CN104651059A - 一种固体碱催化制备生物柴油的方法 - Google Patents
一种固体碱催化制备生物柴油的方法 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 8
- 239000004519 grease Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 5
- 238000007738 vacuum evaporation Methods 0.000 claims abstract description 5
- 239000002551 biofuel Substances 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 235000019198 oils Nutrition 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005204 segregation Methods 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000003225 biodiesel Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000005815 base catalysis Methods 0.000 abstract 1
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000005191 phase separation Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004032 superbase Substances 0.000 description 1
- 150000007525 superbases Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
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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
- C10L2270/00—Specifically adapted fuels
- C10L2270/02—Specifically adapted fuels for internal combustion engines
- C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
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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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- General Chemical & Material Sciences (AREA)
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- Wood Science & Technology (AREA)
- Fats And Perfumes (AREA)
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Abstract
本发明涉及一种固体碱催化法制备生物柴油，解决现有生物柴油技术中催化剂与产物分离工艺复杂、生产过程产生废水的问题。本发明的操作步骤是：在反应釜中，加入300-400克油脂，醇油摩尔比10：1-12：1的甲醇，油脂质量1％-3％的催化剂，反应温度60-70℃，时间2-4h；粗品经离心去除催化剂、分相、真空蒸发去除甲醇，得到脂肪酸甲酯产品。
Description
技术领域
本发明涉及一种合成生物柴油的方法，尤其涉及一种利用固体碱催化合成生物柴油的方法。
背景技术
生物柴油是一种用植物、动物油脂等可再生生物资源生产的石油燃料的清洁替代燃料，其化学组成是一系列长链脂肪酸甲酯、乙酯等。相对于石化柴油，生物柴油中氧含量高，燃烧比较安全；含硫量低，燃烧废气中二氧化硫和硫化物比石化柴油燃烧所排放的二氧化硫和硫化物低70％；且生物柴油燃烧时排放的二氧化碳远低于植物生长过程中所吸收的二氧化碳，从而可以改善由于二氧化碳的排放而导致的全球变暖。生物柴油克服了石化柴油对环境污染的弊端并且能够替代日益短缺的石化柴油，因此成为极具发展前途的石化柴油替代品。
目前，有专利报道使用乙酸甲酯等短链脂肪酸酯作为酯交换试剂的制备生物柴油，但这类专利大多采用酶作为催化剂。酶催化剂活性较低，使得酯交换反应时间长，并且酶的保存以及固定化困难，使得生产的成本高昂。
随着大工业带来的污染日益严重，发展环境友好催化工艺越来越引起人们的重视，越来越多的研究者注意到碱性在非均相中的地位，发现固体碱催化剂有着特殊的催化作用。固体碱或超强碱作为催化剂具有高活性、高选择性、活性组分可以广泛变化、使用温度范围广、反应条件温和、产物易分离、生产工艺简单、副反应少、产率高、不存在挥发性腐蚀性物质等特点，被认为是一种环保型催化剂，在制备和使用过程中达到了零污染的要求，在工业中很有应用前景，在环境友好催化工艺中将会占重要地位，可望成为新一代环境友好催化材料。而采用固体碱催化制各生物柴油不仅可避免在传统的均相酸碱催化酯交换过程中催化剂分离比较难，存在废液多、副反应多和乳化现象等严重问题，而且反应条件温和，催化剂可重复使用。
发明内容
为了解决现有生物柴油技术中催化剂与产物分离工艺复杂、生产过程产生废水的问题，本发明提供一种工艺简单、有利环保的固体碱催化法制备生物柴油。
实现上述目的的技术解决方案如下：
固体碱催化法制备生物柴油包括以下操作步骤：
在反应釜中，加入300-400克油脂，醇油摩尔比10：1-12：1的甲醇，油脂质量1％-3％的催化剂，反应温度60-70℃，时间2-4h；粗品经离心去除催化剂、分相、真空蒸发去除甲醇，得到脂肪酸甲酯产品。
所述油脂为大豆油、菜籽油；
所述催化剂为，以KNO3和K2CO3为前驱体浸渍γ-Al2O3载体通过干燥、焙烧制备的K2O／γ-Al2O3。
具体实施方式
实施例1
在反应釜中，加入300克大豆油，醇油摩尔比10：1的甲醇，油脂质量3％的K2O／γ-Al2O3固体碱催化剂，反应温度65℃，时间3h；粗品经离心去除催化剂、分相、真空蒸发去除甲醇，得到脂肪酸甲酯产品。检测脂肪酸甲酯的产率为87.5％。
实施例2
在反应釜中，加入300克大豆油，醇油摩尔比12：1的甲醇，油脂质量3％的K2O／γ-Al2O3固体碱催化剂，反应温度65℃，时间3h；粗品经离心去除催化剂、分相、真空蒸发去除甲醇，得到脂肪酸甲酯产品。检测脂肪酸甲酯的产率为90.1％。
以上实施例仅用以说明本发明的技术方案，而非对其进行限制，尽管参照上述实施例对本发明进行了详细的说明，对于本领域的普通技术人员来说，依然可以对上述实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换，而这些修改或替换，并不使相应技术方案的本质脱离本发明所要求的技术方案的精神和范围。
Claims (3)
1.固体碱催化法制备生物柴油，其特征在于包括以下操作步骤：在反应釜中，加入300-400克油脂，醇油摩尔比10：1-12：1的甲醇，油脂质量1％-3％的催化剂，反应温度60-70℃，时间2-4h；粗品经离心去除催化剂、分相、真空蒸发去除甲醇，得到脂肪酸甲酯产品。
2.根据权利要求1制备生物柴油的方法，其特征在于：所述油脂可以为大豆油、菜籽油。
3.根据权利要求1制备生物柴油的方法，其特征在于：所述催化剂为，以KNO3和K2CO3为前驱体浸渍γ-Al2O3载体通过干燥、焙烧制备的K2O／γ-Al2O3。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108219981A (zh) * | 2016-12-22 | 2018-06-29 | 内蒙古中细软技术开发有限公司 | 碱催化法合成生物柴油 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108219981A (zh) * | 2016-12-22 | 2018-06-29 | 内蒙古中细软技术开发有限公司 | 碱催化法合成生物柴油 |
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