CN111712323A - 可高选择性转化的碳基贵金属-过渡金属催化剂及其制备方法 - Google Patents
可高选择性转化的碳基贵金属-过渡金属催化剂及其制备方法 Download PDFInfo
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- CN111712323A CN111712323A CN201880083805.3A CN201880083805A CN111712323A CN 111712323 A CN111712323 A CN 111712323A CN 201880083805 A CN201880083805 A CN 201880083805A CN 111712323 A CN111712323 A CN 111712323A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 18
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 44
- 229910017604 nitric acid Inorganic materials 0.000 claims description 43
- 239000006229 carbon black Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 239000011148 porous material Substances 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 9
- 150000001299 aldehydes Chemical group 0.000 claims description 8
- 150000002576 ketones Chemical group 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- BYGQBDHUGHBGMD-UHFFFAOYSA-N 2-methylbutanal Chemical compound CCC(C)C=O BYGQBDHUGHBGMD-UHFFFAOYSA-N 0.000 claims description 6
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- FTZILAQGHINQQR-UHFFFAOYSA-N 2-Methylpentanal Chemical compound CCCC(C)C=O FTZILAQGHINQQR-UHFFFAOYSA-N 0.000 claims description 5
- NUJGJRNETVAIRJ-UHFFFAOYSA-N Caprylic Aldehyde Natural products CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000001893 (2R)-2-methylbutanal Substances 0.000 claims description 3
- PXDSNHKJOOEUKD-ODZAUARKSA-N (z)-but-2-enedioic acid;propanedioic acid Chemical compound OC(=O)CC(O)=O.OC(=O)\C=C/C(O)=O PXDSNHKJOOEUKD-ODZAUARKSA-N 0.000 claims description 3
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 claims description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 3
- YJWJGLQYQJGEEP-UHFFFAOYSA-N 3-methylpentanal Chemical compound CCC(C)CC=O YJWJGLQYQJGEEP-UHFFFAOYSA-N 0.000 claims description 3
- JGEGJYXHCFUMJF-UHFFFAOYSA-N 4-methylpentanal Chemical compound CC(C)CCC=O JGEGJYXHCFUMJF-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- OVYQSRKFHNKIBM-UHFFFAOYSA-N butanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O OVYQSRKFHNKIBM-UHFFFAOYSA-N 0.000 claims description 3
- KSMVZQYAVGTKIV-UHFFFAOYSA-N caprinaldehyde Natural products CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- XEUHNWODXVYLFD-UHFFFAOYSA-N heptanedioic acid Chemical compound OC(=O)CCCCCC(O)=O.OC(=O)CCCCCC(O)=O XEUHNWODXVYLFD-UHFFFAOYSA-N 0.000 claims description 3
- YVSCCMNRWFOKDU-UHFFFAOYSA-N hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCC(O)=O YVSCCMNRWFOKDU-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- WPBWJEYRHXACLR-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O.OC(=O)CCCCCCCC(O)=O WPBWJEYRHXACLR-UHFFFAOYSA-N 0.000 claims description 3
- TWHMVKPVFOOAMY-UHFFFAOYSA-N octanedioic acid Chemical compound OC(=O)CCCCCCC(O)=O.OC(=O)CCCCCCC(O)=O TWHMVKPVFOOAMY-UHFFFAOYSA-N 0.000 claims description 3
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- YKEKYBOBVREARV-UHFFFAOYSA-N pentanedioic acid Chemical compound OC(=O)CCCC(O)=O.OC(=O)CCCC(O)=O YKEKYBOBVREARV-UHFFFAOYSA-N 0.000 claims description 3
- ZFACJPAPCXRZMQ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.OC(=O)C1=CC=CC=C1C(O)=O ZFACJPAPCXRZMQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
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- JRFMZTLWVBLNLM-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1.OC(=O)C1=CC=CC(C(O)=O)=C1 JRFMZTLWVBLNLM-UHFFFAOYSA-N 0.000 claims description 2
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- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明涉及一种碳基贵金属‑过渡金属络合催化剂及其制备方法,其通过对包含规定比例以上的中孔(mesopore)的碳载体进行前处理,能够将羧酸官能团高选择性地转化为醇官能团。
Description
技术领域
本发明涉及一种可高选择性转化的碳基贵金属-过渡金属催化剂及其制备方法,具体涉及通过对包含规定比例以上的中孔(mesopore)的碳载体进行前处理,能够将羧酸官能团高选择性地转化为醇官能团的碳基贵金属-过渡金属复合催化剂及其制备方法。
背景技术
二醇(Diol)被广泛用作聚酯(polyesters)、聚氨酯(polyurethanes)、清漆(vanishes)、粘合剂(adhesives)、药物(pharmaceuticals)等的基础工业材料。并且,最近对环保并可生物降解的二醇(diol)的需求正在大幅增加。这些二醇(diol)化合物可以由二羧酸(dicarboxylic acid)或其衍生物通过加氢催化剂(hydroprocessing catalyst)转化而成。能够实现该转化的现有的催化工艺大部分为基于Cu-Cr或Zr-Cr的催化工艺或基于钌氧化物、钌碳复合物等的催化工艺,然而上述的多种催化工艺需要高压(200~300bar)运行条件。因此,需要开发能够在相对低压条件下运用的催化剂。
在制备聚酯树脂的过程中,当使用多个二醇(diol)化合物,尤其是环己烷二甲醇(cyclohexanedimethanol,CHDM)来替代乙二醇(ethylene glycol)及其它多元醇(polyol)时,其具有高热稳定性,并且绝缘性、透明性以及耐化学性较高,因此,受人瞩目。目前,在工业上,通过使对苯二甲酸(terephthalic acid,TPA)与甲醇(methanol)发生酯化(esterification)以制备对苯二甲酸二甲酯(dimethylterephthalate,DMT)之后,进一步经过两次氢化过程而生产CHDM。然而,最近正在试图通过单个步骤的氢化反应由环己烷二羧酸(cyclohexanedicarboxylic acid,CHDA)生产CHDM,以降低生产成本并简化工艺。
因此,本发明对于使用环己烷二羧酸(cyclohexanedicarboxylic acid,CHDA)作为二羧酸(dicarboxylic acid)的代表物质并且有效地生产作为目标二醇(diol)的环己烷二甲醇(cyclohexanedimethanol,CHDM)的催化剂的合成方法进行说明。
三菱化学(Mitsubishi Chemical,MCC)将RuPtSn/C催化剂作为由CHDA制备CHDM的催化剂申请了专利(USP 6294703),但是由于Pt而导致催化剂昂贵。旭化成(Asahi Kasei)提出了将Ru-Sn-Re/C催化剂作为由CHDA制备CHDM的催化剂(US6495730),但即便使用了昂贵的Re,CHDM的收率也止于75%。LG化学提出了Y型沸石(Y-zeolite)作为RuPtSn的载体(WO2015-156582),但其也会造成高昂的催化剂成本。中国石化(Sinopec)在Al2O3上涂覆碳层并将其用作催化剂的载体,以改良现有的在先专利(CN1911504)RuSn/Al2O3催化剂,并对其申请了专利(CN 104549251)。然而,为了合成上述专利所提出的涂覆有碳层的Al2O3载体而需要多步合成工艺,并且根据CHDA的反应特点,反应溶液为高温酸性条件,因此,水热稳定性比碳低的Al2O3很可能存在铝浸出(Al leaching)问题。据由Zhang Xiaoou申请的专利(CN101982236A),当使用孔隙体积为1.5mL/g~2.5mL/g、比表面积为1,000m2/g~2,000m2/g、孔径为3nm~10nm的有序中孔碳(ordered mesoporous carbon,OMC)作为RuSn催化剂的载体时,能够确保催化剂的性能及寿命。然而,满足上述理化特性的有序中孔碳的合成方法为多步工艺,因此,生产成本高昂,不利于用在实际商业设施中。另外,有序中孔碳以用作模板(template)的材料的反相形成孔隙,因此,当所使用的模板(template)的孔隙连通性(pore connectivity)较低时,构成有序中孔碳的结构的碳框架(framework)的机械强度(mechanical strength)很可能比现有的碳材料低。在在先专利(CN101982236A)中,在室温下使用过氧化氢水溶液或盐酸水溶液对碳载体进行前处理,此时,引入到碳载体表面上的含氧官能团(oxygen functional group)的量较少,因此,不利于有效地固定Ru-Sn活性金属。
发明内容
技术问题
本发明的目的在于,解决上述现有技术的问题和历来被提出的技术问题。
本发明的目的在于提供一种碳基贵金属-过渡金属复合催化剂及其制备方法,其通过对中孔(mesopore)相对于总孔隙的体积比例为规定比例以上的碳载体进行前处理,能够将羧酸官能团高选择性地转化为醇官能团,以缩短并改良现有的催化剂合成过程,从而以低成本表现出高活性。
技术方案
用于达成上述目的的本发明的可高选择性转化的碳基贵金属-过渡金属催化剂为使用多孔性的碳作为载体的氢化催化剂,
在所述碳中,孔径为2nm~50nm的中孔(mesopore)在总孔隙中的体积比例为50%以上,并且相对于总量为100重量份的所述载体,包含1~20重量份的活性金属。
在本发明一优选例中,所述碳可包括选自活性炭、碳黑、石墨、石墨烯、有序中孔碳(OMC,ordered mesoporous carbon)以及碳纳米管中的至少一种。
在本发明一优选例中,所述活性金属可包括:
选自钯(Pd)、铑(Rh)、钌(Ru)以及铂(Pt)中的至少一种贵金属;以及选自锡(Sn)、铁(Fe)、铼(Re)以及镓(Ga)中的至少一种过渡金属。
在本发明一优选例中,所述贵金属可以是钌,所述过渡金属可以是锡。
在本发明一优选例中,可使用硝酸(HNO3)水溶液对所述碳载体进行前处理。
其中,在本发明一优选例中,所述硝酸(HNO3)水溶液中,相对于总量为100重量份的该水溶液,可包含1~50重量份的硝酸。
在本发明一优选例中,所述碳的比表面积可以是100m2/g~1,500m2/g,孔隙体积(pore volume)可以是0.1mL/g~1.5mL/g。
在本发明一优选例中,所述碳可以是具有2nm~25nm的中孔(mesopore)并具有立体杆状或立体管状的孔隙结构的有序中孔碳。即,所述活性金属负载于以立体的有序中孔结构排列的碳载体内部,因此,与现有的催化剂相比,催化活性更高,从而能够提高选择性和生成速率。
另一方面,本发明提供一种氢化催化剂的用途,其使用所述催化剂,将羧酸官能团(carboxylic acid group)氢化为醇官能团(alcohol group)。本发明还提供一种催化剂制备方法,用于制备所述催化剂,使用包含1~50重量份的硝酸的硝酸(HNO3)水溶液对所述碳载体进行至少一次前处理。
在本发明一优选例中,所述前处理过程可以在50℃~150℃温度范围内进行。
在本发明一优选例中,所述前处理过程可以进行1小时~10小时。
在本发明一优选例中,所述前处理过程可以在负载所述活性金属之前进行。
另外,本发明提供一种氢化方法,其使用所述催化剂,将羧酸官能团、醛官能团或酮官能团氢化为醇官能团。
在本发明一优选例中,所述氢化反应的反应压力可以是2MPa~15MPa,反应温度可以是140℃~280℃,反应时间可以是0.5小时~10小时。
在本发明一优选例中,所述羧酸可以是选自乙二酸(oxalic acid)、丙二酸(malonic acid)、丁二酸(succinic acid)、戊二酸(glutaric acid)、己二酸(adipicacid)、庚二酸(pimelic acid)、辛二酸(suberic acid)、壬二酸(azelaic acid)、癸二酸(sebacic acid)、邻苯二甲酸(phthalic acid)、间苯二甲酸(isophthalic acid)、环己烷二羧酸(cyclohexane dicarboxylic acid)以及对苯二甲酸(terephthalic acid)中的一种。
在本发明一优选例中,所述醛官能团可以是选自甲醛、丙醛、正丁醛、异丁醛、戊醛、2-甲基丁醛、3-甲基丁醛、2,2-二甲基丙醛、己醛、2-甲基戊醛、3-甲基戊醛、4-甲基戊醛、2-乙基丁醛、2,2-二甲基丁醛、3,3-二甲基丁醛、辛醛、癸醛以及戊二醛中的一种。
在本发明一优选例中,所述酮官能团可以是选自丙酮、丁酮、戊酮、己酮、环己酮以及苯乙酮中的一种。
有益效果
如上所述,本发明的可高选择性转化的碳基贵金属-过渡金属催化剂通过对具有规定比例的中孔的碳载体进行前处理使用,能够提高环己烷二羧酸(Cyclohexanedicarboxylic acid,CHDA)的转化反应速率,从而以低成本获得高活性。
附图说明
图1是示出本发明的一实施例的碳黑A(Carbon Black A)载体经硝酸处理后的氮气物理吸附分析结果的图。
图2是示出本发明一实施例的碳黑A(Carbon Black A)载体在不同的硝酸前处理浓度下的催化活性的图。
具体实施方式
对后述的本发明的说明将参照作为示例示出的能够实施本发明的特定实施例。详细说明这些实施例,以便本领域技术人员能够充分实施本发明。本发明的多个实施例彼此不同,但不必互斥。例如,记载于此的特定形状、结构及特性与一实施例相关联,在不脱离本发明的技术思想及范围内,能够以其他实施例实现。
因此,后述的详细说明不是限定性的,只要适当地说明,本发明的范围仅由所附的权利要求及其等同的范围限定。
另外,在本说明书中,除非另有说明,否则“取代”或“被取代”表示本发明的官能团中的一个以上的氢原子被选自卤素原子(-F、-Cl、-Br或-I)、羟基、硝基、氰基、氨基、脒基、肼基、腙基、羧基、酯基、酮基、被取代或未被取代的烷基、被取代或未被取代的脂环族有机基团、被取代或未被取代的芳基、被取代或未被取代的烯基、被取代或未被取代的炔基、被取代或未被取代的杂芳基以及被取代或未被取代的杂环基中的至少一种取代基取代,并且多个所述取代基也可以彼此连接而形成环。
在本发明中,除非另有说明,否则所述“取代”表示氢原子被卤素原子、碳原子数1~20的烃基、碳原子数1~20的烷氧基、碳原子数6~20的芳氧基等取代基取代。
另外,除非另有说明,否则所述“烃基”表示线型、支化型或环型的饱和或不饱和烃基,所述烷基、烯基、炔基等可以是线型、支化型或环型。
另外,在本说明书中,除非另有说明,否则“烷基”表示C1~C30的烷基,“芳基”表示C6~C30的芳基。在本说明说中,“杂环基”表示一个环内含有1~3个选自O、S、N、P、Si以及它们的组合中的杂原子的基团,例如,表示吡啶、噻吩、吡嗪等,但不限于此。
在本发明的详细说明中,术语二羧酸(dicarboxylic acid)表示一个分子内包含两个羧酸官能团的有机酸。例如,二羧酸的分子式由HOOC-R-COOH表示,在本发明中,R优选为烷基或芳基。
以下,对本发明的多个优选实施例进行详细说明,以便本领域技术人员能够容易地实施本发明。
对此,本发明提供一种可高选择性转化的碳基贵金属-过渡金属催化剂,其为使用多孔性的碳作为载体的氢化催化剂,使用硝酸水溶液对所述碳载体进行前处理,并且,在所述碳中,孔径为2nm~50nm的中孔(mesopore)在总孔隙中的体积比例为50%以上,并且相对于总量为100重量份的所述载体,包含1~20重量份的活性金属,并由此寻求上述问题的解决方案。
该催化剂能够提高上述的环己烷二羧酸(Cyclohexane dicarboxylic acid,CHDA)的转化反应速率,从而以低成本表现出高活性。
以下,对上述的可高选择性转化的碳基贵金属-过渡金属催化剂的组合物进行更加详细的说明。
首先,所述碳载体不受特别的限制,但可以使用选自活性炭、碳黑、石墨、石墨烯、有序中孔碳以及碳纳米管中的至少一种。可以优选总孔隙中的中孔比例较高的碳黑,在具体例中,所述活性炭可以是SX ULTRA、CGSP、PK1-3、SX 1G、DRACO S51HF、CA-1、A-51、GAS 1240PLUS、KBG、CASP以及SX PLUS等,所述碳黑可以是BLACK 以及等,但不限于此。
其中,根据本发明,在所述碳载体的所述碳中,孔径为2nm~50nm的中孔在总孔隙中的体积比例可以是50%以上。优选地,在所述碳载体的所述碳中,中孔在所述碳的总孔隙中的体积比例可以是70%以上,更优选地,在所述碳载体的所述碳中,中孔在总孔隙中的体积比例可以是75%以上。
此时,当所述中孔的体积比例小于50%时,反应物及产物在碳载体内的微观物质传递速度会存在问题,当所述孔隙的平均孔径大于50nm时,会存在载体的物理强度低的问题,因此,优选上述的范围。
另外,根据本发明,所述碳包括比表面积(BET)为100m2/g~1,500m2/g范围的有序中孔碳。优选地,所述碳可包括比表面积(BET)为200m2/g~1,000m2/g范围的有序中孔碳。此时,当所述碳的比表面积小于100m2/g时,难以高度分散活性金属(Ru、Sn),当所述碳的比表面积大于1,500m2/g时,会存在中孔的比例降低的问题,因此,优选上述的范围。
然后,所述活性金属可包括选自钯(Pd)、铑(Rh)、钌(Ru)以及铂(Pt)中的至少一种贵金属以及选自锡(Sn)、铁(Fe)、铼(Re)以及镓(Ga)中的至少一种过渡金属,但不限于此。
其中,根据本发明,相对于总量为100重量份的所述载体,所述贵金属的含量可以为1~20重量份,优选为3~8重量份。相对于总量为100重量份的所述载体,所述过渡金属的含量可以为1~20重量份,优选为3~8重量份。
另外,根据不同情况,除了中等孔径的中孔以外,本发明的催化剂的所述碳载体可以以适当比例包含微孔(micropore),并且在总孔隙中,可以包括0~25%的体积比例的微孔(micropore)。此时,当包含大于25%的体积比例的所述微孔时,反应物及产物在碳载体内的微观物质传递速度会存在问题,因此,优选上述的范围。
另一方面,本发明提供一种可高选择性转化的碳基贵金属-过渡金属催化剂的制备方法,用于制备催化剂,使用硝酸(HNO3)水溶液,对所述碳载体进行至少一次前处理。
首先,根据本发明,使用硝酸(HNO3)水溶液,对所述碳载体进行至少一次前处理的过程。其中,所述硝酸(HNO3)水溶液中,相对于总量为100重量份的该溶液,可包含1~50重量份的硝酸。优选地,所述硝酸(HNO3)水溶液可以是相对于总量为100重量份的该溶液包含5~40重量份的硝酸的水溶液。更优选地,所述硝酸(HNO3)水溶液可以是相对于总量为100重量份的该溶液包含5~35重量份的硝酸的水溶液。
其中,当相对于总量为100重量份的该溶液,使用小于1重量份的硝酸进行前处理时,难以达到预期的催化活性,当相对于总量为100重量份的该溶液,使用50重量份以上的硝酸进行前处理时,由于碳载体表面的酸度增加及由含氧官能团导致的活性金属中毒,会导致催化剂的活性降低及碳载体结构崩塌,因此,优选上述的范围。
根据本发明,所述前处理过程可以在70℃~150℃温度范围内进行,优选在80℃~110℃温度范围内进行。此时,当所述前处理过程温度低于70℃时,会存在引入到碳载体表面上的含氧官能团减少的问题,当所述前处理过程温度高于150℃时,会存在碳载体结构崩塌的问题,因此,优选上述的范围。
另一方面,本发明能够提供将双羧酸官能团(双羧基(dicarboxyl group))氢化为双醇官能团(dialcohol group)的氢化方法,例如,将所述催化剂用于对羧酸类、醛类以及酮类进行氢化的氢化方法。在具体例中,根据本发明,在所述催化剂上,能够通过环己烷二羧酸(Cyclohexane dicarboxylic acid,CHDA)的加氢反应来制备环己烷二甲醇(Cyclohexane dimethanol,CHDM)。
其中,所述羧酸不受特别的限定,例如,可包括乙二酸(oxalic acid)、丙二酸(malonic acid)、丁二酸(succinic acid)、戊二酸(glutaric acid)、己二酸(adipicacid)、庚二酸(pimelic acid)、辛二酸(suberic acid)、壬二酸(azelaic acid)、癸二酸(sebacic acid)、邻苯二甲酸(phthalic acid)、间苯二甲酸(isophthalic acid)、对苯二甲酸(terephthalic acid)、甲酸、乙酸、己酸、辛酸、月桂酸、肉豆蔻酸、软脂酸、硬脂酸、异硬脂酸、油酸、马来酸、己二酸、癸二酸、环己烷羧酸以及苯甲酸等。
另外,具有所述醛官能团的醛类,例如,可以包括甲醛、丙醛、正丁醛、异丁醛、戊醛、2-甲基丁醛、3-甲基丁醛、2,2-二甲基丙醛、己醛、2-甲基戊醛、3-甲基戊醛、4-甲基戊醛、2-乙基丁醛、2,2-二甲基丁醛、3,3-二甲基丁醛、辛醛、癸醛以及戊二醛等。
另外,具有所述酮官能团的酮类,例如,可包括丙酮、丁酮、戊酮、己酮、环己酮以及苯乙酮等。
以下,提出优选实施例(example),以帮助理解本发明。只是,下述实施例仅用于帮助理解本发明,本发明不限于下述试验例。
[准备例]
<准备例>碳载体的硝酸前处理
使用活性炭(Activated Carbon)、碳黑(碳黑B、碳黑A)作为Ru-Sn催化剂的担体。在浸渍Ru-Sn前体之前,使用5重量%的硝酸水溶液在95℃下对各种碳载体进行前处理3小时。
具体地,在500g的5重量%的硝酸水溶液中,将30g的各种碳载体在95℃下搅拌3小时之后,过滤,并使用蒸馏水持续洗涤,直到滤出的蒸馏水的pH值为7。将以此方式滤出的各个碳载体在373K下干燥24小时,并将经过所述硝酸前处理的碳载体的物理特性示于下表1中。
表1:
[实施例]
<实施例1>碳黑A载体的高浓度硝酸前处理
对于碳黑A载体,在上述准备例中使用5重量%的硝酸水溶液进行前处理,并且使用30重量%、50重量%的硝酸水溶液在95℃下进行前处理3小时。具体地,在500g的30重量%或50重量%的硝酸水溶液中,将30g的碳黑A载体在95℃下搅拌3小时之后,过滤,并使用蒸馏水持续洗涤,直到滤出的蒸馏水的pH值为7。将以此方式滤出的碳黑A载体在373K下干燥24小时。将经过所述硝酸前处理的碳黑A载体的氮气物理吸附分析结果示于图1中,并将物理特性示于下表2中。
表2:
<实施例2>使用5重量%硝酸进行前处理的Ru-Sn/碳黑A催化剂的制备
在上述准备例中,在将1.38g的RuCl3*3H2O、1.12g的SnCl2*2H2O溶解于7g的H2O中而成的水溶液中,对于使用5重量%的硝酸进行前处理的10g的碳黑A碳载体,在室温下,利用初湿浸渍法(incipient wetness impregnation)方法,负载Ru-Sn。之后,在373K下干燥12小时之后,在773K下以引入氢气(流速:20mLmin-1g-1)的方式将其还原3小时之后,以引入氢气(流速:20mLmin-1g-1)的方式冷却至室温。之后,在室温下引入氦气(流速:20mLmin-1g-1)30分钟之后,以引入10%的氧气/氮气混合气体(流速:20mLmin-1g-1)1小时的方式钝化所述催化剂。将以此方式所制备的催化剂标注为“Ru-Sn/碳黑A”。
<实施例3>使用30重量%及50重量%的硝酸进行前处理的Ru-Sn/碳黑A催化剂的制备
在上述准备例中,在将1.38g的RuCl3*3H2O、1.12g的SnCl2*2H2O溶解于7g的H2O中而成的水溶液中,对于分别使用30重量%、50重量%的硝酸进行前处理的10g的碳黑A碳载体,在室温下,利用初湿浸渍法(incipient wetness impregnation)方法,负载Ru-Sn。之后,在373K下干燥12小时之后,在773K下以引入氢气(流速:20mLmin-1g-1)的方式将其还原3小时之后,以引入氢气(流速:20mLmin-1g-1)的方式冷却至室温。之后,在室温下,引入氦气(流速:20mLmin-1g-1)30分钟之后,以引入10%的氧气/氮气混合气体(流速:20mLmin-1g-1)1小时的方式钝化所述催化剂。将以此方式所制备的催化剂标注为“Ru-Sn/碳黑A(30重量%的HNO3)”、“Ru-Sn/碳黑A(50重量%的HNO3)”。
<实施例4>使用5重量%硝酸进行前处理的Ru-Sn/碳黑B催化剂的制备
在上述准备例中,在将1.38g的RuCl3*3H2O、1.12g的SnCl2*2H2O溶解于到7g的H2O中而成的水溶液中,对于使用5重量%的硝酸进行前处理的10g的碳黑B碳载体,在室温下,利用初湿浸渍法(incipient wetness impregnation)方法,负载Ru-Sn。之后,在373K下干燥12小时之后,在773K下以引入氢气(流速:20mLmin-1g-1)的方式还原3小时之后,以引入氢气(流速:20mLmin-1g-1)的方式冷却至室温。之后,在室温下引入氦气(流速:20mLmin-1g-1)30分钟之后,以引入10%的氧气/氮气混合气体(流速:20mLmin-1g-1)1小时的方式钝化所述催化剂。将以此方式所制备的催化剂标注为“Ru-Sn/碳黑B”。
[比较例]
<比较例1>使用5重量%硝酸进行前处理的Ru-Sn/活性炭催化剂的制备
在上述准备例中,在将1.38g的RuCl3*3H2O、1.12g的SnCl2*2H2O溶解于7g的H2O中而成的水溶液中,对于使用5重量%的硝酸进行前处理的10g的活性炭碳载体,在室温下,利用初湿浸渍法(incipient wetness impregnation)方法,负载Ru-Sn。之后,在373K下干燥12小时之后,在773K下以引入氢气(流速:20mLmin-1g-1)的方式还原3小时之后,以引入氢气(流速:20mLmin-1g-1)的方式冷却至室温。然后,在室温下引入氦气(流速:20mLmin-1g-1)30分钟之后,以引入10%的氧气/氮气混合气体(流速:20mLmin-1g-1)1小时的方式钝化所述催化剂。将以此方式所制备的催化剂标注为“Ru-Sn/活性炭”。
[试验例]环己烷二羧酸转化试验
在公称(nominal)体积为250mL、最大运转压力为10.0MPa的衬有二氧化钛的不锈钢高压釜内进行环己烷二羧酸(cyclohexanedicarboxylic acid)转化试验。此时,投入3g的催化剂、11.25g的反应物(环己烷二羧酸(cyclohexanedicarboxylic acid))以及150g的溶剂(H2O),并在503K下进行反应。之后,使用氢气,将反应器加压至反应压力,并通过氢气传感器确认反应器是否泄露(leak)之后,减压并换气(purge),以去除反应器内部的所有氧气。最终将反应器内部压力调成10bar之后,将反应器内部温度加热至反应温度并加压至氢气氛围的反应压力之后,反应6小时。反应是在230℃、90bar下进行6小时的,搅拌是利用顶置式搅拌器(overhead impeller)来保持1000rpm的速度的。反应结束之后,冷却至常温并解压之后,通过过滤法来分离催化剂与液态产物,并利用安装有HP-1色谱柱的气相色谱进行分析。
使用根据实施例2至实施例4及比较例1而制备的催化剂进行环己烷二羧酸(cyclohexanedicarboxylic acid)转化试验并将其结果分别示于图2及表3中。
表3:
催化剂 | 6小时反应基准CHDM收率(%) |
Ru-Sn/碳黑A | 99 |
Ru-Sn/碳黑B | 84 |
Ru-Sn/活性炭 | 10 |
如图2及表3所示,总孔隙中的中孔比例较高的Ru-Sn/碳黑A、Ru-Sn/碳黑B催化剂的活性高于中孔的比例较低的Ru-Sn/活性炭催化剂。
如图2所示,能够确认随碳黑A载体的硝酸前处理浓度而变的催化剂的活性差异。当根据实施例1使用30重量%的硝酸水溶液对碳黑A载体进行前处理时,催化剂的活性最高,随后依次为5重量%的硝酸水溶液、50重量%的硝酸水溶液。
以上,参照本发明实施例的附图进行了说明,但本领域技术人员能够根据上述内容,在本发明的范畴内进行多种应用及变形。
Claims (18)
1.一种可高选择性转化的碳基贵金属-过渡金属催化剂,其为使用多孔性的碳作为载体的氢化催化剂,其特征在于,
在所述碳中,孔径为2nm~50nm的中孔(mesopore)在总孔隙中的体积比例为50%以上,并且,相对于总量为100重量份的所述载体,包含1~20重量份的活性金属。
2.根据权利要求1所述的可高选择性转化的碳基贵金属-过渡金属催化剂,其特征在于,
所述碳包括选自活性炭、碳黑、石墨、石墨烯、有序中孔碳(ordered mesoporouscarbon,OMC)以及碳纳米管中的至少一种。
3.根据权利要求1所述的可高选择性转化的碳基贵金属-过渡金属催化剂,其特征在于,所述活性金属包括:
选自钯(Pd)、铑(Rh)、钌(Ru)以及铂(Pt)中的至少一种贵金属;以及
选自锡(Sn)、铁(Fe)、铼(Re)以及镓(Ga)中的至少一种过渡金属。
4.根据权利要求1所述的可高选择性转化的碳基贵金属-过渡金属催化剂,其特征在于,
所述贵金属为钌,所述过渡金属为锡。
5.根据权利要求1所述的可高选择性转化的碳基贵金属-过渡金属催化剂,其特征在于,
使用硝酸(HNO3)水溶液对所述碳载体进行前处理。
6.根据权利要求5所述的可高选择性转化的碳基贵金属-过渡金属催化剂,其特征在于,
所述硝酸(HNO3)水溶液中,相对于总量为100重量份的该水溶液,包含1~50重量份的硝酸。
7.根据权利要求1所述的可高选择性转化的碳基贵金属-过渡金属催化剂,其特征在于,
所述碳的比表面积为100m2/g~1,500m2/g,孔隙体积(pore volume)为0.1mL/g~1.5mL/g。
8.根据权利要求1所述的可高选择性转化的碳基贵金属-过渡金属催化剂,其特征在于,
所述碳具有2nm~25nm的有序中孔并具有立体杆状或立体管状孔隙结构。
9.一种氢化催化剂的用途,其特征在于,
使用根据权利要求1至8中任一项所述的催化剂,将羧酸官能团(carboxylic acidgroup)氢化为醇官能团(alcohol group)。
10.一种可高选择性转化的碳基贵金属-过渡金属催化剂的制备方法,用于制备根据权利要求1至8中任一项所述的催化剂,其特征在于,
使用包含1~50重量份的硝酸的硝酸(HNO3)水溶液,对所述碳载体进行至少一次前处理。
11.根据权利要求10所述的可高选择性转化的碳基贵金属-过渡金属催化剂的制备方法,其特征在于,
所述前处理过程在50℃~150℃温度范围内进行。
12.根据权利要求10所述的可高选择性转化的碳基贵金属-过渡金属催化剂的制备方法,其特征在于,
所述前处理过程进行1小时~10小时。
13.根据权利要求10所述的可高选择性转化的碳基贵金属-过渡金属催化剂的制备方法,其特征在于,
所述前处理过程在负载所述活性金属之前进行。
14.一种氢化方法,其特征在于,
使用根据权利要求1至8中任一项所述的催化剂,将羧酸官能团、醛官能团或酮官能团氢化为醇官能团。
15.根据权利要求14所述的氢化方法,其特征在于,
所述氢化反应的反应压力为2MPa~15MPa,反应温度为140℃~280℃,反应时间为0.5小时~10小时。
16.根据权利要求14所述的氢化方法,其特征在于,
所述羧酸为选自乙二酸(oxalic acid)、丙二酸(malonic acid)、丁二酸(succinicacid)、戊二酸(glutaric acid)、己二酸(adipic acid)、庚二酸(pimelic acid)、辛二酸(suberic acid)、壬二酸(azelaic acid)、癸二酸(sebacic acid)、邻苯二甲酸(phthalicacid)、间苯二甲酸(isophthalic acid)、对苯二甲酸(terephthalic acid)、甲酸、乙酸、己酸、辛酸、月桂酸、肉豆蔻酸、软脂酸、硬脂酸、异硬脂酸、油酸、马来酸、己二酸、癸二酸、环己烷羧酸以及苯甲酸中的一种。
17.根据权利要求14所述的氢化方法,其特征在于,
含有所述醛官能团的醛类为选自甲醛、丙醛、正丁醛、异丁醛、戊醛、2-甲基丁醛、3-甲基丁醛、2,2-二甲基丙醛、己醛、2-甲基戊醛、3-甲基戊醛、4-甲基戊醛、2-乙基丁醛、2,2-二甲基丁醛、3,3-二甲基丁醛、辛醛、癸醛以及戊二醛中的一种。
18.根据权利要求14所述的氢化方法,其特征在于,
含有所述酮官能团的酮类为选自丙酮、丁酮、戊酮、己酮、环己酮以及苯乙酮中的一种。
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