CN104831311A - Method for preparation of methanol by electrolytic oxidation of coal mine gas - Google Patents
Method for preparation of methanol by electrolytic oxidation of coal mine gas Download PDFInfo
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- CN104831311A CN104831311A CN201510191376.XA CN201510191376A CN104831311A CN 104831311 A CN104831311 A CN 104831311A CN 201510191376 A CN201510191376 A CN 201510191376A CN 104831311 A CN104831311 A CN 104831311A
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Abstract
The invention discloses a method for preparation of methanol by electrolytic oxidation of coal mine gas, relates to a method for preparation of the methanol from the coal mine gas, and provides a method for preparation of the methanol by direct environmentally friendly conversion of the coal mine gas under mild conditions. The method is as follows: an electrolytic tank is arranged in a constant temperature water bath box, an anode electrolyte is added into the electrolytic tank anode region, the anode electrolyte is prepared by mixing distilled water, alcohol, MX and NOH, or the anode electrolyte is prepared by mixing distilled water, alcohol, ionic liquid and NOH, a cathode electrolyte is added into the electrolytic tank cathode region, the cathode electrolyte is prepared by mixing distilled water and M1X1; a blocky graphite electrode is used as an anode, an iron sheet is used as a cathode, the gas is introduced into the anode electrolyte for reaction under electrolytic conditions to obtain a reaction solution in the electrolytic tank anode region, and the reaction solution is separated to obtain the methanol. The method is mainly used for preparation of the methanol from the coal mine gas.
Description
Technical field
The present invention relates to a kind of method utilizing coal-mine gas to prepare methyl alcohol.
Background technology
China is coal production state main in the world, in order to ensure the safety in coal production process, must carry out gas pumping.Be difficult to utilize because mash gas extraction is mixed with a large amount of oxygen, major part has directly been discharged.This not only wastes resource, also severe contamination environment.Therefore, be that the liquid fuel of accumulating is convenient in raw material preparation or industrial chemicals is the focus direction that comprehensive gas utilizes with gas.Methyl alcohol is the desired product that gas transforms, because methyl alcohol remains most energy of methane in gas, be liquid under normal temperature, convenient storage and transport, be considered to clean fuel, can be used as the substitute products of oil and natural gas.Meanwhile, methyl alcohol is again important Chemicals and Organic Chemicals.
Coal-mine gas can regard the mixture of methane and air as.Because the methane in gas can be rated as the most stable organic molecule of structure, c h bond can, up to 439kJ, need extremely harsh reaction conditions to be activated and to transform, and target product methyl alcohol be relatively active, in reaction process, be very easily oxidized to CO and CO
2.Therefore, the directed Efficient Conversion how realized in gas methanol process becomes a huge challenge.At present, with gas or methane for raw material, prepare methyl alcohol mainly based on indirect reformer, be made up of two key steps, that is: the first step, by partial oxidation, obtain synthetic gas (CO+H by gas or methane
2); Second step, under the condition of catalyzer, becomes methyl alcohol by Synthetic holography.The shortcoming of this method is mainly reflected in following several respects: the rate of loss of (1) raw material is high, generally about 40%.(2) methanol yield is not high.(3) complicated by the equipment of unstripped gas preparing synthetic gas, cost is high.
In recent years, certain progress had been obtained by gas or methane one-step synthesis method methyl alcohol.The method of gas or methane one-step synthesis method methyl alcohol mainly contains gas-solid phase catalytic oxidation method, enzymatic oxidation method, liquid phase catalytic oxidation etc.Gas-solid heterogeneous catalytic oxidation method temperature of reaction is higher, is generally 300 ~ 800 DEG C, and most heterogeneous catalytic oxidation catalyzer only just can show high methyl alcohol selectivity under low methane conversion.Enzymatic oxidation method generally adopts methane monooxygenase enzymatic oxidation methane generation methyl alcohol, and enzymic catalytic reaction can carry out at normal temperatures and pressures, but enzyme stability is poor, expensive.Liquid phase catalytic oxidation is a research direction of just having risen in the last few years, and liquid phase catalytic oxidation carries out in liquid medium, makes catalyzer directly contact in molecule rank with reactant and react.But existing liquid phase catalytic oxidation needs under high pressure to carry out, reaction solvent for use is the solvent of strong such as oleum, trifluoroacetic acid substantially, stronger to equipment corrosion.
Summary of the invention
Under the invention provides a kind of mild conditions, the method for the direct Synthesis methyl alcohol of eco-friendly coal-mine gas.
A method for electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1. the positive column, to electrolyzer adds anolyte, described anolyte is mixed by 30mL ~ 50mL distilled water, 100mL ~ 200mL alcohol, 3g ~ 5g MX and 0.2g ~ 0.4g NOH, in wherein said MX, M is K, Na or Li, X is Cl, Br, I or F, and in described NOH, N is K, Na or Li; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is by 150mL ~ 250mL distilled water and 3g ~ 5gM
1x
1mix, wherein said M
1x
1middle M
1for K, Na or Li, X
1for Cl, Br, I or F; 3., with the blocky graphite electrode of 20g ~ 40g for anode, Ni (OH) in described blocky graphite electrode
2content be 0 ~ 15g, being negative electrode with iron plate, is that methane gas passes in anolyte by 5mL/min ~ 60mL/min with flow velocity, 4h is reacted under electric current is 0.05A ~ 0.3A condition, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
A method for electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1. the positive column, to electrolyzer adds anolyte, described anolyte is mixed by 10mL ~ 30mL distilled water, 50mL ~ 100mL alcohol, 20mLg ~ 50mL ionic liquid and 0.2g ~ 0.4g NOH, in wherein said NOH, N is K, Na or Li, and described ionic liquid is [Bmim] Br or [Bmim] Cl; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is mixed by 150mL ~ 250mL distilled water and 3g ~ 5gMX, and in wherein said MX, M is K, Na or Li, and X is Cl, Br, I or F; 3., with 20g ~ 40g blocky graphite electrode for anode, Ni (OH) in described blocky graphite electrode
2content be 0 ~ 15g, being negative electrode with iron plate, is that methane gas passes in anolyte by 5mL/min ~ 60mL/min with flow velocity, 4h is reacted under electric current is 0.05A ~ 0.3A condition, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
Advantage of the present invention: one, the present invention utilizes electrochemical method, adopt electrolytic oxidation method that coal-mine gas is converted into methyl alcohol, reaction conditions of the present invention is gentle, when electrolytic reaction occurs, in anolyte, halogen ion (X-) is oxidized to and has highly active halogen atom (X), and highly active halogen atom (X) carries out oxidation substitution reaction with the methane in the coal-mine gas passed in anolyte and generates CH
3x, halomethane (CH
3x) further catalytic hydrolysis methanol in anolyte (alkaline electrolyte); Two, coal-mine gas is converted into methyl alcohol by the present invention under normal temperature and pressure conditions, when the volumn concentration of methane in coal-mine gas is 30%, methanol yield reaches as high as 14.17%, and when the volumn concentration of methane in coal-mine gas is 100%, methanol yield reaches as high as 40.38%.
Embodiment
Embodiment one: present embodiment is a kind of method of electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1. the positive column, to electrolyzer adds anolyte, described anolyte is mixed by 30mL ~ 50mL distilled water, 100mL ~ 200mL alcohol, 3g ~ 5g MX and 0.2g ~ 0.4g NOH, in wherein said MX, M is K, Na or Li, X is Cl, Br, I or F, and in described NOH, N is K, Na or Li; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is by 150mL ~ 250mL distilled water and 3g ~ 5gM
1x
1mix, wherein said M
1x
1middle M
1for K, Na or Li, X
1for Cl, Br, I or F; 3., with the blocky graphite electrode of 20g ~ 40g for anode, Ni (OH) in described blocky graphite electrode
2content be 0 ~ 15g, being negative electrode with iron plate, is that methane gas passes in anolyte by 5mL/min ~ 60mL/min with flow velocity, 4h is reacted under electric current is 0.05A ~ 0.3A condition, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
Present embodiment utilizes electrochemical method, adopt electrolytic oxidation method that coal-mine gas is converted into methyl alcohol, present embodiment reaction conditions is gentle, when electrolytic reaction occurs, in anolyte, halogen ion (X-) is oxidized to and has highly active halogen atom (X), and reaction formula is: X--e → X.
When highly active halogen atom (X) and the methane in the coal-mine gas passed in anolyte carry out oxidation substitution reaction life, reaction formula is: CH
4+ 2X → CH
3x+HX.
Methyl halide (the CH generated
3x) further catalytic hydrolysis methanol in anolyte (alkaline electrolyte), reaction formula is: CH
3x+OH-→ CH
3oH+X-.
NOH in the HX and the electrolytic solution that generate reacts, and generation NX reenters electrolytic solution and recycles: NOH+HX → NX+H
2o.
Coal-mine gas is converted into methyl alcohol by present embodiment under normal temperature and pressure conditions, when the volumn concentration of methane in coal-mine gas is 30%, methanol yield reaches as high as 14.17%, and when the volumn concentration of methane in coal-mine gas is 100%, methanol yield reaches as high as 40.38%.
Utilize in gas chromatographic analysis reaction solution after methyl alcohol volumn concentration, calculate methanol yield, the productive rate Y (wt%) of methyl alcohol is that the actual mass that generates with methyl alcohol is divided by Theoretical Mass.The actual mass of methanol is the volume (V) of sample and its volumn concentration (v
1), the product of the density (ρ) of methyl alcohol; The Theoretical Mass computation of methyl alcohol is: pass into the flow velocity (s) of methane gas and pass into methane volumetric percentage composition (v in time (t), methane gas
2) product divided by 22.4Lmol
-1, then be multiplied by 2 times of molar mass of methane.Drawn by the reaction equation of methane conversion methyl alcohol, methane and methanol molar ratio are 1:1, and the molar mass of methyl alcohol is 2 times of methane molar mass, therefore, the Theoretical Mass of methanol is actual 2 times of passing into methane mass (M), so the formulate calculating methanol yield is as follows:
Embodiment two: the difference of present embodiment and embodiment one is: described alcohol is methyl alcohol or ethanol.Other are identical with embodiment one.
When present embodiment adopts ethanol as alcohol, the finished product methyl alcohol of electrolytic reaction can be dissolved in ethanol, and the boiling point because of methyl alcohol is 64.7 DEG C, and the boiling point of ethanol is 78.4 DEG C, can heat reaction solution after electrolytic reaction, control temperature is 65 ~ 70 DEG C can realize being separated of methyl alcohol and ethanol.
Embodiment three: one of present embodiment and embodiment one or two difference is: described methane gas is coal-mine gas, and in coal-mine gas, the volumn concentration of methane is 30% ~ 100%.Other are identical with embodiment one or two.
Embodiment four: present embodiment is a kind of method of electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1. the positive column, to electrolyzer adds anolyte, described anolyte is mixed by 10mL ~ 30mL distilled water, 50mL ~ 100mL alcohol, 20mLg ~ 50mL ionic liquid and 0.2g ~ 0.4gNOH, in wherein said NOH, N is K, Na or Li, and described ionic liquid is [Bmim] Br or [Bmim] Cl; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is mixed by 150mL ~ 250mL distilled water and 3g ~ 5g MX, and in wherein said MX, M is K, Na or Li, and X is Cl, Br, I or F; 3., with 20g ~ 40g blocky graphite electrode for anode, Ni (OH) in described blocky graphite electrode
2content be 0 ~ 15g, being negative electrode with iron plate, is that methane gas passes in anolyte by 5mL/min ~ 60mL/min with flow velocity, 4h is reacted under electric current is 0.05A ~ 0.3A condition, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
Present embodiment utilizes electrochemical method, adopt electrolytic oxidation method that coal-mine gas is converted into methyl alcohol, present embodiment reaction conditions is gentle, when electrolytic reaction occurs, in anolyte, halogen ion (X-) is oxidized to and has highly active halogen atom (X), and reaction formula is: X--e → X.
When highly active halogen atom (X) and the methane in the coal-mine gas passed in anolyte carry out oxidation substitution reaction life, reaction formula is: CH
4+ 2X → CH
3x+HX.
Methyl halide (the CH generated
3x) further catalytic hydrolysis methanol in anolyte (alkaline electrolyte), reaction formula is: CH
3x+OH-→ CH
3oH+X-.
NOH in the HX and the electrolytic solution that generate reacts, and generation NX reenters electrolytic solution and recycles: NOH+HX → NX+H
2o.
Coal-mine gas is converted into methyl alcohol by present embodiment under normal temperature and pressure conditions, when the volumn concentration of methane in coal-mine gas is 30%, methanol yield reaches as high as 14.17%, and when the volumn concentration of methane in coal-mine gas is 100%, methanol yield reaches as high as 40.38%.
Utilize in gas chromatographic analysis reaction solution after methyl alcohol volumn concentration, calculate methanol yield, the productive rate Y (wt%) of methyl alcohol is that the actual mass that generates with methyl alcohol is divided by Theoretical Mass.The actual mass of methanol is the volume (V) of sample and its volumn concentration (v
1), the product of the density (ρ) of methyl alcohol; The Theoretical Mass computation of methyl alcohol is: pass into the flow velocity (s) of methane gas and pass into methane volumetric percentage composition (v in time (t), methane gas
2) product divided by 22.4Lmol
-1, then be multiplied by 2 times of molar mass of methane.Drawn by the reaction equation of methane conversion methyl alcohol, methane and methanol molar ratio are 1:1, and the molar mass of methyl alcohol is 2 times of methane molar mass, therefore, the Theoretical Mass of methanol is actual 2 times of passing into methane mass (M), so the formulate calculating methanol yield is as follows:
Embodiment five: the difference of present embodiment and embodiment four is: described alcohol is methyl alcohol or ethanol.Other are identical with embodiment four.
When present embodiment adopts ethanol as alcohol, the finished product methyl alcohol of electrolytic reaction can be dissolved in ethanol, and the boiling point because of methyl alcohol is 64.7 DEG C, and the boiling point of ethanol is 78.4 DEG C, can heat reaction solution after electrolytic reaction, control temperature is 65 ~ 70 DEG C can realize being separated of methyl alcohol and ethanol.
Embodiment six: one of present embodiment and embodiment four or five difference is: described methane gas is coal-mine gas, and in coal-mine gas, the volumn concentration of methane is 30% ~ 100%.Other are identical with embodiment four or five.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of method of electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1., to the positive column of electrolyzer add anolyte, described anolyte is mixed by 40mL distilled water, 160mL ethanol, 3.5g NaCl and 0.4g NaOH; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is mixed by 200mL distilled water and 3.5g NaCl; 3., with the blocky graphite electrode of 30g for anode, not containing Ni (OH) in described blocky graphite electrode
2, be negative electrode with iron plate, be that methane gas passes in anolyte by 15mL/min with flow velocity, under electric current is 0.22A condition, reacts 4h, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
Methane gas described in this test is coal-mine gas, and in coal-mine gas, the volumn concentration of methane is 100%.
Can heat reaction solution after this test electrolytic reaction, control temperature is 70 DEG C can realize being separated of methyl alcohol and ethanol.
The reaction solution obtained this test measures and calculates learns that methanol yield is 39.5%.
Test two: a kind of method of electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1., to the positive column of electrolyzer add anolyte, described anolyte is mixed by 40mL distilled water, 160mL ethanol, 3.5g NaCl and 0.3g NaOH; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is mixed by 200mL distilled water and 3.5g NaCl; 3., with the blocky graphite electrode of 30g for anode, not containing Ni (OH) in described blocky graphite electrode
2, be negative electrode with iron plate, be that methane gas passes in anolyte by 10mL/min with flow velocity, under electric current is 0.15A condition, reacts 4h, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
Methane gas described in this test is coal-mine gas, and in coal-mine gas, the volumn concentration of methane is 100%.
Can heat reaction solution after this test electrolytic reaction, control temperature is 70 DEG C can realize being separated of methyl alcohol and ethanol.
The reaction solution obtained this test measures and calculates learns that methanol yield is 38.1%.
Test three: a kind of method of electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1., to the positive column of electrolyzer add anolyte, described anolyte is mixed by 40mL distilled water, 160mL ethanol, 3.5g NaCl and 0.3g NaOH; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is mixed by 200mL distilled water and 3.5g NaCl; 3., with the blocky graphite electrode of 30g for anode, not containing Ni (OH) in described blocky graphite electrode
2, be negative electrode with iron plate, be that methane gas passes in anolyte by 10mL/min with flow velocity, under electric current is 0.15A condition, reacts 4h, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
Methane gas described in this test is coal-mine gas, and in coal-mine gas, the volumn concentration of methane is 40%.
Can heat reaction solution after this test electrolytic reaction, control temperature is 70 DEG C can realize being separated of methyl alcohol and ethanol.
The reaction solution obtained this test measures and calculates learns that methanol yield is 9.4%.
Test four: a kind of method of electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1., to the positive column of electrolyzer add anolyte, described anolyte is mixed by 40mL distilled water, 160mL ethanol, 3.5g NaCl and 0.2g NaOH; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is mixed by 200mL distilled water and 3.5g NaCl; 3., with the blocky graphite electrode of 30g for anode, Ni (OH) in described blocky graphite electrode
2content be 5g, be negative electrode with iron plate, be that methane gas passes in anolyte by 10mL/min with flow velocity, under electric current is 0.22A condition, reacts 4h, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
Methane gas described in this test is coal-mine gas, and in coal-mine gas, the volumn concentration of methane is 60%.
Can heat reaction solution after this test electrolytic reaction, control temperature is 70 DEG C can realize being separated of methyl alcohol and ethanol.
The reaction solution obtained this test measures and calculates learns that methanol yield is 27.52%.
Test five: a kind of method of electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1., to the positive column of electrolyzer add anolyte, described anolyte is mixed by 40mL distilled water, 160mL ethanol, 3.5g NaCl and 0.3g NaOH; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is mixed by 200mL distilled water and 3.5g NaCl; 3., with the blocky graphite electrode of 30g for anode, Ni (OH) in described blocky graphite electrode
2content be 10g, be negative electrode with iron plate, be that methane gas passes in anolyte by 20mL/min with flow velocity, under electric current is 0.22A condition, reacts 4h, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
Methane gas described in this test is coal-mine gas, and in coal-mine gas, the volumn concentration of methane is 100%.
Can heat reaction solution after this test electrolytic reaction, control temperature is 70 DEG C can realize being separated of methyl alcohol and ethanol.
The reaction solution obtained this test measures and calculates learns that methanol yield is 26.1%.
Test six: a kind of method of electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1., to the positive column of electrolyzer add anolyte, described anolyte is mixed by 20mL distilled water, 60mL ethanol, 30mL [Bmim] Br and 0.2g NaOH; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is mixed by 200mL distilled water and 3.5g NaCl; 3., with the blocky graphite electrode of 36g for anode, not containing Ni (OH) in described blocky graphite electrode
2, be negative electrode with iron plate, be that methane gas passes in anolyte by 20mL/min with flow velocity, under electric current is 0.15A condition, reacts 4h, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
Methane gas described in this test is coal-mine gas, and in coal-mine gas, the volumn concentration of methane is 100%.
Can heat reaction solution after this test electrolytic reaction, control temperature is 70 DEG C can realize being separated of methyl alcohol and ethanol.
The reaction solution obtained this test measures and calculates learns that methanol yield is 39.59%.
Test seven: a kind of method of electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1., to the positive column of electrolyzer add anolyte, described anolyte is mixed by 20mL distilled water, 60mL ethanol, 30mL [Bmim] Cl and 0.2g NaOH; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is mixed by 200mL distilled water and 3.5g NaCl; 3., with the blocky graphite electrode of 36g for anode, Ni (OH) in described blocky graphite electrode
2content be 10g, be negative electrode with iron plate, be that methane gas passes in anolyte by 15mL/min with flow velocity, under electric current is 0.06A condition, reacts 4h, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
Methane gas described in this test is coal-mine gas, and in coal-mine gas, the volumn concentration of methane is 100%.
Can heat reaction solution after this test electrolytic reaction, control temperature is 70 DEG C can realize being separated of methyl alcohol and ethanol.
The reaction solution obtained this test measures and calculates learns that methanol yield is 40.38%.
Test eight: a kind of method of electrolytic oxidation coal-mine gas methyl alcohol, specifically completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1., to the positive column of electrolyzer add anolyte, described anolyte is mixed by 20mL distilled water, 60mL ethanol, 30mL [Bmim] Br and 0.2g NaOH; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is mixed by 200mL distilled water and 3.5g NaCl; 3., with the blocky graphite electrode of 36g for anode, Ni (OH) in described blocky graphite electrode
2content be 10g, be negative electrode with iron plate, be that methane gas passes in anolyte by 15mL/min with flow velocity, under electric current is 0.06A condition, reacts 4h, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
Methane gas described in this test is coal-mine gas, and in coal-mine gas, the volumn concentration of methane is 30%.
Can heat reaction solution after this test electrolytic reaction, control temperature is 70 DEG C can realize being separated of methyl alcohol and ethanol.The reaction solution obtained this test measures and calculates learns that methanol yield is 14.17%.
Claims (6)
1. a method for electrolytic oxidation coal-mine gas methyl alcohol, is characterized in that the method for electrolytic oxidation coal-mine gas methyl alcohol completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1. the positive column, to electrolyzer adds anolyte, described anolyte is mixed by 30mL ~ 50mL distilled water, 100mL ~ 200mL alcohol, 3g ~ 5g MX and 0.2g ~ 0.4g NOH, in wherein said MX, M is K, Na or Li, X is Cl, Br, I or F, and in described NOH, N is K, Na or Li; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is by 150mL ~ 250mL distilled water and 3g ~ 5gM
1x
1mix, wherein said M
1x
1middle M
1for K, Na or Li, X
1for Cl, Br, I or F; 3., with the blocky graphite electrode of 20g ~ 40g for anode, Ni (OH) in described blocky graphite electrode
2content be 0 ~ 15g, being negative electrode with iron plate, is that methane gas passes in anolyte by 5mL/min ~ 60mL/min with flow velocity, 4h is reacted under electric current is 0.05A ~ 0.3A condition, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
2. the method for a kind of electrolytic oxidation coal-mine gas methyl alcohol according to claim 1, is characterized in that described alcohol is methyl alcohol or ethanol.
3. the method for a kind of electrolytic oxidation coal-mine gas methyl alcohol according to claim 1, it is characterized in that described methane gas is coal-mine gas, in coal-mine gas, the volumn concentration of methane is 30% ~ 100%.
4. a method for electrolytic oxidation coal-mine gas methyl alcohol, is characterized in that the method for electrolytic oxidation coal-mine gas methyl alcohol completes according to the following steps:
Electrolyzer is placed in 25 DEG C of constant water bath box, 1. the positive column, to electrolyzer adds anolyte, described anolyte is mixed by 10mL ~ 30mL distilled water, 50mL ~ 100mL alcohol, 20mLg ~ 50mL ionic liquid and 0.2g ~ 0.4g NOH, in wherein said NOH, N is K, Na or Li, and described ionic liquid is [Bmim] Br or [Bmim] Cl; 2., to the cathodic area of electrolyzer add catholyte, described catholyte is mixed by 150mL ~ 250mL distilled water and 3g ~ 5gMX, and in wherein said MX, M is K, Na or Li, and X is Cl, Br, I or F; 3., with 20g ~ 40g blocky graphite electrode for anode, Ni (OH) in described blocky graphite electrode
2content be 0 ~ 15g, being negative electrode with iron plate, is that methane gas passes in anolyte by 5mL/min ~ 60mL/min with flow velocity, 4h is reacted under electric current is 0.05A ~ 0.3A condition, obtain reaction solution in the positive column of electrolyzer, reaction solution is separated, namely obtain methyl alcohol.
5. the method for a kind of electrolytic oxidation coal-mine gas methyl alcohol according to claim 4, is characterized in that described alcohol is methyl alcohol or ethanol.
6. the method for a kind of electrolytic oxidation coal-mine gas methyl alcohol according to claim 4, it is characterized in that described methane gas is coal-mine gas, in coal-mine gas, the volumn concentration of methane is 30% ~ 100%.
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Cited By (2)
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| CN109896948A (en) * | 2019-04-17 | 2019-06-18 | 太原理工大学 | A method of benzene carboxylic acid is prepared using middle low-order coal as raw material |
| FR3131923A1 (en) * | 2022-01-18 | 2023-07-21 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Process for the co-valorization by electrolysis of CO2 and hydrocarbons |
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2015
- 2015-04-22 CN CN201510191376.XA patent/CN104831311A/en active Pending
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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", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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| CN109896948A (en) * | 2019-04-17 | 2019-06-18 | 太原理工大学 | A method of benzene carboxylic acid is prepared using middle low-order coal as raw material |
| FR3131923A1 (en) * | 2022-01-18 | 2023-07-21 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Process for the co-valorization by electrolysis of CO2 and hydrocarbons |
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