US2193562A - Process for the production of aliphatic dicarboxylic acids - Google Patents

Process for the production of aliphatic dicarboxylic acids Download PDF

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Publication number
US2193562A
US2193562A US234030A US23403038A US2193562A US 2193562 A US2193562 A US 2193562A US 234030 A US234030 A US 234030A US 23403038 A US23403038 A US 23403038A US 2193562 A US2193562 A US 2193562A
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United States
Prior art keywords
nitric acid
acid
aliphatic dicarboxylic
concentration
production
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Expired - Lifetime
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US234030A
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English (en)
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Sumner H Mcallister
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Shell Development Co
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Shell Development Co
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Priority to NL53438D priority Critical patent/NL53438C/xx
Priority to BE436616D priority patent/BE436616A/xx
Application filed by Shell Development Co filed Critical Shell Development Co
Priority to US234030A priority patent/US2193562A/en
Priority to GB27246/39A priority patent/GB533066A/en
Priority to FR860764D priority patent/FR860764A/fr
Application granted granted Critical
Publication of US2193562A publication Critical patent/US2193562A/en
Priority to FR51990D priority patent/FR51990E/fr
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B39/00—Locking of screws, bolts or nuts
    • F16B39/22—Locking of screws, bolts or nuts in which the locking takes place during screwing down or tightening
    • F16B39/28—Locking of screws, bolts or nuts in which the locking takes place during screwing down or tightening by special members on, or shape of, the nut or bolt
    • F16B39/32—Locking by means of a pawl or pawl-like tongue
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/316—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with oxides of nitrogen or nitrogen-containing mineral acids

Definitions

  • the present invention relatesto a process for v the production of aliphatic dicarboxylic acids. More particularly, the invention relates to a method -for the production of aliphatic diease with which the ring structure may be sprung.-
  • cyclic compounds oxidized according to the present invention i. e. cyclic alcohols
  • cyclic ketones are intermediate between these two extremes. These compounds, although much harder to oxidize than the cyclic ketones, may be oxidized under fairly strong oxidizing conditions.
  • nitric acid is a relatively expensive oxidizing agent, the economy of the nitric acid oxidation process is primarily dependent upon the consumption of nitric acid. In spite of the ready availability of the cyclic alcohols, the nitric acid oxidation of these compounds has not, in the past, been considered economical.
  • Another object of the invention is to provide a method whereby maximum yields of aliphatic dicarboxylic acids containing the same number of carbon atoms as the cyclic compounds being oxidized may be obtained.
  • a further object of the invention is to provide a nitric acid oxidation process for the production of dicarboxylic acids afiording the leastpossible consumption of nitric acid.
  • Still a further object of the invention is to provide a practical method whereby aliphatic dicarboxylic acids containing an uneven number of carbon atoms-between the carboxyl groups may be prepared.
  • these objects are accomplished by oxidizing cyclic alcohols with dilute nitric acid under certain carefully controlled conditions. In order that the prevailthe reaction system and the reaction mixture withdrawn at suitable rates in essentially a continuous manner.
  • I and 2 represent storage vessels for nitric acid and the cyclic compound to be oxidized; respectively.
  • 3 represents a reaction vessel equipped with stir-' ring means 4, closed coil 5 for'controlling the temperature therein and a condenser l9.
  • the cyclic alcohol is introduced continuously via a pipe 8 and control valve 9 into the reaction vessel containing dilute nitric acid maintained at the desired temperature by means of the closed coil.
  • the desired concentration of nitric acid in the reaction. vessel is maintained by continuously adding stronger (fortifying) acid from storage .vessel l via a pipe l0 and control valve H.
  • An agitating means 4 keeps the reacting mixture at the desired degree of agitation.
  • the crude reaction mixture which consists essentially of the desired aliphatic dicarboxylic acid and-dilute nitric acid, is withdrawn continuously from the reaction vessel via a pipe I2 and control valve l8 and introduced into a fractionating column 6 provided with suitable heating means-,such as, 55
  • the fractionating column is operated to take off unreacted nitric acid overhead via pipe 14, condenser 1 and pipe l5, leaving a concentrated nitric acid solution of the desired dicarboxylic acid.
  • the distilledand condensed dilute nitric acid may be reconcentrated by known methods and returned to storage vessel l.
  • the concentrated nitric acid solution of the desired carboxylic acid is withdrawn from the fractionating column near the bottom via a pipe l6 and control valve ll.
  • dicarboxylic acid may be recovered and purified as more fully described below.
  • the fixed gases produced by the reaction collect in the upper portion of the reaction vessel from where they are withdrawn through a pipe 20 and condenser l9. In passing through the condenser, any vapors of the unreacted alcohol and nitric acid are condensed and return to the reaction vessel. After being freed of more condensable constituents, the gases are withdrawn via pipe 2
  • the concentration of nitric acid maintained in the reaction chamber is much lower than customarily used for the oxidation-of cyclic compounds.
  • the concentration of nitric acid is preferably maintained as low as possible, consistent with a satisfactory reaction rate.
  • the reaction is preferably'executed at a fairly high temperature.
  • nitric acid concentrations ranging from about 8% to about 18% are preferred, although concentrations as low as 4% and as high as 24% may often be employed.
  • the temperature at which the oxidation is executed may range from about 50 C. to.130 C. or even higher. In general, temperatures between C, and 110 C. are preferred.
  • Percent M01 organic acid formed product In the case of the oxidation of the nonalkylated cyclic alcohols, using concentrations of nitric acid of about 10%, the preferred temperature is about 80 C. For higher acid con-- centrations the preferred temperature is some- The' desired.
  • HNOa concentration and temperature may vary considerably within theabove broader limits depending upon the character of the cyclic alcohol being oxidized.
  • nonalkylated monohydric alcohols In general, nonalkylated monohydric alcohols,
  • tuted derivatives thereof are preferably oxidized under more severe conditions, i. e., higher concentrations of nitric acid and/or higher temperatures, than their homologues containing alkyl sidechains.
  • Cyclic alcohols containing long alkyl sidechains and those containing gem. alkyl groups, such as the butyl cyclohexanols, gem. dimethylcyclopentanol-3 and the like in particular are preferably oxidized under the most mild conditions, i. e., acid concentrations of about 4%-8% and moderate temperatures.
  • the yield and purity of the product are somewhat dependent upon the'concentration of the fortifying acid continuously added to maintain the desired concentration in the reaction vessel.
  • Concentrated acid such as 50-70% nitric acid, has been found to be preferable to more dilute acids.
  • the present process may be satisfactorily carried out with or Without the aid of a catalyst.
  • Any of the conventional oxidation catalysts such as the oxides and salts of the polyvalent metals are applicable and may be used if desired.
  • the presence of a catalyst tends, in general, other factors remaining equal, to somewhat increase the yield and throughput capacity, to allow the use of somewhat lower temperatures, and to increase the ratio of Nz/NO in the exit gases, and in these respects is advantageous.
  • the use of a catalyst tends, in general, to increase the amount of lower dicarboxylic acid produced.
  • a cyclic alcohol I mean a cyclic organic compound containing a carbinol group in a non-aromatic ring.
  • suitable cyclic alcohols may be mentioned cyclobutanol, 2-methyl cyclobutanol, cyclopentanol, 3-methyl cyclopentanol, cyclohexanol, gem. di-
  • the schematic arrangement of apparatus shown in the accompanying drawing illustrates a simple plant suitable for the oxidation under substantially atmospheric pressure. It is to be understood, however, that the process is not limited whatsoever to the use of any particular typ of apparatus. In such cases where pressure is to be employed, the assembly of apparatus shown diagrammatically in the attached drawing may be provided with pumps for introducing the reactantsinotshown) or, if desired, in place of .pumps, the reactants may be forced into the reaction vessel by'meansof gas pressure. Numerous equally suitable modifications and variations will be readily apparent to those skilled in the art. For instance, the reactants may be cirequipment having an acid-proof lining and equipment fabricated from corrosion resistant alloys such as duriron, etc., are applicable.
  • the crude reaction product withdrawn from the reaction vessel contains the desired aliphatic dicarboxylic acid in solution in dilute nitric acid along with any unoxidized cyclic alcohol and small amounts of other products of side reactions.
  • This concentration may be most advantageously accomplished by conducting the crude reaction mixture continu-' ously, preferably without first cooling, into a suitable fractionating or stripping apparatus wherein'a substantial portion of the water'and nitric acid are removed.
  • This method I have found, has several advantages. The last traces of unreacted alcohol withdrawn with the re- Although the desired dicarboxylic acid may be recovered from the crude reaction mixaction mixture undergoes reaction during the flashing operation, and this appears to inhibit the further reaction of the dicarboxylic acids during the concentration step.
  • the greater portion of the desired dicarboxylicacid may in most cases be separated from the hot concentrated solution from such a concentration step by simply cooling, whereby the dicarboxylic acid crystallizes out.
  • the crystal. strike thus obtained, after separating from the mother. liquor may be further purified, if desired, by drying at 30-50 0., preferably under diminished pressure, dissolving in a suitable solvent, such as acetone, decolorizing, if desired, by a charcoal treatment, and finally recovered pure from the solvent solution.
  • a suitable solvent such as acetone, decolorizing, if desired, by a charcoal treatment
  • Other conventional methods of purification such as solvent extraction, etc., may also be used.
  • the mother liquor from the first crystallization may still contain appreciable dicarboxylic acids.
  • This solution may be further concentrated, if desired, and a second strike of dicarboxylic acid crystallized.
  • the final liquor remaining after any number of concentrations and crystallizations consists essentially of concentrated nitric acid, but still contains traces of dicarboxylic acid. This final liquor ma be reused in the process.
  • the dicarboxylic acid When destined for this use, the dicarboxylic acid must be free from bodies tending to discolor the resin In a few cases, the dicarboxylic acids produced according to my process, although apthis purpose since they produced discolored resins. I have found, however, that this may be readily remedied by subjecting the dicarboxylic acid to a treatment with activated charcoal which has been degassed by heating in vacuo just prior to use. This treatment is not only helpful in reclaiming occasional ofi batches of dicarboxylic acid, but may also be used as a matter of course to produce a premium product.
  • aliphatic dicarboxylic acids having an uneven number of carbon atoms between the carboxyl groups are much more difficult to prepare by oxidation than those having an even number of carbon atoms in the aliphatic chain.
  • dicarboxylic acids. having an uneven number of carbon atoms in the aliphatic chain can only be prepared-by oxidation with mild oxidizing agents and with poor yields, these acids may be prepared by the oxidation of the odd membered ring compounds of the'class in question, according to the process of my invention, with little difiiculty and with excellent yields.
  • the desired dicarboxylicacid may be obtained inexcellentyields.
  • the amount of dicarboxylic acids depends, of course, upon the material being oxidized, the prevailing conditions and upon the presence or absence of a catalyst, and may vary considerably.- In general, the amount of lower molecular Weight acids does not exceed 10% and, under favorable conditions, may be as low as 3%.
  • the consumption of nitric acid is usually about, and in many cases, even below the theoretical.
  • cyclic alcohols may be oxidized to aliphatic dicarboxylic acids according to my process with a.nitricacid consumption of only 2.42 mol per mol of dicarboxylic acidproduced.
  • the unusually low consumptions of nitric acid realized in the present process are due to the more complete reduction of the nitric-acid and to the fact that under the more favorable conditions used the side reactions are materially decreased.
  • the present process is of particular advantage for the production of dicarboxylic acids containwhich comprises continuously introducing cyclo-- pentanol into a nitric acid solution maintained at a temperature between 70 C, and 0., maintaining the concentration of said nitric acid solution between 8% and 18% by continuously introducing more concentrated nitric acid, continuously removing the crude reaction mixture and recovering glutaric acid therefrom.
  • a process for the production of aliphatic dicarboxylic acid which comprises continuously introducing a non-alkylated cyclic alcohol into a nitricacid solution maintained at a temperature between 70 C. and 110 C., maintaining the concentration of said nitric acid solution between 8% and 18% by continuously introducing more concentrated nitric acid, continuously removing the crude reaction mixture and'recovering aliphatic dicarboxylic acid therefrom.
  • a process for the production of aliphatic dicarboxylic acid which comprises continuously introducing-a non-alkylated cyclic alcohol into a nitric acid solution maintained at a temperature above 50 C., maintaining the concentration of said nitric acid solution between 8% and 18% by continuously introducing more concentrated nitric acid, continuously removing the crude reaction mixture and recovering aliphatic dicarboxylic acid therefrom.
  • a process for the production of aliphatic dicarboxylic acid which comprises continuously introducing a non-alkylated 'cyclic alcohol into a ,nitric acid solution maintained at a temperature above 50 C., maintaining the concentration of said nitric acid solution between 4% and 24% by continuously introducing more concentrated nitric acid, continuously removing the crude reaction mixture and recovering aliphatic dicar-- boxylic acid therefrom] 5.
  • a process for the production of aliphatic dicarboxylic acid which comprises reacting a cyclic alcohol in the presence of an oxidation catalyst with'a nitric acid solution maintained at a temperature between 70 C, and 110 C., maintaining the concentration of said nitric acid solution between 8% and 18% by introducing more concentrated nitric acid, removing the crude reaction mixture and concentrating the same by distillation, crystallizing aliphatic dicarboxylic acid from the concentrated reaction mixture and finally purifying the aliphatic dicarboxylic acid by treatment with degassed charcoal.
  • a process for the production of aliphatic dicarboxylic acid which comprises reacting a cyclic alcohol in the presence of an oxidation catalyst with a nitric acid solution maintained at a temperature between 70 C. and 110 0.,
  • a process for the production of aliphatic dicarboxylic acid which comprises reacting a cyclic centrated nitric acid, removing the crude reaction mixture and recovering aliphatic dicarboxylic acid therefrom.
  • a process for the production of aliphatic dicarboxylic acid which comprises reacting a cyclic alcohol in the presence of an oxidation catalyst with a nitric acid solution maintained at a temperature above50 C., maintaining the concentration of said nitric acid solution between 8%' and 18% by introducing more concentrated nitric acid, removing the crude reaction mixture and recovering aliphatic dicarboxylic acid therefrom.
  • a process for the production of aliphatic dicarboxylic acid which comprises reacting a cyclic alcohol having an uneven number of carbon-atoms in a carbocyclic chain with 'a nitric acid solution maintained at-a temperature above 50 C., maintaining the concentration of said nitric acid solution between 4% and 24% bycintroducing more concentrated acid, removing the crude reaction mixture and recovering aliphatic dicarboxylic acid therefrom.
  • a process for the production of aliphatic dicarboxylic acid which comprises reacting a cyclic alcohol with a nitric acid solution maintained at a temperature above 50 C., maintaining the concentration of said nitric acid solution between 4%,.and 24% by introducing more con- 45 centrated nitric acid, removing the crude reaction mixture and recoveringv aliphatic dicarboxylic acid therefrom.
  • a process for the production of aliphatic dicarboxylic acid the step of continuously oxidizing a cyclic alcohol having an uneven number of carbon atoms in a carbocyclic chain in a nitric acid solution maintained between 4% and 24% nitric acid concentration and a temperature between 70 C. and 110 C.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US234030A 1938-10-08 1938-10-08 Process for the production of aliphatic dicarboxylic acids Expired - Lifetime US2193562A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL53438D NL53438C (xx) 1938-10-08
BE436616D BE436616A (xx) 1938-10-08
US234030A US2193562A (en) 1938-10-08 1938-10-08 Process for the production of aliphatic dicarboxylic acids
GB27246/39A GB533066A (en) 1938-10-08 1939-10-05 A process for the production of aliphatic dicarboxylic acids
FR860764D FR860764A (fr) 1938-10-08 1939-10-07 Procédé pour la production d'acides dicarboxyliques aliphatiques
FR51990D FR51990E (fr) 1938-10-08 1942-03-26 Perfectionnements apportés aux dispositifs d'écrous de blocage

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Application Number Priority Date Filing Date Title
US234030A US2193562A (en) 1938-10-08 1938-10-08 Process for the production of aliphatic dicarboxylic acids

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US2193562A true US2193562A (en) 1940-03-12

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US (1) US2193562A (xx)
BE (1) BE436616A (xx)
FR (2) FR860764A (xx)
GB (1) GB533066A (xx)
NL (1) NL53438C (xx)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2439513A (en) * 1945-11-30 1948-04-13 Du Pont Adipic acid process
US2560156A (en) * 1947-12-18 1951-07-10 Du Pont Method of separating carboxylic acids resulting from the liquid phase oxidation of oleic acid
US2662908A (en) * 1951-03-30 1953-12-15 C P Hall Company Of Illinois Oxidation of fatty acids
US2825741A (en) * 1956-06-05 1958-03-04 American Oil Co Removal of impurities from hydrocarbon oxidation products
US2844626A (en) * 1955-05-27 1958-07-22 Goodyear Tire & Rubber Process for the manufacture of adipic acid
US3087963A (en) * 1959-03-02 1963-04-30 Exxon Research Engineering Co Preparation of 1, 12-dodecanedioic acid
US3950410A (en) * 1971-06-04 1976-04-13 Imperial Chemical Industries Limited Oxidation process

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2439513A (en) * 1945-11-30 1948-04-13 Du Pont Adipic acid process
US2560156A (en) * 1947-12-18 1951-07-10 Du Pont Method of separating carboxylic acids resulting from the liquid phase oxidation of oleic acid
US2662908A (en) * 1951-03-30 1953-12-15 C P Hall Company Of Illinois Oxidation of fatty acids
US2844626A (en) * 1955-05-27 1958-07-22 Goodyear Tire & Rubber Process for the manufacture of adipic acid
US2825741A (en) * 1956-06-05 1958-03-04 American Oil Co Removal of impurities from hydrocarbon oxidation products
US3087963A (en) * 1959-03-02 1963-04-30 Exxon Research Engineering Co Preparation of 1, 12-dodecanedioic acid
US3950410A (en) * 1971-06-04 1976-04-13 Imperial Chemical Industries Limited Oxidation process

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Publication number Publication date
NL53438C (xx)
FR51990E (fr) 1943-05-27
FR860764A (fr) 1941-01-23
GB533066A (en) 1941-02-05
BE436616A (xx)

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