CN101028995A - 环烷醇和/或环烷酮的制造方法 - Google Patents
环烷醇和/或环烷酮的制造方法 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
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- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
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- 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
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- -1 tetramethylene, pentamethylene Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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- C07C27/10—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons
- C07C27/12—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with oxygen
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Abstract
用氧对环烷烃进行氧化时,作为催化剂,使用将周期表第5族~10族的金属担载在载体上、并且该载体被有机硅化合物催化处理的。金属可以是钒、铬、锰、铁、钴、钌或钯,载体可以是镁、铝、硅、钛或锆的氧化物。
Description
技术领域
本发明涉及用氧对环烷烃进行氧化来制造环烷醇和/或环烷酮的方法。
背景技术
作为用氧对环烷烃进行氧化来制造环烷醇和/或环烷酮的方法,很早就已知用如羧酸钴那样的可溶性金属化合物作为催化剂,在均匀体系进行上述氧化的方法。并且还对使用固体催化剂在不均匀体系进行上述氧化进行了各种研究,并提出了以各种金属氧化物催化剂、金属担载催化剂等许多催化剂作为该固体催化剂(例如参见专利文献1~3以及非专利文献1~5)。
专利文献1:EP 0916403A
专利文献2:WO 99/040055
专利文献3:特开2003-261484号公报
非专利文献1:Journal of American Chemical Society,(美国),1999年,第121卷,第11926~11927页
非专利文献2:Chemical Communications,(英国),2004年,第904~905页
非专利文献3:Chemistry Letters,2005年,第34卷,第162~163页
非专利文献4:Applied Catalysis A:General,(荷兰),2005年,第280卷,第175~180页
非专利文献5:Applied Catalysis A:General,(荷兰),2005年,第292卷,第223~228页
发明内容
在催化剂的活性、选择性,即环烷烃的转化率、环烷醇和/或环烷酮的选择率方面,现有的方法有不令人满意之处。因此,本发明的目的在于提供一种方法,该方法能够以良好的转化率氧化环烷烃,以良好的选择率制造环烷醇和/或环烷酮。
本发明是在催化剂存在的条件下用氧对环烷烃进行氧化来制造环烷醇和/或环烷酮的方法,其特征在于,上述催化剂,将周期表5族~10族的金属担载在载体上、并且该载体被有机硅化合物的催化处理。
根据本发明,能以良好的转化率氧化环烷烃,以良好的选择率制造环烷醇和/或环烷酮。
附图说明
图1是参考例1获得的钴担载二氧化硅的红外线吸收光谱。
图2是参考例2获得的钴担载二氧化硅的原硅酸乙酯催化处理品的红外线吸收光谱。
具体实施方式
下面详细说明本发明。本发明中使用环烷烃作为原料,将其在催化剂存在下用氧(分子态氧)进行氧化,从而制造相应的环烷醇和/或环烷酮。
作为原料环烷烃,例如可以举出环丙烷、环丁烷、环戊烷、环己烷、环庚烷、环辛烷、环癸烷、环十八烷等环上没有取代基的单环型环烷烃,此外还可以举出萘烷、金刚烷等多环型环烷烃;甲基环戊烷、甲基环己烷等环上有取代基的环烷烃等,根据需要也可以使用这些环烷烃中的2种以上。
氧源通常使用含氧气体。该含氧气体例如可以是空气,也可以是纯氧,还可以是用氮、氩、氦等惰性气体将空气或纯氧稀释得到的气体。另外,还可以使用在空气中添加纯氧得到的富氧空气。
本发明中,环烷烃的氧氧化用催化剂使用将周期表5族~10族金属担载在载体上、并且该载体被有机硅化合物催化处理的。通过使用所述的催化剂,能够以良好的转化率氧化环烷烃,以良好的选择率制造环烷醇和/或环烷酮。
作为担载于载体的金属的优选例子,可以举出钒、铬、锰、铁、钴、钌、钯,其中优选使用钴。根据需要,还可以使用2种以上的金属。以相对于载体的重量比表示,金属的担载率通常为0.01~20%,优选为0.05~10%,更优选为0.1~5%。
担载金属的载体优选是氧化物载体,具体优选含有选自镁、铝、硅、钛、锆中的至少一种元素的氧化物。其中优选二氧化硅、即二氧化硅(silica)。
作为将金属担载在载体上的方法,例如可以举出使金属的卤化物、羧酸盐、含氧酸盐等金属化合物的溶液含浸到载体中的方法;将载体浸渍在金属的卤化物、羧酸盐、含氧酸盐等金属化合物的溶液中,使金属化合物吸附到载体上或使金属化合物的金属阳离子与载体的阳离子进行离子交换的方法等。
用于载体的催化处理的有机硅化合物优选能与载体反应,结合在其表面的有机硅化合物,典型地可以用下式(1)表示。
Si(R1)x(R2)4-x (1)
(式中,R1表示烷氧基、羟基或者卤原子,R2表示烷氧基、烷基、烯丙基、芳基或者芳烷基,x表示1~3的数)
此处,作为R1和R2表示的烷氧基的例子,可以举出甲氧基、乙氧基、丙氧基、丁氧基等,作为R2表示的烷基的例子,可以举出甲基、乙基、丙基、丁基等。另外,作为R2表示的芳基的例子,可以举出苯基、萘基、甲苯基等,作为R2表示的芳烷基的例子,可以举出苄基、苯乙基等。
作为式(1)表示的有机硅化合物,优选使用R1和R2全部是烷氧基的有机硅化合物,即原硅酸的烷基酯。
作为用有机硅化合物对载体进行催化处理的方法,例如可以举出将载体浸渍于含有有机硅化合物的液体中的方法、使含有有机硅化合物的气体与载体接触的方法等。
相对于100重量份载体,有机硅化合物的使用量通常为1~10000重量份,优选为5~1000重量份,更优选为10~500重量份。
催化处理的温度通常为0~300℃,优选为30~250℃。催化处理的时间通常为0.1~50小时,优选为1~20小时。
此外,用有机硅化合物对载体的催化处理可以在担载金属前进行,也可以在担载金属后进行,还可以在担载金属的同时进行,通常可以在担载金属后进行。
环烷烃的氧化反应可以在如上得到的金属担载催化剂存在的条件下通过使环烷烃与氧接触来进行。相对于100重量份环烷烃,催化剂的使用量通常为0.01~50重量份,优选为0.1~10重量部。
反应温度通常为0~200℃,优选为50~170℃,反应压力通常为0.01~10MPa,优选为0.1~2MPa。可需要根据使用反应溶剂,例如可以使用乙腈、苯甲腈等腈类溶剂;乙酸、丙酸等羧酸溶剂等。
对于氧化反应后的后处理操作没有特别规定,例如可以举出将反应混合物过滤而分离催化剂,然后进行水洗,接着进行蒸馏的方法等。反应混合物中含有相应于原料环烷烃的环烷基过氧化氢时,可通过碱处理或还原处理等,转变为目标环烷醇或环烷酮。
实施例
下面给出本发明的实施例,但本发明不受其限定。此外,反应液中的环己烷、环己酮、环己醇以及环己基过氧化氢的分析通过气相色谱法进行,根据该分析结果,算出环己烷的转化率以及环己酮、环己醇和环己基过氧化氢的各自的选择率。
参考例1
将2.51克热解法二氧化硅(ALDRICH公司)、4.18克醋酸钴(II)四水合物(和光纯药株式会社)以及37.27克水加入到300ml烧瓶中,在47℃搅拌3小时。将得到的混合物冷却到室温后,进行过滤。滤渣用水洗涤后,在100℃进行干燥,得到钴担载二氧化硅。利用下述方法测定该钴担载氧化硅的红外吸收光谱,结果如图1所示。
(红外线吸收光谱的测定)
将钴担载二氧化硅装入催化剂盒(触媒セル)(SPECTRA-TECH公司生产的Diffuse Reflectance Heat Chamber/Model HC900),然后安装在红外线吸收光谱测定装置(NICOLET公司生产的Magna 760-ESP)上,在0.1Torr(13Pa)、200℃脱气1小时后,测定红外线吸收光谱。测定条件如下:测定温度为200℃,测定压力为0.1Torr(13Pa),测定范围为400~4000cm-1,分辨能力为4cm-1。对于所得到的数据,以同样测定溴化钾的红外吸收光谱得到的数据作为空白,对其进行Kubelka-Munk校正。
参考例2
将0.2克参考例1获得的钴担载二氧化硅以及2.0克原硅酸乙酯(和光纯药株式会社)装入烧瓶,在氮气氛中、90℃搅拌7小时。将得到的混合物冷却到室温后,添加乙醇进行搅拌,然后进行过滤。将滤渣用丙酮洗涤后,在0.1Torr(13Pa)、40℃干燥2小时,进一步在60℃进行干燥。与参考例1同样测定这样获得的钴担载氧化硅的原硅酸乙酯催化处理品的红外线吸收光谱,结果见图2。
如图1所示,参考例1获得的钴担载二氧化硅中,在3740cm-1附近观察到归属为所谓末端硅烷醇基的峰,而参考例2获得的钴担载二氧化硅的原硅酸乙酯催化处理品中没有观察到相同的峰,认为末端硅烷醇基被原硅酸乙酯甲硅烷基化了。
实施例1
在300ml高压釜中加入100克环己烷(1.2摩尔)以及0.1克参考例2获得的钴担载二氧化硅的原硅酸乙酯催化处理品,于室温用氮将体系内升压到0.93MPa后,升温到130℃,然后在流通氧浓度为5容量%的气体的条件下,进行8小时反应。
在反应开始后5小时的时刻,环己烷的转化率是5.4%、环己酮的选择率是26.6%、环己醇的选择率是46.6%、环己基过氧化氢的选择率是13.7%(总选择率为86.9%)。在反应开始后8小时的时刻(结束时),环己烷的转化率是9.3%、环己酮的选择率是35.1%、环己醇的选择率是43.0%、环己基过氧化氢的选择率是5.9%(总选择率为84.0%)。
比较例1
使用参考例1得到的钴担载二氧化硅代替参考例2得到的钴担载二氧化硅的原硅酸乙酯催化处理品,除此以外进行与实施例1同样的操作。
反应开始后5小时的时刻,环己烷的转化率是5.9%、环己酮的选择率是30.2%、环己醇的选择率是48.7%、环己基过氧化氢的选择率是3.4%(总选择率为82.3%)。反应开始后8小时的时刻(结束时),环己烷的转化率是9.4%、环己酮的选择率是36.6%、环己醇的选择率42.9%、环己基过氧化氢的选择率是1.9%(总选择率为81.4%)。
Claims (8)
1.一种环烷醇和/或环烷酮的制造方法,其是在催化剂存在的条件下用氧对环烷烃进行氧化来制造环烷醇和/或环烷酮的方法,其特征在于,上述催化剂,将周期表5族~10族的金属担载在载体上、并且该载体被有机硅化合物催化处理。
2.根据权利要求1所述的方法,其中,金属选自钒、铬、锰、铁、钴、钌以及钯。
3.根据权利要求1所述的方法,其中,金属是钴。
4.根据权利要求1~3中任一项所述的方法,其中,载体是含有选自镁、铝、硅、钛以及锆中的元素的氧化物。
5.根据权利要求1~3中任一项所述的方法,其中,载体是二氧化硅。
6.根据权利要求1~3中任一项所述的方法,其中,有机硅化合物以下式(1)表示:
Si(R1)x(R2)4-x (1)
式中,R1表示烷氧基、羟基或者卤原子,R2表示烷氧基、烷基、烯丙基、芳基或者芳烷基,x表示1~3的数。
7.根据权利要求1~3中任一项所述的方法,其中,有机硅化合物是原硅酸烷基酯。
8.根据权利要求1~3中任一项所述的方法,其中,环烷烃是环己烷。
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