CN108558795A - 一种生物质全组分转化利用的新工艺 - Google Patents
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Abstract
本发明公开了一种生物质全组分转化利用的新工艺,以水为溶剂,以NaHSO4、NH4HSO4和KHSO4中的一种、两种或三种按照任意比例混合作为催化剂,分阶段催化生物质反应制备糠醛,5‑羟甲基糠醛和生物质活性炭,本发明避免了现有的以硫酸为催化剂制备糠醛带来的操作不便、环境污染和资源浪费,产品多样化,提高企业抗风险能力,催化剂可以回收重复利,活性不下降,具有很好的环保效益。
Description
技术领域
本发明涉及一种生物质全组分转化利用的新工艺。
背景技术
生物质是丰富的可再生资源,包括陆地生物质和海洋生物质。木质纤维素类生物质主要由半纤维素、纤维素和木质素构成。通过生物质糖类降解可以制备许多次级化合物,这些化合物具有广泛的功能和用途。目前的生物质降解技术分为化学降解和生物降解。化学降解常采用的催化剂为矿物酸(如硫酸,盐酸,硝酸,磷酸等)、有机酸如(醋酸,草酸,对苯磺酸,马来酸等)或路易斯酸(如三氯化铬,二氯化铬,三氯化铁等);生物降解主要利用各种酶催化剂(如纤维素水解酶等)。现有的矿物酸催化剂催化生物质降解存在催化剂毒性大,操作不便,环境污染,设备腐蚀严重,催化剂难以回收利用等以及目标产物选择性差等缺陷,而有机酸存在催化活性低、成本高等缺陷,路易斯酸催化往往活性不高,需要采用离子液体复合催化,造成催化剂成本高,催化剂回收困难等缺陷。而酶催化降解虽然目标产物选择性高,但是存在反应速度慢,生物质预处理成本高等缺陷。另外,当前的糠醛厂家利用生物质中的半纤维素制备糠醛,产生的糠醛渣是一种固体废物,为了处理该固体废物,厂家采用部分糠醛渣作为锅炉燃料,剩余的部分糠醛渣制作成有机肥。这样虽然解决了固体废物问题,但是浪费了非常有用的资源。因为糠醛渣主要是纤维素与木质素,而且,糠醛渣里的纤维素和木质素经过提取糠醛的反应后,结构已经比较松散,非常适合进一步反应制备高附加值的化工品,纤维素可以进一步反应制备5-羟甲基糠醛和乙酰丙酸和甲酸,木质素可以进一步反应液化制备酚类化合物,如愈创木酚等。
发明内容
为了克服以上生物质降解利用存在的资源利用不合理和环境污染问题,本发明采用酸式盐NaHSO4、NH4HSO4和KHSO4作催化剂催化生物质降解液化,制备糠醛并联产5-羟甲基糠醛和生物质活性碳。
本发明解决技术问题所采用的技术方案是:
采用酸式盐NaHSO4、NH4HSO4和KHSO4中的一种或几种配置成一定浓度的水溶液,将所述的水溶液与生物质均匀混合,在一定温度下进行生物质的催化分解反应,通过控制温度、催化剂浓度和反应时间,达到分阶段选择性生成糠醛、五羟甲基糠醛和生物质活性碳的目的,所述的生物质包括但不限于玉米芯,稻草,麦秸,干蔗渣,所述的酸式盐催化剂循环使用。
本发明技术方案的具体操作方法描述如下:
取100个质量份的空气干燥基生物质,所述的空气干燥基生物质含水15-20%,粒度0.05-2厘米,加入150-200个质量份的水,再加入5-20个质量份的酸式盐催化剂,所述酸式盐为NaHSO4、NH4HSO4和KHSO4中的一种、两种或三种按照任意比例混合而成,在室温下搅拌均匀后,载入反应釜,在所述的反应釜底部通入压力8-10个大气压的水蒸气,反应温度170-200℃,反应过程中适当调节反应釜顶部蒸汽出口阀蒸汽流量,利用出口蒸汽携带出糠醛,糠醛提取阶段的反应时间为3-5小时;
糠醛提取完毕后,停止通入水蒸汽,再向反应釜中补充加入酸式盐和水,补充加入的酸式盐和水的质量与糠醛提取阶段的加入量相同,这样,反应釜中催化剂水溶液的浓度基本维持不变,但反应釜中催化剂和水的总量加倍,提高反应釜温度至210-230℃,密闭反应5-8小时,得到5-羟甲基糠醛,反应完毕后,对反应釜中的物质进行固液分离,固体为生物质活性炭,液相为5-羟甲基糠醛和酸式盐催化剂的水溶液,采用辛醇萃取分离出5-羟甲基糠醛,萃余相为酸式盐催化剂的水溶液,循环利用作新一轮反应催化剂。
本发明的有益效果如下:避免了现有的以硫酸为催化剂制备糠醛带来的操作不便和环境污染和资源浪费,产品多样化,提高企业抗风险能力,催化剂可以回收重复利,活性不下降,具有很好的环保效益。
具体实施例
下面结合实施例对本发明作进一步描述:
实施例1
取20千克空气干燥基玉米芯,所述的空气干燥基玉米芯含水18%,加入30千克水,再加入2千克NaHSO4催化剂,在室温下搅拌均匀后,载入直径0.35米,高1米的圆筒形反应釜,在所述的反应釜底部通入压力9个大气压的水蒸气,反应温度190℃,反应过程中适当调节反应釜顶部蒸汽出口阀蒸汽流量,利用出口蒸汽携带出糠醛,糠醛提取阶段的反应时间为5小时,提取糠醛的产率(以原始原料质量为基准)为9.6%,糠醛提取完毕后,停止通入水蒸汽,再向反应釜中补充加入酸式盐和水,补充加入的酸式盐和水的质量与糠醛提取阶段的加入量相同,使反应釜中催化剂和水的总量加倍,提高反应釜温度至210℃,密闭反应7小时,得到5-羟甲基糠醛,反应完毕后,对反应釜中的物质进行固液分离,固体为生物质活性炭,所述生物质活性炭产率(原料和活性炭均以空气干燥剂为基准计算,活性炭的空气干燥基水分为22.4%)为30%,液相为5-羟甲基糠醛和酸式盐催化剂的水溶液,通过萃取分离出5-羟甲基糠醛,提取糠醛的产率(以原始原料质量为基准)为11.3%,萃余相为酸式盐催化剂的水溶液,循环利用作新一轮反应催化剂。
实施例2
取20千克空气干燥基甘蔗渣,所述的空气干燥基甘蔗渣含水19%,加入30千克水,再加入3千克KHSO4催化剂,在室温下搅拌均匀后,载入直径0.35米,高1米的圆筒形反应釜,在所述的反应釜底部通入压力9个大气压的水蒸气,反应温度190℃,反应过程中适当调节反应釜顶部蒸汽出口阀蒸汽流量,利用出口蒸汽携带出糠醛,糠醛提取阶段的反应时间为4.5小时,提取糠醛的产率(以原始原料质量为基准)为8.2%,糠醛提取完毕后,停止通入水蒸汽,再向反应釜中补充加入酸式盐和水,补充加入的酸式盐和水的质量与糠醛提取阶段的加入量相同,使反应釜中催化剂和水的总量加倍,提高反应釜温度至220℃,密闭反应8小时,得到5-羟甲基糠醛,反应完毕后,对反应釜中的物质进行固液分离,固体为生物质活性炭,所述生物质活性炭产率(原料和活性炭均以空气干燥剂为基准计算,活性炭的空气干燥基水分为24.3%)为36%,液相为5-羟甲基糠醛和酸式盐催化剂的水溶液,通过萃取分离出5-羟甲基糠醛,提取糠醛的产率(以原始原料质量为基准)为9.8%,萃余相为酸式盐催化剂的水溶液,循环利用作新一轮反应催化剂。
实施例3
取20千克空气干燥基玉米芯,所述的空气干燥基玉米芯含水18%,加入30千克水,再加入2千克NH4HSO4和催化剂,在室温下搅拌均匀后,载入直径0.35米,高1米的圆筒形反应釜,在所述的反应釜底部通入压力9个大气压的水蒸气,反应温度190℃,反应过程中适当调节反应釜顶部蒸汽出口阀蒸汽流量,利用出口蒸汽携带出糠醛,糠醛提取阶段的反应时间为5小时,提取糠醛的产率(以原始原料质量为基准)为9.2%,糠醛提取完毕后,停止通入水蒸汽,再向反应釜中补充加入酸式盐和水,补充加入的酸式盐和水的质量与糠醛提取阶段的加入量相同,使反应釜中催化剂和水的总量加倍,提高反应釜温度至200℃,密闭反应6小时,得到5-羟甲基糠醛,反应完毕后,对反应釜中的物质进行固液分离,固体为生物质活性炭,所述生物质活性炭产率(原料和活性炭均以空气干燥剂为基准计算,活性炭的空气干燥基水分为23.5%)为33%,液相为5-羟甲基糠醛和酸式盐催化剂的水溶液,通过萃取分离出5-羟甲基糠醛,提取糠醛的产率(以原始原料质量为基准)为10.1%,萃余相为酸式盐催化剂的水溶液,循环利用作新一轮反应催化剂。
应当理解本文所述的例子和实施方式仅为了说明,本领域技术人员可根据它做出各种修改或变化,在不脱离本发明精神实质的情况下,都属于本发明的保护范围。
Claims (1)
1.一种生物质全组分转化利用的新工艺,以水为溶剂,以NaHSO4、NH4HSO4和KHSO4中的一种或两种或三种按照任意比例混合作为催化剂,分阶段催化生物质反应制备糠醛,5-羟甲基糠醛和生物质活性炭,其特征是如下过程操作:
取100个质量份的空气干燥基生物质,所述的空气干燥基生物质含水15-20%,加入150-200个质量份的水,再加入5-20个质量份的所述酸式盐催化剂,在室温下搅拌均匀后,载入反应釜,在所述的反应釜底部通入压力8-10个大气压的水蒸气,反应温度170-200℃,反应过程中适当调节反应釜顶部蒸汽出口阀蒸汽流量,利用出口蒸汽携带出糠醛,糠醛提取阶段的反应时间为3-5小时,糠醛提取完毕后,停止通入水蒸汽,再向反应釜中补充加入酸式盐和水,补充加入的酸式盐和水的质量与糠醛提取阶段的加入量相同,提高反应釜温度至210-230℃,密闭反应5-8小时,得到5-羟甲基糠醛,反应完毕后,对反应釜中的物质进行固液分离,固体为生物质活性炭,液相采用辛醇萃取分离出5-羟甲基糠醛,萃余相为酸式盐催化剂的水溶液,循环利用作新一轮反应催化剂。
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Cited By (3)
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CN111875568A (zh) * | 2020-07-27 | 2020-11-03 | 齐鲁工业大学 | 一种生物质分级炼制综合利用的方法 |
CN114345376A (zh) * | 2022-01-07 | 2022-04-15 | 浙江华康药业股份有限公司 | 一种酸性离子缓冲液催化剂及其制备方法以及使用该催化剂制备糠醛的系统和方法 |
CN115650938A (zh) * | 2022-10-11 | 2023-01-31 | 河南省生物基材料产业研究院有限公司 | 一种从生物质中同时提取糠醛和5-羟甲基糠醛的连续化方法和设备 |
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