CN102676242B - 超临界甲醇微波裂解固体酸催化农林废弃物制备生物油的方法 - Google Patents
超临界甲醇微波裂解固体酸催化农林废弃物制备生物油的方法 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 72
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- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000007171 acid catalysis Methods 0.000 title claims abstract description 8
- 239000002699 waste material Substances 0.000 title abstract description 5
- 238000000197 pyrolysis Methods 0.000 title abstract 4
- 239000003225 biodiesel Substances 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 18
- 239000010815 organic waste Substances 0.000 claims description 18
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- 239000012263 liquid product Substances 0.000 claims description 12
- 238000005336 cracking Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
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- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 6
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract 1
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- 241000609240 Ambelania acida Species 0.000 description 2
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- 240000008042 Zea mays Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
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- 238000005809 transesterification reaction Methods 0.000 description 1
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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
Abstract
本发明涉及超临界甲醇微波裂解固体酸催化农林废弃物制备生物柴油的方法,将农林废弃物与甲醇质量比为100:20~30的比例混合,再加入农林废弃物质量2~5%的固体酸催化剂,开启微波加热裂解,控制反应温度250~350℃,反应压力10~15MPa,反应时间为30~60分钟;反应结束后经静置、分离和回收甲醇即得到脂肪酸甲酯即生物柴油。本发明将微波裂解和超临界甲醇酯化反应有机结合,具有工艺简单,反应时间短,效率高、原料成本低等优点。
Description
技术领域
本发明涉及制备生物柴油的方法,特别涉及超临界甲醇微波裂解固体酸催化农林废弃物制备生物油的方法,属生物能源技术领域。
背景技术
目前,生物柴油主要以各种动植物油脂、微生物油脂、废弃餐饮油、植物油加工的下脚料等为原料制备,经过酯交换反应制备得到。生物柴油制备成本中75%是原料成本,价格高是生物柴油替代燃料商品化的主要障碍,寻求廉价原料和高效的生物柴油加工技术成为生物柴油产业化发展的关键。在我国,每年各种农林废弃物的产量非常可观,将这些原料制备成生物柴油,一方面可为这些废弃物的再利用提供出路,同时也解决了生物柴油的原料问题。
发明内容
为解决生物柴油制备成本高等问题,本发明的目的在于提供一种超临界甲醇微波裂解固体酸催化农林废弃物制备生物油的方法,通过下列技术方案实现。
一种超临界甲醇微波裂解固体酸催化农林废弃物制备生物油的方法,经过下列各步骤:
(1)将粉碎的农林废弃物与甲醇按质量比为100︰20~30的比例混合,再加入农林废弃物质量的2~5%的固体酸催化剂,然后在反应温度为250~350℃、反应压力为10~15MPa的条件下进行微波加热30~60分钟;
(2)反应结束后将步骤(1)所得产物经过滤分离出液态产物和未反应的原料,将液态产物的甲醇进行回收后即得到生物柴油(脂肪酸甲酯)。
所述步骤(1)的农林废弃物为农作物秸秆(如小麦秸秆、玉米秸秆、稻谷秸秆等)、农业加工剩余物(如稻壳、蔗渣、玉米芯等)、锯末。
所述步骤(1)的粉碎是将农林废弃物粉碎至50~100目。
所述步骤(1)的固体酸催化剂为SO4 2-/ZrO2、SO4 2-/TiO2、SO4 2-/ZrO2-TiO2、SO4 2-/TiO2-Fe2O3型固体酸。
所述步骤(1)的微波加热是在功率为500~1000W、频率为50Hz的微波条件下进行。
本发明的优点及积极效果:
本发明将微波裂解和超临界甲醇酯化反应有机结合,一方面利用微波裂解具有快速的特点,另一方面在裂解的同时将裂解产物及时酯化得到生物柴油,具有工艺简单,反应时间短,效率高,原料成本低等优点。
具体实施方式
下面以实例进一步说明本发明的实质内容,但本发明的内容并不限于此。
实施例1
(1)将粉碎至50目的小麦秸秆、与甲醇按质量比为100︰20的比例混合,再加入农林废弃物质量的2%的固体酸催化剂SO4 2-/ZrO2型固体酸,然后在反应温度为250℃、反应压力为10MPa下以功率为500W、频率为50Hz的微波条件进行微波加热30分钟;
(2)反应结束后将步骤(1)所得产物经过滤分离出液态产物和未反应的原料,将液态产物的甲醇进行回收后即得到生物柴油(脂肪酸甲酯)。
实施例2
(1)将粉碎至80目的蔗渣与甲醇按质量比为100︰25的比例混合,再加入农林废弃物质量的3%的固体酸催化剂SO4 2-/TiO2型固体酸,然后在反应温度为300℃、反应压力为12MPa下以功率为800W、频率为50Hz的微波条件进行微波加热60分钟;
(2)反应结束后将步骤(1)所得产物经过滤分离出液态产物和未反应的原料,将液态产物的甲醇进行回收后即得到生物柴油(脂肪酸甲酯)。
实施例3
(1)将粉碎至100目的锯末与甲醇按质量比为100︰30的比例混合,再加入农林废弃物质量的2%的固体酸催化剂SO4 2-/ZrO2-TiO2型固体酸,然后在反应温度为350℃、反应压力为15MPa下以功率为1000W、频率为50Hz的微波条件进行微波加热50分钟;
(2)反应结束后将步骤(1)所得产物经过滤分离出液态产物和未反应的原料,将液态产物的甲醇进行回收后即得到生物柴油(脂肪酸甲酯)。
实施例4
(1)将粉碎至60目的稻谷秸秆与甲醇按质量比为100︰25的比例混合,再加入农林废弃物质量的5%的固体酸催化剂SO4 2-/TiO2-Fe2O3型固体酸,然后在反应温度为300℃、反应压力为12MPa下以功率为800W、频率为50Hz的微波条件进行微波加热40分钟;
(2)反应结束后将步骤(1)所得产物经过滤分离出液态产物和未反应的原料,将液态产物的甲醇进行回收后即得到生物柴油(脂肪酸甲酯)。
Claims (2)
1.一种超临界甲醇微波裂解固体酸催化农林废弃物制备生物油的方法,其特征在于经过下列各步骤:
(1)将粉碎至50~100目的农林废弃物与甲醇按质量比为100︰20~30的比例混合,再加入农林废弃物质量的2~5%的固体酸催化剂,然后在反应温度为250~350℃、反应压力为10~15MPa的条件下进行微波加热30~60分钟,微波加热的功率为500~1000W、频率为50Hz,其中固体酸催化剂为SO4 2-/ZrO2、SO4 2-/TiO2、SO4 2-/ZrO2-TiO2、SO4 2-/TiO2-Fe2O3型固体酸;
(2)反应结束后将步骤(1)所得产物经过滤分离出液态产物和未反应的原料,将液态产物的甲醇进行回收后即得到生物柴油。
2.根据权利要求1所述的超临界甲醇微波裂解固体酸催化农林废弃物制备生物油的方法,其特征在于:所述步骤(1)的农林废弃物为农作物秸秆、农业加工剩余物、锯末。
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