CN115093887A - 一种醇基柴油燃料添加剂的制备方法 - Google Patents
一种醇基柴油燃料添加剂的制备方法 Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000006280 diesel fuel additive Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000002283 diesel fuel Substances 0.000 claims abstract description 42
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 35
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 239000006184 cosolvent Substances 0.000 claims abstract description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims abstract description 7
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims abstract description 7
- 229920000053 polysorbate 80 Polymers 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 12
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000012018 catalyst precursor Substances 0.000 claims description 5
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
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- 238000004458 analytical method Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 239000002816 fuel additive Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 12
- 239000000446 fuel Substances 0.000 abstract description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 8
- -1 butyl ether ester Chemical class 0.000 abstract description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000000386 microscopy Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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Abstract
本发明提供一种醇基柴油燃料添加剂的制备方法,主要包含甲醇、乙醇、甲醇‑乙醇脱氢产物,还包含助溶剂如正丁醇、多元醇甲醚、多元醇丁醚、双多元醇甲醚、多元醇丁醚酯,以及表面活性剂如Span80、OP‑10、Tween80。甲醇‑乙醇脱氢产物是一种由甲醇、乙醇经过脱氢反应后得到的混合物。本发明制备的醇基柴油燃料添加剂是一种很有应用价值的含氧燃料,增加柴油氧含量,为进一步降低排放、提高热效率提供途径。此外,本发明醇基柴油燃料体系所使用的助溶剂、表面活性剂及甲醇、乙醇来源广泛,具体操作过程简单,是一条绿色环保路线,相对于传统方法,其制备的乳化柴油燃料稳定性大幅提高。
Description
技术领域
本发明涉及石油化工技术领域,具体涉及一种醇基柴油燃料添加剂的制备及应用。
背景技术
我国能源结构具有“富煤、贫油、少气”的特点,利用煤炭制取发动机代用燃料已经成为解决我国能源问题的重要手段。煤制甲醇技术在我国早已发展成熟,每年都有大量甲醇产能过剩,“柴油掺醇”是解决甲醇作燃料的重要方法,但由于甲醇与柴油的性质差异巨大,导致甲醇很难与柴油互溶,因此解决甲醇与柴油的互溶问题是实现“柴油掺醇”燃料的核心问题。近几年来,关于甲醇柴油助剂种类的专利很多,但都各有弊端,例如:专利CN110747024A公开了一种微乳化柴油制备方法,其中所使用表面活性剂、清油剂、稳定剂等添加种类繁多,过程复杂,不利于推广使用。专利CN110819398公开了一种柴油用复合乳化剂和微乳化柴油,其中掺杂10-20份的水可能使得微乳化柴油在发动机的性能弱化。总之,多种问题导致甲醇柴油实际应用困难,现有技术对甲醇柴油体系的稳定性提高作用也有限。
发明内容
本发明在前人研究的基础上,结合市场需求,发明了一种方便、高效、成本低的醇基柴油燃料添加剂的制备方法。醇基柴油燃料添加剂的组成主要包含甲醇、乙醇、甲醇-乙醇脱氢产物,还包含助溶剂如正丁醇、多元醇甲醚、多元醇丁醚、双多元醇甲醚、多元醇丁醚酯,以及表面活性剂如Span80、OP-10、Tween80。甲醇-乙醇脱氢产物是一种由甲醇、乙醇经过脱氢反应后得到的混合物。甲醇-乙醇脱氢反应所用催化剂为铜负载氧化硅型催化剂,脱氢反应所用原料为甲醇和乙醇混合物。本醇基柴油燃料添加剂具有来源广泛、价廉易得的优势,并且制备过程中反应后的混合物不需要进行分离和再次加工处理,因此具有操作简便的优势。此外,助溶剂添加量较少,但分散效果优异,组分中所用的表面活性剂为常见的化工产品,来源丰富。表面活性剂与助溶剂使用后有助于醇基燃料的充分分散与长时间稳定存储。此外,本发明的醇基柴油燃料添加剂可根据需要和应用场所对其组成及比例进行调节,以保证醇基柴油燃料添加剂与柴油混合后的稳定性及充分燃烧性。该醇基柴油燃料添加剂能够满足大部分市场要求。通过经济效益的评价,本发明所制备的醇基燃料有着显著的经济效益,具有进一步推广应用的价值。
本发明的醇基柴油燃料添加剂主要组分为甲醇-乙醇脱氢过程中未反应的甲醇、乙醇及甲醇-乙醇脱氢产物,次要组分为助溶剂和表面活性剂。甲醇-乙醇脱氢产物所用催化剂为铜负载氧化硅型催化剂,制备方法是称取一定量的Cu(NO3)2·3H2O和Zn(NO3)2·6H2O固体溶于去离子水中,在搅拌的条件下缓慢加入氨水使其生成铜氨络合物,使得pH值为9~10,充分搅拌后加入硅溶胶,常温下搅拌4h,随后转移至旋转蒸发仪中蒸氨使得最终pH值为6~7,经过过滤、水洗、干燥、焙烧后筛分并得到20~40目的催化剂前驱体,随后在氢气气氛中还原4h,还原温度为350℃,最终得到所需催化剂。其中催化剂中Cu与Zn的比例、Cu在载体SiO2上的负载量均可调节。
甲醇-乙醇脱氢反应是在固定床微型反应器中进行,甲醇、乙醇按照20:1~5:1的比例混合,反应温度为240℃~280℃,反应压力为0.2MPa~0.5MPa、反应空速为1h-1~4h-1,所用气体为氮气,进料流量为0.065~0.103ml/min。,经实验分析证明液相产物主要有甲酸甲酯、乙酸甲酯、乙酸乙酯、甲酸乙酯,上述酯类易溶于甲醇、乙醇等,且与柴油具有良好的混溶性。
助溶剂主要是正丁醇、多元醇甲醚、多元醇丁醚、双多元醇甲醚、多元醇丁醚酯中的一种或几种复配。表面活性剂主要是Span80、OP-10、Tween80、Tween60中的一种或几种复配。
醇基柴油燃料添加剂中各类组分添加比例如下:
甲醇-乙醇脱氢产物占添加剂的比例:50~90wt%,
助溶剂中正丁醇占添加剂的比例:5~30wt%
助溶剂中多元醇甲醚、多元醇丁醚、双多元醇甲醚或多元醇丁醚酯占添加剂的比例:2~10wt%;
表面活性剂中Span80、OP-10、Tween80、Tween60占添加剂的比例:0.05~10wt%,
经过分析甲醇-乙醇脱氢产物中甲酸甲酯的含量为:5~20wt%,乙酸甲酯的含量为:5~25wt%,乙酸乙酯的含量为:2~10wt%,甲酸乙酯的含量为2~10wt%;其他酯类0.1~2wt%。
醇基柴油燃料添加剂和柴油的混合比例为:5~30:100
使用方法:各质量分数的甲醇、乙醇、甲醇-乙醇脱氢产物、助溶剂和表面活性剂组成的醇基柴油燃料添加剂与柴油按比例充分混合后使用超声波分散器超声分散一定时间后,形成稳定的醇基柴油乳化燃料。
注:所用柴油种类可为0#柴油、直镏柴油、加氢柴油;所有助溶剂和表面活性剂均使用超声分散器分散到柴油中。
本发明与现有技术发明对比,主要具有以下优势:
(1)所发明的醇基柴油燃料添加剂相比于单独的甲醇、乙醇柴油混合后的分散性好,稳定性强;
(2)所使用的助溶剂和表面活性剂原料来源广泛,成本较低;
(3)甲醇-乙醇脱氢产物制备过程采用铜负载氧化硅型催化剂,催化效率适当,催化产物无需处理,操作简单,并且以甲醇和乙醇为原料,成本低,性价比高;
(4)添加的甲醇比例能够满足市场要求,在5~30wt%之间灵活可调,且利于节能减排。该醇基柴油燃料添加剂可用于高原发电机、农业机械,船舶发动机等领域,具有高氧含量的优势,在高原环境中能够稳定使用,而且氧含量的增加促进了燃料燃烧,减少了碳烟生成。此外,甲醇、乙醇几乎不含硫氮元素,燃烧后不会排放硫氧化物,限制减少氮化物排放。因此该醇基柴油燃料添加剂是一种含氧清洁燃料。
具体实施方式
本发明涉及的评价醇基柴油燃料添加剂与柴油稳定性的指标主要为两者混合后在室温下开始出现分层前保存的时长。
本发明涉及的醇基柴油燃料添加剂与柴油的混合后稳定性的影响因素主要包括甲醇-乙醇脱氢产物及助溶剂、表面活性剂以及甲醇-乙醇脱氢产物中酯产物的类型和比例。对于甲醇-乙醇脱氢反应前原料比例一定的体系,其稳定性随添加剂添加量的增加而升高,且乳化甲醇柴油中甲醇含量越多,所需添加剂的添加量也相应增加。
实施例1:
按照以下方法称取一定量的Cu(NO3)2·3H2O和Zn(NO3)2·6H2O固体溶于去离子水中,使得铜锌摩尔比为10:1,在搅拌的条件下缓慢滴加氨水,使其生成铜氨络合物,使得pH值为9,充分搅拌30min后加入硅溶胶,使得铜负载量为20wt.%,常温下搅拌4h,随后转移至旋转蒸发仪中蒸氨使得最终pH值为6~7,过滤,水洗3~4次,所得滤饼在真空干燥箱内120℃温度下干燥12h,随后转移至马弗炉500℃下焙烧4h,后经研磨、压片筛分出20~40目的CuO/ZnO/SiO2催化剂前驱体,随后在氢气气氛中还原4h,还原温度为350℃,最终得到所需催化剂。将所得到的催化剂在固定床微型反应器中,通入氮气,甲醇、乙醇按照5:1的比例混合,反应温度为240℃,,压力为0.2MPa、空速为1h-1,进料流量为0.065ml/min,进料一定时间后催化剂的催化活性趋于稳定时,开始收集液相产物,得到甲醇-乙醇脱氢产物。经过分析,其中包含甲酸甲酯、乙酸甲酯、乙酸乙酯、甲酸乙酯和其它少量酯类。
将甲醇-乙醇脱氢产物、助溶剂、表面活性剂按照44:5:1的比例混合,超声20min后得到实施例1醇基柴油燃料添加剂,其组成见表1。
表1实施例1醇基柴油燃料添加剂各组分及其比例
实施例2:
按照以下方法称取一定量的Cu(NO3)2·3H2O和Zn(NO3)2·6H2O固体溶于去离子水中,使得铜锌摩尔比为15:1,在搅拌的条件下缓慢滴加氨水,使其生成铜氨络合物,使得pH值为9,充分搅拌30min后加入硅溶胶,使得铜负载量为25wt.%,常温下搅拌4h,随后转移至旋转蒸发仪中蒸氨使得最终pH值为6~7,过滤,水洗3~4次,所得滤饼在真空干燥箱内120℃温度下干燥12h,随后转移至马弗炉500℃下焙烧4h,后经研磨、压片筛分出20~40目的CuO/ZnO/SiO2催化剂前驱体,随后在氢气气氛中还原4h,还原温度为350℃,最终得到所需催化剂。将所得到的催化剂在固定床微型反应器中,通入氮气,甲醇、乙醇按照8:1的比例混合,反应温度为250℃,,压力为0.3MPa、空速为2h-1,进料流量为0.075ml/min,进料一定时间后催化剂的催化活性趋于稳定时,开始收集液相产物,得到甲醇-乙醇脱氢产物,其中包含甲酸甲酯、乙酸甲酯、乙酸乙酯、甲酸乙酯和其它酯类。
将甲醇-乙醇脱氢产物、助溶剂、表面活性剂按照约为82:15:2的比例混合,超声20min后得到实施例2甲醇柴油燃料添加剂,其组成见表2。
表2实施例2醇基柴油燃料添加剂各组分及其比例
实施例3:
按照以下方法称取一定量的Cu(NO3)2·3H2O和Zn(NO3)2·6H2O固体溶于去离子水中,使得铜锌摩尔比为20:1,在搅拌的条件下缓慢滴加氨水,使其生成铜氨络合物,使得pH值为9,充分搅拌30min后加入硅溶胶,使得铜负载量为30wt.%,常温下搅拌4h,随后转移至旋转蒸发仪中蒸氨使得最终pH值为6~7,过滤,水洗3~4次,所得滤饼在真空干燥箱内120℃温度下干燥12h,随后转移至马弗炉500℃下焙烧4h,后经研磨、压片筛分出20~40目的CuO/ZnO/SiO2催化剂前驱体,随后在氢气气氛中还原4h,还原温度为350℃,最终得到所需催化剂。将所得到的催化剂在固定床微型反应器中,通入氮气,甲醇、乙醇按照8:1的比例混合,反应温度为260℃,,压力为0.4MPa、空速为3h-1,进料流量为0.085ml/min,进料一定时间后催化剂的催化活性趋于稳定时,开始收集液相产物,以此得到甲醇-乙醇脱氢产物,其中包含甲酸甲酯、乙酸甲酯、乙酸乙酯、甲酸乙酯和其它酯类。
将甲醇-乙醇脱氢产物、助溶剂、表面活性剂按照77:20:3的比例混合,超声20min后得到实施例3甲醇柴油燃料添加剂,其组成见表3。
表3实施例3醇基柴油燃料添加剂各组分及其比例
下面通过实例对本发明的一种乳化甲醇柴油燃料添加剂的应用的技术方案进一步具体说明。
应用例1
取116份实施例1中醇基柴油燃料添加剂加入到950份加氢柴油中在室温下使用超声波分散器超声分散30min后即制得甲醇、乙醇总质量分数约为5wt%的乳化柴油燃料。可在室温下保存240h以上,经过显微镜法测定,其平均粒径为1.0μm左右。
应用例2
取473份实施例2中醇基柴油燃料添加剂加入到950份加氢柴油中在室温下使用超声波分散器超声分散30min后即制得甲醇、乙醇总质量分数为15wt%的乳化柴油燃料。可在室温下保存220h以上。经过显微镜法测定,其平均粒径为1.3μm左右。
应用例3
取1759份实施例3中醇基柴油燃料添加剂加入到950份加氢柴油中在室温下使用超声波分散器超声分散30min后即制得甲醇、乙醇总质量分数约为30wt%的乳化柴油燃料。可在室温下保存200h以上。经过显微镜法测定,其平均粒径为1.5μm左右。
应用例4
取1759份实施例3中醇基柴油燃料添加剂加入到950份京博石化商品柴油中在室温下使用超声波分散器超声分散30min后即制得甲醇、乙醇总质量分数约为30wt%的乳化柴油燃料。可在室温下保存200h以上。经过显微镜法测定,其平均粒径为1.4μm左右。
对比例1
取200份甲醇、乙醇混合溶液加入到800份加氢柴油中,其中甲醇:乙醇质量比为10:1,助溶剂中加入的正丁醇63份,多元醇甲醚14份,表面活性剂中加入Span80共18份,Tween80共18份,Tween60共54份,在室温下使用超声分散器超声分散后制备得到甲醇、乙醇总质量分数为20wt%的乳化柴油燃料,超声分散参数:功率384W,时间30min。制备的乳化柴油燃料可在室温下稳定3h。经过显微镜法测定,其平均粒径为2.5μm左右。
对比例2
取200份甲醇、乙醇混合溶液加入到800份京博石化商品柴油中,其中甲醇:乙醇质量比为10:1,助溶剂中加入的正丁醇63份,多元醇甲醚14份,表面活性剂中加入Span80共18份,Tween80共18份,Tween60共54份,在室温下使用超声分散器超声分散后制备得到甲醇、乙醇总质量分数为20wt%的乳化柴油燃料,超声分散参数:功率384W,时间30min。制备的乳化柴油燃料可在室温下稳定3h。经过显微镜法测定,其平均粒径为2.3μm左右
对比例3
取621份实施例1中的甲醇-乙醇脱氢产物加入到800份加氢柴油中,在室温下使用超声分散器超声分散后制备得到甲醇、乙醇总质量分数为20wt%的乳化柴油燃料,超声分散参数:功率384W,时间30min。制备的乳化柴油燃料可在室温下稳定5h。经过显微镜法测定,其平均粒径为3.1μm左右
将对比例1、对比例2、对比例3与本发明的应用例1制备的乳化柴油燃料稳定时间进行对比,结果如图1所示。
附图说明:
本发明的醇基柴油燃料添加剂的使用效果以及和对比例的效果对比情况由附图给出。
图1为应用例与对比例制备的乳化柴油燃料的稳定时间对比。
从图1可以看出,本发明的应用例乳化柴油燃料的稳定时间要明显大于对比例的乳化柴油燃料。通过对比发现,柴油中加入未经反应的甲醇、乙醇的稳定性显著低于加入反应后的甲醇-乙醇脱氢产物,主要原因在于反应后产物中含有的混合酯类对甲醇、乙醇与柴油的稳定性有良好的助溶效果,并且加入助溶剂和表面活性剂有助于该体系稳定性的进一步提升。总的来说,醇基柴油燃料添加剂与柴油稳定的核心在于甲醇-乙醇脱氢产物的制备及与醇醚助剂、表面活性助剂的混合使用。
显然,上述实施例仅仅是为清楚地说明一种醇基柴油燃料添加剂及应用所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (6)
1.一种醇基柴油燃料添加剂的制备方法,其特征在于,以甲醇和乙醇为原料使用专用催化剂进行催化脱氢反应后得到的甲醇-乙醇脱氢产物、并与助溶剂和表面活性剂按一定比例经过超声分散混合得到醇基柴油燃料添加剂。
2.甲醇-乙醇脱氢反应是在固定床微型反应器中进行,甲醇、乙醇按照20:1~5:1的比例混合,反应温度为240℃~280℃,反应压力为0.2MPa~0.5MPa、反应空速为1h-1~4h-1,所用气体为氮气,进料流量为0.065~0.103ml/min,经实验分析证明液相产物主要有甲酸甲酯、乙酸甲酯、乙酸乙酯、甲酸乙酯和其它酯类。
3.根据权利要求1所述的一种醇基柴油燃料添加剂的制备方法,其特征在于,助溶剂主要是正丁醇、多元醇甲醚、多元醇丁醚、双多元醇甲醚、多元醇丁醚酯中的一种或几种复配。
4.根据权利要求1所述的一种醇基柴油燃料添加剂的制备方法,其特征在于,表面活性剂主要是Span80、OP-10、Tween80、Tween60中的一种或几种复配。
5.根据权利要求1所述的一种醇基柴油燃料添加剂的制备方法,其特征在于,所用铜负载氧化硅型催化剂的制备方法具体包括:
(1)称取一定量的Cu(NO3)2·3H2O和Zn(NO3)2·6H2O固体溶于去离子水中,在搅拌的条件下缓慢加入氨水使其生成铜氨络合物,使得pH值为9~10;
(2)充分搅拌后加入硅溶胶,常温下搅拌4h,随后转移至旋转蒸发仪中蒸氨使得最终pH值为6~7;
(3)经过过滤、水洗、干燥、焙烧后筛分并得到20~40目的催化剂前驱体,随后在氢气气氛中还原4h,还原温度为350℃,最终得到催化剂;
(4)其中催化剂中Cu与Zn的比例和Cu在载体上的负载量均可调节。
6.根据权利要求1所述的一种醇基柴油燃料添加剂的制备方法,其特征在于,添加剂中甲醇-乙醇脱氢产物占比为50~90wt%、助溶剂占比为7~40wt%、表面活性剂占比为0.05~10wt%、醇基燃料添加剂和柴油的混合比例为5~30:100。
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