技术领域technical field
本发明属于有机催化合成技术领域，具体涉及一种γ-戊内酯的合成方法。The invention belongs to the technical field of organic catalytic synthesis, and in particular relates to a synthesis method of gamma-valerolactone.
背景技术Background technique
γ-戊内酯具有无毒、可生物降解的特性，被认为是最具应用前景的生物质基平台化合物之一，可作为可再生的碳源生产碳基化学品及能源。近年来越来越受到学术界和工业界的重视。γ-戊内酯作为原料可以参与Ivanov反应合成药物，可以和苯基芳香化合物的Friedel-Crafts反应及环化、还原和脱水等反应合成各种多取代萘蒽菲类化合物，γ-戊内酯还可以经过环化和脱羧/加氢分别合成戊烯酸、丁烯、戊酸和5-壬酮；此外，γ-戊内酯开环位置不同，得到的产物也不同，1，4-戊二醇和2-甲基四氢呋喃都是精细化工中间体。1，4-戊二醇可以用于制备高性能的生物可降解聚酯，2-甲基四氢呋喃则是一种性能优良的溶剂和燃料添加剂。另一方面，γ-戊内酯同样可以用作合成聚合材料的原料。γ-戊内酯与甲醛在Ba/SiO2催化下具有类似丙烯酸酯结构的新型单体α-亚甲基-γ-戊内酯，其分子中独特的环酯结构，使得聚α-亚甲基-γ-戊内酯材料具有比传统聚丙烯酸酯材料更好的热稳定性，其玻璃化温度(Tg)可以达到200℃以上。催化转化γ-戊内酯也可合成二羧酸酯类单体或者另一种非常重要的聚合材料---聚氨酯。也有研究表明，γ-戊内酯本身就是比乙醇更好的汽油添加剂，因为γ-戊内酯具有更低的饱和蒸气压和更高的能量密度。而且不同于乙醇的是，γ-戊内酯与水不会形成共沸物，发酵液中分离提纯乙醇更节能。γ-valerolactone is non-toxic and biodegradable, and is considered to be one of the most promising biomass-based platform compounds, which can be used as a renewable carbon source to produce carbon-based chemicals and energy. In recent years, it has received more and more attention from academia and industry. As a raw material, γ-valerolactone can participate in the Ivanov reaction to synthesize drugs, and can synthesize various multi-substituted naphthalenthrenyl compounds through Friedel-Crafts reaction and cyclization, reduction and dehydration reactions of phenyl aromatic compounds, γ-valerolactone It is also possible to synthesize pentenoic acid, butene, valeric acid and 5-nonanone through cyclization and decarboxylation/hydrogenation respectively; in addition, the products obtained are also different depending on the ring-opening position of γ-valerolactone, 1,4-pentane Both diol and 2-methyltetrahydrofuran are fine chemical intermediates. 1,4-pentanediol can be used to prepare high-performance biodegradable polyester, and 2-methyltetrahydrofuran is a solvent and fuel additive with excellent performance. On the other hand, γ-valerolactone can likewise be used as a starting material for the synthesis of polymeric materials. γ-valerolactone and formaldehyde have a new type of monomer α-methylene-γ-valerolactone with a similar acrylate structure under the catalysis of Ba/SiO2 . The unique cyclic ester structure in its molecule makes polyα-methylene The base-γ-valerolactone material has better thermal stability than traditional polyacrylate materials, and its glass transition temperature (Tg ) can reach above 200°C. Catalytic conversion of γ-valerolactone can also be used to synthesize dicarboxylate monomers or another very important polymeric material---polyurethane. Studies have also shown that γ-valerolactone itself is a better gasoline additive than ethanol because γ-valerolactone has a lower saturated vapor pressure and higher energy density. Moreover, unlike ethanol, gamma-valerolactone and water do not form an azeotrope, and the separation and purification of ethanol in the fermentation broth is more energy-saving.
中国专利104496945A公开了一种乙酰丙酸加氢环化制备γ-戊内酯的方法。将二氧化钛加入乙酰丙酸异丙醇反应液中，同时加入贵金属源溶液，磁力搅拌下抽真空或通入氩气除氧后，利用紫外灯源通过原位光催化将贵金属源还原成贵金属颗粒，负载到二氧化钛表面，开始光催化乙酰丙酸加氢环化制备γ-戊内酯。该方法不仅需要贵重金属催化剂，而且反应时间较长，需要10-36小时。Chinese patent 104496945A discloses a method for preparing γ-valerolactone by hydrogenation and cyclization of levulinic acid. Titanium dioxide is added to the isopropanol levulinic acid reaction solution, and the noble metal source solution is added at the same time. After vacuuming under magnetic stirring or argon gas for deoxygenation, the precious metal source is reduced into noble metal particles by in-situ photocatalysis using an ultraviolet lamp source. Loaded on the surface of titanium dioxide, the photocatalytic hydrocyclization of levulinic acid to prepare γ-valerolactone started. This method not only needs a precious metal catalyst, but also requires a long reaction time of 10-36 hours.
中国专利104693159A公开了一种液相加氢制备γ-戊内酯的方法及其使用的催化剂。在低温低压条件下，采用负载型催化剂对α-当归内酯进行高度选择性加氢，反应制备得到γ-戊内酯，并公开了所述负载型催化剂及其制备方法、以及其在液相加氢制备γ-戊内酯方法中的应用。该负载型催化剂的活性金属是贵金属钯或钯镍合金，成本高昂，需要一定的外加氢压才能实现较高的加氢选择性。Chinese patent 104693159A discloses a method for preparing γ-valerolactone by liquid-phase hydrogenation and a catalyst used therefor. Under low temperature and low pressure conditions, α-angelica lactone is highly selectively hydrogenated by using a supported catalyst to prepare γ-valerolactone, and the supported catalyst and its preparation method, as well as its liquid phase The application in the method of preparing γ-valerolactone by hydrogenation. The active metal of the supported catalyst is noble metal palladium or palladium-nickel alloy, which is expensive and requires a certain external hydrogen pressure to achieve high hydrogenation selectivity.
中国专利105566258A公开了一种乙酰丙酸乙酯制备γ-戊内酯的方法.在还原性气氛下，将乙酰丙酸乙酯、分子筛负载的Pt催化剂和反应溶剂混合反应后，得到γ-戊内酯。分子筛负载Pt催化剂体系可高效催化生物质基乙酰丙酸乙酯氢化制备γ-戊内酯，可循环使用5次以上，反应产物γ-戊内酯的产率降低在5％以内。但是该催化剂使用的是贵金属Pt，且需要较高的外加氢压(4～8MPa)，反应的温度在200-240℃下仍然需要反应6-24小时，催化过程整体成本高。Chinese patent 105566258A discloses a method for preparing γ-valerolactone from ethyl levulinate. Under a reducing atmosphere, ethyl levulinate, molecular sieve supported Pt catalyst and reaction solvent are mixed and reacted to obtain γ-valerolactone Lactone. The molecular sieve supported Pt catalyst system can efficiently catalyze the hydrogenation of biomass-based ethyl levulinate to prepare γ-valerolactone, which can be recycled for more than 5 times, and the yield of the reaction product γ-valerolactone is reduced within 5%. However, the catalyst uses noble metal Pt, and requires high external hydrogen pressure (4-8MPa), and the reaction temperature still needs to be reacted for 6-24 hours at 200-240° C., and the overall cost of the catalytic process is high.
中国专利1349853A公开了一种制备内脂用的催化剂及内脂的制备方法。催化剂载体选自二氧化硅、氧化铝及其混合物中的一种，并负载铜化合物、锌化合物及至少一种碱土金属化合物。可催化二醇于气相中进行脱氢反应，制备包括γ-戊内酯在内的11种内脂。催化剂需要在180-250℃下活化6-20h，活化后于固定床上在氢气和1，4-二丁醇摩尔比12∶1的氛围下进行催化。制备该催化剂所需原料较多，制备流程复杂，活化耗时长，催化制备内脂时候需要消耗大量氢气，这些因素直接限制了该方法用于γ-戊内酯在生物质化工领域中的大规模生产。Chinese patent 1349853A discloses a catalyst for preparing lactone and a preparation method of lactone. The catalyst carrier is selected from one of silica, alumina and mixtures thereof, and supports copper compound, zinc compound and at least one alkaline earth metal compound. It can catalyze the dehydrogenation reaction of diols in the gas phase to prepare 11 kinds of lactones including γ-valerolactone. The catalyst needs to be activated at 180-250° C. for 6-20 hours. After activation, the catalyst is catalyzed on a fixed bed in an atmosphere with a molar ratio of hydrogen to 1,4-dibutanol of 12:1. The preparation of the catalyst requires more raw materials, the preparation process is complicated, the activation time is long, and a large amount of hydrogen is consumed in the preparation of lactone by catalysis. These factors directly limit the large-scale application of this method in the field of γ-valerolactone in the field of biomass chemical industry. Production.
CN 102617519A公开了一种由乙酰丙酸加氢制备γ-戊内酯的方法。采用骨架铜作为催化剂，作为催化剂前驱物的铜铝合金中含有第VIII族过渡金属，用以提高催化剂的活性和选择性。铜铝合金经无机碱水溶液抽提活化可得到骨架铜催化剂。乙酰丙酸液相加氢体系中需加入适量骨架铜催化剂、助剂和溶剂，催化剂可以连续套用。但是该催化剂制备的流程相对冗长，体系组成较为复杂，也对后续产物的分离造成一定的困难，整体成本不低。CN 102617519A discloses a method for preparing γ-valerolactone by hydrogenating levulinic acid. Skeleton copper is used as the catalyst, and the copper-aluminum alloy as the catalyst precursor contains transition metals of group VIII to improve the activity and selectivity of the catalyst. The copper-aluminum alloy can be extracted and activated by an aqueous inorganic alkali solution to obtain a skeleton copper catalyst. The liquid-phase hydrogenation system of levulinic acid needs to add an appropriate amount of skeleton copper catalyst, auxiliary agent and solvent, and the catalyst can be used continuously. However, the preparation process of the catalyst is relatively tedious, and the system composition is relatively complicated, which also causes certain difficulties in the separation of subsequent products, and the overall cost is not low.
CN104844542A公开了一种由乙酰丙酸酯无溶剂制备γ-戊内酯的方法。在乙酰丙酸酯中加入亚铬酸铜催化剂，在2-8MP氢气气氛下反应，得固液混合物经减压抽滤，得到含有γ-戊内酯及相应醇类的二元混合液；再经蒸馏回收醇类，即得γ-戊内酯。该催化剂廉价易分离，在体系中原位活化并实现无溶剂体系中一步制备γ-戊内酯。但是该催化剂除了组成包括对人体和环境不友好的铬之外，亚铬酸铜催化剂本身也容易团聚，导致催化效果的不稳定，且反应过程需要外加氢源，提高了对设备的要求，增加了整体成本。CN104844542A discloses a method for preparing gamma-valerolactone from levulinic acid ester without solvent. Add copper chromite catalyst to levulinic acid ester, react under 2-8MP hydrogen atmosphere, obtain solid-liquid mixture and filter under reduced pressure to obtain binary mixed liquid containing γ-valerolactone and corresponding alcohols; then Alcohols are recovered by distillation to obtain γ-valerolactone. The catalyst is cheap and easy to separate, can be activated in situ in the system and realizes the one-step preparation of gamma-valerolactone in a solvent-free system. However, in addition to the composition of the catalyst including chromium which is unfriendly to the human body and the environment, the copper chromite catalyst itself is also easy to agglomerate, resulting in unstable catalytic effect, and the reaction process requires an external hydrogen source, which increases the requirements for equipment. Increased overall cost.
CN 104829559A公开了一种由乙酰丙酸甲酯制备γ-戊内酯的方法。在乙酰丙酸甲酯与甲醇的混合液中加入未经加氢预处理的铜铬氧化物催化剂，反应后得固液混合物；经减压抽滤可将铜铬氧化物回收并得到γ-戊内酯粗液。回收得到的铜铬氧化物催化剂直接用于下一次反应。添加的甲醇的质量可以低达乙酰丙酸甲酯的8％，仅作为氢供体。该催化剂价格低廉高效，同时催化甲醇的原位产氢反应及乙酰丙酸甲酯的加氢反应。但是该催化剂的组成包括对人体和环境不友好的铬，出于环保要求，需要考虑对该催化剂中铬和铜的综合回收。CN 104829559A discloses a method for preparing γ-valerolactone from methyl levulinate. In the mixture of methyl levulinate and methanol, copper chromium oxide catalyst without hydrogenation pretreatment is added, and a solid-liquid mixture is obtained after reaction; copper chromium oxide can be recovered by vacuum filtration to obtain γ-amyl Lactone crude solution. The recovered copper chromium oxide catalyst is directly used for the next reaction. The mass of methanol added can be as low as 8% of methyl levulinate, only as a hydrogen donor. The catalyst is cheap and efficient, and simultaneously catalyzes the in-situ hydrogenation reaction of methanol and the hydrogenation reaction of methyl levulinate. However, the composition of the catalyst includes chromium which is unfriendly to the human body and the environment. Due to environmental protection requirements, it is necessary to consider the comprehensive recovery of chromium and copper in the catalyst.
发明内容Contents of the invention
本发明的目的在于克服现有技术缺陷，提供一种γ-戊内酯的合成方法。The purpose of the present invention is to overcome the defects of the prior art and provide a synthetic method of gamma-valerolactone.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种γ-戊内酯的合成方法，包括如下步骤：A synthetic method for gamma-valerolactone, comprising the steps of:
(1)将乙酰丙酸甲酯与醇充分混合，得混合原料液，混合原料液中乙酰丙酸甲酯的浓度为2～12wt％；(1) fully mixing methyl levulinate and alcohol to obtain a mixed raw material liquid, the concentration of methyl levulinate in the mixed raw material liquid is 2 to 12 wt %;
(2)在上述混合原料液中加入双金属催化剂，于高压反应釜中加热至170～290℃反应0.5～9h，冷却至室温即成；(2) Add a bimetallic catalyst to the above mixed raw material solution, heat it to 170-290°C in an autoclave for 0.5-9 hours, cool to room temperature and serve;
上述双金属催化剂中的双金属包括第一金属和第二金属，其中第一金属为Cu，第二金属为Zr、Al、Mg、Ca、Zn、Ba或Ni，且第一金属和第二金属的摩尔比为1～10∶1～10。The bimetal in the above-mentioned bimetallic catalyst comprises a first metal and a second metal, wherein the first metal is Cu, the second metal is Zr, Al, Mg, Ca, Zn, Ba or Ni, and the first metal and the second metal The molar ratio is 1～10:1～10.
在本发明的一个优选实施方案中，所述醇为甲醇、乙醇、异丙醇或1-丁醇。In a preferred embodiment of the invention, the alcohol is methanol, ethanol, isopropanol or 1-butanol.
在本发明的一个优选实施方案中，所述混合原料液中乙酰丙酸甲酯的浓度为2～10wt％。In a preferred embodiment of the present invention, the concentration of methyl levulinate in the mixed raw material liquid is 2-10 wt%.
在本发明的一个优选实施方案中，所述步骤(2)为：在上述混合原料液中加入双金属催化剂，于高压反应釜中加热至180～280℃反应0.5～8h，冷却至室温即成。In a preferred embodiment of the present invention, the step (2) is: add a bimetallic catalyst to the above-mentioned mixed raw material solution, heat it in a high-pressure reactor to 180-280 ° C for 0.5-8 hours, and cool to room temperature. .
在本发明的一个优选实施方案中，所述第一金属和第二金属的摩尔比为1～8∶1～8。In a preferred embodiment of the present invention, the molar ratio of the first metal to the second metal is 1-8:1-8.
本发明的有益效果：Beneficial effects of the present invention:
1、本发明应用铜基双金属催化剂，通过掺杂第二活性金属调节催化剂活性，进而可以实现催化醇类原位产氢和选择性地催化乙酰丙酸甲酯加氢制备γ-戊内酯。1. The present invention uses a copper-based bimetallic catalyst, and adjusts the activity of the catalyst by doping the second active metal, so as to realize the in-situ hydrogen production of alcohols and selectively catalyze the hydrogenation of methyl levulinate to prepare γ-valerolactone .
2、本发明的催化剂廉价易得，催化性能稳定，可重用性好，也不会出现过度加氢产物，并且整个反应不需要在氢气环境下加氢，具有较强工业生产的操作安全性，具有非常好的工业化应用潜力。2. The catalyst of the present invention is cheap and easy to obtain, has stable catalytic performance, good reusability, and no excessive hydrogenation products, and the whole reaction does not need to be hydrogenated in a hydrogen environment, and has strong operational safety in industrial production. It has very good industrial application potential.
3、本发明使用醇同时作为氢供体和反应媒介，不需要外部氢源和其他溶剂，反应体系简单，有利于目的产物的分离。3. The present invention uses alcohol as a hydrogen donor and a reaction medium at the same time, does not require an external hydrogen source and other solvents, and has a simple reaction system, which is beneficial to the separation of the target product.
4、本发明通过环化加氢选择性地还原乙酰丙酸甲酯，不会产生过度加氢产物。4. The present invention selectively reduces methyl levulinate through cyclohydrogenation without producing excessively hydrogenated products.
5、本发明的催化剂组成活性金属和载体廉价易得，经济性好。5. The active metal and carrier of the catalyst composition of the present invention are cheap and easy to obtain, and the economy is good.
附图说明Description of drawings
图1为本发明实施例8制备的γ-戊内酯的GC图谱。Figure 1 is the GC spectrum of γ-valerolactone prepared in Example 8 of the present invention.
具体实施方式detailed description
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述。The technical solutions of the present invention will be further illustrated and described below through specific embodiments.
实施例1～7Examples 1-7
向100mL的高压釜中加入0.5乙酰丙酸甲酯和19.5g甲醇(2.5wt％)，再分别加入0.2g CuMgO2、CuZnO2、CuCaO2、CuZrO3、CuAlO2.5、CuNiO2.5、CuBaO2(两种金属的摩尔比为1：1)作为催化剂，密封反应釜，剧烈搅拌(500rpm)，加热到220℃并保持4小时，结束反应冷却至室温并取样，使用GC-MS(岛津)和GC(安捷伦)进行定性和定量检测，检测结果列于表1中序号为1～7。Add 0.5 g of methyl levulinate and 19.5 g of methanol (2.5 wt%) into a 100 mL autoclave, then add 0.2 g of CuMgO2 , CuZnO2 , CuCaO2 , CuZrO3 , CuAlO2.5 , CuNiO2.5 , CuBaO2 (two The molar ratio of the two metals is 1:1) as a catalyst, the reaction vessel was sealed, vigorously stirred (500rpm), heated to 220°C and maintained for 4 hours, the reaction was completed, cooled to room temperature and sampled, using GC-MS (Shimadzu) and GC (Agilent) carried out qualitative and quantitative detection, and the detection results are listed in Table 1 as serial numbers 1-7.
实施例8Example 8
向100mL的高压釜中加入1.0g乙酰丙酸甲酯和19.0异丙醇(5wt％)，再加入0.2gCu4MgO5(铜和镁的摩尔比为4∶1)作为催化剂，密封反应釜，剧烈搅拌(500rpm)，加热到240℃并保持2小时，结束反应冷却至室温并取样，使用GC-MS(岛津)和GC(安捷伦)进行定性和定量检测(如图1所示)，检测结果列于表1中序号为8。Add 1.0g methyl levulinate and 19.0 isopropanol (5wt%) in the autoclave of 100mL, then add 0.2gCu4 MgO5 (the molar ratio of copper and magnesium is 4: 1) as catalyst, seal reaction kettle, Stir vigorously (500rpm), heat to 240°C and keep for 2 hours, finish the reaction, cool to room temperature and take samples, use GC-MS (Shimadzu) and GC (Agilent) for qualitative and quantitative detection (as shown in Figure 1), detection The results are listed in Table 1 as number 8.
实施例9～12Examples 9-12
向100mL的高压釜中加入0.8g乙酰丙酸甲酯和19.2g 1-丁醇(4wt％)，再分别加入0.2g CuMg2O3、CuZn2O3、CuCa2O3、CuBa2O3(Cu和另一种活性金属的摩尔比为1∶2)作为催化剂，密封反应釜，剧烈搅拌(500rpm)，加热到260℃并保持1小时，结束反应冷却至室温并取样，使用GC-MS(岛津)和GC(安捷伦)进行定性和定量检测，不同催化剂的检测结果列于表1中序号为9～12。Add 0.8g methyl levulinate and 19.2g 1-butanol (4wt%) into a 100mL autoclave, then add 0.2g CuMg2 O3 , CuZn2 O3 , CuCa2 O3 , CuBa2 O3 (the molar ratio of Cu and another active metal is 1:2) as a catalyst, seal the reactor, stir vigorously (500rpm), heat to 260°C and keep for 1 hour, finish the reaction, cool to room temperature and take samples, use GC-MS (Shimadzu) and GC (Agilent) for qualitative and quantitative detection, and the detection results of different catalysts are listed in Table 1 as serial numbers 9-12.
实施例13～14Examples 13-14
向100mL的高压釜中加入2g乙酰丙酸甲酯和18g乙醇(10wt％)，再分别加入0.2gCu2NiO3.5、Cu2ZrO4作为催化剂(Cu和另一种活性金属的摩尔比为2∶1)，密封反应釜，剧烈搅拌(500rpm)，加热到280℃并保持0.5小时，结束反应冷却至室温并取样，使用GC-MS(岛津)和GC(安捷伦)进行定性和定量检测，检测结果列于表1中序号为13～14。Add 2g methyl levulinate and 18g ethanol (10wt%) in the autoclave of 100mL, then add0.2gCu2NiO3.5 ,Cu2ZrO4 respectively as catalyst( the molar ratio of Cu and another kind of active metal is2 : 1), seal the reaction kettle, stir vigorously (500rpm), heat to 280°C and keep it for 0.5 hours, finish the reaction, cool to room temperature and take samples, use GC-MS (Shimadzu) and GC (Agilent) for qualitative and quantitative detection, detection The results are listed in Table 1, numbered 13-14.
实施例15～18Examples 15-18
向100mL的高压釜中加入0.4g乙酰丙酸甲酯和19.6g甲醇(2wt％)，再加入0.2gCu8ZnO9、Cu8MgO9、CuZn8O9、CuMg8O9(Cu/Zn以及Cu/Mg摩尔比为8∶1和1∶8)作为催化剂，密封反应釜，剧烈搅拌(500rpm)，分别加热到180℃～240℃并保持2～8小时，结束反应冷却至室温并取样，使用GC-MS(岛津)和GC(安捷伦)进行定性和定量检测，不同反应条件的检测结果列于表1中序号为15～18。Add 0.4g methyl levulinate and 19.6g methanol (2wt%) to a 100mL autoclave, then add 0.2g Cu8 ZnO9 , Cu8 MgO9 , CuZn8 O9 , CuMg8 O9 (Cu/Zn and Cu/Mg molar ratio is 8: 1 and 1: 8) as a catalyst, seal the reactor, vigorously stir (500rpm), heat to 180 ℃ ~ 240 ℃ respectively and keep for 2 ~ 8 hours, finish the reaction and cool to room temperature and take a sample, GC-MS (Shimadzu) and GC (Agilent) were used for qualitative and quantitative detection, and the detection results of different reaction conditions are listed in Table 1 with serial numbers 15-18.
实施例19～22Examples 19-22
向100mL的高压釜中加入0.6g乙酰丙酸甲酯和19.4g甲醇(3wt％)，再加入0.2gCu6AlO7.5、CuAl6O10、Cu6CaO7、CuCa6O(Cu/Al以及Cu/Ca摩尔比为6∶1和1∶6)作为催化剂，密封反应釜，剧烈搅拌(500rpm)，加热到180℃并保持3小时，结束反应冷却至室温并取样，使用GC-MS(岛津)和GC(安捷伦)进行定性和定量检测，不同反应条件的检测结果列于表1中序号为19～22。Add 0.6g methyl levulinate and 19.4g methanol (3wt%) in the autoclave of 100mL, then add 0.2gCu6 AlO7.5 , CuAl6 O10 , Cu6 CaO7 , CuCa6 O (Cu/Al and Cu /Ca molar ratio is 6: 1 and 1: 6) as catalyst, sealed reactor, stirred vigorously (500rpm), heated to 180 ℃ and kept 3 hours, finished reaction and cooled to room temperature and sampling, using GC-MS (Shimadzu ) and GC (Agilent) for qualitative and quantitative detection, and the detection results of different reaction conditions are listed in Table 1 as serial numbers 19-22.
实施例23～24Examples 23-24
向100mL的高压釜中加入1.6g乙酰丙酸甲酯和18.4g甲醇(8wt％)，再加入0.2gCu5Ni2O8、Cu2Ni5O9.5(Cu/Ni摩尔比为5∶2和2∶5)作为催化剂，密封反应釜，剧烈搅拌(500rpm)，分别加热到200℃并保持7小时，结束反应冷却至室温并取样，使用GC-MS(岛津)和GC(安捷伦)进行定性和定量检测，不同反应条件的检测结果列于表1中序号为23～24。Add 1.6g methyl levulinate and 18.4g methanol (8wt%) to a 100mL autoclave, then add 0.2g Cu5 Ni2 O8 , Cu2 Ni5 O9.5 (Cu/Ni molar ratio is 5:2 and 2:5) as a catalyst, seal the reaction vessel, stir vigorously (500rpm), heat to 200°C and keep for 7 hours respectively, finish the reaction, cool to room temperature and take samples, use GC-MS (Shimadzu) and GC (Agilent) for qualitative and quantitative detection, the detection results of different reaction conditions are listed in Table 1 as serial numbers 23-24.
实施例25Example 25
向100mL的高压釜中加入1.2g乙酰丙酸甲酯和18.8g甲醇(6wt％)，再加入0.2gCuZr4O9(Cu/Zr摩尔比为1∶4)作为催化剂，密封反应釜，剧烈搅拌(500rpm)，分别加热到230℃并保持2小时，结束反应冷却至室温并取样，使用GC-MS(岛津)和GC(安捷伦)进行定性和定量检测，不同反应条件的检测结果列于表1中序号为25。Add 1.2g methyl levulinate and 18.8g methanol (6wt%) to a 100mL autoclave, then add 0.2g CuZr4 O9 (Cu/Zr molar ratio is 1:4) as a catalyst, seal the reaction vessel, and stir vigorously (500rpm), respectively heated to 230°C and maintained for 2 hours, finished the reaction and cooled to room temperature and took samples, using GC-MS (Shimadzu) and GC (Agilent) for qualitative and quantitative detection, the detection results of different reaction conditions are listed in the table The sequence number in 1 is 25.
表1各实施例中的检测结果The detection result in each embodiment of table 1
本领域普通技术人员可知，本发明的技术方案，在下述范围内变化时，仍然能够得到与上述实施例相同或相近的技术效果，仍然属于本发明的保护范围：Those of ordinary skill in the art will know that the technical solution of the present invention can still obtain the same or similar technical effects as the above-mentioned embodiments when changing within the following ranges, and still belong to the protection scope of the present invention:
一种γ-戊内酯的合成方法，包括如下步骤：A synthetic method for gamma-valerolactone, comprising the steps of:
(1)将乙酰丙酸甲酯与醇充分混合，得混合原料液，混合原料液中乙酰丙酸甲酯的浓度为2～12wt％，优选2～10wt％；所述醇为甲醇、乙醇、异丙醇或1-丁醇；(1) Methyl levulinate is fully mixed with alcohol to obtain mixed raw material liquid, and the concentration of methyl levulinate in the mixed raw material liquid is 2～12wt%, preferably 2～10wt%; Described alcohol is methyl alcohol, ethanol, Isopropanol or 1-butanol;
(2)在上述混合原料液中加入双金属催化剂，于高压反应釜中加热至170～290℃(优选180～280℃)反应0.5～9h(优选0.5～8h)，冷却至室温即成；(2) Add a bimetallic catalyst to the above mixed raw material solution, heat it to 170-290°C (preferably 180-280°C) in an autoclave for 0.5-9h (preferably 0.5-8h), cool to room temperature and serve;
上述双金属催化剂中的双金属包括第一金属和第二金属，其中第一金属为Cu，第二金属为Zr、Al、Mg、Ca、Zn、Ba或Ni，且第一金属和第二金属的摩尔比为1～10∶1～10(优选1～8∶1～8)。The bimetal in the above-mentioned bimetallic catalyst comprises a first metal and a second metal, wherein the first metal is Cu, the second metal is Zr, Al, Mg, Ca, Zn, Ba or Ni, and the first metal and the second metal The molar ratio is 1-10:1-10 (preferably 1-8:1-8).
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。The above is only a preferred embodiment of the present invention, so the scope of the present invention cannot be limited accordingly, that is, equivalent changes and modifications made according to the patent scope of the present invention and the content of the specification should still be covered by the present invention In the range.
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| CN201710659480.6ACN107253937B (en) | 2017-08-03 | 2017-08-03 | A kind of synthetic method of gamma-valerolactone |
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| CN201710659480.6ACN107253937B (en) | 2017-08-03 | 2017-08-03 | A kind of synthetic method of gamma-valerolactone |
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| CN201710659480.6AActiveCN107253937B (en) | 2017-08-03 | 2017-08-03 | A kind of synthetic method of gamma-valerolactone |
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