CN105037103A - 一种木质素高效解聚的方法 - Google Patents
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- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
- C07C37/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes by hydrolysis of lignin or sulfite waste liquor
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Abstract
本发明公开了一种木质素高效解聚的方法。该方法以金属氯化物与贵金属为复合催化剂,以小分子有机溶剂为介质,在温和的条件下可实现木质素等难以利用的可再生能源的高效催化解聚,制备高附加值的酚类化学品和高热值生物油。本发明具备工艺简单、条件温和、单酚收率高、产物可控、催化剂可实现循环使用等显著优点。可避免目前的生产方法中存在的设备要求高,能耗大,目标产物收率低,催化剂失活严重等不足。
Description
技术领域
本发明属于环境保护技术,农业废弃物高效利用技术及新能源技术开发和利用领域,特别涉及一种采用金属氯化物与贵金属协同作用形成的复合催化剂,在小分子有机溶剂中高效解聚木质素,获得高收率的脂肪醇、碳氢化合物、单体酚类和酚类低聚体。
背景技术
随着化石燃料的日益枯竭,能源需求越来越紧张。与此同时,大量燃烧化石燃料排放的CO2、SO2、NO和灰尘,导致温室效应更加严重,对环境可持续发展构成威胁。因此,寻求低碳的、低污染的可再生的替代能源成为了世界各国的共识。生物质直接来源于植物的光合作用,具有富碳含量、储量大、分布广、污染低、廉价以及可再生等优点,与化石燃料相比,其含硫和含氮量均较低,同时灰分含量也很小,被认为是一种潜在的石化替代能源。当前,大部分的研究集中在构成木质生物质的三种主要成分(纤维素、半纤维素和木质素)中较容易转化的纤维素和半纤维素上。剩下的木质素则常常以废物的形式排出,仅在生物炼制工厂里作为燃料提供能量和蒸汽。然而,由三种苯丙烷结构单元随机键合而成的木质素,具有芳香基、甲氧基、酚(醇)羟基、羰基和羧基等多种功能基团和不饱和双键等活性位点,以及与石油相近的C/H含量比,是自然界中唯一能直接提供芳环的可再生资源。因此,开发新技术以充分利用可再生生物质中木质素制备生物燃料和生物化学品显得尤为重要。
近年来,生物酶解、热裂解、催化氢解、催化氧化等系列木质素解聚及转化手段被广泛利用,但其也存在较多的不足。如:生物酶解耗时太长;热裂解温度高、能耗大;催化氢解容易结焦失活;催化氧化需要加入氧化剂、对设备要求高;尤其是当前许多技术过程的强酸催化剂,易造成设备腐蚀,且催化剂积碳失活严重。
发明内容
为了克服现有技术中存在的不足和缺点,本发明的首要目的在于提供一种采用金属氯化物与贵金属协同作用形成的复合催化剂,在小分子有机溶剂中高效解聚木质素,获得高收率的脂肪醇、碳氢化合物、单体酚类和酚类低聚体。通过对催化剂和反应介质的调控,增加木质素原料与催化剂之间的接触,强化传热与传质过程,降低过程能耗,并抑制催化剂由结焦积碳引起的失活现象。
本发明的目的通过下述技术方案来实现:
一种木质素高效解聚的方法。该方法利用金属氯化物与贵金属催化剂协同形成复合催化剂,在小分子有机溶剂中、温和条件下实现木质素及富木质素生物质废弃物高效解聚制备酚类化合物,强化传质与传热、降低过程能耗,并抑制催化剂积碳。该方法主要包括以下步骤:
在2~5MPa的氮气或氢气气体氛围中,按照0.5~2mmol金属氯化物催化剂、0.01~0.2g贵金属加氢催化剂、0.5~1.0g木质素和40~80mL反应介质的比例,充分混合各物质,加热至240~300℃,在搅拌下反应3~6h即可得到解聚产物,经过分离(比如过滤、溶剂萃取等方式)、提纯即可获得所需物质;所述金属氯化物催化剂选自ZnCl2、MgCl2、AlCl3、CrCl3中的一种或两种,所述贵金属加氢催化剂选自Pd/C、Pt/C或Ru/C(贵金属加氢催化剂中,活性组分的负载量优选为5wt%),所述反应介质为小分子有机溶剂或小分子有机溶剂与水的混合物。
进一步地,上述木质素选自碱木质素、磺酸钠木质素、脱碱木质素、有机溶剂木质素(如有机溶狼尾草木质素)或酸解木质素(可以来源于玉米秸秆水解残渣等富木质素生物质废弃物)。
进一步地,上述小分子有机溶剂选自甲醇、乙醇、正丙醇或乙二醇。对于与水的混合物,优选甲醇-水混合物(体积比优选为4:1)。
进一步地,上述反应的解决产物主要包括脂肪醇、碳氢化合物、单体酚类和酚类低聚体。
本发明的原理是:金属氯化物与贵金属协同作用形成的复合催化剂具有良好的催化性能及抗积碳能力,在小分子有机溶剂中,一定工艺条件下,实现木质素及富木质素生物质的高效定向催化解聚制备脂肪醇、碳氢化合物、单体酚类和酚类低聚体。
本发明相对现有技术具有如下的优点和效果:
(1)本发明方法构建的催化体系具有协同作用催化效果,与现有的催化体系相比,具有活性高、抗积碳能力强,操作简单,易于产物分离,环境友好等显著优点;
(2)本发明所采用的溶剂为甲醇、乙醇、正丙醇、乙二醇或上述物质与水的混合物,可直接来源于生物质,因此,具有可再生、绿色等显著优点、且上述溶剂经简单分离后可实现循环利用;
(3)本发明方法可以选用碱木质素、磺酸钠木质素、脱碱木质素,有机溶剂木质素与酸解木质素等不同原料,因此,原料来源广泛,含量丰富,价格低廉;
(4)本发明方法与现有技术相比,最大的优势在于在上述体系中,木质素的转化率高,脂肪醇、碳氢化合物、单体酚类等目标产物收率高,且能有效抑制结焦积碳的形成;
(5)本发明提供的催化体系具备良好的循环使用性能。
具体实施方式
下面结合实施例对本发明做进一步详细的描述,但本发明的实施方式不限于此。
实施例1
称取0.5g脱碱木质素和1mmolCrCl3和0.1g5wt%Pd/C置于40mL甲醇溶剂中,体系经H2置换3次后充气3MPa,于280℃反应5h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现82.9%转化,其中脂肪醇收率3.1%,碳氢化合物收率1.7%,愈创木酚类收率2.6%,苯酚类收率13.5%,酚类低聚体收率48.4%。在该过程中未见明显结焦积碳现象。
实施例2
称取0.5g磺酸钠木质素和1mmolCrCl3和0.1g5wt%Pd/C置于40mL甲醇溶剂中,体系经H2置换3次后充气3MPa,于300℃反应5h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现81.0%转化,其中脂肪醇收率11.9%,碳氢化合物收率1.1%,愈创木酚类收率1.1%,苯酚类收率5.3%,酚类低聚体收率44.8%。在该过程中未见明显结焦积碳现象。
实施例3
称取0.5g有机溶狼尾草木质素和1mmolCrCl3和0.1g5wt%Ru/C置于40mL甲醇溶剂中,体系经H2置换3次后充气4MPa,于260℃反应5h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现65.3%转化,其中脂肪醇收率0.8%,碳氢化合物收率1.1%,愈创木酚类收率1.8%,苯酚类收率9.6%,酚类低聚体收率42.6%。在该过程中未见明显结焦积碳现象。
实施例4
称取0.5g碱木质素和1mmolCrCl3和0.1g5wt%Pd/C置于40mL甲醇溶剂中,体系经N2置换3次后充气3MPa,于260℃反应5h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现68.4%转化,其中脂肪醇收率11.9%,碳氢化合物收率3.2%,愈创木酚类收率0.4%,苯酚类收率7.4%,酚类低聚体收率35.8%。在该过程中未见明显结焦积碳现象。
实施例5
称取0.5g碱木质素,1mmolCrCl3,1mmolZnCl2和0.1g5wt%Pd/C置于40mL甲醇溶剂中,体系经H2置换3次后充气4MPa,于260℃反应5h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现67.4%转化,其中脂肪醇收率0.2%,碳氢化合物收率0.5%,愈创木酚类收率1.7%,苯酚类收率1.3%,酚类低聚体收率27.3%。在该过程中未见明显结焦积碳现象。
实施例6
称取0.5g碱木质素,1mmolCrCl3和0.1g5wt%Pd/C置于40mL甲醇水(4:1)混合溶剂中,体系经H2置换3次后充气4MPa,于260℃反应5h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现63.6%转化,其中脂肪醇收率0.1%,碳氢化合物收率0.1%,愈创木酚类收率1.8%,苯酚类收率2.4%,酚类低聚体收率52.8%。
实施例7
称取0.5g碱木质素,0.5mmolMgCl2和0.1g5wt%Pt/C置于40mL乙醇溶剂中,体系经H2置换3次后充气4MPa,于260℃反应5h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现81.5%转化,其中脂肪醇收率1.3%,碳氢化合物收率1.1%,愈创木酚类收率2.6%,苯酚类收率4.5%,酚类低聚体收率51.1%。在该过程中未见明显结焦积碳现象。
实施例8
称取0.75g碱木质素,1mmolAlCl3和0.1g5wt%Pd/C置于40mL正丙醇溶剂中,体系经H2置换3次后充气4MPa,于260℃反应4h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现85.6%转化,其中脂肪醇收率5.6%,碳氢化合物收率1.3%,愈创木酚类收率0.7%,苯酚类收率4.6%,酚类低聚体收率54.3%。在该过程中未见明显结焦积碳现象。
实施例9
称取0.5g碱木质素,1mmolCrCl3和0.1g5wt%Pd/C置于40mL乙二醇溶剂中,体系经H2置换3次后充气3MPa,于240℃反应6h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现56.0%转化,其中脂肪醇收率0.1%,碳氢化合物收率0.1%,愈创木酚类收率0.8%,苯酚类收率1.2%,酚类低聚体收率44.6%。在该过程中,由溶剂引发的副反应增多。
实施例10
称取1g碱木质素,2mmolCrCl3和0.2g5wt%Pd/C置于80mL乙醇溶剂中,体系经H2置换3次后充气2MPa,于260℃反应5h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现79.5%转化,其中脂肪醇收率1.1%,碳氢化合物收率1.2%,愈创木酚类收率2.3%,苯酚类收率4.1%,酚类低聚体收率53.4%。在该过程中未见明显结焦积碳现象。
实施例11
称取0.5g玉米秸秆水解残渣(酸解木质素),0.01g5wt%Pd/C和1mmolCrCl3和置于60mL甲醇溶剂中,体系经H2置换3次后充气5MPa,于260℃反应3h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现71.2%转化,其中脂肪醇收率1.6%,碳氢化合物收率1.5%,愈创木酚类收率3.6%,苯酚类收率12.7%,酚类低聚体收率48.0%。在该过程中未见明显结焦积碳现象。
对照例1
称取0.5g碱木质素,1mmolCrCl3和1mmolZnCl2置于40mL甲醇溶剂中,体系经H2置换3次后充气4MPa,于260℃反应5h。快速将其冷却至室温,依次采用过滤、溶剂萃取等方式对其中产物进行分离。采用GC-MS定性分析、采用GC结合内标法对挥发性产物进行定量分析;采用GPC、FT-IR等手段对不挥发性产物的分子量分布及主要结构单元进行表征。结果表明:经该催化处理后,木质素可实现42.9%转化,其中脂肪醇收率0.1%,碳氢化合物收率0.3%,愈创木酚类收率1.6%,苯酚类收率1.0%,酚类低聚体收率29.1%。在该过程中未见明显结焦积碳现象。
通过实施例和对照例的对比可以看出,通过金属氯化物催化剂和贵金属加氢催化剂的协同作用,在本发明所限定的反应条件下,能够明显提高木质素的转化率。
上述实施例中为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (4)
1.一种木质素高效解聚的方法,其特征在于,包括以下步骤:
在2~5MPa的氮气或氢气气体氛围中,按照0.5~2mmol金属氯化物催化剂、0.01~0.2g贵金属加氢催化剂、0.5~1.0g木质素和40~80mL反应介质的比例,充分混合各物质,加热至240~300℃,在搅拌下反应3~6h即得到解聚产物;所述金属氯化物催化剂选自ZnCl2、MgCl2、AlCl3、CrCl3中的一种或两种,所述贵金属加氢催化剂选自Pd/C、Pt/C或Ru/C,所述反应介质为小分子有机溶剂或小分子有机溶剂与水的混合物。
2.如权利要求1所述的木质素高效解聚的方法,其特征在于,所述木质素选自碱木质素、磺酸钠木质素、脱碱木质素、有机溶剂木质素或酸解木质素。
3.如权利要求1或2所述的木质素高效解聚的方法,其特征在于,所述小分子有机溶剂选自甲醇、乙醇、正丙醇或乙二醇。
4.如权利要求1或2所述的木质素高效解聚的方法,其特征在于,所述解聚产物包括脂肪醇、碳氢化合物、单体酚类和酚类低聚体。
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