CN110029355B - Electrochemical preparation method of propane - Google Patents
Electrochemical preparation method of propane Download PDFInfo
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- CN110029355B CN110029355B CN201910276288.8A CN201910276288A CN110029355B CN 110029355 B CN110029355 B CN 110029355B CN 201910276288 A CN201910276288 A CN 201910276288A CN 110029355 B CN110029355 B CN 110029355B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
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Abstract
The invention discloses an electrochemical preparation method of propane, which takes an inert electrode as a working electrode and a counter electrode and takes a solution of glutaric acid in a protic or aprotic solvent as an electrolyte to carry out electrolysis to obtain the propane. The invention adopts an electrochemical method to prepare propane for the first time, glutaric acid is a renewable green raw material, an aqueous solution system can be completely adopted, the obtained propane is naturally separated, and the product purity is high.
Description
Technical Field
The invention belongs to the technical field of electrochemical synthesis, and particularly relates to a method for preparing propane by electrolyzing glutaric acid.
Background
With the increasing exhaustion of non-renewable fossil and the increasing prominence of environmental pollution, the research and development of renewable carbon neutral chemical products have strategic significance for relieving petroleum crisis, improving environmental pollution conditions and realizing sustainable development
Propane is an important chemical raw material. Most of the propane preparation methods reported in the prior art have relatively long production period, complex and complicated preparation process, high requirements on energy consumption and equipment due to high requirements on conditions such as temperature and pressure in reaction, often need to add a catalyst, troublesome post-product separation and low atom economy.
The electrochemical organic synthesis method has the following outstanding advantages: the method has the advantages of simple required instruments, fewer preparation procedures, mild reaction conditions, shorter time for obtaining reaction products, simple post-treatment of products, no need of additional catalyst, high atom economy, green reaction process and the like. The Kolbe reaction can be used for electrolyzing monocarboxylic acid R-COOH to obtain R-R alkane, but the electrolytic preparation of propane by using single dicarboxylic acid has not been reported.
The invention firstly provides a method for preparing propane by taking glutaric acid from biomass as a raw material through electrocatalysis.
Disclosure of Invention
The invention adopts glutaric acid with wide biomass sources as a raw material for preparing propane by electrocatalysis for the first time. The technical scheme of the invention is as follows:
the invention discloses a preparation method of propane, which takes an inert electrode as a working electrode and a counter electrode and glutaric acid dissolved in protons or non-protonsThe solution in the agent is used as electrolyte to carry out electrolysis to obtain the propane. The molecular formula of glutaric acid is HOOC-C3H6-COOH, the present invention catalyzes the electrolysis of glutaric acid to give propane. Generally, the concentration of the glutaric acid solution is not less than 0.01 mol/L.
Preferably, the protic or aprotic solvent is one or more of deionized water, methanol, acetone or acetonitrile.
Preferably, a supporting electrolyte is further added to the electrolytic solution, and the supporting electrolyte is an acidic substance or a neutral substance.
Preferably, the inert electrode is metallic platinum or graphite.
Preferably, the operating voltage is generally not less than 3.5V.
Preferably, the faradaic efficiency of the production process and the selectivity of the product propane are increased by selecting a platinum electrode as the working electrode.
Preferably, the faradaic efficiency of the production process and the selectivity of the product propane are increased by selecting an acidic or neutral compound as the supporting electrolyte and increasing the concentration of the supporting electrolyte and the acidity of the electrolyte.
Preferably, the faradaic efficiency of the production process and the selectivity of the product propane are increased by increasing the operating voltage.
The present invention may or may not use a reference electrode. A reference electrode is used in a common laboratory, and the reference electrode is not needed in industrial production.
The invention has the beneficial effects that:
1. the method adopts an electrochemical method to prepare the propane, uses current as a reaction reagent and a catalyst, does not need to add dangerous and toxic additives, has simple reaction process, can generate reaction at normal temperature and normal pressure, generates less waste in the reaction process, has short reaction period, high reaction conversion rate, lower reaction cost compared with the traditional method, does not discharge tail gas harmful to the environment, and has green reaction process.
2. The invention adopts glutaric acid as raw material to prepare propane. Glutaric acid is a renewable green raw material, has the advantages of wide source, low price, biodegradability, no toxicity and the like, and can be obtained by fermenting cellulose, hemicellulose, plant starch and the like.
3. The method can completely adopt an aqueous solution system as the electrolyte to prepare the propane. The water is used as an environment-friendly solvent, the water is used as the solvent, the requirement of 'green chemistry' is met, the generated propane gas is insoluble in water, the density of the propane gas is lower than that of the water, the propane gas naturally escapes from the water, and the propane gas can be naturally separated from the water solution. Therefore, the collection process of the product after electrolysis is more simplified compared with the traditional preparation method, not only saves a large amount of time, but also reduces the energy consumption of the whole process, and has the advantages of environmental friendliness, low cost and high product purity. Is easy for industrialized production.
Detailed Description
The following specific examples illustrate the processes described in the present invention, but the present invention is not limited to these examples.
The invention adopts an electrocatalysis method to catalyze glutaric acid to obtain propane. The propane generated after the reaction is finished directly escapes from the water, so that the reaction kettle is easy to collect, and the purity of the propane can reach more than 99%. The whole electrolysis process can be carried out in an aqueous solution of glutaric acid.
Example 1
Medicine preparation: deionized water (18.2 M.OMEGA., Merck Milli-QaddvantageA 10 ultrapure water system), the glutaric acid, potassium hydroxide, potassium sulfate, and sulfuric acid used were purchased and used directly without further purification.
An electrolytic cell: the electrolytic cell used in the reaction is 50mm3The screw can seal the diaphragm-free park glass electrolytic cell. The electrolytic system is a three-electrode system, wherein a Pt sheet (1cm multiplied by 1cm) is used as a working electrode, a Pt net (60 meshes, 1cm multiplied by 1cm) is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode.
1.65g of glutaric acid and 6.25ml of H with a concentration of 2mol/L2SO4The aqueous solution (as supporting electrolyte) was added sequentially to the beaker and mixed, then deionized water was added to a volume of 25 ml. The magnetons are put into a beaker, and are stirred for 10min after being started at 600rpm, and then are added into the electrolytic cell. The cell was placed in a water bath at about 30 ℃ and three electrodes were connected in sequence toA workstation. Firstly, a Cyclic Voltammetry (CV) test is carried out, wherein the CV scanning range is 0V-4V, and the scanning rate is as follows: 5mV/s, number of scan cycles: 5 circles. Then constant potential electrolysis is carried out for 10min at constant voltage of 3.5V.
Analysis of electrolytic products: the gaseous products were continuously collected from the cell during the reaction and immediately analyzed by gas chromatography.
Examples 2 to 13
The effect of variation in the concentration of glutaric acid, type of solvent, type of supporting electrolyte, concentration and applied voltage on the selectivity for propane is shown in table 1. In examples 2 to 9 and 11 to 13, working electrodes were used as in example 1, and the working electrode used in example 10 was a graphite electrode. The rest is the same as example 1.
Table 1 examples 1-13
As can be seen from the data in table 1: under the condition that the solvent is deionized water and other conditions are certain, the higher the concentration of glutaric acid is, the higher the Faraday efficiency and the propane selectivity are; the glutaric acid concentration is generally selected to be 0.5mol/L, taking into account other factors. Under other conditions, the supporting electrolyte is acidic, the Faraday efficiency and the propane selectivity are high, and the stronger the acidity, the higher the Faraday efficiency and the propane selectivity are; the supporting electrolyte is alkaline, and the selectivity of propane is low; h is generally chosen in consideration of other factors2SO4As a supporting electrolyte, and the molar ratio of the supporting electrolyte to glutaric acid is 1: 1. Under other conditions, the higher the voltage is, the higher the Faraday efficiency and the propane selectivity are; at voltages below 3.5V, faradaic efficiency and propane selectivity are very low; when the voltage is higher than 3.5V, the Faraday efficiency and the propane selectivity are slowly increased; at the voltage of 6.5V, the propane selectivity exceeds 90 percent, and the Faraday efficiency exceeds 92 percent; in view of itOther factors, the voltage is selected to be more than 3.5V. When the solvent is an organic solvent such as methanol, acetone, or acetonitrile, the faradaic efficiency and propane selectivity are rather low, and therefore, deionized water is generally selected as the solvent without using an organic solvent. As is clear from examples 1 and 10, the faradaic efficiency and propane selectivity of the working electrode as a platinum electrode were higher than those of the working electrode as a graphite electrode under other conditions; the working electrode is typically selected to be a platinum electrode.
While specific embodiments of, and examples for, the invention are described herein for illustrative purposes, various changes in detail will be apparent to those skilled in the art without departing from the invention.
Claims (2)
1. An electrochemical preparation method of propane is characterized in that an inert electrode is used as a working electrode and a counter electrode, and a solution of glutaric acid in a protic or aprotic solvent is used as an electrolyte to carry out electrolysis to obtain propane; the protic or aprotic solvent is deionized water; also adding a supporting electrolyte to the electrolyte, the supporting electrolyte being selected from H2SO4(ii) a The working voltage is 3.5-9.5V; the working electrode is platinum metal.
2. The method of claim 1, wherein the faradaic efficiency of the production process and the selectivity to product propane are increased by increasing the operating voltage.
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| CN201910276288.8A CN110029355B (en) | 2019-04-08 | 2019-04-08 | Electrochemical preparation method of propane |
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| CN201910276288.8A CN110029355B (en) | 2019-04-08 | 2019-04-08 | Electrochemical preparation method of propane |
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| CN110029355B true CN110029355B (en) | 2021-01-15 |
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