CN107185552A - 一种多元复合金属氧化物催化剂催化制备间苯二酚的方法 - Google Patents
一种多元复合金属氧化物催化剂催化制备间苯二酚的方法 Download PDFInfo
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- CN107185552A CN107185552A CN201710443833.9A CN201710443833A CN107185552A CN 107185552 A CN107185552 A CN 107185552A CN 201710443833 A CN201710443833 A CN 201710443833A CN 107185552 A CN107185552 A CN 107185552A
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- oxide
- metal
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- resorcinol
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 54
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 16
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 37
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007791 liquid phase Substances 0.000 claims abstract description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 22
- 239000002905 metal composite material Substances 0.000 claims abstract description 17
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 13
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 9
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010931 gold Substances 0.000 claims abstract description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 4
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- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 4
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- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims abstract description 4
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 4
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 4
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 25
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000010970 precious metal Substances 0.000 claims description 10
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种多元复合金属氧化物催化剂催化制备间苯二酚的方法,多元复合金属氧化物为氧化镍与其他金属氧化物复合的氧化物,并且氧化物中附着有贵金属的纳米颗粒,多元复合金属氧化物中其他金属氧化物的质量分数为5~20%,贵金属的质量分数为0.5~2.0%;其中,其他金属氧化物为三氧化二铁、五氧化二钒、氧化铜、氧化镁、氧化钙、氧化钾、氧化钠、氧化锆、氧化锡、氧化锌、氧化钴、氧化铅、氧化铋、氧化铝、氧化钛、氧化锰、氧化铷、氧化锶、氧化钯、氧化铑、氧化钡、氧化银或氧化铂;贵金属为金、铂、钯、银、钌、锇或铱。该类复合金属氧化物在间苯二甲酸液相合成间苯二酚工艺中具有催化性能,间苯二酚收率最高可达30.4%。
Description
技术领域
本发明属于固相催化领域,涉及一种多元复合金属氧化物催化剂用于液相间苯二甲酸催化氧化脱羧制取间苯二酚的方法。
背景技术
间苯二酚是一种重要的精细有机化工原料和有机中间体,广泛应用于医药化工、染料、涂料、感光材料、防腐剂、胶粘剂、电子化学品、塑料、橡胶、农业等领域,主要用于合成轮胎帘子布用的间苯二酚-甲醛粘合剂和木材胶合板用高性能粘合剂等。
目前已经工业化的间苯二酚的合成方法主要是:苯磺化碱熔法、间二异丙苯氧化法和间苯二胺水解法。其中苯磺化碱熔法是生产间苯二酚的传统方法,工艺条件简单,反应平缓,技术成熟。该方法以苯为原料,分两次加入发烟硫酸进行磺化反应,生成间苯二磺酸。再加碱中和制得间苯二磺酸盐,无水氢氧化钠碱熔,产物加水溶解稀释,酸化,有机溶剂萃取。主要包括磺化、中和、碱熔和酸化四个过程。但磺化碱熔法生产效率低,能耗大,三废产生量多,对环境污染影响严重,废液处理难度较高。间二异丙苯氧化法是以间二异丙苯为原料,经氧化成为二过氧化氢二异丙苯,酸性分解生成间苯二酚,同时副产丙酮。该方法环境污染小,过程便于连续化生产,但工艺复杂,设备要求高。间苯二胺水解是在硫酸作用下经高温反应生成间苯二酚,该方法工艺先进,装置水平高,几乎实现了零污染排放,而且原料间苯二胺来源充足、廉价易得。但此方法还不成熟,焦油产生量太多。
天津理工大学肖如亭教授提出了间苯二甲酸合成间苯二酚的工艺路线,通过热力学计算及相关研究,阐述了反应原理,分析结果可知:可以通过液相催化氧化间苯二甲酸生成间苯二酚,并对催化剂及助剂进行了研究。结果表明,在间苯二甲酸液相反应中,氧化铜表现出很好的催化作用,氧化镁具有很好的助催化作用。间苯二甲酸的转化率为38.5%,间苯二酚产率为19.5%。
现有的间苯二酚合成工艺中,存在工艺较为复杂,副产物较多,反应产率低,而且产生大量的“三废”污染物,对环境产生较大的影响。而利用间苯二甲酸氧化制备间苯二酚,工艺路线简单,不涉及强酸强碱,反应条件要求低,催化剂及助剂可再生回收利用,污染较小,基本可以实现“绿色生产”,具有较大的环保优势。合成原料—间苯二甲酸可由间二甲苯在催化条件下液相空气氧化得到,工艺简单成熟,因此原料来源简单、丰富、价廉,制取无污染。但现有的方法产率较低,副产物较多。
发明内容
虽然肖如亭教授提出了间苯二甲酸合成间苯二酚的工艺路线,但是在其研究中,并未发现NiO、NiO-Fe2O3等以氧化镍为主体的复合金属氧化物在该工艺路线中具有催化性能。
为了解决现有技术的不足,本发明的目的之一是提供一种多元复合金属氧化物在间苯二甲酸液相催化合成间苯二酚中的应用,通过对以氧化镍为主体的复合金属氧化物的进一步研究发现,该类复合金属氧化物在间苯二甲酸液相合成间苯二酚工艺中具有催化性能,间苯二酚收率最高可达30.4%。
为了实现上述目的,本发明的技术方案为:
一种多元复合金属氧化物在间苯二甲酸液相催化合成间苯二酚中的应用,所述多元复合金属氧化物为氧化镍与其他金属氧化物复合的氧化物,并且所述氧化物中附着有贵金属的纳米颗粒,所述多元复合金属氧化物中其他金属氧化物的质量分数为5~20%,贵金属的质量分数为0.5~2.0%;
其中,所述其他金属氧化物为三氧化二铁、五氧化二钒、氧化铜、氧化镁、氧化钙、氧化钾、氧化钠、氧化锆、氧化锡、氧化锌、氧化钴、氧化铅、氧化铋、氧化铝、氧化钛、氧化锰、氧化铷、氧化锶、氧化钯、氧化铑、氧化钡、氧化银或氧化铂;
所述贵金属为金、铂、钯、银、钌、锇或铱。
本发明通过与氧化镍配合的其他金属氧化物和贵金属的选择,并确定氧化镍、其他金属氧化物和贵金属的组成配比,使得组合的多元复合金属氧化物在间苯二甲酸液相合成间苯二酚工艺中具有催化性能。
为了更好的发挥多元复合金属氧化物在间苯二甲酸液相催化合成间苯二酚工艺中的催化效果,本发明的目的之二是提供一种多元复合金属氧化物催化剂催化制备间苯二酚的方法,其技术方案为:以上述多元复合金属氧化物作为催化剂,将催化剂加入至液相的间二苯甲酸中,通入空气后加热分解得到氧化产物,采用水热法将所述氧化产物水解得到水解产物,所述水解产物中含有间苯二酚。
本发明的优点为:
1.本发明通过化学成分的组合获得了用于间苯二甲酸液相催化合成间苯二酚工艺中的催化剂,该催化剂具有较强的氧化性,可以使间苯二甲酸充分氧化为过氧基化合物,后又被水解形成羟基,生成间苯二酚。反应过程中的副产物较少,反应后催化剂可重复循环使用。
2.本发明通过对以氧化镍为主体的多元复合氧化物进行优化,使得以氧化镍为主体的多元复合氧化物在间苯二甲酸液相合成间苯二酚工艺中具有催化性能,且间苯二酚收率最高可达30.4%。
附图说明
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解,本申请的示意性实施例及其说明用于解释本申请,并不构成对本申请的不当限定。
图1为实施例1制备的NiO-MgO-Pt的X射线衍射(XRD)谱图;
图2为实施例1制备的NiO-MgO-Pt的透射电子显微镜(TEM)照片。
具体实施方式
应该指出,以下详细说明都是例示性的,旨在对本申请提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本申请的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也意图包括复数形式,此外,还应当理解的是,当在本说明书中使用术语“包含”和/或“包括”时,其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
本发明中所述的分解为间苯二甲酸液相催化氧化脱羧的反应。
本发明中所述的水热法为在密封的压力容器中,以水为溶剂,在高温高压的条件下进行的化学反应。
正如背景技术所介绍的,现有技术中存在现有研究中以氧化镍为主体的复合金属氧化物在间苯二甲酸液相催化合成间苯二酚的工艺路线中不具备催化性能的问题,为了解决如上的技术问题,本申请提出了一种多元复合金属氧化物在间苯二甲酸液相催化合成间苯二酚中的应用。
本申请的一种典型实施方式中,提供了一种多元复合金属氧化物在间苯二甲酸液相催化合成间苯二酚中的应用,所述多元复合金属氧化物为氧化镍与其他金属氧化物复合的氧化物,并且所述氧化物中附着有贵金属的纳米颗粒,所述多元复合金属氧化物中其他金属氧化物的质量分数为5~20%,贵金属的质量分数为0.5~2.0%;
其中,所述其他金属氧化物为三氧化二铁、五氧化二钒、氧化铜、氧化镁、氧化钙、氧化钾、氧化钠、氧化锆、氧化锡、氧化锌、氧化钴、氧化铅、氧化铋、氧化铝、氧化钛、氧化锰、氧化铷、氧化锶、氧化钯、氧化铑、氧化钡、氧化银或氧化铂;
所述贵金属为金、铂、钯、银、钌、锇或铱。
本发明通过与氧化镍配合的其他金属氧化物和贵金属的选择,并确定氧化镍、其他金属氧化物和贵金属的组成配比,使得组合的多元复合金属氧化物在间苯二甲酸液相合成间苯二酚工艺中具有催化性能。
优选的,所述多元复合金属氧化物中其他金属氧化物的质量分数为10~15%,贵金属的质量分数为1.0~1.5%
为了保证多元复合金属氧化物的催化活性,优选的,所述贵金属的纳米颗粒的粒径为1~6nm。
为了制备上述多元复合金属氧化物,本申请优选了一种所述多元复合金属氧化物的制备方法,
1)将含有上述其他金属氧化物的金属离子的金属盐与镍盐配置成混合盐溶液,向混合盐溶液中加入碱性溶液,使混合盐溶液中的金属离子完全沉淀,将沉淀物煅烧获得二元复合金属氧化物;
2)将含有上述贵金属的盐配置成贵金属盐溶液,将所述二元复合金属氧化物浸渍于所述贵金属盐溶液中,使贵金属盐完全浸渍至所述二元复合金属氧化物中,将浸渍后的二元复合金属氧化物在空气煅烧一段时间后,然后在氮氢混合气气氛中充分还原后即得多元复合金属氧化物。
所述的金属盐包括铜、铁、钙、镁、钾、钠、铷、锶、铑、钯、锡、锌、钴、铅、铋、铝、钛、锆、锰、铯、钡、银、铂的金属卤化物、硝酸盐、硫酸盐、磷酸盐和醋酸盐,优选铁、钴、镁的硝酸盐和硫酸盐。
所述镍盐为阳离子为镍离子的化合物,例如硝酸镍、硫酸镍等。
所述含有上述贵金属的盐为含有贵金属元素的化合物,其中,贵金属可以为贵金属阳离子,也可以为含有贵金属的酸根阴离子。
所述碱性溶液为pH大于7的溶液,其溶质可以为能够提供氢氧根离子的碱,也可以为能够结合水中氢离子的产生氢氧根离子的强碱弱酸盐。为了方便后续处理,碱性溶液优选氢氧化钠溶液或氨水。
为了将沉淀物冲溶液中提出出来,本申请进一步优选的方法为,将完全沉淀后的物料进行离心分离,将分离后的沉淀烘干。
进一步优选的,所述煅烧温度为200~1200℃,更进一步优选为550~650℃。
进一步优选的,所述煅烧时间为1~12h,更进一步优选为3~9h。
为了将贵金属盐完全浸渍至二元复合金属氧化物中,进一步优选的,二元复合金属氧化物浸渍至等体积贵金属盐溶液中。
进一步优选的,浸渍后的二元复合金属氧化物在空气于550~650℃下煅烧4~6h。
进一步优选的,所述氮氢混合气中氮气和氢气的体积比为1:1。
进一步优选的,氮氢混合气气氛中的还原温度为150~200℃。
为了更好的发挥多元复合金属氧化物在间苯二甲酸液相催化合成间苯二酚工艺中的催化效果,本发明的目的之二是提供一种多元复合金属氧化物催化剂催化制备间苯二酚的方法,以上述多元复合金属氧化物作为催化剂,将催化剂加入至液相的间二苯甲酸中,通入空气后加热分解得到氧化产物,采用水热法将所述氧化产物水解得到水解产物,所述水解产物中含有间苯二酚。
优选的,将间苯二甲酸溶于有机溶剂中,加入催化剂,通入空气加热至200~300℃后产生芳羧酸盐,然后继续升温至230~280℃,反应一段时间得到氧化产物。
优选的,水热法采用的温度为200~300℃。
为了使得本领域技术人员能够更加清楚地了解本申请的技术方案,以下将结合具体的实施例与对比例详细说明本申请的技术方案。
实施例1NiO-MgO-Pt三元复合催化剂
称取47.9340g Ni(NO3)2·6H2O和3.4965g Mg(NO3)2·2H2O溶于去离子水中,边搅拌边滴加浓氨水,调节pH约为9.5。过滤,室温干燥10h,80℃干燥12h;将所得固体程序升温至600℃下焙烧5h得到二元复合氧化物。称取4.2870g上述NiO-MgO二元复合催化剂氧化物,浸渍于等体积浓度为0.01g/mL的氯铂酸溶液中,干燥,在600℃先于空气中焙烧5h,再于氮氢混合气(氮氢比为1:1)中180℃还原得NiO-MgO-Pt三元复合催化剂。获得的NiO-MgO-Pt三元复合催化剂的结构表征如图1~2所示,图1~2中可以看出铂的粒径为1~6nm。
上述催化剂在间苯二甲酸催化氧化脱羧反应中的应用方法,按照下述步骤进行:
步骤1,将间苯二甲酸溶于丙酮中,加入催化剂,盐浴加热,通入空气,空气流量为120mL/min,生产芳羧酸盐。
步骤2,升温至分解温度180℃,维持此反应温度反应3h,得到氧化产物。
步骤3,将氧化产物置于高压釜中,加入过量水,260℃下水解,收集所得产物。
所收集的产物用高效液相色谱仪进行分析测试,计算间苯二甲酸的转化率和间苯二酚的选择性。其转化率和选择性的计算公式为:
收率(%)=转化率(%)×选择性(%)×100%
该催化剂的催化效果为:间苯二甲酸的转化率为95%,间苯二酚的选择性为32%,收率为30.4%。
实施例2NiO-MgO-Pd三元复合催化剂
本实施例与实施例1相同,不同之处在于,将NiO-MgO二元复合氧化物,浸渍于等体积浓度为0.01g/mL的氯化钯溶液中,获得NiO-MgO-Pd三元复合催化剂。
该催化剂的催化效果为:间苯二甲酸的转化率为93%,间苯二酚的选择性为31%,收率为28.83%。
实施例3NiO-Fe2O3-Pt三元复合催化剂
称取31.9560g Ni(NO3)2·6H2O和10.1196g Fe(NO3)3·9H2O溶于去离子水中,边搅拌边滴加浓氨水,调节pH约为9.4。过滤,室温干燥10h,80℃干燥12h;将所得固体程序升温至600℃下焙烧5h得到二元复合氧化物。称取5.1038g上述NiO-Fe2O3二元复合氧化物,浸渍于等体积浓度为0.01g/mL的氯铂酸溶液中,干燥,在600℃先于空气中焙烧5h,再于氮氢混合气(氮氢比为1:1)中180℃还原得NiO-Fe2O3-Pt三元复合催化剂。
该催化剂间苯二甲酸催化氧化脱羧反应中的应用方法与实施例1相同,不同之处在于,分解温度为190℃。
该催化剂的催化效果为:间苯二甲酸的转化率为88%,间苯二酚的选择性为26%,收率为22.9%。
实施例4NiO-Fe2O3-Pd三元复合催化剂
本实施例与实施例3相同,不同之处在于,将NiO-Fe2O3二元复合氧化物,浸渍于等体积浓度为0.01g/mL的氯化钯溶液中,获得NiO-Fe2O3-Pd三元复合催化剂。
该催化剂的催化效果为:间苯二甲酸的转化率为92%,间苯二酚的选择性为24%,收率为22.08%。
实施例5NiO-CuO-Pt三元复合催化剂
本实施例与实施例1相同,不同之处在于,先制备了NiO-CuO二元复合氧化物,然后制备NiO-CuO-Pt三元复合催化剂。
该催化剂的催化效果为:间苯二甲酸的转化率为75%,间苯二酚的选择性为12.5%,收率为9.38%。
实施例6NiO-CuO-Pd三元复合催化剂
本实施例与实施例3相同,不同之处在于,将NiO-CuO二元复合氧化物,浸渍于等体积浓度为0.01g/mL的氯化钯溶液中,获得NiO-CuO-Pd三元复合催化剂。该催化剂在间苯二甲酸液相催化氧化脱羧反应中,分解温度为190℃。
该催化剂的催化效果为:间苯二甲酸的转化率为65%,间苯二酚的选择性为10.6%,收率为6.89%。
实施例7
本实施例与实施例1相同,不同之处在于,先制备了NiO-V2O5二元复合氧化物,然后制备NiO-V2O5-Au三元复合催化剂。
实施例8
本实施例与实施例1相同,不同之处在于,先制备了NiO-CaO二元复合氧化物,然后制备NiO-CaO-Ag三元复合催化剂。
实施例9
本实施例与实施例1相同,不同之处在于,先制备了NiO-ZrO2二元复合氧化物,然后制备NiO-ZrO2-Pt三元复合催化剂。
实施例10
本实施例与实施例1相同,不同之处在于,先制备了NiO-SnO2二元复合氧化物,然后制备NiO-SnO2-Pd三元复合催化剂。
实施例11
本实施例与实施例1相同,不同之处在于,先制备了NiO-ZnO2二元复合氧化物,然后制备NiO-ZnO2-Ru三元复合催化剂。
实施例12
本实施例与实施例1相同,不同之处在于,先制备了NiO-CoO二元复合氧化物,然后制备NiO-CoO-Pd三元复合催化剂。
实施例13
本实施例与实施例1相同,不同之处在于,先制备了NiO-PbO二元复合氧化物,然后制备NiO-PbO-Pt三元复合催化剂。
实施例14
本实施例与实施例1相同,不同之处在于,先制备了NiO-Bi2O3二元复合氧化物,然后制备NiO-Bi2O3-Pt三元复合催化剂。
实施例15
本实施例与实施例1相同,不同之处在于,先制备了NiO-Al2O3二元复合氧化物,然后制备NiO-Al2O3-Os三元复合催化剂。
实施例16
本实施例与实施例1相同,不同之处在于,先制备了NiO-TiO2二元复合氧化物,然后制备NiO-TiO2-Ir三元复合催化剂。
实施例17
本实施例与实施例1相同,不同之处在于,先制备了NiO-MnO2二元复合氧化物,然后制备NiO-MnO2-Pd三元复合催化剂。
实施例18
本实施例与实施例1相同,不同之处在于,先制备了NiO-Nd2O3二元复合氧化物,然后制备NiO-Nd2O3-Pd三元复合催化剂。
实施例19
本实施例与实施例1相同,不同之处在于,先制备了NiO-SrO二元复合氧化物,然后制备NiO-SrO-Pt三元复合催化剂。
实施例20
本实施例与实施例1相同,不同之处在于,先制备了NiO-PdO二元复合氧化物,然后制备NiO-PdO-Ag三元复合催化剂。
实施例21
本实施例与实施例1相同,不同之处在于,先制备了NiO-Rh2O3二元复合氧化物,然后制备NiO-Rh2O3-Pt三元复合催化剂。
实施例22
本实施例与实施例1相同,不同之处在于,先制备了NiO-BaO二元复合氧化物,然后制备NiO-BaO-Pd三元复合催化剂。
实施例23
本实施例与实施例1相同,不同之处在于,先制备了NiO-AgO二元复合氧化物,然后制备NiO-AgO-Pd三元复合催化剂。
实施例24
本实施例与实施例1相同,不同之处在于,先制备了NiO-PtO二元复合氧化物,然后制备NiO-PtO-Pd三元复合催化剂。
实施例7-24制备的三元复合催化剂在间苯二甲酸液相合成间苯二酚工艺中均具有催化性能。
对比例
称取Ni(NO3)2·6H2O和Fe(NO3)3·9H2O溶于去离子水中,边搅拌边滴加浓氨水,调节pH约为9.4。过滤,室温干燥10h,80℃干燥12h;将所得固体程序升温至600℃下焙烧5h得到NiO-Fe2O3二元复合氧化物。
该二元复合氧化物无法在液相中将间苯二甲酸催化合成间苯二酚。
以上所述仅为本申请的优选实施例而已,并不用于限制本申请,对于本领域的技术人员来说,本申请可以有各种更改和变化。凡在本申请的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本申请的保护范围之内。
Claims (10)
1.一种多元复合金属氧化物在间苯二甲酸液相催化合成间苯二酚中的应用,其特征是,所述多元复合金属氧化物为氧化镍与其他金属氧化物复合的氧化物,并且所述氧化物中附着有贵金属的纳米颗粒,所述多元复合金属氧化物中其他金属氧化物的质量分数为5~20%,贵金属的质量分数为0.5~2.0%;
其中,所述其他金属氧化物为三氧化二铁、五氧化二钒、氧化铜、氧化镁、氧化钙、氧化钾、氧化钠、氧化锆、氧化锡、氧化锌、氧化钴、氧化铅、氧化铋、氧化铝、氧化钛、氧化锰、氧化铷、氧化锶、氧化钯、氧化铑、氧化钡、氧化银或氧化铂;
所述贵金属为金、铂、钯、银、钌、锇或铱。
2.如权利要求1所述的应用,其特征是,所述多元复合金属氧化物中其他金属氧化物的质量分数为10~15%,贵金属的质量分数为1.0~1.5%。
3.如权利要求1所述的应用,其特征是,所述贵金属的纳米颗粒的粒径为1~6nm。
4.如权利要求1所述的应用,其特征是,所述多元复合金属氧化物的制备方法,
1)将含有上述其他金属氧化物的金属离子的金属盐与镍盐配置成混合盐溶液,向混合盐溶液中加入碱性溶液,使混合盐溶液中的金属离子完全沉淀,将沉淀物煅烧获得二元复合金属氧化物;
2)将含有上述贵金属的盐配置成贵金属盐溶液,将所述二元复合金属氧化物浸渍于所述贵金属盐溶液中,使贵金属盐完全浸渍至所述二元复合金属氧化物中,将浸渍后的二元复合金属氧化物在空气煅烧一段时间后,然后在氮氢混合气气氛中充分还原后即得多元复合金属氧化物。
5.如权利要求4所述的应用,其特征是,将完全沉淀后的物料进行离心分离,将分离后的沉淀烘干。
6.如权利要求4所述的应用,其特征是,所述煅烧温度为200~1200℃,优选为550~650℃;
所述煅烧时间为1~12h,优选为3~9h。
7.如权利要求4所述的应用,其特征是,二元复合金属氧化物浸渍至等体积贵金属盐溶液中;
或,浸渍后的二元复合金属氧化物在空气于550~650℃下煅烧4~6h。
8.如权利要求4所述的应用,其特征是,所述氮氢混合气中氮气和氢气的体积比为1:1;
或,氮氢混合气气氛中的还原温度为150~200℃。
9.一种多元复合金属氧化物催化剂催化制备间苯二酚的方法,其特征是,以权利要求1~8任一所述应用中的多元复合金属氧化物作为催化剂,将催化剂加入至液相的间二苯甲酸中,通入空气后加热分解得到氧化产物,采用水热法将所述氧化产物水解得到水解产物,所述水解产物中含有间苯二酚。
10.如权利要求9所述的方法,其特征是,将间苯二甲酸溶于有机溶剂中,加入催化剂,通入空气加热至200~300℃后产生芳羧酸盐,然后继续升温至230~280℃,反应一段时间得到氧化产物;
或,水热法采用的温度为200~300℃。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107961779A (zh) * | 2017-11-24 | 2018-04-27 | 江西省隆南药化有限公司 | 一种用于合成麝香草酚的催化剂及其制备方法,及应用该催化剂制备麝香草酚的方法 |
CN115193440A (zh) * | 2022-09-02 | 2022-10-18 | 中北大学 | 一种铜基固体碱催化剂及其制备方法和应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH061726A (ja) * | 1992-06-17 | 1994-01-11 | Nippon Steel Chem Co Ltd | 水素化方法 |
CN1557543A (zh) * | 2004-02-12 | 2004-12-29 | 北京化工大学 | 气相法苯甲酸制苯酚新型五氧化二钒多元复合金属氧化物催化剂 |
CN101659598A (zh) * | 2008-08-29 | 2010-03-03 | 中国石油天然气股份有限公司 | 一种过氧化氢直接氧化苯制备苯酚的方法 |
CN106622280A (zh) * | 2016-09-06 | 2017-05-10 | 中国海洋石油总公司 | 一种耐硫甲烷化催化剂及其制备方法 |
-
2017
- 2017-06-13 CN CN201710443833.9A patent/CN107185552B/zh not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH061726A (ja) * | 1992-06-17 | 1994-01-11 | Nippon Steel Chem Co Ltd | 水素化方法 |
CN1557543A (zh) * | 2004-02-12 | 2004-12-29 | 北京化工大学 | 气相法苯甲酸制苯酚新型五氧化二钒多元复合金属氧化物催化剂 |
CN101659598A (zh) * | 2008-08-29 | 2010-03-03 | 中国石油天然气股份有限公司 | 一种过氧化氢直接氧化苯制备苯酚的方法 |
CN106622280A (zh) * | 2016-09-06 | 2017-05-10 | 中国海洋石油总公司 | 一种耐硫甲烷化催化剂及其制备方法 |
Non-Patent Citations (2)
Title |
---|
V. DUMA ET AL.: "Gas phase oxidation of benzoic acid to phenol over nickel oxide catalysts", 《CHEMICAL ENGINEERING JOURNAL》 * |
崔建新: "间苯二甲酸合成间苯二酚研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107961779A (zh) * | 2017-11-24 | 2018-04-27 | 江西省隆南药化有限公司 | 一种用于合成麝香草酚的催化剂及其制备方法,及应用该催化剂制备麝香草酚的方法 |
CN115193440A (zh) * | 2022-09-02 | 2022-10-18 | 中北大学 | 一种铜基固体碱催化剂及其制备方法和应用 |
CN115193440B (zh) * | 2022-09-02 | 2024-06-07 | 中北大学 | 一种铜基固体碱催化剂及其制备方法和应用 |
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