CN112301372B - Method for preparing ethylene glycol from methane by one-step method - Google Patents
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Abstract
The invention discloses a method for efficiently preparing ethylene glycol by a methane one-step method, which comprises the following steps: in a reactor containing an electrolyte solution, a methane gas or a methane-containing gas as a raw material gas is reacted at 0 to 100 ℃ for 10 to 1200min under light irradiation and electrolysis conditions in the presence of tungsten trioxide as a catalyst. The method of the invention can obtain the target product ethylene glycol with high yield, the target product is easy to separate, and the used catalyst is cheap and easy to obtain, has high catalytic performance and can be repeatedly used. Moreover, the method has the advantages of simple reaction process, short period, mild reaction conditions, wide sources of reactant raw materials, low price and easy obtainment, can particularly directly use natural gas, shale gas, combustible ice or methane as raw material gas and the like, is environment-friendly, provides a new synthesis way for preparing high-value glycol from the natural gas, the shale gas, the combustible ice, the methane and the like, and has wide industrial application prospect.
Description
Technical Field
The invention relates to a novel method for efficiently preparing ethylene glycol by a methane one-step method.
Background
Ethylene Glycol (EG), also known as glycol, hydroextracts, is widely used in solvents, antifreezes and synthetic dacron and sheeting, closely related to the basic needs of clothing and housing. Currently, the synthesis routes of ethylene glycol are mainly divided into two types: ethylene route and oxalate route. The two routes both need to consume fossil resources such as coal, petroleum and the like, and discharge gases such as carbon dioxide, nitrogen oxides and the like, so that not only is the environmental problem increasingly serious, but also fossil resources on the earth are increasingly exhausted. On the other hand, with the development of technologies such as biogas, the sources of methane are more and more extensive. Meanwhile, methane is also a main component of natural gas, shale gas, combustible ice or methane, and is a very abundant resource. Therefore, efficient conversion of methane has attracted extensive research interest in industry and academia.
Currently, the industrial conversion of methane to alcohols is mainly carried out by indirect processes, i.e. the methane is first converted to synthesis gas (CO and H) by high temperature and pressure2Etc.), and further alcohols are produced from the syngas. However, such processes typically require severe conditions of high temperature (700-. Therefore, there is a need for a method for more economically, simply and gently realizing industrial methane-to-ethylene glycol production, which can overcome the above-mentioned drawbacks.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a novel process for the preparation of ethylene glycol solving some or all of the problems of the prior art.
To this end, the present invention provides a method for preparing ethylene glycol from methane by a one-step process, the method comprising: in a reactor containing an electrolyte solution, a methane gas or a methane-containing gas as a raw material gas is reacted at 0 to 100 ℃ for 10 to 1200min under light irradiation and electrolysis conditions in the presence of tungsten trioxide as a catalyst.
In a preferred embodiment, the electrolyte solution is an aqueous solution of one or more selected from the group consisting of sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, sodium nitrate, and potassium nitrate.
In a preferred embodiment, the pH of the electrolyte solution is in the range of 0.5 to 10, preferably in the range of 1 to 7.
In a preferred embodiment, the reactor is a polytetrafluoroethylene reaction cell, a glass reaction cell, a quartz reaction cell, or a stainless steel reaction cell.
In a preferred embodiment, the illumination intensity is from 10 to 1000mW/cm2。
In a preferred embodiment, the light source for the illumination is one or more selected from a xenon lamp, an LED lamp, a tungsten lamp, and a mercury lamp.
In a preferred embodiment, the voltage for the electrolysis is in the range of 0.05-10V relative to a standard hydrogen electrode.
In a preferred embodiment, the catalyst is a tungsten trioxide thin film or tungsten trioxide particles supported on an electrode substrate serving as a working electrode; preferably, the electrode substrate is one or more selected from the group consisting of conductive glass, conductive carbon paper, conductive PET polyester, conductive carbon cloth, and a metal electrode.
In a preferred embodiment, the catalyst is synthesized by a hydrothermal method, a solvothermal method, a sol-gel method or a pyrogenic method; preferably, the synthesized catalyst is subjected to calcination treatment at 100-1000 ℃, more preferably at 400-800 ℃.
In preferred embodiments, the methane-containing gas is natural gas, shale gas, combustible ice, or biogas.
The method of the invention obtains the target product ethylene glycol with high yield (over 70 percent in total), and the obtained target product is easy to separate, for example, can be separated by a rotary evaporation extraction method well known in the art;
in addition, the catalyst used by the method is cheap and easy to obtain, has high catalytic performance and can be repeatedly used.
In addition, the method has the advantages of simple reaction process, short period, mild reaction conditions, wide source of reactant raw materials, low price and easy obtainment, can especially directly use natural gas, shale gas or methane as raw material gas and the like, is environment-friendly, provides a new synthesis way for preparing high-value glycol from natural gas, shale gas, methane and the like, and has wide industrial application prospect. In addition, the invention provides reference and a new idea for exploring the preparation of high value-added chemicals by directly converting methane under mild conditions.
Drawings
Fig. 1 is a nuclear magnetic resonance hydrogen spectrum of a target product, ethylene glycol, obtained according to one embodiment of the present invention.
Fig. 2 is a graph showing the effect of the reuse of the catalyst according to the present invention.
Detailed Description
As a result of intensive and extensive studies by the inventors of the present invention, a novel method for efficiently producing ethylene glycol from methane in a one-step process, which can not only achieve the production of methyl chloride from methane in a one-step process under mild conditions at a high yield, but also greatly alleviate the energy crisis and environmental pollution problems in a simple and cost-effective manner, has been unexpectedly found.
The method for preparing the ethylene glycol by the methane one-step method comprises the following steps: in a reactor containing an electrolyte solution, a methane gas or a methane-containing gas as a raw material gas is reacted at 0 to 100 ℃ for 10 to 1200min in the presence of tungsten trioxide as a catalyst and under illumination and electrolysis conditions, thereby converting methane in the methane gas or the methane-containing gas into ethylene glycol in high yield.
In the process of the present invention, after the reaction is completed, the desired product, ethylene glycol, can be isolated simply by conventional means, such as, but not limited to, using rotary evaporation extraction.
In the process of the invention, after the end of the reaction, it is possible to carry out the reaction by conventional means, for example, but not limited to, using hydrogen nuclear magnetic resonance spectroscopy1H NMR was used to determine the yield of the desired product, ethylene glycol.
In the process of the present invention, the feed gas used may be in the form of a pure methane gas or a methane-containing gas. The term "methane-containing gas" refers to a gas mixture containing methane therein, preferably a methane-containing gas having a methane content of more than 50% by volume, examples of which are, but not limited to, natural gas, shale gas, combustible ice or biogas, and the like.
In the method of the present invention, although there is no particular limitation on the pressure of the methane gas or the methane-containing gas in the reactor, it is preferable that the pressure of the methane gas or the methane-containing gas in the reactor is from 0.1MPa to 10 MPa.
In the method of the present invention, the electrolyte in the electrolyte solution is not particularly limited. Preferably, the electrolyte solution used may be, for example, sodium sulfate (NaSO)4) Potassium sulfate (KSO)4) Sodium chloride (NaCl), potassium chloride (KCl) and sodium nitrate (NaNO)3) And potassium nitrate (KNO)3) An aqueous solution of one or more of (a).
In the method of the present invention, the electrolyte solution is preferably used at a pH in the range of 0.5 to 10, preferably 1 to 7 (i.e., an acidic pH).
In the process of the present invention, the catalyst used is tungsten trioxide (WO)3) A compound is provided. The inventors have found that tungsten trioxide has very excellent optical properties, chemical stability and thermal stability. In addition, the tungsten trioxide is simple in preparation method, cheap and mass-produced, and can efficiently and lowly convert methane into ethylene glycol by one-step method when being applied in combination with the illumination condition and the electrolysis condition. In addition, the catalyst can be repeatedly used in the method of the invention, so that the whole process has high industrial application prospect.
In the method of the present invention, it is further preferred that the catalyst used is a tungsten trioxide thin film or tungsten trioxide particles, which are preferably supported (e.g., attached or deposited) on an electrode substrate serving as a working electrode for electrolysis.
In the process of the present invention, it is further preferred that the catalyst used is synthesized by a hydrothermal method, a solvothermal method, a sol-gel method or a pyrogenic method; it is further preferred that the synthesized catalyst is subjected to calcination treatment at 100-1000 deg.C, more preferably at 400-800 deg.C.
In the method of the present invention, preferably, the electrode substrate used may be one or more selected from the group consisting of conductive glass, conductive carbon paper, conductive PET polyester, conductive carbon cloth, and metal electrodes.
In the method of the present invention, the reactor used is not particularly limited as long as it can withstand a certain pressure and perform electrolysis and is a container that can be sealed, and for example, the reactor used may be a polytetrafluoroethylene reaction cell, a glass reaction cell, a quartz reaction cell, a stainless steel reaction cell, or the like.
In the method of the present invention, preferably, the illumination condition used may have an illumination intensity of 10 to 1000mW/cm2。
In the method of the present invention, the light source used for the illumination condition is not particularly limited as long as it can emit light radiation. Preferably, the light source for the lighting conditions may be one or more selected from a xenon lamp, an LED lamp (i.e., a light emitting diode), a tungsten lamp, and a mercury lamp.
In the method of the present invention, it is preferable that the voltage for the electrolysis is in the range of 0.05 to 10V with respect to a standard hydrogen electrode. Further preferably, the applied voltage is a voltage applied by a Direct Current (DC) power supply.
In the process of the present invention, the reaction temperature of the reactor is usually 0 to 100 ℃; preferably, the reaction temperature used may be 20-50 deg.C, most preferably the reaction is carried out at ambient temperature (i.e., about 25-30 deg.C). If desired, the reactor may be heated to the desired reaction temperature by conventional means, such as a water bath or oil bath.
In the method of the present invention, the reaction time is usually 10 to 1200min from the viewpoint of efficiency, and more preferably the reaction time may be 100-480 min, for example, about 360 min.
The present invention is further described with reference to the following embodiments, which are only some preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Unless otherwise specified, all starting materials used in the present invention are not particularly limited in their source and are commercially available; meanwhile, the purity is not particularly limited, and analytical purification is preferably employed in the present invention.
The reaction or detection apparatus or device used in the present invention is not particularly limited as long as the object can be achieved, and any conventional apparatus or device known to those skilled in the art can be used.
Catalyst preparation
3Hydrothermal preparation method of tungsten trioxide thin film catalyst (WO-1)
In a 250mL flask, 1g of ammonium paratungstate was added to 97mL of deionized water and sufficiently dissolved by magnetic stirring at room temperature, followed by adding 3mL of an aqueous hydrochloric acid solution (mass concentration of about 36%) thereto and stirring for 30 min. Then, 2mL of hydrogen peroxide (30%) was added to the resultant mixture and stirred for 30min, after which the resultant mixture was transferred to a reaction vessel containing conductive glass as an electrode substrate and sealed. Then, the reaction was carried out in an oven heated to 160 ℃ for 240 min. After the reaction is finished, the reaction product is naturally cooled to room temperature. Opening the reaction kettle, taking out the conductive glass on which a layer of tungsten trioxide (namely tungsten trioxide film) grows on the surface, washing the conductive glass with deionized water, and calcining the conductive glass in air at 500 ℃ for 60min in a muffle furnace to obtain the required tungsten trioxide film catalyst (WO)3-1) supported on a conductive glass.
3Hydrothermal preparation method of tungsten trioxide thin film catalyst (WO-2)
In a 250mL flask, 1g of ammonium tungstate was added to 97mL of deionized water and sufficiently dissolved by magnetic stirring at room temperature, followed by adding 3mL of an aqueous hydrochloric acid solution (mass concentration of about 36%) thereto and stirring for 30 min. Then, 2mL of hydrogen peroxide (30%) and 0.5g of sodium citrate were added to the resultant mixture and stirred for 30min, after which the resultant mixture was transferred to a reaction vessel containing a conductive carbon cloth as an electrode substrate and sealed. Then, the reaction was carried out in an oven heated to 160 ℃ for 240 min. After the reaction is finished, the reaction solution is naturally cooled to room temperature. Opening the reaction kettle, taking out the conductive glass on which a layer of tungsten trioxide (namely tungsten trioxide film) grows on the surface, washing the conductive glass with deionized water, and calcining the conductive glass in air at 500 ℃ for 60min in a muffle furnace to obtain the required tungsten trioxide film catalyst (WO)3-2) supported on a conductive carbon cloth.
3Hydrothermal preparation method of tungsten trioxide particle catalyst (WO-3)
In a 100mL beaker, 0.8g of sodium tungstate dihydrate, 0.25g of citric acid and 0.64g of glucose are added into 30mL of deionized water, and the mixture is stirred for 10min to disperse and dissolve all the raw materials; then, an aqueous hydrochloric acid solution (mass concentration of about 18%) was added dropwise to the resulting solution to adjust the pH thereof to 0.3, followed by stirring for 30 min. Subsequently, the resulting mixed solution was transferred to a 50mL teflon reaction kettle containing conductive glass as an electrode base and sealed, heated in an oven at 120 ℃ for 720min, and then naturally cooled to room temperature. The obtained sample was washed with deionized water, then dried in a drying oven at 60 ℃ and then calcined in air in a muffle furnace at 500 ℃ for 120min to obtain the desired tungsten trioxide particle catalyst (WO)3-3) carried on a conductive glass.
Example 1
Adding a sodium sulfate aqueous solution with the pH value of 2 into a polytetrafluoroethylene H-type reaction tank as an electrolyte, and using the tungsten trioxide thin film catalyst WO prepared in the way3-1 conductive glass as working electrode and Pt as counter electrode, after passing high purity (purity greater than 99.9%) methane gas through a methane cylinderThe reaction cell was sealed (the pressure in the reaction cell was about 0.2 MPa). At room temperature (about 25 ℃ C.), 100mW/cm using a xenon lamp as a light source2The irradiation is carried out by the illumination intensity of the gas, and the preparation of the ethylene glycol by the methane one-step method is carried out under the photoelectric condition that the external direct current power supply applies 0.9V voltage on the working electrode and the counter electrode, and the reaction time is 360 min. The ethylene glycol product can be isolated using rotary evaporation extraction.
After the reaction is completed, taking the electrolyte solution as a sample to pass through nuclear magnetic resonance hydrogen spectrum1H NMR detection (superconducting nuclear magnetic AV III 400 liquid Bruker AVANCE AV III 400). FIG. 1 shows a nuclear magnetic resonance hydrogen spectrum of a target product, ethylene glycol, obtained according to this example, in which dimethyl sulfoxide (DMSO) was used as an internal standard and water (H) was present in the electrolyte solution2O)), thereby determining that the obtained product was ethylene glycol, and the yield of the product ethylene glycol was calculated to be 76%.
It should be noted that, in this example, the rate of formation of the resulting monochloromethane was about 8mmol/g catalyst/h in view of the rate of formation of the desired product, and it can be seen that the process of the present invention has potential for industrial application.
Example 2
The specific reaction process and detection method were the same as in example 1 except that the light intensity was increased to 200mW/cm2. The yield of the product ethylene glycol was found to be 82%.
Example 3
The specific reaction process and detection method are the same as those of example 1, except that the illumination intensity is increased to 400mW/cm2. The yield of the product ethylene glycol was found to be 87%.
Example 4
The specific reaction process and detection method were the same as in example 1, except that an LED lamp was used as the light source instead of the xenon lamp. The yield of the product ethylene glycol was found to be 83%.
Example 5
The specific reaction process and detection method were the same as in example 1 except that the applied voltage was increased to 1.3V. The yield of the product ethylene glycol was found to be 83%.
Example 6
The specific reaction process and detection method were the same as in example 1 except that the applied voltage was increased to 1.5V. The yield of the product ethylene glycol was determined to be 81%.
Example 7
The specific reaction procedure and detection method were the same as in example 1, except that the tungsten trioxide-loaded thin film catalyst WO prepared as described above was used3-2 conductive carbon cloth as working electrode. The yield of the product ethylene glycol was determined to be 72%.
Example 8
The specific reaction process and detection method are the same as those in example 1, except that the polytetrafluoroethylene reaction cell is replaced with a glass reaction cell. The yield of the product ethylene glycol was found to be 75%.
Example 9
The specific reaction process and detection method are the same as those in example 1, except that the polytetrafluoroethylene reaction cell is replaced by a quartz reactor. The yield of the product ethylene glycol was found to be 78%.
Example 10
The specific reaction procedure and detection method were the same as in example 1 except that the electrolyte was replaced with an aqueous solution of sodium sulfate having a pH of 6. The yield of the product ethylene glycol was found to be 70%.
Example 11
The specific reaction procedure and detection method were the same as in example 1 except that the sodium sulfate electrolyte solution having pH 2 was replaced with a sodium nitrate electrolyte solution having pH 2. The yield of the product ethylene glycol was found to be 77%.
Example 12
The specific reaction procedure and detection method were the same as in example 1, except that the tungsten trioxide-supported particulate catalyst WO prepared as described above was used3-3 as working electrode. The yield of the product ethylene glycol was found to be 69%.
Example 13
The specific reaction process and detection method were the same as in example 1 except that the reaction was carried out by keeping the temperature of the reaction cell at 50 ℃ by heating in a water bath. The yield of the product ethylene glycol was found to be 83%.
Example 14
The specific reaction procedure and detection method were the same as in example 1 except that a natural gas containing methane (wherein the methane content was 85% by volume) was used instead of the high-purity methane gas. The yield of the product ethylene glycol was determined to be 72%.
Example 15
The specific reaction process and detection method were the same as in example 1 except that methane-containing biogas (wherein the methane content by volume was 60%) was used instead of the high-purity methane gas. The yield of the product ethylene glycol was determined to be 72%.
Examples 16 to 20
The specific reaction process and detection method were the same as in example 1 except that the catalyst recovered after separation by filtration and drying at 65 c from example 1 was used 1, 2, 3, 4, 5 and 6 times (i.e., repeatedly used 5 times), respectively. Fig. 2 is a graph showing the effect of reuse (yield of product ethylene glycol) of the catalyst according to the present invention, and in this fig. 2, the abscissa is the number of times of reuse of the catalyst and the ordinate is the yield of product ethylene glycol. As can be seen from fig. 2, it can be seen from fig. 2 that the catalytic efficiency (i.e., the yield of the product) of the catalyst of the present invention is not significantly reduced after five times of repeated use.
While the invention has been described in detail with reference to the preferred forms thereof, it is not intended to limit the invention to the specific embodiments described. Modifications and variations which may be made by those skilled in the art without departing from the technical principles of the present invention are to be considered within the scope of the present invention as defined in the claims.
Claims (14)
1. A process for the one-step production of ethylene glycol from methane, said process comprising: in a reactor containing an electrolyte solution, a methane gas or a methane-containing gas as a raw material gas is reacted at 0 to 100 ℃ for 10 to 1200min under light irradiation and electrolysis conditions in the presence of tungsten trioxide as a catalyst.
2. The method of claim 1, wherein the electrolyte solution is an aqueous solution of one or more selected from the group consisting of sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, sodium nitrate, and potassium nitrate.
3. The method of claim 1, wherein the pH of the electrolyte solution is in the range of 0.5-10.
4. The method according to claim 3, wherein the pH of the electrolyte solution is in the range of 1 to 7.
5. The method of claim 1, wherein the reactor is a polytetrafluoroethylene reaction cell, a glass reaction cell, a quartz reaction cell, or a stainless steel reaction cell.
6. The method as claimed in claim 1, wherein the illumination intensity is 100-1000 mW/cm2。
7. The method according to claim 1, characterized in that a light source for the illumination is one or more selected from a xenon lamp, an LED lamp, a tungsten lamp, and a mercury lamp.
8. The method of claim 1, wherein the voltage for said electrolysis is in the range of 0.9-10V relative to a standard hydrogen electrode.
9. The method according to claim 1, wherein the catalyst is a tungsten trioxide thin film or tungsten trioxide particles supported on an electrode substrate serving as a working electrode.
10. The method of claim 9, wherein the electrode substrate is one or more selected from the group consisting of conductive glass, conductive PET polyester, conductive carbon paper, conductive carbon cloth, and metal electrodes.
11. The process according to claim 9, characterized in that the catalyst is synthesized by hydrothermal, solvothermal, sol-gel or pyrogenic processes.
12. The method as claimed in claim 11, wherein the synthesized catalyst is subjected to calcination treatment at 100-1000 ℃.
13. The method as claimed in claim 11, wherein the synthesized catalyst is subjected to calcination treatment at 400-800 ℃.
14. The method of claim 11, wherein the methane-containing gas is natural gas, shale gas, combustible ice, or biogas.
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| CN110054224A (en) * | 2019-05-30 | 2019-07-26 | 福州大学 | A kind of stratiform tungsten trioxide photoelectrode material and preparation method thereof |
| CN111254471A (en) * | 2020-02-11 | 2020-06-09 | 山东大学 | Porous metal foil and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110054224A (en) * | 2019-05-30 | 2019-07-26 | 福州大学 | A kind of stratiform tungsten trioxide photoelectrode material and preparation method thereof |
| CN111254471A (en) * | 2020-02-11 | 2020-06-09 | 山东大学 | Porous metal foil and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| 钨氧化物的缺陷工程调控与催化性能研究;张宁;《中国优秀博士学位论文全文数据库》;20181015;全文 * |
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