CN111683747A - 负载于碳涂覆二氧化硅-氧化铝载体上的贵金属-过渡金属复合催化剂及其制备方法 - Google Patents
负载于碳涂覆二氧化硅-氧化铝载体上的贵金属-过渡金属复合催化剂及其制备方法 Download PDFInfo
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- CN111683747A CN111683747A CN201880083887.1A CN201880083887A CN111683747A CN 111683747 A CN111683747 A CN 111683747A CN 201880083887 A CN201880083887 A CN 201880083887A CN 111683747 A CN111683747 A CN 111683747A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- 239000002905 metal composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 52
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 46
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- 238000004519 manufacturing process Methods 0.000 claims description 18
- 229910000510 noble metal Inorganic materials 0.000 claims description 18
- 150000003624 transition metals Chemical class 0.000 claims description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 14
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 13
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- 239000007833 carbon precursor Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- GHXRKGHKMRZBJH-UHFFFAOYSA-N boric acid Chemical compound OB(O)O.OB(O)O GHXRKGHKMRZBJH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 4
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- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
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- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- HOZBSSWDEKVXNO-BXRBKJIMSA-N (2s)-2-azanylbutanedioic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O.OC(=O)[C@@H](N)CC(O)=O HOZBSSWDEKVXNO-BXRBKJIMSA-N 0.000 claims description 2
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- XEUHNWODXVYLFD-UHFFFAOYSA-N heptanedioic acid Chemical compound OC(=O)CCCCCC(O)=O.OC(=O)CCCCCC(O)=O XEUHNWODXVYLFD-UHFFFAOYSA-N 0.000 claims description 2
- YVSCCMNRWFOKDU-UHFFFAOYSA-N hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCC(O)=O YVSCCMNRWFOKDU-UHFFFAOYSA-N 0.000 claims description 2
- WPBWJEYRHXACLR-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O.OC(=O)CCCCCCCC(O)=O WPBWJEYRHXACLR-UHFFFAOYSA-N 0.000 claims description 2
- TWHMVKPVFOOAMY-UHFFFAOYSA-N octanedioic acid Chemical compound OC(=O)CCCCCCC(O)=O.OC(=O)CCCCCCC(O)=O TWHMVKPVFOOAMY-UHFFFAOYSA-N 0.000 claims description 2
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 claims description 2
- YKEKYBOBVREARV-UHFFFAOYSA-N pentanedioic acid Chemical compound OC(=O)CCCC(O)=O.OC(=O)CCCC(O)=O YKEKYBOBVREARV-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- ZWPWUVNMFVVHHE-UHFFFAOYSA-N terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.OC(=O)C1=CC=C(C(O)=O)C=C1 ZWPWUVNMFVVHHE-UHFFFAOYSA-N 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 41
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- 239000005720 sucrose Substances 0.000 description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
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- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明涉及负载于碳涂覆二氧化硅‑氧化铝载体上的贵金属‑过渡金属复合催化剂及使用该贵金属‑过渡金属复合催化剂的环己烷二甲醇的制备方法,当使用碳涂覆负载催化剂在水溶液中通过环己烷二羧酸(Cyclohexane dicarboxylic acid,CHDA)的氢化反应来生产环己烷二甲醇(Cyclohexane dimethanol,CHDM)时,能够获得比现有的催化剂更快的反应速率及催化稳定性。
Description
技术领域
本发明涉及负载于碳涂覆二氧化硅-氧化铝载体上的贵金属-过渡金属复合催化剂及其制备方法,具体涉及当使用涂覆有碳的负载催化剂在水溶液中通过环己烷二羧酸(Cyclohexane dicarboxylic acid,CHDA)的氢化反应来生产环己烷二甲醇(Cyclohexanedimethanol,CHDM)时,能够获得比现有的催化剂更快的反应速率及催化稳定性的负载于碳涂覆二氧化硅-氧化铝载体上的贵金属-过渡金属复合催化剂及其制备方法。
背景技术
环己烷二甲醇(CHDM,1,4-cyclohexanedimethanol)是用于生产聚酯或聚酰胺树脂的基础原料,目前,在亚洲由SK化学、三菱(Mitsubishi)商事以及作为新日本理化(ShinNippon Rika)的合资企业的SK NJC进行商业性生产,在全球范围内由Indorama((前)伊士曼(Eastman))公司抢占整个市场。CHDM市场对高附加价值的聚酯树脂的需求呈增长趋势,并且预计将来还会增长,因此需要供需稳定。据悉,目前,CHDM产量由Indorama保持在100KTA规模并且由SK NJC保持在20KTA规模,并且SK NJC计划到18年增产至60KTA,并且最近已在现有的两条生产线的基础上增设一条生产线。
由文献获悉,使用精对苯二甲酸(PTA,Purified terephthalic acid)制备CHDM的方法粗分为三种。第一种方法是,在水溶液中,使用NaOH,对住友精化化学(Sumitomo seikachemical)的PTA进行电离(ionization)后,制成盐(Salt),以提高PTA溶解度并进行加氢反应的方法。该合成法具有能够在低温下随着PTA溶解度提高而降低加氢反应温度的优点(40~130℃),但反应结束之后需要使用HCl来中和处理,因此,回收Na+离子的工序是不必可少的,并且反应结束之后,残留的Na+盐(Salt)会影响PETG聚合,而且含有NaCl的卤水(Brine)溶液会导致废水处理成本过高,因此,会给生产工艺带来不好的影响。第二种方法作为由Indorama和SK NJC采用的制备方法,是在将PTA通过酯化(esterification)制备对苯二甲酸二甲酯(DMT,Dimethyl terephthalate)之后,再经环己烷二羧酸二甲酯(DMCD,Dimethylcyclohexane dicarboxylate)制备CHDM的工艺。该工艺在使用DMCD生产CHDM时,使用铜(Cu)基催化剂或铬(Cr)基催化剂,因此,催化剂价格方面比较低廉,但整体为三步(PTA DMT→DMCD CHDM)制备工艺,因此,在工艺方面不利。另外,在上述过程中,两个工序使用彼此不同的溶剂,因此,存在产生大量废水的问题,并且实际上使用比原料PTA昂贵的DMT作为原材料。
相反,作为第三种方法,由PTA经CHDA生产CHDM的工艺,在进行CHDA氢化反应时,活性金属使用贵金属钌,因此,在催化剂的价格方面不利,但能够通过两步工艺(PTA CHDA→CHDM)获得最终产物CHDM,因此,只要能够通过缩短工艺来降低产品成本并确保工艺技术的竞争力,就能够视为在经济性方面有利。
在由PTA生产CHDA及CHDM的两步工艺中,比起使TPA的芳香环(aromatic ring)饱和(saturation)的第一步骤反应,作为通过二羧酸(di-carboxylic acid)的加氢脱氧(hydrodeoxygenation)而转化为醇(alcohol)的反应的第二步骤反应的难度更高,并因此构成了在商业化阶段中的瓶颈(huddle)。因此,迫切需要开发适用于作为第二步骤反应的CHDA的氢化工艺的高效/使用寿命长的催化剂。
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负载于碳涂覆二氧化硅-氧化铝载体上的贵金属-过渡金属复合催化剂及其制备方法,能够在使用负载于涂覆有碳的二氧化硅-氧化铝(SiO2-Al2O3)的贵金属-过渡金属复合催化剂由二羧酸(dicarboxylic acid)生产二醇(diol)时保持高活性及催化反应稳定性。
技术方案
用于达成这些目的的本发明的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂,在碳涂覆二氧化硅-氧化铝载体上负载贵金属-过渡金属,
相对于总量为100重量份的所述载体,可包含40~95重量份的所述氧化铝(Al2O3)和5~60重量份的二氧化硅(SiO2),
并且相对于100重量份的所述碳,可包含1~20重量份的所述贵金属和所述过渡金属。
在本发明一优选例中,所述贵金属可包括选自钯(Pd)、铑(Rh)、钌(Ru)以及铂(Pt)中的至少一种。
在本发明一优选例中,相对于100重量份的所述载体,可包含1~10重量份的所述贵金属。
在本发明一优选例中,所述过渡金属可包括选自锡(Sn)、铁(Fe)、铼(Re)以及镓(Ga)中的至少一种。
在本发明一优选例中,相对于100重量份的所述载体,可包含1~10重量份的所述过渡金属。
在本发明一优选例中,所述贵金属的前体和过渡金属的前体可以以相同的摩尔比负载于所述载体。
在本发明一优选例中,所述碳可通过碳化过程(carbonization process)涂覆到二氧化硅-氧化铝表面上。
另一方面,本发明提供使用所述催化剂对二羧酸官能团(dicarboxylic acidgroup)进行氢化的氢化方法以及使用所述催化剂进行环己烷二羧酸的氢化反应而制备的环己烷二甲醇。
在本发明一优选例中,所述二羧酸可包括选自乙二酸(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)、苹果酸(malic acid)、天冬氨酸(aspartic acid)、谷氨酸(glutamicacid)、邻苯二甲酸(phthalic acid)、间苯二甲酸(isophthalic acid)、对苯二甲酸(terephthalic acid)以及环己烷二羧酸(cyclohexane dicarboxylic acid)中的一种。
另外,本发明提供负载于碳涂覆二氧化硅-氧化铝载体上的贵金属-过渡金属复合催化剂的制备方法,其可包括如下步骤:
(a)将硼酸(boric acid)溶解在碳前体水溶液中后,负载到二氧化硅-氧化铝(SiO2-Al2O3)上,以制备复合物;
(b)对所述复合物进行碳化;
(c)在涂覆有所述碳的二氧化硅-氧化铝(SiO2-Al2O3)载体上,负载贵金属-过渡金属;以及
(d)使用氢气,对所述负载于碳涂覆二氧化硅-氧化铝(SiO2-Al2O3)载体上的贵金属-过渡金属氧化物进行还原。
在本发明一优选例中,在所述步骤(a)中,可以以1∶0.005~0.1的重量比投入所述碳前体和所述硼酸。
在本发明一优选例中,在所述步骤(a)中,所述复合物可通过初湿浸渍法(incipient-wetness impregnation负载到所述载体上而制备。
在本发明一优选例中,所述碳化过程可以在氮气氛围且在300~700℃的温度范围内进行。
在本发明一优选例中,在所述步骤(c)中,相对于100重量份的所述载体,可负载1~20重量份的所述贵金属和过渡金属。
在本发明一优选例中,在所述步骤(d)中,所述还原过程可在400~600℃的温度范围内进行。
有益效果
如上所述,本发明的负载于碳涂覆二氧化硅-氧化铝载体上的贵金属-过渡金属催化剂及其制备方法能够在使用负载于涂覆有碳的二氧化硅-氧化铝(SiO2-Al2O3)的贵金属-过渡金属催化剂并由二羧酸(dicarboxylic acid)生产二醇(diol)时保持高活性及催化反应稳定性。
附图说明
图1是示出本发明一实施例的在碳涂覆二氧化硅-氧化铝载体上负载贵金属-过渡金属的过程的制备过程的概略图。
图2是示出本发明一实施例的使用在碳涂覆二氧化硅-氧化铝载体上负载有贵金属-过渡金属的催化剂的CHDM生产反应结果的图。
图3是示出本发明一实施例的使用在未涂覆碳的二氧化硅-氧化铝载体上负载有贵金属-过渡金属的催化剂的CHDM生产反应结果的图。
图4是示出本发明一实施例的使用在碳涂覆二氧化硅-氧化铝载体及未涂覆碳的二氧化硅-氧化铝载体上分别负载有贵金属-过渡金属的催化剂的CHDM生产反应效率结果的图。
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,则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可优选为烷基或芳基。
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。
如上所述,在现有的环己烷二羧酸的氢化反应技术中,在使用廉价的载体并使用确保比现有的催化剂更高的反应活性及水热稳定性的催化剂来制备环己烷二甲醇方面存在局限性。
对此,本发明提供一种负载于碳涂覆载体上的贵金属-过渡金属催化剂,在碳涂覆二氧化硅-氧化铝载体上负载贵金属-过渡金属,相对于总量为100重量份的所述载体,包含40~95重量份的所述氧化铝(Al2O3)和5~60重量份的二氧化硅(SiO2),并且相对于100重量份的所述碳,包含1~20重量份的所述贵金属和所述过渡金属,并由此寻求上述问题的解决方案。
载体会因受到酸的影响而起到催化剂毒物的作用,因此,可以使用诸如二氧化硅、氧化铝、氧化锆、二氧化钛等的金属氧化物、诸如二氧化硅-氧化铝等的复合氧化物、酸性活性炭、沸石等。
其中,通常,氧化铝载体存在γ-氧化铝的结构在水热反应条件下改变为勃姆石结构的缺点,因此,作为用于提高氧化铝的水热稳定性的方法,介绍了使用第二种其他组分进行前处理的各种方法。另外,在使用二氧化硅作为载体时,与氧化铝载体相比,因钴与载体的强烈键合,能够观察到在还原过程中金属钴的还原性降低及由此导致的活性降低现象,作为用于克服该问题的方法,介绍了使用锆等金属对二氧化硅表面进行前处理的方法等现有技术。
因此,本发明的载体内同时存在Al2O3和SiO2两种组分,从而改善分别单独使用氧化铝和二氧化硅组分时的缺点,并且在通过初湿浸渍法(incipient-wetnessimpregnation)在所述氧化铝-二氧化硅载体上负载包含碳前体的溶液以形成复合物之后,经碳化过程,将其用作二羧酸(dicarboxylic acid)氢化反应用催化剂。
以下,对上述的负载于碳涂覆载体上的贵金属-过渡金属催化剂的组合物进行更加具体的说明。
首先,根据本发明,优选地,相对于总量为100重量份的所述载体,所述氧化铝组分的含量可以为40~95重量份,优选为55~85重量份,更优选为80~85重量份。此时,当所述氧化铝组分的含量小于40重量份时,存在的问题在于,因二氧化硅-氧化铝载体的高酸性位点,会在反应中因加氢裂化(hydrocracking)而生成过多的副产物,当所述氧化铝组分的含量大于95重量份时,会存在氧化铝的水热稳定性问题,因此,优选上述的范围。
另外,优选地相对于总量为100重量份的所述载体,所述二氧化硅组分的含量可以为5~60重量份,优选为5~35重量份,更优选为5~10重量份。此时,当所述二氧化硅组分的含量小于5重量份时,会存在氧化铝的水热稳定性问题,当所述二氧化硅组分的含量大于50重量份时,存在的问题在于,因二氧化硅-氧化铝载体的高酸性位点,会存在加氢裂化(hydrocracking)问题,因此,优选上述的范围。
接下来,所述贵金属可包括选自钯(Pd)、铑(Rh)、钌(Ru)以及铂(Pt)中的至少一种。其中,根据本发明,相对于100重量份的涂覆有所述碳的二氧化硅-氧化铝载体,所述贵金属的含量可以为1~20重量份,优选为1~10重量份,更优选为3~8重量份。此时,当所述贵金属的含量小于1重量份时,存在转化效率低而导致生产效率降低的问题,当所述贵金属的含量大于10重量份时,存在的问题在于,因高昂的催化剂价格和目的产物的低选择性,工艺上会产生附加成本,因此,优选上述的范围。
接下来,所述过渡金属可包括选自锡(Sn)、铁(Fe)、铼(Re)以及镓(Ga)中的至少一种。其中,根据本发明,相对于100重量份的涂覆有所述碳的二氧化硅-氧化铝载体,所述过渡金属的含量可以为1~20重量份,优选为1~10重量份,更优选为3~8重量份。此时,当所述过渡金属的含量小于1重量份时,存在的问题在于,因反应的转化效率降低或目的产物的选择性降低,工艺上的分离成本、回收成本过高,当所述过渡金属的含量大于10重量份时,存在因产生较多的副产物而需要附加工序的缺点,因此,优选上述的范围。
另一方面,本发明提供使用所述催化剂的氢化方法,在具体例中,能够通过在催化剂上进行环己烷二羧酸的加氢反应来制备环己烷二甲醇。
以下,对包含上述的组合物的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂的制备方法进行说明。
本发明提供上述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂的制备方法,其具体包括如下步骤:将硼酸(boric acid)溶解在碳前体水溶液中后,负载到二氧化硅-氧化铝(SiO2-Al2O3)上,以制备复合物;对所述复合物进行碳化;在涂覆有所述碳的二氧化硅-氧化铝(SiO2-Al2O3)载体上,负载贵金属-过渡金属;以及使用氢气,对负载于所述二氧化硅-氧化铝(SiO2-Al2O3)载体上的贵金属-过渡金属氧化物进行还原。
参照图1,将硼酸(boric acid)溶解在碳前体水溶液中后,负载到二氧化硅-氧化铝(SiO2-Al2O3)上,以制备复合物之后,在氮气氛围、500℃的温度下,引入所述复合物,并进行碳化过程。之后,通过共浸渍法(co-impregnation),将包含上述的含量比的所述贵金属前体和所述过渡金属前体分别同时负载到碳涂覆二氧化硅-氧化铝(SiO2-Al2O3)载体上,并使用氢气对贵金属-过渡金属氧化物进行还原,从而制备在碳涂覆载体上包含贵金属-过渡金属的催化剂。
其中,根据本发明,投入于所述碳前体水溶液中的所述碳前体和所述硼酸可以以1∶0.005~0.1的重量比投入,优选以1∶0.007~0.07的重量比投入,更优选以1∶0.01~0.05的重量比投入。此时,当所述硼酸的含量小于0.005的重量比时,存在的问题在于,活性金属的电荷密度(electronic charge density)减小并导致氢气吸附量减小,最终导致催化剂反应活性降低,当所述硼酸的韩浪大于0.1的重量比时,过量的硼酸会溶解到目的产物中并导致产物的品质存在问题,因此,优选上述的范围。
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。
[实施例]
<实施例1>在SiO2-Al2O3上涂覆碳以制备复合物
首先,将9.75g的蔗糖(Sucrose,奥德里奇公司)加入到10mL的蒸馏水中并利用磁力搅拌器进行搅拌。在蔗糖完全地溶解于蒸馏水之后,向蔗糖水溶液添加0.2g的硼酸(奥德里奇公司)并溶解2小时。之后,通过初湿浸渍法(incipient-wetness impregnation)方法将所述溶液负载到SiO2-Al2O3载体上。
通过碳化过程(carbonization process),对涂覆于以此方式所制备的复合物上的蔗糖进行碳化。碳化在300℃下实施3小时。此时,蔗糖通过SiO2-Al2O3表面的羟基(hydroxyl group)与蔗糖之间的脱水(dehydration)而粘附到SiO2-Al2O3表面上。之后,确认了在500℃下,再次通过3小时的碳化过程,粘附于表面(surface)的蔗糖变为多环芳烃碳片(polycyclic aromatic carbon sheet)。该碳化过程在以100cc/min引入氮气且升温速率(ramping rate)为5℃/min的条件下进行。
<实施例2>在C-SiO2-Al2O3载体上负载贵金属钌-锡
将钌前体(RuCl3,小岛公司)和锡前体(SnCl2,奥德里奇)溶解在蒸馏水水溶液中后,通过共浸渍法(co-impregnation)负载两种前体,以在C-SiO2-Al2O3载体上负载钌和锡。相对于100重量份的C-SiO2-Al2O3载体,该催化剂负载有5重量份的钌,此时,以与钌相同的摩尔数的量负载锡,并在500℃下,还原3小时(100cc/min H2:30/N2:70),以用作二羧酸(dicarboxylic acid)氢化反应用催化剂.
<实施例3>通过使用Ru-Sn/C-SiO2-Al2O3催化剂来转化CHDA的CHDM生产反应
将负载于C-SiO2-Al2O3的钌-锡催化剂(Ru-Sn/C-SiO2-Al2O3)用于由二羧酸(dicarboxylic acid)至二醇(diol)的加氢转化反应。在加氢转化反应中,选定代表二羧酸的环己烷二羧酸(cyclohexanedicarboxylic acid,由CHDA表示),并通过选择加氢转化为环己烷二甲醇(cyclohexanedimethanol,由CHDM表示)。本反应以液相反应的方式进行,并使用了具有耐酸性的二氧化钛(titania)材料的间歇反应器(batch reactor)。以3.75∶1的重量比向高温高压用高压釜(autoclave)反应器填充作为反应物的CHDA和催化剂,并填充蒸馏水作为反应溶剂,以进行反应。此时,相对于反应溶剂,将反应物的量固定为7重量%。之后,使用氢气,将反应器加压至反应压力,并通过氢气传感器来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,搅拌是利用顶置式叶轮(overheadimpeller)来保持1000rpm的速率的。反应结束之后,冷却至常温并解压,之后,通过过滤法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。利用数学式1至数学式3,计算随着CHDA的转化而生成的CHDM、甲基丙烯酸环己酯(CHMA)、酯类(ester)等的转化率、选择性以及收率。
<数学式1>
<数学式2>
<数学式3>
CHDM的收率(Yield for CHDM)(%)=(CHDA的转化率)×(CHDM的选择性)
与此相关联,在通过CHDA的加氢反应来生产CHDM的过程中,反应进行了共10次的长期稳定性试验,以评价Ru-Sn/C-SiO2-Al2O3催化剂的性能,并将其结果示于图2中。反应在230℃、90bar的氢气氛围下进行6小时。
其结果,确认了对CHDA的转化率的10次反应结果全部为99%以上,且CHDM的收率具有93%~97%范围的值。
[比较例]
<比较例1>Ru-Sn/SiO2-Al2O3催化剂的制备及CHDA加氢反应试验
除了删除实施例1中的涂覆(coating)碳(carbon)的过程以外,以相同的方法制备Ru-Sn/SiO2-Al2O3催化剂。
具体地,相对于100重量份的SiO2-Al2O3载体,负载5重量份的钌,此时,以与钌相同的摩尔数的量负载锡,并在500℃下,还原3小时(100cc/min H2:30/N2:70),以用作二羧酸(dicarboxylic acid)氢化反应用催化剂。
与此相关联,在反应条件下对催化剂进行水热处理60小时之后,与初始反应活性进行比较评价,以确认Ru-Sn/SiO2-Al2O3催化剂的水热稳定性,并示于图3中。
其结果,能够确认Ru-Sn/SiO2-Al2O3催化剂表现出与Ru-Sn/C-SiO2-Al2O3催化剂相同的优秀的初始活性,但在水热条件下暴露60小时之后,反应活性大幅降低。
<比较例2>Ru-Sn/C-Al2O3催化剂的制备及CHDA加氢反应试验
为了验证Ru-Sn/C-SiO2-Al2O3催化剂的性能及耐久性,使用Al2O3载体来替代SiO2-Al2O3载体以制备Ru-Sn/C-Al2O3催化剂。除了将实施例1中的制备C-SiO2-Al2O3载体的方法中的SiO2-Al2O3变更为Al2O3以外,以相同的催化剂制备方法进行。
具体地,将9.75g的蔗糖(奥德里奇公司)加入到10mL的蒸馏水中并利用磁力搅拌器进行搅拌。在所述蔗糖完全地溶解于蒸馏水之后,向蔗糖水溶液添加0.2g的硼酸(奥德里奇公司)并溶解2小时。之后,通过初湿浸渍法(incipient-wetness impregnation)方法将所述溶液负载到Al2O3载体上。
通过碳化过程,对涂覆于所述复合物上的蔗糖进行碳化。该碳化在300℃下实施3小时,此时,蔗糖通过Al2O3表面的羟基与蔗糖之间的脱水而粘附到Al2O3表面上。之后,在500℃下,通过3小时的碳化过程,粘附于表面(surface)的蔗糖变为多环芳烃碳片。所述碳化过程在以100cc/min引入氮气且升温速率(ramping rate)为5℃/min的条件下进行。
将钌前体(RuCl3,小岛公司)和锡前体(SnCl2,奥德里奇)溶解在蒸馏水水溶液中后,通过共浸渍法(co-impregnation)来负载两种前体,以在C-Al2O3载体上负载钌和锡。相对于100重量份的C-Al2O3载体,所述催化剂负载有5重量份的钌,此时,以与钌相同的摩尔数的量负载锡,并在500℃下,还原3小时(100cc/min H2:30/N2:70),以用作二羧酸(dicarboxylic acid)氢化反应用催化剂。
与此相关联,为了与在实施例3中所使用的Ru-Sn/C-SiO2-Al2O3催化剂比较性能及耐久性,在CHDA转化反应中使用了在比较例2中所生产的负载于涂覆(coating)有碳(carbon)的Al2O3(C-Al2O3)的双金属催化剂(Ru-Sn/C-Al2O3)。试验过程与实施例3中的过程相同,并且为了比较反应速率,按照时间示出了各个催化剂的5次活性结果,并示于图4中。
根据反应结果能够确认Ru-Sn/C-SiO2-Al2O3催化剂比Ru-Sn/C-Al2O3催化剂更快地生产CHDM。这表示催化剂更加高效地生产CHDM。
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 (16)
1.一种负载于碳涂覆载体上的贵金属-过渡金属复合催化剂,在碳涂覆二氧化硅-氧化铝载体上负载贵金属-过渡金属,其特征在于,
相对于总量为100重量份的所述载体,包含40~95重量份的所述氧化铝(Al2O3)和5~60重量份的二氧化硅(SiO2),
并且相对于100重量份的所述碳涂覆二氧化硅-氧化铝载体,包含1~20重量份的所述贵金属和所述过渡金属。
2.根据权利要求1所述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂,其特征在于,
所述贵金属包括选自钯(Pd)、铑(Rh)、钌(Ru)以及铂(Pt)中的至少一种。
3.根据权利要求1所述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂,其特征在于,
相对于100重量份的所述载体,包含1~10重量份的所述贵金属。
4.根据权利要求1所述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂,其特征在于,
所述过渡金属包括选自锡(Sn)、铁(Fe)、铼(Re)以及镓(Ga)中的至少一种。
5.根据权利要求1所述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂,其特征在于,
相对于100重量份的所述载体,包含1~10重量份的所述过渡金属。
6.根据权利要求1所述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂,其特征在于,
所述贵金属的前体和过渡金属的前体以相同的摩尔比负载于所述载体。
7.根据权利要求1所述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂,其特征在于,
所述碳通过碳化过程(carbonization process)涂覆到所述二氧化硅-氧化铝表面上。
8.一种氢化方法,其特征在于,
使用权利要求1至7中任一项所述的催化剂,对二羧酸官能团(dicarboxylic acidgroup)进行氢化。
9.根据权利要求8所述的氢化方法,其特征在于,
所述二羧酸为选自乙二酸(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)、苹果酸(malic acid)、天冬氨酸(aspartic acid)、谷氨酸(glutamic acid)、邻苯二甲酸(phthalic acid)、间苯二甲酸(isophthalic acid)、对苯二甲酸(terephthalic acid)以及环己烷二羧酸(cyclohexane dicarboxylic acid)中的一种。
10.一种环己烷二甲醇(Cyclohexane dimethanol,CHDM),其特征在于,
使用权利要求1至7中任一项所述的催化剂,进行环己烷二羧酸(Cyclohexanedicarboxylic acid,CHDA)的氢化反应而制备。
11.一种负载于碳涂覆载体上的贵金属-过渡金属复合催化剂的制备方法,其特征在于,包括如下步骤:
(a)将硼酸(boric acid)溶解在碳前体水溶液中后,负载到二氧化硅-氧化铝(SiO2-Al2O3)上,以制备复合物;
(b)对所述复合物进行碳化;
(c)在涂覆有所述碳的二氧化硅-氧化铝(SiO2-Al2O3)载体上,负载贵金属-过渡金属;以及
(d)使用氢气,对负载于涂覆有所述碳的二氧化硅-氧化铝(SiO2-Al2O3)载体上的贵金属-过渡金属氧化物进行还原。
12.根据权利要求11所述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂的制备方法,其特征在于,
在所述步骤(a)中,以1∶0.005~0.1的重量比投入所述碳前体和所述硼酸。
13.根据权利要求11所述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂的制备方法,其特征在于,
在所述步骤(a)中,所述复合物通过初湿浸渍法(incipient-wetness impregnation)负载到所述载体上而制备。
14.根据权利要求11所述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂的制备方法,其特征在于,
在所述步骤(b)中,所述碳化过程在氮气氛围且在300~700℃的温度范围内进行。
15.根据权利要求11所述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂的制备方法,其特征在于,
在所述步骤(c)中,相对于100重量份的所述载体,负载1~20重量份的所述贵金属及过渡金属。
16.根据权利要求11所述的负载于碳涂覆载体上的贵金属-过渡金属复合催化剂的制备方法,其特征在于,
在所述步骤(d)中,所述还原过程在400~600℃的温度范围内进行还原。
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