CN113549034B - 一种采用两段全混流串联釜式反应器一步制备四氢糠醇的方法 - Google Patents
一种采用两段全混流串联釜式反应器一步制备四氢糠醇的方法 Download PDFInfo
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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Abstract
本发明公开了一种采用两段全混流串联釜式反应器一步制备四氢糠醇的方法,属于精细化工领域。即以糠醛水溶液为原料,采用两段全混流串联釜式反应器,以蛋壳型镍基合金催化剂,在反应温度为80‑160℃,氢气压力为0.5‑7MPa,一步加氢生成四氢糠醇,其收率在96%以上。本方法采用两段全混流串联釜式反应工艺,实现四氢糠醇连续化生产;以水为溶剂,即符合绿色化学理念又降低了反应成本和分离难度;催化剂制备工艺简单、价格低廉,具有较高的活性、选择性及良好的稳定性,适用于工业生产。
Description
技术领域
本发明属于精细化工领域,涉及到一种采用两段全混流串联釜式反应器一步制备四氢糠醇的方法。
背景技术
四氢糠醇作为一种高附加值精细化工品,广泛用于涂料、树脂、油脂、工业和电子清洁剂等,可作为油脂、蜡、树脂、染料、醋酸纤维素、硝酸纤维素、乙基纤维素等的溶剂。此外,四氢糠醇也用于制备二氢呋喃、赖氨酸、聚酰胺类塑料,增塑剂等,也可以用作明胶溶液稳定剂、印染工业的润湿剂、分散剂以及某些药品的脱色、脱臭剂等。目前,四氢糠醇主要通过糠醛选择加氢来实现,然而,糠醛催化加氢过程相对复杂,存在很大副产物,如:糠醇、2-甲基呋喃、2-甲基四氢呋喃、环戊酮,1,5-戊二醇等。因此,高效、高选择性实现糠醛选择加氢制备四氢糠醇对催化剂和工艺工程提出了很高的要求。
传统的四氢糠醇的制备方法是以糠醛为起始底物,通过两步法制取,该过程中糠醇作为中间产物,先由Cu-Cr催化剂催化糠醛加氢转化为糠醇,糠醇进一步由贵金属催化剂催化加氢生成四氢糠醇。然而,该反应过程条件苛刻且环境不友好,一定程度上限制了其大规模的发展。因此,探究由糠醛加氢制取四氢糠醇的方法,期望在温和条件下一步实现该过程,从而达到绿色化和经济性的目的。目前关于糠醛一步加氢制备四氢糠醇的方法主要通过在固定床反应器和搅拌釜式反应器中,通过催化剂的构筑和工艺过程的优化而实现。中国专利CN105693659公开了在搅拌釜式反应器中以碱土金属Mg、Ca、Sr、Ba中的一种或二种以上改性的氧化铝负载的镍基催化剂作用下,在140℃、4MPa下水相中实现四氢糠醇的高收率(98%)。然而,该反应过程为间歇式,操作复杂,产品稳定性差,且该催化剂水相稳定性较差,难以实现大规模的应用。中国专利CN106967018公开了一种在搅拌釜式反应器中,以磷灰石负载金属为催化剂用于糠醛加氢制备四氢糠醇。虽然,该反应体系可实现四氢糠醇的高收率,且载体磷灰石具有一定水热稳定性,但金属与载体之间作用力较差,在长时间循环实验中容易导致活性中心的流失。此外,间歇性操作容易带来一些安全隐患。中国专利CN109529946公开了一种固载型Cu-Ni双金属催化剂及其催化糠醛完全加氢制备四氢糠醇的方法。该方法在固定床反应器下,采用端氨基修饰的微球硅胶负载CuNi双金属催化剂,在80℃,0.3MPa,0.2h-1下,可实现糠醛转化率80%,四氢糠醇的选择性为100%。虽然该反应体系可实现连续化生产,但糠醛的转化率较低,导致后续分离成本增加。因此,寻求一种即可高效连续转化糠醛,又可实现对四氢糠醇的高选择性的催化剂和工艺过程,为实现糠醛一步加氢制备高附加值四氢糠醇精细化学品成为目前研究的热点和难点。
发明内容
由于采用不同的加氢操作工艺及催化剂体系,糠醛加氢可以得到复杂的下游产物,涉及到C=O双键加氢、呋喃环C=C双键加氢、呋喃环开环及重排,可生成包括糠醇、四氢糠醇、γ-戊内酯、环戊酮等石油化工产业中重要的高附加值化学品。目前研究较为***的高活性糠醛加氢用催化剂主要包括Ir、Pt、Pd等贵金属及其与过渡金属的负载型合金催化剂。然而,考虑到其经济性及工业扩大生产的局限性,近年来,糠醛选择加氢的研究重点开始向过渡金属(如Cu、Co、Ni等)基催化剂的开发及应用转移。由于糠醛加氢反应网络复杂,产物杂多,如何设计高效、高选择性过渡金属催化剂,在一定的工艺条件下实现糠醛一步选择加氢制四氢糠醇;深入剖析催化剂及其性能的构效关系及反应机制,实现催化剂的可控优化,是糠醛加氢产业链中的关键科学问题。
针对上述的糠醛选择加氢催化体系中的技术瓶颈和科学问题,本发明提供了一种采用两段全混流串联釜式反应器一步制备四氢糠醇的方法。该技术通过开发蛋壳型镍基合金催化剂,采用温和条件下选择一步选择加氢糠醛获取高附加值的四氢糠醇高端精细化学品,有效解决了传统贵金属催化剂价格昂贵的问题,突破了过渡金属催化剂选择性差,产物分布杂的瓶颈。通过优化化工工艺过程,采用两段全混流串联釜式反应器,相比于采用釜式反应器弥补了间歇性操作稳定差的问题,同时相比于采用固定床反应器,显著降低的投资成本。此外,该技术以生物基可再生资源—糠醛为原料,积极延伸下游产品产业链、实现产品方案多元化,提高产品的价值链向中高端跃进,实现绿色可持续发展。
本发明的技术方案:
一种采用两段全混流串联釜式反应器一步制备四氢糠醇的方法,步骤如下:
以5-30wt.%糠醛水溶液为原料,采用两段全混流串联釜式反应器,以蛋壳型镍基合金催化剂,在反应温度为80-180℃,氢气压力为0.5-7MPa,停留时间2-5h,反应后,反应溶液经脱溶剂塔,常压蒸馏,塔顶蒸馏出的水溶剂打循环重新稀释糠醛,塔底产品进入精馏塔,脱除重质副产物,获得高纯度的四氢糠醇。
所述的蛋壳型镍基合金催化剂,镍基合金为NiM,M是Cu、Fe、Co、Zn中的一种或两种以上。
所述的Ni与M的摩尔比为3:1,Ni的质量含量为5-30wt.%,其载体是碳微球、TiO2微球、Al2O3微球中的一种。
本发明的有益效果:采用两段全混流串联釜式反应工艺,实现四氢糠醇连续化生产;以水为溶剂,即符合绿色化学理念又降低了反应成本和分离难度;催化剂制备工艺简单、价格低廉,具有较高的活性、选择性及良好的稳定性,适用于工业生产。
附图说明
图1是在两段全混流串联釜式反应器中实现糠醛一步选择加氢制备四氢糠醇的流程图。
具体实施方式
以下结合附图和技术方案,进一步说明本发明的具体实施方式。
实施例1蛋壳型碳微球负载Ni3Cu催化剂的制备
称取1486.5g硝酸镍和319.58g硝酸铜配置成2L水溶液为金属前驱体,其中Ni:Cu摩尔比为3:1,以1000g碳微球为载体,采用旋转涂覆机,控制涂覆机转速为200rpm,温度80℃,气体流速为500mL/min携带金属前驱体沉积到碳微球表面,喷涂结束后,将固体物在120℃下过夜干燥,然后在氢气气氛下于400℃还原3h制得Ni担载量为30wt.%的蛋壳型碳微球负载Ni3Cu催化剂。
实施例2蛋壳型TiO2微球负载Ni3Zn催化剂的制备
称取1486.5g硝酸镍和322.7g硝酸锌配置成2L水溶液为金属前驱体,其中Ni:Zn摩尔比为3:1,以1000gTiO2微球为载体,采用旋转涂覆机,控制涂覆机转速为200rpm,温度90℃,气体流速为800mL/min携带金属前驱体沉积到TiO2微球表面,喷涂结束后,将固体物在120℃下过夜干燥,然后在氢气气氛下于400℃还原3h制得Ni担载量为30wt.%的蛋壳型TiO2微球负载Ni3Zn催化剂。
实施例3蛋壳型Al2O3微球负载Ni3Fe催化剂的制备
称取247.8g硝酸镍和68.7g硝酸铁配置成1L水溶液为金属前驱体,其中Ni:Fe摩尔比为3:1,以1000gAl2O3微球为载体,采用旋转涂覆机,控制涂覆机转速为200rpm,温度80℃,气体流速为800mL/min携带金属前驱体沉积到Al2O3微球表面,喷涂结束后,将固体物在120℃下过夜干燥,然后在氢气气氛下于450℃还原4h制得Ni担载量为5wt.%的蛋壳型Al2O3微球负载Ni3Fe催化剂。
实施例4蛋壳型碳微球负载Ni3Co催化剂的制备
称取1486.5g硝酸镍和311.7g硝酸钴配置成2L水溶液为金属前驱体,其中Ni:Co摩尔比为3:1,以1000g碳微球为载体,采用旋转涂覆机,控制涂覆机转速为200rpm,温度80℃,气体流速为500mL/min携带金属前驱体沉积到碳微球表面,喷涂结束后,将固体物在120℃下过夜干燥,然后在氢气气氛下于400℃还原3h制得Ni担载量为30wt.%的蛋壳型碳微球负载Ni3Co催化剂。
实施例5在两段全混流串联釜式反应器中蛋壳型碳微球负载Ni3Cu催化糠醛选择加氢在两段1L全混流串联釜式反应器中对所制备的蛋壳型碳微球负载Ni3Cu催化剂进行糠醛选择加氢活性测试,如图1所示。分别称量10g催化剂置于两个釜式反应器中,质量分数为30%糠醛水溶液,在180℃,6.0MPa氢压下连续搅拌反应,停留时间2h,在线取样通过色谱-质谱联用仪分析,其糠醛转化率>99%,对四氢糠醇的选择性>93%。反应溶液经脱溶剂塔,常压蒸馏,塔顶蒸馏出的水溶剂打循环重新稀释糠醛,塔底产品进入精馏塔,脱除重质副产物,获得高纯度的四氢糠醇,纯度>99.3%。
实施例6在两段全混流串联釜式反应器中蛋壳型TiO2微球负载Ni3Zn催化糠醛选择加氢在两段1L全混流串联釜式反应器中对所制备的蛋壳型TiO2微球负载Ni3Zn催化剂进行糠醛选择加氢活性测试。分别称量10g催化剂置于两个釜式反应器中,质量分数为20%糠醛水溶液,在80℃,7.0MPa氢压下连续搅拌反应,停留时间5h,在线取样通过色谱-质谱联用仪分析,其糠醛转化率>99%,对四氢糠醇的选择性>95%。反应溶液经脱溶剂塔,常压蒸馏,塔顶蒸馏出的水溶剂打循环重新稀释糠醛,塔底产品进入精馏塔,脱除重质副产物,获得高纯度的四氢糠醇,纯度>99.6%。
实施例7在两段全混流串联釜式反应器中蛋壳型Al2O3微球负载Ni3Fe催化糠醛选择加氢在两段1L全混流串联釜式反应器中对所制备的蛋壳型Al2O3微球负载Ni3Fe催化剂进行糠醛选择加氢活性测试。分别称量10g催化剂置于两个釜式反应器中,质量分数为5%糠醛水溶液,在120℃,0.5MPa氢压下连续搅拌反应,停留时间5h,在线取样通过色谱-质谱联用仪分析,其糠醛转化率>99%,对四氢糠醇的选择性>96%。反应溶液经脱溶剂塔,常压蒸馏,塔顶蒸馏出的水溶剂打循环重新稀释糠醛,塔底产品进入精馏塔,脱除重质副产物,获得高纯度的四氢糠醇,纯度>99.9%。
实施例8在两段全混流串联釜式反应器中蛋壳型碳微球负载Ni3Co催化糠醛选择加氢在两段1L全混流串联釜式反应器中对所制备的蛋壳型碳微球负载Ni3Co催化剂进行糠醛选择加氢活性测试。分别称量10g催化剂置于两个釜式反应器中,质量分数为30%糠醛水溶液,在180℃,4.0MPa氢压下连续搅拌反应,停留时间2h,在线取样通过色谱-质谱联用仪分析,其糠醛转化率>99%,对四氢糠醇的选择性>92%。反应溶液经脱溶剂塔,常压蒸馏,塔顶蒸馏出的水溶剂打循环重新稀释糠醛,塔底产品进入精馏塔,脱除重质副产物,获得高纯度的四氢糠醇,纯度>99.5%。
实施例9在两段全混流串联釜式反应器中蛋壳型碳微球负载Ni3Cu催化糠醛选择加氢稳定性测试结果在两段1L全混流串联釜式反应器中对所制备的蛋壳型碳微球负载Ni3Cu催化剂进行糠醛选择加氢稳定性测试。在实施例5的基础上,反应条件为:180℃,4.0MPa氢压下连续搅拌反应,停留时间2h,糠醛浓度为20wt.%,进行1000h稳定性测试,通过在线取样色谱-质谱联用仪分析,其结果如下表1所示。反应溶液经脱溶剂塔,常压蒸馏,塔顶蒸馏出的水溶剂打循环重新稀释糠醛,塔底产品进入精馏塔,脱除重质副产物,获得高纯度的四氢糠醇,纯度>99.8%。
Claims (1)
1.一种采用两段全混流串联釜式反应器一步制备四氢糠醇的方法,其特征在于,步骤如下:
以5-30 wt.%糠醛水溶液为原料,采用两段全混流串联釜式反应器,以蛋壳型镍基合金催化剂,在反应温度为80-180 oC,氢气压力为0.5-7 MPa,停留时间2-5 h反应后,反应溶液经脱溶剂塔常压蒸馏,塔顶蒸馏出的水溶剂打循环重新稀释糠醛,塔底产品进入精馏塔,脱除重质副产物,获得高纯度的四氢糠醇;
所述的蛋壳型镍基合金催化剂,镍基合金为NiM,M是Cu、Fe、Co、Zn中的一种或两种以上;
所述的Ni与M的摩尔比为3:1,Ni的质量含量为5-30 wt.%,其载体是碳微球、TiO2微球、Al2O3微球中的一种。
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