CN111138367B - 一种钴金属有机骨架材料及其制备方法和应用 - Google Patents
一种钴金属有机骨架材料及其制备方法和应用 Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 63
- 239000010941 cobalt Substances 0.000 title claims abstract description 63
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 45
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 12
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 claims description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 239000003208 petroleum Substances 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 3
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
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- 239000002245 particle Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- AROCLDYPZXMJPW-UHFFFAOYSA-N 1-(octyldisulfanyl)octane Chemical compound CCCCCCCCSSCCCCCCCC AROCLDYPZXMJPW-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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Abstract
本发明提供了一种钴金属有机骨架材料及其制备方法和应用,属于催化材料技术领域。本发明提供的钴金属有机骨架材料的制备方法,包括以下步骤:将钴源、2‑甲基咪唑和溶剂混合后于室温~60℃条件下进行反应,得到钴金属有机骨架材料。本发明以钴离子为活性中心,以2‑甲基咪唑为配体,在特定温度条件下进行反应,制备得到的钴金属有机骨架材料具有催化氧化硫醇的作用,能够作为催化剂应用于汽油脱硫醇中。实施例的结果显示,在无水甲醇环境中,本发明提供的钴金属有机骨架材料催化氧化硫醇的转化率可达99%,在石油醚(沸程30~60℃)环境中,硫醇的转化率可达33%。
Description
技术领域
本发明涉及催化材料技术领域,尤其涉及一种钴金属有机骨架材料及其制备方法和应用。
背景技术
随着汽车工业的蓬勃发展,汽油被大量燃烧并导致了大气环境的污染,随着人们环保意识的不断增强,世界各国对于发动机燃料的组成要求越发严格,尤其是对汽油中硫含量的要求越来越严格。硫醇是汽油主要含硫化合物中的一类,不仅具有恶臭气味,而且具有较强的反应活性,容易造成下游工艺中催化剂的失活,因此脱除汽油中硫醇类化合物的任务迫切而艰巨。
现有的汽油脱硫醇技术分为加氢脱硫技术和非加氢脱硫技术。其中,加氢脱硫技术已经很成熟,但深度加氢脱硫会导致液收低、辛烷值损失,同时存在着能耗高、耗氢高、投资和操作费用高等缺点。相对而言,非加氢脱硫技术反应条件温和且工艺流程较为简单,但通常有废碱液排放,不环保,而无碱脱臭工艺需要连续添加活化剂,且需要定期更换固定床的催化剂,这导致操作费用较高。
发明内容
本发明的目的在于提供一种钴金属有机骨架材料及其制备方法和应用,本发明提供的钴金属有机骨架材料具有催化氧化硫醇的作用,能够作为催化剂应用于汽油脱硫醇中,且脱硫醇效果较好。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种钴金属有机骨架材料的制备方法,包括以下步骤:
将钴源、2-甲基咪唑和溶剂混合后于室温~60℃条件下进行反应,得到钴金属有机骨架材料。
优选地,所述钴源包括硝酸钴、氯化钴、硫酸钴或醋酸钴。
优选地,所述钴源中钴与2-甲基咪唑的摩尔比为1:(2~16)。
优选地,所述溶剂包括水、甲醇或乙醇。
优选地,所述溶剂的体积与钴源和2-甲基咪唑的总质量比为(180~220)mL:(4.5~5.0)g。
优选地,所述反应的温度为60℃。
优选地,所述反应的时间为3h~5d。
优选地,所述反应完成后还包括:将所得体系进行固液分离,将所得固体物料洗涤后进行干燥,得到钴金属有机骨架材料。
本发明提供了上述技术方案所述制备方法制备得到的钴金属有机骨架材料,分子式为C8H10N4Co。
本发明提供了上述技术方案所述钴金属有机骨架材料在汽油脱硫醇中的应用。
本发明提供了一种钴金属有机骨架材料的制备方法,包括以下步骤:将钴源、2-甲基咪唑和溶剂混合后于室温~60℃条件下进行反应,得到钴金属有机骨架材料。本发明以钴离子为活性中心,以2-甲基咪唑为配体,在特定温度条件下进行反应,制备得到的钴金属有机骨架材料具有催化氧化硫醇的作用,能够作为催化剂应用于汽油脱硫醇中。具体的,所述钴金属有机骨架材料中含有大量钴离子,具有催化氧化硫醇的能力;同时其配体上含有大量氮原子,氮原子为硫醇的催化氧化反应提供了碱性环境,使钴金属有机骨架材料可以在无外加碱的环境下催化氧化硫醇。实施例的结果显示,在无水甲醇环境中,本发明提供的钴金属有机骨架材料催化氧化硫醇的转化率可达99%,在石油醚环境中,硫醇的转化率可达33%。
本发明提供的钴金属有机骨架材料的制备方法操作简单,反应条件温和,适宜规模化生产。
附图说明
图1为本发明提供的钴金属有机骨架材料的分子结构示意图;
图2为本发明实施例1制备的ZIF-67的SEM图;
图3为本发明实施例1制备的ZIF-67的XRD图。
具体实施方式
本发明提供了一种钴金属有机骨架材料的制备方法,包括以下步骤:
将钴源、2-甲基咪唑和溶剂混合后于室温~60℃条件下进行反应,得到钴金属有机骨架材料。
在本发明中,所述钴源优选包括硝酸钴、氯化钴、硫酸钴或醋酸钴,更优选为硝酸钴;在本发明的实施例中,具体是采用Co(NO3)2·6H2O。
在本发明中,所述钴源中钴与2-甲基咪唑的摩尔比优选为1:(2~16),更优选为1:(4~12),进一步优选1:8。本发明优选将钴源中钴与2-甲基咪唑的摩尔比控制在上述范围内,能够保证最终制备得到的钴金属有机骨架材料为ZIF-67,且有利于保证所得ZIF-67为形貌更规整的菱形十二面体颗粒。
在本发明中,所述溶剂优选包括水、甲醇或乙醇,更优选为甲醇,其中,所述水优选为去离子水,所述甲醇优选为无水甲醇,所述乙醇优选为无水乙醇;当采用水作为溶剂时,具体是将钴源、2-甲基咪唑和水混合后于室温~60℃条件下进行水热反应,当采用甲醇(或乙醇)作为溶剂时,具体是将钴源、2-甲基咪唑和甲醇(或乙醇)混合后于室温~60℃条件下进行溶剂热反应。
在本发明中,所述溶剂的体积与钴源和2-甲基咪唑的总质量比优选为(180~220)mL:(4.5~5.0)g,更优选为200mL:4.68g。本发明优选将溶剂的用量控制在上述范围内,有利于形成形貌更规整的产物。
在本发明中,所述钴源、2-甲基咪唑和溶剂混合优选是将钴源溶解于溶剂中,控制体系温度为室温~60℃,得到钴源溶液;将2-甲基咪唑溶解于溶剂中,控制体系温度为室温~60℃,得到2-甲基咪唑溶液;然后将所述钴源溶液和2-甲基咪唑溶液混合。
在本发明中,所述反应的温度为室温~60℃,优选为60℃;本发明所述室温即不需要额外的加热或降温;所述反应的时间优选为3h~5d,更优选为10h~2d,进一步优选为20~24h。本发明控制反应的温度和时间在上述范围内,在保证生产效率的基础上有利于获得合适粒径、形貌规整的产物。在本发明中,所述反应优选在常压和搅拌条件下进行,本发明对于所述搅拌的速率没有特殊的限定,常规搅拌速率即可。
在本发明中,所述反应完成后优选还包括:将所得体系进行固液分离,将所得固体物料洗涤后进行干燥,得到钴金属有机骨架材料。本发明对于所述固液分离的方式没有特殊的限定,采用本领域技术人员熟知的方式即可,具体如离心分离。本发明对于洗涤所用试剂的种类没有特殊的限定,优选与上述进行反应时所用溶剂一致;所述洗涤的次数优选为2~3次。在本发明中,所述干燥优选为真空干燥;所述真空干燥的温度优选为140~160℃,优选为150℃;时间优选为6~10h,更优选为8h。
本发明提供了上述技术方案所述制备方法制备得到的钴金属有机骨架材料,其分子式为C8H10N4Co,分子结构示意图如图1所示。本发明提供的钴金属有机骨架材料为菱形十二面体,粒径为50nm~5μm。
本发明提供了上述技术方案所述钴金属有机骨架材料在汽油脱硫醇中的应用。在本发明中,所述钴金属有机骨架材料可以作为催化剂应用于汽油脱硫醇中,所述硫醇优选包括正辛硫醇、正丁硫醇和异丁硫醇中的至少一种。在本发明的实施例中,具体通过以下方法验证所述钴金属有机骨架材料的脱硫醇效果:
在一容器中加入硫醇和溶剂,充分搅拌使硫醇溶解,得到硫醇溶液;在另一容器中加入钴金属有机骨架材料,放入磁子,将所述硫醇溶液加入到装有钴金属有机骨架材料的容器中,在搅拌条件下进行催化氧化反应,反应过程中硫醇转化为对应的二硫化物;反应结束后通过测定硫醇的转化率表征钴金属有机骨架材料的脱硫醇效果。
在本发明中,所述溶剂优选包括水、无水甲醇、无水乙醇、无水丙醇、石油醚(沸程优选为30~60℃、60~90℃或90~120℃)、正戊烷、正己烷、正庚烷和乙腈中的至少一种。
在本发明中,所述钴金属有机骨架材料、硫醇和溶剂的用量比优选为1mg~10g:(0.01~500)mmol:(1~1000)mL,更优选为(0.04~0.1)g:(2~5)mmol:(10~100)mL。
在本发明中,所述催化氧化反应的温度优选为10~50℃,更优选为25~50℃;时间优选为10~600min,更优选为120~150min。
下面将结合本发明中的实施例,对本发明中的技术方案进行清楚、完整地描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
将1.436g的Co(NO3)2·6H2O溶解在100mL无水甲醇中,加热到60℃,得到硝酸钴溶液;将3.244g的2-甲基咪唑溶解在100mL无水甲醇中,加热到60℃,得到2-甲基咪唑溶液;将所述硝酸钴溶液和2-甲基咪唑溶液搅拌混合12min,之后在60℃、常压条件下搅拌反应20h;反应完成后,将所得体系离心,得到紫色沉淀,用无水甲醇将所述紫色沉淀洗涤3次,然后于150℃条件下真空干燥8h,得到紫色钴金属有机骨架材料,记为ZIF-67。
图2为实施例1制备的ZIF-67的SEM图,由图2可知,所述ZIF-67的粒径约为800nm,且形貌为菱形十二面体,粒径分布均匀。
图3为实施例1制备的ZIF-67的XRD图,通过与ZIF-67的标准XRD图谱比较,其与ZIF-67的标准XRD图谱相吻合。
应用例1
在一容器中加入5mmol正辛硫醇和10mL无水甲醇,在50℃恒温油浴中充分搅拌使正辛硫醇溶解,得到正辛硫醇溶液;在另一容器中加入0.1g实施例1制备的ZIF-67,放入磁子,放置于50℃恒温油浴中,再将所述正辛硫醇溶液加入到装有ZIF-67的容器中,在50℃条件下搅拌反应2h,反应过程中正辛硫醇转化为二辛基二硫醚;反应结束后经测定,正辛硫醇的转化率为97%。
应用例2~7
按照应用例1的方法对实施例1制备的ZIF-67的性能进行测定,具体测试条件及硫醇转化率列于表1中。
表1应用例1~7中ZIF-67的性能测试条件及硫醇转化率
由表1可知,实施例1制备的ZIF-67具有催化氧化硫醇的作用,在无水甲醇为溶剂的条件下,硫醇的转化率可达99%,在石油醚(沸程30~60℃)为溶剂的条件下,硫醇的转化率可达33%,能够作为催化剂应用于汽油脱硫醇中。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (1)
1.一种钴金属有机骨架材料在汽油脱硫醇中的应用,包括以下步骤:
在一容器中加入硫醇和溶剂,充分搅拌使硫醇溶解,得到硫醇溶液;
在另一容器中加入钴金属有机骨架材料,放入磁子,将所述硫醇溶液加入到装有钴金属有机骨架材料的容器中,在搅拌条件下进行催化氧化反应;
所述硫醇选自正辛硫醇、正丁硫醇和异丁硫醇中的至少一种,所述溶剂为无水甲醇,所述钴金属有机骨架材料、硫醇和溶剂的用量比为(0.04~0.1)g:(2~5)mmol:(10~100)mL;所述催化氧化反应的温度为25~50℃,时间为120~150min;
所述钴金属有机骨架材料的分子式为C8H10N4Co,按以下步骤制备得到:
将1.436g的Co(NO3)2·6H2O溶解在100mL无水甲醇中,加热到60℃,得到硝酸钴溶液;将3.244g的2-甲基咪唑溶解在100mL无水甲醇中,加热到60℃,得到2-甲基咪唑溶液;将所述硝酸钴溶液和2-甲基咪唑溶液搅拌混合12min,之后在60℃、常压条件下搅拌反应20h;反应完成后,将所得体系离心,得到紫色沉淀,用无水甲醇将所述紫色沉淀洗涤3次,然后于150℃条件下真空干燥8h,得到紫色钴金属有机骨架材料。
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