CN106457230B - 结晶微孔材料调节的c1-3含氧化合物至c4-含氧化合物的转化 - Google Patents

结晶微孔材料调节的c1-3含氧化合物至c4-含氧化合物的转化 Download PDF

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CN106457230B
CN106457230B CN201580026932.6A CN201580026932A CN106457230B CN 106457230 B CN106457230 B CN 106457230B CN 201580026932 A CN201580026932 A CN 201580026932A CN 106457230 B CN106457230 B CN 106457230B
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S·舒恩姆加维尔
I·萨达巴苏比里
E·塔亚尔宁
M·S·霍尔姆
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Abstract

本发明涉及一种用于由包含C1‑3含氧化合物(例如甲醛、乙醇醛、乙二醛、丙酮醛或丙酮醇)的组合物制备C4含氧化合物(例如苏糖、赤藓糖或赤藓酮糖)的方法，其中该方法在结晶微孔材料的存在下进行，该结晶微孔材料具有选自八元环孔结构和十元环孔结构的环孔结构。

Description

结晶微孔材料调节的C1-3含氧化合物至C4-含氧化合物的 转化
背景：
C4含氧化合物，例如C4糖(例如赤藓糖、苏糖和赤藓酮糖)的选择性和高收率制备对于其在化学工业中用于制备例如以下物质的用途能够被证明是有价值的：C4多元醇；乙烯基乙醇酸甲酯或由其获得的产物；2-羟基-4-甲氧基丁酸或其盐或酯(如2-羟基-4-甲氧基丁酸甲酯)。
制备C4含氧化合物的已知方法包括乙醇醛的醛醇自缩合。已经观察到，醛醇缩合对于C4含氧化合物的制备不是选择性的；随着C4产物继续反应以形成具有更大碳原子数的含氧化合物时，观察到产物的混合物。为了控制反应对于C4含氧化合物的选择性，需要形成C4含氧化合物和硅酸盐或硼酸盐的复合物，或使用C4含氧化物选择性催化剂。
硅酸盐复合物用于选择性形成C4含氧化合物的实例包括在含水硅酸钠存在下的乙醇醛的醇醛缩合；Science(2010)327,pp 984-986。在反应期间，形成硅酸盐-C4-糖复合物，从而控制反应的选择性。另一个实例包括乙醇醛在硼酸盐缓冲液存在下的缩合。获得高收率(86％)的C4含氧化合物(C4糖)；J.Am.Chem.Soc.(2011)133,pp 9457-9468。
C4-含氧化合物选择性催化剂的实例包括在同手性二肽催化剂的存在下通过乙醇醛的醛醇缩合来制备C4含氧化合物。C4含氧化合物产物的收率高达63％；PNAS(2006)103，pp12712-12717。或者，可以使用锌-脯氨酸催化剂。C4-糖产物的总收率为约51％。C6-糖以约30％的收率形成；Org.Biomol.Chem.(2005)3,pp 1850-1855。
来自乙醇醛的C4含氧化合物的替代制备包括所提出的在2-羟基-4-甲氧基-丁酸酯(C4)和乙烯基乙醇酸甲酯(C4)的制备中的四糖瞬时中间体。反应在沸石型催化剂的存在下进行。该沸石型材料是Sn-BEA，一种十二元环孔结构；Green Chemistry(2012)14,pp702-706。
替代的沸石型材料，例如十元环孔结构化沸石型(例如Sn-MFI或Ti-MFI)，可用于使C2含氧化合物异构化。这种沸石型材料已用于使乙二醛异构化为乙醇酸。乙醇酸的收率为约90％；Green Chemistry(2014)16,pp1176-1186。
本发明的一个目的是提供一种用于由包含C1-3含氧化合物的组合物制备C4含氧化合物的方法，其中该方法对于C4含氧化合物的生产是选择性的，并且产物以高收率获得。
发明内容
现已发现，在包含小孔或中孔结构的结晶微孔材料的存在下，可以将乙醇醛选择性地转化为C4含氧化合物。该反应以高收率进行。另外，可在其他化合物存在下进行反应，以选择性地形成期望的C4含氧化合物。
本发明还定义了一种用于由包含C1-3含氧化合物的组合物制备C4含氧化合物的方法，其中该方法在结晶微孔材料的存在下进行，该结晶微孔材料包含小孔或中孔结构。
C4含氧化合物可以被称为C4糖或具有四个碳原子的碳链长度的含氧化合物。C4含氧化合物的分子式可以是C4H8O4。C4含氧化合物也可以被描述为四糖。C4含氧化合物选自苏糖、赤藓糖和赤藓酮糖中的一种或多种。
在本发明的一个实施方案中，包含C1-3含氧化合物的组合物包括选自C1含氧化合物、C2含氧化合物和C3含氧化合物的一种或多种含氧化合物。C1、C2和C3含氧化合物是指分别具有一个、两个或三个碳原子的碳链长度的化合物。C1-3含氧化合物的分子式是选自以下的一种或多种化学式：CH2O、C2H4O2、C2H2O2、C3H6O2和C3H4O2。优选地，包含C1-3含氧化合物的组合物包含选自甲醛、乙醇醛、乙二醛、丙酮醛和丙酮醇的一种或多种化合物。在第二个实施方案中，包含C1-3含氧化合物的组合物优选为包含选自乙醇醛(2-羟基乙醛)和乙二醛的一种或多种C2含氧化合物的组合物。乙醇醛是具有两个碳原子的碳链长度的化合物，也称为C2含氧化合物或C2糖。
包含C1-3含氧化合物的组合物可以是溶液形式，其中溶剂选自水、甲醇和水与甲醇的混合物。例如，包含C1-3含氧化合物的组合物可以是乙醇醛的水溶液或甲醇溶液或包含选自甲醛、乙醇醛、乙二醛、丙酮醛和丙酮醇的一种或多种化合物的组合物的水溶液或甲醇溶液。
包含C1-3含氧化合物的组合物可以通过生物质的热解或选自C5含氧化合物、C6含氧化合物和蔗糖的一种或多种含氧化合物的热解而获得。C5含氧化合物和C6含氧化合物化合物是指选自葡萄糖、果糖、木糖及其异构体的一种或多种化合物。在US7,094,932B2和PCT/EP2014/053587中提供了示例性的热解反应。
结晶微孔材料包括沸石材料和沸石型材料。根据Corma et al.,Chem.Rev.1995,95pp 559-614，沸石材料是具有微孔结晶结构的结晶铝硅酸盐。沸石材料的铝原子可以部分或完全被金属(金属原子)如锆(Zr)、钛(Ti)和锡(Sn)取代，这些材料被称为沸石型材料。
包含小孔结构的结晶微孔材料是指包含八元环孔结构的结晶微孔材料；包含中孔结构的结晶微孔材料是指包含十元环孔结构的结晶微孔材料。具有小孔或中孔结构的晶体微孔材料的实例提供于文献Chem.Rev.1995,95pp 559-614中并且包括诸如LTA、CHA、MFI(ZSM-5)、MEL、MTT、MWW、TON、HEU、AEL、AFO、MWW和FER的结构。
具有BEA结构的结晶微孔材料包含大的十二元环孔结构(Chem.Rev.1995,95pp559-614)，并且被认为不是本发明的特征。
具有中等孔径的沸石型材料的实例包括诸如Sn-MFI、Ti-MFI和Zr-MFI的结构。具有小孔径的沸石型材料的实例是Sn-LTA。
可以认为包含小孔或中孔结构的结晶微孔材料作为催化剂起作用。
通过本发明的方法制备的C4含氧化合物的百分比收率为等于或大于20％、等于或大于24％、等于或大于27％、等于或大于30％、等于或大于35％。
包含小孔或中孔结构的结晶微孔材料中的金属(金属原子)含量为0.1至15wt％、0.5至5.0wt％、0.5至1.5wt％。
该方法可以在溶剂中进行；其中溶剂可选自水、醇和水与醇的混合物(水和醇)中的一种或多种。醇可选自甲醇和乙醇中的一种或多种。
该方法可在25-150℃、50-120℃和70-100℃的温度下进行。
通过本发明制备的C4含氧化合物可以通过氢化转化为C4-多元醇。这样的氢化反应可以在负载的金属催化剂的存在下进行，其中金属是例如铜、镍、钼、钴、铁、铬、锌和铂族金属。在优选的实施方案中，金属催化剂选自负载在碳上的钯或钌或雷尼镍。示例性的氢化反应条件公开在US6,300,494B1和US 4,487,980B1中。用于氢化反应的其它合适的金属催化剂和反应条件的实例公开在Ullmann’s Encyclopaedia of Industrial Chemistry:Hydrogenation and Dehydrogenation中。
通过本发明的方法制备的C4含氧化合物可以被转化为乙烯基乙醇酸甲酯和2-羟基-4-甲氧基丁酸或其盐或酯。Science(2010)328,pp 602–605和Green Chemistry(2012)14,pp 702-706公开了合适的合成方法。另外，可以在相同的条件下或在如ACS Catal.,2013,3(8),pp 1786-1800中描述的条件下由C4含氧化合物制备α-羟基-γ-丁内酯。
乙烯基乙醇酸甲酯化合物可以进一步反应，形成α-羟基蛋氨酸类似物；该转化的一个实例公开于WO 98/32735中。α-羟基蛋氨酸类似物包括选自2-羟基-4-(C1-5烷硫基)丁酸、其盐和酯的化合物。
C1-5烷硫基是指选自以下的烷基硫醇：甲硫醇、乙硫醇、直链或支链丙硫醇、直链或支链丁硫醇和直链或支链戊硫醇。
C1-8烷基酯是指包含选自以下的烷基基团的酯：甲基、乙基、丙基、丁基、异丙基、异丁基、戊基、己基、庚基、辛基和2-乙基己基。
在本发明的一个实施方案中，蛋氨酸α-羟基类似物是2-羟基-4-(甲硫基)丁酸。
在本发明的第二个实施方案中，蛋氨酸α-羟基类似物选自2-羟基-4-(甲硫基)丁酸甲酯、2-羟基-4-(甲硫基)丁酸乙酯、2-羟基-4-(甲硫基)丁酸丙酯、2-羟基-4-(甲硫基)丁酸丁酯、2-羟基-4-(甲硫基)丁酸异丙酯、2-羟基-4-(甲硫基)丁酸戊酯、2-羟基-4-(甲硫基)丁酸己酯、2-羟基-4-(甲硫基)丁酸庚酯、2-羟基-4-(甲硫基)丁酸辛酯和2-羟基-4-(甲硫基)丁酸2-乙基己酯。
通过本发明的方法制备的C4含氧化合物可以被转化为丁二醇，如ChemSusChem(2012)5,pp 1991-1999中所述。
用于由C1-3含氧化合物制备C4含氧化合物的方法也可以与由C4含氧化合物形成C4多元醇的氢化反应同时进行。因此，反应可以在一个步骤中进行，即“一锅”反应。“一步”或“一锅”反应是指用于将乙醇醛转化为C4含氧化合物的结晶微孔材料和用于使C4含氧化合物氢化的金属催化剂同时存在于反应容器中。当氢化产物(C4多元醇)存在时，反应被淬灭。
C4多元醇是指包含链长为四个碳原子的化合物并且每个碳原子与醇(OH)官能团键合的C4含氧化合物。C4多元醇也可以称为四碳糖醇，并且具有分子式C4H10O4。C4多元醇是选自赤藓糖醇和苏糖醇的一种或多种化合物。赤藓糖醇和苏糖醇包括所有的立体异构体，例如D-和L-苏糖醇。赤藓糖醇可用作食品、甜味剂和用于丁二醇的制备。ChemSusChem(2012)5,pp1991-1999说明了由赤藓糖醇制备丁二醇。
实施例1：
结晶微孔材料(Sn-MFI、Ti-MFI、Sn-BEA和Sn-LTA)制备：
Sn-MFI：
根据Mal等人描述的方法(Mal,N.K.；Ramaswamy,V.；Rajamohanan,P.R.；Ramaswamy,A.V.Sn-MFI molecular sieves:Synthesis methods,29Siliquid and solidMAS-NMR,119Sn static and MAS NMR studies.Microporous Mater.,1997,12,331-340)制备200Sn-MFI(Si/Sn＝200)。根据该方法，将NH4F(5.35g)溶解在软化水(25.0g)中。在快速搅拌下添加SnCl4.5H2O(0.25g)在H2O(10.0g)中的溶液。此后，缓慢添加四丙基溴化铵[TPABr(9.8g)]在H2O(56.0g)中的溶液。将热解法二氧化硅(8.6g)溶解在混合物中。将混合物搅拌3小时，然后将凝胶转移到特氟隆衬里的高压釜中并在200℃下结晶6天。然后将产物用充足的水抽滤并在80℃下干燥过夜。将回收的粉末在550℃下煅烧(2℃/min)6小时。根据相同方法制备400Sn-MFI(Si/Sn＝400)，不同之处在于调节SnCl4.5H2O的量。
Sn-MFI(替代制备)：
可以由ZSM-5(Zeochem,
Figure BDA0001157279370000051
PZ-2 100H)制备200Sn-MFI(Si/Sn＝200)。将ZSM-5在450℃下在蒸汽下处理6小时，用1M的HCl在100℃下酸洗16小时，并用充足的水洗涤。将固体在120℃下干燥16小时，用SnCl2水溶液浸渍并在550℃下煅烧(2℃/min)6小时。
Ti-MFI：
根据修改的Mal等人描述的方法(Mal,N.K.；Ramaswamy,V.；Rajamohanan,P.R.；Ramaswamy,A.V.Sn-MFI molecular sieves:Synthesis methods,29Si liquid and solidMAS-NMR,119Sn static and MAS NMR studies.Microporous Mater.,1997,12,331-340)制备200Ti-MFI(Si/Ti＝200)。根据该方法，将NH4F(5.35g)溶解在软化水(25.0g)中。在快速搅拌下添加乙氧基钛(IV)(0.17g)在H2O(3.5g)中的溶液和H2O2(6.5g)。此后，缓慢添加四丙基溴化铵[TPABr(9.8g)]在H2O(56.0g)中的溶液。将热解法二氧化硅(8.6g)溶解在混合物中。将混合物搅拌20小时，然后将凝胶转移到特氟隆衬里的高压釜中并在200℃下结晶6天。然后将产物用充足的水抽滤并在80℃下干燥过夜。将回收的粉末在550℃下煅烧(2℃/min)6小时。
Sn-BEA：
根据EP 2184270B1中所述的方法制备Sn-BEA。
Sn-LTA：
可以从LTA沸石(Sigma-Aldrich,Molecular sieves,
Figure BDA0001157279370000061
)制备具有(Si/Sn＝125)的125Sn-LTA。将LTA在450℃下在蒸汽下处理6小时，用1M的HCl在100℃下酸洗16小时，并用充足的水洗涤。将固体在120℃下干燥16小时，用SnCl2水溶液浸渍并在550℃下煅烧(2℃/min)6小时。
从乙醇醛制备C4含氧化合物：
实施例2：
将根据实施例1制备的结晶微孔材料(0.15g)、乙醇醛二聚物[SAFC，0.25g]和去离子水(5g)加入到20mL小瓶(Ace压力管)中，并在80℃下在剧烈搅拌(600rpm)下加热。在选定的时间(0.5-24小时)取出反应样品。使用配备有BIORAD Amminex HPX-87H柱的HPLCAgilent 1200在65℃下和0.004M的H2SO4水溶液中以0.6ml min-1对过滤后的液体样品进行分析。
表1：用各种结晶微孔材料从乙醇醛水溶液生产的C4含氧化合物的百分比收率随时间的变化
Figure BDA0001157279370000071
实施例3：
可以通过生物质或C5-6糖(C5-6含氧化合物)如葡萄糖、蔗糖、果糖或木糖的热解来制备包含C1-3含氧化合物的组合物。在US 7,094,932B2和PCT/EP2014/053587中提供了示例性的热解反应。C1-3含氧化合物组合物包含5wt％或更高例如5wt％至65wt％的乙醇醛。
将根据US 7,094,932B2由葡萄糖的热解获得的包含C1-3含氧化合物的组合物在水中稀释，以获得5g包含8wt％乙醇醛的溶液。将根据实施例1制备的结晶微孔材料(0.15g)添加至20mL小瓶(Ace压力管)中的混合物中，并将该反应在80℃下在剧烈搅拌(600rpm)下加热。在选定的时间(0.5-24小时)提取反应样品。过滤后，如前所述进行液体样品的分析。
表2：由根据实施例2的C1-3含氧化合物混合物的水溶液制备的C4含氧化合物的百分比收率随时间的变化。示出了各种结晶微孔材料。
Figure BDA0001157279370000072
实施例4：
在高压釜反应器中在30-90巴的H2压力下进行C4含氧化合物的氢化。通过将根据实施例2或3制备的包含C4含氧化合物(15g)的组合物与Ru/C催化剂(0.2g；活性炭上5％，来自Aldrich)一起添加至Parr高压釜(50mL)中来进行反应。将反应器加热至80℃并在500rpm下搅拌3小时。
实施例5：
乙醇醛至C4含氧化合物的同时转化以及随后的氢化(“一锅”或“一步”转化和氢化)。
将乙醇醛二聚物(SAFC，0.25g)、根据实施例1制备的Sn-MFI(0.1g)、Ru/C催化剂(0.075g；活性炭上5％，来自Aldrich)和水(15g)添加至50mL的Parr高压釜中。在80℃下在空气气氛中进行第一缩合反应。反应3小时后，用90巴的氢气对高压釜加压，并使反应进行3小时。在缩合步骤和氢化之后获得产物样品，并在过滤后的如前所述地在HPLC中进行分析。
或者，可以通过根据实施例1或2制备的包含C4含氧化合物的组合物与Sn-BEA催化剂分别在水或甲醇中反应来获得乙烯基乙醇酸或乙烯基乙醇酸甲酯(MVG)；GreenChemistry(2012)14,pp 702-706。
图1：根据实施例2制备的C4含氧化合物的百分比收率随时间的变化。示出了各种结晶微孔材料。结晶微孔材料是：
正方形：200Sn-MFI；
圆圈：Ti-MFI；
三角形：Sn-BEA。
图2：根据实施例3制备的C4含氧化合物的百分比收率随时间的变化。示出了各种结晶微孔材料。
结晶微孔材料是：
正方形：200Sn-MFI；
圆圈：Ti-MFI；
三角形：Sn-BEA。

Claims (14)

1.一种用于由包含C1-3含氧化合物的组合物制备一种或多种分子式为C4H8O4的C4含氧化合物的方法，其中所述包含C1-3含氧化合物的组合物包含乙醇醛，且其中所述C4含氧化合物在溶剂和结晶微孔材料的存在下选择性地由乙醇醛形成，所述结晶微孔材料包含选自八元环孔结构和十元环孔结构的一种或多种环孔结构，其中包含八元环孔结构或十元环孔结构的结晶微孔材料包含选自锆、铝、锡或钛的一种或多种金属；且其中所述结晶微孔材料是沸石型材料，其具有选自CHA、LTA、MFI、MEL、MTT、MWW、TON、HEU、AEL、AFO和FER的结构。
2.根据权利要求1所述的方法，其中所述C4含氧化合物是选自苏糖、赤藓糖和赤藓酮糖的一种或多种化合物。
3.根据权利要求1或2所述的方法，其中所述包含C1-3含氧化合物的组合物包含选自甲醛、乙二醛、丙酮醛和丙酮醇的一种或多种化合物。
4.根据权利要求3所述的方法，其中所述包含C1-3含氧化合物的组合物包含至少5wt％的乙醇醛。
5.根据权利要求1或2所述的方法，其中所述溶剂选自水、醇和水与醇的混合物的一种或多种。
6.根据权利要求5所述的方法，其中所述醇选自甲醇和乙醇中的一种或多种。
7.根据权利要求1所述的方法，其中包含八元环孔结构或十元环孔结构的结晶微孔材料包含0.1wt％至15wt％的金属。
8.根据权利要求1或2所述的方法，其中所述方法在25℃至150℃的温度下进行。
9.根据权利要求1或2所述的方法，其中进行在前的使生物质或选自果糖、葡萄糖、蔗糖、木糖或其异构体的一种或多种含氧化合物热解的步骤，以生产包含C1-3含氧化合物的组合物。
10.根据权利要求1或2所述的方法，其中使C4含氧化合物氢化。
11.根据权利要求10所述的方法，其中所述方法是一步法。
12.根据权利要求1或2所述的方法，其中所述C4含氧化合物在Sn-BEA的存在下被异构化和酯化。
13.根据权利要求1或2所述的方法，其中所述C4含氧化合物被转化为选自赤藓醇和苏糖醇的一种或多种化合物。
14.根据权利要求1至13中任一项所制备的C4含氧化合物用于制备一种或多种α-羟基蛋氨酸类似物的用途。
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