化剂具有高催化性和高稳定性，适用于MDEA等胺液废水的处理；催化剂合成工艺简单可控，对催化剂的应用亦操作方便，适合工业化生产和应用。
Description
技术领域
本发明涉及一种催化剂，具体涉及一种处理废胺液的催化剂、其制备方法及其应用。
背景技术
N-甲基二乙醇胺，简称MDEA，由于其良好的选择性和较高的溶解度，被广泛应用天然气、油田气、Claus尾气等气体的脱硫和脱碳过程。特别是对于石油化工行业来说，采用MDEA胺液，吸收Claus尾气中的硫化氢气体，成为提高总硫回收率，降低排空尾气中二氧化硫浓度的必要手段。由于胺液吸收/再生单元MDEA的降解、装置检修及事故停车等情况的发生，不可避免的会产生一定量含有MDEA的废水，该废水的化学需氧量(COD)及氨氮含量较高，直接排放至水处理单元时，会造成对微生物的冲击，甚至造成排口COD及氨氮超标。因此，开发MDEA废水处理技术对于石化企业解决日益严峻的环保问题意义重大。
对于MDEA废水的处理目前国外报道的专利及文献多集中于生物法或高级氧化，如光催化及其组合工艺等。Fürhacker等报道了好氧型微生物处理MDEA废水技术，在连续的装置上(40L/天)MDEA降解率可达96％；Harimurti等在采用双氧水/紫外光(H2O2/UV)高级氧化技术处理含MDEA废水，UV光可以强化双氧水产生更多的羟基自由基用于分解矿化MDEA分子；目前国内对于MDEA的研究多集中于MDEA胺液吸收/再生过程中净化工艺的研究，而对于MDEA废水处理技术研究报道较少，如生物降解，高级氧化等技术。上述已报道处理废胺液技术均在处理时间长，氧化效率不高等问题。
金属有机骨架材料(Metal-Organic Frameworks,MOFs)作为一种新兴的多孔材料，在分离、催化、氢气、甲烷存储、二氧化碳捕集、传感、药物缓释等方面展现出巨大的潜力。通常，MOFs由无机金属中心和有机配体通过自组装的配位反应形成不同拓扑结构和孔道尺寸的分子骨架。以UiO-66为例，它由次级结构单元ZrO4(OH)4与对苯二甲酸以12配位形成直径分别为
的八面体笼和四面体笼，通过直径为
的三角形孔口相互连通构成三维孔道结构。UiO-66具有良好的热稳定性和化学稳定性，在空气中框架能稳定存在到450℃，其BET比表面为1200m2/g，孔容约为0.47cm3/g。在去离子水、甲醇、异丙醇、丙酮、氯仿和0.1mol/L的HCl中浸泡一夜后仍然保持了完整的晶型结构。鉴于UiO-66系列金属有机骨架材料的众多特点，如何使其在工业应用中发挥更好的优势是现今研究的一个重点。
发明内容
为了解决现有的处理废胺液存在处理时间长，效率低等问题，本发明提供一种处理废胺液的催化剂、其制备方法及其应用。
为解决上述技术问题，本发明所采用的技术方案如下：
一种处理废胺液的催化剂，由90-99％的载体和1-10％的活性组分构成，其中，载体为具有多级孔结构的金属有机骨架材料UiO-66，活性组分为铜、钴、镍、铁、银、铬、钼或锰中的至少一种，活性组分的存在形式为金属单质、金属硫化物或金属氧化物，所述百分比为质量百分比。
本申请处理废胺液的催化剂的比表面积为1200～1500m2/g，总孔容为0.8～1.8m3/g，微孔孔容为0.4～5.5m3/g，且大量的介孔存在，介孔孔容与微孔孔容比率为1～2.5。
孔径小于2纳米的称为微孔；孔径大于50纳米的称为大孔；孔径在2到50纳米之间的称为介孔(或称中孔)。
本发明提供的负载型催化剂的活性组分优选为氧化铜。这样能进一步缩短处理时间，提高处理效率。
上述用于处理废胺液的催化剂的制备方法，包括顺序相接的如下步骤：
A、将金属锆盐和对苯二甲酸加入非质子极性溶剂中，室温搅拌至透明；
B、向步骤A所得物料中加入碱性溶液，室温搅拌至透明；
C、将步骤B所得物料移至具有聚四氟乙烯内衬的反应釜中，密封反应釜，控制反应温度为30～200℃，反应时间为5～50h；待反应结束后温度降至室温，反应物料经离心分离所得固体物料经过溶剂洗涤、干燥，得催化剂载体金属有机骨架材料UiO-66；
D、将活性组分的盐配置为浸渍液；
E、采用浸渍法将步骤D所得的浸渍液中的有效组分负载于步骤C所得的金属有机骨架材料UiO-66上，得到催化剂前驱体；
F、将步骤E所得催化剂前驱体干燥，并在温度为300±10℃的条件下，在氢气气氛下还原，得处理废胺液的催化剂。
制备方法中未提及的技术参照现有技术。步骤F中的还原时间一般控制在10h左右。
为了提高载体对活性组分的吸附性能，步骤A中，金属锆盐为四氯化锆、氯氧化锆、硝酸氧锆、正丁醇锆、正丙醇锆或乙酸锆；非质子极性溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙腈、二甲基亚砜或1，3-二甲基-咪唑烷酮。
步骤A中，金属锆盐与对苯二甲酸的摩尔比为0.5～1﹕1，金属锆盐与非质子型极性溶剂的摩尔比为1﹕500～1500。这样可进一步提高载体对活性组分的吸附性能，及活性组分在载体上的分散效果。
采用本方法合成的催化剂载体UiO-66，是一种具有多级孔结构的催化剂载体，碱性溶液的添加能够加快了结晶速率，有利于小晶粒UiO-66的生成，小晶粒由于表面能较高，相互堆积形成了永久性的晶间介孔，优选，步骤B中，碱性溶液为氢氧化钠溶液、氢氧化钾溶液、氢氧化钡溶液或氢氧化铵溶液。这样能获得更好的多介孔结构。
优选，步骤B中，碱性溶液的浓度为1～15mol/L。
优选，步骤C中，反应温度为100～150℃，反应时间为10～24h。
上述用于处理废胺液的催化剂的使用条件为：反应器温度为150～250℃，反应压力不低于4MPa，反应时间为20min～90min，催化剂的用量与废胺液的质量比为1﹕100～300。
本发明未提及的技术均参照现有技术。
有益效果：
本发明处理废胺液的催化剂，同时具有微孔及介孔分布，这种具有多级孔分布的载体有利于反应过程中分子扩散，大大提高了反应催化氧化效率，更利于活性组分的吸附，显著提高了催化性能；活性组分通过化学键或氢键作用负载在UiO-66上，减少了活性组分的溶出；本发明充分利用UiO-66高稳定性特点，通过本专利的方法得到具有多级孔结构的载体与活性组分匹配，获得了具有高催化性和高稳定性的催化剂，适用于MDEA等胺液废水的处理；该负载型催化剂的合成方法简单可控，所得催化剂的应用操作方便，适合工业化生产和应用。
具体实施方式
为了更好地理解本发明，下面结合实施例对本发明进行进一步的阐明。
各实施例中负载活性组分的方法为：将活性组分的盐配置为浸渍液；采用浸渍法将浸渍液中的有效组分负载于步骤C所得的金属有机骨架材料UiO-66上，得到催化剂前驱体；将所得催化剂前驱体干燥，并在温度为300℃的条件下，在氢气气氛下还原10h，得处理废胺液的催化剂。
实施例1
将0.23mmol的ZrCl4和0.23mmol对苯二甲酸加入到25mL的DMF中，室温下搅拌至固体全部溶解(透明)后加入2mL浓度为5mol/L的氢氧化钠，室温下搅拌均匀(透明)；将上述混合液移至具有聚四氟乙烯内衬的反应釜中，密封反应釜，控制反应温度为100℃，反应时间为10h；反应结束后经离心分离、洗涤和干燥得UiO-66-1，用该载体负载质量分数为1％的氧化铜得催化剂UiO-66-1@1％Cu。
所得到的催化剂UiO-66-1@1％Cu的比表面积为1321m2/g，总孔容为1.04m3/g，微孔孔容为0.48m3/g，且大量的介孔存在，介孔孔容与微孔孔容比率为1.17。
实施例2
将0.23mmol的ZrOCl2·8H2O和0.23mmol对苯二甲酸加入到15mL的DMAC中，室温下搅拌至固体全部溶解后加入1mL浓度为8mol/L的氢氧化钾，室温下搅拌均匀；将上述混合液移至具有聚四氟乙烯内衬的反应釜中，密封反应釜，控制反应温度为120℃，反应时间为12h；反应结束后经离心分离、洗涤和干燥得目标产物UiO-66-2。用该载体负载质量分数为3％的氧化铜得催化剂UiO-66-2@3％Cu。
所得到的催化剂UiO-66-2@3％Cu的比表面积为1481m2/g，总孔容为1.35m3/g，微孔孔容为0.53m3/g，且大量的介孔存在，介孔孔容与微孔孔容比率为1.55。
实施例3
将0.23mmol的ZrCl4和0.46mmol对苯二甲酸加入到10mL的DMF中，室温下搅拌至固体全部溶解后加入0.5mL浓度为10mol/L的氢氧化铵，室温下搅拌均匀；将上述混合液移至具有聚四氟乙烯内衬的反应釜中，密封反应釜，控制反应温度为150℃，反应时间为24h；反应结束后经离心分离、洗涤和干燥得目标产物UiO-66-3。用该载体负载质量分数为5％的氧化铜得催化剂UiO-66-3@5％Cu。
所得到的催化剂UiO-66-3@5％Cu的比表面积为1410m2/g，总孔容为1.58m3/g，微孔孔容为0.49m3/g，且大量的介孔存在，介孔孔容与微孔孔容比率为2.22。
应用例1
取上述1g催化剂UiO-66-1@1％Cu以及COD(化学需氧量)为150g/L废胺液150mL于300mL的高压反应釜中，升温至200℃，通入空气至4MPa，反应40min。得到反应液的COD为10g/L。
应用例2
取上述1g催化剂UiO-66-2@3％Cu以及COD为150g/L废胺液150mL于300mL的高压反应釜中，升温至200℃，通入空气至5MPa，反应30min。得到反应液的COD为8g/L。
应用例3
取上述1g催化剂UiO-66-3@5％Cu以及COD为150g/L废胺液150mL于300mL的高压反应釜中，升温至250℃，通入空气至6MPa，反应50min。得到反应液的COD为6g/L。
对比例1
以活性炭为载体负载3％Cu，得到催化剂AC@3％Cu，取上述1g催化剂UiO-66-3@5％Cu及COD为150g/L废胺液150mL于300mL的高压反应釜中，升温至200℃，通入空气至5MPa，反应30min。得到反应液的COD为50g/L。
上述实施例仅仅是较佳的实施例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。凡依本发明申请专利范围的内容所作的等效变化与修饰，都应作为本发明的技术范畴。
Claims (7)
1.一种处理废胺液的催化剂，其特征在于：由90-99％的载体和1-10％的活性组分构成，其中，载体为具有多级孔结构的金属有机骨架材料UiO-66，活性组分为铜、钴、镍、铁、银、铬、钼或锰中的至少一种，活性组分的存在形式为金属单质、金属硫化物或金属氧化物，所述百分比为质量百分比；处理废胺液的催化剂的比表面积为1200～1500m2/g，总孔容为0.8～1.8m3/g，微孔孔容为0.4～0.53m3/g，介孔孔容与微孔孔容比率为1～2.5。
2.如权利要求1所述的处理废胺液的催化剂，其特征在于：活性组分为氧化铜。
3.权利要求1或2所述的处理废胺液的催化剂的制备方法，其特征在于：包括顺序相接的如下步骤：
A、将金属锆盐和对苯二甲酸加入非质子极性溶剂中，室温搅拌至透明；
B、向步骤A所得物料中加入碱性溶液，室温搅拌至透明，碱性溶液为氢氧化钠溶液、氢氧化钾溶液、氢氧化钡溶液或氢氧化铵溶液，碱性溶液的浓度为5～15mol/L，碱性溶液和非质子极性溶剂的体积比为1:12.5、1:15或1:20；
C、将步骤B所得物料移至具有聚四氟乙烯内衬的反应釜中，密封反应釜，控制反应温度为30～200℃，反应时间为5～50h；待反应结束后温度降至室温，反应物料经离心分离所得固体物料经过溶剂洗涤、干燥，得催化剂载体金属有机骨架材料UiO-66；
D、将活性组分的盐配置为浸渍液；
E、采用浸渍法将步骤D所得的浸渍液中的有效组分负载于步骤C所得的金属有机骨架材料UiO-66上，得到催化剂前驱体；
F、将步骤E所得催化剂前驱体干燥，并在温度为300±10℃的条件下，在氢气气氛下还原，得处理废胺液的催化剂。
4.如权利要求3所述的方法，其特征在于：步骤A中，金属锆盐为四氯化锆、氯氧化锆、硝酸氧锆、正丁醇锆、正丙醇锆或乙酸锆；非质子极性溶剂为N ,N-二甲基甲酰胺、N ,N-二甲基乙酰胺、乙腈、二甲基亚砜或1，3-二甲基-咪唑烷酮。
5.如权利要求3所述的方法，其特征在于：步骤A中，金属锆盐与对苯二甲酸的摩尔比为0 .5～1﹕1，金属锆盐与非质子型极性溶剂的摩尔比为1﹕500～1500。
6.如权利要求3所述的方法，其特征在于：步骤C中，反应温度为100～150℃，反应时间为10～24h。
7.权利要求1或2所述的处理废胺液的催化剂的应用，其特征在于：其使用条件为：反应器温度为150～250℃，反应压力不低于4MPa，反应时间为20min～90min，催化剂的用量与废胺液的质量比为1﹕100～300。
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