CN101775614B - Electrochemical method for directly preparing carbinol by using methane - Google Patents
Electrochemical method for directly preparing carbinol by using methane Download PDFInfo
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- CN101775614B CN101775614B CN2010101062882A CN201010106288A CN101775614B CN 101775614 B CN101775614 B CN 101775614B CN 2010101062882 A CN2010101062882 A CN 2010101062882A CN 201010106288 A CN201010106288 A CN 201010106288A CN 101775614 B CN101775614 B CN 101775614B
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- methane
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- methyl alcohol
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Abstract
The invention relates to an electrochemical method for directly preparing carbinol by using methane, which belongs to the field of natural gas chemical industry technology and applied electrochemistry. The invention adopts a closed electrolyzer, and takes hollow porous graphite as an anode and stainless steel as a cathode, electrolyte is prepared by distilled water, chlorate solution is prepared by 40-50g/L of NaCl and 16-54g/L of NaOH, or by 30-40g/L of NaF and 16-36g/L of NaOH, and the temperature is 18-60 DEG C; methane gas enters the hollow porous graphite anode the surface area of which is 1dm2 at 4.6ml/min, the connection strength is current of 0.1-0.3A, carbinol is generated in the electrolyte, the productivity of methane is 0.34-2.74%; the electrolyte is heated again, cabinol is evaporated under the condition with the temperature of 65 -75 DEG C, and then the electrolyte returns the electrolyzer. The generated HCl or HF reacts with NaOH of the electrolyte to re-generate NaCl or NaF, NaOH, NaCl or NaF of the electrolyte are recycled in the whole process without energy consumption. The invention has the advantages of low production cost and simple operation.
Description
Technical field:
The present invention relates to a kind ofly directly produce the electrochemical method of methyl alcohol, belong to gas chemical industry's technology and Applied Electrochemistry field with methane.
Background technology:
Methane is the main component of Sweet natural gas and biogas.The content of methane in Sweet natural gas is generally 83-99%, and the conversion of methane and utilization occupy very important position in the gas chemical industry, be gas chemical industry's main research contents.Equally, the content of methane in biogas is generally 50-80%, and as the principal constituent of biogas cleaning, renewable energy source, the conversion of methane and utilization have important potential value.
In the trans-utilization process of methane, the activation of methane molecule is the basis that methane conversion is utilized, no matter be direct or indirect conversion, all must be through the activation of methane, and the methane conduct is the simplest, the most stable, and content is maximum, the easy alkane of regeneration (as biogas) also has very big reference and directive significance to the activation of other inert molecules again.
The conversion of methane and utilization comprise with methane being all processes of raw material synthol and Essential Chemistry product, utilize technology from existing gas chemical industry, and the trans-utilization approach of methane can be divided into two classes: directly transform and indirect reformer.
Methane is as industrial chemicals, and large-scale industrialization is used the indirect reformer that mainly concentrates on methane at present, is about to methane and at first is converted into synthetic gas (CO+H
2), and then be converted into important foundation industrial chemicals such as methyl alcohol, ammonia, dme, mixture of lower alcohols, low-carbon alkene or synthetic liquid fuel etc., the fund that its process need consumption is a large amount of and the energy.
The direct conversion of methane need not through synthetic gas, in theory the potential advantage is arranged, and its traditional Application Areas comprises Chemicals such as methane direct production acetylene, hydrogen, carbon black, methyl chloride, prussic acid, Nitromethane 99Min., dithiocarbonic anhydride.But because methane molecule is highly stable, the production of the said products all need be carried out under the severe condition of high temperature, high pressure, high energy consumption, has greatly limited the direct trans-utilization of methane.
Methyl alcohol and formaldehyde are important Organic Chemicals, the formaldehyde in the world 80% all is to adopt methane to make through synthetic gas at present, in this method, the preparation of synthetic gas and compression account for more than 60% of whole process investment, and therefore industrial optimal method is by directly oxidizing methane synthesizing methanol, formaldehyde.People have all carried out a large amount of exploratory developments to relevant catalyzer, catalytic mechanism, thermomechanical analysis, processing condition etc.
[1-13]The subject matter that directly oxidizing methane system methyl alcohol, formaldehyde are faced is because the activation energy of methane is very high, in a single day methane molecule is activated, be difficult to the degree that the control reaction is carried out, the methyl alcohol that makes generation is not by further oxidation, result normally methane conversion and methyl alcohol selectivity is inverse relation substantially, and the productive rate of methyl alcohol is too low
[14]
By literature search, do not see the open report identical with the present invention.
Reference:
[1] Wang Hua, Liu Zhongmin. the direct Study on Transformation progress of methane [J]. chemical industry progress, 2004,16 (4), 593-602
[2] Chen Liyu etc. the research of the phosphotungstic acid catalyst of partial oxidation reaction of methane [J]. colleges and universities' chemical engineering journal, 2007,21 (4): 650-653.
[3] .V such as Chen Liyu
2O
5Catalytic methane performing liquid-phase partial oxidation technological process research [J]. colleges and universities' chemical engineering journal, 2006,20 (3): 417-421.
[4] .CoMoO such as Wang Lijuan
4The research [J] of methane portion oxidation on the load Mo-V-Cr-Bi oxide catalyst. Liaoning chemical industry, 2006,35 (9): 503-505.
[5] Pei Supeng etc. the methane selective oxidation reaction [J] on the loading type P-Mo-V/SBA-15 catalyzer. chemical journal, 2008,66 (8): 902-908
[6] Zhang Xin, He Dehua etc. methane gas phase homogeneous phase selective oxidation synthesizing methanol [J]. petrochemical complex, 2003,32 (3): 195-199
[7] Wang Chengxue, Li Shaofen. methane part catalyzed oxidation synthesizing methanol and formaldehyde [J]. Industrial Catalysis, 1997,2,3-10
[8] Zhang Yiqun, Zhang Pei, Ma Jianxin, MoO
3/ La
2O
3Methane selectively oxidizing system methyl alcohol [J] on the catalyzer. catalysis journal, 1997,18 (5), 425-427
[9] Zhang Xin, He Dehua etc., methane selective oxidation making methyl alcohol reaction [J] on the Mo/La-Co-O catalyzer. catalysis journal, 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 are originally. aqueous porous TiO
2The preliminary study of photocatalytic molecules oxidizing of methylene [J]. Journal of Molecular Catalysis, 2000,14 (4): 243-244
[13] peak, clock is genial. and laser promotes the research [J] of phosphoric acid salt surface directly oxidizing methane synthesizing methanol. chemistry of fuel journal, 2000,28 (5): 402-405
[14] Su Yongqing, Wang Ping, Ren Nianjun, etc. present Research that methane directly transforms and prospect, Yunnan chemical, 2009,36 (4): 1-6.
Summary of the invention:
The object of the present invention is to provide a kind of methane directly to make the electrochemical process method of methyl alcohol.
Principle of the present invention and reaction process are:
In the electrolyzer of the alkaline electrolyte that contains muriate or fluorochemical, pass to direct current, on anode, chlorion (Cl
-) or fluorion (F
-) at first being oxidized to highly active atomic chlorine (Cl) or atomic fluorine (F), reaction formula is:
Anode: Cl
--e → Cl or F
--e → F
Negative electrode: H
2O+e → OH
-+ H
2↑
Highly active atomic chlorine [Cl] or atomic fluorine (F) are with near the methane (CH that is adsorbed on the electrode surface or the electrode
4) substitution reaction can take place, by being controlled at 1dm
2The methane flow of anode surface is 4.6ml/min. and anodic current density 0.1-0.3A/dm
2, obtain methyl chloride (CH
3Cl) or fluoromethane (CH
3F), reaction formula is:
CH
4+2Cl·→CH
3Cl+HCl
CH
4+2F·→CH
3F+HF
Methyl chloride (CH
3Cl) or fluoromethane (CH
3F) in alkaline electrolyte, further catalytic hydrolysis generates target product methyl alcohol (CH
3OH), reaction formula is:
CH
3Cl+OH→CH
3OH+Cl
-
The methyl alcohol that generates by electrolytic solution is heated, evaporates methyl alcohol (64.8 ℃ of methyl alcohol boiling points) in 65-75 ℃ temperature range in electrolytic solution, electrolytic solution returns electrolyzer.HCl that generates or the reaction of the NaOH in HF and the electrolytic solution regenerate NaCl or NaF.NaOH in the electrolytic solution, NaCl or NaF recycle and no consumption in whole process.
The reaction conditions of present method:
Adopting the electrolyzer of sealing, is anode with the porous graphite of hollow, and stainless steel is a negative electrode, sees accompanying drawing 1.The preparation of used for electrolyte distilled water is mixed with chlorate solution by the NaCl of 40-50g/l and the NaOH of 16-54g/l, or is mixed with fluoride salt solution by the NaF of 30-40g/l and the NaOH of 16-36g/l, and temperature is 18-60 ℃.It is 1dm that methane gas feeds outer surface area with 4.6ml/min.
2The porous graphite anode of hollow.Making current, strength of current are 0.1-0.3A.In electrolytic solution, just there is methyl alcohol to generate the productive rate 0.34-2.74% of methyl alcohol.
It is low, easy and simple to handle that the present invention has a production cost, and NaOH, the NaCl or the NaF that form electrolytic solution recycle the advantage of no consumption in whole process.
Description of drawings:
Fig. 1 is the structural representation of the closed electrolysis cells that adopts of the present invention.
1 is electrolyzer among the figure, the 2nd, and cathode compartment, the 3rd, negative electrode, the 4th, cathode compartment exhaust-duct, the 5th, cathode wire, the 6th, barrier film, the 7th, positive wire, the 8th, methane gas admission passage, the 9th, exhaust-duct, anolyte compartment, the 10th, electrolyte outlet, the 11st, the porous anode of hollow, the 12nd, anolyte compartment, the 13rd, electrolytic solution import.
Embodiment:
The closed electrolysis cells that the embodiment of the invention adopts is for the material of buying on the market, according to a conventional method with the structure of Fig. 1 preparation.The electrolyzer 1 of sealing is made by the material of acid-proof, alkali prevention, anti-brine corrosion, as organic glass or fluorinated ethylene propylene plastics; Cathode compartment 2 and anolyte compartment 12 are same electrolytic solution, and the gas space is left on electrolytic solution top; Negative electrode 3 is the metal or alloy of acid-and base-resisting, brine corrosion, as metal platinum, or stainless steel, or titanium alloy.Cathode compartment exhaust-duct 4 is used for the hydrogen that negative electrode produces is drawn collection; Cathode wire 5 adopts the copper core that coats polyvinyl chloride, and an end is connected with negative electrode 3, and the other end is connected with the negative pole of external power source; Barrier film 6 is a nylon cloth, and electrolyzer is separated into cathode compartment 2 and anolyte compartment 12, and electrolytic solution can pass through nylon cloth, but gas can not pass through.Positive wire 7 is the same with cathode wire 5, adopts the copper core that coats polyvinyl chloride, and an end is connected with the porous anode 11 of hollow, and the other end is connected with the positive pole of external power source; One termination of methane gas admission passage 8 is gone into the inner chamber of porous anode 11, and the other end and outside methane supply source join; Exhaust-duct, anolyte compartment 9 is used for the not reacted methane gas in anolyte compartment is drawn, and methane gas is returned methane gas admission passage 8 and carried out circulating reaction after the air pump pressurization.Electrolyte outlet 10 is used for the electrolytic solution that contains methyl alcohol is drawn, and behind the evaporation methyl alcohol, returns electrolyzer by electrolytic solution import 13 in the evaporation equipment externally; The porous anode 11 of hollow is the coreless armature of being made by graphite, and heart portion and outside surface are by the little hole link of intensive micron order, and the methane gas of input heart portion can arrive the electrode outside surface by the aperture road.
Embodiment 1:
Adopt the electrolyzer of sealing, see accompanying drawing 1.Surface-area with outside surface is 1dm
2The porous graphite of hollow make anode, surface-area is 1dm
2Stainless steel sheet (thick is 0.5mm) is a negative electrode.Electrolytic solution is formed chlorate solution by the NaCl of 40g/l and the NaOH of 16g/l, 18 ℃ of electrolyte temperatures.Methane gas is with the porous graphite of 4.6ml/min. feeding hollow, and making current, strength of current are 0.1A, methanol yield 1.17%.
Embodiment 2:
Adopt the electrolyzer of sealing, see accompanying drawing 1.Surface-area with outside surface is 1dm
2The porous graphite of hollow make anode, surface-area is 1dm
2Stainless steel sheet (thick is 0.5mm) is a negative electrode.Electrolytic solution is formed chlorate solution by the NaCl of 50g/l and the NaOH of 18g/l, 40 ℃ of electrolyte temperatures.Methane gas is with the porous graphite of 6ml/min. feeding hollow, and making current, strength of current are 0.3A.Methanol yield 2.74%.
Embodiment 3:
Adopt the electrolyzer of sealing, see accompanying drawing 1.Surface-area with outside surface is 1dm
2The porous graphite of hollow make anode, surface-area is 1dm
2Stainless steel sheet (thick is 0.5mm) is a negative electrode.Electrolytic solution is formed chlorate solution by the NaCl of 45g/l and the NaOH of 54g/l, 60 ℃ of electrolyte temperatures.Methane gas is with the porous graphite of 4.6ml/min. feeding hollow, and making current, strength of current are 0.2A, methanol yield 1.99%.
Embodiment 4:
Adopt the electrolyzer of sealing, see accompanying drawing 1.Surface-area with outside surface is 1dm
2The porous graphite of hollow make anode, surface-area is 1dm
2Stainless steel sheet (thick is 0.5mm) is a negative electrode.Electrolytic solution is formed fluoride salt solution by the NaF of 30g/l and the NaOH of 16g/l, 18 ℃ of electrolyte temperatures.Methane gas is with the porous graphite of 4.6ml/min. feeding hollow, and making current, strength of current are 0.1A, methanol yield 0.98%.
Embodiment 5:
Adopt the electrolyzer of sealing, see accompanying drawing 1.Surface-area with outside surface is 1dm
2The porous graphite of hollow make anode, surface-area is 1dm
2Stainless steel sheet (thick is 0.5mm) is a negative electrode.。Electrolytic solution is formed chlorate solution by the NaF of 40g/l and the NaOH of 36g/l, 40 ℃ of electrolyte temperatures.Methane gas is with the porous graphite of 6ml/min. feeding hollow, and making current, strength of current are 0.3A, methanol yield 0.34%.
Embodiment 6:
Adopt the electrolyzer of sealing, see accompanying drawing 1.Surface-area with outside surface is 1dm
2The porous graphite of hollow make anode, surface-area is 1dm
2Stainless steel sheet (thick is 0.5mm) is a negative electrode.Electrolytic solution is formed chlorate solution by the NaF of 35g/l and the NaOH of 26g/l, 60 ℃ of electrolyte temperatures.Methane gas is with the porous graphite of 6ml/min. feeding hollow, and making current, strength of current are 0.2A, methanol yield 0.85%.
Claims (1)
1. directly produce the electrochemical method of methyl alcohol with methane for one kind, it is characterized in that this method is specially: adopting the electrolyzer of sealing, is anode with the porous graphite of hollow, and stainless steel is a negative electrode; The preparation of used for electrolyte distilled water is mixed with chlorate solution by the NaCl of 40-50g/l and the NaOH of 16-54g/l, or is mixed with fluoride salt solution by the NaF of 30-40g/l and the NaOH of 16-36g/l, and temperature is 18-60 ℃; It is 1dm that methane gas feeds outer surface area with 4.6ml/min
2The porous graphite anode of hollow, connecting intensity is the electric current of 0.1-0.3A, generates methyl alcohol in electrolytic solution, the productive rate 0.34-2.74% of methyl alcohol; Subsequently to containing the electrolytic solution heating of methyl alcohol, under the condition of 65-75 ℃ temperature, evaporate methyl alcohol, electrolytic solution returns electrolyzer again, HCl that generates or the reaction of the NaOH in HF and the electrolytic solution, regenerate NaCl or NaF, the NaOH in the electrolytic solution, NaCl or NaF recycle and no consumption in whole process.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101062882A CN101775614B (en) | 2010-02-05 | 2010-02-05 | Electrochemical method for directly preparing carbinol by using methane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101062882A CN101775614B (en) | 2010-02-05 | 2010-02-05 | Electrochemical method for directly preparing carbinol by using methane |
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| Publication Number | Publication Date |
|---|---|
| CN101775614A CN101775614A (en) | 2010-07-14 |
| CN101775614B true CN101775614B (en) | 2011-04-27 |
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| CN106229534A (en) * | 2016-08-30 | 2016-12-14 | 云南师范大学 | A kind of second alcohol-based electrolyte producing methanol for methane electrolytic oxidation |
| SG11202007310WA (en) * | 2018-02-12 | 2020-08-28 | Thrunnel Ltd Oy | Method and device for the preparation of alcohols from hydrocarbons |
| CN114214652B (en) * | 2021-12-16 | 2023-02-14 | 大连理工大学 | Electrochemical aeration assembly capable of constructing three-dimensional gas-solid-liquid three-phase interface |
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Granted publication date: 20110427 Termination date: 20120205 |