CN114806653A - 一种生物质基酯类复配燃料及其制备方法 - Google Patents
一种生物质基酯类复配燃料及其制备方法 Download PDFInfo
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- -1 ester compound Chemical class 0.000 title claims abstract description 63
- 239000000446 fuel Substances 0.000 title claims abstract description 43
- 239000002028 Biomass Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229940058352 levulinate Drugs 0.000 claims abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 15
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 13
- 229930182478 glucoside Natural products 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002283 diesel fuel Substances 0.000 claims description 18
- 239000007791 liquid phase Substances 0.000 claims description 16
- JOOXCMJARBKPKM-UHFFFAOYSA-N laevulinic acid Natural products CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 15
- 229940040102 levulinic acid Drugs 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 6
- 235000019253 formic acid Nutrition 0.000 claims 3
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
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- 238000000746 purification Methods 0.000 abstract description 3
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- 239000003209 petroleum derivative Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical group CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ISBWNEKJSSLXOD-UHFFFAOYSA-N Butyl levulinate Chemical compound CCCCOC(=O)CCC(C)=O ISBWNEKJSSLXOD-UHFFFAOYSA-N 0.000 description 4
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 description 4
- OUGPMNMLWKSBRI-UHFFFAOYSA-N Hexyl formate Chemical compound CCCCCCOC=O OUGPMNMLWKSBRI-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 4
- HBBVKEXMLPMFQQ-UHFFFAOYSA-N hexyl 4-oxopentanoate Chemical compound CCCCCCOC(=O)CCC(C)=O HBBVKEXMLPMFQQ-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DIQMPQMYFZXDAX-UHFFFAOYSA-N Pentyl formate Chemical compound CCCCCOC=O DIQMPQMYFZXDAX-UHFFFAOYSA-N 0.000 description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940005460 butyl levulinate Drugs 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NLDFWNCRMVSDMC-UHFFFAOYSA-N pentyl 4-oxopentanoate Chemical compound CCCCCOC(=O)CCC(C)=O NLDFWNCRMVSDMC-UHFFFAOYSA-N 0.000 description 3
- BZANQLIRVMZFOS-ZKZCYXTQSA-N (3r,4s,5s,6r)-2-butoxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound CCCCOC1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O BZANQLIRVMZFOS-ZKZCYXTQSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JVAZJLFFSJARQM-RMPHRYRLSA-N (2r,3r,4s,5s,6r)-2-hexoxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound CCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O JVAZJLFFSJARQM-RMPHRYRLSA-N 0.000 description 1
- HOVAGTYPODGVJG-UVSYOFPXSA-N (3s,5r)-2-(hydroxymethyl)-6-methoxyoxane-3,4,5-triol Chemical compound COC1OC(CO)[C@@H](O)C(O)[C@H]1O HOVAGTYPODGVJG-UVSYOFPXSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JDRSMPFHFNXQRB-CMTNHCDUSA-N Decyl beta-D-threo-hexopyranoside Chemical compound CCCCCCCCCCO[C@@H]1O[C@H](CO)C(O)[C@H](O)C1O JDRSMPFHFNXQRB-CMTNHCDUSA-N 0.000 description 1
- WYUFTYLVLQZQNH-JAJWTYFOSA-N Ethyl beta-D-glucopyranoside Chemical compound CCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O WYUFTYLVLQZQNH-JAJWTYFOSA-N 0.000 description 1
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229940073499 decyl glucoside Drugs 0.000 description 1
- 238000007257 deesterification reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003365 short chain fatty acid esters Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- 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
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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
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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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
- C10L10/00—Use of additives to fuels or fires for particular purposes
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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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
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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
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Abstract
本发明公开了一种生物质基酯类复配燃料及其制备方法,以烷基葡萄糖苷为原料,用酸化介孔碳材料催化一步转化制备乙酰丙酸酯和甲酸酯,直接做为燃料添加剂使用,无需进行分离提纯步骤,无需从乙酰丙酸酯中除去甲酸酯副产物,进而提高了原料的利用率,进而降低制备成本,并以部分替代柴油,改善能源结构。
Description
技术领域:
本发明涉及生物质基液体燃料技术领域,具体涉及一种生物质基酯类复配燃料及其制备方法。
背景技术:
目前随着全世界经济的快速持续发展,石化能源需求量不断增加,而作为不可再生的化石能源将会逐渐枯竭,有限的石化燃料已难以满足人们对能源的需求。此外燃用化石燃料会由于燃料含氧量低,燃烧不充分,进而产生大量如一氧化碳(CO)、未燃碳氢(UHC)、二氧化硫(SO2)、氮氧化物(NOx)和颗粒(PM)等有害物。因此,为有效延缓化石燃料的消耗和减少有害物的排放,开发新的石油替代能源越来越得到人们的关注。已有的研究表明:由纤维素类生物质水(醇)解酯化得到的乙酰丙酸酯和甲酸酯等短链脂肪酸酯,是一类重要的酯类含氧液体燃料,其在燃烧过程中,能提供额外的氧,能使燃料燃烧更加充分,进而达到降低有害物质排放、提高燃烧性能的目的。但是,目前国内外关于乙酰丙酸酯燃料并未在工业规模上大量使用,这主要是因于乙酰丙酸酯作为燃料使用,还是一个比较新兴的燃料,制备成本较高,大多数合成方法获得乙酰丙酸的收率较低。再一个原因是现有的乙酰丙酸酯制备过程中,伴随着甲酸酯副产物生成,且相应的乙酰丙酸酯、甲酸酯为成对出现的,如:乙酰丙酸甲酯、甲酸甲酯;乙酰丙酸乙酯、甲酸乙酯;乙酰丙酸丁酯、甲酸丁酯;乙酰丙酸戊酯、甲酸戊酯;乙酰丙酸己酯、甲酸己酯等。在乙酰丙酸酯合成制备过程中往往伴随着甲酸酯副产物的形成及其与乙酰丙酸酯的分离问题,导致生产乙酰丙酸酯需要较高的分离配套成本。
发明内容:
本发明的目的是提供一种生物质基酯类复配燃料及其制备方法,以烷基葡萄糖苷为原料,用酸化介孔碳材料催化一步转化制备乙酰丙酸酯和甲酸酯,直接做为燃料添加剂使用,无需进行分离提纯步骤,无需从乙酰丙酸酯中除去甲酸酯副产物,进而提高了原料的利用率,进而降低制备成本,并以部分替代柴油,改善能源结构。
本发明是通过以下技术方案予以实现的:
一种生物质基酯类复配燃料,由乙酰丙酸酯、甲酸酯和柴油混合而成,按总体积百分比为100%计,其体积百分比如下:乙酰丙酸酯1~7%,甲酸酯1~3%,闪点改进剂0.1~0.3%,柴油99~89.7%;所述为柴油市场上销售的0#柴油;所述闪点改进剂选择市售闪点提高剂GK-T21773;所述乙酰丙酸酯是通式为CH3COC2H4COOR的化合物中的一种或两种以上,R为C1~C10直链烷基,优选地,R为C4~C6直链烷基;所述甲酸酯是通式为CH3COOR′的化合物中的一种或两种以上,R′为C1~C10直链烷基,优选地,R′为C4~C6直链烷基。
所述生物质基酯类复配燃料的制备方法如下:将烷基葡萄糖苷、脂肪醇和酸化介孔碳材料催化剂混合,置于高压反应釜中,在惰性气体氛围中3~5MPa,180℃下,反应2~4h后,冷却静置,所得乙酰丙酸酯和甲酸酯液相混合物中加入闪点改进剂混合均匀,搅拌下慢慢加入到柴油中,即得。
乙酰丙酸酯和甲酸酯液相混合物的用量为1%-10%体积,优选为1%-7%,更优选为3-5%。
所用烷基葡萄糖苷为甲基葡萄糖苷、丙基葡萄糖苷、丁基葡萄糖苷、葵基葡萄糖苷等烷基为C1~C10直链烷基的烷基葡萄糖苷。
脂肪醇为甲醇、乙醇、丁醇、葵醇等C1~C10直链脂肪醇的一种或两种以上。
酸化介孔碳材料催化剂为酸化CMK-3(H-CMK-3)或酸化CMK-5(H-CMK-5);其制备方法可采用如下步骤:将介孔碳材料CMK-3或CMK-5置于含对氨基苯磺酸和亚硝酸异戊酯的水溶液中,80℃下搅拌回流12h,过滤所得固体经乙醇反复浸泡,过滤,除去未反应有机物后,水洗过滤,干燥即得酸化介孔碳材料催化剂H-CMK-3或H-CMK-5。
本发明的有益效果如下:
1)以烷基葡萄糖苷为原料,用酸化介孔碳材料催化一步转化制备乙酰丙酸酯和甲酸酯,直接做为燃料添加剂使用,无需进行分离提纯步骤,无需从乙酰丙酸酯中除去甲酸酯副产物,进而提高了原料的利用率,进而降低制备成本,并以部分替代柴油,改善能源结构。
2)本发明的生物质基酯类复配燃料,可以长期保持稳定不分层,具有良好的互溶性、低温流动性、氧化安定性、闪点、密度、馏程、抗爆性、防腐性、蒸气压和十六烷值与柴油水平相当,能够使柴油发动机稳定可靠工作,满足车用燃料安全要求。
3)本发明开发的生物质基酯类复配燃料与纯乙酰丙酸酯相比,具有更优良的含氧值,在燃烧过程中,可提供额外的氧,能使燃料进行充分燃烧,且由于生物质基酯类复配燃料不含有硫、氮等元素,其在柴油机中燃烧的碳烟、一氧化碳、二氧化碳、氮氧化物等污染物排放比燃烧柴油有明显降低,故在一定程度上能够达到节能减排的作用。
4)本发明的生物质基酯类复配燃料由可再生的生物质经水(醇)解酯化制得,原料来源可再生,具有良好的工业应用前景。
具体实施方式:
以下是对本发明的进一步说明,而不是对本发明的限制。
实施例1:
取100g丁基葡萄糖苷,800mL丁醇,2g酸化介孔碳材料催化剂置于高压反应釜中,在氮气压力3MPa,180℃下搅拌反应2h,冷却静置,得到乙酰丙酸丁酯和甲酸丁酯的液相混合物,将上述获得的乙酰丙酸丁酯和甲酸丁酯液相混合物与闪点改进剂混合均匀后,在搅拌情况下缓慢地倒入到0#柴油中,即制得生物质基酯类复配燃料。生物质基酯类复配燃料,其体积百分比组成为:乙酰丙酸丁酯3%,甲酸丁酯1%,闪点改进剂0.1%,0#柴油95.9%,性能见表1。
实施例2
取100g戊基葡萄糖苷,1000mL戊醇,3g酸化介孔碳材料催化剂置于高压反应釜中,在氮气压力3MPa,180℃下搅拌反应4h,冷却静置,得到乙酰丙酸戊酯和甲酸戊酯的液相混合物。将上述获得的乙酰丙酸戊酯和甲酸戊酯的液相混合物与闪点改进剂混合均匀后,在搅拌情况下缓慢地倒入到0#柴油中,即制得生物质基酯类复配燃料。生物质基酯类复配燃料,其体积百分比组成为:乙酰丙酸戊酯7%,甲酸戊酯3%,闪点改进剂0.2%,0#柴油89.9%。
实施例3
取100g已基葡萄糖苷,1000mL己醇,4g酸化介孔碳材料催化剂置于高压反应釜中,在氮气压力3MPa,180℃下搅拌反应4h,冷却静置,得到乙酰丙酸己酯和甲酸己酯的液相混合物。将上述获得的乙酰丙酸己酯和甲酸己酯的液相混合物与闪点改进剂混合均匀后,在搅拌情况下缓慢地倒入到0#柴油中,即制得生物质基酯类复配燃料。生物质基酯类复配燃料,其体积百分比组成为:乙酰丙酸己酯5%,甲酸己酯2%,闪点改进剂0.1%,0#柴油92.9%,性能见表1。
实施例4
取100g乙基葡萄糖苷,800mL乙醇,2g酸化介孔碳材料催化剂置于高压反应釜中,在氮气压力3MPa,180℃下搅拌反应2h,冷却静置,得到乙酰丙酸乙酯和甲酸乙酯的液相混合物。将上述获得的乙酰丙酸乙酯和甲酸乙酯的液相混合物与闪点改进剂混合均匀后,在搅拌情况下缓慢地倒入到0#柴油中,即制得生物质基酯类复配燃料。生物质基酯类复配燃料,其体积百分比组成为:乙酰丙酸乙酯3%,甲酸乙酯1%,闪点改进剂0.3%,0#柴油95.7%,性能见表1。
实施例5
取100g丙基葡萄糖苷,900mL丙醇,2g酸化介孔碳材料催化剂置于高压反应釜中,在氮气压力3MPa,180℃下搅拌反应4h,冷却静置,得到乙酰丙酸丙酯和甲酸丙酯的液相混合物。将上述获得的乙酰丙酸丙酯和甲酸丙酯的液相混合物与闪点改进剂混合均匀后,在搅拌情况下缓慢地倒入到0#柴油中,即制得生物质基酯类复配燃料。生物质基酯类复配燃料,其体积百分比组成为:乙酰丙酸丙酯4%,甲酸丙酯1%,闪点改进剂0.2%,0#柴油94.8%,性能见表1。
对实施例1-5制得的生物质基酯类复配燃料进行理化特性的测定。
互溶性:将制得的生物质基酯类复配燃料密封于蓝盖瓶中,分别在4℃、10℃、15℃、20℃、25℃、30℃下放置一个月,观察无分层和浑浊现象。密度:采用石油产品密度测定器(KD-R1023)测定,方法参考GB/T 1884,1185;硫含量:采用石油产品硫含量测定器(KD-R3041)测定,方法参考SH/T 0689;灰分:采用石油产品灰分测定器(KD-R0901)测定,方法参考GB/T 508;铜片腐蚀(50℃,3h):采用石油产品铜片腐蚀测定器(KD-R1093)测定,方法参考GB/T 5096;运动黏度:采用石油产品运动黏度测定器(KD-R0515)测定,方法参考GB/T265;冷滤点:采用石油产品冷滤点测定器(KD-R3000)测定,方法参考SH/T0248;闪点:采用石油产品全自动闭口闪点测定器(KD-R0210)测定,方法参考GB/T 261;镏程:采用石油产品蒸馏测定器测定(KD-R2015),方法参考GB/T 6536。热值:采用热值测定仪(5E-KCIII)测定,方法参考GB/T 384-1981;氧化安定性测试:采用石油产品蒸馏测定仪(JSR1008B)测定,方法参考SH/T0175-2004。
由表1可知,生物质基酯类复配燃料具有与柴油十分接近的理化特性,密闭储存2个月不分层,性质稳定;氧化安定性指标基本不变;对柴油的馏程影响不明显;密度增幅不大;运动黏度有所降低,冷滤点明显下降,说明本发明的生物质基酯类复配燃料具有优异的低温流动性,有利于在寒冷地区以高体积百分含量推广使用;硫含量降低,有利于降低发动机的PM排放。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种生物质基酯类复配燃料,其特征在于,由乙酰丙酸酯、甲酸酯和柴油混合而成,按总体积百分比为100%计,其体积百分比如下:乙酰丙酸酯1~7%,甲酸酯1~3%,闪点改进剂0.1~0.3%,柴油99~89.7%;所述乙酰丙酸酯是通式为CH3COC2H4COOR的化合物中的一种或两种以上,R为C1~C10直链烷基,所述甲酸酯是通式为CH3COOR′的化合物中的一种或两种以上,R′为C1~C10直链烷基;所述生物质基酯类复配燃料的制备方法如下:将烷基葡萄糖苷、脂肪醇和酸化介孔碳材料催化剂混合,置于高压反应釜中,在惰性气体氛围中3~5MPa,180℃下,反应2~4h后,冷却静置,所得乙酰丙酸酯和甲酸酯液相混合物中加入闪点改进剂混合均匀,搅拌下慢慢加入到柴油中,即得。
2.根据权利要求1所述生物质基酯类复配燃料,其特征在于,乙酰丙酸酯和甲酸酯液相混合物的用量为1%-10%体积。
3.根据权利要求2所述生物质基酯类复配燃料,其特征在于,乙酰丙酸酯和甲酸酯液相混合物的用量为1%-7%。
4.根据权利要求3所述生物质基酯类复配燃料,其特征在于,乙酰丙酸酯和甲酸酯液相混合物的用量为3-5%。
5.根据权利要求1所述生物质基酯类复配燃料,其特征在于,R为C4~C6直链烷基;R′为C4~C6直链烷基。
6.根据权利要求1所述生物质基酯类复配燃料,其特征在于,所用烷基葡萄糖苷为C1~C10直链烷基的烷基葡萄糖苷。
7.根据权利要求1所述生物质基酯类复配燃料,其特征在于,脂肪醇为C1~C10直链脂肪醇的一种或两种以上。
8.根据权利要求1所述生物质基酯类复配燃料,其特征在于,所述柴油为0#柴油;所述闪点改进剂选择闪点提高剂GK-T21773。
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