US3488266A - Electrochemical reduction of benzene using a carbon anode - Google Patents
Electrochemical reduction of benzene using a carbon anode Download PDFInfo
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- US3488266A US3488266A US689784A US3488266DA US3488266A US 3488266 A US3488266 A US 3488266A US 689784 A US689784 A US 689784A US 3488266D A US3488266D A US 3488266DA US 3488266 A US3488266 A US 3488266A
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- benzene
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- anode
- alcohol
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 20
- 229910052799 carbon Inorganic materials 0.000 title description 12
- 230000009467 reduction Effects 0.000 title description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- -1 sodium alkoxide Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241001647090 Ponca Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MWOBKFYERIDQSZ-UHFFFAOYSA-N benzene;sodium Chemical compound [Na].C1=CC=CC=C1 MWOBKFYERIDQSZ-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Definitions
- This invention relates to a method of electrochemically reducing benzene to selectively produce 1,4-cyclohexadiene.
- benzene can be reduced to selectively produce 1,4-cyclohexadiene when said reduction is carried out electrolytically in the presence of liquid ammonia, an anode selected from the group consisting of carbon and graphite, about 3.0 weight percent to about 4.0 weight percent of an alcohol, and a current carrier of sodium chloride.
- an anode selected from the group consisting of carbon and graphite
- a current carrier of sodium chloride for highest yields it has been discovered that said reaction should be carried out in the absence of iron contamination and under anhydrous conditions. No reduction of benzene occurs when the anode is carbon or graphite unless the amount of alcohol present is controlled within rather narrow limits. At about 3.0 to 4.0 weight percent alcohol concentration the current efficiencies are sufficiently high to allow the reaction to proceed rapidly. At concentrations above and below this amount the current efficiencies are very low.
- anodes Numerous materials were tested as anodes. Included were platinum, gold, titanium, cast iron, stainless steel, nickel, zirconium, molybdenum, tungsten, antimony, tin, carbon and graphite. Good current efficiencies can be obtained with a platinum anode with 1 percent alcohol present. When the anode is carbon or graphite, good current efficiencies can only be obtained with the alcohol concentration controlled between about 3.0 and 4.0 weight percent.
- the alcohol is regenerated by the reaction of the sodium alkoxide with ammonium ions which are formed at the anode.
- Mass spectroscopy analysis showed the presence of nitrogen and hydrogen in the off-gases. Nitrogen was liberated at the anode from the oxidation of ammonia. Hydrogen was formed by the reaction of sodium with ammonia.
- EXAMPLE I Twenty-five grams of benzene were dissolved in ,150 grams of liquid ammonia along with 8 grams of sodium chloride and 6 grams of methanol. The solution was maintained at -33 C. in an aluminum pressure vessel. The cathode was aluminum and the anode was carbon. Current density was maintained at 100 ma./in. for a period of 20 hours. Benzene was reduced at the cathode to 1,4-cyclohexadiene. No other reduction products were formed during the electrolysis. The current efliciency was 40.5 percent.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
United States Patent 3,488,266 ELECTROCHEMICAL REDUCTION OF BENZENE USING A CARBON ANODE Eddie C. French, Aubrey, Tex., assignor to Continental Oil Company, Ponca City, Okla.
No Drawing. Filed Dec. 12, 1967, Ser. No. 689,784 Int. Cl. B01k 1/00; C07b 29/06 US. Cl. 204-59 9 Claims ABSTRACT OF THE DISCLOSURE A process for electrochemically reducing benzene to 1,4-cyclohexadiene in the presence of liquid ammonia, an alkali metal chloride, a carbon or graphite anode, and a controlled amount of an alcohol, all in the absence of iron and under anhydrous conditions.
DISCLOSURE This invention relates to a method of electrochemically reducing benzene to selectively produce 1,4-cyclohexadiene.
Benzene can be reduced chemically to a mixture of products, such as 1,3 and 1,4 cyclohexadienes, cyclohexene, and cyclohexane in anhydrous low molecular weight amines with metallic lithium or sodium. These alkali metal reductions are of considerable synthetic use, however, the cost of lithium or sodium metal and the amines makes this process too expensive for large scale use. The products formed by this chemical reduction have similar properties and separation into pure components is nearly impossible. Aromatic compounds have been reduced electrolytically. Benzene has been reduced in methylamine while using lithium chloride as a current carrier. All the foregoing methods used platinum as the anode. Platinum is chemically attacked when used as an anode in liquid ammonia with sodium chloride as a current carrier.
It has now been unexpectedly discovered that benzene can be reduced to selectively produce 1,4-cyclohexadiene when said reduction is carried out electrolytically in the presence of liquid ammonia, an anode selected from the group consisting of carbon and graphite, about 3.0 weight percent to about 4.0 weight percent of an alcohol, and a current carrier of sodium chloride. For highest yields it has been discovered that said reaction should be carried out in the absence of iron contamination and under anhydrous conditions. No reduction of benzene occurs when the anode is carbon or graphite unless the amount of alcohol present is controlled within rather narrow limits. At about 3.0 to 4.0 weight percent alcohol concentration the current efficiencies are sufficiently high to allow the reaction to proceed rapidly. At concentrations above and below this amount the current efficiencies are very low.
Table I shows the effect of alcohol concentration.
TABLE I Weight percent Percent current methanol efficiency These data clearly show that good current efiiciencies can only be obtained with a carbon anode if the alcohol concentration is carefully controlled.
An outstanding feature of thisreaction is its selectivity of products. Benzene was converted to 1,4-cyclohexadiene ice with selectivity of greater than 98 percent. The remaining 2 percent was cyclohexene, probably formed by the reduction of the 1,4-cyclohexadiene. If the reaction was carried to near completion (reduction of all the benzene), the amount of cyclohexene would increase; however, the reaction can be carried to 55 percent conversion to 1,4- cyclohexadiene with only 2 percent cyclohexene by-prodnot and still maintain high current efficiencies. The remainder was unreacted benzene.
Current efficiencies vary over a wide range and are dependent on many factors. Efficiencies of 40 percent can be obtained by using the best known conditions and not carrying the reaction past 25 percent conversion. A current efficiency of 30 to 33 percent was obtained where the conversion was 55 percent.
Numerous materials can be used as cathodes. The desirable properties of the cathode are: (1) high hydro gen overvoltages, (2) resistance to attack by anhydrous ammonia, (3) good conductor, (4) readily available, and (5) low cost. Aluminum, zinc, and platinum have been used with aluminum being preferred because of its availability and low cost.
Numerous materials were tested as anodes. Included were platinum, gold, titanium, cast iron, stainless steel, nickel, zirconium, molybdenum, tungsten, antimony, tin, carbon and graphite. Good current efficiencies can be obtained with a platinum anode with 1 percent alcohol present. When the anode is carbon or graphite, good current efficiencies can only be obtained with the alcohol concentration controlled between about 3.0 and 4.0 weight percent.
Methanol, ethanol and isopropanol are among the alcohols which may be used to produce the beneficial effect with the carbon or graphite anode.
The effect of current density is closely related to the cathode potential as shown in Table II.
TABLE II Effect of cathode current density on current efficiency Current density Percent current ma./in. efficiency Sodium formed at the cathode by the reduction of sodium ions present will react rapidly with any water present rather than the benzene. This results in a drop in current efficiency. Also, iron catalyzes the reaction of sodium with ammonia. If iron or other transition metals are present the sodium reacts with the ammonia and no reduction of benzene occurs.
The effect of benzene concentration was not as critical as other variables; however, highest current efficiencies were obtained when the benzene concentration was 15 to 20 percent.
Temperatures near -33 C. were necessary to obtain good current efliciencies. The yield was not affected by the temperature.
The over-all reaction for the reduction of benzene to 1,4-cyclohexadiene is:
a@ GNHa 3( am This is a chemical reaction. The electrode reactions are:
Cathode: 6Na++6e -6Na Anode: 8NH 6e- N +6NH Total electrode reaction:
8NH 6Na+ 6Na N 6NH 3 (Na 3Na- Na The alcohol then acts as an acid in the ammonia, displaces the sodium, and forms the 1,4-cyclohexadiene.
The alcohol is regenerated by the reaction of the sodium alkoxide with ammonium ions which are formed at the anode.
Mass spectroscopy analysis showed the presence of nitrogen and hydrogen in the off-gases. Nitrogen was liberated at the anode from the oxidation of ammonia. Hydrogen was formed by the reaction of sodium with ammonia.
This reaction is catalyzed by the presence of iron and other transition metals. The competition between this reaction and the benzene-sodium reaction thus accounts for the observed 40% current efiiciency.
Separation of the products formed can be accomplished by fractional crystallization or fractional distillation.
For a fuller understanding of the present invention, reference will be had to the following examples.
EXAMPLE I Twenty-five grams of benzene were dissolved in ,150 grams of liquid ammonia along with 8 grams of sodium chloride and 6 grams of methanol. The solution was maintained at -33 C. in an aluminum pressure vessel. The cathode was aluminum and the anode was carbon. Current density was maintained at 100 ma./in. for a period of 20 hours. Benzene was reduced at the cathode to 1,4-cyclohexadiene. No other reduction products were formed during the electrolysis. The current efliciency was 40.5 percent.
4 EXAMPLE II This example was run in exactly the same manner and under the same conditions as Example I except that only 2 grams of methanol were added. The current efiiciency was only 0.7 percent.
EXAMPLE III This example was run in exactly the same manner and under the same conditions as Example I except that 8.6 grams of methanol were added. The current efliciency was only 0.5 percent.
Having thus described the invention by providing specific examples thereof, it is to be understood that no undue limitations or restrictions are to be drawn by reason thereof and that many variations and modifications are within the scope of the invention.
What is claimed is:
1. In a pr0cess for the electrochemical reduction of benzene to 1,4-cyclohexadiene in liquid ammonia with sodium chloride as a current carrier, under substantial absence of iron, the improvement which comprises adding between about 3.0 weight percent and about 4.0 weight percent of an alcohol and using an anode selected from the group consisting of carbon and graphite.
2. The process of claim 1 wherein said alcohol is selected from the group consisting of methanol, ethanol and isopropanol.
3. The proces of claim 2 wherein the anode is carbon.
4. The process of claim 2 wherein the anode is graphite.
5.1 The process of claim 2 wherein the alcohol is methano 6. The process of claim 2 wherein the alcohol is ethanol.
7. The process of claim 2 wherein the alcohol is isopropanol.
8. The process of claim 2 wherein about 3.0 percent alcohol is added.
9. The process of claim 2 wherein about 4.0 percent alcohol is added.
' References Cited UNITED STATES PATENTS 3,361,653 1/1968 Miller 204-59 HOWARD S. WILLIAMS, Primary Examiner
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68978467A | 1967-12-12 | 1967-12-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3488266A true US3488266A (en) | 1970-01-06 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US689784A Expired - Lifetime US3488266A (en) | 1967-12-12 | 1967-12-12 | Electrochemical reduction of benzene using a carbon anode |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3488266A (en) |
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| US20050214609A1 (en) * | 2003-03-24 | 2005-09-29 | Ion America Corporation | Solid oxide fuel cell with selective anode tail gas circulation |
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| US3361653A (en) * | 1963-11-04 | 1968-01-02 | Hooker Chemical Corp | Organic electrolytic reactions |
-
1967
- 1967-12-12 US US689784A patent/US3488266A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3361653A (en) * | 1963-11-04 | 1968-01-02 | Hooker Chemical Corp | Organic electrolytic reactions |
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