CN106542949A - 一种洁净液体生物燃料的制备方法 - Google Patents

一种洁净液体生物燃料的制备方法 Download PDF

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CN106542949A
CN106542949A CN201610949730.5A CN201610949730A CN106542949A CN 106542949 A CN106542949 A CN 106542949A CN 201610949730 A CN201610949730 A CN 201610949730A CN 106542949 A CN106542949 A CN 106542949A
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catalyst
pentose
aldehyde
zsm
tetrahydrofuran
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王君
袁同群
王�华
李兵
鲍勇
陈林
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Anhui University of Science and Technology
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    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
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    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
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    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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Abstract

本发明公开了一种液体生物燃料的制备方法，即由五碳糖制备十碳脂肪烃燃料的方法。本发明的三个反应步骤是：五碳糖分解得到糠醛；糠醛加氢得到四氢呋喃醛；四氢呋喃醛缩合得到二聚体中间产物，二聚体加氢脱水得到液体燃料。其中第一步采用无机酸作催化剂，第二步采用纳米Cu/ZSM‑5作催化剂，第三步采用纳米Pd/Pt/ZSM‑5复合催化剂。本发明制备的液体燃料纯净，热值高，比能耗低，原料是可再生的生物质资源，价格便宜，目标产物产率高，因此本发明具有非常好的应用前景。

Description

一种洁净液体生物燃料的制备方法
技术领域
本发明涉及一种液体生物燃料的制备方法，即由五碳糖制备十碳脂肪烃燃料的方法。
背景技术
目前能源和环境问题是全球关注的焦点。煤炭、石油和天然气等化石能源仍然是世界能源的支柱和许多有机化工产品的来源，但是它们的储量都是有限的，属于不可再生资源；它们的大规模开发利用过程中排放的二氧化碳、氮氧化物、硫氧化物以及颗粒物造成的雾霾等大气污染严重威胁人类的生存环境。
为了获得可再生的液体燃料，乙醇和生物柴油作为一种清洁能源已经得到部分运用，但乙醇目前主要采用玉米和甘蔗等作为原料制备，需要占用耕地，难以进一步扩大规模，生物柴油的原料是大豆、菜籽等农作物，同样存在与粮争地的问题。五碳糖包括阿拉伯糖、核糖、脱氧核糖和木糖等，五碳糖是广泛存在于生物界的糖类，尤其是木糖，它作为半纤维素的一种结构单糖，在植物中含量丰富。如果采用五碳糖制备成清洁液体燃料，则可以扩大可再生清洁能源的生产规模，同时减少化石能源带来的环境影响。
发明内容
本发明是为了避免上述现有技术所存在的问题，提供一种五碳糖制备洁净液体生物燃料的方法。以克服现有技术存在的环境污染、不可再生、占用耕地、生产规模小等缺点。
本发明制备洁净液体生物燃料的反应步骤是：1、五碳糖分解得到糠醛；2、糠醛加氢得到四氢呋喃醛；3、四氢呋喃醛缩合得到二聚体中间产物，二聚体加氢脱水得到液体燃料。
本发明制备洁净液体生物燃料的化学反应方程式如下：
1、C5H10O5→C5H4O2+3H2O；2、C5H4O2+2H2→C5H8O2；3、2C5H8O2→C10H16O4，C10H16O4+7H2→C10H30O4,C10H30O4→C10H22+4H2O
以上C5H10O5五碳糖；C5H4O2为糠醛；C5H8O2为四氢呋喃醛，C10H16O4为四氢呋喃醛二聚体，C10H30O4为四氢呋喃醛二聚体加氢产物，C10H22为液体燃料产品十碳烷。
本发明制备洁净液体生物燃料的具体操作过程是：
将适量原料五碳糖水溶液(如木糖等，可来自于半纤维素如玉米芯等的水解)置于高压釜中，糖水比控制在1：3-1：4之间，控制压力2-2.5atm，温度160-180℃，加入适量的酸催化剂，控制反应液pH值为3-5；所述的酸催化剂可以是硫酸、磷酸或盐酸等无机酸，搅拌反应2-2.5小时，糠醛产率可以达到95％-97％；将上述反应得到的糠醛进行加氢反应，控制加氢反应器中氢气的压力20-23atm，温度220-225℃，采用纳米Cu/ZSM-5催化剂，催化剂用量占起始五碳糖质量的5-7％；搅拌反应4-4.5小时，得到四氢呋喃醛的产率为90-93％；过滤，除去纳米Cu/ZSM-5催化剂，四氢呋喃醛仍然留在反应器中，加入纳米Pd/Pt/ZSM-5复合催化剂，催化剂用量占起始五碳糖质量的6-8％；维持氢气压力20-23atm，将温度提升到260-275℃，搅拌反应2-4小时，经过油水分离得到产品液体燃料十碳烷，此反应过程总的产率达到80-85％，上述所有氢气纯度为99.9999％，纳米催化剂的粒度范围100-200纳米，酸纯度为分析纯。
本发明的有益效果体现在：原料来源于地球上含量丰富、分布广泛的生物质，生产过程不产生二氧化硫和氮的氧化物等污染大气的气体，中间产物和目标产物的产率高，最终目标产物液体燃料的热值高，可以直接作为高品位液体燃料使用，反应过程的催化剂均可以循环利用，过程能耗低，经济性好。
具体实施方式
下面结合实施例对本发明作进一步描述：
实施例1
将50克木糖的水溶液置于高压釜中，糖水比控制在1:3，控制压力2atm，温度160℃，加入适量的硫酸作催化剂，控制pH＝3，搅拌反应2小时，糠醛产率可以达到96％；将上述反应得到的糠醛进行加氢反应，控制加氢反应器中氢气的压力20atm，温度223℃，加入3克纳米Cu/ZSM-5催化剂，搅拌反应4小时，得到四氢呋喃醛的产率为91％；过滤，除去纳米Cu/ZSM-5催化剂，四氢呋喃醛仍然留在反应器中，再加入3克纳米Pd/Pt/ZSM-5复合催化剂，维持氢气压力20atm，将温度提升到260℃，搅拌反应3小时，采用油水分离得到产品液体燃料十碳烷，最终目标产物产率达到80.0％。
实施例2
将50克木糖的水溶液置于高压釜中，糖水比控制在1:4，控制压力2.3atm，温度165℃加入适量的硫酸作催化剂，控制pH＝4，搅拌反应2.5小时，糠醛产率可以达到97％；将上述反应得到的糠醛进行加氢反应，控制加氢反应器中氢气的压力23atm，温度225℃，加入3克纳米Cu/ZSM-5催化剂，搅拌反应4.2小时，得到四氢呋喃醛的产率为91.9％，过滤，除去纳米Cu/ZSM-5催化剂，四氢呋喃醛仍然留在反应器中，再加入3克纳米Pd/Pt/ZSM-5复合催化剂，维持氢气压力23atm，将温度提升到268℃，搅拌反应2.5小时，得到产品液体燃料十碳烷，最终目标产物产率达到81.5％。
应当理解本文所述的例子和实施方式仅为了说明，本领域技术人员可根据它做出各种修改或变化，在不脱离本发明精神实质的情况下，都属于本发明的保护范围。

Claims (4)

1.一种制备洁净液体生物燃料的反应步骤：1、五碳糖分解得到糠醛；2、糠醛加氢得到四氢呋喃醛；3、四氢呋喃醛缩合得到二聚体中间产物，二聚体加氢脱水得到液体燃料。
2.如权利要求1所述的反应步骤1中，糖水比控制在1：3-1：4之间，反应压力范围2-2.5atm，温度范围160-180℃，搅拌反应时间为2-2.5小时，使用无机酸为催化剂，反应液pH值控制为3-5；所述的无机酸可以是硫酸、磷酸或盐酸等。
3.如权利要求1所述的反应步骤2中，反应氢气压力范围20-23atm，温度范围220-225℃，采用纳米Cu/ZSM-5催化剂，催化剂用量占起始五碳糖质量的5-7％；搅拌反应4-4.5小时。
4.如权利要求1所述的反应步骤3中，采用纳米Pd/Pt/ZSM-5复合催化剂，催化剂用量占起始五碳糖质量的6-8％；维持氢气压力20-23atm，反应温度范围260-275℃，搅拌反应2-4小时。
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Cited By (1)

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CN107032284A (zh) * 2017-05-04 2017-08-11 北京航空航天大学 一种仿瓶子草液膜快速搬运表面织构

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Publication number Priority date Publication date Assignee Title
CN107032284A (zh) * 2017-05-04 2017-08-11 北京航空航天大学 一种仿瓶子草液膜快速搬运表面织构
CN107032284B (zh) * 2017-05-04 2018-12-28 北京航空航天大学 一种仿瓶子草液膜快速搬运表面织构

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