US2419515A - Preparation of 1, 3-butylene glycol - Google Patents
Preparation of 1, 3-butylene glycol Download PDFInfo
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- US2419515A US2419515A US468959A US46895942A US2419515A US 2419515 A US2419515 A US 2419515A US 468959 A US468959 A US 468959A US 46895942 A US46895942 A US 46895942A US 2419515 A US2419515 A US 2419515A
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- United States
- Prior art keywords
- aldol
- acetaldehyde
- ethyl alcohol
- butylene glycol
- reduction
- Prior art date
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 title description 43
- 229940058015 1,3-butylene glycol Drugs 0.000 title description 17
- 235000019437 butane-1,3-diol Nutrition 0.000 title description 17
- 238000002360 preparation method Methods 0.000 title description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 75
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 70
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 68
- 235000019441 ethanol Nutrition 0.000 description 40
- 230000003647 oxidation Effects 0.000 description 23
- 238000007254 oxidation reaction Methods 0.000 description 23
- 239000003792 electrolyte Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 238000009833 condensation Methods 0.000 description 16
- 230000005494 condensation Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical group [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
Definitions
- This invention relates to an improved process for the preparation of 1,3-butylene glycol from ethyl alcohol as a starting material.
- butylene glycol may he readily dehydrated to form butadiene which is employed as a monomeric raw material in the preparation of synthetic rubber.
- 1,3-butylene glycol is a very important chemical compound and its ready and economical preparation from a material as cheap and readily obtainable as ethyl alcohol assumes great importance.
- the principal object of the present invention is to provide an improved process for the production of 1,3-butylene glycol from ethyl alcohol. Another object is to devise such a method involving electrochemical steps in an integrated relationship. Another object is to provide such a process involving electrochemical steps wherein substantial savings in power are effected along withv other improvements, since one of the principal objections to ordinary electrolytic organic reactions is the relatively large cost of power consumed in carrying out the electrolytic reaction. Another object is to simultaneously carry out one step oi the integrated Process in the anode compartment of a divided electrolytic cell and another step in the cathode compartment of the same cell. Numerous other objects and advantages of the present invention will be at once apparent to those skilled in the art in the light of this disclosure.
- ethyl alcohol is oxidized to acetaldehyde in the anode compartment of an electrolytic cell, the acetaldehyde so formed is condensed to aldol, and the aldol is reduced t-o 1,3-butylene glycol in the cathode compartment of an electrolytic cell, preferably of the same cell as that in which the acetaldehyde is formed.
- the effluent from the anode compartment may be introduced into a receptacle and maintained at condensation temperature for the required period of time to complete condensation of the acetaldehyde to aldol.
- the aldol solution containing alkali, unreacted alcohol and possiblysome uncondensed acetaldehyde may then be introduced into the cathode compartment of the same electrolytic cell where the aldol is reduced vto 1,3- butylene glycol.
- the aldol-containing solution may be treated in any known manner to concentrate the aldol content thereof prior to introduction of the aldol to the cathode compartment wherein it is reduced to butylene glycol.
- the acetaldehyde-containing anolyte removed from the anode compartment in which the acetaldehyde is formed may be treated in any suitable manner, if desired, to concentrate the acetaldehyde prior to its introduction to the unit or zone in which it is condensed to aldol.
- a mercury or an amalgamated metal cathode on the surface of which sodium amalgam forms.
- r I may use a cathode of platinum, palladium, nickel, iron, copper, zinc, tin, lead, or other metal having catalytic properties for the reaction.
- Noncatalytic cathodes may aise be used since nascent hydrogen is an active reducing agent.
- the catholyte is treated in any suitable manner to recover the 1,3-butylene glycol content thereof.
- present in the catholyte is reconverted to ethyl alcohol, and the ethyl alcohol so formed may be separated from the butylene glycol by distillation and recycled. It is preferred to recover essentially pure butylene glycol Where, as ordinarily, it is to be used as a chemical intermediate, for example, as a starting material for the preparation of butadiene.
- a batch process may be used. At least the electro-organic oxidation and reduction steps may be conducted batchwise since they may not lend themselves too readily to truly continuous operation. However, continuous operation may be employed throughout if desired. In such case a series of cells may be utilized in order to provide a longer residence time.
- divided cells be used for both the oxidation and the reduction in order to prevent the oxidation products from being reduced at the cathode and the reductionr products from being oxidized at the cathode, to preclude other undesirable effects, and to keep the anolyte and catholyte separate.
- the selection of a suitable diaphragm for this purpose is well within the skill of the art.
- I may periodically or continuously during the electrolysis adjust the composition of anolyte or. catholyte or both in any desiredy manner, for example, by addition of a neutralizing acidic or acid-forming or a basic or base-forming material in suitable amount to prevent the building up of an excessive acidity or alkalinity.
- any uncondensed acetaldehyde It will be understood that where a single cell is used, the oxidation being conducted in the anode compartment and the reduction being carried out in the cathode compartment, the conditions for each will have to be so selected as to be compatible with one another. This is especially true of the electrolyte.
- both the anolyte and catholyte may be either acid or alkaline in reaction, or one may be acid and the other alkaline, provided other conditions are adjusted accordingly.
- I may use an electrolyte containing a salt such as an alkali sulfate, for example, sodium sulfate, whereby sulfuric acid is continuously formed in the anolyte and maintains it acid while alkali hydroxide is formed in the catholyte.
- a salt such as an alkali sulfate, for example, sodium sulfate
- the oxidatio-n of the ethyl alcohol to acetaldehyde is conducted in an acid anoiyte which may be especially desirable where it is sought to produce acetaldehyde in maximum yield and to minimize side reactions such as polymerization, etc., while the reduction of aldol to butylene glycol is carried out in an alkaline catholyte which is frequently very desirable.
- free sulfuric acid may be used as an initial componemL of the anolytewhen such a salt is used, if desired.
- an alkali carbonate as an electrical conducting salt in the anolyte and catholyte.
- the acetaldehyde formed in the anolyte may be largely or completely condensed to aldol as it is formed, since alkali carbonate is a well-known catalyst for aldol condensation.
- the withdrawn anolyte with or without additional treatment steps such as adjustment of composition, partial neutralization, concentration of aldol, a separate condensation step to complete condensation of the acetaldehyde to aldol, may then be passed to the cathode compartment where reduction to butylene glycol takes place especially well in the presence of alkali carbonate.
- the bicarbonate may be used.
- carbon dioxide may be intermittently or continuously passed into the catholyte to keep the alkalinity therein from becoming excessive.
- An especially desirable mode of operation is to use a common divided cell and a common electrolyte, nameiy, dilute sulfuric acid in both anode and cathode compartments, whereby the oxidation of the ethyl alcohol is done in a sulfuric acid anolyte which frequently gives maximum yields of acetaldchyde and eliminates condensation thereof to aldol or other reactions which would occur in an alkaline anolyte, and whereby the reduction cf the aldol (which is produced by condensation of the acetaldehyde in a separate unit apart from the cell) to butylene glycol takes place in a sulfuric acid catholyte.
- the electrolytic oxidation and reduction steps of the process of the present invention, and especially the reduction, are ordinarily and preferably carried out at low temperature, i. e., at below room temperature (commonly taken as 20 C.). Generally temperatures not above lo C. and varying downwardly therefrom to the freezing point of the electrolyte are employed. Useof such low temperatures promotes the desired reactions to a maximum and minimizes objectionable side reactions, polymerization, formation of resins,
- the aldol is reduced to 1,3-butylene glycol, while residual acetaldehyde is re-converted to ethyl alcohol. Simultaneously, a fresh quantity of alkaline aqueous ethyl alcohol is being oxidized in the anode compartment.
- the catholyte is distilled after reduction to separate the glycol from the ethyl alcohol and water; which may be recycled to the anode compartment, after wash ing to remove alkali, substantially pure 1,3- butylene glycol is obtained.
- the anolyte iiows continuously through the anode compartment while being oxidized and may then ow either through a storage zone where the acetaldehyde will have a sufficient residence time to complete condensation to aldol, or where the aldol formation has taken place in the anode compartment, may flow directly into and through the cathode compartment.
- the major portion of the electrolyte in each cell may be continuously recycled, or a series of cells in parallel may be used.
- electrolytes such as sulfuric acid or sodium sulfate
- electrolytes such as sulfuric acid or sodium sulfate
- the electrolyte must be neutralized after oxidation and made alkaline in order that the aldol condensation may take place in an alkaline medium.
- the alcohol concentration in the anolyte may Vary over a wide range; ordinarily 50-95% alcohol is suitable.
- alkali concentrations corresponding to 1-10% or more of NaOH may be used.
- electrolytes acidied with acids, such as sulfuric acid are used, the acid concentration may desirably be from 5-15%.
- the most important advantage is that the invention accomplishes production of very valuable 1,3-butylene glycol in a simple and economical manner from ethyl alcohol. Yields in each step, and consequently, the overall yield, are very good -The in- Vention permits utilization of the same electric power for both the oxidation and the reduction step. It conducts both oxidation and reduction in the same electrolyte. It permits at least partial condensation of the acetaldehyde in the oxidation zone. It eliminates the necessity for separation of the aldol prior to the reduction step.
- the process of making 1,3-butylene glycol from ethyl alcohol which comprises introducing an alcoholic aqueous solution containing 10% water and 90% ethyl alcohol to which about 4% NaCl-l has been added into the anode compartment of an electrolytic cell having its cathode compartment separated from its anode compartment by a porous diaphragm, subjecting said solution to electrolytic oxidation at a carbon anode in said anode compartment with a current density of 5 amperes per square decimeter at 6 volts and at a temperature of about 10 C.
- the process of making 1,3-butylene glycol from ethyl alcohol which comprises introducing an alcoholic aqueous solution containing from to 95 per cent ethyl alcohol to which solution has been added about 4% NaOH into the anode compartment of an electrolytie cell having its cathode compartment separated from its anode compartment by a porous diaphragm, subjecting said solution to electrolytic oxidation at a carbon anode in said anode compartment with a current density of 3 to 6 amperes per square decimeter at 3 to l5 volts and at a temperature of about 10 C.
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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
April 2z, 1947.
l. L. woLK PREPARATION 0F l 5BUT-YLENE GLYvCOL Filed Dec. 14, 1952 JOD... OP
.zormzunzou Patented pr. 22, 1947 PREPARATION 0F LS-BUTYLENE GLYCOL I. Louis Wolk, Bartlesville, Okla., assigner to Phillips Petroleum Company, a corporation of Delaware Application December 14, 1942, Serial No. 468,959
2 claims. l
This invention relates to an improved process for the preparation of 1,3-butylene glycol from ethyl alcohol as a starting material. As is now well-known, butylene glycol may he readily dehydrated to form butadiene which is employed as a monomeric raw material in the preparation of synthetic rubber. Accordingly, 1,3-butylene glycol is a very important chemical compound and its ready and economical preparation from a material as cheap and readily obtainable as ethyl alcohol assumes great importance.
The principal object of the present invention is to provide an improved process for the production of 1,3-butylene glycol from ethyl alcohol. Another object is to devise such a method involving electrochemical steps in an integrated relationship. Another object is to provide such a process involving electrochemical steps wherein substantial savings in power are effected along withv other improvements, since one of the principal objections to ordinary electrolytic organic reactions is the relatively large cost of power consumed in carrying out the electrolytic reaction. Another object is to simultaneously carry out one step oi the integrated Process in the anode compartment of a divided electrolytic cell and another step in the cathode compartment of the same cell. Numerous other objects and advantages of the present invention will be at once apparent to those skilled in the art in the light of this disclosure.
The accompanying drawing, Iwhich is self-explanatory, portrays diagrammatically one embodiment of the present invention.
In accordance with my invention, ethyl alcohol is oxidized to acetaldehyde in the anode compartment of an electrolytic cell, the acetaldehyde so formed is condensed to aldol, and the aldol is reduced t-o 1,3-butylene glycol in the cathode compartment of an electrolytic cell, preferably of the same cell as that in which the acetaldehyde is formed. By simultaneously carrying out the oxidation of the starting ethyl al-- cohol to acetaldehyde and the reduction of the aldol to Lil-butylene glycol in the anode and cathode compartments respectively, of one and the same electrochemical cell, great -ec0nomies and convenience of operation are effected and the same electric current is used for both the electrolytlc oxidation and reduction whereby -very great savings in power cost are attained. The condensation of the acetaldehyde to aldol may conveniently be carried out in a separate step. Methods of effecting this condensation are welk-known vto the art, as illustrated by U. 'S.
2 Patents to Earle et al., 1,094,314; Grunstein, 1,437,139; Matheson, 1,450,984; and Mueller- Cunradi et al., 1,881,853. However, since the condensation of acetaldehyde to aldol may take place in an alkaline alcoholic aqueous solution, this condensation may be-effected in the compartment of thecell wherein the acetaldehyde is formed from the ethyl alcohol, by utilizing an alkaline electrolyte for the oxidation of the ethyl alcohol, unreacted alcohol serving to render the anolyte alcoholic. If desired or necessary, the effluent from the anode compartment may be introduced into a receptacle and maintained at condensation temperature for the required period of time to complete condensation of the acetaldehyde to aldol. The aldol solution containing alkali, unreacted alcohol and possiblysome uncondensed acetaldehyde may then be introduced into the cathode compartment of the same electrolytic cell where the aldol is reduced vto 1,3- butylene glycol. If desired, the aldol-containing solution may be treated in any known manner to concentrate the aldol content thereof prior to introduction of the aldol to the cathode compartment wherein it is reduced to butylene glycol.
Likewise, the acetaldehyde-containing anolyte removed from the anode compartment in which the acetaldehyde is formed may be treated in any suitable manner, if desired, to concentrate the acetaldehyde prior to its introduction to the unit or zone in which it is condensed to aldol.
The electrochemical oxidation of ethyl alcohol to acetaldehyde in the anode compartment is a matter well within the skill of the art and the selection of anolyte composition, temperature, anode, current density and other conditions of this operation will be obvious to those skilled in the art in the light of this disclosure taken in conjunction with the prior art. Accordingly, speciilc conditions need not be given here in detail.
Ordinarily a current of 3-6 amperes/square decimeter and 3-15 volts will provide suitable current conditions for both the anodic and cathodio reactions described herein.
In many cases it will be desirable to carry out the oxidation of the ethyl alcohol to acet'aldehyde in an acid anolyte since under many circumstances use of an acid electrolyte, for eX- ample, dilute sulfuric acid, favors the production of acetaldehyde as the principalor main product, as is well known to the art. However, the use of an alkaline electrolyte in the anolyte is not precluded and may be desirableespecially where the same divided cell is used forlthe production of the acetaldehyde and for the reduction of the aldol and where an alkaline cletrolyte in the catholyte is used. As pointed out above, such use of an alkaline anolyte may be especially desirable where partial or complete condensation of the acetaldehyde to aldol in the anode compartment is sought.
The reduction of the aldol to 1,3-butylene glycol is carried out in the cathode compartment of an electrolytic cell. Here again the selection of conditions and materials is well within the skill of those versed in the art, this reduction per se being well disclosed in the literature as typied by the U. S. Patents to Earle et al., 1,094,315 and 1,094,316; and Delbruck et al., 1,094,539. This reduction may be conducted with either an alkaline or an acid catholyte. Where the catholyte contains alkali metal ions, such as sodium,
it is especially desirable to use a mercury or an amalgamated metal cathode on the surface of which sodium amalgam forms. Alternatively,r I may use a cathode of platinum, palladium, nickel, iron, copper, zinc, tin, lead, or other metal having catalytic properties for the reaction. Noncatalytic cathodes may aise be used since nascent hydrogen is an active reducing agent.
Following reduction in the cathodey compartment the catholyte is treated in any suitable manner to recover the 1,3-butylene glycol content thereof. present in the catholyte is reconverted to ethyl alcohol, and the ethyl alcohol so formed may be separated from the butylene glycol by distillation and recycled. It is preferred to recover essentially pure butylene glycol Where, as ordinarily, it is to be used as a chemical intermediate, for example, as a starting material for the preparation of butadiene.
A batch process may be used. At least the electro-organic oxidation and reduction steps may be conducted batchwise since they may not lend themselves too readily to truly continuous operation. However, continuous operation may be employed throughout if desired. In such case a series of cells may be utilized in order to provide a longer residence time.
It will be understood that while operation with simultaneous oxidation to acetaldehyde and reduction to butylene glycol in anode and cathode compartments, respectively, of the same cell, is highly preferred, I am not limited thereto but may carry out these steps in different cells, as for example, where it is desired to use conditions' for one of the reduction and oxidation steps which would be incompatible with the conditions desired for the other of said steps. Such conditions might involve temperature, electrolyte composition, voltage, current, time, etc.
Almost invariably it is preferred that divided cells be used for both the oxidation and the reduction in order to prevent the oxidation products from being reduced at the cathode and the reductionr products from being oxidized at the cathode, to preclude other undesirable effects, and to keep the anolyte and catholyte separate. The selection of a suitable diaphragm for this purpose is well within the skill of the art.
As will be obvious, I may periodically or continuously during the electrolysis adjust the composition of anolyte or. catholyte or both in any desiredy manner, for example, by addition of a neutralizing acidic or acid-forming or a basic or base-forming material in suitable amount to prevent the building up of an excessive acidity or alkalinity.
Any uncondensed acetaldehyde It will be understood that where a single cell is used, the oxidation being conducted in the anode compartment and the reduction being carried out in the cathode compartment, the conditions for each will have to be so selected as to be compatible with one another. This is especially true of the electrolyte. Thus both the anolyte and catholyte may be either acid or alkaline in reaction, or one may be acid and the other alkaline, provided other conditions are adjusted accordingly. If desired I may use an electrolyte containing a salt such as an alkali sulfate, for example, sodium sulfate, whereby sulfuric acid is continuously formed in the anolyte and maintains it acid while alkali hydroxide is formed in the catholyte. In this way, especially in the preierred embodiment involving simultaneous oxidation in the anode compartment and reduction in the cathode compartment of the same cell, the oxidatio-n of the ethyl alcohol to acetaldehyde is conducted in an acid anoiyte which may be especially desirable where it is sought to produce acetaldehyde in maximum yield and to minimize side reactions such as polymerization, etc., while the reduction of aldol to butylene glycol is carried out in an alkaline catholyte which is frequently very desirable. Of course free sulfuric acid may be used as an initial componemL of the anolytewhen such a salt is used, if desired.
In some cases it may be desirable to use an alkali carbonate as an electrical conducting salt in the anolyte and catholyte. In such case the acetaldehyde formed in the anolyte may be largely or completely condensed to aldol as it is formed, since alkali carbonate is a well-known catalyst for aldol condensation. The withdrawn anolyte with or without additional treatment steps such as adjustment of composition, partial neutralization, concentration of aldol, a separate condensation step to complete condensation of the acetaldehyde to aldol, may then be passed to the cathode compartment where reduction to butylene glycol takes place especially well in the presence of alkali carbonate. Instead of alkali carbonate, the bicarbonate may be used. Likewise, if desired, carbon dioxide may be intermittently or continuously passed into the catholyte to keep the alkalinity therein from becoming excessive.
In many cases it will be desirable to carry out the electrolytic reduction of the aldol to the 1:3 butylene glycol in the presence of dilute sulfuric acid. An especially desirable mode of operation is to use a common divided cell and a common electrolyte, nameiy, dilute sulfuric acid in both anode and cathode compartments, whereby the oxidation of the ethyl alcohol is done in a sulfuric acid anolyte which frequently gives maximum yields of acetaldchyde and eliminates condensation thereof to aldol or other reactions which would occur in an alkaline anolyte, and whereby the reduction cf the aldol (which is produced by condensation of the acetaldehyde in a separate unit apart from the cell) to butylene glycol takes place in a sulfuric acid catholyte.
The electrolytic oxidation and reduction steps of the process of the present invention, and especially the reduction, are ordinarily and preferably carried out at low temperature, i. e., at below room temperature (commonly taken as 20 C.). Generally temperatures not above lo C. and varying downwardly therefrom to the freezing point of the electrolyte are employed. Useof such low temperatures promotes the desired reactions to a maximum and minimizes objectionable side reactions, polymerization, formation of resins,
Example An alcoholic aqueous solution containing 10% water and 90% ethyl alcohol to which solution has been added about 4% NaOH, is introduced into the anode compartment of an electrolytic cell separated from the cathode compartment by a porous clay diaphragm. Initially, the same electrolyte may be placed in the cathode compartment. The electrolyte is subjected to electrolysis using a carbon anode and a current density of amperes/square decimeter at a voltage of 6 volts. The electrolysis is conducted at a temperature of about 10 C. with stirring for a suicient length of time to eectsubstantial conversion of ethyl alcohol to acetaldehyde, along with at least partial condensation of acetalde-` hyde to aldol, say Zelt) hours. The resulting electrolyte containing ethyl alcohol, water, NaOH, aldol and acetaldehyde, is then introduced into the cathode compartment of the cell using an amalgamated lead cathode and the same current conditions as in the anode compartment.v
The aldol is reduced to 1,3-butylene glycol, while residual acetaldehyde is re-converted to ethyl alcohol. Simultaneously, a fresh quantity of alkaline aqueous ethyl alcohol is being oxidized in the anode compartment. The catholyte is distilled after reduction to separate the glycol from the ethyl alcohol and water; which may be recycled to the anode compartment, after wash ing to remove alkali, substantially pure 1,3- butylene glycol is obtained.
The above example describes a batch operation. If it is desired to operate in a continuous manner, the anolyte iiows continuously through the anode compartment while being oxidized and may then ow either through a storage zone where the acetaldehyde will have a sufficient residence time to complete condensation to aldol, or where the aldol formation has taken place in the anode compartment, may flow directly into and through the cathode compartment. In order to increase reaction time the major portion of the electrolyte in each cell may be continuously recycled, or a series of cells in parallel may be used.
Similar operating conditions are used with other electrolytes, such as sulfuric acid or sodium sulfate, except that where the oxidation of the alcohol takes place in an acid medium, the electrolyte must be neutralized after oxidation and made alkaline in order that the aldol condensation may take place in an alkaline medium.
The alcohol concentration in the anolyte may Vary over a wide range; ordinarily 50-95% alcohol is suitable. When an alkaline solution is desired, alkali concentrations corresponding to 1-10% or more of NaOH may be used. Where electrolytes acidied with acids, such as sulfuric acid, are used, the acid concentration may desirably be from 5-15%.
A great many advantageous featuresof the process of the present invention will be apparent to those skilled in the art. Among these, the following may be enumerated. The most important advantage is that the invention accomplishes production of very valuable 1,3-butylene glycol in a simple and economical manner from ethyl alcohol. Yields in each step, and consequently, the overall yield, are very good -The in- Vention permits utilization of the same electric power for both the oxidation and the reduction step. It conducts both oxidation and reduction in the same electrolyte. It permits at least partial condensation of the acetaldehyde in the oxidation zone. It eliminates the necessity for separation of the aldol prior to the reduction step. It eiiects reconversion in the cathode compartment of unreacted acetaldehyde to alcohol which may then be recycled. It makes possible a semicontinuous or even a continuous method. Recycle of unreacted materials is readily accomplished and to a maximum extent whereby yields are improved.
I claim:
1. The process of making 1,3-butylene glycol from ethyl alcohol which comprises introducing an alcoholic aqueous solution containing 10% water and 90% ethyl alcohol to which about 4% NaCl-l has been added into the anode compartment of an electrolytic cell having its cathode compartment separated from its anode compartment by a porous diaphragm, subjecting said solution to electrolytic oxidation at a carbon anode in said anode compartment with a current density of 5 amperes per square decimeter at 6 volts and at a temperature of about 10 C. with stirring for a length of time of from 2-10 hours suilicient to eiect substantial conversion of ethyl alcohol to acetaldehyde by electrolytic oxidation and simultaneous condensation of said acetaldehyde to aldol in said anode compartment, introducing the resulting electrolyte containing ethyl alcohol, water, NaOH, aldol and acetaldehyde into the cathode compartment of the same cell, and subjecting said electrolyte to electrolytic reduction therein at an amalgamated lead cathode under the same current conditions as in the anode compartment and thereby reducing-said aldol to 1,3-butylene glycol at said cathode and re-converting said acetaldehyde to ethyl alcohol, simultaneously oxidizing a fresh quantity of said aqueous alkaline ethyl alcohol solution in said anode compartment, maintaining the anolyte and catholyte separate during the process by means of said diaphragm, withdrawing the catholyte from said cathode compartment after reduction of said aldol to 1,3-butylene glycol therein, separately recovering the 1,3-butylene glycol in substantially pure form and the ethyl alcohol from the catho-lyte, and recycling said ethyl alcohol to the anode compartment.
2. The process of making 1,3-butylene glycol from ethyl alcohol which comprises introducing an alcoholic aqueous solution containing from to 95 per cent ethyl alcohol to which solution has been added about 4% NaOH into the anode compartment of an electrolytie cell having its cathode compartment separated from its anode compartment by a porous diaphragm, subjecting said solution to electrolytic oxidation at a carbon anode in said anode compartment with a current density of 3 to 6 amperes per square decimeter at 3 to l5 volts and at a temperature of about 10 C. with stirring for a length oi time of 'from 2-10 hours sufcient to effect substantial conversion of ethyl alcohol to acetaldehyde by electrolytic oxidation and concomitant condensation of said acetalydehyde to aldol in said anode compartment, introducing the resulting elec trolyte containing ethyl alcohol, water, NaOH, aldol and acetaldehyde into the cathode compartment of the same electrolytic cell, subjecting said electrolyte to electrolytic reduction therein at an arnalgamated lead cathode under the same range of current conditions as in the anode compartment and thereby reducing said aldcl to l,3bui.ylene glycol at said cathode and recon- Verting said acetaldehyde to ethyl alcohol, simultaneously oxidizing electrolytically a fresh quantity of said aqueous aikaline ethyl alcohol solution in said anode compartment at the foregoing conditions, maintaining the ariolyte and catholyte separate during the process by means of said diaphragm, withdrawing the catholyte from said cathode compartment after reduction o said aldol to 1,3-butylene glycol therein, separately recovering the 1,3-loutylene glycol in substantially pure form and the ethyl alcohol from the catholyte, and recycling said ethyl alcohol to the anode compartment.
I. LOUIS WOLK.
REFERENCES crrao The following references are of record in the le of this patent:
UNITED STATES PATENTS Number Name Date 1,094,315 Earle et al. Apr. 21, 1914 1,094,224 Kyriakdes et al. Apr. 21, 1914 1,094,559 Delbruck et al Apr. 28, 1914 1,544,357 Thatcher June 20, 1925 1,885,242 Durians Nov. 1, 1932 FOREIGN PATENTS Number Country y Date 140,115 British Mar. 25, 1920 OTHER REFERENCES Muller, article in Zeitschrift fur Chemie, vol. 27, p. 564 (1921).
Glasstone etal., Electrolytic Oxidation and Reduction, publ. 1936 by D. Van Nostrand Co.
Stscherbakow et al., article in Zeitschrift fur 20 chemie, v01. 35, pp. 826-830 (1929
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US468959A US2419515A (en) | 1942-12-14 | 1942-12-14 | Preparation of 1, 3-butylene glycol |
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US2543763A (en) * | 1949-02-08 | 1951-03-06 | Hercules Powder Co Ltd | Electrolytic reduction of hydroperoxides |
US4347109A (en) * | 1980-05-19 | 1982-08-31 | Electrohol Corporation | Method for making acetaldehyde from ethanol |
US4375394A (en) * | 1982-03-11 | 1983-03-01 | Eastman Kodak Company | Electrolytic process for the preparation of ethylene glycol and glycerine |
US4457809A (en) * | 1980-10-23 | 1984-07-03 | Meshbesher Thomas M | Method for oxidizing lower alkanols to useful products |
US9068171B2 (en) | 2012-09-06 | 2015-06-30 | Mycotechnology, Inc. | Method for myceliating coffee |
US9427008B2 (en) | 2012-09-06 | 2016-08-30 | Mycotechnology, Inc. | Method of myceliation of agricultural substates for producing functional foods and nutraceuticals |
US10010103B2 (en) | 2016-04-14 | 2018-07-03 | Mycotechnology, Inc. | Methods for the production and use of myceliated high protein food compositions |
US10806101B2 (en) | 2016-04-14 | 2020-10-20 | Mycotechnology, Inc. | Methods for the production and use of myceliated high protein food compositions |
US11166477B2 (en) | 2016-04-14 | 2021-11-09 | Mycotechnology, Inc. | Myceliated vegetable protein and food compositions comprising same |
US11992025B2 (en) | 2014-03-15 | 2024-05-28 | Mycotechnology, Inc. | Myceliated products and methods for making myceliated products from cacao and other agricultural substrates |
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US1094315A (en) * | 1912-11-16 | 1914-04-21 | Hood Rubber Co Inc | PROCESS FOR PRODUCING 1.3-GLYCOLS, (β-GLYCOLS.) |
US1094224A (en) * | 1912-12-21 | 1914-04-21 | Hood Rubber Co Inc | Process for producing 1,3-diols. |
US1094539A (en) * | 1913-01-21 | 1914-04-28 | Farbenfab Vorm Bayer F & Co | Process of producing 1.3-butyleneglycol. |
GB140115A (en) * | 1917-04-03 | 1920-03-25 | Paul Victor Henri Pascal | Improved process for the synthetic manufacture of ethyl alcohol and ethyl acetate |
US1544357A (en) * | 1923-04-02 | 1925-06-30 | Charles J Thatcher | Electrolytic process |
US1885242A (en) * | 1930-03-21 | 1932-11-01 | Boake Roberts & Co Ltd | Manufacture of aldols |
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US1094315A (en) * | 1912-11-16 | 1914-04-21 | Hood Rubber Co Inc | PROCESS FOR PRODUCING 1.3-GLYCOLS, (β-GLYCOLS.) |
US1094224A (en) * | 1912-12-21 | 1914-04-21 | Hood Rubber Co Inc | Process for producing 1,3-diols. |
US1094539A (en) * | 1913-01-21 | 1914-04-28 | Farbenfab Vorm Bayer F & Co | Process of producing 1.3-butyleneglycol. |
GB140115A (en) * | 1917-04-03 | 1920-03-25 | Paul Victor Henri Pascal | Improved process for the synthetic manufacture of ethyl alcohol and ethyl acetate |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2543763A (en) * | 1949-02-08 | 1951-03-06 | Hercules Powder Co Ltd | Electrolytic reduction of hydroperoxides |
US4347109A (en) * | 1980-05-19 | 1982-08-31 | Electrohol Corporation | Method for making acetaldehyde from ethanol |
US4457809A (en) * | 1980-10-23 | 1984-07-03 | Meshbesher Thomas M | Method for oxidizing lower alkanols to useful products |
US4375394A (en) * | 1982-03-11 | 1983-03-01 | Eastman Kodak Company | Electrolytic process for the preparation of ethylene glycol and glycerine |
US9068171B2 (en) | 2012-09-06 | 2015-06-30 | Mycotechnology, Inc. | Method for myceliating coffee |
US9427008B2 (en) | 2012-09-06 | 2016-08-30 | Mycotechnology, Inc. | Method of myceliation of agricultural substates for producing functional foods and nutraceuticals |
US11992025B2 (en) | 2014-03-15 | 2024-05-28 | Mycotechnology, Inc. | Myceliated products and methods for making myceliated products from cacao and other agricultural substrates |
US10010103B2 (en) | 2016-04-14 | 2018-07-03 | Mycotechnology, Inc. | Methods for the production and use of myceliated high protein food compositions |
US11166477B2 (en) | 2016-04-14 | 2021-11-09 | Mycotechnology, Inc. | Myceliated vegetable protein and food compositions comprising same |
US11343978B2 (en) | 2016-04-14 | 2022-05-31 | Mycotechnology, Inc. | Methods for the production and use of myceliated high protein food compositions |
US11950607B2 (en) | 2016-04-14 | 2024-04-09 | Mycotechnology, Inc. | Myceliated vegetable protein and food compositions comprising same |
US10806101B2 (en) | 2016-04-14 | 2020-10-20 | Mycotechnology, Inc. | Methods for the production and use of myceliated high protein food compositions |
US12120987B2 (en) | 2016-04-14 | 2024-10-22 | Mycotechnology, Inc. | Methods for the production and use of myceliated high protein food compositions |
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