CN101255348B - 由固定化脂肪酶-透醇膜生物反应器制备生物柴油的方法 - Google Patents
由固定化脂肪酶-透醇膜生物反应器制备生物柴油的方法 Download PDFInfo
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Abstract
本发明公开了一种利用固定化脂肪酶-透醇膜生物反应器制备生物柴油的方法。将脂肪酶通过物理吸附固定于中空纤维透醇膜的表面，制备固定化脂肪酶的膜组件，然后组装为酶-膜生物反应器。油脂走膜组件的壳程，低碳醇则走膜组件的管程，在固定化脂肪酶的催化作用下油脂化为生物柴油。利用低碳醇选择性透过中空纤维膜来提供生物柴油制备过程中所需的低碳醇，从而有效避免了由底物引起的酶活抑制作用，能够高效制备生物柴油。而且，避免了溶剂清洗与分批加料，符合绿色化学的发展方向，能降低成本、简化工艺、实现连续化生产。
Description
技术领域
本发明属于生物能源技术领域。具体涉及一种能选择性透过低碳醇的固定化脂肪酶聚合物膜及其生物反应器用于制备生物柴油的方法。
背景技术
生物柴油是由可再生的油脂原料经酯交换所合成的长链脂肪酸甲酯(或乙酯等)，是一种可代替柴油的环保燃料油。固定化酶法制备生物柴油具有效率高、能耗低(反应条件温和)、选择性好、醇用量小、副产物少、环境友好(无需进行废液处理)等优点。脂肪酶能够高效催化醇与脂肪酸甘油酯进行酯交换反应，但是固定化酶法又存在脂肪酶价格偏高、副产物甘油在酶表面的吸附使酶的稳定性下降和使用寿命缩短、底物甲醇或乙醇(即低碳醇)能剥夺脂肪酶的必需水进而破坏维持酶蛋白功能构象的氢键体系和导致酶活性下降乃至失活等一系列问题。
CN1181161C、CN1325606C、CN1190471C等专利公开了利用短链脂肪酸酯作为酰基受体制备生物柴油的方法。专利US6398707B1则公开了一种采用不少于三个碳原子的醇来“清洗”固定化酶以恢复酶活的方法。对脂肪酶进行预处理以及分批添加甲醇等方法也得到采用，对此黄凌云等人在“预处理固定化脂肪酶催化合成生物柴油”一文中有所描述(《中国油脂)》，2007，32(7)：47-50)。直接用低碳醇作为酰基受体更有利于生物柴油制备，但对酶进行预处理或清洗需要耗费大量溶剂，增加了生产成本和实际操作困难，同时不利于环境保护。
有关聚合物分离膜用于生物柴油制备的报道很少。Guerreiro等人报道了聚合物膜在生物柴油制备过程中的应用(Transesterification of soybean oil oversulfonic acid functionalised polymeric membranes，Catalysis Today，2006，118：166-171)，但他们所使用的聚合物膜主要是作为固体酸催化剂，属于化学催化法。CN1276962C公开了一种通过膜过滤技术将生物柴油制备与甘油转化为丙二醇两个过程偶联起来的方法，但该方法的主要目的是偶联生产丙二醇，生物酶催化制备生物柴油过程中所需的甲醇仍然采用分批加料或滴加的方式。由此可见，在避免底物抑制而降低酶活的同时实现连续化生产并简化生产工艺等方面，现有工艺存在明显不足。
发明内容
本发明的目的是提供一种制备生物柴油的方法，将脂肪酶通过物理吸附固定于透醇中空纤维膜表面，制备固定化脂肪酶的膜组件，然后组装为酶-膜生物反应器，油脂经泵走膜组件的壳程，流速为1～5L/h，同时流速为2～100L/h的低碳醇走膜组件的管程，并透过中空纤维膜进入膜组件壳程，在固定化脂肪酶的催化作用下油脂与低碳醇循环反应2～10h后即转化为生物柴油。由于采用选择性透醇膜连续提供低碳醇，低碳醇在油脂相浓度较低，固定化酶的活性显著提高。
一种制备生物柴油的方法，包括如下步骤：
(1)将脂肪酶通过物理吸附固定于透醇中空纤维膜表面，制备固定化脂肪酶的膜组件，然后组装为酶-膜生物反应器。
所述透醇中空纤维膜为聚丙烯、聚乙烯、聚偏氟乙烯。
所述脂肪酶可以为本领域通用的脂肪酶，例如来源于Candida antarctica、Rhizomucor miehei、Thermomyces lanuginosus、Burkholderia acepacia、Pesudomonas fluorescens、Aspergillus niger、Mucor miehei或Candida rugosa的脂肪酶。
(2)将5L油脂注入油脂储罐1，经泵2走膜组件3壳程，流速为1～5L/h。其中油脂为生物油脂，包括鱼油、猪油、蓖麻油、菜籽油、大豆油、花生油、玉米油、棉籽油、米糠油、藻类油脂、废食用油和炼油脚料等。
(3)低碳醇储罐9内的甲醇或乙醇由泵8走膜组件3管程，并透过中空纤维膜进入壳程，在固定化酶的催化作用下与壳程的油脂进行反应。低碳醇的流速为2～100L/h，不断循环。
(4)油脂循环2～10h后由阀门4经分液器5分离后收集于生物柴油储罐6，即得到生物柴油；甘油经分液器5进入甘油储罐7。
本发明的效果和益处在于利用低碳醇选择性透过中空纤维膜来提供生物柴油制备过程中所需的低碳醇，从而有效避免了由底物低碳醇引起的酶活抑制作用，能够高效制备生物柴油。而且，避免了溶剂清洗与分批加料，符合绿色化学的发展方向，能降低成本、简化工艺、实现连续化生产。
附图说明
图1为本发明制备生物柴油装置结构示意图。
具体实施方式
参照附图说明本发明技术方案的实施方式，其中原料储罐1中的油脂经泵2走固定化酶膜组件3的壳程，循环反应一定时间后经阀门4进入分液器5，分液后生物柴油进入生物柴油储罐6，甘油进入甘油储罐7；低碳醇由低碳醇储罐9经泵8走固定化酶膜组件3的管程，循环使用。其中壳程指固定化酶膜组件3的中空纤维膜之间或中空纤维膜与壳体之间的空间；管程指固定化酶膜组件3的中空纤维膜内部空间。
以下实施例对本发明做更详细的描述，但所述实例不构成对本发明的限制。
实施例1
将来源于Candida antarctica的脂肪酶通过物理吸附固定于聚二甲基硅氧烷中空纤维膜表面，制成膜组件，联入酶-膜生物反应器。将5L鱼油注入油脂储罐1，经泵2走膜组件3壳程，流速为4L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为20L/h。循环2h后生物柴油得率约为95％。
实施例2
将来源于Rhizomucor miehei的脂肪酶通过物理吸附固定于聚三甲基硅丙炔中空纤维膜表面，制成膜组件，联入酶-膜生物反应器。将5L猪油注入油脂储罐1，经泵2走膜组件3壳程，流速为4L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为20L/h。循环4h后生物柴油得率约为96％。
实施例3
将来源于Thermomyces lanuginosus的脂肪酶通过物理吸附固定于壳聚糖中空纤维膜表面，制成膜组件，联入酶-膜生物反应器。将5L蓖麻油注入油脂储罐1，经泵2走膜组件3壳程，流速为5L/h；低碳醇储罐9内的乙醇由泵7走膜组件3管程，流速为100L/h。循环10h后生物柴油得率约为100％。
实施例4
将来源于Burkholderia acepacia的脂肪酶通过物理吸附固定于以聚酯为基膜和壳聚糖为透醇表层的复合中空纤维膜表面，制成膜组件，联入酶-膜生物反应器。将5L菜籽油注入油脂储罐1，经泵2走膜组件3壳程，流速为4L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为40L/h。循环6h后生物柴油得率约为100％。
实施例5
将来源于Pesudomonas fluorescens的脂肪酶通过物理吸附固定于以聚丙烯为基膜及聚二甲基硅氧烷为透醇表层的复合中空纤维膜表面，制成膜组件，联入酶膜反应器。将5L大豆油注入油脂储罐1，经泵2走膜组件3壳程，流速为4L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为40L/h。循环6h后生物柴油得率约为99％。
实施例6
将来源于Aspergillus niger的脂肪酶通过物理吸附固定于以聚乙烯为基膜及聚二甲基硅氧烷为透醇表层的复合中空纤维膜表面，制成膜组件，联入酶膜反应器。将5L花生油注入油脂储罐1，经泵2走膜组件3壳程，流速为4L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为20L/h。循环4h后生物柴油得率约为96％。
实施例7
将来源于Mucor miehei的脂肪酶通过物理吸附固定于以聚偏氟乙烯为基膜及聚三甲基硅丙炔为透醇表层的复合中空纤维膜表面，制成膜组件，联入酶膜反应器。将5L玉米油注入油脂储罐1，经泵2走膜组件3壳程，流速为4L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为40L/h。循环6h后生物柴油得率约为99％。
实施例8
将来源于Candida rugosa的脂肪酶通过物理吸附固定于以聚丙烯腈为基膜及聚二甲基硅氧烷为透醇表层的复合中空纤维膜表面，制成膜组件，联入酶膜反应器。将5L棉籽油注入油脂储罐1，经泵2走膜组件3壳程，流速为4L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为20L/h。循环6h后生物柴油得率约为98％。
实施例9
将来源于Candida antarctica的脂肪酶通过物理吸附固定于以聚醚砜为基膜及聚二甲基硅氧烷为透醇表层的复合中空纤维膜表面，制成膜组件，联入酶膜反应器。将5L米糠油注入油脂储罐1，经泵2走膜组件3壳程，流速为4L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为20L/h。循环6h后生物柴油得率约为98％。
实施例10
将来源于Candida antarctica的脂肪酶通过物理吸附固定于以聚乙烯醇为基膜和聚二甲基硅氧烷为透醇表层的复合中空纤维膜表面，制成膜组件，联入酶膜反应器。将5L藻类油脂注入油脂储罐1，经泵2走膜组件3壳程，流速为4L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为20L/h。循环6h后生物柴油得率约为97％。
实施例11
将来源于Candida antarctica的脂肪酶通过物理吸附固定于以纤维素为基膜和聚二甲基硅氧烷复合为透醇表层的中空纤维膜表面，制成膜组件，联入酶膜反应器。将5L废食用油注入油脂储罐1，经泵2走膜组件3壳程，流速为4L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为20L/h。循环10h后生物柴油得率约为95％。
实施例12
将来源于Candida antarctica的脂肪酶通过物理吸附固定于以聚酰亚胺为基膜及聚二甲基硅氧烷为透醇表层的复合中空纤维膜表面，制成膜组件，联入酶膜反应器。将0.5L炼油脚料注入油脂储罐1，经泵2走膜组件3壳程，流速为1L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为2L/h。循环10h后生物柴油得率约为95％。
实施例13
将来源于Candida antarctica的脂肪酶通过物理吸附固定于以聚偏氟乙烯为基膜和聚二甲基硅氧烷为透醇表层的复合中空纤维膜表面，制成膜组件，联入酶膜反应器。将2L菜籽油和3L大豆油的混合物注入油脂储罐1，经泵2走膜组件3壳程，流速为4L/h；低碳醇储罐9内的甲醇由泵8走膜组件3管程，流速为20L/h。循环6h后生物柴油得率约为96％。
Claims (5)
1.一种由固定化脂肪酶-透醇膜生物反应器制备生物柴油的方法，其特征在于：将脂肪酶通过物理吸附固定于透醇中空纤维膜表面，制备固定化脂肪酶的膜组件，然后组装为酶-膜生物反应器，油脂经泵走膜组件的壳程，流速为1～5L/h，同时流速为2～100L/h的低碳醇走膜组件的管程，并透过中空纤维膜进入膜组件壳程，在固定化脂肪酶的催化作用下油脂与低碳醇循环反应2～10h后即转化为生物柴油。
2.按权利要求1所述的由固定化脂肪酶-透醇膜生物反应器制备生物柴油的方法，其特征在于所述的脂肪酶为来源于Candida antarctica、Rhizomucor miehei、Thermomyces lanuginosus、Burkholderia acepacia、Pesudomonas fluorescens、Aspergillus niger、Mucor miehei或Candida rugosa的脂肪酶。
3.按权利要求1所述的由固定化脂肪酶-透醇膜生物反应器制备生物柴油的方法，其特征在于所述透醇中空纤维膜为能选择性渗透甲醇或乙醇的硅橡胶膜或壳聚糖膜，或是以硅橡胶膜或壳聚糖膜为表层的复合膜；所述硅橡胶膜为聚二甲基硅氧烷或聚三甲基硅丙炔，所述复合膜的基膜为聚酯、聚丙烯、聚乙烯、聚偏氟乙烯、聚丙烯腈、聚醚砜、聚乙烯醇、纤维素或聚酰亚胺。
4.按权利要求1所述的由固定化脂肪酶-透醇膜生物反应器制备生物柴油的方法，其特征在于所述油脂为鱼油、猪油、蓖麻油、菜籽油、大豆油、花生油、玉米油、棉籽油、米糠油、藻类油脂、废食用油和炼油脚料中的一种或混合物。
5.按权利要求1所述的由固定化脂肪酶-透醇膜生物反应器制备生物柴油的方法，其特征在于所述低碳醇为甲醇或乙醇或它们的混合物。
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