CN110431127A - 将糖或糖醇化学转化为二元醇的方法 - Google Patents
将糖或糖醇化学转化为二元醇的方法 Download PDFInfo
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- CN110431127A CN110431127A CN201880018459.0A CN201880018459A CN110431127A CN 110431127 A CN110431127 A CN 110431127A CN 201880018459 A CN201880018459 A CN 201880018459A CN 110431127 A CN110431127 A CN 110431127A
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- sugar
- carbon
- alcohol
- catalyst
- doping
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Classifications
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
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Abstract
本发明涉及一种将糖或糖醇化学转化为多元醇/二元醇的方法,其中所述糖或糖醇在包含至少一种金属且在碳载体上的催化剂的存在下通过氢解进行转化,其中氮掺杂的碳载体被用作催化剂载体。本发明提供了一种将糖或糖醇化学转化为二元醇的方法,该方法允许以较高选择性制备二元醇并减少了作为副产物的乳酸的形成。
Description
本发明涉及将糖或糖醇化学转化为多元醇/二元醇的方法。
由石油、煤和天然气制备基础和精细化学品以及从中提取能量是现有技术。然而,这些碳源通常难以获取且不可再生。化石燃料的提取和加工是能源密集型的,并产生大量的温室气体。生物质的使用代表了可持续且二氧化碳持平的替代品。植物生物质通过发酵或其它方法分解。裂解产物的进一步后处理对于从生物质的成分产生价值是必要的。因此,本发明涉及生物基糖和糖醇向二元醇的化学转变。
在常规方法中,乙二醇由乙烯制备,乙烯转化为环氧乙烷,然后水合得到乙二醇。丙二醇通常通过水合环氧丙烷来制备。
糖和糖醇向二元醇的转化同样从文献中已知。举例来说,WO 03/035593 A1描述了一种在大于120℃的高温下、碱性pH和另外含有镍的含铼催化剂的存在下使用氢气来转化5-C糖和糖醇的方法。在这种情况下,存在C-C键和CO键的氢解,结果是5-C糖和糖醇被裂解了,并且通过中间步骤,形成丙二醇(CH3-CHOH-CH2OH)作为产物。提到的替代性金属催化剂还有Ru、Pt、Pd、Ir和Rh。
甘油和乳酸在氢解成乙二醇和丙二醇时作为副产物形成。因此,上述方法中的挑战是抑制乳酸形成和优化二元醇的选择性。
含氮碳载体和碳纳米管(CNT)可以通过各种合成途径获得,并且根据生产包含不同的氮含量。它们主要用于气体吸附、电化学和氧化反应的催化。
US2010/0276644A1描述了一种制备氮掺杂的碳纳米管的方法,其中首先从金属盐在溶剂中的溶液中沉淀出金属,结果得到悬浮液,从中除去固体,得到非均相金属催化剂。将该催化剂引入流化床中,使其在流化床中与含碳和氮的材料反应,由此获得氮掺杂的碳纳米管。用作起始点的金属盐优选是钴、锰、铁或钼的盐。非均相金属催化剂还包含Al2O3和MgO。含碳和氮的材料是,例如,气态的有机化合物,其可以例如选自乙腈、二甲基甲酰胺、丙烯腈、丙腈、丁腈、吡啶、吡咯、吡唑、吡咯烷和哌啶。所述美国说明书US 2010/0276644 A1提出使用碳纳米管作为添加剂用于机械增强材料并且还用于增加其导电性或导热性。举例来说,氮掺杂的碳纳米管适用于制造导体路径、电池或照明装置,或作为膜中氢或锂的存储介质。此外,还提到了在燃料电池或在医疗领域中作为控制细胞组织生长的框架的应用。因此,在该文献中,提到了在各种各样领域中的非常广泛的应用。
WO2016/119568A1描述了含杂原子的纳米碳材料及其制备。该材料含有至多2重量%的氮和1重量%至6重量%的氧。其中描述的纳米碳材料旨在在烃的脱氢中具有良好的催化性质。
本发明所解决的问题是提供一种将糖或糖醇化学转化为二元醇的方法,具有前序中所述类型的特征,其允许以更高选择性制备二元醇并减少作为副产物的乳酸的形成。
通过具有前序中提到的类型并且具有权利要求1的特征的方法提供了对上述问题的解决方案。
根据本发明,提供了氮掺杂的碳载体用作催化剂载体。
本发明解决问题的方案的一个优选方式提供了氮掺杂的碳载体,尤其是氮掺杂的活性炭,用作催化剂载体。作为替代方案,例如,氮掺杂的炭黑可用作碳载体。
在本发明的上下文中,氮掺杂的碳载体被理解为:
碳载体,其表面包括氮掺杂。该氮掺杂的碳载体可以在碳载体本身的制备过程中通过合适的前体材料,并且随后例如通过还原方法来制备。在实施例中描述了在本发明的上下文中使用的两种可能的方法。
根据本发明方法的另一优选变体,氮掺杂的碳纳米管被用作催化剂载体。
氮掺杂的碳纳米管根据本发明如下进行定义:
在制造碳中空体之前、期间或之后用氮掺杂的直径为3至90nm的圆柱形碳中空体。
碱优选被用作助催化剂。在本发明的上下文中,可以考虑以下碱:
所有碱金属氢氧化物,尤其是氢氧化钠(NaOH)、氢氧化钾(KOH)和氢氧化锂(LiOH)。
所有碱土金属氢氧化物,尤其是氢氧化镁(Mg(OH)2)、氢氧化钙(Ca(OH)2)、氢氧化锶(Sr(OH)2)和氢氧化钡(Ba(OH)2)。
如果在根据本发明的方法中,糖是起始点,则存在两步法,其中首先以本身已知的方式将糖氢化以得到糖醇,然后在第二步中使用催化剂,将在糖的氢化过程中形成的糖醇氢解,以产生多元醇。这里通常也可以仅在一个步骤中或在反应器中以反应顺序进行两个反应过程,结果将糖直接转化为多元醇。由于各种相互干扰的反应机制并行发生,因此该变体的产率较差。
根据本发明的方法特别适用于氢化、随后氢解以下糖和所得糖醇:
C5糖,例如下文提到的化合物:
核糖、阿拉伯糖、木糖、来苏糖;
C5糖醇,例如下文提到的化合物:
核糖醇、阿糖醇(arabitol)、木糖醇、来苏醇(lyxitol);
C6和其它糖和糖醇,例如:
阿洛糖、阿卓糖(altrose)、葡萄糖、甘露糖、古洛糖(gulose)、艾杜糖、半乳糖、塔罗糖(talose)、蒜糖醇(allitol)、塔罗糖醇(talitol)、山梨糖醇、甘露醇、艾杜糖醇、盐藻糖醇(fucitol)、半乳糖醇、赤藓糖醇、苏糖醇(threitol)、甘油。
当氢解C5糖时,形成下文提到的产物:
木糖醇、核糖醇、阿糖醇、来苏醇。
当氢解C5糖醇时,形成下文提到的裂解产物:甘油、乙二醇、丙二醇、乳酸、乙醇酸以及在某些反应条件下赤藓糖醇和脱水木糖醇。
根据本发明的一个改进方案,转化优选在约170℃至约200℃范围内的反应温度下进行。
上述温度范围是有利的,因为如果选择较低的温度,则反应非常缓慢或根本不发生。
如果选择更高的温度,则会增加脱氧和脱羰反应、以及环化等。形成了相当多的副产物,例如赤藓糖醇、苏糖醇和脱水木糖醇。
根据本发明方法的一个优选的改进方案,氢解在约50巴至约80巴范围内的氢气压力下进行。
已经发现上述氢气压力是特别有利的,因为如果选择较低的压力,则形成更多的副产物。羰基形成是优选的。
如果选择高于所述范围的氢气压力,则其缺点是首先反应难以在工业上实施,其次反应物的转化速度显著降低。举例来说,在本发明的范围内,催化剂可含有钌和/或铂和/或镍作为金属。铂族(Os、Rh、Ir、Pd)的剩余元素以及Au、Ni、Cu、Fe和Co也是有用的。在这种情况下,根据本发明的催化剂可含有一种或多种所述金属。
下面参考附图基于示例性实施方式更详细地描述本发明。在图中:
图1示出了对于N-600,5-Ru来说产物随时间的形成(条件:T=200℃,p(H2)=80巴,m(cat)=0.1563g,m(木糖醇)=1.50g,m(Ca(OH)2)=0.225g,15ml H2O);
图2示出了对于C-Ru来说产物随时间的形成;
图3示出了催化剂的比较(条件:T=200℃,p(H2)=80巴,m(Ru)=0.01g,m(木糖醇)=1.50g,m(Ca(OH)2)=0.225g,15ml H2O);
图4示出了含氮碳上金属的筛选(条件:T=200℃,p(H2)=80巴,m(M)=5mg,m(木糖醇)=1.00g,m(Ca(OH)2)=0.150g,10ml H2O);
图5示出了对于Ru/N-900-C来说温度和压力变化(条件:m(Ru)=5mg,m(木糖醇)=1g,m(Ca(OH)2)=0.150g,10ml H2O);
图6示出了山梨糖醇在N-900,5-Ru上的氢解(条件:T=200℃,p(H2)=80巴,m(Ru)=5mg,m(山梨糖醇)=1.20g,m(Ca(OH)2)=0.150g,10ml H2O)。
实施例1:含氮碳载体(N-C)的制备
该实施例说明了氮掺杂的碳载体的制备。将5g活性炭与35ml HNO3(30%)混合并回流8小时。随后用水将碳洗涤至中性并干燥。将1g经氧化的碳放入装有8巴NH3和52巴N2的50毫升高压釜中。在搅拌下将高压釜加热至200℃。碳的还原进行4个小时。对于所述的碳载体(N-HNO3),根据CHN分析得到5.54%的氮含量。如果随后在350℃下用氢气(N-HNO3,H2)进一步还原载体7小时,则得到4.65%的氮含量。然而,以这种方式,碳上氧的比例也减少了。C、H和N的总和现在是91.50%,而在N-HNO3的情况下,它是84.62%。
用氮掺杂碳载体的不同方式是用气态氨还原。选择600至900℃的温度和1至5小时的时间用于还原并获得各种碳。也可以使用商业氮掺杂的碳纳米管(N-CNT)。在使用之前,将NCNT在回流下与10重量%的HCl一起加热2小时。随后用水将它们洗涤至中性并干燥。表1中给出了各种碳载体获得的氮含量的汇总。
实施例2:载体的浸渍
该实施例说明了用贵金属负载含氮碳载体。以钌为例,将产生的500mg碳载体与75.72mg二氯(对甲基异丙苯)钌(II)二聚体一起加入到145ml乙醇中,并在60℃保护气体下在油浴中配位。71小时后终止配位,滤除催化剂。通过该方法用钌负载的最大可能量为5重量%。借助ICP MS分析溶剂中未配位的钌,并通过计算确定催化剂的负载量。负载量与氮含量无关并且从表1中可以看出。
实施例3:木糖醇的氢解
举例来说,该实施例说明了基于使用木糖醇(Xyl)的糖和糖醇的氢解。氢解在200℃和80巴的氢气压力下在50ml高压釜中进行。将1.50g木糖醇、0.225g Ca(OH)2和15ml水加入高压釜中。另外,加入足以使反应溶液中含有7.5mg Ru的催化剂。因此,催化剂N-800,1-Ru的量为0.1563g,Ru/C(C-Ru)的量为0.1500g。该反应进行3至4小时。定期取样以获得动力学。对于N-600,5-Ru和C-Ru来说,产物随时间的形成示于图1和2中。形成所需产物乙二醇(EG)和丙二醇(PG)作为主要产物。甘油(Gly)和乳酸(LA)仅作为副产物少量形成。
对于所有含氮催化剂,在这些条件下形成EG(乙二醇)和PG(丙二醇)作为主要产物。对于氮掺杂的载体,在任何一个情况下两种选择性(S(二元醇))的总和达到67%以上。然而,对于C-Ru,由于不希望的副反应,所以在反应时间较长的情况下可以观察到产物的分解(图2)。催化剂的比较如图3所示。获得的二元醇的最大选择性为83%(N-600,5-Ru)。数值可以在表1中找到。
表1.制备的碳载体、氮含量、金属负载量和氢解结果。
实施例4:在含氮碳上筛选金属
比较金属Ni、Pt和Ru。将它们负载到载体N-800,5上。以与实施例2相同的方式进行浸渍。负载后,在氢气流中还原N-800,5-Pt和N-800,5-Ni。还原在350℃下进行7小时。以与实施例3相同的方式进行氢解。结果示于图4和表2中。很明显,N-800,5-Pt和N-800,5-Ni的催化活性降低,但是获得的对二元醇的选择性不变且很高。
表2.在含氮碳上金属的筛选-金属负载量、氢解结果
实施例5:与文献比较
以下将来自本发明的糖和糖醇的氢解结果与来自相关现有技术的其它催化剂和工艺在产物选择性和催化剂活性方面进行比较。在类似条件下并使用类似的底物进行比较(参见表3)。
表3.本发明与现有技术的比较。
*本发明
[1]T.Werpy,J.Frye,A.Zacher,D.Miller,US20030119952A1,2003
[2]SP Chopade,DJ Miller,JE Jackson,TA Werpy,JG Frye,Jr.,AH Zacher,WO2001066499
[3]JG Frye,DJ Miller,TA Werpy,AH Zacher,WO2003035593 B1,2003。
实施例6:对于Ru/N-C来说温度和压力的变化
对催化剂N-900-Ru来说进行温度和压力的变化。除了200℃之外,还使用170℃,并且除了80巴H2之外,还使用50巴H2。氢解以与实施例3相同的方式进行,结果以比较的方式显示在图5和表4中。反应在较低温度下进行得更慢。难以比较选择性,因为在相同转化率下的比较是不可能的。然而,二元醇仍然是反应的主要产物。
表4.制备的碳载体、氮含量、金属负载量和氢解结果。
实施例7:山梨糖醇的氢解
该实施例说明了基于使用山梨糖醇(Sor)的糖和糖醇的氢解。氢解在200℃和80巴氢气压力下在50ml高压釜中进行。将1.197g山梨糖醇、0.150g Ca(OH)2和10ml水加入高压釜中。另外,加入足以使反应溶液中含有5mg Ru的催化剂。因此,催化剂N-900,5-Ru的量为0.100g。反应进行3小时。定期取样以获得动力学。对于N-900,5-Ru来说产物随时间的形成如图6所示。反应2小时后EG的选择性为18%,PG的选择性为30%。
在本发明的上下文中进行对比实验,其中使用未掺杂氮的碳纳米管作为催化剂载体。这里,使用与根据本发明的前述实施例中的那些可比较的条件。确定了根据本发明的催化剂载体在这里是优异的,因为它们对目标产物的选择性具有影响。
在本发明的上下文中进行对比实验,其中使用未掺杂氮的活性炭作为催化剂载体。这里,使用与根据本发明的前述实施例中的那些可比较的条件。确定了根据本发明的催化剂载体在这里是优异的,因为氮掺杂对目标产物的选择性具有显著的积极影响。此外,通过碳载体的氮掺杂,产物的分解(例如在Ru/C vs Ru/N-C的情况下)显著减慢/降低。
Claims (12)
1.一种将糖或糖醇化学转化为多元醇/二元醇的方法,其中所述糖或糖醇在包含至少一种金属且在碳载体上的催化剂的存在下通过氢解进行转化,其特征在于氮掺杂的碳载体被用作催化剂载体。
2.如权利要求1所述的方法,其特征在于,在两步法中,首先将糖氢化得到糖醇,然后在第二步中通过氢解将所述糖醇转化为多元醇。
3.如权利要求1或2所述的方法,其特征在于,通过氢化/氢解将C6糖或C6糖醇或C5糖或C5糖醇转化为多元醇/二元醇。
4.如权利要求1至3中任一项所述的方法,其特征在于,氮掺杂的活性炭或氮掺杂的炭黑被用作催化剂载体。
5.如权利要求4所述的方法,其特征在于,碳载体被用作催化剂,其表面通过还原方法特别是使用氨和/或氮和/或氢用氮原子掺杂。
6.如权利要求1至3中任一项所述的方法,其特征在于,氮掺杂的碳纳米管被用作催化剂载体。
7.如权利要求6所述的方法,其特征在于,使用直径为0.4至100nm的圆柱形碳中空体作为碳纳米管,所述碳纳米管在其制备过程中被额外地用氮掺杂。
8.如权利要求1至7中任一项所述的方法,其特征在于,所述催化剂包含一种或多种选自下组的金属:
Ru、Pt、Ni、Os、Rh、Ir、Pd、以及Au、Ni、Cu、Fe和Co。
9.如权利要求1至8中任一项所述的方法,其特征在于,碱被用作助催化剂。
10.如权利要求9所述的方法,其特征在于,碱金属氢氧化物或碱土金属氢氧化物被用作碱,尤其选自下组:(NaOH)、KOH、LiOH、Mg(OH)2、Ca(OH)2、Sr(OH)2和Ba(OH)2。
11.如权利要求1至10中任一项所述的方法,其特征在于,所述转化在20℃至约400℃、特别是在170℃至约200℃范围内的反应温度下进行。
12.如权利要求1-11中任一项所述的方法,其特征在于,所述氢解在约1巴至约300巴、特别是在50巴至约80巴范围内的氢气压力下进行。
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DE102017204322.9A DE102017204322A1 (de) | 2017-03-15 | 2017-03-15 | Verfahren zur chemischen Umsetzung von Zuckern oder Zuckeralkoholen zu Glykolen |
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PCT/DE2018/100236 WO2018166566A1 (de) | 2017-03-15 | 2018-03-15 | Verfahren zur chemischen umsetzung von zuckern oder zuckeralkoholen zu glykolen |
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EP (1) | EP3596034B1 (zh) |
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MY193158A (en) * | 2016-06-03 | 2022-09-26 | Iowa Corn Promotion Board | Continuous processes for the highly selective conversion of aldohexose-yielding carbohydrate to ethylene glycol |
DE102018215394A1 (de) | 2018-09-11 | 2020-03-12 | Rheinisch-Westfälische Technische Hochschule Aachen | Verfahren zur chemischen Umsetzung von Zuckern oder Zuckeralkoholen zu Glykolen |
CN109999880B (zh) * | 2019-04-19 | 2022-02-25 | 中国科学院青岛生物能源与过程研究所 | 氮掺杂多孔碳负载双金属催化剂及其制备方法及用途 |
DE102019113135A1 (de) * | 2019-05-17 | 2020-11-19 | Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen | Verfahren zur Herstellung von Glycolen aus Zuckern und Zuckeralkoholen |
WO2022015956A1 (en) | 2020-07-15 | 2022-01-20 | Sorrento Therapeutics, Inc. | Improved process for dna integration using rna-guided endonucleases |
CN115073263B (zh) * | 2022-06-28 | 2024-01-02 | 南京工业大学 | 一种催化剂连续催化制备小分子多元醇的方法 |
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WO2008071642A1 (de) * | 2006-12-15 | 2008-06-19 | Basf Se | Verfahren zur herstellung von 1,2-ethylenglycol und 1,2-propylenglycol durch heterogen katalysierte hydrogenolyse eines polyols |
WO2016119568A1 (zh) * | 2015-01-27 | 2016-08-04 | 中国石油化工股份有限公司 | 一种含杂原子纳米碳材料及其制备方法和应用以及一种烃脱氢反应方法 |
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US6479713B1 (en) | 2001-10-23 | 2002-11-12 | Battelle Memorial Institute | Hydrogenolysis of 5-carbon sugars, sugar alcohols, and other methods and compositions for reactions involving hydrogen |
US6841085B2 (en) * | 2001-10-23 | 2005-01-11 | Battelle Memorial Institute | Hydrogenolysis of 6-carbon sugars and other organic compounds |
DE102007062421A1 (de) | 2007-12-20 | 2009-06-25 | Bayer Technology Services Gmbh | Verfahren zur Herstellung von Stickstoff-dotierten Kohlenstoffnanoröhrchen |
DE102008028070A1 (de) * | 2008-06-12 | 2009-12-17 | Bayer Technology Services Gmbh | Katalysator und Verfahren zur Hydrierung von organischen Verbindungen |
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WO2016119568A1 (zh) * | 2015-01-27 | 2016-08-04 | 中国石油化工股份有限公司 | 一种含杂原子纳米碳材料及其制备方法和应用以及一种烃脱氢反应方法 |
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EP3596034B1 (de) | 2020-12-02 |
DE102017204322A1 (de) | 2018-09-20 |
EP3596034A1 (de) | 2020-01-22 |
US20200239393A1 (en) | 2020-07-30 |
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