CN117623926A - A method for synthesizing methyl formate using carbon monoxide and methanol - Google Patents
A method for synthesizing methyl formate using carbon monoxide and methanol Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 154
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 34
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000005286 illumination Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
- C07B61/02—Generation of organic free radicals; Organic free radicals per se
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种利用一氧化碳和甲醇合成甲酸甲酯的方法，包括以下步骤：在室温条件下，将一氧化碳与甲醇的混合物于密闭的反应容器内，以波段为300‑700nm的氙灯进行光照反应，生成甲酸甲酯；其中，一氧化碳的分压为1‑3atm，每1mL甲醇对应1‑6mL的一氧化碳。本发明的利用一氧化碳和甲醇合成甲酸甲酯的方法，其合成甲酸甲酯的方法相对于传统技术路线，该反应体系全程没有金属催化剂的参与，节省了成本，而且投料物种简单，副产物少，目标产物选择性高，全程使用光催化，绿色环保，反应条件温和，操作方便。
A method for synthesizing methyl formate using carbon monoxide and methanol, including the following steps: at room temperature, a mixture of carbon monoxide and methanol is placed in a sealed reaction vessel, and a xenon lamp with a wavelength band of 300-700nm is used for an illumination reaction to generate methyl formate. Ester; among them, the partial pressure of carbon monoxide is 1-3atm, and every 1mL of methanol corresponds to 1-6mL of carbon monoxide. The present invention uses carbon monoxide and methanol to synthesize methyl formate. Compared with the traditional technical route, the reaction system does not involve the participation of metal catalysts in the entire process, which saves costs, and the input species are simple and have few by-products. The target product has high selectivity, uses photocatalysis throughout the process, is green and environmentally friendly, has mild reaction conditions and is easy to operate.
Description
技术领域Technical field
本发明涉及甲酸甲酯合成技术领域，具体涉及一种利用一氧化碳和甲醇合成甲酸甲酯的方法。The invention relates to the technical field of methyl formate synthesis, and specifically relates to a method for synthesizing methyl formate by utilizing carbon monoxide and methanol.
背景技术Background technique
近些年以来，煤制甲醇技术发展迅速，甲醇产能呈爆发式增长。因此，合理的开发甲醇下游产业，既能有效解决甲醇产能过剩问题，又能丰富甲醇下游产品产业链。甲酸甲酯作为甲醇下游的新型产品，是重要的有机合成中间体。甲酸甲酯含有醛基和酯基官能团，化学性质活泼，被广泛用于制备酯类、酰胺类，及酸类各种化学品。甲酸甲酯合成路线主要有合成气合成法、甲醛二聚法、二氧化碳与甲醛加氢缩合法、甲醇与甲酸酯化反应、液相甲醇羰基化反应，以及甲醇直接脱氢法。其中，甲醇直接脱氢法工艺相对简单，目前应用较多。In recent years, coal-to-methanol technology has developed rapidly, and methanol production capacity has experienced explosive growth. Therefore, the rational development of the methanol downstream industry can not only effectively solve the problem of excess methanol production capacity, but also enrich the methanol downstream product industry chain. Methyl formate, as a new product downstream of methanol, is an important organic synthesis intermediate. Methyl formate contains aldehyde and ester functional groups and has active chemical properties. It is widely used in the preparation of various chemicals such as esters, amides, and acids. The synthesis routes of methyl formate mainly include synthesis gas synthesis method, formaldehyde dimerization method, carbon dioxide and formaldehyde hydrogenation condensation method, methanol and formic acid esterification reaction, liquid phase methanol carbonylation reaction, and direct methanol dehydrogenation method. Among them, the direct methanol dehydrogenation process is relatively simple and is currently widely used.
目前开发的甲醇制甲酸甲酯的催化剂主要分为贵金属和非贵金属。在贵金属催化剂表面，甲醛分子以η2(C,O)吸附构型存在，高温下容易发生脱羰反应生成CO和H2。在非贵金属催化剂表面，甲醛分子呈η1(O)构型，但产物选择性和收率低，反应条件相对苛刻。The currently developed catalysts for producing methyl formate from methanol are mainly divided into precious metals and non-noble metals. On the surface of the precious metal catalyst, formaldehyde molecules exist in the eta 2 (C,O) adsorption configuration, and decarbonylation reactions easily occur at high temperatures to generate CO and H 2 . On the surface of non-noble metal catalysts, formaldehyde molecules assume the eta 1 (O) configuration, but product selectivity and yield are low, and the reaction conditions are relatively harsh.
发明内容Contents of the invention
现有工艺的甲酸甲酯合成路线中，多采用热催化完成甲醇到甲酸甲酯的转化，该过程通常需要金属参与，导致分离程序复杂，能源和后处理成本升高，环境污染。基于此，本发明提供了一种利用一氧化碳和甲醇合成甲酸甲酯的方法，该方法为光催化绿色制备甲酸甲酯的方法路线，即在无金属参与下利用甲醇和一氧化碳于可见光照下合成甲酸甲酯。In the existing methyl formate synthesis route, thermal catalysis is often used to complete the conversion of methanol to methyl formate. This process usually requires the participation of metals, resulting in complex separation procedures, increased energy and post-processing costs, and environmental pollution. Based on this, the present invention provides a method for synthesizing methyl formate using carbon monoxide and methanol. This method is a photocatalytic green method for preparing methyl formate, that is, using methanol and carbon monoxide to synthesize formic acid under visible light without the participation of metals. Methyl ester.
为实现上述目的，本发明提供了一种利用一氧化碳和甲醇合成甲酸甲酯的方法，其包括以下步骤：In order to achieve the above object, the present invention provides a method for synthesizing methyl formate using carbon monoxide and methanol, which includes the following steps:
在室温条件下，将一氧化碳与甲醇的混合物于密闭的反应容器内，以波段为300-700nm的氙灯进行光照反应，反应过程中辅以搅拌，生成甲酸甲酯；At room temperature, a mixture of carbon monoxide and methanol is placed in a sealed reaction vessel, and a xenon lamp with a wavelength band of 300-700nm is used for an illumination reaction. Stirring is supplemented during the reaction to generate methyl formate;
其中，一氧化碳的分压为1-3atm，每1mL甲醇对应1-6mL的一氧化碳。Among them, the partial pressure of carbon monoxide is 1-3atm, and every 1mL of methanol corresponds to 1-6mL of carbon monoxide.
作为本发明的进一步优选技术方案，所述光照反应的时间为1-14小时，优选为5-14小时。As a further preferred technical solution of the present invention, the light reaction time is 1-14 hours, preferably 5-14 hours.
作为本发明的进一步优选技术方案，所述光照反应的温度为0-35℃，优选为20-35℃。As a further preferred technical solution of the present invention, the temperature of the light reaction is 0-35°C, preferably 20-35°C.
作为本发明的进一步优选技术方案，所述一氧化碳与甲醇的混合物体系中还含有水，以每1mL的甲醇对应水的量为0-2.5μL，反应体系在有水的情况下，水能在合成甲酸甲酯的过程中起促进作用。As a further preferred technical solution of the present invention, the mixture system of carbon monoxide and methanol also contains water, and the amount of water corresponding to 1 mL of methanol is 0-2.5 μL. When there is water in the reaction system, water can be synthesized Methyl formate plays a promoting role in the process.
作为本发明的进一步优选技术方案，所述反应容器内还通入有氧气。As a further preferred technical solution of the present invention, oxygen is also introduced into the reaction vessel.
作为本发明的进一步优选技术方案，所述氧气的分压为1-3atm，氧气与一氧化碳的体积比为1:1。As a further preferred technical solution of the present invention, the partial pressure of oxygen is 1-3 atm, and the volume ratio of oxygen to carbon monoxide is 1:1.
作为本发明的进一步优选技术方案，所述反应容器内还加入有三氟甲磺酸。As a further preferred technical solution of the present invention, trifluoromethanesulfonic acid is also added to the reaction vessel.
作为本发明的进一步优选技术方案，每1mL甲醇对应三氟甲磺酸的量为1-50μL。As a further preferred technical solution of the present invention, the amount of triflate per 1 mL of methanol is 1-50 μL.
本发明利用一氧化碳和甲醇合成甲酸甲酯的方法在光照条件下，CH3O-H键均裂生成CH3O·自由基和H·自由基，CH3O·自由基进攻CO得到CH3OCO·自由基，CH3OCO·自由基与H·自由基偶联得到甲酸甲酯。此外，向该体系中通入氧气或者加入质子酸可显著促进甲酸甲酯的生成：路径1，光照下CO由基态变为激发态，随后被O2氧化，在水或/和酸的存在下生成甲酸，甲酸与甲醇酯化生成甲酸甲酯；路径2，光照下O2由基态变为激发态，随后氧化CO，在水或/和酸的存在下生成甲酸，甲酸与甲醇酯化生成甲酸甲酯。本发明可通过气相色谱(GC)检测到甲酸甲酯的生成，且该反应体系全程没有金属催化剂的参与。In the method of synthesizing methyl formate by utilizing carbon monoxide and methanol, under light conditions, the CH 3 OH bond is homolytically split to generate CH 3 O·free radicals and H·free radicals, and CH 3O ·free radicals attack CO to obtain CH 3 OCO·free. radical, CH 3 OCO·free radical is coupled with H·free radical to obtain methyl formate. In addition, introducing oxygen into the system or adding protonic acid can significantly promote the generation of methyl formate: Path 1, CO changes from the ground state to the excited state under light, and is subsequently oxidized by O2 , in the presence of water or/and acid Formic acid is generated, and formic acid and methanol are esterified to generate methyl formate; Path 2, O 2 changes from the ground state to an excited state under light, and then oxidizes CO, generating formic acid in the presence of water or/and acid, and formic acid and methanol are esterified to generate formic acid. Methyl ester. The present invention can detect the generation of methyl formate through gas chromatography (GC), and the reaction system does not involve the participation of metal catalysts in the entire process.
本发明利用一氧化碳和甲醇合成甲酸甲酯的方法，由一氧化碳与甲醇在光照条件下生成甲酸甲酯，相对于传统技术路线，该反应体系全程没有金属催化剂的参与，节省了成本；该反应体系投料物种简单，副产物少，目标产物选择性高；该反应体系全程使用光催化，绿色环保；该反应体系全程反应条件温和，操作方便。The present invention uses carbon monoxide and methanol to synthesize methyl formate. The carbon monoxide and methanol generate methyl formate under light conditions. Compared with the traditional technical route, the reaction system does not involve the participation of metal catalysts in the entire process, saving costs; the reaction system feeds The species is simple, there are few by-products, and the target product is highly selective; the reaction system uses photocatalysis throughout the entire process, which is green and environmentally friendly; the reaction system has mild reaction conditions throughout the process and is easy to operate.
附图说明Description of drawings
下面结合附图和具体实施方式对本发明作进一步详细的说明。The present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments.
图1是本发明一氧化碳和甲醇反应生成甲酸甲酯的反应方程式。Figure 1 is a reaction equation for the reaction of carbon monoxide and methanol to generate methyl formate according to the present invention.
图2是本发明实施例1、2及对比例2中生成甲酸甲酯的GC谱图。Figure 2 is a GC spectrum of methyl formate produced in Examples 1 and 2 and Comparative Example 2 of the present invention.
图3是基于发明实施例3在不同酸浓度条件下一氧化碳和甲醇反应生成甲酸甲酯的GC谱图。Figure 3 is a GC spectrum of methyl formate produced by the reaction between carbon monoxide and methanol under different acid concentration conditions based on Example 3 of the invention.
图4是基于发明实施例3在不同反应时间条件下一氧化碳和甲醇反应生成甲酸甲酯的GC谱图。Figure 4 is a GC spectrum of methyl formate produced by the reaction of carbon monoxide and methanol under different reaction time conditions based on Example 3 of the invention.
本发明目的实现、功能特点及优点将结合实施例，参照附图做进一步说明。The realization of the purpose, functional features and advantages of the present invention will be further described with reference to the embodiments and the accompanying drawings.
具体实施方式Detailed ways
以下结合附图对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
除有定义外，以下实施例中所用的技术术语具有与本发明创造所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂，如无特殊说明，均为常规生化试剂；所述实验方法，如无特殊说明，均为常规方法。Unless otherwise defined, the technical terms used in the following examples have the same meanings as commonly understood by those skilled in the art to which this invention belongs. The test reagents used in the following examples are all conventional biochemical reagents, unless otherwise stated; the experimental methods, unless otherwise stated, are all conventional methods.
本发明由一氧化碳与甲醇在光照条件下生成甲酸甲酯，其反应方程式如图1所示。In the present invention, carbon monoxide and methanol are used to generate methyl formate under light conditions, and the reaction equation is shown in Figure 1.
对比例1Comparative example 1
在25mL的Schlenk flask容器中，装入4mL甲醇，抽真空后通入过量的CO(1atm，21mL)，在没有光照的条件下室温搅拌10小时(容器距离光源20-30cm)，反应溶液过滤后通过GC测定，没有检测到甲酸甲酷的生成。Put 4 mL of methanol into a 25 mL Schlenk flask container, evacuate and add excess CO (1 atm, 21 mL), stir at room temperature for 10 hours without light (the container is 20-30 cm away from the light source), and filter the reaction solution By GC measurement, no formation of methyl formate was detected.
实施例1Example 1
在25mL的Schlenk flask容器中，装入4mL甲醇，抽真空后通入过量的CO(1atm，21mL)，在氙灯光照下室温搅拌10小时(容器距离光源20-30cm)，反应溶液过滤后通过GC测定，图2为测试结果，反应结束后甲酸甲酯的浓度为0.002mol/L。Put 4 mL of methanol into a 25 mL Schlenk flask container, evacuate and add excess CO (1 atm, 21 mL), stir at room temperature for 10 hours under xenon lamp illumination (the container is 20-30 cm away from the light source), filter the reaction solution and pass it through GC Measurement, Figure 2 shows the test results. The concentration of methyl formate after the reaction is 0.002mol/L.
对比例2Comparative example 2
在25mL的Schlenk flask容器中，装入4mL甲醇，抽真空后通入过量的O2(1atm，21mL)，在氙灯光照下室温搅拌10小时(容器距离光源20-30cm)，反应溶液过滤后通过GC测定，图2为测试结果，反应结束后甲酸甲酯的浓度为0.001mol/L。Put 4 mL of methanol into a 25 mL Schlenk flask container, evacuate and add excess O 2 (1 atm, 21 mL), stir at room temperature for 10 hours under xenon lamp illumination (the container is 20-30 cm away from the light source), filter the reaction solution and pass GC measurement, Figure 2 shows the test results, the concentration of methyl formate after the reaction is 0.001mol/L.
实施例2Example 2
在25mL的Schlenk flask容器中，装入4mL甲醇，抽真空后通入过量的O2(1atm，21mL)，经液氮冷冻，向该反应器中通入过量的CO(1atm，21mL)，在氙灯光照下室温搅拌10小时(容器距离光源20-30cm)，反应溶液过滤后通过GC测定，图2为测试结果，反应结束后甲酸甲酯的浓度为0.011mol/L。Put 4 mL of methanol into a 25 mL Schlenk flask container, evacuate and pass in excess O 2 (1 atm, 21 mL), freeze it with liquid nitrogen, pass excess CO (1 atm, 21 mL) into the reactor, and Stir at room temperature for 10 hours under xenon lamp illumination (the container is 20-30cm away from the light source). The reaction solution is filtered and measured by GC. Figure 2 shows the test results. After the reaction, the concentration of methyl formate is 0.011mol/L.
实施例3Example 3
在25mL的Schlenk flask容器中，装入4mL甲醇，加入100μL的三氟甲磺酸，抽真空后通入过量的O2(1atm，21mL)，经液氮冷冻，向该反应器中通入过量的CO(1atm，21mL)，在氙灯光照下室温搅拌10小时(容器距离光源20-30cm)，反应溶液过滤后通过GC测定，如图3和图4为测试结果，反应结束后甲酸甲酯的浓度为0.067mol/L。In a 25 mL Schlenk flask container, put 4 mL of methanol, add 100 μL of triflate, vacuum and pass in excess O 2 (1 atm, 21 mL), freeze with liquid nitrogen, and pass excess O 2 (1 atm, 21 mL) into the reactor. of CO (1atm, 21mL), stirred at room temperature for 10 hours under xenon lamp illumination (the container is 20-30cm away from the light source), the reaction solution was filtered and measured by GC. Figures 3 and 4 show the test results. After the reaction, the concentration of methyl formate The concentration is 0.067mol/L.
进一步，在实施例3的基础上，仅通过改变三氟甲磺酸的浓度(其用量分别为10μL、20μL、50μL、100μL、200μL)，经GC测定结果如图3所示,其中甲酸甲酷的浓度分别为，0.012moL、0.018mol/L、0.030mol/L、0.067mol/L、0.100mol/L，随着酸浓度的增加甲酸甲酷产率明显增加，其三氟甲磺酸的用量超过200μL，虽然甲酸甲酷的产率还会有一定提升，但酸浓度增大，则不够环保了。本发明中每1mL甲醇对应三氟甲磺酸的量优选为5-50μL。Further, on the basis of Example 3, only by changing the concentration of triflate (the dosage is 10 μL, 20 μL, 50 μL, 100 μL, 200 μL respectively), the GC measurement results are shown in Figure 3, in which methyl formate The concentrations are respectively, 0.012moL, 0.018mol/L, 0.030mol/L, 0.067mol/L, 0.100mol/L. As the acid concentration increases, the yield of methyl formate increases significantly, and the dosage of trifluoromethanesulfonic acid If it exceeds 200 μL, although the yield of methyl formate will increase to a certain extent, the increase in acid concentration will not be environmentally friendly enough. In the present invention, the amount of trifluoromethanesulfonic acid per 1 mL of methanol is preferably 5-50 μL.
此外，在实施例3的基础上，仅通过改变搅拌反应的时间(2h、4h、6h、10h、14h)，经GC测定结果如图4所示，其中甲酸甲酷的浓度分别为，0.010mol/L、0.015mol/L、0.020mol/L、0.067mol/L、0.075mol/L，随着反应时间的增加甲酸甲酷产率明显增加，且当反应时间超过14h后，产率增加不再明显。本发明中光照反应的时间优选为6-14小时。In addition, on the basis of Example 3, only by changing the stirring reaction time (2h, 4h, 6h, 10h, 14h), the GC measurement results are shown in Figure 4, in which the concentrations of methyl formate are respectively 0.010 mol /L, 0.015mol/L, 0.020mol/L, 0.067mol/L, 0.075mol/L. As the reaction time increases, the yield of methyl formate increases significantly, and when the reaction time exceeds 14h, the yield no longer increases. obvious. The time of light reaction in the present invention is preferably 6-14 hours.
虽然以上描述了本发明的具体实施方式，但是本领域熟练技术人员应当理解，这些仅是举例说明，可以对本实施方式做出多种变更或修改，而不背离本发明的原理和实质，本发明的保护范围仅由所附权利要求书限定。Although the specific embodiments of the present invention have been described above, those skilled in the art should understand that these are only examples, and various changes or modifications can be made to the embodiments without departing from the principles and essence of the present invention. The scope of protection is limited only by the appended claims.
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