WO2021168998A1 - 2,5-四氢呋喃二甲醇二脂肪酸酯制备方法及其在柴油添加剂的应用 - Google Patents

2,5-四氢呋喃二甲醇二脂肪酸酯制备方法及其在柴油添加剂的应用 Download PDF

Info

Publication number
WO2021168998A1
WO2021168998A1 PCT/CN2020/084089 CN2020084089W WO2021168998A1 WO 2021168998 A1 WO2021168998 A1 WO 2021168998A1 CN 2020084089 W CN2020084089 W CN 2020084089W WO 2021168998 A1 WO2021168998 A1 WO 2021168998A1
Authority
WO
WIPO (PCT)
Prior art keywords
tetrahydrofurandimethanol
preparation
acid
reaction
acid ester
Prior art date
Application number
PCT/CN2020/084089
Other languages
English (en)
French (fr)
Inventor
王磊
金海涛
张建
张永淳
杨勇
卢国文
Original Assignee
浙江糖能科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 浙江糖能科技有限公司 filed Critical 浙江糖能科技有限公司
Priority to DE112020005955.3T priority Critical patent/DE112020005955T5/de
Publication of WO2021168998A1 publication Critical patent/WO2021168998A1/zh

Links

Images

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
    • C10L1/10—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
    • 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
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • 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
    • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • 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
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines

Definitions

  • the application relates to a diesel fuel additive, in particular to a bio-based 2,5-tetrahydrofurandimethanol difatty acid ester and a preparation method thereof, belonging to the field of fuels.
  • Diesel is a component obtained through catalytic cracking, hydrogenation catalysis, coking and other methods after crude oil distillation. Diesel engines have strict requirements on the ignition performance and anti-riot performance of diesel during use, and are used to measure the ignition performance and An important indicator of anti-knock performance is the cetane number in diesel.
  • the size of the cetane number affects the emission of harmful substances, start-up performance and fuel consumption of diesel. When the cetane number in diesel is high, the emissions of harmful substances and the occurrence of knocking during vehicle startup and driving are significantly less than those of diesel with low cetane number. Therefore, the use of diesel with high cetane number will reduce the engine The damage will also reduce fuel consumption.
  • the more commonly used additives to increase the cetane number of diesel fuel on the market include nitrate esters, azide compounds, peroxy compounds, ethers, and esters. Most of these additives are produced with non-renewable petrochemicals. With the exhaustion of fossil energy and environmental pollution, it is very necessary to find renewable resources that can replace them.
  • a method for preparing 2,5-tetrahydrofurandimethanol difatty acid ester and its application in diesel fuel additives are provided.
  • HMF 5-Hydroxymethylfurfural
  • DHMTHF 2,5-Tetrahydrofurandimethanol
  • HMF 5-hydroxymethylfurfural
  • the dibasic acid ester produced by the esterification reaction is added to diesel, which can effectively increase the cetane number of diesel. Therefore, it has good practical significance for the development and utilization of clean energy.
  • the preparation method of the 1, 2, 5-tetrahydrofurandimethanol difatty acid ester includes the following steps:
  • reaction system containing 2,5-tetrahydrofurandimethanol and monobasic acid is subjected to an esterification reaction to obtain the 1, 2,5-tetrahydrofurandimethanol difatty acid ester;
  • the structural formula of the monobasic acid is R-COOH; wherein, R is a C5-C20 alkyl group.
  • R is a C7-C14 alkyl group.
  • the monobasic acid is selected from at least one of n-octanoic acid, n-nonanoic acid, n-decanoic acid, undecanoic acid, dodecanoic acid, and myristic acid.
  • the catalyst is selected from at least one of Candida lipase B, calcium acetate, titanium tetraalkoxy, manganese acetate, cobalt acetate, aluminum oxide, zinc oxide, and zinc aluminum spinel.
  • the titanium tetraalkoxide is at least one selected from titanium tetraethoxide.
  • Candida lipase B is used after being dried.
  • the drying method includes:
  • Candida lipase B into a flask, and store it with phosphorus pentoxide at room temperature and high vacuum conditions for 16h-24h before drying for use.
  • the particle size of the calcium acetate, titanium tetraalkoxy, manganese acetate, cobalt acetate, aluminum oxide, zinc oxide, and zinc aluminum spinel are all less than or equal to 80 mesh.
  • the molar ratio of the monobasic acid to 2,5-tetrahydrofurandimethanol is 2 to 4:1.
  • the molar ratio of the monobasic acid to 2,5-tetrahydrofurandimethanol is in the range of 2:1, 3:1, 4:1, and any two ratios thereof.
  • the mass ratio of the 2,5-tetrahydrofurandimethanol to the catalyst is 50-200:1.
  • reaction system is a substance-solvent system
  • the reaction system further includes a solvent; the solvent is selected from at least one of dimethyl sulfoxide and dimethyl formamide; the volume ratio of the solvent to 2,5-tetrahydrofuran dimethanol is 10-20:1 .
  • the conditions of the esterification reaction are: the reaction temperature is 60-120° C., and the reaction time is 10-24 hours.
  • the upper limit of the reaction temperature is selected from 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C; the lower limit is selected from 60°C, 70°C, 80°C, 90°C, 100°C, or 110°C .
  • the upper limit of the reaction time is selected from 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours Or 24 hours; the lower limit is selected from 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours or 23 hours.
  • the water produced during the esterification reaction is removed by means of vacuum distillation.
  • the obtained mixture is purified to obtain the diesel fuel additive
  • the purification includes washing with alkali solution, drying and distillation in organic solvent;
  • the alkaline solution includes at least one of sodium carbonate solution and potassium carbonate solution;
  • the organic solvent is selected from at least one of ethanol, ethyl acetate, and petroleum ether.
  • the purification includes:
  • the obtained mixture is washed with sodium carbonate solution and water, dried with anhydrous sodium sulfate, and rotary evaporated with at least one of ethanol, ethyl acetate and petroleum ether.
  • the addition amount of the 2,5-tetrahydrofurandimethanol difatty acid ester in the diesel fuel is 5-10% by weight of the diesel fuel.
  • the 2,5-tetrahydrofurandimethanol difatty acid ester is used as a diesel fuel additive.
  • CALB refers to Candida lipase B.
  • C5 to C20, C7 to C14, etc. all refer to the number of carbon atoms contained in the group.
  • alkyl refers to a group formed by the loss of any hydrogen atom on the molecule of an alkane compound.
  • the method for preparing 2,5-tetrahydrofurandimethanol difatty acid esters uses a catalyst to generate biobased difatty acid esters with 2,5-tetrahydrofurandimethanol and monobasic acids of different chain lengths.
  • the method has low equipment and technical requirements, easy preparation process, high selectivity, and simple purification process.
  • Figure 1 is the theoretical reaction process of 2,5-tetrahydrofurandimethanol and monobasic acids with different chain lengths in the examples of this application.
  • Figure 3 is a time-of-flight mass spectrum of 2,5-tetrahydrofurandimethanol monodecanoate produced by the reaction of 2,5-tetrahydrofurandimethanol and n-decanoic acid in Example 7 of the application.
  • Figure 4 is the liquid chromatography of 2,5-tetrahydrofurandimethanol monocaprate and 2,5-tetrahydrofurandimethanol dicaprate produced by the reaction of 2,5-tetrahydrofurandimethanol and n-decanoic acid in Example 7 of the application picture.
  • the 4600 time-of-flight mass spectrometer produced by American AB Sciex was used for flight mass spectrometry analysis.
  • the gas-phase mass spectrometry analysis was performed using the 7890B-7977A gas-phase mass spectrometer produced by Agilent Company in the United States.
  • the liquid phase analysis was performed using the 1260 high performance liquid chromatograph produced by Agilent Company in the United States.
  • the conversion rate of 2,5-tetrahydrofurandimethanol the mass of 2,5-tetrahydrofurandimethanol after the reaction/the mass of 2,5-tetrahydrofurandimethanol in the input reaction.
  • the selectivity of 2,5-tetrahydrofurandimethanol diester the mass of 2,5-tetrahydrofurandimethanol diester/the mass of the total reaction product.
  • the yield of 2,5-tetrahydrofurandimethanol diester the mass of purified 2,5-tetrahydrofurandimethanol diester/the theoretically produced mass of 2,5-tetrahydrofurandimethanol xx.
  • the concentration of the sodium carbonate solution in the example is 2 mol/L.
  • an application of 2,5-tetrahydrofurandimethanol difatty acid ester in diesel fuel additives is provided.
  • the 2,5-tetrahydrofurandimethanol difatty acid ester can be used as a bio-based diesel fuel additive to increase the cetane number of diesel fuel and improve its combustion performance.
  • the preparation method of the 2,5-tetrahydrofurandimethanol difatty acid ester includes the following steps:
  • the molar ratio of the monobasic acids with different chain lengths to 2,5-tetrahydrofurandimethanol is 2:1 to 4:1;
  • the monobasic acid is one or more of n-octanoic acid, n-nonanoic acid, n-decanoic acid, undecanoic acid, dodecanoic acid, and myristic acid.
  • the catalyst is one of biological enzyme CALB, calcium acetate, titanium tetraalkoxy, manganese acetate, cobalt acetate, aluminum oxide, zinc oxide, zinc aluminum spinel, or Many kinds. Since 2,5-tetrahydrofurandimethanol has good thermal stability, it can produce di-fatty acid esters at higher temperatures and has good selectivity.
  • 2,5-tetrahydrofuran dimethanol has better thermal stability, it can either use the biological enzyme catalyst CALB with better catalytic activity to carry out the esterification reaction at a lower temperature, or it can be combined with calcium acetate, Basic compounds such as titanium tetraalkoxide, or weak alkali salts such as manganese acetate and cobalt acetate are used as esterification catalysts.
  • the particle size of the catalyst should be less than or equal to 80 mesh.
  • the system contains one or more of solventless, dimethyl sulfoxide, and dimethyl formamide.
  • the reaction temperature is high, the reaction raw materials are required to not decompose at the reaction temperature, the reaction raw material ratio is strict, the reaction materials have high viscosity, small molecules are not easy to remove, and the tightness of the reaction equipment is required.
  • 2,5-tetrahydrofurandimethanol will be oxidized to generate new by-products at higher temperatures. Therefore, when there is no solvent in the system, the reaction temperature should be strictly controlled to reduce the presence of by-products.
  • the presence of the solvent can reduce the reaction temperature, avoid the decomposition of raw materials and products, the reaction is stable and easy to control, and can be easily controlled.
  • the small molecules azeotrope or react with them to remove them.
  • the disadvantage is that the presence of solvent increases the process of esterification reaction separation, refining, and solvent recovery.
  • the biological enzyme catalyst CALB in S100, is put into a flask, and it is stored with phosphorus pentoxide under high vacuum conditions at room temperature for 16 to 24 hours before being dried for use.
  • the particle size of calcium acetate, titanium tetraalkoxide, manganese acetate, cobalt acetate, aluminum oxide, zinc oxide, and zinc aluminum spinel is less than or equal to 80 mesh.
  • the reaction temperature is 60°C to 120°C.
  • the reaction time is 10h-24h.
  • the water generated during the reaction is subjected to vacuum distillation treatment.
  • the product in S200, is washed with sodium carbonate solution and water, and dried with anhydrous sodium sulfate.
  • one or more of ethanol, ethyl acetate, and petroleum ether is used for rotary evaporation.
  • the obtained product is washed with a certain concentration of sodium carbonate solution and water for multiple washings, and the excess fatty acid is removed and then dried with anhydrous sodium sulfate.
  • step (2) Put the product obtained in step (1) into the prepared sodium carbonate solution for full washing, then rinse with deionized water, dry with anhydrous sodium sulfate, and use ethanol solution to remove by-products by rotary evaporation to obtain The final higher purity 2,5-tetrahydrofurandimethanol dioctanoate.
  • the conversion rate of 2,5-tetrahydrofurandimethanol was 100%.
  • the yield of 2,5-tetrahydrofurandimethanol dicaprylate was 59%.
  • the selectivity of 2,5-tetrahydrofurandimethanol dicaprylate is 80%.
  • Example 1 Compared with Example 1, the concentration of n-octanoic acid in the raw materials used in this example has changed, and the rest of the preparation conditions have not changed. As the concentration of n-octanoic acid increases, the final 2,5-tetrahydrofurandimethanol The yield of dicaprylate will increase. The conversion rate of 2,5-tetrahydrofurandimethanol was 100%. The yield of 2,5-tetrahydrofurandimethanol dioctanoate was 71%. The selectivity of 2,5-tetrahydrofurandimethanol dicaprylate is 85%.
  • Example 1 Compared with Example 1, the reaction temperature used in this example has changed, and the rest of the preparation conditions have not changed. As the temperature rises, the final yield of 2,5-tetrahydrofurandimethanol dioctanoate will be Will improve. The conversion rate of 2,5-tetrahydrofurandimethanol was 100%. The yield of 2,5-tetrahydrofurandimethanol dioctanoate was 73%. The selectivity of 2,5-tetrahydrofurandimethanol dicaprylate is 92%.
  • Example 1 Compared with Example 1, the reaction time used in this example has changed, and the rest of the preparation conditions have not changed. As the reaction time increases, the final yield of 2,5-tetrahydrofurandimethanol dioctanoate will be Will improve. The conversion rate of 2,5-tetrahydrofurandimethanol was 100%. The yield of 2,5-tetrahydrofurandimethanol dioctanoate was 66%. The selectivity of 2,5-tetrahydrofurandimethanol dicaprylate is 84%.
  • step (2) Put the product obtained in step (1) into the prepared sodium carbonate solution for full cleaning, then rinse with deionized water, dry with anhydrous sodium sulfate, and use ethyl acetate solution to remove by-products by rotary evaporation , To obtain the final higher purity 2,5-tetrahydrofuran dimethanol dipelargonate.
  • step (2) Put the product obtained in step (1) into the prepared sodium carbonate solution for full cleaning, then rinse with deionized water, dry with anhydrous sodium sulfate, and then use petroleum ether to remove by-products by rotary evaporation to obtain The final higher purity 2,5-tetrahydrofurandimethanol dicaprate.
  • step (2) Put the product obtained in step (1) into the prepared sodium carbonate solution for full washing, then rinse with deionized water, dry with anhydrous sodium sulfate, and use ethyl acetate to remove by-products by rotary evaporation. The final 2,5-tetrahydrofurandimethanol dicaprate of higher purity is obtained.
  • step (2) Put the product obtained in step (1) into the prepared sodium carbonate solution for full washing, then rinse with deionized water, dry with anhydrous sodium sulfate, and use ethyl acetate to remove by-products by rotary evaporation.
  • the final 2,5-tetrahydrofurandimethanol dicaprate of higher purity is obtained.
  • the conversion rate of 2,5-tetrahydrofurandimethanol was 100%.
  • the yield of 2,5-tetrahydrofurandimethanol dicaprate was 85%.
  • the selectivity of 2,5-tetrahydrofurandimethanol dicaprate is 95%.
  • step (2) Put the product obtained in step (1) into the prepared sodium carbonate solution for full cleaning, then rinse with deionized water, dry with anhydrous sodium sulfate, and then use ethanol to remove by-products through rotary evaporation to obtain the final Higher purity 2,5-tetrahydrofurandimethanol undecanoic acid diester.
  • step (2) Put the product obtained in step (1) into the prepared sodium carbonate solution for full cleaning, then rinse with deionized water, dry with anhydrous sodium sulfate, and then use ethanol to remove by-products through rotary evaporation to obtain the final High purity 2,5-tetrahydrofurandimethanol dodecanoic acid diester.
  • step (2) Put the product obtained in step (1) into the prepared sodium carbonate solution for full cleaning, then rinse with deionized water, dry with anhydrous sodium sulfate, and then use ethanol to remove by-products through rotary evaporation to obtain the final Higher purity 2,5-tetrahydrofuran dimethanol myristate diester.
  • Figure 4 is a liquid chromatogram, in which the 2,5-tetrahydrofuran-decanoate with the trans structure with a retention time of 5.17 minutes, and the cis-structure 2,5-tetrahydrofuran-decanoate with a retention time of 6.13 minutes, retained The time 14.83 minutes is 2,5-tetrahydrofuran didecanoate.
  • the bio-based di-fatty acid esters prepared in Examples 1-11 were used as diesel fuel additives to test the cetane number of the diesel.
  • the diesel used was the biodiesel from the Romania biodiesel gas station.
  • the cetane number of the diesel is 57.4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

种2,5-四氢呋喃二甲醇二脂肪酸酯的制备方法及其作为柴油添加剂的应用。在催化剂存在下，使2,5-四氢呋喃二甲醇与一元酸进行酯化反应，所述一元酸的结构式为R-COOH，其中，R为C5〜C20的烷基。2,5-四氢呋喃二甲醇二脂肪酸酷可以提升柴油的十六烷值。

Description

2,5-四氢呋喃二甲醇二脂肪酸酯制备方法及其在柴油添加剂的应用 技术领域
本申请涉及一种柴油添加剂，具体涉及一种生物基2,5-四氢呋喃二甲醇二脂肪酸酯及其制备方法，属于燃料领域。
背景技术
柴油是原油蒸馏后经过催化裂化、加氢催化、焦化等方式得到的组分，使用过程中柴油发动机对柴油的着火性能和抗暴性能都有较为严格的要求，而用来衡量柴油的着火性能和抗爆性能的重要指标就是柴油当中的十六烷值。十六烷值的大小影响了柴油有害物质的排放、启动性能和耗油量等。当柴油中十六烷值较高时，有害物质的排放、车辆启动和行驶时发生爆震的现象明显少于十六烷值低的柴油，因此使用十六烷值高的柴油将会减轻发动机的损坏，也会使得油耗减少。
目前市面上较为常用的提升柴油十六烷值的添加剂包括硝酸酯类、叠氮化合物类、过氧化合物类、醚类和酯类等。在这其中大部分的添加剂是用不可再生的石油基化学品进行生产的，伴随着化石能源的枯竭以及环境污染等问题，寻找可代替其作用的可再生资源是十分必要的。
发明内容
根据本申请的一个方面，提供了一种2,5-四氢呋喃二甲醇二脂肪酸酯制备方法及其在柴油添加剂的应用。
5-羟甲基糠醛(HMF)是生物质衍生的碳水化合物如果糖、葡萄糖、淀粉和纤维素等脱水得到的，由于其能经氧化或还原生成各种具有高价值的单体，因此被誉为最重要的基本化合物之一。虽然许多5-羟甲基糠醛(HMF)衍生物，如醚、缩醛、内酯等能够作为生物质衍生燃料和添加剂，但直接酯化这些化合物以生产生物燃料的研究较少。
2,5-四氢呋喃二甲醇(DHMTHF)可以通过5-羟甲基糠醛(HMF)加氢还原生成，由于结构对称，且具有较好的热稳定性，可以与一元酸在较高的温度下发生酯化反应，产生的二元酸酯加入到柴油中，可以有效的提升柴油的十六烷值，因此，对清洁能源的开发和利用具有较好的实际意义。
可选地，所述1、2,5-四氢呋喃二甲醇二脂肪酸酯的制备方法包括以下步骤：
在催化剂存在的条件下，使含有2,5-四氢呋喃二甲醇与一元酸的反应体系进行酯化 反应，得到所述1、2,5-四氢呋喃二甲醇二脂肪酸酯；
所述一元酸的结构式为R-COOH；其中，R为C5～C20的烷基。
可选地，R为C7～C14的烷基。
可选地，所述一元酸选自正辛酸、正壬酸、正癸酸、十一酸、十二酸、十四酸中的至少一种。
可选地，所述催化剂选自假丝酵母脂肪酶B、醋酸钙、四烷氧基钛、醋酸锰、醋酸钴、氧化铝、氧化锌、锌铝尖晶石的至少一种。
可选地，所述四烷氧基钛选自四乙氧基钛中的至少一种。
可选地，所述假丝酵母脂肪酶B经干燥后使用。
可选地，所述干燥的方式包括：
将假丝酵母脂肪酶B放入的烧瓶中，与五氧化二磷在室温、高真空条件下保存16h～24h干燥后使用。
可选地，所述醋酸钙、四烷氧基钛、醋酸锰、醋酸钴、氧化铝、氧化锌、锌铝尖晶石的粒度均小于或等于80目。
可选地，所述一元酸与2,5-四氢呋喃二甲醇的摩尔比为2～4:1。
可选地，所述一元酸与2,5-四氢呋喃二甲醇的摩尔比为2:1、3:1、4:1及其任意两个比值之间的范围值。
可选地，所述2,5-四氢呋喃二甲醇与催化剂的质量比为50～200:1。
可选地，所述反应体系为物溶剂体系；或者
所述反应体系还包括溶剂；所述溶剂选自二甲基亚砜、二甲基甲酰胺中的至少一种；所述溶剂与2,5-四氢呋喃二甲醇的体积比为10～20:1。
可选地，所述酯化反应的条件为：反应温度为60～120℃，反应时间为10～24小时。
可选地，所述反应温度的上限选自70℃、80℃、90℃、100℃、110℃或120℃；下限选自60℃、70℃、80℃、90℃、100℃或110℃。
可选地，所述反应时间的上限选自11小时、12小时、13小时、14小时、15小时、16小时、17小时、18小时、19小时、20小时、21小时、22小时、23小时或24小时；下限选自10小时、11小时、12小时、13小时、14小时、15小时、16小时、17小时、18小时、19小时、20小时、21小时、22小时或23小时。
可选地，所述酯化反应过程中产生的水采用减压蒸馏的方式除去。
可选地，酯化反应结束后，得到的混合物经过提纯得到所述柴油添加剂；
所述提纯包括碱溶液洗涤、干燥和有机溶剂中蒸馏；
所述碱溶液包括碳酸钠溶液、碳酸钾溶液中的至少一种；
所述有机溶剂选自乙醇、乙酸乙酯、石油醚中的至少一种。
可选地，所述提纯包括：
得到的混合物用碳酸钠溶液和水洗涤，无水硫酸钠干燥，用乙醇、乙酸乙酯、石油醚的至少一种进行旋蒸。
根据本申请的另一个方面，提供上述任一种制备方法制备的所述2,5-四氢呋喃二甲醇二脂肪酸酯在柴油添加剂中的应用。
可选地，2,5-四氢呋喃二甲醇二脂肪酸酯在柴油中的添加量为柴油的5～10wt％。
可选地，所述2,5-四氢呋喃二甲醇二脂肪酸酯作为柴油添加剂的应用。
本申请中，“CALB”，是指假丝酵母脂肪酶B。
在本申请中，C5～C20、C7～C14等均是指基团中所包含的碳原子数。
在本申请中，术语“烷基”是指由烷烃化合物分子上失去任意一个氢原子所形成的基团。
本申请能产生的有益效果包括：
1)本申请所提供的2,5-四氢呋喃二甲醇二脂肪酸酯在柴油添加剂中的应用，所得的生物基二脂肪酸酯加入到柴油中，可以有效提升柴油的十六烷值，具有较高的应用价值。
2)本申请所提供的2,5-四氢呋喃二甲醇二脂肪酸酯的制备方法，通过催化剂作用2,5-四氢呋喃二甲醇与不同链长的一元酸生成生物基二脂肪酸酯，本发明的方法对设备和技术要求低，制备过程容易，选择性较高，提纯过程简单。
附图说明
图1为本申请实施例中2,5-四氢呋喃二甲醇与不同链长的一元酸的理论反应过程。
图2为本申请实施例7中2,5-四氢呋喃二甲醇与正癸酸反应生成的2,5-四氢呋喃二甲醇二癸酸酯的飞行时间质谱图。
图3为本申请实施例7中2,5-四氢呋喃二甲醇与正癸酸反应生成的2,5-四氢呋喃 二甲醇一癸酸酯的飞行时间质谱图。
图4为本申请实施例7中2,5-四氢呋喃二甲醇与正癸酸反应生成的2,5-四氢呋喃二甲醇一癸酸酯和2,5-四氢呋喃二甲醇二癸酸酯的液相色谱图。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
如无特别说明，本申请的实施例中的原料和催化剂均通过商业途径购买。
本申请的实施例中分析方法如下：
利用美国AB Sciex公司生产的型号为4600飞行时间质谱仪进行飞行质谱分析。
利用美国安捷伦公司生产的型号为7890B-7977A气相质谱联用仪进行气相质谱分析。
利用美国安捷伦公司生产的型号为1260高效液相色谱仪进行液相分析。
实施例中，2,5-四氢呋喃二甲醇的转化率＝反应后2,5-四氢呋喃二甲醇的质量/投入反应2,5-四氢呋喃二甲醇的质量。
实施例中，2,5-四氢呋喃二甲醇二酸酯的选择性＝2,5-四氢呋喃二甲醇二酸酯的质量/反应总产物的质量。
实施例中，2,5-四氢呋喃二甲醇二酸酯的产率＝提纯后2,5-四氢呋喃二甲醇二酸酯的质量/理论生产2,5-四氢呋喃二甲醇二酸酯的质量xx。
实施例中的碳酸钠溶液的浓度为2mol/L。
根据本申请的一种实施方式，提供一种2,5-四氢呋喃二甲醇二脂肪酸酯在柴油添加剂中的应用。该2,5-四氢呋喃二甲醇二脂肪酸酯可以作为生物基柴油添加剂，提高柴油的十六烷值从而提升其燃烧性能。
根据本申请的一种实施方式，所述2,5-四氢呋喃二甲醇二脂肪酸酯的制备方法包括以下步骤：
S100:将2,5-四氢呋喃二甲醇和不同链长的一元酸按照一定的比例混合后进行酯化反应；
其中，所述的不同链长的一元酸与2,5-四氢呋喃二甲醇的摩尔比为2:1～4:1；
S200：对所得的产物进行洗涤干燥，旋蒸去除副产物后得到二脂肪酸酯柴油添加剂。
在其中一个实施例中，S100中，所述的一元酸为正辛酸、正壬酸、正癸酸、十一 酸、十二酸、十四酸中的一种或多种。
在其中一个实施例中，S100中，所述的催化剂为生物酶CALB、醋酸钙、四烷氧基钛、醋酸锰、醋酸钴、氧化铝、氧化锌、锌铝尖晶石中的一种或者多种。由于2,5-四氢呋喃二甲醇具有较好的热稳定性，可以在较高的温度下产生二脂肪酸酯，具有较好的选择性。
本申请中，2,5-四氢呋喃二甲醇由于具有较好的热稳定性，其既可以使用催化活性较好的生物酶催化剂CALB在较低的温度下进行酯化反应，也可以与醋酸钙、四烷氧基钛等碱性化合物，或者弱碱盐醋酸锰、醋酸钴等作为酯化反应催化剂。同时，为了使催化剂和反应物充分接触，催化剂的粒度应该小于等于80目。
在其中一个实施例中，S100中，体系内为无溶剂、二甲基亚砜、二甲基甲酰胺中的一种或多种。当体系中不添加溶剂进行酯化反应时，其生产工艺过程简单，反应时间短。但是其缺点是反应温度高，要求反应原料在反应温度下不分解，反应原料配比要求严格，反应物料黏度高，小分子不易脱除，对反应设备密封性要求高。但2,5-四氢呋喃二甲醇在较高的温度下会被氧化生成新的副产物，因此，在体系内没有溶剂存在时，应该严格控制反应温度，减少副产物的存在。而以二甲基亚砜、二甲基甲酰胺中的一种或多种作为溶剂进行酯化反应时，溶剂的存在可以降低反应温度，避免原料和产物分解，反应平稳容易控制，可与产生的小分子共沸或与之反应而使其脱除。缺点是溶剂的存在增加了酯化反应分离、精制、溶剂回收等工序。
在其中一个实施例中，S100中，将生物酶催化剂CALB放入的烧瓶中，与五氧化二磷在室温、高真空条件下保存16h～24h干燥后使用。
在其中一个实施例中，S100中，醋酸钙、四烷氧基钛、醋酸锰、醋酸钴、氧化铝、氧化锌、锌铝尖晶石的粒度小于等于80目。
在其中一个实施例中，S100中，反应温度为60℃～120℃。
在其中一个实施例中，S100中，反应时间为10h～24h。
在其中一个实施例中，S100中，对反应过程中产生的水进行减压蒸馏处理。
在其中一个实施例中，S200中，产物用碳酸钠溶液和水洗涤，无水硫酸钠干燥。
在其中一个实施例中，S200中，用乙醇、乙酸乙酯、石油醚的一种或者多种进行旋蒸。较佳地，将所得的产物用一定浓度的碳酸钠溶液和水洗涤进行多次洗涤，去除多余的脂肪酸后无水硫酸钠干燥。再用乙醇、乙酸乙酯、石油醚的一种或者多种进行旋蒸，充分去除副产物后得到高纯度的生物基脂肪酸二酯。
实施例1
(1)在三颈烧瓶中加入1.32g的2,5-四氢呋喃二甲醇和2.88g正辛酸，再加入0.02g醋酸锰(粒度为80目)在100℃下充分搅拌，用减压蒸馏的方式抽除体系内产生的水，促进反应进程提高转化率，充分反应10h。其中，正辛酸与2,5-四氢呋喃二甲醇的摩尔比为2:1。
(2)将步骤(1)得到的产物置于配置的碳酸钠溶液中充分清洗，再用去离子水冲洗干净，用无水硫酸钠干燥，再用乙醇溶液经行旋蒸去除副产物，得到最终较高纯度的2,5-四氢呋喃二甲醇二辛酸酯。2,5-四氢呋喃二甲醇的转化率为100％。2,5-四氢呋喃二甲醇二辛酸酯的产率为59％。2,5-四氢呋喃二甲醇二辛酸酯的的选择性为80％。
实施例2
(1)在三颈烧瓶中加入1.32g的2,5-四氢呋喃二甲醇和4.32g正辛酸，再加入0.02g醋酸锰(粒度为80目)在100℃下充分搅拌，用减压蒸馏的方式抽除体系内产生的水，促进反应进程提高转化率，充分反应10h。其中，正辛酸与2,5-四氢呋喃二甲醇摩尔比为3:1。
(2)同实施例1。
与实施例1相比，本实施例所使用的原料中的正辛酸的浓度发生了变化，其余制备条件未发生改变，随着正辛酸的浓度的升高，最终的2,5-四氢呋喃二甲醇二辛酸酯的产率将会提升。2,5-四氢呋喃二甲醇的转化率为100％。2,5-四氢呋喃二甲醇二辛酸酯的产率为71％。2,5-四氢呋喃二甲醇二辛酸酯的的选择性为85％。
实施例3
(1)在三颈烧瓶中加入1.32g的2,5-四氢呋喃二甲醇和2.88g正辛酸，再加入0.02g醋酸锰(粒度为80目)在120℃下充分搅拌，用减压蒸馏的方式抽除体系内产生的水，促进反应进程提高转化率，充分反应10h。其中，正辛酸与2,5-四氢呋喃二甲醇的摩尔比为2:1。
(2)同实施例1。
与实施例1相比，本实施例所使用的反应温度发生了变化，其余制备条件未发生改变，随着温度的升高，最终的2,5-四氢呋喃二甲醇二辛酸酯的产率将会提升。2,5-四氢呋喃二甲醇的转化率为100％。2,5-四氢呋喃二甲醇二辛酸酯的产率为73％。2,5-四氢呋喃二甲醇二辛酸酯的的选择性为92％。
实施例4
(1)在三颈烧瓶中加入1.32g的2,5-四氢呋喃二甲醇和2.88g正辛酸，再加入0.02g醋酸锰(粒度为80目)在100℃下充分搅拌，用减压蒸馏的方式抽除体系内产生的水，促进反应进程提高转化率，充分反应24h。其中，正辛酸与2,5-四氢呋喃二甲醇的摩尔比为2:1。
(2)同实施例1
与实施例1相比，本实施例所使用的反应时间发生了变化，其余制备条件未发生改变，随着反应时间的增加，最终的2,5-四氢呋喃二甲醇二辛酸酯的产率将会提升。2,5-四氢呋喃二甲醇的转化率为100％。2,5-四氢呋喃二甲醇二辛酸酯的产率为66％。2,5-四氢呋喃二甲醇二辛酸酯的的选择性为84％。
实施例5
(1)在三颈烧瓶中加入1.32g的2,5-四氢呋喃二甲醇和3.16g正壬酸，加入10mL的二甲基亚砜，再加入0.02g四烷氧基钛(粒度为80目)在100℃下充分搅拌，用减压蒸馏的方式抽除体系内产生的水，促进反应进程提高转化率，充分反应10h。其中，正壬酸与2,5-四氢呋喃二甲醇的摩尔比为2:1。
(2)将步骤(1)得到的产物置于配置的碳酸钠溶液中充分清洗，再用去离子水冲洗干净，用无水硫酸钠干燥，再用乙酸乙酯溶液经行旋蒸去除副产物，得到最终较高纯度的2,5-四氢呋喃二甲醇二壬酸酯。
实施例6
(1)在三颈烧瓶中加入1.32g的2,5-四氢呋喃二甲醇和3.44g正癸酸，加入10mL二甲基甲酰胺，再加入0.02g醋酸锰(粒度为80目)在100℃下充分搅拌，用减压蒸馏的方式抽除体系内产生的水，促进反应进程提高转化率，充分反应10h。其中，正癸酸与2,5-四氢呋喃二甲醇的摩尔比为2:1。
(2)将步骤(1)得到的产物置于配置的碳酸钠溶液中充分清洗，再用去离子水冲洗干净，用无水硫酸钠干燥，再用石油醚经行旋蒸去除副产物，得到最终较高纯度的2,5-四氢呋喃二甲醇二癸酸酯。
实施例7
(1)在三颈烧瓶中加入1.32g的2,5-四氢呋喃二甲醇和3.44g正癸酸，再加入0.02g醋酸钙(粒度为80目)在120℃下充分搅拌，用减压蒸馏的方式抽除体系内产生的水，促进反应进程提高转化率，充分反应24h。其中，正癸酸与2,5-四氢呋喃二甲醇的摩尔比为2:1。
(2)将步骤(1)得到的产物置于配置的碳酸钠溶液中充分清洗，再用去离子水冲洗干净，用无水硫酸钠干燥，再用乙酸乙酯经行旋蒸去除副产物，得到最终较高纯度的2,5-四氢呋喃二甲醇二癸酸酯。
实施例8
(1)将生物酶催化剂CALB放入的烧瓶中，与五氧化二磷在室温、高真空条件下保存16h干燥后使用。在三颈烧瓶中加入1.32g的2,5-四氢呋喃二甲醇和3.44g正癸酸，再加入0.02g生物酶CALB(粒度为80目)在60℃下充分搅拌，用减压蒸馏的方式抽除体系内产生的水，促进反应进程提高转化率，充分反应24h。其中，正癸酸与2,5-四氢呋喃二甲醇的摩尔比为2:1。
(2)将步骤(1)得到的产物置于配置的碳酸钠溶液中充分清洗，再用去离子水冲洗干净，用无水硫酸钠干燥，再用乙酸乙酯经行旋蒸去除副产物，得到最终较高纯度的2,5-四氢呋喃二甲醇二癸酸酯。2,5-四氢呋喃二甲醇的转化率为100％。2,5-四氢呋喃二甲醇二癸酸酯的产率为85％。2,5-四氢呋喃二甲醇二癸酸酯的的选择性为95％。
实施例9
(1)在三颈烧瓶中加入1.32g的2,5-四氢呋喃二甲醇和3.72g十一酸，加入10mL二甲基亚砜，再加入0.02g醋酸钴(粒度为80目)在120℃下充分搅拌，用减压蒸馏的方式抽除体系内产生的水，促进反应进程提高转化率，充分反应24h。其中，十一酸与2,5-四氢呋喃二甲醇的摩尔比为2:1。
(2)将步骤(1)得到的产物置于配置的碳酸钠溶液中充分清洗，再用去离子水冲洗干净，用无水硫酸钠干燥，再用乙醇经行旋蒸去除副产物，得到最终较高纯度的2,5-四氢呋喃二甲醇十一酸二酯。
实施例10
(1)在三颈烧瓶中加入1.32g的2,5-四氢呋喃二甲醇和4.00g十二酸，加入10mL二甲基亚砜，再加入0.02g醋酸钴(粒度为80目)在120℃下充分搅拌，用减压蒸馏 的方式抽除体系内产生的水，促进反应进程提高转化率，充分反应24h。其中，十二酸与2,5-四氢呋喃二甲醇的摩尔比为2:1。
(2)将步骤(1)得到的产物置于配置的碳酸钠溶液中充分清洗，再用去离子水冲洗干净，用无水硫酸钠干燥，再用乙醇经行旋蒸去除副产物，得到最终较高纯度的2,5-四氢呋喃二甲醇十二酸二酯。
实施例11
(1)在三颈烧瓶中加入1.32g的2,5-四氢呋喃二甲醇和4.56g十四酸，加入10mL二甲基亚砜，再加入0.02g醋酸钴(粒度为80目)在120℃下充分搅拌，用减压蒸馏的方式抽除体系内产生的水，促进反应进程提高转化率，充分反应24h。其中，十四酸与2,5-四氢呋喃二甲醇的摩尔比为2:1。
(2)将步骤(1)得到的产物置于配置的碳酸钠溶液中充分清洗，再用去离子水冲洗干净，用无水硫酸钠干燥，再用乙醇经行旋蒸去除副产物，得到最终较高纯度的2,5-四氢呋喃二甲醇十四酸二酯。
实施例12
将实施例1～11制备的生物基二元酸酯进行飞行时间质谱测试，测试结果表明，均制备得到了相应的产物。典型的测试结果如图2、图3、图4中图所示，对应实施例7制备的产物。图2所示为2,5-四氢呋喃二癸酸酯的分子离子峰和碎片离子峰，图3为未反应完全的2,5-四氢呋喃一癸酸酯的分子离子峰和碎片离子峰。图4为液相色谱图，其中保留时间5.17分钟的为反式结构的2,5-四氢呋喃一癸酸酯，保留时间6.13分钟的为顺式结构的2,5-四氢呋喃一癸酸酯，保留时间14.83分钟的为2,5-四氢呋喃二癸酸酯。
实施例13应用
将实施例1～11制备的生物基二脂肪酸酯作为柴油添加剂，测试柴油的十六烷值，所用的柴油为罗马利亚生物柴油加油站的生物柴油。
典型地，2,5-四氢呋喃二甲醇癸酸二酯添加量为生物柴油质量的5％wt时，柴油的十六烷值为57.4。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在 不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (12)

  1. 一种2,5-四氢呋喃二甲醇二脂肪酸酯的制备方法，其特征在于，所述2,5-四氢呋喃二甲醇二脂肪酸酯的制备方法包括以下步骤：
    在催化剂存在的条件下，使含有2,5-四氢呋喃二甲醇与一元酸的反应体系进行酯化反应，得到所述2,5-四氢呋喃二甲醇二脂肪酸酯；
    所述一元酸的结构式为R-COOH；其中，R为C5～C20的烷基；
    所述2,5-四氢呋喃二甲醇二脂肪酸酯具如式I所示结构式；
    Figure PCTCN2020084089-appb-100001
    其中，R选自C5～C20的烷基中的一种。
  2. 根据权利要求1所述的制备方法，其特征在于，所述一元酸选自正辛酸、正壬酸、正癸酸、十一酸、十二酸、十四酸中的至少一种。
  3. 根据权利要求1所述的制备方法，其特征在于，所述催化剂选自假丝酵母脂肪酶B、醋酸钙、四烷氧基钛、醋酸锰、醋酸钴、氧化铝、氧化锌、锌铝尖晶石的至少一种。
  4. 根据权利要求3所述的制备方法，其特征在于，所述醋酸钙、四烷氧基钛、醋酸锰、醋酸钴、氧化铝、氧化锌、锌铝尖晶石的粒度均小于或等于80目。
  5. 根据权利要求1所述的制备方法，其特征在于，所述一元酸与2,5-四氢呋喃二甲醇的摩尔比为2～4:1。
  6. 根据权利要求1所述的制备方法，其特征在于，所述2,5-四氢呋喃二甲醇与催化剂的质量比为50～200:1。
  7. 根据权利要求1所述的制备方法，其特征在于，所述反应体系为物溶剂体系；或者
    所述反应体系还包括溶剂；所述溶剂选自二甲基亚砜、二甲基甲酰胺中的至少一种；所述溶剂与2,5-四氢呋喃二甲醇的体积比为10～20:1。
  8. 根据权利要求1所述的制备方法，其特征在于，所述酯化反应的条件为：反应温度为60～120℃，反应时间为10～24小时。
  9. 根据权利要求1所述的制备方法，其特征在于，所述酯化反应过程中产生的水采用减压蒸馏的方式除去。
  10. 根据权利要求1所述的制备方法，其特征在于，酯化反应结束后，得到的混合物经过提纯得到所述2,5-四氢呋喃二甲醇二脂肪酸酯。
  11. 根据权利要求10所述的制备方法，其特征在于，所述提纯包括碱溶液洗涤、干燥和有机溶剂中蒸馏；
    所述碱溶液包括碳酸钠溶液、碳酸钾溶液中的至少一种；
    所述有机溶剂选自乙醇、乙酸乙酯、石油醚中的至少一种。
  12. 权利要求1至11任一项所述的制备方法制备的2,5-四氢呋喃二甲醇二脂肪酸酯在柴油添加剂的应用。
PCT/CN2020/084089 2020-02-28 2020-04-10 2,5-四氢呋喃二甲醇二脂肪酸酯制备方法及其在柴油添加剂的应用 WO2021168998A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE112020005955.3T DE112020005955T5 (de) 2020-02-28 2020-04-10 Verfahren zur Herstellung eines 2,5-Tetrahydrofurandimethanoldifettsäureesters und seine Verwendung in einem Dieseladditiv

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010131494.2 2020-02-28
CN202010131494.2A CN111349492B (zh) 2020-02-28 2020-02-28 2,5-四氢呋喃二甲醇脂肪酸二酯在柴油添加剂的应用

Publications (1)

Publication Number Publication Date
WO2021168998A1 true WO2021168998A1 (zh) 2021-09-02

Family

ID=71190847

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/084089 WO2021168998A1 (zh) 2020-02-28 2020-04-10 2,5-四氢呋喃二甲醇二脂肪酸酯制备方法及其在柴油添加剂的应用

Country Status (3)

Country Link
CN (1) CN111349492B (zh)
DE (1) DE112020005955T5 (zh)
WO (1) WO2021168998A1 (zh)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102994172A (zh) * 2007-09-07 2013-03-27 福兰尼克斯科技公司 5-取代的2-(烷氧基甲基)呋喃
CN106146300A (zh) * 2015-04-24 2016-11-23 中国科学院大连化学物理研究所 一种二羧酸二元醇酯增塑剂的制备方法
US20170001971A1 (en) * 2013-12-20 2017-01-05 Archer Daniels Midland Company Direct synthesis of bio-based alkyl & furanic diol ethers, acetates, ether-acetates, and carbonates
CN107686470A (zh) * 2017-09-26 2018-02-13 中国科学院宁波材料技术与工程研究所 一种2,5‑呋喃二甲醇二酯类增塑剂及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150140367A (ko) * 2013-04-12 2015-12-15 바스프 에스이 테트라히드로푸란 유도체 및 가소제로서의 그의 용도
RU2016112345A (ru) * 2013-09-04 2017-10-09 Басф Се Производные тетрагидрофурана и их применение в качестве пластификаторов
AU2014369062A1 (en) * 2013-12-20 2016-06-30 Archer Daniels Midland Company Direct synthesis of bio-based alkyl and furanic diol ethers, acetates, ether-acetates, and carbonates
WO2016055196A1 (de) * 2014-10-07 2016-04-14 Basf Se Langkettige mono- und diester des 2,5-di(hydroxymethyl)tetrahydrofurans, deren herstellung und verwendung
CN106946820B (zh) * 2017-03-29 2019-08-27 厦门大学 2,5-呋喃二甲醇及其醚化产物的合成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102994172A (zh) * 2007-09-07 2013-03-27 福兰尼克斯科技公司 5-取代的2-(烷氧基甲基)呋喃
US20170001971A1 (en) * 2013-12-20 2017-01-05 Archer Daniels Midland Company Direct synthesis of bio-based alkyl & furanic diol ethers, acetates, ether-acetates, and carbonates
CN106146300A (zh) * 2015-04-24 2016-11-23 中国科学院大连化学物理研究所 一种二羧酸二元醇酯增塑剂的制备方法
CN107686470A (zh) * 2017-09-26 2018-02-13 中国科学院宁波材料技术与工程研究所 一种2,5‑呋喃二甲醇二酯类增塑剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIANG WENYUAN: "Master Thesis", 30 April 2013, QINGDAO UNIVERSITY OF SCIENCE AND TECHNOLOGY, CN, article LIANG WENYUAN: "Catalytic Synthesis of2,5-Bismethoxymethylfuran: A Promising Cetane Number Improver for Diesel", pages: 1 - 69, XP055841700 *

Also Published As

Publication number Publication date
CN111349492A (zh) 2020-06-30
DE112020005955T5 (de) 2022-09-22
CN111349492B (zh) 2021-05-25

Similar Documents

Publication Publication Date Title
Tan et al. Efficient production of ethyl levulinate from cassava over Al2 (SO4) 3 catalyst in ethanol–water system
CN1643116A (zh) 由生物质和烯烃制备乙酰丙酸酯和甲酸酯
CN104711007A (zh) 一种航空煤油或柴油范围液态烷烃的制备方法
US20170001944A1 (en) Chemical process to convert mucic acid to adipic acid
CN113788793B (zh) 磺酸功能化的咪唑离子液体催化剂及其制备方法和应用
Ma et al. Conversion of cellulose to butyl levulinate in bio-butanol medium catalyzed by acidic ionic liquids
CN109734687B (zh) 5-羟甲基糠醛还原醚化制备2,5-二烷氧基甲基呋喃的方法
WO2021168998A1 (zh) 2,5-四氢呋喃二甲醇二脂肪酸酯制备方法及其在柴油添加剂的应用
CN108947943B (zh) 一种固体磷钨酸直接催化5-甲基糠醇二聚的方法
CN107141208B (zh) 1,3-二羟基丙酮的制备方法
CN113372302A (zh) 2,5-四氢呋喃二甲醇二酸酯及其制备方法、应用
WO2016066071A1 (zh) 一种碳水化合物制备乙醇酸酯的方法
CN109999907B (zh) 一种磺酸功能化无机有机杂化聚合物催化剂的制备方法及其应用
WO2023193425A1 (zh) 一种利用废弃生物质制备2-甲基四氢呋喃的方法
CN111434657B (zh) 一种γ-戊内酯与乙酰丙酸酯类化合物的制备方法
CN111744553B (zh) 十二烷基苯磺酸锆催化剂及其在糠醇醇解反应中的应用
CN112279758B (zh) 一种由葡萄糖制备及分离乙酰丙酸的方法
CN113512030A (zh) 一种生物质基呋喃化合物的醛基保护方法
WO2022141457A1 (zh) 单锡有机化合物、制备方法及其应用
Su et al. The driving effect of substituent size changes on reaction: a novel reaction for direct production of triacetylglycerol from oils and fats
CN111057594B (zh) 一种醇基燃料添加剂的制备方法
CN111841527A (zh) 一种复合双金属氧化物介孔材料的制备方法及应用
CN105658632A (zh) 在来源于生物质的基于乙二醇的化合物溶剂的存在下使用酸催化剂制备5-羟甲基-2-糠醛的方法
CN113209986B (zh) 一种负载型锆基催化剂及制备方法和应用
Krishnasamy et al. One-pot liquefaction of cellulose to ethyl levulinate via 1-sulfonic acid-3-methyl imidazolium trichlorozincate as Brønsted-Lewis catalyst

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20921606

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 20921606

Country of ref document: EP

Kind code of ref document: A1