CN109609209B - 一种高热值清洁环保型生物柴油 - Google Patents
一种高热值清洁环保型生物柴油 Download PDFInfo
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- CN109609209B CN109609209B CN201910010838.1A CN201910010838A CN109609209B CN 109609209 B CN109609209 B CN 109609209B CN 201910010838 A CN201910010838 A CN 201910010838A CN 109609209 B CN109609209 B CN 109609209B
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 83
- 244000197813 Camelina sativa Species 0.000 claims abstract description 26
- 235000014595 Camelina sativa Nutrition 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 235000019198 oils Nutrition 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 4
- 239000004280 Sodium formate Substances 0.000 claims description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 3
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 3
- ZIMBPNXOLRMVGV-UHFFFAOYSA-M rubidium(1+);formate Chemical compound [Rb+].[O-]C=O ZIMBPNXOLRMVGV-UHFFFAOYSA-M 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- SJRDNQOIQZOVQD-UHFFFAOYSA-M sodium;2,2-dimethylpropanoate Chemical compound [Na+].CC(C)(C)C([O-])=O SJRDNQOIQZOVQD-UHFFFAOYSA-M 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 4
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- 230000003647 oxidation Effects 0.000 description 14
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 6
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
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- 241000196324 Embryophyta Species 0.000 description 4
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
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- 239000000243 solution Substances 0.000 description 3
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 3
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000272201 Columbiformes Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000750002 Nestor Species 0.000 description 1
- 241000337007 Oceania Species 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
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- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 239000010687 lubricating oil Substances 0.000 description 1
- -1 maleic anhydride triethylene glycol monomethyl ether Chemical compound 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
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- 150000004671 saturated fatty acids Chemical class 0.000 description 1
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- 239000003549 soybean oil Substances 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/10—Production of fats or fatty oils from raw materials by extracting
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Fats And Perfumes (AREA)
Abstract
本发明涉及一种高热值清洁环保型生物柴油。所述生物柴油含有基础生物柴油和添加剂,所述基础生物柴油是由亚麻荠提取得到。所述基础生物柴油通过下述方法制备得到的:将亚麻荠干燥粉碎,提取;将步骤1)得到的提取液与醇发生反应;有机溶剂洗涤、水洗,减压蒸馏得到基础生物柴油。所述生物柴油在热值等方面具有更优异的性能。
Description
技术领域
本发明涉及生物柴油及其制备方法,具体而言,本发明涉及一种高热值清洁环保型生物柴油。
背景技术
随着经济增长和人均消费水平的提高,从2005到2035年,全球对运输能源的需求以1.8%年平均速率增长。世界正面临着化石燃料紧缺和环境恶化等问题。生物柴油作为一种可再生、可持续、可生物降解的替代化石燃料的绿色能源备受关注。生物柴油是指以油料作物(大豆、油菜、棉、棕榈等)、野生油料植物、工程微藻等水生植物油脂、动物油脂和餐饮废弃油等为原料油与短链醇(甲醇、乙醇)经酯化或酯交换等一系列加工处理而制成的一种液体燃料,它是优质的石化柴油替代品,是典型的“绿色能源”。生物柴油具有优势如下:具有优良的环保性能;具有可再生性能,可作为石油产品的替代品;具有较好的安全性能;具有优良的燃料性能,可以一定比例与石化柴油调和使用;具有较好的润滑性能,延长发动机的使用寿命;应用简便也。可作为一种战略石油资源储备,促进农业发展,带动产业结构的调整;生产过程中的各类副产品均可利用。目前生物柴油无法普及主要是因为成本偏高以及技术还不够成熟,而原料成本占制备生物柴油总成本70%以上。所以解决当今这个问题的关键之一就是要寻找到合适的原料。我国是一个人口大国,人均耕地不到0.1hm2,为保证粮食安全,要以农产品为主要的生物柴油燃料显然不太现实“少占、不占粮食耕地,充分利用林地、荒地”己成为我国生物质能发展的土地利用战略,这样的国情决定了木本生物质能资
源的开发利用将成为我国未来生物质能源研发的重点和核心。
亚麻荠(Camelina s ativa L.Crantz)也是一种十字花科的油料作物,并且其生育期短(80-100d),高抗逆境和病虫草害。亚麻荠栽培历史可追溯到青铜时代(大约公元前1500年-公元前400年),一直到第二次世界大战,以及20世纪50年代,亚麻荠在欧洲仍是一些国家和俄罗斯等地的重要油料作物。现今,作为一种重新发掘出来的“低投入、环保型”的替代性工业油料作物,亚麻荠已在美洲、欧洲和大洋洲开始大面积种植,种子油也已应用于炼制航空燃油、生物柴油和其他油脂工业我国北方一些地区也不同规模地试种亚麻荠。
发明内容
本发明的目的之一提供了一种由亚麻荠制备得到的生物柴油。
本发明的另一目的在提供了制备上述由亚麻荠制备得到的生物柴油的方法。
本发明还有一目的是提供了一种用于上述生物柴油的添加剂。
本发明另一目的是提供了利用上述添加剂用于生物柴油的用途。
目前生物柴油亟需提高的特性有低温流动性、氧化安定性以及热值。
在生物柴油中加入少量降凝剂以提高低温流动性能,这是从柴油流动性能的改善所想到的方法。Chuang-WeiChiu等将BioFlow-870、BioFlow-875加入到生物柴油中,考察其对生物柴油凝点的影响。实验表明,两种添加剂在加入量为0.1%时,可分别使凝点从-6℃降至-9℃和-18℃。Dunn等将市售十二种降凝剂对生物柴油低温性能为影响进行研究,结果表明其对生物柴油凝点的降低有着一定的作用。Nestor等采用臭氧化处理植物油作为生物柴油降凝剂,结果表明,1%~1.5%的添加量对降低生物柴油凝点具有很好的效果,可使由葵花籽油、大豆油、菜籽油制备生物柴油凝点分别降低-24℃、-12℃、-30℃。降凝剂的加入主要是能改变饱和脂肪酸甲酯的结晶习性,阻止三维网状结构生长,使生物柴油保持流动性。
氧化安定性是生物柴油的重要性质之一,因为在使用和贮存过程中不可避免地会与空气中的氧气接触,在一定的条件下,油品与氧彼此会起反应,在初期产生过氧化物和氢过氧化物,后期产生醛、酮,并最终形成聚合物,从而影响油品的性能和寿命,并且在使用过程中对发动机也会产生不良影响。欧盟标准规定生物柴油在110℃下的氧化诱导期不低于6h。20世纪30年代以来,国内外对油脂的氧化以及抗氧化剂进行了深入的研究,并取得了一定的成果,与油脂类似,生物柴油的氧化速率与脂肪酸甲酯的种类、温度、与空气的接触、催化剂、油脂中所含天然抗氧化剂、光照强度有关。徐鸽等考察了不同氧气流量、金属等对生物柴油氧化速率的影响,结果表明,生物柴油随氧气流量改变氧化安定性较好,但在有金属如铜存在时,生物柴油的氧化安定性下降。目前常用的抑制生物柴油氧化的有效途径是添加抗氧化剂。YungCheeLiang等研究发现天然(维生素E)和合成的氧化剂(BHT,TBHQ)对于提高生物柴油的氧化稳定性有着很大的作用,并且合成抗氧化剂在相同的抗氧化效果下需要的剂量更少。Dunn等研究了5种抗氧化剂BHT、TBHQ、BHA、PrG、Ve对于提高生物柴油氧化的起始温度中的作用,结果表明,TBHQ、BHT和BHA能够保护生物柴油在储存中免于氧化,PrG由于不互溶性应用起来较为困难,Ve在抗氧化过程中效果最差。另外有报告研究表明合成抗氧化剂的抗氧化效果优于天然抗氧化,添加低剂量的抗氧化剂对生物柴油的燃烧性能和对柴油引擎性能没有明显的负面影响。目前中国农科院油料所已经开发出一系列高效生物柴油改良剂,能同时提高生物柴油氧化安定性和改善低温流动性能。
热值是评价一种燃料燃烧性能的重要指标,由于生物柴油即脂肪酸甲酯中含有氧元素,尽管其燃烧更加充分,但是导致其质量热值比柴油低10%;其密度高于矿物柴油,因此其体积热值仅低于矿物柴油3%~4%。Monyem等对纯生物柴油、B20与2号柴油的燃烧热效率进行了比较,发现在达到相同的效率时,纯生物柴油的消耗量要高,但是混合使生物柴油的消耗量增加并不十分明显。因此可以考虑采用生物柴油与柴油混合法来提高热值,更重要的是去研究提升热值的助剂,使其优化碳链结构,调整燃烧催化特性,改善燃烧效率,从而降低燃油消耗。
为实现上述目的,本发明采用了下述技术方案:
一种高热值清洁环保型生物柴油,所述生物柴油含有基础生物柴油和添加剂,所述基础生物柴油是由亚麻荠提取得到。
所述基础生物柴油是由下述方法制备得到的:
1)将亚麻荠干燥粉碎,提取;
2)将步骤1)得到的提取液与醇发生反应;
3)有机溶剂洗涤、水洗,减压蒸馏得到基础生物柴油。
优选地,所述基础生物柴油是由下述方法制备得到的:
1)将亚麻荠种子干燥,粉碎180-220目,石油醚浸泡提取3-5次,提取过程中加热至30-40℃,合并提取液,减压蒸馏得到亚麻荠种子油;
2)将步骤1)得到的亚麻荠种子在催化剂存在下,与甲醇或乙醇在60-70℃下发生反应,反应时间为1-2h,催化剂用量为油料质量的1%-2%,甲醇用量为油料质量的30-40%,甲醇用量为油料质量的40-55%;
3)按步骤2)所得油品的2-3倍体积加入石油醚,静置,分层,减压蒸馏即得基础生物柴油。
其中,所述催化剂选自甲酸锂、甲酸纳、甲酸钾、甲酸铷、甲酸钝、醋酸锂、醋酸钠、氢氧化钠、氢氧化钾、二甲基丙酸钠、二甲基丙酸钾、草酸钾、草酸钠中的一种或多种。
本发明还提供了所述基础生物柴油的制备方法,其包括下述步骤:
1)将亚麻荠干燥粉碎,提取;
2)将步骤1)得到的提取液与醇发生反应;
3)有机溶剂洗涤、水洗,减压蒸馏得到基础生物柴油。
更优选地,包括下述步骤:
1)将亚麻荠种子干燥,粉碎180-220目,石油醚浸泡提取3-5次,提取过程中加热至30-40℃,合并提取液,减压蒸馏得到亚麻荠种子油;
2)将步骤1)得到的亚麻荠种子在催化剂存在下,与甲醇或乙醇在60-70℃下发生反应,反应时间为1-2h,催化剂用量为油料质量的1%-2%,甲醇用量为油料质量的30-40%,甲醇用量为油料质量的40-55%;
3)按步骤2)所得油品的2-3倍体积加入石油醚,静置,分层,减压蒸馏即得基础生物柴油;
所述催化剂选自甲酸锂、甲酸纳、甲酸钾、甲酸铷、甲酸钝、醋酸锂、醋酸钠、氢氧化钠、氢氧化钾、二甲基丙酸钠、二甲基丙酸钾、草酸钾、草酸钠中的一种或多种。
本发明还提供了一种高热值清洁环保型生物柴油的添加剂,为下述式I聚合物:
优选地,为下述聚合物:
本发明还提供了一种用于生物柴油的聚合物,以下述式I所示:
最优选地,下述聚合物:
上述聚合物可用于生物柴油。
实施例
下面通过实施例对本发明作进一步说明。应该理解的是,本发明实施例所述方法仅仅是用于说明本发明,而不是对本发明的限制,在本发明的构思前提下对本发明制备方法的简单改进都属于本发明要求保护的范围。实施例中用到的所有原料和溶剂均为市售产品。
式I聚合物的制备实施例1:
氮气气氛下,用滴液漏斗加入聚异丁烯马来酸酐(n=15)加入到500毫升的圆底烧瓶中,然后加热到约80℃,保温10分钟,然后加入聚异丁烯马来酸酐2.2当量的四甘醇单甲醚,升温至回流温度,TLC跟踪反应至结束,冷却得到下述结构式的聚合物。
1HNMR(DMSO):δ4,82(s,H,1H),4,57(s,H,1H),4.25(m,CH2,2H),4.20(m,CH2,2H),3.63(t,CH2,4H),3.55(s,CH2,4H),3.52(m,CH2,20H),3.40(s,CH3,6H),2.99(m,CH,1H),2.94(t,CH2,2H),2.42(q,CH2,2H),1.82(s,CH2,2H),0.94(s,CH3,9H).
式I聚合物的制备实施例2:
氮气气氛下,用滴液漏斗加入聚异丁烯马来酸酐(n=20)加入到500毫升的圆底烧瓶中,然后加热到约75℃,保温15分钟,然后加入聚异丁烯马来酸酐2.2当量的三甘醇单甲醚,升温至回流温度,TLC跟踪反应至结束,冷却得到下述结构式的聚合物。
1HNMR(DMSO):δ4,82(s,H,1H),4,57(s,H,1H),4.25(m,CH2,2H),4.20(m,CH2,2H),3.63(t,CH2,4H),3.55(s,CH2,4H),3.52(m,CH2,12H),3.40(s,CH3,6H),2.99(m,CH,1H),2.94(t,CH2,2H),2.42(q,CH2,2H),1.82(s,CH2,2H),0.94(s,CH3,9H).
基础生物柴油的制备实施例1:
1)将亚麻荠种子干燥,粉碎至200目,称取5Kg,用5L石油醚浸泡提取3次,加热至30-40℃,合并提取液,减压蒸馏得到亚麻荠种子油;
2)称取步骤1)得到的亚麻荠种子油0.5Kg,加入催化剂氢氧化钾0.01Kg,0.2Kg乙醇,回流反应,2小时。
3)在按步骤2)所得油品中加入2L石油醚,静置,分层,减压蒸馏即得基础生物柴油。对所制得产品利用气相色谱进行测定,脂肪酸乙酯含量为96.6%。气相色谱条件如下
色谱柱:AT-FFAP(30m×0.32mm×0.50μm)。
程序升温:初始温度为80℃,保持3min,以10℃/min的升温速率升温至230℃,后恒温保持12min。
检测器:氢火焰离子检测器,检测器温度250℃,进样口温度250℃。
载气:干燥的高纯氮气。
燃气:高纯氢气,用压缩空气作为助燃气。
进样量:1μL
下表给出了本发明生物柴油和0#柴油的性能对比
生物柴油的制备实施例2:
取基础生物柴油的制备实施例1中的产品0.1Kg×2,分别加入其质量分数10%的制备实施例1和制备实施例2的式I聚合物,制备得到相关样品,记为TB-1和TB-2
本发明所述生物柴油性能测试研究:
试验用发动机为R4105T型柴油机,主要技术参数为:
汽缸数4;缸径/mm:105;活塞行程/mm:105;排量/L:3.6;标定油耗率/g·(kW·h)-1:≤239;额定功率/kW:55;额定转速/r·min-1:2000。
试验时,利用本发明基础生物柴油、TB-1、TB-2、0#柴油作为燃料,测定所述燃料在2000r/min转速下,柴油机的燃油消耗率随负荷的变化。如下所示:
从上表可以看出:相同转速下,随负荷的增大,0#柴油和其它三种生物柴油燃油消耗率都呈现下降的趋势,当柴油机运转在2000r/min的小负荷时,除纯柴油外,其它三种生物柴油燃油消耗率相对较低,而添加了本申请添加剂的TB-1和TB-2#燃油,相对于未添加的燃油,消耗更低。
Claims (3)
2.根据权利要求1所述的一种高热值清洁环保型生物柴油,其特征在于所述基础生物柴油是由下述方法制备得到的:
1)将亚麻荠种子干燥,粉碎180-220目,石油醚浸泡提取3-5次,提取过程中加热至30-40℃,合并提取液,减压蒸馏得到亚麻荠种子油;
2)将步骤1)得到的亚麻荠种子油在催化剂存在下,与甲醇或乙醇在60-70℃下发生反应,反应时间为1-2h,催化剂用量为油料质量的1%-2%,甲醇用量为油料质量的30-40%,乙醇用量为油料质量的40-55%;
3)按步骤2)所得油品的2-3倍体积加入石油醚,静置,分层,减压蒸馏即得基础生物柴油。
3.根据权利要求2所述的一种高热值清洁环保型生物柴油,其特征在于:所述催化剂选自甲酸锂、甲酸钠、甲酸钾、甲酸铷、醋酸锂、醋酸钠、氢氧化钠、氢氧化钾、二甲基丙酸钠、二甲基丙酸钾、草酸钾、草酸钠中的一种或多种。
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