US2439513A - Adipic acid process - Google Patents

Adipic acid process Download PDF

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Publication number
US2439513A
US2439513A US632081A US63208145A US2439513A US 2439513 A US2439513 A US 2439513A US 632081 A US632081 A US 632081A US 63208145 A US63208145 A US 63208145A US 2439513 A US2439513 A US 2439513A
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United States
Prior art keywords
oxidation
cyclohexane
nitric acid
acid
adipic acid
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US632081A
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English (en)
Inventor
Clement H Hamblet
Mcalevy Ambrose
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to US632081A priority Critical patent/US2439513A/en
Priority to GB35436/46A priority patent/GB633354A/en
Priority to FR953498D priority patent/FR953498A/fr
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    • 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

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  • This invention relates to the production of adipic acid and related aliphatic dibasic acids and more particularly to the production, of adipic acid bythe oxidation of cyclohexane.
  • the unreacted cyclohexane may be first stripped from the crude reaction product by steam distillation under a fractionating column and recycled as feed to the preliminary oxidation step.
  • cyclohexanol and cyclohexanone may be recovered as a mixture by further distillation with fractionation techniques.
  • the cyclohexanol may 3 Claims. (Cl. 260-533) inary stage' is far from theoretical and is usually in the neighborhood of 40%.
  • Such processes suffer from the further disadvantage that extensive and expensive refining, accompanied by considerable handling losses, is required in the intermediate stages in order to give a final product of satisfactory purity.
  • This invention has as one of its objectives an improved process for converting cyclohexane to adipic acid. Another object is to provide a process for the preparation of adipic acid from cyclohexane whereby excellent yields of adipic acid of high purity are obtained. Another object is to provide an improved process for the production, from cyclic saturated hydrocarbons, of dibasic acids containing the same number of carbon atoms as the hydrocarbon treated, and more particularly to obtain adipic acid from cyclohexane by air oxidation of cyclohexane followed by nitric acid oxidation of the air oxidation product. A further object is to provide an improved technique for nitric acid oxidation of organic compounds. Other objects and advantages of the invention will hereinafter appear.
  • a surprisingly better yield of adipic acid can be obtained from the cyclic hydrocarbon, cyclohexane, by the process of this invention than can be obtained from heretofore known processes.
  • the process involves subjecting cyclohexane to air oxidation and thereafter subjecting all of the air oxidation products after the removal of the hydrocarbons toa nitric acid oxidation step.
  • dibasic acids produced are predominantly of the same number of carbon atoms as the hydrocaramount of cyclohexane consumed in the prelimbon oxidized.
  • One feature of the invention involves the nitric acid oxidation of the oxidized cyclic hydrocarbon product.
  • Any suitable process for the oxidation of the cyclane may be employed such, for example, as the lmown liquid-phase air-oxidation process conducted at temperatures between 75 and 200 C. and under pressures from 50 to 500 p. s. i. in which process catalysts such as the metal salts of organic acids have been found useful and more particularly the cobalt naphthenates, cobalt stearates, and the like.
  • Other oxidation processes may. however, be employed such as, for example, those disclosed in the U. S. Patents 2,223,493 and 2,223,494.
  • any other suitable method for the oxidation of the cyclane may be employed although it has been found advisable that in oxidizing these cyclic hydrocarbons to products which are subsequently to be nitric 'acid oxidized togive organic acids, the oxidation of the cyclic hydrocarbon should result in what is called a partial oxidation in which from Vi to 2 moles of oxygen reacts per mole of the reacted cyclic hydrocarbon. and preferably from 0.75 to 1 mole of oxygen per mole of reacted cyclic hydrocarbon. It has been found that while improvements can be obtained in overall yield of dibasic acid, when the oxidation of the hydrocarbon falls outside these ranges, nevertheless, for optimum results it is recommended that the preliminary oxidation be conducted within these ranges.
  • hydrocarbons present Prior to subjecting the products from the oxidation of cyclohexane or other cyclanes to nitric acid oxidation, it is desirable first to remove the hydrocarbons present and this may be accomplished by distillation although preferably steam distillation is employed to remove unreacted cyclohexane.
  • the hydrocarbon may be recycled to the air or equivalent oxidation process. If desired livesteam may be passed directly into the oxidation product and the hydrocarbon stripped from this product prior to the nitric acid oxidation of the product.
  • This feature involves the nitric acid oxidation of the product, obtained after removing the cyclane from the preliminary oxidation products, which is effected by subjecting such a product to nitric acid oxidation under pressures above atmospheric and in the presence of a suitable catalyst.
  • the oxidation with nitric acid may be effected in a single stage but is preferably effected in two stages.
  • nitric acid oxidation If the single stage nitric acid oxidation is employed, he reaction is eflected at a temperature between and 150 C. and under a pressure above atmospheric preferably between 15 and 500 p. s. 1. While oxidation in accord with the single step nitric acid procedure will give yields superior to those heretofore obtainable; nevertheless, its superiority over heretofore known processes can be augmented by conducting this phase of the process in two stages. 1
  • the first stage is carried out under mild conditions in which the reactants fiow around a closed circuit; and in the second stage, the products from the first or circulating stage are further oxidized at a somewhat higher temperature.
  • FIG. 1 is a diagrammatic crosssectional plane view of a tubular converter.
  • the jacketed tube l is of considerable length and .formed as shown in the drawing in a rectangular shape although it may be constructed in any desired shape with inlets 2 and 3 for the introduction of the reactants. Tube is surrounded by jacket 4 through which circulates a heat-exchange fluid for controlling the reaction in the desired temperature range.
  • a pump 5 is provided in tube l for maintaining a flow of reactants through this tube.
  • An automatically controlled valve 8 operates to deliver prodcatalyst into tube I through inlet 3 and forcing it around through the tube by means of pump I.
  • the cyclone is then introduced-through inlet 2 and the flow of heatzexchange fluid in the jacket I regulated to maintain 'the temperature of the reaction within the designated. range.
  • the valvet is brought into operation and a part of the str'e'am of reactants passing through tube I is introduced into preheater 9 and reaction tube 'I-Mherein its temperature is raised and theoxidationcompIeted.
  • the exidation products issue f the. reactor through the outlet l0.
  • the essential features tinuous nitric-acid oxi' step are:
  • the cyclane-free product of pelin' inary oxidation and a nitric acid solution 9 ⁇ 30-70% ,strength, preferably 50-60% strength, based on volatile content, containing a-suitable catalyst are septhe two-stage conarately and continuously introduced under a pressure of 2-10 atm. into the rapidly flowing stream containing nitric acid, catalyst, water, and productsof the reaction in tube l. .
  • the weight ratio of flows of the nitric acid are:
  • mixture to organic feed added to the circulating mixture should be in the range of 5-40, preferably -25, at the point of mixture; weight ratios of 100% nitric acid in the feed to organic feed should be in the range 2.5-6.0.
  • gPump 5 recirculates the nitric acid mixture through the tubular system, the rate of recirculation being such that the fluid flow is in the turbulent range.
  • the temperature of the recirculating mixture should be maintained between 4090 0., preferably between 6080 C. by means of suitable jacket coolants. Gases formed in the oxidation are preferably separated at some point in the recirculation system, as for example, a pipe (not shown in the drawing) vertically positioned on tube l.
  • the rate of admit tance of organic feed to the recirculation system should be such that the average contact time in this part of the equipment is of the order of 110 minutespreferably about 5 minutes.
  • the vanadium catalyst may be obtained in soluble form by, e. g. treatment of an aqueous or nitric acid suspension of vanadium pentoxide with nitrogen dioxide, nitric oxide, or nitrogen trioxide or gaseous mixtures containing one or more of these nitrogen oxides.
  • the oxidation mixture is continuously with-
  • the rate of withdrawal hearing such a relation to the rate of feeding that the volume of liquid mixture in the circulating system remains substantially constant.
  • the eilluent is then conducted to the second nitric acid oxidizing reaction, preferably after being preheated.
  • the mixture is held during this phase of the reaction (which may be conducted in, a tubular unit as illustrated in the drawing or an autoclave) at a higher temperature between 90- 120 C., and preferably between 95-100 0., for
  • the reaction is exothermic and the low temperature. In the case of adipic acid crystallization, the preferred temperature is in the vicinity of 5 C.
  • the crude acid may be recovered from the slurry by known techniques such as filtration or centrifuging, and the mother liquor may be recycled as part of the nitric acid feed to the oxidation step. To assure purity of the recovered acid, a portion of the mother liquor is vacuum flash distilled under pressures in the range 30-300 mm. and at temperatures in the range -150 C., the distillate being preferably recycled with the remainder of the mother liquor.
  • this element may be recovered from the tails from the flash distillation of themother liquor by diluting to give a solution which is homogeneous at room temperature and adjusting the pH of the solution to a value in excess of 1.0 by addition of an inorganic base such as sodium carbonate or hydroxide. Under these conditions the vanadium has been found to practically quantitatively precipitate in the form of an organic complex. The latter may be recovered by filtration and recycled to "the nitric acid oxidation step.
  • a charge containing 1997.1 parts of cyclohexane, 6.0 parts of cyclohexanone and 1.2 parts of cobalt naphthanate was air oxidized in a one gallon stainless steel autoclave operated at 142-445 C. under 100 p. s. 1. pressure for 77 minutes at an air space velocity of 91 volumes (S. T). P.) per volume of charge per hour.
  • the product was then discharged and unreacted hydrocarbon was recovered by steam distillation under a fractionating column operating at atmospheric pressure. Unreacted hydrocarbon, recovered as the water azeotrope boiling in the range ,68-80 C. amounted to 1748.8 parts, corresponding to a consumption of 248.3 parts or 12.5% during oxidation.
  • the reacted mixture issuing from the second stage reaction may be bleached by countercurrent treatment with'air at a temperature between 70 and 100 C. and preferably at about 90 C.
  • the off-gas from the bleaching operation contains nitrogen oxides which may be recovered as nitric acid by adsorption in water or nitric acid solution by known methods.
  • the air flow to the bleaching operation should consequently be at least great enough to provide sufficient oxygen for complete oxidation of the nitrogen oxides to nitric acid.
  • Monobasic acids are formed in the oxidation of many cyclanes.
  • products from air oxidation of cyclohexane are converted to adipic acid by nitric acid treatment
  • the presence of n-vaierlc and n-caproic acids in particular make the recovery of high quality adipic acid difflcult and these and similar acids should be removed by fractional distillation prior to the crysoil 'boiling azeotropically with water in the range 93-100" C.
  • adipic acid yield based on cyclohexanone and cyclohexanol was invariably less than 176 partsor 70%, corresponding to an overall adipic acid yield of less than 0.71 part of adipic acid per v part of cyclohexane consumed.
  • a similar cyclohexane oxidation product after stripping of the unconverted cyclohexane and partially drying but without removing any cyclohexanone or cyclohexanol was found by analysis to contain 28.4% cyclohexanone, 29.6% cyclohexanol, 0.6% cyclohexcnyl cyclohexyl ether, 3.2 cyclohexyl esters, some cyclohexanediol- 71.2. and 222% of material which was not volatile with steam.
  • the non-volatile traction was found to contain adipate mters. t-iorinyl valeric acid, e-hydron caproic acid and its esters, along with lower homologues.
  • dibasic acids may be obtained in acceptable yields from cyclopentane-glutaric, cyclobutanesuccinic and from higher cyclanes correspondingly higher dibasic acids.
  • eiliuents were cooled, the unconverted cyclohex-' ane removed by distillation and the residue subjected to nitric acid oxidation by a process simi lar to that described in Example 2.
  • Abetter yield. of adipic acid is obtainable by this method than is obtainable by a separation or the cyclohexanone and cyelohexanol from the oxidized cyclohexane and subjecting these alcohols and ketones to a separate oxidation.
  • Example l.-Nitric acid oxidation at two temperature levels Mixtures containing 50% cyclohexanol and 50% cyclohexanone were passed with approximately 7' parts of 60% nitric acid containing 0.05% ammonium vanadate catalysts through a jacketed tubular'converter similar to that illustrated by the drawing maintained at 71-76 C. at such rates that the total contact time varied in.the range 8.5-17.6 minutes. At the different rates of flow. yield of adipic acid did not vary outside the range Gil-70.6%. Furthermore by changing the temperature inthe range 71-125 C.,.yield did not vary outside the range 64.3-
  • the crude reaction mixture obtained from the second nitric acidoxidation stage contains appreciable quantities of nitric acid and it likewise contains along with. the adipic acid, monobasic acids in amounts ranging from 0.4 to about 1% based on the-crude reaction mixture.
  • the monobasic acids contaminants must be removed if a pure acid is desired and various methods have been .tried torattaining this result.
  • the monobasic acids may be removed from the crude reaction mixture by subjecting it to steam distillation. By this method a clean separation is possible.
  • nitric acid can be recovered without unconscionable losses if the crude reaction mixture is introduced into a mid section of a distillation column.
  • the vapors resulting from boiling the tails from those portions 9 of the reaction mixture that descend the column are introduced into the bottom of the column and water is introduced into the top of the column.
  • adipic acid can be crystallized from the tails of the column free from substantial impurities of the monobasic acid and from the mother liquor the nitric acid can be easily recovered.
  • Example 6 illustrates this feature of the invention.
  • Example 6.-360.5 parts of the same crude mixture were fed to the center of a distillling column which it descended countercurrent to 240 parts of its own tails vapor. Simultaneously 160 parts of distilled water were fed, to the top of the column.
  • the distillate contained only 0.2% nitric acid and adipic acid crystallized from the tails contained only 0.07% monobasic organic acids calculated as valeric.
  • the example given below illustrates a preferred method of purifying the reaction mixture to recover adipic acid free from monobasic acids and to recover appreciable quantities of the nitric acid used.
  • Example 7 When the nitric acid oxidation of cyclohexane oxidation products was carried out as described in Example 2 and the crude product was concentrated in a column with water reflux as described in Example 6, crude adipic acid, after dryin melted at 151.5-151.9 C. and had a purity of 98.9:0.4% in a large number of batches. Recrystallization from water gave refined acid which after drying melted at 151.9-152.1 C. and had a purity of 99.9i0.05%. Cf. Gi-lmans product, supra.
  • adipic acid by the oxidation of cyclohexane
  • steps which. comprise oxidizing cyclohexane with air at a temperature between 50 and 175 C. and under a pressure between 50 and 500 p. s. 1. until from 0.5 to 2 moles of oxygen react per mole of cyclohexane attacked, separating the unoxidized cyclohexane from the reaction mixture and oxidizing the cyclohexane-free reaction.
  • mixture with nitric acid at a temperature between 50 and 150 C. and at a pressure between and 500 p. s. i. to adipic acid.

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  • Engineering & Computer Science (AREA)
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US632081A 1945-11-30 1945-11-30 Adipic acid process Expired - Lifetime US2439513A (en)

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US632081A US2439513A (en) 1945-11-30 1945-11-30 Adipic acid process
GB35436/46A GB633354A (en) 1945-11-30 1946-11-29 Process for the production of dibasic carboxylic acids
FR953498D FR953498A (fr) 1945-11-30 1947-09-25 Procédé de préparation de diacides

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US2557281A (en) * 1951-06-19 Oxidation op petroleum cyclohexane
US2565087A (en) * 1947-10-30 1951-08-21 Allied Chem & Dye Corp Process for oxidation of cycloaliphatic compounds
US2617835A (en) * 1950-02-24 1952-11-11 Du Pont Polyhydric alcohol process
US2623072A (en) * 1946-09-27 1952-12-23 Phillips Petroleum Co Separation of cyclopentanone
US2675407A (en) * 1952-04-10 1954-04-13 Standard Oil Dev Co Air oxidation of cycloalkanes
US2684984A (en) * 1952-03-31 1954-07-27 Shell Dev Production of cyclic alcohols and ketones
US2800504A (en) * 1952-10-15 1957-07-23 Distillers Co Yeast Ltd Production of lower aliphatic acids
US2825742A (en) * 1954-05-04 1958-03-04 Du Pont Liquid phase oxidation of cyclohexane
US2831024A (en) * 1955-04-04 1958-04-15 Gulf Research Development Co Process for producing dibasic carboxylic acids
US2847431A (en) * 1955-02-07 1958-08-12 Celanese Corp Oxidation of ethylenically unsaturated fatty acids
US2878276A (en) * 1955-05-03 1959-03-17 Gulf Research Development Co Process for producing dibasic carboxylic acids
US2982772A (en) * 1959-01-12 1961-05-02 Monsanto Chemicals Octahydro-5ah, 10ah, 4a, 9a-epoxydibenzo-p-dioxin-5a, 10a-diol
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US3359308A (en) * 1963-05-17 1967-12-19 Du Pont Preparation of dicarboxylic acids by nitric acid oxidation
US3365491A (en) * 1963-05-27 1968-01-23 Ici Ltd Oxidation of cyclohexane
US3459512A (en) * 1965-01-20 1969-08-05 Ici Ltd Centrifugal recovery of copper-vanadium catalyst from adipic acid reaction mixture
US3513194A (en) * 1965-11-15 1970-05-19 Toa Gosei Chem Ind Process for producing adipic acid
US5801273A (en) * 1996-08-21 1998-09-01 Twenty-First Century Research Corporation Methods and devices for controlling the reaction rate of a hydrocarbon to an intermediate oxidation product by pressure drop adjustments
US5817868A (en) * 1996-11-12 1998-10-06 Twenty-First Century Research Corporation Method and devices for controlling the oxidation of a hydrocarbon to an acid by regulating temperature/conversion relationship in multi-stage arrangements
US5824819A (en) * 1996-12-18 1998-10-20 Twenty-First Century Research Corporation Methods of preparing an intermediate oxidation product from a hydrocarbon by utilizing an activated initiator
US5908589A (en) * 1997-12-08 1999-06-01 Twenty-First Century Research Corporation Methods for separating catalyst from oxidation mixtures containing dibasic acids
US5922908A (en) * 1996-06-24 1999-07-13 Twenty-First Century Research Corporation Methods for preparing dibasic acids
US5929277A (en) * 1997-09-19 1999-07-27 Twenty-First Century Research Corporation Methods of removing acetic acid from cyclohexane in the production of adipic acid
US5939582A (en) * 1996-01-17 1999-08-17 Twenty-First Century Research Corporation Reaction control by regulating internal condensation inside a reactor
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US6037491A (en) * 1997-07-25 2000-03-14 Rpc Inc. Methods and devices for controlling hydrocarbon oxidations to respective acids by adjusting the solvent to hydrocarbon ratio
US6039902A (en) * 1996-06-24 2000-03-21 Rpc Inc. Methods of recycling catalyst in oxidations of hydrocarbons
US6103933A (en) * 1996-11-07 2000-08-15 Rpc Inc. Methods for controlling the oxidation rate of a hydrocarbon by adjusting the ratio of the hydrocarbon to a rate-modulator
US6129875A (en) * 1998-02-19 2000-10-10 Rpc Inc. Process of separating catalyst from oxidation mixtures
US6143927A (en) * 1996-06-24 2000-11-07 Rpc Inc. Methods for removing catalyst after oxidation of hydrocarbons
US6218573B1 (en) 1998-07-02 2001-04-17 Rpc Inc. Methods of recovering catalyst in solution in the oxidation of cyclohexane to adipic acid
US6232495B1 (en) 1998-02-09 2001-05-15 Rpc Inc. Methods for treating cobalt catalyst in oxidation mixtures resulting from oxidation of hydrocarbons to dibasic acids
US6288274B1 (en) 1996-08-21 2001-09-11 Rpc Inc. Methods and devices for controlling the reaction rate and/or reactivity of hydrocarbon to an intermediate oxidation product by adjusting the oxidant consumption rate
US6288270B1 (en) 1996-06-24 2001-09-11 Rpc Inc. Methods for controlling the reaction rate of a hydrocarbon to an acid by making phase-related adjustments
US20010053864A1 (en) * 1996-08-21 2001-12-20 Decoster David C. Devices for controlling the reaction rate and/or reactivity of hydrocarbon to an intermediate oxidation product by adjusting the oxidant consumption rate
US6337051B1 (en) 1996-06-24 2002-01-08 Rpc Inc. Device for detecting formation of a second liquid phase
US6340420B1 (en) 1998-07-06 2002-01-22 Rpc Inc. Methods of treating the oxidation mixture of hydrocarbons to respective dibasic acids
US6417128B1 (en) 1999-04-20 2002-07-09 Rpc, Inc. Methods and replacing water and cyclohexanone with acetic acid in aqueous solutions of catalyst
WO2012174451A1 (fr) 2011-06-17 2012-12-20 Invista Technologies S.A.R.L. Utilisation d'hydrolases pour augmenter la teneur en monomères dans un flux de déchets
US9102958B2 (en) 2011-12-16 2015-08-11 Invista North America S.á.r.l. Methods of producing 6-carbon chemicals via CoA-dependent carbon chain elongation associated with carbon storage
US9102960B2 (en) 2011-12-16 2015-08-11 Invista North America S.á.r.l. Methods of producing 6-carbon chemicals via CoA-dependent carbon chain elongation associated with carbon storage
WO2016102343A1 (fr) * 2014-12-22 2016-06-30 Rhodia Operations Catalyseurs d'oxydation de cycloalcane et procédé pour produire des alcools et des cétones
US9580731B2 (en) 2012-12-31 2017-02-28 Invista North America S.A.R.L. Methods of producing 7-carbon chemicals via c1 carbon chain elongation associated with coenzyme B synthesis
US9580733B2 (en) 2012-12-31 2017-02-28 Invista North America S.A.R.L. Methods of producing 6-carbon chemicals via methyl-ester shielded carbon chain elongation
US9617572B2 (en) 2012-12-31 2017-04-11 Invista North America S.A.R.L. Methods of producing 7-carbon chemicals via aromatic compounds
US9637764B2 (en) 2012-12-31 2017-05-02 Invista North America S.A.R.L. Methods of producing 7-carbon chemicals via carbon chain elongation associated with cyclohexane carboxylate synthesis
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US9738911B2 (en) 2012-12-31 2017-08-22 Invista North America S.A.R.L. Methods of producing 7-carbon chemicals via pyruvate and succinate semialdehyde aldol condensation
US9738914B2 (en) 2014-06-16 2017-08-22 Invista North America S.A.R.L. Methods, reagents and cells for biosynthesizing compounds
US9745607B2 (en) 2014-05-15 2017-08-29 Invista North America S.A.R.L. Methods of producing 6-carbon chemicals using 2,6-diaminopimelate as precursor to 2-aminopimelate
US9790525B2 (en) 2012-12-14 2017-10-17 Invista North America S.A.R.L. Methods of producing 7-carbon chemicals via CoA-dependent carbon chain elongation associated with carbon storage
US9896702B2 (en) 2014-06-16 2018-02-20 Invista North America S.A.R.L. Methods, reagents and cells for biosynthesizing compounds
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US9920336B2 (en) 2012-12-31 2018-03-20 Invista North America S.A.R.L. Methods of producing 7-carbon chemicals from long chain fatty acids via oxidative cleavage
US9957535B2 (en) 2014-06-16 2018-05-01 Invista North America S.A.R.L. Methods, reagents and cells for biosynthesizing compounds
US10196657B2 (en) 2012-12-31 2019-02-05 Invista North America S.A.R.L. Methods of producing 7-carbon chemicals via methyl-ester shielded carbon chain elongation
CN113651685A (zh) * 2021-09-25 2021-11-16 侯凤芹 环链烷两步氧化制备二羧酸的方法
WO2022029583A1 (fr) 2020-08-07 2022-02-10 Inv Nylon Chemicals Americas, Llc Production de dinitriles

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FR953498A (fr) 1949-12-07
GB633354A (en) 1949-12-12

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