CN110665505B - 一种高效催化乙酰丙酸加氢制γ-戊内酯的Cu@mZrO2核壳催化剂及应用 - Google Patents
一种高效催化乙酰丙酸加氢制γ-戊内酯的Cu@mZrO2核壳催化剂及应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 229940040102 levulinic acid Drugs 0.000 title claims abstract description 43
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims abstract description 78
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Abstract
本发明公开了一种高效催化乙酰丙酸加氢制γ‑戊内酯的Cu@mZrO2核壳催化剂及应用,所述的Cu@mZrO2核壳催化剂为介孔二氧化锆包裹铜纳米颗粒,其是先采用沉淀法制备氢氧化锆包裹氢氧化铜核前驱体,前驱体干燥后在空气中热解,得到二氧化锆包裹型氧化铜核,然后在H2/Ar混合气氛下热还原,即得到介孔二氧化锆包裹铜核壳型催化剂。本发明催化剂制备方法简单,负载量低,其用于催化乙酰丙酸加氢制γ‑戊内酯活性高、稳定性好,在较低反应温度下γ‑戊内酯收率也可高达100%,且反应以去离子水作为反应溶剂,绿色环保。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种高效催化乙酰丙酸加氢制γ-戊内酯的Cu@mZrO2核壳催化剂及其催化合成γ-戊内酯的应用。
背景技术
化石能源日益贫乏,生态环境保护形势严峻,使得开发利用可再生的、环境友好的生物质资源替代石化资源成为国内外研究人员关注的热点。以生物质制备平台化学品和燃料,有利于缓解能源危机,保护生态环境。
乙酰丙酸是美国能源部筛选出的12种最重要的平台化合物之一。乙酰丙酸主要由木质纤维素的酸水解转化得到,它是多种轻化工产品的基本原料,在有机合成、工农业和医药行业具有广泛应用,也可用于制备燃料添加剂、聚合物单体等高附加值化学品。乙酰丙酸同时含有酮羰基、羧基和α-氢,具有高反应活性和极好的亲核反应特性,能进行酯化、氧化还原、取代、聚合等多种化学反应,可用于生产乙酰丙酸乙酯、γ-戊内酯和2-甲基四氢呋喃等化学品。
γ-戊内酯具有高沸点(207~208℃)、高闪点(96℃)、高热值、不易挥发、稳定性好、低温流动性、低毒可降解以及易于储存运输等特点。γ-戊内酯可以作为绿色溶剂,汽柴油和生物油等燃料的添加剂,还可用于制备液体燃料;γ-戊内酯是一种重要的平台化合物,在化工和制药行业用作各种有关化合物的中间体;γ -戊内酯也可用作润滑剂、增塑剂、非离子表面活性剂的凝胶剂等。
乙酰丙酸加氢制γ-戊内酯,这是生物质转化路径中一个非常关键的反应。目前关于乙酰丙酸加氢制γ-戊内酯的催化剂分为均相和非均相两种。其中均相催化剂由于配体较为复杂、昂贵,贵金属作为活性中心,难以回收再利用,而限制了其大规模应用。非均相催化剂多以贵金属作为活性中心,如Ru、Pd、Rh、Pt、Ir和 Au等。Manzer等将5%的贵金属Ru、Pd、Re、Rh、Pt和Ir分别负载在活性炭上,发现5%Ru/C具有最高的活性,在150℃、5.5MPa H2下反应4h收率达到97%(Applied Catalysis A:General,2004,272(1):249-256)。朱玉雷等利用3-氨丙基三乙氧基硅烷对Ru/γ-Al2O3进行改性Al2O3,在25℃、4MPa H2下反应13h收率达到99.1% (Catalysis Science&Technology,2016,6(5):1469-1475)。Swarha等用Ru负载在Mg-LaO上,在80℃、0.5MPa H2下反应4h收率达到91%(RSC Advances,2015, 5(12):9044-9049)。贵金属催化剂昂贵的价格限制了其大规模应用。非贵金属催化剂多采用Ni和Cu作为活性中心,反应活性不高,但反应温度高,反应时间长;考虑到以非贵金属作为活性中心,反应活性低,而将活性金属制备成纳米颗粒,提高分散度,暴露出更多的活性位点,以提高反应活性;但制备出的非贵金属催化剂在热处理、还原及反应过程,催化剂中的纳米活性金属颗粒会发生聚集,在反应过程中还会发生活性金属的流失,这些都导致了催化剂反应活性的降低,同时使得部分催化剂存在稳定性不足或需要采用有机溶剂作为反应溶剂的问题。Long等使用 Co/Al2O3在180℃、5MPa H2下反应3h收率达到99%(Chinese Journal ofCatalysis, 2015,36(9):1512-1518)。Fu等采用Ni/Al2O3在180℃、3MPa H2下反应2h收率达到99.2%(Catalysts,2015,6(1):6)。Yan等使用Cu-Fe作为催化剂,在200℃、 7MPa H2下反应10h收率达到90.1%(Fuel,2014,115:101-108)。Xu等在乙醇体系中采用Cu(30%)-WO3(10%)/ZrO2-CP-300,在140℃、5MPa H2下反应6h收率达到 81%(Green Chemistry,2016,18(5):1287-1294)。Hengne等使用Cu/ZrO2(Cu与 ZrO2的摩尔比为1:1)在200℃、3.5MPa H2下反应5h收率达到100%,然而在水溶液体系中Cu严重流失;需要采用甲醇作为反应溶剂,同等条件下,收率降到90%。该催化剂铜负载量高,反应温度高(GreenChemistry,2012,14(4):1064-1072)。
发明内容
本发明的目的是解决现有乙酰丙酸加氢制γ-戊内酯催化剂昂贵或活性不高等问题,提供一种负载量低、活性高、稳定性好的Cu@mZrO2核壳型催化剂,以及该催化剂催化乙酰丙酸加氢制γ-戊内酯的应用。
针对上述目的,本发明的Cu@mZrO2核壳型催化剂为介孔二氧化锆包裹铜纳米颗粒,催化剂中铜核与二氧化锆壳的质量比为1%~10%,优选催化剂中铜核与二氧化锆壳的质量比为5%~10%。
本发明催化剂的制备为:将硝酸铜与聚乙烯吡咯烷酮溶于无水乙醇,得到溶液 A;将十六烷基三甲基溴化铵、去离子水、无水乙醇、质量浓度为6%~25%的氢氧化氨水溶液混合,超声分散均匀,得到溶液B;将正丁醇锆均匀分散于无水乙醇中,得到溶液C;在搅拌下将溶液A滴加入溶液B中,室温搅拌老化2~4h,然后滴加溶液C,继续搅拌老化48~60h,离心分离,沉淀用去离子水及无水乙醇洗涤,80~ 100℃干燥12~15h;将干燥产物在空气中380~550℃处理4~6h,然后在H2与Ar 摩尔比为1:8~1:10的混合气氛下280℃~500℃热还原2~12h,得到Cu@mZrO2核壳催化剂。
上述溶液A中,硝酸铜与聚乙烯吡咯烷酮的质量比为1:2~1:5,优选硝酸铜与聚乙烯吡咯烷酮的质量比为1:4~1:5。
上述催化剂的制备方法中,将溶液A滴加入溶液B时,控制十六烷基三甲基溴化铵与聚乙烯吡咯烷酮的质量比为1:4~10:1,硝酸铜与氢氧化氨的摩尔比为 1:70~1:1300,硝酸铜与去离子水的质量比为1:450~1:7200,溶液B中无水乙醇与去离子水的体积比为1:1~2:1;优选控制十六烷基三甲基溴化铵与聚乙烯吡咯烷酮的质量比为1:2~7:1,硝酸铜与氢氧化氨的摩尔比为1:100~1:1200。
上述催化剂制备方法中,进一步优选将干燥产物在空气中400~450℃处理4~5h,然后在H2与Ar摩尔比为1:9的混合气氛下300℃~350℃热还原2~3h。
上述催化剂制备方法中,所述聚乙烯吡咯烷酮的重均分子量为44000~54000。
本发明催化剂催化乙酰丙酸加氢制γ-戊内酯的应用,具体方法为:将Cu@mZrO2核壳催化剂、乙酰丙酸、去离子水置于不锈钢反应釜中,在2.5~3.5MPa氢气气氛下100~200℃恒温密闭搅拌反应4~6h,得到γ-戊内酯。
上述应用中,优选催化剂的加入量为乙酰丙酸质量的40%~45%。
上述应用中,进一步优选在3MPa氢气气氛下130~150℃恒温密闭搅拌反应5h。
本发明核壳型催化剂是先采用沉淀法制备氢氧化锆包裹氢氧化铜核前驱体,前驱体干燥后在空气中热解,得到二氧化锆包裹型氧化铜核,然后在还原气氛下热还原,得到介孔二氧化锆包裹铜核壳型催化剂。与现有技术相比,本发明的有益效果如下:
1、本发明在提高活性金属分散度的同时,采用介孔二氧化锆包裹铜活性中心,有效抑制了活性金属颗粒的聚集及流失,显著提高了反应活性及催化剂稳定性。
2、本发明核壳型催化剂以非贵金属为活性中心,制备方法简单,负载量低,活性高,稳定性好,催化乙酰丙酸加氢制γ-戊内酯以去离子水作为反应溶剂,γ- 戊内酯最高收率达100%。
附图说明
图1是不同负载量Cu@mZrO2的H2-TPR。
图2是5Cu@mZrO2在固定床反应器中催化乙酰丙酸加氢制γ-戊内酯反应100h 的稳定性实验结果。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明,但本发明的保护范围不仅限于这些实施例。
实施例1
按照催化剂中铜核与二氧化锆的质量比为10%,称取1.1405g Cu(NO3)2·3H2O 和4.5935g聚乙烯吡咯烷酮K30溶于634mL无水乙醇中,得到溶液A;称取3g十六烷基三甲基溴化铵超声分散于818mL去离子水、1028mL无水乙醇和144mL 6.25wt%氢氧化氨水溶液组成的混合液中,得到溶液B;称取9.34g正丁醇锆均匀分散于 200mL无水乙醇中,得到溶液C;在搅拌下将溶液A滴加入溶液B中,室温搅拌老化2h,然后滴加溶液C,继续搅拌老化48h,离心分离,沉淀用去离子水及无水乙醇洗涤后80℃干燥12h;将干燥产物在空气中400℃处理4h,然后在H2与Ar摩尔比为1:9的混合气氛300℃热还原2h,得到介孔二氧化锆包裹铜纳米颗粒的核壳型催化剂10Cu@mZrO2。
实施例2
本实施例中,按照催化剂中铜核与二氧化锆的质量比为7%,称取0.7983g Cu(NO3)2·3H2O和3.2154g聚乙烯吡咯烷酮K30溶于444mL无水乙醇中,得到溶液A,其他步骤与实施例1相同,得到介孔二氧化锆包裹铜纳米颗粒的核壳型催化剂 7Cu@mZrO2。
实施例3
本实施例中,按照催化剂中铜核与二氧化锆的质量比为5%,称取0.5702g Cu(NO3)2·3H2O和2.2967g聚乙烯吡咯烷酮K30溶于317mL无水乙醇中,其他步骤与实施例1相同,得到介孔二氧化锆包裹铜纳米颗粒的核壳型催化剂5Cu@mZrO2。
实施例4
本实施例中,按照催化剂中铜核与二氧化锆的质量比为3%,称取0.3421g Cu(NO3)2·3H2O和1.3780g聚乙烯吡咯烷酮K30溶于190ml无水乙醇中,得到溶液A,其他步骤与实施例1相同,得到介孔二氧化锆包裹铜纳米颗粒的核壳型催化剂 3Cu@mZrO2。
实施例5
本实施例中,按照催化剂中铜核与二氧化锆的质量比为1%,称取0.1140g Cu(NO3)2·3H2O和0.4593g聚乙烯吡咯烷酮K30溶于63ml无水乙醇中,得到溶液A,其他步骤与实施例1相同,得到介孔二氧化锆包裹铜纳米颗粒的核壳型催化剂 1Cu@mZrO2。
对上述实施例1~5制备的催化剂进行H2-TPR表征,结果见图1。由图1可见,随Cu负载量减少,ZrO2的相对含量增加,与CuO之间的相互作用增强,所以还原温度升高,但负载量降低,还原峰减弱。
进一步对实施例1~5制备的催化剂进行了N2O-AD表征,研究催化剂活性中心铜的平均粒径及铜的分散度,所得结果见表1。
表1不同催化剂中铜的平均粒径及分散度
由表1可见,本发明制备的催化剂的活性中心Cu的平均粒径小,分散度高,且随Cu负载量的降低,其平均粒径减小,分散度增大。
实施例6
采用实施例1~5制备的催化剂催化乙酰丙酸加氢制γ-戊内酯的应用,具体方法如下:
将0.2g催化剂、0.4mL(0.4534g)乙酰丙酸、20mL去离子水装入35mL不锈钢反应釜中,关闭反应釜后,用氮气置换反应釜内气体3次,然后充入3MPa氢气,在500转/分钟搅拌条件下,分别加热至130℃、150℃,恒温反应5h,反应结束后用冰水浴冷却反应釜,离心分离催化剂,反应液用0.22μm有机滤头过滤后用HPLC 检测。各实施例反应结果见表2和表3。
表2不同催化剂在130℃反应时乙酰丙酸转化率及γ-戊内酯收率
表3不同催化剂在150℃反应时乙酰丙酸转化率及γ-戊内酯收率
由表2和表3可见,本发明催化剂催化乙酰丙酸加氢制γ-戊内酯活性高。
为了进一步对比说明本发明催化剂催化乙酰丙酸加氢制γ-戊内酯的高活性,发明人采用Hengne等用共沉淀制备Cu/ZrO2的方法(Green Chemistry,2012, 14(4):1064-1072)制备了铜与二氧化锆质量比为5%的5Cu/ZrO2,与实施例3的铜与二氧化锆质量比为5%的5Cu@mZrO2进行对比,分别在100℃、130℃及150℃恒温反应5h,其他条件与实施例6相同。反应结果见表4及表5。
表4不同温度下5Cu/ZrO2催化乙酰丙酸制备γ-戊内酯
表5不同温度下5Cu@mZrO2催化乙酰丙酸制备γ-戊内酯
由表4和表5可见,本发明Cu@mZrO2催化剂与Cu/ZrO2催化剂相比,用于催化乙酰丙酸加氢制γ-戊内酯的活性明显提高。
为了证明本发明催化剂催化乙酰丙酸加氢制γ-戊内酯的高稳定性,发明人使用内径为12mm的固定床反应器对实施例3的5Cu@mZrO2进行稳定性测试,具体方法为:将0.6g5Cu@mZrO2放置于反应器等温段,催化剂两端以20~40目石英砂装填。反应前以40mL/min H2在300℃下热还原2h;然后降温至200℃,以24mL/min H2充压至3MPa,5wt%乙酰丙酸水溶液以0.15mL/min进样反应。收集固定床反应器冷阱中的反应后液体,用0.22μm有机滤头过滤后,用HPLC检测。反应结果见图2。
由图2可见,5Cu@mZrO2催化剂催化乙酰丙酸加氢制γ-戊内酯稳定性高,连续催化乙酰丙酸加氢制γ-戊内酯100h活性无明显下降;催化剂连续反应15~100h,乙酰丙酸转化率仅下降10.7%。
Claims (9)
将硝酸铜与聚乙烯吡咯烷酮溶于无水乙醇,得到溶液A;将十六烷基三甲基溴化铵、去离子水、无水乙醇、质量浓度为6%~25%的氢氧化氨水溶液混合,超声分散均匀,得到溶液B;将正丁醇锆均匀分散于无水乙醇中,得到溶液C;在搅拌下将溶液A滴加入溶液B中,室温搅拌老化2~4h,然后滴加溶液C,继续搅拌老化48~60h,离心分离,沉淀用去离子水及无水乙醇洗涤,80~100℃干燥12~15h;将干燥产物在空气中380~550℃处理4~6h,然后在H2与Ar摩尔比为1:8~1:10的混合气氛下280℃~500℃热还原2~12h,得到核壳催化剂;
上述溶液A中,硝酸铜与聚乙烯吡咯烷酮的质量比为1:2~1:5;将溶液A滴加入溶液B时,控制十六烷基三甲基溴化铵与聚乙烯吡咯烷酮的质量比为1:4~10:1,硝酸铜与氢氧化氨的摩尔比为1:70~1:1300,硝酸铜与去离子水的质量比为1:450~1:7200,溶液B中无水乙醇与去离子水的体积比为1:1~2:1。
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CN105195146A (zh) * | 2015-09-30 | 2015-12-30 | 中国科学院新疆理化技术研究所 | 黑色TiO2包覆金属铜纳米光催化剂的制备方法和应用 |
WO2019020086A1 (zh) * | 2017-07-28 | 2019-01-31 | 中国石油化工股份有限公司 | 碳包覆过渡金属纳米复合材料、其制备及应用 |
CN109482185A (zh) * | 2018-11-28 | 2019-03-19 | 中触媒新材料股份有限公司 | 一种高分散稳定型铜基催化剂及其制备方法 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105195146A (zh) * | 2015-09-30 | 2015-12-30 | 中国科学院新疆理化技术研究所 | 黑色TiO2包覆金属铜纳米光催化剂的制备方法和应用 |
CN105170151A (zh) * | 2015-10-23 | 2015-12-23 | 中国科学院上海高等研究院 | 一种核壳结构铜基催化剂及制备方法和应用 |
WO2019020086A1 (zh) * | 2017-07-28 | 2019-01-31 | 中国石油化工股份有限公司 | 碳包覆过渡金属纳米复合材料、其制备及应用 |
CN109482185A (zh) * | 2018-11-28 | 2019-03-19 | 中触媒新材料股份有限公司 | 一种高分散稳定型铜基催化剂及其制备方法 |
Non-Patent Citations (1)
Title |
---|
改性的Cu/ZrO2催化乙酰丙酸加氢制γ-戊内酯性能的研究;何青青;《中国优秀博硕士学位论文全文数据库(硕士)工程科技I辑》;20181115(第11期);第1页、第17页 * |
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