CN113860979B - 一种以醛糖为氢源的室温转移加氢不饱和化合物制备高附加值化学品的方法 - Google Patents
一种以醛糖为氢源的室温转移加氢不饱和化合物制备高附加值化学品的方法 Download PDFInfo
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- CN113860979B CN113860979B CN202111306972.XA CN202111306972A CN113860979B CN 113860979 B CN113860979 B CN 113860979B CN 202111306972 A CN202111306972 A CN 202111306972A CN 113860979 B CN113860979 B CN 113860979B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B31/00—Reduction in general
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
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Abstract
本发明属于生物质催化转化技术领域,提出一种以醛糖为氢源的室温转移加氢不饱和化合物制备高附加值化学品的方法。一种催化转移加氢制备高附加值化学品的新途径,以负载型金属催化剂为催化剂,在室温常压下,通过脱氢,加氢两个半反应分别将作为氢源的醛糖氧化为醛糖酸并将氢受体加氢同时生成两种高附加值产物。根据萨巴蒂尔极值理论利用醛糖半缩醛的特性,使得反应在室温常压下即可进行,无须额外引入能量。催化剂具有良好的稳定性可以循环使用,同时本技术还可以对其他转移加氢技术提供指导,并具有良好的工业前景。面向可再生生物质生产高附加值化学品,在应对温室效应、资源替代战略及国家能源安全等方面有着非常重要的意义。
Description
技术领域
本发明属于生物质催化转化技术领域,涉及一种以醛糖为氢源的室温转移加氢不饱和化合物制备高附加值化学品的方法。
背景技术
使用催化转化的方式高效利用生物质基化合物将其转化为高附加值化学品是解决目前人类社会环境,安全,能源问题的重要技术途径之一。其中醛糖类化合物是半纤维素生物质原料的单体,来源广泛且极具研究价值。半缩醛官能团是非常活泼的,而醛糖因其独特的多羟基结构使其以吡喃糖环的形式稳定保留半缩醛官能团。因此,根据萨巴蒂尔极值理论,开发利用醛糖的半缩醛官能团代表了一个高性价比,低门槛的机会。
催化转移加氢是有机合成中的一种有效还原手段,是指某些有机化合物在催化剂存在下成为氢的给予体,针对不饱和官能团进行加氢反应的过程。应当指出,这里释放的氢并不是变成氢气后参与反应,否则就与通常的加氢无异。其中氢的转移可以是发生在同一个分子内、同一种分子间或不同分子之间。其中研究得较多的是不同分子间的转移加氢,这也是本专利讨论的重点。目前最有效的催化转移加氢方法是以贵金属催化为代表的多相催化法。贵金属催化的转移加氢因其催化剂可循环使用等优点引起了越来越多的关注。
综上,利用醛糖的半缩醛特性,以醛糖为氢源将不饱和化合物转化为高附加值产物,同时副产醛糖酸,这种以醛糖为氢源进行催化转移加氢高附加值化学品的方法,可以挑战温和条件下的生物质催化转化,对人类社会的可持续发展具有重要意义。我们成功开发了纳米贵金属催化剂用于以醛糖为氢源的转移加氢反应,在常温常压条件下生成两种高附加值产品。
对于目前转移加氢生产高附加值化学品的方法,都存在一些不足:
中国专利,申请号:CN202011155772.4,介绍一种催化转移加氢的催化剂及其制备方法与应用。以醇类溶剂为氢源进行糠醛的转移加氢,使用了大量的醇类溶剂,且醇类溶剂脱氢生成醛或酮类化合物无法定量,产物难以分离。已公开的大多数糠醛转移加氢专利都具有这样的缺点,并且底物不具有普适性,应用受到限制。
中国专利,申请号:CN202011014028.2,介绍一种硝基苯转移加氢制备对氨基苯酚的方法。以甲酸或异丙醇为氢源,将硝基苯转移加氢制备对氨基苯,值得注意的是当使用异丙醇为氢源同样生成丙酮造成体系组成复杂,而使用甲酸为氢源时,由于硝基苯和对氨基苯酚对pH敏感,所以其应用受到限制。
中国专利,公开号:CN201711207097.3,介绍一种基于多相催化剂的甲酸转移加氢乙酰丙酸制备γ-戊内酯的方法。以甲酸为氢源转移加氢乙酰丙酸制备γ-戊内酯,当使用甲酸为氢源时溶液pH不可控,当进行工业放大非常困难。
中国专利,公开号:CN103436910A,介绍一种炭载碱性离子液体-金属催化剂及其制备和在催化转移加氢反应中的应用。尽管选择性很高,但是因为离子液体与产物难以分离,使得成本高昂。
已公开的技术大多使用远超过化学计量数的甲酸或醇类为氢源,当进行转移加氢时,甲酸被消耗溶液pH改变,醇类脱氢生成一系列醛、酮产物,使得目标产物难以分离,并且反应温度较高。这是目前转移加氢技术通用的弊端,而本技术使用醛糖为氢源,以化学计量数参与反应,不改变溶液环境,来源广泛,通过利用其半缩醛特性,可以在温和条件下进行反应,是催化转移加氢技术的显著进步。
发明内容
本发明公开了一种以醛糖为氢源的室温转移加氢不饱和化合物制备高附加值化学品的方法,属于生物质催化转化技术领域。本发明旨在提供一种以醛糖为氢源转移加氢生成高附加值化学品的新途径,即进行醛糖脱氢和不饱和化合物加氢生成两种等摩尔量的加氢和脱氢产物。
本发明的技术方案如下:一种以醛糖为氢源的室温转移加氢不饱和化合物制备高附加值化学品的方法,其特征在于,在水相体系中,在无氧、碱性、常温、常压条件下,以醛糖为氢供体利用负载型金属催化剂对不饱和化合物进行转移加氢催化反应,同时生成两种高附加值化合物的方法;其中,水相体系是含水有机溶剂;有机溶剂的体积分数为5-90%,醛糖的浓度为1-40wt%;负载型金属催化剂与醛糖的摩尔比为0.01-0.2,醛糖与不饱和化合物的摩尔比为n:1,n为不饱和化合物的不饱和度。
所述的水相体系是含水有机溶剂,为水、水-甲醇、水-乙醇、水-四氢呋喃或水-二氧六环。
所述的醛糖是该单糖中氧化数最高的C原子是一个醛基或半缩醛基,有醇和醛的性质,例如葡萄糖,半乳糖,甘露糖等。
所述的不饱和化合物是含有不饱和键的且溶于水相体系的化合物;包括含有C=O键的碳酸盐或碳酸氢盐、醛、酮、羧酸及羧酸衍生物(包括羧酸盐、酸酐、酰卤、酰胺、酯等),含有NO2基团的硝基或亚硝基化合物。
碱性条件指的是向溶液中加入碱金属氢氧化物(或碱土金属氢氧化物)控制溶液pH为8-14或使用其他方法提供反应需要的碱性位。所述的负载型金属催化剂是铂系催化剂或含铂合金,如:铂钯,铂金,铂铑,铂铱,铂镍,铂钴等铂系合金催化剂;金属担载量是载体的0.5-10.0wt%。
所述的负载型金属催化剂的制备,步骤如下:将载体加入贵金属前体溶液中,采用还原剂将贵金属还原,并进行后处理:包括固液分离,用去离子水洗涤除去可能干扰催化剂性能的阴离子如氯离子等,固形物的干燥和焙烧:干燥温度60-200oC,干燥时间0.5-72小时;焙烧温度200-1000oC;焙烧时间2-20小时;催化剂的焙烧选马弗炉或管式炉,焙烧气氛选氮气、氦气、氢气、空气或氧气等,气体流量为10mL/min~100mL/min。
所述的贵金属前体是硝酸盐、氯化盐、醋酸盐、氯盐酸中一种或两种以上混合。
所述的载体是指碳载体如活性炭、石墨烯和碳纳米管,金属氧化物如氧化铈、氧化镁、水滑石或类水滑石,分子筛类等常用催化剂载体。所述的还原剂是尿素、乙二醇、硼氢化钠、水合肼中一种或两种以上混合。
本发明与已知的催化转移加氢转化技术相比,具有以下优点:
1、以来源广泛的生物质醛糖原料为氢源,较其他常用的醇类溶剂更为廉价易得,且用量更少,以化学计量数的含量参与反应,同时得到高附加值的生物质醛糖下游产品。
2、本发明中反应条件为室温常压、较其他催化转移加氢反应来说条件更为温和,不需要额外引入能量,代表着低成本,高性价比的一种技术。
3、通过醛糖生成活性H物种可以实现在室温条件下对诸多不饱和化合物进行加氢,底物产物极具普适性,对其他转移加氢技术具有指导作用。
具体实施方式
为了进一步说明本发明,列举以下实施例,但它并不限制各附加权利要求所定义的发明范围。
实施例1:将四氨合硝酸铂溶解在60mL水中,Pt的质量为0.05g,加入一定量尿素,尿素的浓度为0.08mol/L,调节溶液pH值大于载体等电点,将1g石墨烯缓慢加入上述溶液中,控制反应温度为95oC,反应时间为24h,经过滤洗涤后,80oC干燥12h,400oC氩气气氛焙烧2h,氩气流量30mL/min,300oC氢气氩气混合气氛焙烧2h,氩气流量20mL/min,氢气流量10mL/min,即形成Pt /Gr催化剂,Pt的担载量为5%。
实施例2:将硝酸钯溶解在60mL水中,Pd的质量为0.05g,加入一定量尿素,尿素的浓度为0.08mol/L,调节溶液pH值大于载体等电点,将1g石墨烯缓慢加入上述溶液中,控制反应温度为95oC,反应时间为24h,经过滤洗涤后,80oC干燥12h,400oC氩气气氛焙烧2h,氩气流量30mL/min,300oC氢气氩气混合气氛焙烧2h,氩气流量20mL/min,氢气流量10mL/min,即形成Pd/Gr催化剂,Pd的担载量为5%。
实施例3:将四氨合硝酸铂和硝酸钯溶解在60mL水中,金属Pt和金属Pd的质量比为1:1,贵金属总质量为0.05g,加入一定量尿素,尿素的浓度为0.08mol/L,调节溶液pH值大于载体等电点,将1g石墨烯缓慢加入上述溶液中,控制反应温度为95oC,反应时间为24h,经过滤洗涤后,80oC干燥12h,400oC氩气气氛焙烧2h,氩气流量30mL/min,300oC氢气氩气混合气氛焙烧2h,氩气流量20mL/min,氢气流量10mL/min,即形成Pt-Pd/Gr,Pt和Pd的总担载量为5%。
实施例4:进行催化转移加氢实验并考察活性金属对转移加氢的影响,将实施例1-实施例3制备的催化剂用于催化转移加氢反应。首先将0.4324g半乳糖和0.4324g果糖溶解于40mL水-甲醇溶液中,水的体积分数为40%,加入0.7405gKOH,用Ar气氛置换反应器中的气体,反应温度30oC,反应压力为常压,催化剂分别为0.15g 的Pt/ Gr,Pd/ Gr,Pt-Pd/ Gr。收集产物使用液相色谱分析,检测器为示差检测器和紫外检测器,色谱柱为Hi-Plex H色谱柱,色谱显示半乳糖脱氢生成半乳糖酸,果糖生成山梨醇和甘露醇,反应结果见表1。
实施例5:进一步考察反应的底物普适性,进行催化转移加氢实验,首先将0.4324g半乳糖和等摩尔量的其他不饱和化合物:碳酸氢铵,顺丁烯二酸,乙醛,丙酮、硝基苯溶解于40mL水-乙醇溶液中,水的体积分数为40%,加入0.7405gKOH,用Ar气氛置换反应器中的气体,反应温度30oC,反应压力为常压,催化剂为0.15gPt-Pd/ Gr。收集产物使用液相色谱分析,检测器为示差检测器和紫外检测器,色谱柱为Hi-Plex H色谱柱,色谱显示半乳糖脱氢生成半乳糖酸,碳酸氢铵生成甲酸盐,顺丁烯二酸生成丁二酸,乙醛生成乙醇,丙酮生成异丙醇,硝基苯加氢生成苯胺,反应结果见表2。
实施例6:考察醛糖对产物收率的影响。进行催化转移加氢实验并考察活性金属对转移加氢的影响,将实施例3制备的催化剂用于催化转移加氢反应。首先将实施例4的半乳糖换成相同质量的塔罗糖、葡萄糖、甘露糖、古洛糖,分别与0.4324g果糖溶解于40mL水-甲醇溶液中,水的体积分数为40%,加入0.7405gKOH,用Ar气氛置换反应器中的气体,反应温度30oC,反应压力为常压,催化剂为0.15g Pt-Pd/ Gr。收集产物使用液相色谱分析,检测器为示差检测器和紫外检测器,色谱柱为Hi-Plex H色谱柱,色谱显示醛糖生成醛糖酸,果糖生成山梨醇和甘露醇,反应结果见表3。
实施例7:催化剂循环利用的考评。将实施例4中,反应4h后的Pt-Pd/Gr催化剂离心,真空干燥回收。首先将0.4324g半乳糖和0.4324g果糖溶解于40mL水-甲醇溶液中,水的体积分数为40%,加入0.7405gKOH,用Ar气氛置换反应器中的气体,反应温度30oC,反应压力为常压,催化剂为回收后的Pt-Pd/ Gr催化剂。收集产物使用液相色谱分析,检测器为示差检测器和紫外检测器,色谱柱为Hi-Plex H色谱柱,色谱显示半乳糖脱氢生成半乳糖酸,果糖生成山梨醇和甘露醇,反应结果见表1。该催化剂循环利用5次,反应结果见表4。
表1活性金属对催化转移加氢反应的影响
催化剂 | 糖酸收率(mol%) | 糖醇收率(mol%) |
Pt/Gr | 91 | 44 |
Pd/Gr | 31 | 15 |
Pt-Pd/Gr | 88 | 85 |
表2 底物拓展实验
底物 | 糖酸收率(mol%) | 还原产物收率(mol%) |
碳酸氢铵 | 71 | 68 |
顺丁烯二酸 | 75 | 72 |
乙醛 | 85 | 80 |
丙酮 | 55 | 46 |
硝基苯 | 31 | 25 |
表3醛糖对产物收率的影响
底物 | 糖酸收率(mol%) | 糖醇收率(mol%) |
塔罗糖 | 71 | 75 |
葡萄糖 | 85 | 83 |
甘露糖 | 75 | 82 |
古洛糖 | 90 | 91 |
表4催化剂稳定性测试
循环次数 | 糖酸收率(mol%) | 糖醇收率(mol%) |
1 | 87 | 86 |
2 | 86 | 85 |
3 | 87 | 84 |
4 | 85 | 85 |
5 | 82 | 84 |
Claims (6)
1.一种以醛糖为氢源的室温转移加氢不饱和化合物制备高附加值化学品的方法,其特征在于,在水相体系中,在无氧、碱性、常温、常压条件下,以醛糖为氢供体利用负载型金属催化剂对不饱和化合物进行转移加氢催化反应,同时生成两种高附加值化合物的方法;其中,水相体系是含水有机溶剂;有机溶剂的体积分数为5-90%,醛糖的浓度为1-40wt%;负载型金属催化剂与醛糖的摩尔比为0.01-0.2,醛糖与不饱和化合物的摩尔比为n:1,n为不饱和化合物的不饱和度;
所述的负载型金属催化剂是铂系催化剂或含铂合金;金属担载量是载体的0.5-10.0wt%;
所述的负载型金属催化剂的制备,步骤如下:将载体加入贵金属前体溶液中,采用还原剂将贵金属还原,并进行后处理:包括固液分离,用去离子水洗涤;固形物的干燥和焙烧:干燥温度60-200℃,干燥时间0.5-72小时;焙烧温度200-1000℃,焙烧时间2-20小时;焙烧气氛选氮气、氦气、氢气、空气或氧气,气体流量为10mL/min~100mL/min;
所述的不饱和化合物是包括含有C=O键的碳酸盐或碳酸氢盐,醛、酮、羧酸及羧酸衍生物,含有NO2基团的硝基或亚硝基化合物。
2.根据权利要求1所述的制备高附加值化学品的方法,其特征在于,所述的水相体系是水或含水有机溶剂,含水有机溶剂为水-甲醇、水-乙醇、水-四氢呋喃或水-二氧六环。
3.根据权利要求1或2所述的制备高附加值化学品的方法,其特征在于,所述的碱性条件是控制溶液pH为8-14。
4.根据权利要求1所述的制备高附加值化学品的方法,其特征在于,所述的贵金属前体是硝酸盐、氯化盐、醋酸盐、氯盐酸中一种或两种以上混合。
5.根据权利要求1或4所述的制备高附加值化学品的方法,其特征在于,所述的载体是碳载体、金属氧化物、分子筛、碳化物、磷化物或硅化物。
6.根据权利要求1或4所述的制备高附加值化学品的方法,其特征在于,所述的还原剂是尿素、乙二醇、硼氢化钠、水合肼中一种或两种以上混合。
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