CN112191269A - 氧化铝负载离子液体-铜催化剂及其制备和在乙炔加氢反应中的应用 - Google Patents
氧化铝负载离子液体-铜催化剂及其制备和在乙炔加氢反应中的应用 Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 48
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 48
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- 238000011068 loading method Methods 0.000 claims description 11
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- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 2
- HDXFBBSZRMZTFF-UHFFFAOYSA-N 1-methyl-3-pentyl-2h-imidazole Chemical compound CCCCCN1CN(C)C=C1 HDXFBBSZRMZTFF-UHFFFAOYSA-N 0.000 claims description 2
- JFYZBXKLRPWSGV-UHFFFAOYSA-N 1-methyl-3-propyl-2h-imidazole Chemical compound CCCN1CN(C)C=C1 JFYZBXKLRPWSGV-UHFFFAOYSA-N 0.000 claims description 2
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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Abstract
本发明提供了一种氧化铝负载离子液体‑铜催化剂及其制备和在乙炔加氢反应中的应用,将咪唑类离子液体和铜的混合液负载于氧化铝载体上,咪唑类离子液体一方面在载体表面形成一层液膜,利用氢气在离子液体中低溶解度的特性,使得在催化剂表面有着相对平衡的氢气和乙炔比例,防止过度加氢,提高反应的乙烯选择性;另一方面咪唑类离子液体与活性组分铜形成特殊的卡宾结构,该结构所产生的电子效应使得铜处于富电子状态,促进了乙烯从铜活性组分表面脱附,这使得催化剂在保持高乙炔转化率的同时,也大大提高了该反应中乙烯的选择性。
Description
技术领域
本发明涉及一种氧化铝负载离子液体-铜催化剂及其制备方法和在乙炔选择性加氢制乙烯反应中的应用。
背景技术
乙烯作为重要的有机化工原料,被广泛应用于各个领域。工业生产所得的乙烯原料气中,往往含有1%的乙炔。乙烯原料气中混杂的微量乙炔会毒化后续乙烯聚合反应的催化剂,并降低聚乙烯产品的品质。因此,将原料气中的乙炔除至5ppm以下具有重要意义。
乙烯装置中常采用溶剂吸收法、选择性加氢法脱除乙烯原料中的乙炔。与溶剂吸收法相比,催化选择加氢污染小,在除去乙炔杂质的同时,还能提高乙烯的产量。然而工业上所采用的传统催化剂,当乙炔在高转化率时,乙烯的选择性很低。这是由于在反应过程中乙烯没有及时脱附,过度加氢所导致的。
基于以上背景,设计一种合适的催化剂以提高乙炔选择性加氢反应中乙烯的选择性对于乙烯的工业化生产具有重要意义,同时由于铜的廉价性,设计一种高转化率、高选择性的铜基催化剂具有巨大的市场空间。
发明内容
本发明旨在提供一种用于乙炔选择性加氢的氧化铝负载离子液体-铜催化剂及其制备方法,本发明制备方法工艺简单,制得的催化剂在乙炔选择性加氢反应中具有乙炔转化率高、乙烯选择性高的优点。
本发明的技术方案如下:
一种氧化铝负载离子液体-铜催化剂,由氧化铝载体、负载在载体表面上的离子液体和铜化合物组成;所述铜化合物选自氯化亚铜、碘化亚铜、溴化亚铜或氯化铜;所述离子液体为咪唑类离子液体,离子液体在载体表面形成一层液膜;基于载体的质量,铜的负载量为2~10wt%,离子液体的负载量为8~50wt%。
进一步,
所述氧化铝载体的比表面积为58~420m2/g;
所述铜化合物优选氯化亚铜;
所述咪唑类离子液体中,咪唑阳离子为1-乙基-3-甲基咪唑、1-丙基-3-甲基咪唑、1-丁基-3-甲基咪唑或1-戊基-3-甲基咪唑形成的阳离子,阴离子为硫酸氢根、六氟膦酸根、四氟硼酸根、氯离子、溴离子或碘离子;
优选铜的负载量为2~8wt%,更优选3~5wt%;
优选离子液体的负载量为10~30wt%,更优选20~30wt%。
本发明所述氧化铝负载离子液体-铜催化剂的制备方法为:
将铜化合物溶于溶剂,得到铜化合物浸渍液,然后将其与离子液体混合,搅拌分散均匀,得到离子液体-铜复合物浸渍液,将氧化铝加入离子液体-铜复合物浸渍液中,在室温(20~30℃)下浸渍8~14h,之后在110~130℃下干燥8~14h,制得氧化铝负载离子液体-铜催化剂;
所述溶剂根据铜化合物的种类而定,可以是水、盐酸溶液、乙醇等,本发明对此没有特殊要求;
所述铜化合物浸渍液中铜的浓度为0.02~0.1g/mL;
若离子液体-铜复合物浸渍液无法浸没加入的氧化铝,可加入一定量的浓盐酸(36~38wt%),使氧化铝被完全浸没(浓盐酸的用量没有特殊要求,能够使氧化铝浸没即可);加入氧化铝后,优选通过超声处理使氧化铝在浸渍液中分散均匀;
同时,优选将制得的催化剂置于微波反应器中,在100~120℃下微波10~30min,该操作可以进一步促进卡宾结构的形成;
本发明所述催化剂的制备方法中,铜化合物和离子液体可认为是全部负载,本领域技术人员可以根据需要的负载量选择铜化合物和离子液体的加入量。
本发明所述氧化铝负载离子液体-铜催化剂可应用于乙炔选择性加氢反应中;
在应用前,先用氢气对催化剂进行还原,还原温度为120~200℃,还原时间为1~5h;
具体的,乙炔选择性加氢的条件是:反应温度为120~210℃,反应压力为0.02~0.2MPa,空速为300~6000h-1;
本发明乙炔选择性加氢中,一般反应温度越高,反应活性越好,但是选择性也会相应降低,同时反应评价为诱导期内的活性;优选反应温度为120~180℃,优选反应压力为0.05~0.1MPa,更优选为常压,优选空速为500~3000h-1。
与现有技术相比,本发明的有益效果在于:
(1)本发明的氧化铝负载离子液体-铜催化剂,将咪唑类离子液体和铜的混合液负载于氧化铝载体上,咪唑类离子液体一方面在载体表面形成一层液膜,利用氢气在离子液体中低溶解度的特性,使得在催化剂表面有着相对平衡的氢气和乙炔比例,防止过度加氢,提高反应的乙烯选择性;另一方面咪唑类离子液体与活性组分铜形成特殊的卡宾结构,该结构所产生的电子效应使得铜处于富电子状态,促进了乙烯从铜活性组分表面脱附,这使得催化剂在保持高乙炔转化率的同时,也大大提高了该反应中乙烯的选择性。此外,本发明制成负载型催化剂,一方面可以减少昂贵的离子液体的用量,降低成本;另一方面由于离子液体传质效果不好,将其负载在载体上形成一层液膜,可以改善传质效果。
(2)本发明氧化铝负载离子液体-铜催化剂的制备方法工艺简单,通过引入微波处理步骤,可进一步提高反应中乙炔的活性。
(3)本发明氧化铝负载离子液体-铜催化剂应用于乙炔选择性加氢制备乙烯,具有乙炔转化率高、乙烯选择性高的优点。
具体实施方式
下面通过具体实施例对本发明作进一步描述,但不能理解为对本发明保护范围的限制。
实施例1-13
称取一定量的氯化亚铜溶解于浓盐酸水中,转移至容量瓶中,加入一定量的浓盐酸到相应刻度,制得铜的质量浓度为0.05g/mL的氯化亚铜溶液。按照表1所列的负载量及其配比,将计量的氯化亚铜溶液和咪唑类离子液体混合,并加入一定量的浓盐酸,搅拌均匀后,均匀地将氧化铝载体(比表面积为400m2/g)倒入浸渍液中,超声使其分散均匀。将润湿的氧化铝在室温浸渍12h,并在110℃下在真空干燥箱中干燥12h,即制得氧化铝负载离子液体-铜催化剂。
实施例14
参照实施例6的操作,区别仅在于载体换成比表面积为58m2/g的氧化铝,制得氧化铝负载离子液体-铜催化剂。
实施例15
参照实施例6的操作,区别仅在于载体换成比表面积为420m2/g的氧化铝,制得氧化铝负载离子液体-铜催化剂。
实施例16
将实施例6制备的氧化铝负载离子液体-铜催化剂在微波反应器中于100℃反应30min,得到成品催化剂。
实施例17
将实施例6制备的氧化铝负载离子液体-铜催化剂在微波反应器中于120℃反应10min,得到成品催化剂。
实施例18-19
称取一定量的碘化亚铜溶解于乙腈溶液中,转移至容量瓶中,加入一定量的乙腈溶液到相应刻度,制得铜的质量浓度为0.05g/mL的碘化亚铜溶液。按照表1所列的负载量及其配比,将计量的碘化亚铜溶液和咪唑类离子液体混合,并加入一定量的乙腈溶液,搅拌均匀后,均匀地将氧化铝载体(比表面积为400m2/g)倒入浸渍液中,超声使其分散均匀。将润湿的氧化铝在室温浸渍12h,并在110℃下在真空干燥箱中干燥12h,即制得氧化铝负载离子液体-铜催化剂。
实施例20-21
称取一定量的溴化亚铜溶解于浓盐酸水中,转移至容量瓶中,加入一定量的浓盐酸到相应刻度,制得铜的质量浓度为0.05g/mL的溴化亚铜溶液。按照表1所列的负载量及其配比,将计量的溴化亚铜溶液和咪唑类离子液体混合,并加入一定量的浓盐酸,搅拌均匀后,均匀地将氧化铝载体(比表面积为400m2/g)倒入浸渍液中,超声使其分散均匀。将润湿的氧化铝在室温浸渍12h,并在110℃下在真空干燥箱中干燥12h,即制得氧化铝负载离子液体-铜催化剂。
实施例22-23
称取一定量的氯化铜溶解于去离子水中,转移至容量瓶中,加入一定量的去离子水到相应刻度,制得铜的质量浓度为0.05g/mL的氯化铜溶液。按照表1所列的负载量及其配比,将计量的氯化铜溶液和咪唑类离子液体混合,并加入一定量的去离子水,搅拌均匀后,均匀地将氧化铝载体(比表面积为400m2/g)倒入浸渍液中,超声使其分散均匀。将润湿的氧化铝在室温浸渍12h,并在110℃下在真空干燥箱中干燥12h,即制得氧化铝负载离子液体-铜催化剂。
制得的催化剂按照下面方法进行催化剂活性及选择性评价:
将0.3g催化剂置于小型石英管反应器中,将石英管放置于可控温的加热炉中,反应前,通入纯H2在170℃下还原1h,还原气流速为40mL/min;还原后,将温度控制在170℃下进行反应。反应气体组成为(体积分数):0.33%乙炔,0.66%氢气,33%乙烯,余量氮气。反应气出口接气相色谱在线检测,催化剂的评价结果见下表1所示。
表1实施例1-23氧化铝负载离子液体-铜催化剂的乙炔选择性加氢反应评价结果
对比例1-3
称取一定量的氯化亚铜溶解于浓盐酸水中,转移至容量瓶中,加入一定量的浓盐酸到相应刻度,制得铜的质量浓度为0.05g/mL的氯化亚铜溶液。按照表2所列的负载量及其配比,将计量的氯化亚铜溶液和非咪唑类离子液体混合,并加入一定量的浓盐酸,搅拌均匀后,均匀地将氧化铝载体(比表面积为400m2/g)倒入浸渍液中,超声使其分散均匀。将润湿的氧化铝在室温浸渍12h,并在110℃下在真空干燥箱中干燥12h,即制得氧化铝负载离子液体-铜催化剂。
催化剂活性和选择性评价方法同上,催化剂的评价结果见下表2所示。
表2对比例1-3氧化铝负载离子液体-铜催化剂的乙炔选择性加氢反应评价结果
Claims (8)
1.一种氧化铝负载离子液体-铜催化剂,其特征在于,由氧化铝载体、负载在载体表面上的离子液体和铜化合物组成;所述铜化合物选自氯化亚铜、碘化亚铜、溴化亚铜或氯化铜;所述离子液体为咪唑类离子液体,离子液体在载体表面形成一层液膜;基于载体的质量,铜的负载量为2~10wt%,离子液体的负载量为8~50wt%。
2.如权利要求1所述的氧化铝负载离子液体-铜催化剂,其特征在于,所述氧化铝载体的比表面积为58~420m2/g。
3.如权利要求1所述的氧化铝负载离子液体-铜催化剂,其特征在于,所述咪唑类离子液体中,咪唑阳离子为1-乙基-3-甲基咪唑、1-丙基-3-甲基咪唑、1-丁基-3-甲基咪唑或1-戊基-3-甲基咪唑形成的阳离子,阴离子为硫酸氢根、六氟膦酸根、四氟硼酸根、氯离子、溴离子或碘离子。
4.如权利要求1所述的氧化铝负载离子液体-铜催化剂的制备方法,其特征在于,所述的制备方法为:
将铜化合物溶于溶剂,得到铜化合物浸渍液,然后将其与离子液体混合,搅拌分散均匀,得到离子液体-铜复合物浸渍液,将氧化铝加入离子液体-铜复合物浸渍液中,在室温下浸渍8~14h,之后在110~130℃下干燥8~14h,制得氧化铝负载离子液体-铜催化剂。
5.如权利要求4所述的制备方法,其特征在于,所述铜化合物浸渍液中铜的浓度为0.02~0.1g/mL。
6.如权利要求4所述的制备方法,其特征在于,将制得的催化剂置于微波反应器中,在100~120℃下微波10~30min。
7.如权利要求1所述的氧化铝负载离子液体-铜催化剂在乙炔选择性加氢反应中的应用。
8.如权利要求7所述的应用,其特征在于,在应用前,先用氢气对催化剂进行还原,还原温度为120~200℃,还原时间为1~5h;乙炔选择性加氢的条件是:反应温度为120~210℃,反应压力为0.02~0.2MPa,空速为300~6000h-1。
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