CN117758285A - Electrochemical oxidation method for producing DMF (dimethyl formamide) by TMA (time stamp oxidation) - Google Patents
Electrochemical oxidation method for producing DMF (dimethyl formamide) by TMA (time stamp oxidation) Download PDFInfo
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- CN117758285A CN117758285A CN202211134654.4A CN202211134654A CN117758285A CN 117758285 A CN117758285 A CN 117758285A CN 202211134654 A CN202211134654 A CN 202211134654A CN 117758285 A CN117758285 A CN 117758285A
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- tma
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 230000003647 oxidation Effects 0.000 title abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title abstract description 14
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 68
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 19
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims abstract description 15
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- -1 N, N-disubstituted formamide Chemical class 0.000 claims abstract description 5
- 150000003335 secondary amines Chemical class 0.000 claims abstract 3
- 150000003512 tertiary amines Chemical class 0.000 claims abstract 3
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims abstract 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000007784 solid electrolyte Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000011244 liquid electrolyte Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 7
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- FEWLNYSYJNLUOO-UHFFFAOYSA-N 1-Piperidinecarboxaldehyde Chemical compound O=CN1CCCCC1 FEWLNYSYJNLUOO-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229940021013 electrolyte solution Drugs 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003011 anion exchange membrane Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- ONMYGQXQPLQWSQ-UHFFFAOYSA-N sodium formic acid methanolate Chemical compound C(=O)O.C[O-].[Na+] ONMYGQXQPLQWSQ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses an electrochemical oxidation method for producing DMF by TMA oxidation. The electrochemical oxidation method comprises the following steps: the N, N-disubstituted formamide is obtained by electrochemical oxidation with the following secondary amine or tertiary amine as raw materials: trimethylamine, dimethylamine, N-diethylmethylamine, N-methylpyrrolidine, N-methylpiperidine or N-methylmorpholine. Compared with the industrial DMF method, TMA which is usually a byproduct is adopted as a raw material instead of DMA with larger demand; compared with the industrial DMF preparation method, the water system reaction is adopted, a large amount of industrial methanol is not needed, and the method is more environment-friendly; compared with the industrial DMF preparation method, the reaction can be carried out at normal temperature and normal pressure, high temperature and high pressure are not needed, and the conditions are milder.
Description
Technical Field
The invention relates to an electrochemical oxidation method for producing DMF by TMA oxidation, belonging to the field of amine compound electrooxidation upgrading conversion and utilization.
Background
DMF has the name of "universal solvent" and good solubility for many organic and inorganic compounds; and it is also a chemical raw material with extremely wide application: wet spinning of synthetic fibers, synthesis of polyurethane, plastic film making, paint stripping and other fields. One of the main processes for the industrial production of DMF is a one-step process: dimethyl amine (DMA) and carbon monoxide (CO) are directly synthesized into DMF under the conditions of taking sodium methoxide-formate as a system, the temperature being 100-200 ℃ and the pressure being 1.5-5 Mpa. The process needs high temperature and high pressure, has harsh conditions and is environment-friendly.
Dimethylamine (DMA) as a raw material for DMF production is generally produced by a catalytic ammonification method using methanol and ammonia. The reaction of methanol and ammonia is a reversible reaction, the distribution ratio of the three amine products is controlled by thermodynamic equilibrium, and the equilibrium in general forms monomethylamine (MMA): dimethylamine (DMA): trimethylamine (TMA) is 23:27:50. the DMA demand of the markets at home and abroad is the largest, and TMA produced by the method is relatively excessive. The separation of dimethylamine from the three amines by fractional distillation requires a considerable amount of energy. Rebalancing by mixture return after dimethylamine separation requires a bulky refining separation system. The direct conversion of overproduced TMA into DMF is an effective way to solve the mismatch between the required proportion of methylamine products and the proportion of the production structure. The electrochemical method is used for directly producing DMF from TMA, and the method is mild, efficient and environment-friendly.
Therefore, the electrochemical oxidation way realizes the production from TMA to DMF, not only can solve the problem of excessive TMA production and realize direct TMA elevation and high-valued, but also can provide a brand new way for efficient and green production of DMF.
Disclosure of Invention
The invention aims to provide an electrochemical oxidation method for producing DMF by TMA oxidation, which is used for upgrading and converting a large amount of byproduct TMA generated by industrial DMA and directly oxidizing the byproduct TMA into DMF with industrial utilization value.
The preparation method of the N, N-dimethylformamide provided by the invention comprises the following steps:
trimethylamine is used as a raw material, and N, N-dimethylformamide is obtained through electrochemical oxidation.
Preferably, the electrolyte used for the electrochemical oxidation is a solid electrolyte or a liquid electrolyte;
wherein the solid electrolyte may be a polymer solid electrolyte or an oxide solid electrolyte;
wherein the liquid electrolyte may be a solution of at least one of lithium hydroxide, potassium hydroxide, sodium hydroxide, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, sodium sulfate, and potassium sulfate, preferably a solution of potassium carbonate;
the molar concentration of the liquid electrolyte is 0.1 to 5M, preferably 0.3 to 1M, 0.5 to 0.7M or 0.7M.
Preferably, the anode used for the electrochemical oxidation may be at least one of carbon cloth, graphite sheet, carbon paper, carbon rod, foam nickel, nickel sheet, copper mesh, copper sheet, foam copper, titanium mesh, stainless steel, iron sheet and FTO conductive glass, preferably carbon rod or graphite sheet.
Preferably, the cathode used for electrochemical oxidation is made of at least one of a metal platinum/carbon catalyst, a metal ruthenium/carbon catalyst, a metal iridium/carbon catalyst, a platinum sheet and a carbon rod, and preferably a platinum sheet.
Preferably, the trimethylamine is added to the electrolyte in the form of an aqueous solution thereof or a hydrochloride solid, the aqueous solution having a concentration of 5 to 500mM, such as 10 to 50mM, preferably 20mM.
Preferably, the electrochemical oxidation is in an H-type electrolytic cell;
the electrochemical oxidation adopts the voltage of 0.5-3.0V (vs. Hg/HgO) for 1-10 h;
the adopted ion exchange membrane is AEM anion exchange membrane;
preferably, the electrochemical oxidation is performed in a flow cell;
the current adopted by the electrochemical oxidation is 0.01-5A, and the time is 1-10 h.
The amines suitable for use in the process of the present invention also include other N-methyl containing secondary and tertiary amines, such as: dimethylamine, N-diethylmethylamine, N-methylpiperidine, N-methylmorpholine, etc., and the corresponding DMF, N-formyldiethylamine, N-formylpiperidine, N-formylmorpholine, etc.
The method for preparing DMF by electrooxidation TMA has the following advantages:
1) Compared with the industrial DMF method, TMA which is usually a byproduct is adopted as a raw material instead of DMA with larger demand; 2) Compared with the industrial DMF preparation method, the water system reaction is adopted, a large amount of industrial methanol is not needed, and the method is more environment-friendly; 3) Compared with the industrial DMF preparation method, the reaction can be carried out at normal temperature and normal pressure, high temperature and high pressure are not needed, and the conditions are milder.
Drawings
FIG. 1 is a schematic diagram of a process for preparing DMF by electrooxidation of TMA according to the invention.
FIG. 2 is an electrochemical (time-current) test of TMA oxidation in example 1 of the invention.
FIG. 3 is a linear voltammetric scan test of TMA oxidation performance in example 1 of the present invention.
FIG. 4 is a comparison of the results of liquid chromatography of DMF product obtained in example 1 of the present invention.
FIG. 5 shows the yields of DMF obtained under the conditions of different concentrations of potassium carbonate solution in example 1 of the present invention.
FIG. 6 shows the yields of DMF obtained under the conditions of different kinds of electrolytes in example 1 of the present invention.
FIG. 7 shows the yields of DMF obtained under the conditions of different electrode materials in example 2 of the present invention.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1 oxidation of TMA to DMF
The electrochemical oxidation method is adopted, and the schematic diagram is shown in figure 1.
a. The carbon rod is used as an anode, the platinum sheet is used as a cathode, the Hg/HgO electrode is used as a reference electrode, a three-electrode system is built, and the ion exchange membrane is an AEM anion exchange membrane.
b. In the electrochemical performance test, a 20mM TMA solution was reacted at a voltage of 1.1V (vs. Hg/HgO) for 2 hours in different kinds and concentrations of electrolyte solutions.
Wherein the electrolyte is respectively potassium hydroxide solution, potassium carbonate solution, dipotassium hydrogen phosphate solution and PBS solution (pH is respectively 14.03, 11.92, 10.83 and 7.00), and the concentration is 0.3-1M.
c. The solution after the reaction was subjected to liquid phase test, and the highest yield of DMF was 82%.
Fig. 2 is an electrochemical (time-current) test curve of TMA oxidation in this example, and it can be seen that the reaction current is closely related to the TMA concentration and decreases with decreasing TMA concentration.
FIG. 3 shows a linear voltammetric scan of TMA oxidation performance in this example, with the lower curve being the control curve, and it can be seen that TMA oxidation has better reactivity than water oxidation under this system.
FIG. 4 is a comparison of the results of liquid chromatography of DMF products obtained in this example, and it can be seen that the main product of the system after the reaction is DMF.
Fig. 5 shows the yields of DMF (left plot shows the yields and right plot shows the faraday efficiencies) at different concentrations of electrolytes in this example, and it can be seen that the yields are highest when the concentration is 0.7M.
FIG. 6 shows the yield of DMF (DMF on the left and NMF on the right) under the conditions of different electrolyte types (concentration of 0.7M) in this example, when the electrolyte type is K 2 CO 3 The yield was highest.
EXAMPLE 2 preparation of DMF by TMA Oxidation
The electrochemical oxidation method is adopted, and the schematic diagram is shown in figure 1.
a. The method comprises the steps of taking a carbon rod, a graphite sheet, a carbon felt, a platinum sheet, palladium carbon, foam copper, foam nickel and nickel hydroxide as anodes, taking the platinum sheet as a cathode, and taking an Hg/HgO electrode as a reference electrode, and constructing a three-electrode system.
b. In the electrochemical performance test, a 20mM TMA solution was reacted at a voltage of 1.1V (vs. Hg/HgO) for 2 hours using a 0.7M potassium carbonate solution as an electrolyte solution.
c. The solution after the reaction was subjected to liquid phase test, and the highest yield of DMF was 82%.
FIG. 7 shows the DMF yield under the different electrode materials in this example, with the highest yield when the electrode material is carbon rod or graphite flake.
EXAMPLE 3 preparation of DMF by TMA Oxidation
The electrochemical oxidation method is adopted, and the schematic diagram is shown in figure 1.
a. Graphite flake is used as anode, platinum flake is used as cathode, and a flow cell system with the electrode area of 2 x 2 (cm) is built.
b. In the electrochemical performance test, a solution of 20mM TMA was reacted at 800mA constant current for 2 hours using a 0.7M potassium carbonate solution as an electrolyte solution.
c. The solution after the reaction is subjected to liquid phase test, and the DMF generation rate is 80 mu mol.h -1 。
Example 4 electrooxidation of other substrates
The electrochemical oxidation method is adopted, and the schematic diagram is shown in figure 1.
a. The carbon rod is used as an anode, the platinum sheet is used as a cathode, the Hg/HgO electrode is used as a reference electrode, a three-electrode system is built, and the ion exchange membrane is an AEM anion exchange membrane.
b. In the electrochemical performance test, a solution of 20mM dimethylamine, N-methylmorpholine, N-methylpiperidine, N-diethylmethylamine was reacted at a voltage of 1.1V (vs. Hg/HgO) for 2 hours using a 0.7M potassium carbonate solution as an electrolyte solution.
c. And (3) carrying out liquid phase test on the solution after the reaction, wherein the yields of N-formylmorpholine, N-formylpiperidine and N-formyldiethylamine generated by N-methylmorpholine, N-methylpiperidine and N, N-diethylmethylamine are respectively 60%, 20% and 20%. In particular, dimethylamine is electrooxidized with formaldehyde to produce DMF in 70% yield.
Claims (10)
1. A preparation method of N-formamides substance comprises the following steps:
the N-formamido amine substance is obtained by electrochemical oxidation by taking the following secondary amine or tertiary amine as raw materials:
trimethylamine, dimethylamine, N-diethylmethylamine, N-methylpyrrolidine, N-methylpiperidine or N-methylmorpholine.
2. The method of manufacturing according to claim 1, characterized in that: the electrolyte adopted by the electrochemical oxidation is solid electrolyte or liquid electrolyte.
3. The preparation method according to claim 2, characterized in that: the solid electrolyte is a polymer solid electrolyte or an oxide solid electrolyte.
4. The preparation method according to claim 2, characterized in that: the liquid electrolyte is a solution of at least one of lithium hydroxide, potassium hydroxide, sodium hydroxide, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, sodium sulfate and potassium sulfate;
the molar concentration of the liquid electrolyte is 0.1-5M.
5. The method according to any one of claims 1 to 4, wherein: the anode used for electrochemical oxidation is made of at least one of carbon cloth, graphite sheet, carbon paper, carbon rod, foam nickel, nickel sheet, copper net, copper sheet, foam copper, titanium net, stainless steel, iron sheet and FTO conductive glass.
6. The production method according to any one of claims 1 to 5, characterized in that: the cathode used for electrochemical oxidation is made of at least one of a metal platinum/carbon catalyst, a metal ruthenium/carbon catalyst, a metal iridium/carbon catalyst, a platinum sheet and a carbon rod.
7. The production method according to any one of claims 1 to 6, characterized in that: the secondary amine or the tertiary amine is added to the electrolyte in the form of its aqueous solution or as a solid of the hydrochloride salt.
8. The production method according to any one of claims 1 to 7, characterized in that: the electrochemical oxidation is performed in an H-type electrolytic cell;
the electrochemical oxidation adopts the voltage of 0.5-3.0V (vs. Hg/HgO) for 1-10 h.
9. The production method according to any one of claims 1 to 7, characterized in that: the electrochemical oxidation is performed in a flow cell;
the current adopted by the electrochemical oxidation is 0.01-5A, and the time is 1-10 h.
10. The application of trimethylamine in preparing N, N-dimethylformamide by electrochemical oxidation.
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|---|---|---|---|
| CN202211134654.4A CN117758285A (en) | 2022-09-19 | 2022-09-19 | Electrochemical oxidation method for producing DMF (dimethyl formamide) by TMA (time stamp oxidation) |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211134654.4A CN117758285A (en) | 2022-09-19 | 2022-09-19 | Electrochemical oxidation method for producing DMF (dimethyl formamide) by TMA (time stamp oxidation) |
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| CN202211134654.4A Pending CN117758285A (en) | 2022-09-19 | 2022-09-19 | Electrochemical oxidation method for producing DMF (dimethyl formamide) by TMA (time stamp oxidation) |
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