CN105073706B - 生产可用作生物燃料的生物柴油和甘油醚混合物的单罐方法 - Google Patents

生产可用作生物燃料的生物柴油和甘油醚混合物的单罐方法 Download PDF

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CN105073706B
CN105073706B CN201480007373.XA CN201480007373A CN105073706B CN 105073706 B CN105073706 B CN 105073706B CN 201480007373 A CN201480007373 A CN 201480007373A CN 105073706 B CN105073706 B CN 105073706B
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G·尼古洛希
C·德拉戈
L·F·廖塔
V·拉帕罗拉
M·L·特斯塔
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Abstract

本发明涉及将含有一种或多种脂肪酸甘油三酯的原料转化为含有一种或多种脂肪酸烷基酯和叔烷基甘油的混合物的方法，该方法包括所述原料与式(I)化合物R‑O‑RI(I)的反应，其中：RI是具有1‑18个碳原子的烷基、链烯基或炔基；R是H或叔烷基；其中所述反应在酸性酯交换催化剂的存在下、通过用微波和/或超声和/或无线电波照射而进行。R‑O‑RI(I)。

Description

生产可用作生物燃料的生物柴油和甘油醚混合物的单罐方法
本发明涉及用于将各种来源的油和脂肪转化为含有脂肪酸甲基酯和叔丁基甘油的混合物(其可用作生物燃料)的“单罐”方法。
生物柴油是由可更新来源获得的无毒、生物可降解的代用燃料。由生物柴油燃烧产生的废气不含硫，并且所含有的颗粒物质的量比常规柴油少；因此，考虑到减少温室气体排出，生物柴油是矿物燃料的优良替代物。生物柴油是由植物油、主要是甘油三酯与甲醇在酸、碱或酶催化存在下进行的酯交换反应获得的脂肪酸甲基酯(FAME)混合物。
与醇进行的酯交换反应导致形成了FAME和甘油。该反应所产生的甘油必须从反应混合物中除去，或者通过进一步转化进行回收。因此，甘油的生成对方法的经济具有相当大的影响。
甘油被用于合成丙烯醛、丙二醇、1,3-丙二醇、甘油酸和碳酸甘油酯。但是，考虑到如今所生产的甘油的量非常大，其最便利的用途可以是将其转化为燃料添加剂。对于该目的，为了使甘油可挥发，已经研发了由(用磺酸基进行了官能化的中结构化(mesostructured)二氧化硅)和羟基化氟化镁催化的直接乙酰化方法以便以令人满意的方式获得三醋汀。但是，甘油的醚化仍然是生产用于内燃机和柴油机的添加剂的最佳方案。具体而言，甘油叔丁基醚(GTBE)是如今最广泛使用的，最便利的是二醚，因为单醚较不溶于常规燃料中，而三醚由于它们的制备要求大量的异丁烯而是特别不经济的。
在采用异丁烯或叔丁醇作为试剂进行的GTBE合成中，催化剂的酸性是关键的，在本文中已经研究了诸如硫酸或用磺酸基进行了官能化的中结构化二氧化硅的催化剂(J.A.Melero等人,Advances in the Synthesis and Catalytic Applications ofOrganosulfonic-Functionalized Mesostructured Materials.Chem.Rev.,106,2006,3790；J.A.Melero等人,Acid-catalyzed etherification of bio-glycerol andisobutylene over sulfonic mesostructured silicas.Appl.Catal.A-Gen.,346(2008)44–51；F.Frusteri等人,Catalytic etherification of glycerol by tert-butylalcohol to produce oxygenated additives for diesel fuel.Appl.Catal.A:Gen.,367(2009),77-83)。
专利申请WO2009/115274公开了生产生物柴油的方法，该方法包括含有脂肪酸甘油三酯的生物来源的混合物与甲基叔丁基醚在酸催化剂的存在下反应生产含有脂肪酸甲基酯和叔丁基甘油的混合物。该反应以两个阶段在不同温度下进行；第一个阶段在120-150℃的温度下进行2-3小时，第二个阶段在50-100℃的温度下进行5-6小时(第8页第1-9行)。实施例证明：甘油向醚的转化为30-40％，因此必须从最终反应混合物中除去未反应的甘油。
现在已经发现：通过用电磁波如微波、超声和/或无线电波在酸催化剂的存在下照射含有脂肪酸甘油三酯和甲基叔丁基醚的反应混合物，获得了几乎完全的脂肪酸甲基酯和叔丁基甘油的转化，而没有形成甘油。反应时间也相当大地减少。因此，从工业角度来看，该方法提供了重要的优点，因为它消除了甘油分离的最后阶段，并且能量消耗低于已知的方法。
还已经观察到：用含有大量游离脂肪酸的油有效地进行了该转化，游离脂肪酸通常限制了在生物柴油生产中使用常规工业方法，除非所述油进行了预处理以除去游离脂肪酸。这种优点证实了该方法的多样性，允许使用含有游离脂肪酸的不可食用的和废弃的植物油，例如来自公共饮食业的废弃的油炸油。
本发明的目的是将含有一种或多种脂肪酸甘油三酯的原料转化为含有一种或多种脂肪酸烷基酯和叔烷基甘油的混合物的方法，该方法包括所述原料与式(I)化合物的反应，
R-O-RI (I)
其中：
RI是具有1-18个碳原子的烷基、链烯基或炔基；
R是H或式(II)的叔烷基：
其中RIII、RIV和RV独立地是具有1-6个碳原子的直链或支链烷基、链烯基或炔基；
其中所述反应在酸性酯交换催化剂的存在下、通过用微波和/或超声和/或无线电波照射而进行，条件是，当R是H时，以与RI-OH等摩尔的量加入其中R如上文所定义的式R-OH的醇。
RIII、RIV和RV优选选自甲基、乙基、丙基、异丙基、丁基、叔丁基、乙烯基、丙烯基、异丙烯基、丁烯基、异丁烯基、己烯基、乙炔基、丙炔基和丁炔基。RIII、RIV和RV更优选是甲基。
R优选是叔丁基。
RI优选是甲基、乙基、丙基、异丙基或丁基。RI更优选是甲基。
该反应在下文流程中以图示进行了解释说明：
其中R和RI如上文所定义；
RII是饱和或不饱和的酰基，其以结构上同源或异质的方式存在于甘油结构中，以便例如构成棕榈酸甘油酯或棕榈油。
当RI是H时，必须加入等量的RI-OH醇。
在其中生物柴油将作为最终混合物获得的具体情况中，甘油三酯可以是生物柴油生产中常用的植物油之一，并且可以使用叔丁基甲基醚作为醚。如果使用相应的叔丁基醇代替叔丁基醚，则必须加入等量的甲醇。
含有一种或多种脂肪酸甘油三酯的原料可以含有：
-植物油，例如选自以下的那些：
椰子油、玉米油、棉籽油、橄榄油、棕榈油、花生油、菜子油、卡诺拉(canola)油、红花油、芝麻油、大豆油、葵花油、杏仁油、山毛榉坚果油、腰果油、榛子油、澳洲坚果油、松果油、阿月浑子油、核桃油、柑橘油、葡萄柚籽油、柠檬油、橙油、蓖麻油、大麻油(hemp oil)、芥子油、萝卜油、米糠油、海蓬子油(salicornia oil)、麻风树油(jatropha oil)、西蒙得木油、亚麻籽油、罂粟油、乌柏油(stillingia oil)、果树油、朝鲜蓟油、胡萝卜子油、芒果油和沙棘油；
-动物脂肪，例如选自以下的那些：牛脂、猪脂、禽脂肪和鱼油；
-各种来源的废油和脂肪，例如选自以下的那些：通常在餐馆和公共饮食业中使用的油和脂肪，存在于来自农业食品和鱼工业的废弃物中的，等等。
游离的或固定在载体上的酸催化剂优选选自：
-强的矿物酸如H2SO4、HNO3、HCl和HF和有机酸如CH3COOH、对甲苯磺酸及衍生物、烷基磺酸及衍生物；
-沸石、分子筛、磷酸盐、锆酸盐、高岭土、蒙脱石、柱撑粘土(pillared clays)、水滑石和酸离子交换树脂；
-固体酸或被酸适宜地官能化的物质，例如全氟氧化物和/或聚合物；具有不同的形态学如无定形和中结构化的二氧化硅和掺有Al、Ti或Zr的二氧化硅，吸收和/或共价结合于金属氧化物的杂多酸；金属氧化物，例如Al2O3和ZrO2，用磷酸和/或硫酸基进行了官能化；固定在无定形二氧化硅和/或中-和微-结构化二氧化硅上的有机磺酸和/或有机羧酸；稳定在二氧化硅和/或二氧化钛上的多金属氧酸盐(polyoxymetalates)；含有铌离子的Keggin结构，离子液体和/或碳纳米管(单和多层)，用有机磺酸和/或有机羧酸进行了官能化。
照射可以在微波、超声或无线电波电磁频率下或者在同时或依次的不同类型的电磁频率下进行。
“微波”指频率为0.3-300GHz的电磁辐射；优选使用频率为0.9-25GHz、特别是2-3GHz的微波。
“超声”指频率超出20KHz的机械声波；优选使用频率为20-100KHz的照射。
“无线电波”指频率为0-300GHz的电磁辐射；优选使用频率为1-100MHz、更优选10-50MHz的无线电波。
反应混合物优选被照射0.15至3-4小时。
反应中所用的酸催化剂可以是游离的酸催化剂或者被固定在载体上。
酸催化剂优选选自：
-强的矿物酸如H2SO4、HNO3、HCl和HF和有机酸如CH3COOH、对甲苯磺酸及衍生物、烷基磺酸及衍生物；
-沸石，例如ZSM-5、丝光沸石、Y、USY和β沸石、SAPO-11、SAPO-34，分子筛，磷酸盐，锆酸盐，高岭土，蒙脱石，柱撑粘土，水滑石，和酸离子交换树脂如和Nafion等；
-固体酸或被酸适宜地官能化的物质，例如全氟氧化物和/或聚合物如NafionSAC-13，固定在二氧化硅上；具有不同的形态学、例如无定形干凝胶或气凝胶、中-和微-结构化的二氧化硅和掺有Al、Ti或Zr的二氧化硅，如MCM41、MCM48、SBA-15和HMS，杂多酸(HPA)，吸收和/或共价结合于金属氧化物的酸，例如用磷酸和/或硫酸基进行了官能化的Al2O3和/或ZrO2氧化物；固定在无定形二氧化硅和/或中-和微-结构化二氧化硅上的有机磺酸和/或有机羧酸；稳定在二氧化硅和/或二氧化钛上的多金属氧酸盐；含有铌离子的Keggin结构；氧化铌；离子液体和/或碳纳米管(单和多层)，用有机磺酸和/或有机羧酸进行了官能化。
实施例
实施例1–棕榈酸甘油酯向棕榈酸甲基酯和甘油叔丁基醚的转化
将溶于1.6ml叔丁基-甲基醚(d 0.744mg/ml,MW 88.15,24.5mmol)中的500mg三棕榈酸甘油酯(MW 807.32,0.619mmol)放置在微波试管中，向溶液中加入30mg催化剂，所述催化剂由用磺酸基进行了官能化的无定形二氧化硅10％组成。将反应混合物在搅拌下通过20瓦特微波进行照射达一直到3小时的反应时间。HPLC分析证明三棕榈酸甘油酯几乎完全转化为棕榈酸甲基酯和比例为70:30的单-和二-叔丁基甘油醚混合物。如图1所示，没有形成游离甘油。
实施例2–大豆油向FAME和甘油叔丁基醚的转化
将溶于3.2ml叔丁基-甲基醚(d 0.744mg/ml,MW 88.15,24.5mmol)中的1g大豆油(d 0.917mg/ml,0.619mmol)放置在微波小瓶中，向溶液中加入30mg催化剂，所述催化剂由用磺酸基进行了官能化的无定形二氧化硅10％组成。将反应混合物在搅拌下通过20瓦特微波进行照射达一直到3小时的反应时间。HPLC分析证明大豆油几乎完全转化为脂肪酸甲基酯FAME和比例为70:30的单-和二-叔丁基甘油醚的混合物。如图2所示，没有形成游离甘油。

Claims (11)

1.将含有一种或多种脂肪酸甘油三酯的原料转化为含有一种或多种脂肪酸烷基酯和叔烷基甘油的混合物的方法，该方法包括所述原料与式(I)化合物的反应：
R-O-RI (I)
其中：
RI是甲基、乙基或丙基；
R是式(II)的叔烷基：
其中RIII、RIV和RV独立地是甲基、乙基或丙基；
其中所述反应在酸性酯交换催化剂的存在下、通过用微波照射而进行。
2.根据权利要求1的方法，其中式(II)中的RIII、RIV和RV选自甲基、乙基。
3.根据权利要求2的方法，其中式(II)中的RIII、RIV和RV是甲基。
4.根据权利要求1的方法，其中式(I)中的RI是甲基。
5.根据权利要求1的方法，其中式(I)化合物是叔丁基甲基醚。
6.根据权利要求1的方法，其中所述原料选自：
-植物油；
-动物脂肪。
7.根据权利要求1的方法，其中所述原料选自废油和脂肪。
8.根据权利要求6的方法，其中所述植物油选自椰子油、玉米油、棉籽油、橄榄油、棕榈油、花生油、菜子油、卡诺拉油、红花油、芝麻油、大豆油、葵花油、杏仁油、山毛榉坚果油、腰果油、榛子油、澳洲坚果油、松果油、阿月浑子油、核桃油、柑橘油、葡萄柚籽油、柠檬油、橙油、蓖麻油、大麻油、芥子油、萝卜油、米糠油、海蓬子油、麻风树油、西蒙得木油、亚麻籽油、罂粟油、乌柏油、果树油、朝鲜蓟油、胡萝卜子油、芒果油和沙棘油。
9.根据权利要求1-8任一项的方法，其中反应中所用的酸催化剂可以是游离的酸催化剂或者被固定在载体上。
10.根据权利要求9的方法，其中所述酸催化剂选自：
-强的矿物酸和有机酸；
-沸石、分子筛、磷酸盐、锆酸盐、高岭土、蒙脱石、柱撑粘土、水滑石和酸离子交换树脂；
-固体酸或被酸适宜地官能化的物质，其中所述固体酸或被酸适宜地官能化的物质是全氟氧化物和/或聚合物；具有不同的形态学的二氧化硅和掺有Al、Ti或Zr的二氧化硅，杂多酸，吸收和/或共价结合于金属氧化物的酸；固定在无定形二氧化硅和/或中-和微-结构化二氧化硅上的有机磺酸和/或有机羧酸；稳定在二氧化硅和/或二氧化钛上的多金属氧酸盐；含有铌离子的Keggin结构；氧化铌；离子液体和/或碳纳米管，用有机磺酸和/或有机羧酸进行了官能化。
11.根据权利要求10的方法，其中所述酸催化剂是与无定形二氧化硅结合的烷基磺酸。
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