CN1238469C - 有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺 - Google Patents
有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺 Download PDFInfo
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Abstract
本发明公开了属于生物油脂合成领域的利用有机溶剂作为反应介质的一种有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺。该工艺是以短链醇ROH作为反应酰基受体，用一些对酶反应活性没有负面影响的相对亲水的有机溶剂作为反应介质，利用生物酶催化油脂原料进行转酯反应合成生物柴油。将短链醇、油脂和脂肪酶装入具塞三角瓶中或酶反应器中混合均匀，置于可自动控温的往复摇床中或适于酶催化反应的各种生化反应器中加热反应后，油脂原料几乎可完全转化生成生物柴油和副产物甘油，生物柴油得率达94%以上。这些新型有机介质反应体系可以促进甲醇等短链醇在油脂中的溶解，并且可以部分溶解副产物甘油，从而可显著提高酶反应活性、缩短酶促反应时间并延长酶的使用寿命。
Description
技术领域
本发明属于生物油脂合成领域，特别涉及利用有机溶剂作为反应介质的一种有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺。
背景技术
油脂工业的新前景-生物柴油是由生物油脂原料通过转酯反应生成的长链脂肪酸酯类物质，是一种新型的无污染可再生能源，被称为生物柴油。其燃烧性能可以与传统的石油系柴油媲美，由于生物柴油燃烧后发动机排放出的尾气里有害物质比传统石化柴油降低了50％。目前生物柴油的研究和应用已经受到了广泛的关注。
目前生物柴油主要是用化学法生产，即用动植物油脂和一些低碳醇(甲醇或乙醇)在碱或者酸性催化剂作用下进行转酯反应，生成相应的脂肪酸甲酯或乙酯。化学法制备生物柴油存在如下一些不可避免的缺点：①油脂原料中的游离脂肪酸和水严重影响反应的进行；②甲醇在油脂中溶解性不好，易导致乳化液的形成从而使得后续处理过程复杂；③工艺要求甲醇用量大大超过反应摩尔比，过量甲醇的蒸发回流增大过程能耗。
由于利用生物酶法合成生物柴油具有反应条件温和、无污染物排放、油脂原料中的游离脂肪酸和少量水不影响酶促反应等优点，符合绿色化学的发展方向，因而日益受到人们的重视。
但同化学方法相比，生物酶法也存在如下一些亟待解决的问题。在[Shimada Yujiet al.Enzymatic al coholysis for biodiesel fuel production and applicationof the reaction to oil processing，Journal of Molecular Catalysis B：Enzymatic，2002，17：133-142]文献中报道：甲醇、乙醇等短链醇在油脂原料中的溶解性较差，不利于反应的进行；其次，过量醇的存在会导致脂肪酶严重失活，故在利用生物酶法生产生物柴油的工艺过程中，多采用分批加入短链醇的方式以缓解其对酶的毒害作用。这种方式操作繁琐，反应时间较长；另外，以短链醇作为反应的酰基受体，反应过程中有副产物甘油产生，亲水性的甘油容易附着在固定化酶内孔及外表面，从而对酶的活性位点形成“屏蔽”，严重影响酶反应活性；而且，同化学方法相比，酶法合成生物柴油的得率相对较低。为改善以上情况，一些学者尝试采用有机溶剂反应体系合成生物柴油，文献[Shimada Yuji et al.Enzymatic alcoholysis for biodiesel fuel production and application ofthe reaction to oil processing，Journal of Molecular Catalysis B：Enzymatic，2002，17：133-142]报道：采用一些疏水性较强的有机溶剂如己烷、环己烷、石油醚等作为反应介质。这些疏水性有机溶剂可以很好的溶解油脂，在一定程度上能促进反应的进行；但由于这些疏水性较强的有机溶剂并不能有效溶解甲醇等低碳醇以及副产物甘油，故对酶反应活性、酶的使用寿命以及生物柴油得率等并未有明显改善。
发明内容
本发明的目的在于提出一种有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺。该工艺是以短链醇ROH作为反应酰基受体，用一些对酶反应活性没有负面影响的相对亲水的有机溶剂作为反应介质，利用生物酶催化油脂原料进行转酯反应合成生物柴油。其特征在于：将醇脂摩尔比为3∶1～6∶1的短链醇和油脂、为油脂体积20-200％的叔丁醇、或短链脂肪酸酯RCOOR’作为相对亲水的有机溶剂和占油脂质量2～30％的Lipozyme TL、Lipozyme RM、Novozym 435或它们的混合物作微生物脂肪酶，装入具塞三角瓶中混合均匀，置于可自动控温的往复摇床中加热20℃至小于30℃或大于30℃至60℃，反应5-24小时后，油脂原料可完全转化生成生物柴油和副产物甘油。
所述短链脂肪酸酯RCOOR’中R和R’为具有1-4个碳原子的烷基。
本发明的有益效果是提高了酶反应活性、延长了酶的使用寿命并显著提高了生物柴油得率。这些新型有机介质反应体系可以促进甲醇等短链醇在油脂中的溶解，有效降低短链醇对酶反应活性的负面影响；其次，在这种有机介质反应体系中，可以一次性加入反应所需低碳醇，从而可显著缩短酶促反应时间、提高生物柴油得率，生物柴油得率达94％以上；另外，这些相对亲水的有机溶剂在一定程度上可以部分溶解甘油，可以有效降低反应物低碳醇以及副产物甘油对酶反应活性的负面影响、显著提高酶反应活性，有效改善甘油对固定化酶孔径的“屏蔽”状况，提高酶反应活性并延长酶的使用寿命。
具体实施方式
本发明提出一种有机介质反应体系中脂肪酶转化油脂生产生物柴油新工艺。该工艺是以短链醇ROH(R为具有1-5个碳原子的烷基)作为反应酰基受体，用一些对酶反应活性没有负面影响的相对亲水的有机溶剂叔丁醇、1，4-二氧六环或短链脂肪酸酯RCOOR’(R和R’为具有1-4个碳原子的烷基)作为反应介质，利用生物酶催化油脂原料进行转酯反应合成生物柴油。其工艺是将醇脂摩尔比为3∶1～6∶1的短链醇和油脂、为油脂体积20-200％的有机溶剂和油脂质量2～30％的脂肪酶(该脂肪酶为微生物脂肪酶，包括Lipozyme TL，Lipozyme RM，Novozym435或它们的混合物)，装入具塞三角瓶中或适于酶催化反应的各种生化反应器中混合均匀，置于可自动控温的往复摇床中加热至20℃～60℃，反应5-24小时后，油脂原料可完全转化生成生物柴油和副产物甘油。
上述油脂为生物油脂包括植物油脂(蓖麻油、菜籽油、大豆油、花生油、玉米油、棉子油、米糠油或藻类油脂)、动物油脂(鱼油、猪油)、废食用油或炼油脚料。上述短链醇为甲醇、乙醇、丙醇、丁醇或戊醇。
下面通过实施例来进一步说明本发明。
实施例1
将摩尔比为4∶1的甲醇和菜籽油(菜籽油9.65g)和基于油脂体积100％的叔丁醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至40℃后，加入油脂质量10％的固定化脂肪酶Novozym 435开始反应，经6小时后生产出生物柴油9.64g，生物柴油得率约为100％。
实施例2
将摩尔比为3∶1的甲醇和大豆油(大豆油9.65g)和基于油脂体积20％的叔丁醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至20℃后，加入油脂质量2％的固定化脂肪酶Novozym 435开始反应，经24小时后生产出生物柴油9.17g，生物柴油得率为95％。
实施例3
将摩尔比为5∶1的乙醇和棉籽油(棉籽油9.65g)、基于油脂体积200％的甲酸甲酯，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至60℃后，加入基于油脂质量10％的固定化脂肪酶Novozym 435开始反应，经12小时后生产出生物柴油9.1g，生物柴油得率为94％。
实施例4
将摩尔比为3∶1的丁醇和废食用油(废食用油9.65g)、基于油脂体积80％的叔丁醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至40℃后，加入基于油脂质量10％的固定化脂肪酶Novozym 435开始反应，经7小时后生产出生物柴油9.65g，生物柴油得率为100％。
实施例5
将摩尔比为4∶1的甲醇和猪油(猪油9.65g)、基于油脂体积100％的1，4二氧六环，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至50℃后，加入基于油脂质量20％的固定化脂肪酶Novozym 435开始反应，经10小时后生产出生物柴油9.46g，生物柴油得率为98％。
实施例6
将摩尔比为3∶1的甲醇和大豆油(大豆油9.65g)、基于油脂体积50％的叔于醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至40℃后，加入基于油脂质量20％的固定化脂肪酶Lipozyme TL开始反应，经10小时后生产出生物柴油9.1g，生物柴油得率为94％。
实施例7
将摩尔比为4∶1的戊醇和菜籽油(菜籽油9.65g)、基于油脂体积100％的丁酸丁酯，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至50℃后，加入基于油脂质量30％的固定化脂肪酶Lipozyme TL开始反应，经8小时后生产出生物柴油9.17g，生物柴油得率为95％。
实施例8
将摩尔比为3∶1的乙醇和棉籽油(棉籽油9.65g)、基于油脂体积80％的叔丁醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至40℃后，加入基于油脂质量20％的固定化脂肪酶Lipozyme RM开始反应，经10小时后生产出生物柴油9.1g，生物柴油得率为94％。
实施例9
将摩尔比为3∶1的甲醇和鱼油(鱼油9.65g)、基于油脂体积50％的1，4-二氧六环，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至50℃后，加入基于油脂质量2％的固定化脂肪酶Novozym 435和10％的Lipozyme TL开始反应，经18小时后生产出生物柴油9.46g，生物柴油得率为98％。
实施例10
将摩尔比为4∶1的乙醇和米糠油(米糠油9.65g)、基于油脂体积150％的叔丁醇，装入具塞三角瓶中混合均匀，并置于可自动控温的往复摇床中加热至40℃后，加入基于油脂质量2％的固定化脂肪酶Novozym 435和10％的Lipozyme RM开始反应，经10小时后生产出生物柴油9.36g，生物柴油得率为97％。
实施例11：
将实施例1中反应后的脂肪酶直接滤出用于下一批次反应，其他反应条件同实施例1，如此将脂肪酶连续回用10次。在第10个反应批次中，反应6小时可生产出生物柴油9.62g，生物柴油得率仍高达99％。
根据上述实施例，以叔丁醇、1，4-二氧六环、短链脂肪酸酯RCOOR’(R、R’为具有1-4个碳原子数的烷基)作为有机介质反应体系，短链醇ROH(R为具有1-5个碳原子数的烷基)作为反应酰基受体时，在适宜的温度范围下加入油脂质量2％～30％的固定化脂肪酶Novozym 435(来源于Candida antarctica)、LipozymeRM(来源于Rhizomucor miehei)或Lipozyme TL(来源于Thermomyceslanuginosus)，不同生物油脂原料(蓖麻油、菜籽油、棉籽油、废食用油、大豆油、鱼油、猪油、炼油下脚料、藻类油脂等)都能被高效转化生成生物柴油。短链醇与油脂最优的反应摩尔比为3∶1～5∶1，最优的有机溶剂添加量为基于油脂体积的50％-100％，最优的反应温度为30℃～50℃。
Claims (3)
1.一种有机介质反应体系中脂肪酶转化油脂生产生物柴油工艺，该工艺是以短链醇ROH作为反应酰基受体，用叔丁醇或短链脂肪酸酯RCOOR’作为溶剂，其中短链脂肪酸酯RCOOR’中R和R’为具有1-4个碳原子的烷基，并利用生物酶催化油脂原料进行转酯反应合成生物柴油；其特征在于：将醇脂摩尔比为3∶1～6∶1的短链醇和油脂、以油脂体积20-200％的有机溶剂为反应介质，和占油脂质量2～30％的脂肪酶，装入具塞三角瓶中或其它酶反应器中混合均匀，加热20℃至小于30℃或大于30℃至60℃，反应5-24小时后，油脂原料可完全转化生成生物柴油和副产物甘油。
2.根据权利要求1所述有机介质反应体系中脂肪酶转化油脂生产生物柴油工艺，其特征在于：所述脂肪酶为微生物脂肪酶，包括Lipozyme TL、Lipozyme RM、Novozym435或它们的混合物。
3.根据权利要求1所述有机介质反应体系中脂肪酶转化油脂生产生物柴油工艺，其特征在于：所述油脂为生物油脂，包括蓖麻油、棉籽油、猪油、酸化油、炼油下脚料或藻类油脂。
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| EP04797388A EP1705238B1 (en) | 2004-01-16 | 2004-11-29 | A new process for producing biodiesel from oils and fats catalyzed by lipase in organic medium reaction system |
| BRPI0418062A BRPI0418062B1 (pt) | 2004-01-16 | 2004-11-29 | processo para a produção de biodiesel a partir de óleo renovável na presença de catálise por lipase em um sistema de reação em meio orgânico |
| PCT/CN2004/001372 WO2005075615A1 (fr) | 2004-01-16 | 2004-11-29 | Nouveau procede de production de biodiesel a partir d'huiles et de graisses catalysees par lipase dans un systeme de reaction a milieu organique |
| US10/597,123 US7550278B2 (en) | 2004-01-16 | 2004-11-29 | Process for producing biodiesel from renewable oil under lipase catalysis in an organic medium reaction system |
| AT04797388T ATE446353T1 (de) | 2004-01-16 | 2004-11-29 | Neues verfahren zur herstellung von biodiesel aus ölen und fetten unter lipasekatalyse in einem organischen medium als reaktionssystem |
| CA2553653A CA2553653C (en) | 2004-01-16 | 2004-11-29 | A process for producing biodiesel from renewable oil under lipase catalysis in an organic medium reaction system |
| DE602004023761T DE602004023761D1 (de) | 2004-01-16 | 2004-11-29 | Neues verfahren zur herstellung von biodiesel aus ölen und fetten unter lipasekatalyse in einem organischen medium als reaktionssystem |
| HK06114093.1A HK1094229A1 (en) | 2004-01-16 | 2006-12-22 | A new process for producing biodiesel from oils and fats catalyzed by lipase in organic medium reaction system |
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| CN101418322B (zh) * | 2008-12-11 | 2011-09-14 | 清华大学 | 膜回收脂肪酶催化可再生油脂制备生物柴油的方法 |
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| US7550278B2 (en) | 2009-06-23 |
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| WO2005075615A1 (fr) | 2005-08-18 |
| DE602004023761D1 (de) | 2009-12-03 |
| CN1557913A (zh) | 2004-12-29 |
| CA2553653A1 (en) | 2005-08-18 |
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