木质素水热转化及其产物基础应用研究
摘要
木质纤维素类生物质具有分布广泛、资源丰富、可再生等特点，近年来以木质纤维素类生物质制备高价值化学品和燃料引起了广泛的关注。水热转化是一种很有前景的环境友好热处理技术，在水热条件下可以解聚生物质以获得生物质基平台化学品。目前大部分研究集中在生物质水热气化和液化的工艺研究上，而对水热碳化过程以及水热转化产物（液态产物、水热焦）的基础应用研究尚未引起足够的重视。本文以木质素为原料进行水热液化，率先证实木质素液化产物具有抗氧化性能，并进一步设计出有机溶剂-碱溶液复合萃取法对液化产物进行分类分离。首次提出以甲醛为添加剂对木质素进行水热碳化制备高产率水热焦，并对这些水热焦作为固体燃料和吸附材料进行探索。对包括木质素在内的几种生物质组分水热碳化产物（水热焦）进行了系统的对比分析研究，进一步拓展了生物质水热焦的高价值应用方向--合成水热焦磺化催化剂。然后依据所得水热焦磺化催化剂，设计出“一步法”取代常规两步法降解菊糖制备5-羟基糠醛的工艺思路，以及提出了利用水热焦磺化催化剂代替均相催化剂进行催化水解木质素模型化合物的研究。
采用黑液碱木质素、木质素磺酸盐等原料在水热条件（280-350℃）下液化，检测出液态产物中主要组分是酚类化合物。发现黑液碱木质素液化产物总酚含量与1，1-二苯基-2-三硝基苯肼（DPPH）清除率有一定的线性关系。相对于原料木质素，木质素液化产物中的单位总酚含量、DPPH清除率、铁还原抗氧化能力都有极大的提高，且黑液碱木质素液化产物抗氧化性能效果高于木质素磺酸盐液化产物的效果。综合考虑液化产物产率、单位总酚含量、DPPH清除率等因素，黑液碱木质素适合的水热液化条件为300℃、30min或者320℃、15min。桐油的热稳定性实验发现木质素液化产物在较低的温度下（如130℃）有优良的抗热氧化性能。因此以木质素水热转化制备具有抗氧化性的液化产物是一个很有希望、把低价值原料转化为高值化产物的新技术。
在270-330℃水热条件下对碱木质素进行液化，当反应温度为300℃时，总油（液态产物）可以达到28.3%，且发现其中一半以上的产物为酚类化合物。设计出碱溶液-有机溶剂复合萃取法成功的把液化产物分类分离为四大类：苯二酚类化合物、单酚类化合物、弱极性化合物（主要为烷基苯等）、以及水溶性产物（低分子有机酸、醇、酯等）。此萃取法工艺简单、成本低、分离效率高，是一种有希望应用于分离生物油获取各类化学品的方法。进一步提出了木质素水热转化机理分为三步反应：醚键断裂、去甲氧基以及苯环烷基化反应等，且发现去甲氧基化和苯环烷基化反应随着温度的提高而增强。
在225-265℃条件下对木质素、纤维素、D-木糖（半纤维素模型化合物）、木粉等进行了水热碳化对比研究，并对各种水热焦进行了系统的表征分析。这些水热焦的产率处于45%到60%之间，且各种生物质原料的水热焦产率顺序为木质素>木粉>纤维素>D-木糖。这些水热焦的碳含量、碳回收率、能量回收率、碳氧比、碳氢比分别处于63-75%、80-87%、78-89%、2.3-4.1、12-15之间。水热焦的热值处于24-30MJ/kg之间，与原料相比，提高了45-91%。以上结果说明水热碳化是一种很有前景的把生物质转化为富碳含量且高能量密度产物的技术。另外，推断出木质素水热焦生成机理：木质素水热焦由两部分组分，一部分是木质素聚合结构热解缩合而成，另一部分是由木质素水热降解产物酚类化合物聚合而成。
首次报道了甲醛有利于促进黑液固形物的水热碳化。与没有添加甲醛生成的水热焦相比，添加甲醛所得水热焦的产率、高热值、碳回收效率、总能量回收效率分别提高为1.27-2.13、1.02-1.36、1.20-2.31、1.20-2.44倍，而硫含量和灰分含量分别降低为0.51-0.64和0.48-0.89倍。这些添加甲醛所生成的水热焦的热值处于2.2104到3.0104kJ/kg之间，与原料相比，在285℃下所得水热焦的热值提高了1.90倍。甲醛也用来作为添加剂在320℃下水热碳化木质素磺酸盐，添加甲醛后产率和比表面积分别提高了33.8%和46.4%。添加甲醛生成的木质素磺酸盐水热焦对铜离子和甲基橙的Langmuir饱和吸附容量分别为19.6mg/g和16.3mg/g；没有添加甲醛生成的木质素磺酸盐水热焦甲基橙的Langmuir饱和吸附容量分别为18.9mg/g。
拓展了木质素等生物质水热焦的高价值应用方向--合成高性能磺化催化剂。这些催化剂产率处在36-56%之间，对于不同原料所得的水热焦产率顺序为：木质素>木粉>纤维素>D-木糖，且所有这些催化剂在245℃时得到最大的产率。发现水热焦磺化催化剂都拥有羟基、羧基和磺酸根，其中磺酸根的含量处于0.56-0.87mmol/g，总的氢离子交换容量处于1.11-1.44mmol/g。设计了在离子液体中利用水热焦磺化催化剂等非均相催化剂“一步法”催化降解菊糖制备5-羟甲基糠醛的新思路，部分这些催化剂表现出比传统固体酸催化剂（如HZSM-5、732强酸性阳离子交换树脂、amberlyst-15阳离子交换树脂、超强酸硫酸化氧化锆等）更好的催化活性。在反应条件为100℃、60min的不同催化体系中，5-羟甲基糠醛的产率可以达到47-65%之间。且水热焦磺化催化剂/离子液体反应体系在重复使用5次后，5-羟甲基糠醛的产率仍然可以达到61%。
与常规的无机酸碱均相催化水解木质素模型化合物的研究不同，本研究选择以木质素水热焦磺化催化剂、Amberlyst-15阳离子交换树脂等非均相固体酸催化剂对木质素模型化合物酚基甘油-β-愈创木基醚和4-苄氧基苯酚进行水解。在所有这些固体酸催化剂的作用下，4-苄氧基苯酚水解产物对苯二酚的收率和产率分别处于5.6-47.7%和57.1-92.0%之间。酚基甘油-β-愈创木基醚的主要产物为邻甲氧基苯酚，其收率和产率分别处于22.2-38.0%和63.0-100%。与均相催化剂硫酸相比，这两种木质素模型化合物在水热焦磺化催化剂的作用下转化率略低，但对主要酚类产物的选择性明显增强。这些水热焦磺化催化剂在催化降解、水解反应中表现出相当高的催化活性和选择性，考虑到生物质资源的可再生性、丰富性和廉价性，开发水热焦磺化催化剂是生物质水热转化潜在的工业化方向之一。
Recently, studies on high-value chemicals and fuels from biomass have become aresearch hot spot, as biomass is widely existed, abundant and renewable. Hydrothermalconversion is a promising and environmentally friendly technology, with which the biomasscan be depolymerized and platform chemicals can be obtained. However, most of theresearchers have focused on the process studies of hydrothermal gasification and liquefactionof biomass. The biomass hydrothermal carbonization technologies as well as the applicationstudies of hydrothermal conversion products (liquefied products, hydrochar, etc.) are lacking.In this work, hydrothermal conversion of lignin was conducted, and the antioxidant abilitiesof the liquefied products were explored, and the liquefied products were successfullyclassified separated. The lignin derived hydrochars were tested as solid fuel and carbon-basedadsorption materials, respectively. Moreover, various biomass constituents (lignin, cellulose,etc.) were hydrothermally carbonized, and all of these biomass derived hydrochars werecharacterized and compared. These hydrochars were further newly applied for carbon basedsulfonated catalyst preparation.
Black liquor alkaline lignin and lignosulfonate were liquefied from280-350℃. Theantioxidant abilities of liquefaction products were tested and compared with the raw materials.Results showed that after hydrothermal liquefaction, both the total phenol content and unitantioxidant power of the two lignin liquefaction products were improved, and alkaline ligninliquefaction products had a larger increase than lignosulfonate liquefaction products. Theinfluences of reaction time and temperature on oil yield, total phenol content and antioxidantpower of alkaline lignin liquefaction products were discussed. The total phenol content wasfound to have certain relationships with the antioxidant abilities. The suitable conditions foralkaline lignin hydrothermal liquefaction were at300℃,30min or320℃,15min. Moreover,thermal oxidation stability tests of tung oil showed that the addition of lignin liquefactionproducts obviously increased the oxidation stability time of tung oil at a relative lowtemperature (130℃), however, the antioxidant activity of lignin liquefaction products at150℃was somewhat low. So, it can be inferred that lignin hydrothermal liquefaction productshave the potential to become the valueable antioxidant.
Alkaline lignin was liquefed under hydrothermal conditions at270-330℃, and the totaloil yield reached28.3wt%at a reaction temperature of300℃. The liquefed products wereeffectively separated into four main types of substances: benzenediols, monophenolichydroxyl products, weak-polar products, and water-soluble products (low-molecular-weightorganic acids, alcohols, etc.). The production process and yield of each classifed productswere discussed. More than half of the oil products were phenolics. A mechanism for phenolicproducts production from lignin liquefaction was proposed. The results indicated that thedecomposition of lignin under hydrothermal conditions occured mainly by three steps:hydrolysis and cleavage of the ether bond and the C-C bond, demethoxylation, and alkylation.Moreover, we found that higher temperature would favour the demethoxylation and alkylationreactions.
Hydrothermal carbonization of cellulose, lignin, D-xylose (substitute for hemicelluloses),and wood meal (WM) was experimentally conducted between225and265℃, and thechemical and structure properties of the hydrochars were investigated. The hydrochar yieldwas between45and60%, and the yield trend of the feedstock was lignin> WM> cellulose>D-xylose. The hydrochars seemed stable before300℃, and aromatic structure was formed inall of these hydrochars. The C content, C recovery, energy recovery, ratios of C/O and C/H inall of these hydrochars were among63-75%,80-87%,78-89%,2.3-4.1, and12-15,respectively. The higher heating value (HHV) of the hydrochars was among24-30MJ/kg,with an increase of45-91%compared with the corresponding feedstock. Temperature wasvery important in the hydrothermal carbonization process. Higher temperatures generallyaccelerated the hydrothermal carbonization of biomass, resulting in hydrochars with loweryield, lower volatile matter content, lower ion exchange capacity, lower O-containingfunctional groups, but higher C content. The lignin hydrothermal carbonization mechanismwas that lignin hydrothermal carbonization products were made of polyaromatic hydrocharsand phenolic hydrochars.
Formaldehyde was originally used as a polymerization agent to perform hydrothermalcarbonization of black liquor for solid fuel production from220to285℃. Compared tohydrochar prepared without formaldehyde, hydrochar produced in the presence of a2.8wt%formaldehyde solution (hydrochar-F) had0.27~1.13times higher yield,0.021~0.36times higher heating value (HHV),0.20~1.31times higher C recovery efficiency,0.20~1.44timeshigher total energy recovery efficiency,0.36~0.49times lower sulfur content, and0.11~0.52times lower ash content. The HHV of hydrochar-Fs were ranged from2.2×104to3.0×104kJ/kg, while the HHV of hydrochar-F produced at285℃was1.90times greater than that ofthe raw material (black liquor solid). Hydrothermal conversion of lignosulfonate with orwithout formaldehyde as polymerization agent was conducted at320℃. Compared with thehydrochar produced without formaldehyde addition (WF-hydrochar), the yield and surfacearea of the hydrochar produced with formaldehyde addition (F-hydrochar) increased33.8%and46.4%respectively. The Langmuir saturated adsorption capacity of Cu2+, methyl orange(MO) for F-hydrochar was19.6,16.3mg·g-1respectively. The Langmuir saturated adsorptioncapacity of MO for WF-hydrochar was18.9mg·g-1.
Amorphous hydrochar sulfonated catalysts were generated from four kinds of biomass(lignin, cellulose, wood meal and D-xylose) by hydrothermal carbonization at varioustemperatures (225,245and265℃) followed by sulfonation, with a yield of36-56%. All ofthese catalysts owned aromatic structure, hydroxyl and carboxyl groups, and with a density ofSO3H groups between0.56and0.87mmol/g.5-Hydroxymethylfurfural (HMF) was directlyproduced from inulin in ionic liquids (ILs) through one step with the addition of hydrocharsulfonated catalysts, with a factual yield of47-65%at100℃,60min. Moderate extension ofreaction time (from30to90min) and increase of temperature (from80to120℃) promotedHMF production. The hydrochar sulfonated catalysts showed high reusability (the factualyield retained61%even after being used five times), as well as good catalytic activitycompared with traditional solid acid catalysts.
Hydrolysis of two kinds of lignin model compounds was originally conducted with sixdifferent solid acid catalysts (732cation resin, HZSM-5, sulfated zirconia, Amberlyst-15cation resin, C225-SO3H and L225-SO3H). Monobenzone was used as the-O-4bond type oflignin model compound, and hydroquinone was the main product with a yield andproductivity of among5.6-47.7%,57.1-92.0%, respectively. Guaiacylglycerol--guaiacylether (GG) was employed as the-O-4bond type of lignin model compound, while guaiacolwas found the main product with a yield and productivity of among22.2-38.0%and63.0-100%, respectively. Compared with the homogeneous catalyst H2SO4, Amberlyst-15 cation resin, C-SO3H and L-SO3H showed comparable efficiency of conversion ratio butmuch higher selectivity of the phenolic products. These hydrochar sulfonated catalystsshowed unique advantages in the catalytic degradation and hydrolysis reactions, consideringthe renewable, aboundant, and low-cost properties of biomass, application of hydrocharsulfonated catalysts should be one of the potential industrialization way for biomasshydrothermal conversion.
采用黑液碱木质素、木质素磺酸盐等原料在水热条件（280-350℃）下液化，检测出液态产物中主要组分是酚类化合物。发现黑液碱木质素液化产物总酚含量与1，1-二苯基-2-三硝基苯肼（DPPH）清除率有一定的线性关系。相对于原料木质素，木质素液化产物中的单位总酚含量、DPPH清除率、铁还原抗氧化能力都有极大的提高，且黑液碱木质素液化产物抗氧化性能效果高于木质素磺酸盐液化产物的效果。综合考虑液化产物产率、单位总酚含量、DPPH清除率等因素，黑液碱木质素适合的水热液化条件为300℃、30min或者320℃、15min。桐油的热稳定性实验发现木质素液化产物在较低的温度下（如130℃）有优良的抗热氧化性能。因此以木质素水热转化制备具有抗氧化性的液化产物是一个很有希望、把低价值原料转化为高值化产物的新技术。
在270-330℃水热条件下对碱木质素进行液化，当反应温度为300℃时，总油（液态产物）可以达到28.3%，且发现其中一半以上的产物为酚类化合物。设计出碱溶液-有机溶剂复合萃取法成功的把液化产物分类分离为四大类：苯二酚类化合物、单酚类化合物、弱极性化合物（主要为烷基苯等）、以及水溶性产物（低分子有机酸、醇、酯等）。此萃取法工艺简单、成本低、分离效率高，是一种有希望应用于分离生物油获取各类化学品的方法。进一步提出了木质素水热转化机理分为三步反应：醚键断裂、去甲氧基以及苯环烷基化反应等，且发现去甲氧基化和苯环烷基化反应随着温度的提高而增强。
在225-265℃条件下对木质素、纤维素、D-木糖（半纤维素模型化合物）、木粉等进行了水热碳化对比研究，并对各种水热焦进行了系统的表征分析。这些水热焦的产率处于45%到60%之间，且各种生物质原料的水热焦产率顺序为木质素>木粉>纤维素>D-木糖。这些水热焦的碳含量、碳回收率、能量回收率、碳氧比、碳氢比分别处于63-75%、80-87%、78-89%、2.3-4.1、12-15之间。水热焦的热值处于24-30MJ/kg之间，与原料相比，提高了45-91%。以上结果说明水热碳化是一种很有前景的把生物质转化为富碳含量且高能量密度产物的技术。另外，推断出木质素水热焦生成机理：木质素水热焦由两部分组分，一部分是木质素聚合结构热解缩合而成，另一部分是由木质素水热降解产物酚类化合物聚合而成。
首次报道了甲醛有利于促进黑液固形物的水热碳化。与没有添加甲醛生成的水热焦相比，添加甲醛所得水热焦的产率、高热值、碳回收效率、总能量回收效率分别提高为1.27-2.13、1.02-1.36、1.20-2.31、1.20-2.44倍，而硫含量和灰分含量分别降低为0.51-0.64和0.48-0.89倍。这些添加甲醛所生成的水热焦的热值处于2.2104到3.0104kJ/kg之间，与原料相比，在285℃下所得水热焦的热值提高了1.90倍。甲醛也用来作为添加剂在320℃下水热碳化木质素磺酸盐，添加甲醛后产率和比表面积分别提高了33.8%和46.4%。添加甲醛生成的木质素磺酸盐水热焦对铜离子和甲基橙的Langmuir饱和吸附容量分别为19.6mg/g和16.3mg/g；没有添加甲醛生成的木质素磺酸盐水热焦甲基橙的Langmuir饱和吸附容量分别为18.9mg/g。
拓展了木质素等生物质水热焦的高价值应用方向--合成高性能磺化催化剂。这些催化剂产率处在36-56%之间，对于不同原料所得的水热焦产率顺序为：木质素>木粉>纤维素>D-木糖，且所有这些催化剂在245℃时得到最大的产率。发现水热焦磺化催化剂都拥有羟基、羧基和磺酸根，其中磺酸根的含量处于0.56-0.87mmol/g，总的氢离子交换容量处于1.11-1.44mmol/g。设计了在离子液体中利用水热焦磺化催化剂等非均相催化剂“一步法”催化降解菊糖制备5-羟甲基糠醛的新思路，部分这些催化剂表现出比传统固体酸催化剂（如HZSM-5、732强酸性阳离子交换树脂、amberlyst-15阳离子交换树脂、超强酸硫酸化氧化锆等）更好的催化活性。在反应条件为100℃、60min的不同催化体系中，5-羟甲基糠醛的产率可以达到47-65%之间。且水热焦磺化催化剂/离子液体反应体系在重复使用5次后，5-羟甲基糠醛的产率仍然可以达到61%。
与常规的无机酸碱均相催化水解木质素模型化合物的研究不同，本研究选择以木质素水热焦磺化催化剂、Amberlyst-15阳离子交换树脂等非均相固体酸催化剂对木质素模型化合物酚基甘油-β-愈创木基醚和4-苄氧基苯酚进行水解。在所有这些固体酸催化剂的作用下，4-苄氧基苯酚水解产物对苯二酚的收率和产率分别处于5.6-47.7%和57.1-92.0%之间。酚基甘油-β-愈创木基醚的主要产物为邻甲氧基苯酚，其收率和产率分别处于22.2-38.0%和63.0-100%。与均相催化剂硫酸相比，这两种木质素模型化合物在水热焦磺化催化剂的作用下转化率略低，但对主要酚类产物的选择性明显增强。这些水热焦磺化催化剂在催化降解、水解反应中表现出相当高的催化活性和选择性，考虑到生物质资源的可再生性、丰富性和廉价性，开发水热焦磺化催化剂是生物质水热转化潜在的工业化方向之一。
Recently, studies on high-value chemicals and fuels from biomass have become aresearch hot spot, as biomass is widely existed, abundant and renewable. Hydrothermalconversion is a promising and environmentally friendly technology, with which the biomasscan be depolymerized and platform chemicals can be obtained. However, most of theresearchers have focused on the process studies of hydrothermal gasification and liquefactionof biomass. The biomass hydrothermal carbonization technologies as well as the applicationstudies of hydrothermal conversion products (liquefied products, hydrochar, etc.) are lacking.In this work, hydrothermal conversion of lignin was conducted, and the antioxidant abilitiesof the liquefied products were explored, and the liquefied products were successfullyclassified separated. The lignin derived hydrochars were tested as solid fuel and carbon-basedadsorption materials, respectively. Moreover, various biomass constituents (lignin, cellulose,etc.) were hydrothermally carbonized, and all of these biomass derived hydrochars werecharacterized and compared. These hydrochars were further newly applied for carbon basedsulfonated catalyst preparation.
Black liquor alkaline lignin and lignosulfonate were liquefied from280-350℃. Theantioxidant abilities of liquefaction products were tested and compared with the raw materials.Results showed that after hydrothermal liquefaction, both the total phenol content and unitantioxidant power of the two lignin liquefaction products were improved, and alkaline ligninliquefaction products had a larger increase than lignosulfonate liquefaction products. Theinfluences of reaction time and temperature on oil yield, total phenol content and antioxidantpower of alkaline lignin liquefaction products were discussed. The total phenol content wasfound to have certain relationships with the antioxidant abilities. The suitable conditions foralkaline lignin hydrothermal liquefaction were at300℃,30min or320℃,15min. Moreover,thermal oxidation stability tests of tung oil showed that the addition of lignin liquefactionproducts obviously increased the oxidation stability time of tung oil at a relative lowtemperature (130℃), however, the antioxidant activity of lignin liquefaction products at150℃was somewhat low. So, it can be inferred that lignin hydrothermal liquefaction productshave the potential to become the valueable antioxidant.
Alkaline lignin was liquefed under hydrothermal conditions at270-330℃, and the totaloil yield reached28.3wt%at a reaction temperature of300℃. The liquefed products wereeffectively separated into four main types of substances: benzenediols, monophenolichydroxyl products, weak-polar products, and water-soluble products (low-molecular-weightorganic acids, alcohols, etc.). The production process and yield of each classifed productswere discussed. More than half of the oil products were phenolics. A mechanism for phenolicproducts production from lignin liquefaction was proposed. The results indicated that thedecomposition of lignin under hydrothermal conditions occured mainly by three steps:hydrolysis and cleavage of the ether bond and the C-C bond, demethoxylation, and alkylation.Moreover, we found that higher temperature would favour the demethoxylation and alkylationreactions.
Hydrothermal carbonization of cellulose, lignin, D-xylose (substitute for hemicelluloses),and wood meal (WM) was experimentally conducted between225and265℃, and thechemical and structure properties of the hydrochars were investigated. The hydrochar yieldwas between45and60%, and the yield trend of the feedstock was lignin> WM> cellulose>D-xylose. The hydrochars seemed stable before300℃, and aromatic structure was formed inall of these hydrochars. The C content, C recovery, energy recovery, ratios of C/O and C/H inall of these hydrochars were among63-75%,80-87%,78-89%,2.3-4.1, and12-15,respectively. The higher heating value (HHV) of the hydrochars was among24-30MJ/kg,with an increase of45-91%compared with the corresponding feedstock. Temperature wasvery important in the hydrothermal carbonization process. Higher temperatures generallyaccelerated the hydrothermal carbonization of biomass, resulting in hydrochars with loweryield, lower volatile matter content, lower ion exchange capacity, lower O-containingfunctional groups, but higher C content. The lignin hydrothermal carbonization mechanismwas that lignin hydrothermal carbonization products were made of polyaromatic hydrocharsand phenolic hydrochars.
Formaldehyde was originally used as a polymerization agent to perform hydrothermalcarbonization of black liquor for solid fuel production from220to285℃. Compared tohydrochar prepared without formaldehyde, hydrochar produced in the presence of a2.8wt%formaldehyde solution (hydrochar-F) had0.27~1.13times higher yield,0.021~0.36times higher heating value (HHV),0.20~1.31times higher C recovery efficiency,0.20~1.44timeshigher total energy recovery efficiency,0.36~0.49times lower sulfur content, and0.11~0.52times lower ash content. The HHV of hydrochar-Fs were ranged from2.2×104to3.0×104kJ/kg, while the HHV of hydrochar-F produced at285℃was1.90times greater than that ofthe raw material (black liquor solid). Hydrothermal conversion of lignosulfonate with orwithout formaldehyde as polymerization agent was conducted at320℃. Compared with thehydrochar produced without formaldehyde addition (WF-hydrochar), the yield and surfacearea of the hydrochar produced with formaldehyde addition (F-hydrochar) increased33.8%and46.4%respectively. The Langmuir saturated adsorption capacity of Cu2+, methyl orange(MO) for F-hydrochar was19.6,16.3mg·g-1respectively. The Langmuir saturated adsorptioncapacity of MO for WF-hydrochar was18.9mg·g-1.
Amorphous hydrochar sulfonated catalysts were generated from four kinds of biomass(lignin, cellulose, wood meal and D-xylose) by hydrothermal carbonization at varioustemperatures (225,245and265℃) followed by sulfonation, with a yield of36-56%. All ofthese catalysts owned aromatic structure, hydroxyl and carboxyl groups, and with a density ofSO3H groups between0.56and0.87mmol/g.5-Hydroxymethylfurfural (HMF) was directlyproduced from inulin in ionic liquids (ILs) through one step with the addition of hydrocharsulfonated catalysts, with a factual yield of47-65%at100℃,60min. Moderate extension ofreaction time (from30to90min) and increase of temperature (from80to120℃) promotedHMF production. The hydrochar sulfonated catalysts showed high reusability (the factualyield retained61%even after being used five times), as well as good catalytic activitycompared with traditional solid acid catalysts.
Hydrolysis of two kinds of lignin model compounds was originally conducted with sixdifferent solid acid catalysts (732cation resin, HZSM-5, sulfated zirconia, Amberlyst-15cation resin, C225-SO3H and L225-SO3H). Monobenzone was used as the-O-4bond type oflignin model compound, and hydroquinone was the main product with a yield andproductivity of among5.6-47.7%,57.1-92.0%, respectively. Guaiacylglycerol--guaiacylether (GG) was employed as the-O-4bond type of lignin model compound, while guaiacolwas found the main product with a yield and productivity of among22.2-38.0%and63.0-100%, respectively. Compared with the homogeneous catalyst H2SO4, Amberlyst-15 cation resin, C-SO3H and L-SO3H showed comparable efficiency of conversion ratio butmuch higher selectivity of the phenolic products. These hydrochar sulfonated catalystsshowed unique advantages in the catalytic degradation and hydrolysis reactions, consideringthe renewable, aboundant, and low-cost properties of biomass, application of hydrocharsulfonated catalysts should be one of the potential industrialization way for biomasshydrothermal conversion.
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