CN103756794A - 一种地沟油加氢生产第二代生物柴油的方法 - Google Patents
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Abstract
本发明属于化工技术和可再生能源技术领域，涉及一种地沟油加氢生产第二代生物柴油的方法。该方法首先将收集的地沟油进行过滤、脱水、脱盐等预处理，在过渡金属磷化物催化剂的作用下经过加氢脱氧，加氢脱羧和加氢脱羰等反应得到第二代生物柴油。本发明充分利用过渡金属磷化物的类贵重金属性质和优异的加氢性能，直接将地沟油转化为不含氧的脂肪烷烃，且不产生污染环境的副产物，同时拥有工艺简单、清洁环保、能耗低等优点，所得柴油十六烷值高、凝点低，具有良好的经济和社会效益，对日益增长的燃料需求有重要现实意义。
Description
技术领域
本发明属于石油加工、石油化工和煤化工领域，涉及石油馏分油（汽油、煤油和柴油等）和煤焦油的加氢精制工艺中所用的固体加氢催化剂。
背景技术
随着经济快速发展对石化燃料需求的日益增加和人们环保意识的提高，绿色可再生能源成为研究的焦点，尤其是生物柴油，但是我国人口众多，发展生物柴油应做到不与民争粮争油，因此生产生物柴油从原料上受到一定制约。
地沟油泛指在生活中存在的各类质量、卫生极差，水分、过氧化值和酸值严重超标的劣质油脂，主要包括以下三类：一是狭义的地沟油，即将下水道中的油腻漂浮物或者将宾馆、酒楼的剩饭、剩菜(通称潲水)经过简单加工、提炼出的油；二是劣质猪肉、猪内脏、猪皮加工以及提炼后产出的油；三是用于油炸食品的油使用次数超过规定要求后，再被重复使用或往其中添加一些新油后重新使用的油。地沟油中含有大量的细菌和有毒物质，其中黄曲霉素的毒性是砒霜的100倍，长期食用对人体的危害极大，但目前现有的提炼技术下难以加工成食用油，为此以地沟油为原料生产生物柴油，可使地沟油变成一种有用的工业资源，打开了其回收利用的“瓶颈”，从而切断流入餐桌的途径。
目前将地沟油转化为生物柴油的方法很多，其中酯交换法为最常用的方法，即甲醇和油脂在酸或碱性条件下发生酯交换反应生成脂肪酸甲酯（第一代生物柴油），但由于其结构与来自石油的普通柴油的分子结构存在明显不同，传统生物柴油含氧量高，热值相对较低，生产中还会产生大量含酸、碱和油脂的工业废水，严重限制了其作为汽柴油替代燃料的广泛使用。
发明内容
本发明是针对目前对新能源的需求日益增加和大量地沟油的存在等现实问题而提供一种以地沟油为原料加氢生产第二代生物柴油的方法，充分利用负载型过渡金属磷化物催化剂类贵重金属性能，将地沟油的主要成分甘油三酯、脂肪酸等直接转化为不含氧的烷烃，产物十六烷值高达100左右，燃烧热值达到49.2MJ/kg高，尾气污染物含量低；同时该工艺不使用污染环境的强酸、强碱，清洁环保，拥有良好的经济和社会效益。
本发明所采用的技术方案：
一种以地沟油为原料加氢生产第二代生物柴油的方法，其特点在于包括如下步骤：
（1）预处理地沟油成分如表1所示，将收集的地沟油经过滤，脱水和脱盐预处理得到主要成分为甘油三酯和脂肪酸的地沟油；
（2）加氢精制将上述地沟油导入高压反应器，在过渡金属磷化物催化剂作用下进行加氢精制，反应条件：反应氢气压力为0.5-10MPa，反应温度为200-480℃，氢油体积比为10-2000，反应时间4-6小时；加氢精制产物为脂肪烷烃(高十六烷值柴油)、水(H2O)、丙烷(C3H8)、甲烷(CH4)、二氧化碳(CO2)和一氧化碳(CO)的气液混合物；
（3）产物分离将步骤（2）中得到的气液混合物在气液分离装置中分离成液相产物和气相产物；液相产物包含高十六烷值柴油(脂肪烷烃)和H2O，通过油水分离装置分离出粗产品,进一步分离出其中的丙三醇得到第二代生物柴油。
本发明所述过渡金属磷化物催化剂活性组分为磷化镍、磷化钴、磷化铜或磷化钼。
本发明所述反应器是固定床反应器、釜式反应器或流化床反应器。
本发明所述地沟油的过滤步骤是指将地沟油加热至90℃趁热过滤除杂。
本发明催化剂为负载型过渡金属磷化物，活性组分（MO）含量为0.5-35%；载体为具有孔道和介孔结构的多孔材料，包括沸石分子筛、炭载体和氧化物等，例如A型沸石分子筛、β型沸石分子筛、X型沸石分子筛、Y型沸石分子筛、ZSM-5型沸石分子筛、MCM-41型沸石分子筛、丝光型沸石分子筛、活性炭、碳纳米管、氧化铝、二氧化硅、二氧化钛、二氧化锆、氧化镁或二元、多元复合体等。
以金属磷化镍催化剂为例，其制备方法如下：
配制含有75.5克的次磷酸镍120mL浸渍液，等体积浸渍于100克大孔SiO2载体，在室温下放置2小时，然后60℃真空干燥箱中4小时；将得到的样品置于管式炉中，在250℃下通氮气处理3小时，得到催化剂Ni2P/SiO2。
本发明负载型过渡金属磷化物对地沟油加氢精制制备第二代生物柴油具有较高的活性，相对于母体过渡金属（Ni/Al2O3,Co/Al2O3等）具有类贵重金属性能，从而使地沟油加氢脱羧和加氢脱羰的选择性大大提高，降低氢气消耗量；其使用该催化剂其反应活性在120小时内活性不下降，产品为脂肪烃具有较高的十六烷值。
为了进一步说明本发明，列举以下实施例，但是它并不限制各附加权利要求所定义的发明范围。
具体实施方式
下面将结合具体实施例来详述本发明的技术特点。
实施例1：
配制含有75.5克的次磷酸镍的120mL浸渍液，等体积浸渍于100克大孔SiO2载体（青岛海洋化工有限公司）在室温下放置2小时，然后60℃真空干燥箱中4小时。将得到的样品置于管式炉中，在250℃下通氮气处理3小时，得到催化剂Ni2P/SiO2（C1，活性组分NiO：16%）。
催化剂C1的活性评价
在拓川100ml小型连续加氢反应装置上进行催化剂的加氢精制活性评价，反应器为24×800mm的不锈钢管，催化剂的装填量100ml，评价所用预处理的地沟油，将100ml催化剂C1装入加氢反应器中，接通氢气，将反应压力调整为4.0MPa，氢气流量为75L/h，空速1.5h-1，氢油比500，反应温度360℃，保持该温度稳定6小时后取样分析，第二代生物柴油的产率为79.38%（质量百分数），与理论产率（82.80%）非常接近，且成份与石化柴油非常相似，其十六烷值为93（高于第一代生物柴油十六烷值52～70），评价结果见表2。
实施例2：
取73.9克硝酸镍[Ni(NO3)2.6H2O]完全溶解于水中配置120浸渍液，等体积浸渍于100克大孔SiO2载体，在室温下放置2小时，然后60℃鼓风干燥箱中过夜，然后在马弗炉中500℃焙烧4h，将煅烧后的固体冷却到室温并转移到管式石英炉中，然后向管式石英炉中持续通入氢气(H2)，并将炉温逐渐升至450℃并保持在450℃4h，得到催化剂Ni/SiO2（C2，活性组分NiO：16%），
催化剂C2活性评价所用的评价装置、装填量、原料、实验条件与实施例1完全相同，评价结果见表2。
实施例3：
催化剂C3为工业上常用的CoMoS催化剂，其活性评价所用的评价装置、装填量、原料、实验条件与实施例1完全相同，评价结果见表2。
表1地沟油的主要成分(质量百分比wt%)
表2地沟油在不同催化剂上的加氢产物分布
| <C15 | C15～18 | >C18 | 密度 | 十六烷值 | 产率 | |
| CoMoS | 2.24 | 95.07 | 2.69 | 0.775 | 84 | 78.92 |
| Ni/SiO2 | 1.96 | 95.9 | 2.14 | 0.771 | 86 | 76.26 |
| Ni2P/SiO2 | 8.56 | 90.02 | 1.42 | 0.756 | 93 | 79.38 |
Claims (5)
1.一种以地沟油为原料加氢生产第二代生物柴油的方法，其特征在于包括如下步骤：
（1）预处理将收集的地沟油经过滤，脱水和脱盐预处理得到主要成分为甘油三酯和脂肪酸的地沟油；
（2）加氢精制将上述地沟油导入高压反应器，在过渡金属磷化物催化剂作用下进行加氢精制，反应条件：反应氢气压力为0.5-10MPa，反应温度为200-480℃，氢油体积比为10-2000，反应时间4-6小时；得气液混合物；
（3）产物分离将步骤（2）中得到的气液混合物在气液分离装置中分离成液相产物和气相产物；液相产物通过油水分离装置分离出粗产品,进一步分离出其中的丙三醇得到第二代生物柴油。
2.根据权利要求1所述的一种以地沟油为原料加氢生产第二代生物柴油的方法，其特征在于：所述过渡金属磷化物催化剂活性组分为磷化镍、磷化钴、磷化铜或磷化钼。
3.根据权利要求1所述的一种以地沟油为原料加氢生产第二代生物柴油的方法，其特征在于：所述反应器是固定床反应器、釜式反应器或流化床反应器。
4.根据权利要求1所述的一种以地沟油为原料加氢生产第二代生物柴油的方法，其特征在于：所述地沟油的过滤步骤是指将地沟油加热至90℃趁热过滤除杂。
5.一种制备过渡金属磷化镍催化剂的方法，其特征在于：配制含有75.5克的次磷酸镍120mL浸渍液，等体积浸渍于100克大孔SiO2载体，在室温下放置2小时，然后60℃真空干燥箱中4小时；将得到的样品置于管式炉中，在250℃下通氮气处理3小时，得到催化剂Ni2P/SiO2。
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| CN106118709A (zh) * | 2016-08-03 | 2016-11-16 | 江苏大学 | 一种废弃动植物油脂加氢生产二代生物柴油的直燃利用方法 |
| CN107376984A (zh) * | 2017-06-19 | 2017-11-24 | 中国海洋石油总公司 | 一种用于c10+重芳烃轻质化的非贵金属催化剂的制备方法 |
| CN112592731A (zh) * | 2020-10-10 | 2021-04-02 | 中国科学院青岛生物能源与过程研究所 | 一种液态催化剂生产第二代生物柴油的方法 |
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