CN112585247B - 生物燃料的制造方法 - Google Patents
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Abstract
本发明提供一种生物燃料的制造方法,其是在固体酸催化剂的存在下使含有游离脂肪酸的动植物油脂原料和低级醇反应的生物燃料的制造方法,其中,抑制低级醇的使用量,并选择性地进行游离脂肪酸和低级醇的酯化反应,从而使动植物油脂改质。该生物燃料的制造方法中,使用选择自SiO2/Al2O3系固体酸催化剂、在介孔二氧化硅导入有一部分SiO2/Al2O3的固体酸催化剂、Al2O3/B2O3系固体酸催化剂、硫酸化氧化锆系固体酸催化剂的催化剂作为固体酸催化剂,在游离脂肪酸和低级醇的摩尔比为1~6进行。
Description
技术领域
本发明涉及一种从油脂制造适合柴油发动机的生物燃料的制造方法。
背景技术
当今,可利用石油资源的减少及地球环境的恶化、发展中国家的发展带来了对燃料的需求的问题。
因此,需要开发替代化石资源的清洁且可再生的燃料及化学制品的制造工艺。
由此,生物燃料及生物化学制品有望对国内产业及温室气体的减排、降低对化石资源的依赖度、地域的经济发展、国内的能源安全保障做出大的贡献。
现在,生物柴油燃料的制造方法方面,在氢氧化钾、氢氧化钠等碱催化剂的存在下,通过酯交换反应由以甘油三酯作为主成分的油脂制造脂肪酸酯的方法得到了实用化。
但是,在这种方法中,作为原料的油脂中存在大量的游离脂肪酸(FFA),因为其对酯交换反应、生成物的分离或精炼造成不良影响,因此必须通过预处理去除。
另外,为了保护环境及减少使用化石燃料带来的CO2排放量,以往在柴油发动机发电中使用的来自于石油的燃料油的一部分或全部使用来自于油脂的燃料油的方法备受瞩目。但是,如上所述,因为油脂中含有的游离酸会腐蚀柴油发动机,必须从燃料油中去除游离酸。
对此,提出了一种方法,其中,在存在固体酸催化剂的条件下,使甘油三酯与甲醇、乙醇等低级醇反应,同时进行甘油三酯的酯交换反应和游离脂肪酸的酯化。
现有技术文献
专利文献
专利文献1:日本特开平6-313183号公报
专利文献2:日本特开2009-114289
发明内容
发明所要解决的课题
但是,在这些方法中,酯交换反应和游离脂肪酸的酯化的两者使用低级醇,低级醇的使用量变多,在成本方面有问题。
在此,本发明中使用新型固体酸催化剂控制低级醇的使用量,对反应条件进行研究,使得基本上不发生油脂中的甘油三酯和低级醇的酯交换,而选择性进行游离脂肪酸与低级醇的酯化反应,从而达成了本发明。
用于解决课题的手段
本发明涉及一种生物燃料的制造方法,其是在固体酸催化剂的存在下使含有游离脂肪酸的油脂原料和低级醇反应的生物燃料的制造方法,其中,使用选择自SiO2/Al2O3系固体酸催化剂、在介孔二氧化硅导入有一部分铝的SiO2/Al2O3系固体酸催化剂、Al2O3/B2O3系固体酸催化剂、硫酸化氧化锆等的催化剂作为固体酸催化剂,在游离脂肪酸和低级醇的摩尔比为1~4的条件进行反应。
作为本发明中使用的固体酸催化剂,采用固体载体表面具有酸性官能团的催化剂。
作为能够用作载体的物质,只要是能够固定官能团且具有酸性的物质即可,没有特别限制。另外,也可以是载体本身在其表面结构中具备规定的官能团的物质。
例如,可以举出聚苯乙烯载体的表面上固定有酸的阳离子交换树脂;其表面结构中具有酸性基团或羟基等的二氧化硅、氧化铝、氧化硼、锆、钛、沸石、活性炭等;进一步,可以举出这些中二种以上组合而成的混合物。
通过调整阳离子交换树脂的种类、调整二氧化硅、氧化铝载体的烧制处理温度,能够适当调整其表面存在的酸性基团而改变其酸性。
进一步,可以举出以这些中二种以上组合而成的混合物作为载体。如此,在本发明中,通过调整阳离子交换树脂的种类、调整表面含有酸性基团的氧化锆、二氧化钛、二氧化硅、氧化铝、氧化硼等载体的烧制处理温度,能够适当调整其表面存在的酸性基团而改变其酸性度。
作为载体表面的官能团,例如,可以举出具有布朗斯特酸(强酸性的磺酸基或氢离子等)、路易斯酸(具有能够接受电子对的性质)的官能团。
作为本发明中能够使用的原料油,能够举出各种植物油、动物油脂、以及来自于这些油脂的脂肪酸、酯的混合物等。
作为低级醇,可以举出甲醇、乙醇等。
在使含有30%以上游离酸的油脂原料油中的游离脂肪酸和低级醇的摩尔比为6以下、优选1~4的情况下,能够抑制醇的使用量,使原料油中的游离脂肪酸比原料油中的甘油三酯优先酯化,取得游离脂肪酸的高转化率。
例如,通过使用选择自SiO2/Al2O3系固体酸催化剂、在介孔二氧化硅导入有一部分铝的固体酸催化剂、Al2O3/B2O3系固体酸催化剂的催化剂作为固体酸催化剂,能够选择性地使原料油中的游离脂肪酸和醇发生酯化,提高游离脂肪酸的转化率。
特别是,关于Al2O3/B2O3系的催化剂,能够在提高原料油中的游离脂肪酸的高转化率的同时,抑制原料油中的甘油三酯的转化率。
另外,本发明中,通过在150℃以下、优选150℃~70℃的反应温度进行反应,能够选择性地进行游离脂肪酸和低级醇的酯化反应。
另外,作为反应装置,可以使用如图1所示的间歇式反应装置,也可以使用如图2所示的流通式反应装置。
发明的效果
本发明中,使原料油中的游离脂肪酸优先和醇发生酯化,提高游离脂肪酸的转化率,由此对油脂进行改质,能够提供适合于柴油发动机的生物燃料。
另外,本发明中,在提高原料油中的游离脂肪酸的高转化率的同时,抑制原料油中的甘油三酯的转化率,从而能抑制醇的使用量。
附图说明
[图1]本发明中使用的间歇式反应装置的概略图
[图2]本发明中使用的流通式反应装置的概略图
具体实施方式
一种生物燃料的制造方法,在固体酸催化剂存在下,使含有游离脂肪酸的动植物油脂原料和低级醇反应的生物燃料,该制造方法中,使用选择自SiO2/Al2O3系固体酸催化剂、在向介孔二氧化硅导入有一部分铝的固体酸催化剂、Al2O3/B2O3系固体酸催化剂、硫酸化氧化锆系固体酸催化剂的催化剂作为固体酸催化剂,在游离脂肪酸和低级醇的摩尔比为1~6进行反应。
实施例
本发明中使用的反应装置
图1是间歇式反应装置的概略图,反应器的外周设有加热器,原料油和醇同催化剂一起收纳于反应器内。反应在用控制器对反应器内的温度和反应试样的搅拌速度进行控制下进行。
图2是流通式反应装置的概略图,在填充有催化剂的反应器的外周设有加热器。在各自的贮存室收纳的原料油和醇通过泵送至反应器内,使其通过催化剂层,由此进行反应。
反应液通过浓缩器而被减压,并被送至分离槽,在分离槽从上部回收改质油,下部的层被送至分离塔,从其顶部回收少量的未反应的醇,回収的醇收纳于贮存室,被送至反应器用于再次反应。
(2)本发明中使用的固体酸催化剂的制造例
(铝插入SBA-15(Al-SBA-15(5)))
作为本发明中使用的固体酸催化剂的一例,如下所示,制作了介孔二氧化硅(SBA-15)中导入有适量的铝的催化剂。用盐酸溶解聚合物P123,将其与TEOS(TetraethylOrthoslilcate)混合。然后,添加适量的硫酸铝盐的盐酸溶液,使该混合物中铝和硅氧烷的原子比为5后,用氨水中和,把铝导入SBA-15。接着,使二氧化硅的结晶生长,通过在空气中450℃烧制的方式去除聚合物P123等,得到铝插入SBA-15(5)。另外,若改变硫酸铝盐的添加量,得到铝和硅氧烷的原子比不同的Al-SBA-15。
(硫酸化氧化锆(ZrO2/SO4 2-))
作为本发明中使用的固体酸催化剂的一例,如下所示制备了硫酸化锆。使用(JRC-ZRO-2~5)作为氧化锆,粉碎成其粒径为32~50目。之后,采取2g上述氧化锆于圆锥形烧杯中,溶解、分散于0.5摩尔/升的硫酸水溶液中,并放置1小时后,抽吸过滤约10分,得到硫酸化锆。进一步,由上述操作得到的硫酸化氧化锆在30℃下干燥24小时,之后用坩埚在600℃空气中烧制3小时,制备成固体酸。另外,使用硝酸或者盐酸替代硫酸的情况下,则制备成硝酸氧化锆、盐酸氧化锆。
间歇式反应装置的实验结果列于表1。
表1中,反应时间为小时单位,动粘度为在40℃时的测量结果。
另外,Amberlyst 70为作为比较例给出的阳离子交换树脂类的市售固体酸催化剂。
[表1]
注1转化率1)为原料油中的甘油三酯的转化率(%)
注2转化率2)为原料油中的游离脂肪酸(FFA)的转化率(%)
注3原料油为含有约37.4%的游离脂肪酸的棕榈酸油(PAO),其酸值为75.5mgKOH/g原料油,动粘度为34.4mPa·s。
从表1可知,关于固体酸催化剂,SiO2/Al2O3系固体酸催化剂、Al2O3/B2O3系固体酸催化剂、向介孔二氧化硅SBA-15导入有铝的Al-SBA-15系固体酸催化剂,可获得原料油中的游离脂肪酸的高转化率。
特别是,关于Al2O3/B2O3系固体酸催化剂、Al-SBA-15系固体酸催化剂,在原料油中的游离脂肪酸的高转化率的同时,能够降低原料油中的甘油三酯的转化率。
另外,游离脂肪酸和低级醇在摩尔比在6以下,优选在1~4时,能够减少低级醇的使用量,得到原料油中的游离脂肪酸的高转化率。
进一步,关于反应温度,通过在150℃以下,优选150℃~100℃下进行进行反应,能够选择性地进行游离脂肪酸和低级醇的酯化反应。
利用流通式反应装置的实验
使介孔二氧化硅导入有一部分铝的SiO2/Al2O3系固体酸催化剂(Al-SBA-15)填充至如图2所示的流通式反应装置的反应器,送入原料油和低级醇进行酯化反应。其结果是,能够得到规定的效果。
工业实用性
根据本发明,通过提高原料油中的游离脂肪酸的转化率,能够使动植物油脂改质,提供适合于柴油发动机的生物燃料的同时抑制原料油中的甘油三酯的转化率,能够提供一种成本方面优异的生物燃料的制造方法。
Claims (3)
1.一种生物燃料的制造方法,其中,其是在固体酸催化剂的存在下使含有游离脂肪酸的油脂和低级醇反应的生物燃料的制造方法,其中,使用选择自SiO2/Al2O3系固体酸催化剂、在介孔二氧化硅导入有一部分铝的固体酸催化剂、Al2O3/B2O3系固体酸催化剂、硫酸化氧化锆系固体酸催化剂的催化剂作为固体酸催化剂,在低级醇和游离脂肪酸的摩尔比为6以下进行,选择性地进行游离脂肪酸和低级醇的酯化。
2.如权利要求1所述的生物燃料的制造方法,其中,低级醇和游离脂肪酸的摩尔比为1~4。
3.如权利要求1或2所述的生物燃料的制造方法,其中,反应温度在150℃以下。
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