CN115125025A - 一种生物燃油及其制备方法 - Google Patents
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- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
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Abstract
本发明公开了一种生物燃油及其制备方法,所述生物燃油包括60~80wt%的A组分和20~40wt%的B组分,其中,A组分按重量百分比包括如下组分:蓝藻提取油50~70份,表面活性剂1~5份,水1~10份;B组分按重量份计包括下述组分:柴油10~28份,油酸2~10份,乙醇2~10份,改性剂1~8份,防爆剂0.1~2份。本发明的生物燃油可以替代柴油,节能环保,且制备方法简单,成本相对较低,容易实现工程产业化。
Description
技术领域
本发明涉及化工环保领域,具体涉及一种生物燃油及其制备方法。
背景技术
柴油作为一种重要的石油炼制产品,在各国燃料结构中占有很高的份额,是许多大型车辆(如卡车、内燃机及发电机等)的主要动力燃料,具有动力大,价格便宜等优点。随着世界范围内车辆柴油化趋势的加快,未来柴油的需求量会越来越大,而石油资源的日益枯竭和人们环保意识的提高,大大促进了世界各国加快柴油替代燃料的开发步伐。
柴油在应用过程中也存在许多问题,例如燃烧效率低、对空气污染严重,产生大量的颗粒粉尘、二氧化碳排放量高等。
生物燃油是指通过生物资源生产的燃料乙醇、生物柴油和航空生物燃料,可以替代由石油制取的汽油和柴油,是可再生能源开发利用的重要方向。所谓的生物资源是指利用大气、水、土地等通过光合作用而产生的各种有机体,即一切有生命的可以生长的有机物质。它包括植物、动物和微生物,不同于石油、煤炭、核能等传统燃料,这些新兴的燃料是可再生燃料。
目前生物柴油作为一种可替代柴油的燃料被研究得较多。生物柴油即脂肪酸甲酯是一种含氧清洁燃料,由于其具有燃烧率高、污染少,可再生等优点,为人们所关注。目前生物柴油主要是用化学法生产,即用动物和植物油脂和甲醇或乙醇等低碳醇在酸或碱性催化剂和高温(230~250℃)下进行转酯化反应,生成相应的脂肪酸甲酯或乙酯。
目前生物燃油主要存在生产成本高,转化率低等问题。
发明内容
有鉴于此,本发明的目的是针对现有技术存在的上述缺陷,所要解决的技术问题之一是提供一种生物燃油。
本发明所要解决的技术问题之二是提供上述生物燃油的制备方法。
本发明提供的一种生物燃油,其包括60~80wt%的A组分和20~40wt%的B组分;
A组分按重量份计包括下述组分:
蓝藻提取油 | 50~70份, |
表面活性剂 | 1~5份, |
水 | 1~10份; |
B组分按重量份计包括下述组分:
柴油 | 10~28份, |
油酸 | 2~10份, |
乙醇 | 2~10份, |
改性剂 | 1~8份, |
抗暴剂 | 0.1~2份。 |
为了实现上述发明目的,本发明采用以下技术方案制备蓝藻提取油:
S1、将蓝藻与质量分数为60%~90%的乙醇按固液比(g/ml)1:5~1:20混合置于反应釜中,加入催化剂,催化剂的加入量为蓝藻重量的0.1~2%,加热反应,反应条件为:温度为260~360℃,压力为7~22Mpa,反应时间为15~45min;得到反应液;
S2、加入无水乙醇萃取反应液,抽滤分离出固体残留物,液相静置分层为有机相和乙醇水溶液相;
S3、将有机相减压蒸馏,得到的油状液体为蓝藻提取油;减压蒸馏条件为:0.085~0.1Mpa,温度为20~40℃。;
所述的S1方法,其特征在于,所使用的催化剂有40~60wt%的三水合磷酸铵和40~60wt%的六水合硫酸铵锰组成。
所述的S2方法,其特征在于,使用无水乙醇作为萃取剂。
所述的S3方法,其特征在于,所述改性剂选自甲基叔丁基醚、丙二醇丁醚、环氧丙烷中的一种或多种的混合物,优选的,所述改性剂为甲基叔丁基醚、丙二醇丁醚、环氧丙烷按重量比1:1:2复配而成。
所述的上述方法,其特征在于,抗爆剂为甲基环戊二烯三羰基锰,表面活性剂为十二烷基磺酸钠。
本发明中,甲基叔丁基醚,CAS号:1634-04-4。
丙二醇丁醚,又名:1,2-丙二醇-1-单丁醚,CAS号:15821-83-7。
环氧丙烷,CAS号:75-569。
甲基环戊二烯三羰基锰,CAS号:120-54-5。
十二烷基苯磺酸钠,CAS号:25155-30-0。
具体实施方式
下面通过实施例对本发明进行具体的描述,有必要在此指出的是以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制。该领域的技术熟练人员可以根据上述本发明的内容,对本发明做出一些非本质的改进和调整。特别需要指出的是,所有类似的替换和改动对本领域技术人员来说是显而易见的,它们都被视为包括在本发明当中。本发明的方法及应用已经通过较佳实施例进行了描述,相关人员明显能在不脱离本发明内容和范围内对本文所述的方法和应用进行改动或适当变更与组合,来实现和应用本发明技术。
为了使本领域技术人员能够更好的理解本发明,下面结合具体实施方式对本发明作进一步的详细说明。
实施例1
蓝藻提取油是按照如下步骤制备:
S1、将蓝藻与质量分数为75%的乙醇按固液比(g/ml)1:10混合置于反应釜中,加入三水合磷酸铵,三水合磷酸铵的加入量为蓝藻重量的0.5%,加热反应,反应条件为:温度为320℃,压力为12MPa,反应时间为30min,得到反应液;
S2、加入无水乙醇萃取反应液,抽滤分离出固体残留物,液相静置分层为有机相和乙醇水溶液相;
S3、将有机相减压燕馏,减压蒸馏条件为0.09MPa,温度为25℃,得到的油状液体为蓝藻提取油,蓝藻提取油的产油率为26.2%,热值为26.3MJ/kg;
S4、计算蓝藻提取油的产油滤。蓝藻提取油的产油率(%)=蓝藻提取油的重量/蓝藻重量×100%。
实施例2
蓝藻提取油的制备:
按照实施例1所述方法,将三水合磷酸铵替换为六水合硫酸铵锰,蓝藻提取油的产油率为27.3%,热值为26.0MJ/kg。
实施例3
蓝藻提取油的制备:
按照实施例1所述方法,将三水合磷酸铵替换为三水合磷酸铵与六水合硫酸铵锰重量比1:1的混合物,蓝藻提取油的产油率为30.1%,热值为27.5MJ/kg。
实施例4
生物燃油的制备:
S1、取实施例3制得的蓝藻提取油60公斤,十二烷基苯磺酸钠5公斤,水5公斤,混合均匀,制得组分A;
S2、取0#柴油20公斤,油酸3.8公斤,乙醇3.8公斤,改性剂2公斤,甲基环戊二烯三羰基锰0.4公斤,混合均匀,制得组分B;其中,所述改性剂为甲基叔丁基醚0.5公斤、丙二醇丁醚0.5公斤和环氧丙烷1公斤;
S3、将B组分添加入A组分,混合均匀,即得到实施例4的生物燃油,热值为40.7MJ/kg;
实施例5
生物燃油的制备:
按照实施例4所述方法制备,将改性剂替换为甲基叔丁基醚1公斤和环氧丙烷1公斤,得到实施例5的生物燃油,热值为38.4MJ/kg。
实施例6
生物燃油的制备:
按照实施例4所述方法制备,将改性剂替换为丙二醇丁醚1公斤和环氧丙烷1公斤,得到实施例6的生物燃油,热值为36.9MJ/kg。
实施例7
生物燃油的制备:
按照实施例4所述方法制备,将改性剂替换为甲基叔丁基醚1公斤和丙二醇丁醚1公斤,得到实施例7的生物燃油,热值为38.1MJ/kg。
由实施例可以看出,本发明制得的生物柴油,基本可以替代柴油,节能环保,且制备方法简单,成本低,容易实现工程产业化。
另外,在一些营养丰富的水体中,有些蓝藻常于夏季大量繁殖,并在水面形成一层蓝绿色而有腥臭味的浮沫,称为“水华”,大规模的蓝藻爆发,被称为“绿潮”。绿潮引起水质恶化,严重时耗尽水中氧气而造成鱼类的死亡。更为严重的是,蓝藻中有些种类还会产生微囊藻毒素,对鱼类、人畜产生毒害。
本发明也是对蓝藻的有效利用,尤其是实施例3使用了三水合磷酸铵与六水合硫酸铵锰复配的催化剂进行蓝藻提取油的提取,使得产油率,比单一使用催化剂时有了明显提高。
以蓝藻提取油为主要成分制成的生物燃油,热值也较高,尤其是实施例4使用了甲基叔丁基醚0.5公斤、丙二醇丁醚0.5公斤和环氧丙烷1公斤复配的改性剂,相比较于实施例5-7使用单一改性剂制得的生物燃油,热值有了明显提高。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (9)
1.一种生物燃油及其制备方法,其特征在于,其包括60~80wt%的A组分和20~40wt%的B组分;A组分按重量份计包括下述组分:
B组分按重量份计包括下述组分:
包括以下步骤:
S1、将蓝藻与质量分数为60%~90%的乙醇按固液比(g/ml)1:5~1:20混合置于反应釜中,加入催化剂,催化剂的加入量为蓝藻重量的0.1~2%,加热反应,反应条件为:温度为260~360℃,压力为7~22MPa,反应时间为15~45min;得到反应液;
S2、加入无水乙醇萃取反应液,抽滤分离出固体残留物,液相静置分层为有机相和乙醇水溶液相;
S3、将有机相减压蒸馏,得到的油状液体为蓝藻提取油;减压蒸馏条件为:0.085~0.1MPa,温度为20~40℃。
2.如权利要求1所述的S1方法,其特征在于,所使用的催化剂有40~60wt%的三水合磷酸铵和40~60wt%的六水合硫酸铵锰组成。
3.如权利要求1所述的S2方法,其特征在于,使用无水乙醇作为萃取剂。
4.如权利要求1所述的S3方法,其特征在于,其特征在于,所述改性剂选自甲基叔丁基醚、丙二醇丁醚、环氧丙烷中的一种或多种的混合物,且所述改性剂为甲基叔丁基醚、丙二醇丁醚、环氧丙烷按重量比1:1:2复配而成。
5.如权利要求1所述的生物燃油,其特征在于,所述改性剂为甲基叔丁基醚、丙二醇丁醚、环氧丙烷中的一种或多种的混合物。
6.如权利要求5所述的生物燃油,其特征在于,所述改性剂为甲基叔丁基醚、丙二醇丁醚、环氧丙烷按重量比1:1:2复配而成。
7.如权利要求1~6中任一项所述的生物燃油,其特征在于,所述抗暴剂为甲基环戊二烯三羰基锰。
8.如权利要求1~6中任一项所述的生物燃油,其特征在于,所述表面活性剂为十二烷基磺酸钠。
9.如权利要求1~8中任一项所述的生物燃油的制备方法,其特征在于,包括以下步骤:
(1)按重量比称取蓝藻提取油、表面活性剂和水,混合均匀制得A组分;
(2)按重量比称取柴油、油酸、乙醇、改性剂和抗爆剂,混合均匀,制得B组分;
(3)将B组分添加入A组分,混合均匀,即得到本发明所述生物燃油。
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