CN106229534A - A kind of second alcohol-based electrolyte producing methanol for methane electrolytic oxidation - Google Patents
A kind of second alcohol-based electrolyte producing methanol for methane electrolytic oxidation Download PDFInfo
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- CN106229534A CN106229534A CN201610772053.4A CN201610772053A CN106229534A CN 106229534 A CN106229534 A CN 106229534A CN 201610772053 A CN201610772053 A CN 201610772053A CN 106229534 A CN106229534 A CN 106229534A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention relates to a kind of alcoholic base solutions directly producing methanol for being electrolysed methane, belong to gas chemical industry's technology and Applied Electrochemistry technical field.Alcoholic base solutions is by concentration of alcohol 80 95vol%, and surplus is in the solution of water, adds NaCl 0.21 3.76g L‑1, NaOH 0.21 0.71g L‑1Obtaining, its electrical conductivity is 2 × 102‑1.5×103μs·cm‑1, the meltage of methane is 0.04 6.3g L‑1.In the electrolysis bath closed, doing anode with graphite, rustless steel does negative electrode, adds the second alcohol-based electrolyte of the present invention in the anode region of electrolysis bath, and cathode chamber adds 20g L‑1NaCl solution, under room temperature condition, the anode region that methane gas is passed through electrolysis bath carries out electrolytic oxidation, it is thus achieved that methanol, and methanol yield is 5.27 10.34wt%, and current efficiency is 46.00 95.71%.The alcoholic base solutions of the present invention has that methane meltage is high, electrical conductivity of solution is good, produces methanol for electrolytic oxidation methane, the advantage that methanol yield is high.
Description
Technical field:
The present invention relates to a kind of alcoholic base solutions directly producing methanol for being electrolysed methane, belong to gas chemical industry's technology and
Applied Electrochemistry technical field.
Background technology:
Methane is the main component of natural gas, biogas.Methane content in natural gas is usually 83-99%, methane
Convert and utilize in gas chemical industry, occupy very important position, be the main research of gas chemical industry.Equally, first
Alkane content in biogas is usually 50-80%, as the main constituent of cleaning, regenerative resource biogas.Methanol is a kind of
Clean liquid fuel and basic chemical industry raw material, it stores and transport is the most more convenient, and therefore, methane is current energy for methanol
The key areas of source strategic research.
Methane synthesizing methanol mainly has direct translation method and indirect reformer method two ways.The indirect reformer side of methane is first
Synthesis gas (CO+H is made by methane2), the most again by synthesis gas Synthesis methanol, in current commercial production, application is indirect mostly
Conversion method, in this approach, the preparation of synthesis gas and compression account for more than the 60% of whole process investment, and process energy consumption is big,
Operating cost is high, conversion ratio is low.Directly converting of methane needs not move through synthesis gas, has potential advantage in theory, and it passes
The application of system includes that methane is directly produced acetylene, hydrogen, carbon black, chloromethanes, hydrocyanic acid, nitromethane, Carbon bisulfide etc.
Chemical products, but owing to methane molecule is highly stable, the production of the said goods is required in high temperature, high pressure, the harshness of high energy consumption
Under the conditions of carry out, and by-product is many, needs complicated subsequent treatment.It is industrial the most preferable by directly oxidizing methane synthesizing methanol
Method, people have all carried out a large amount of exploration to relevant catalyst, catalytic mechanism, thermodynamic analysis, process conditions etc. and have ground
Study carefully[1-13], but the subject matter faced is that methane molecule is once activated owing to the activation energy of methane is the highest, is difficult to control instead
The degree that should carry out, makes the methanol of generation not be further oxided, and result is typically methane conversion and methanol selectivity is basic
In inverse relation, the productivity of methanol is the lowest[14], significantly limit the direct trans-utilization of methane.
The method producing methanol by the method methane of electrolytic oxidation, can carry out at ambient temperature, have reaction bar
Part is gentle, and response speed can be controlled by anode current, and the advantage that methanol selectivity is high belongs to methane direct conversion methanol
Type[15], but owing to methane is insoluble in water, in water based electrolyte, methane concentration is the lowest, can only be electrolysed with smaller current, and difficult
In the productivity and the production efficiency that improve methanol.
The present invention be directed to electrolytic oxidation methane and directly produce the electro-chemical systems of methanol and the second alcohol-based electrolyte invented,
By literature search, have no that the disclosure identical with the present invention is reported.
List of references:
[1] Wang Hua, Liu Zhongmin. Progress in Direct Conversion of Methane [J]. chemical industry is in progress, 2004,16 (4), 593-602
[2] Chen Liyu etc. the research [J] of the phosphotungstic acid catalyst of partial oxidation reaction of methane. colleges and universities' Chemical Engineering journal,
2007,21(4):650-653.
[3] .V such as Chen Liyu2O5Catalytic methane performing liquid-phase partial oxidation technical process research [J]. colleges and universities' Chemical Engineering journal,
2006,20(3):417-421.
[4] .CoMoO such as Wang Lijuan4The research [J] of methane portion oxidation on load Mo-V-Cr-Bi oxide catalyst.
Liaoning chemical industry, 2006,35 (9): 503-505.
[5] Pei Supeng etc. methane selective oxidation reaction [J] on support type P-Mo-V/SBA-15 catalyst. Science of Chemistry
Report, 2008,66 (8): 902-908
[6] Zhang Xin, He Dehua etc. methane gas phase Homogeneous Selective Oxidation synthesizing methanol [J]. petrochemical industry, 2003,32 (3):
195-199
[7] Wang Chengxue, Li Shaofen. Partial Oxidation of Methane synthesizing methanol and formaldehyde [J]. Industrial Catalysis, 1997,2,3-
10
[8] Zhang Yiqun, Zhang Pei, Ma Jianxin, MoO3/La2O3Methane selectively oxidizing methanol [J] on catalyst. catalysis
Journal, 1997,18 (5), 425-427
[9] Zhang Xin, methane selective oxidation making methanol reaction [J] on He Dehua etc., Mo/La-Co-O catalyst. catalysis is learned
Report, 2003,24 (4), 305-311
[10]Shilov A E.Activation and Functionalization of Alkanes[M].New
York:Wiley,1989
[11]Labinger J A,Bercaw J E.Understanding and exploiting C-H bond
Activation[J].Nature,2002,417:507-514
[12] Chen Xihui, Japanese plum is originally. aqueous porous TiO2The preliminary study [J] of photocatalytic molecules oxidizing of methylene. molecule
Catalysis, 2000,14 (4): 243-244
[13] peak, clock is genial. the research [J] of Behavior of Laser Stimulated Methane Direct Oxidation To Methanol On Surface of Phosphates. and fuel
Chemistry journal, 2000,28 (5): 402-405
[14] Su Yongqing, Wang Ping, Ren Nianjun, etc. the status and prospectives [J] of methane direct conversion. Yunnan chemical,
2009,36(4):1-6.
[15] Su Yongqing, Ren Nianjun, Che Guangkun. a kind of methane directly produces the electrochemical method [P] of methanol. and China is specially
Profit, ZL201010106288.2
Summary of the invention:
It is an object of the invention to provide a kind of second alcohol-based electrolyte producing methanol for electrolytic oxidation methane.
The present invention uses ethanol as the base fluid of electrolyte, adds a small amount of water, NaCl, NaOH prepare ethanol in base fluid
Base electrolyte.Containing Cl in second alcohol-based electrolyte–Ion, OH–Ion, H2O molecule, has electric conductivity, can dissolved methane.
The second alcohol-based electrolyte of the present invention is by concentration of alcohol 80-95vol%, and surplus is in the solution of water, adds
NaCl 0.21-3.76g·L-1, NaOH 0.21-0.71g L-1Obtaining, its electrical conductivity is 2 × 102-1.5×103μs·cm-1,
The meltage of methane is 0.04-6.3g L-1。
The second alcohol-based electrolyte of the present invention is used for being electrolysed methane and directly produces methanol, it may be assumed that
Selecting existing graphite to do anode, rustless steel does in the closed electrolysis cells of negative electrode, adds in the anode region of electrolysis bath
The second alcohol-based electrolyte of the present invention, cathode chamber adds 20g L-1NaCl solution, at ambient temperature, methane gas is passed through
The anode region of electrolysis bath carries out electrolytic oxidation, it is thus achieved that methanol；Methanol yield is 5.27-10.34wt%, and current efficiency is 46.00-
95.71%.
The present invention has that methane meltage is high, electrical conductivity of solution is good, produces methanol, methanol yield for electrolytic oxidation methane
High advantage.
Detailed description of the invention:
Below by embodiment, the present invention is described in further detail.
Embodiment 1:
The second alcohol-based electrolyte of the present invention is by concentration of alcohol 80vol%, and surplus is in the solution of water, adds
0.21g·L-1NaCl and 0.21g L-1NaOH obtains, its Methane solubility 1.93g L-1, electrical conductivity 8.6 × 102μs·cm-1。
The second alcohol-based electrolyte of the present invention is used for being electrolysed methane and directly produces methanol, it may be assumed that
Selecting existing graphite to do anode, rustless steel does the closed electrolysis cells of negative electrode, adds this in the anode region of electrolysis bath
The second alcohol-based electrolyte 602ml of invention, cathode chamber adds 500ml water and 10g (20g L-1) solution that is made into of NaCl.At 25 DEG C
Under constant temperature, methane gas being passed through the anode region of electrolysis bath, the flow velocity of methane gas is 13mL min-1, Faradaic current is close
Degree is 0.17A dm-2, methanol yield is 7.51wt%, and current efficiency is 69.92%.
Embodiment 2:
The second alcohol-based electrolyte of the present invention is by concentration of alcohol 80%, and surplus is in the solution of water, adds 3.758g
L-1NaCl and 0.626g L-1NaOH obtains, its Methane solubility 0.8g L-1, electrical conductivity 1.5 × 103μs·cm-1。
The second alcohol-based electrolyte of the present invention is used for being electrolysed methane and directly produces methanol, it may be assumed that
Selecting existing graphite to do anode, rustless steel does the closed electrolysis cells of negative electrode, adds second in the anode region of electrolysis bath
Alcohol-based electrolyte 539ml, cathode chamber adds 500ml water and 10g (20g L-1) solution that is made into of NaCl.At 25 DEG C of constant temperatures
Under, methane gas is passed through the anode region of electrolysis bath, the flow velocity of methane gas is 13mL min-1, electrolytic current density is
0.21A·dm-2, methanol yield is 9.44wt%, and current efficiency is 67.84%.
Embodiment 3:
The second alcohol-based electrolyte of the present invention is by concentration of alcohol 90%, and surplus is in the solution of water, adds 0.238g
L-1NaCl and 0.238g L-1NaOH obtains, its Methane solubility 4.34g L-1, electrical conductivity 2.7 × 103μs·cm-1。
The second alcohol-based electrolyte of the present invention is used for being electrolysed methane and directly produces methanol, it may be assumed that
Selecting existing graphite to do anode, rustless steel does in the closed electrolysis cells of negative electrode, adds in the anode region of electrolysis bath
Second alcohol-based electrolyte 539ml, cathode chamber adds 500ml water and 10g (20g L-1) solution that is made into of NaCl.At 25 DEG C of constant temperature bars
Under part, methane gas being passed through the anode region of electrolysis bath, the flow velocity of methane gas is 13mL min-1, electrolytic current density is
0.21A·dm-2, methanol yield is 10.34wt%, and current efficiency is 60.33%.
Embodiment 4:
The second alcohol-based electrolyte of the present invention is by concentration of alcohol 90%, and surplus is in the solution of water, adds 0.714g
L-1NaCl and 0.714g L-1NaOH obtains, its Methane solubility 1.5g L-1, electrical conductivity 6.4 × 102μs·cm-1。
The second alcohol-based electrolyte of the present invention is used for being electrolysed methane and directly produces methanol, it may be assumed that
Selecting existing graphite to do anode, rustless steel does in the closed electrolysis cells of negative electrode, adds in the anode region of electrolysis bath
Second alcohol-based electrolyte 539ml, cathode chamber adds 500ml water and 10g (20g L-1) solution that is made into of NaCl.At 25 DEG C of constant temperature bars
Under part, methane gas being passed through the anode region of electrolysis bath, the flow velocity of methane gas is 13mL min-1, electrolytic current density is
0.21A·dm-2, methanol yield is 8.99wt%, and current efficiency is 64.55%.
Embodiment 5:
The second alcohol-based electrolyte of the present invention is by concentration of alcohol 95%, and surplus is in the solution of water, adds 0.238g
L-1NaCl and 0.238g L-1NaOH obtains, its Methane solubility 0.32g L-1, electrical conductivity 2.0 × 102μs·cm-1。
The second alcohol-based electrolyte of the present invention is used for being electrolysed methane and directly produces methanol, it may be assumed that
Selecting existing graphite to do anode, rustless steel does in the closed electrolysis cells of negative electrode, adds in the anode region of electrolysis bath
Second alcohol-based electrolyte 544ml, cathode chamber adds 500ml water and 10g (20g L-1) solution that is made into of NaCl.At 25 DEG C of constant temperature bars
Under part, methane gas being passed through the anode region of electrolysis bath, the flow velocity of methane gas is 13mL min-1, electrolytic current density is
0.13A·dm-2, methanol yield is 10.25wt%, and current efficiency is 95.71%.
Embodiment 6:
The second alcohol-based electrolyte of the present invention is by concentration of alcohol 95%, and surplus is in the solution of water, adds 0.714g
L-1NaCl and 0.714g L-1NaOH obtains, its Methane solubility 1.27g L-1, electrical conductivity 6.4 × 102μs·cm-1。。
The second alcohol-based electrolyte of the present invention is used for being electrolysed methane and directly produces methanol, it may be assumed that
Selecting existing graphite to do anode, rustless steel does in the closed electrolysis cells of negative electrode, adds in the anode region of electrolysis bath
Second alcohol-based electrolyte 544ml, cathode chamber adds 500ml water and 10g (20g L-1) solution that is made into of NaCl.At 25 DEG C of constant temperature bars
Under part, methane gas being passed through the anode region of electrolysis bath, the flow velocity of methane gas is 13mL min-1, electrolytic current density is
0.21A·dm-2, methanol yield is 7.88wt%, and current efficiency is 46.00%.
Claims (1)
1. the second alcohol-based electrolyte producing methanol for electrolytic oxidation methane, it is characterised in that this electrolyte is by ethanol
Concentration 80-95vol%, surplus is in the solution of water, adds NaCl 0.21-3.76g L-1, NaOH 0.21-0.71g L-1
Obtaining, its electrical conductivity is 2 × 102-1.5×103μs·cm-1, the meltage of methane is 0.04-6.3g L-1。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610772053.4A CN106229534A (en) | 2016-08-30 | 2016-08-30 | A kind of second alcohol-based electrolyte producing methanol for methane electrolytic oxidation |
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| CN201610772053.4A CN106229534A (en) | 2016-08-30 | 2016-08-30 | A kind of second alcohol-based electrolyte producing methanol for methane electrolytic oxidation |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775614A (en) * | 2010-02-05 | 2010-07-14 | 云南师范大学 | Electrochemical method for directly preparing carbinol by using methane |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775614A (en) * | 2010-02-05 | 2010-07-14 | 云南师范大学 | Electrochemical method for directly preparing carbinol by using methane |
Non-Patent Citations (1)
| Title |
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| 李晓飞: "用于电解甲烷制甲醇的电极、电解质溶液体系研究", 《中国优秀硕士学位沦为全文数据库 工程科技I辑》 * |
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Application publication date: 20161214 |