US3651135A - Preparation of oxalic acid - Google Patents

Preparation of oxalic acid Download PDF

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Publication number
US3651135A
US3651135A US876220A US3651135DA US3651135A US 3651135 A US3651135 A US 3651135A US 876220 A US876220 A US 876220A US 3651135D A US3651135D A US 3651135DA US 3651135 A US3651135 A US 3651135A
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United States
Prior art keywords
propylene
nitric acid
reactor
oxalic acid
acid
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Expired - Lifetime
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US876220A
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English (en)
Inventor
Jacques Boichard
Bernard Pierre Brossar
Jacques Marius Duroux
Raymond Marc Clement Janin
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Rhone Poulenc SA
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Rhone Poulenc SA
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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
    • C07C51/27—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with oxides of nitrogen or nitrogen-containing mineral acids
    • C07C51/275—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with oxides of nitrogen or nitrogen-containing mineral acids of hydrocarbyl groups

Definitions

  • Oxalic acid is made by oxidizing propylene with at least 50% nitric acid at 40 to 80 C.
  • the present invention relates to the preparation of oxalic acid by oxidation of propylene.
  • the process most commonly employed in industry for the preparation of oxalic acid is the alkali metal formate process, which consists in decomposing alkali metal formates, such as sodium formate, to alkali metal oxalates by heatin converting the alkali metal oxalates into insolu ble calcium oxalate and then liberating the oxalic acid with sulphuric acid.
  • alkali metal formate process which consists in decomposing alkali metal formates, such as sodium formate, to alkali metal oxalates by heatin converting the alkali metal oxalates into insolu ble calcium oxalate and then liberating the oxalic acid with sulphuric acid.
  • the nitric acid concentration decreases in the course of the reaction, on the one hand because of the increase in the weight of the reaction mass and on the other hand because of the consumption of nitric acid and its entrainment in the nitrous vapours.
  • the quantity of propylene entering into the reaction decreases, which results in a considerable lowering of the yield and in the formation of a gaseous mixture of propylene and nitrous vapours.
  • nitric acid concentration at 50% or above makes possible a total conversion of the propylene and the production of excellent yields of oxalic acid, in the absence of sulphuric acid.
  • the quantity of acid which disappears in the form of irrecoverable nitrogen is low. It is known that, when organic compounds are oxidised with nitric acid, the latter is reduced in some cases as far as the irrecoverable nitrogen and nitrous oxide (N 0), in addition to the recoverable nitrous vapours formed of NO and N0 variably combined in the form of N 0 which may be oxidized to regenerate nitric acid.
  • consumption of nitric acid means the quantity of nitric acid converted into irrecoverable nitrogen or N 0; it is expressed in mol. of HNO per mol. of oxalic acid formed.
  • the new process may be carried out with highly concentrated nitric acid, it is possible to obtain good yields even with nitric acid of concentrations ranging from 60% to by weight, and the use of such concentrations is preferred.
  • the experimentally determined necessary quantity of fresh nitric acid may be introduced throughout the duration of the reaction.
  • an acid of higher concentration than the starting acid is preferably employed. It is also possible to combine the addition of fresh nitric acid with a recycling through the reactor of nitric acid obtained by oxidation and treatment with water of the nitrous vapours produced by the reaction.
  • the temperature of the reaction depends upon the nitric acid concentration in the reactor. Generally speaking, the operation may be carried out at temperatures ranging from 40 to C., and preferably from 50 to 70 C.
  • the reactor is charged with a predetermined amount of nitric acid, and propylene is gradually introduced in highly divided form (i.e. as a very fine stream of bubbles) and at a rate which, for a predetermined constant concentration of nitric acid in the reactor, depends upon the speed of the reaction (and therefore upon the temperature).
  • the maximum rate of supply is that at which propylene begins to be detectable in the efiluent gases.
  • fresh nitric acid and where appropriate regenerated nitric acid, are added to maintain the nitric acid concentration of the medium at a fixed value of 5 0% or above.
  • the reaction medium is subjected to a finishing to complete the oxidation of the propylene taken up by the reaction medium.
  • a finishing phase it is unnecessary to maintain a constant nitric acid concentration in the medium.
  • the temperature of the finishing phase may be the same as that adopted for the addition of the propylene.
  • the duration of the finishing phase depends upon the temperature. This finishing makes possible a considerable improvement in the oxalic acid yield without increasing the consumption of nitric acid as irrecoverable nitrogen in relation to the amount of propylene introduced.
  • the reaction mass is cooled and dihydrated oxalic acid precipitates as white crystals.
  • the oxalic acid obtained in this way has a purity of 100%.
  • the reactants and the operating conditions employed in the process according to the invention lend themselves particularly well to continuous industrial working.
  • EXAMPLE 1 The apparatus employed is illustrated in the accompanying drawing. It is composed of the following elements: a cylindrical glass reactor 1 having a height of 520 mm., a diameter of 40 mm. and a useful volume of 700 cc.; a conical chamber 2 connected to the lower part of the reactor and connected thereto by a plate 3 of fritted glass No.
  • a coiled condenser 11 (height 150 mm.) supplied with ice-cold water (250 litres per hour) and the atmosphere of which may be placed in communication with an oxygen source 12; a column 13 (height 400 mm., diameter 58 mm.) packed with Raschig rings, below which is mounted a round-bottomed receiver flask 17 which is provided, on the one hand, with a lower lateral pipe connected to the upper part of the condenser 11 and adapted to be connected to the oxygen source 12, and, on the other hand, with an upper lateral pipe; a circulating pump 14 between the receiver flask 17 and the top of the column 13; a column (height 200 mm., diameter 31 mm.), also packed with 'Raschig rings, on which is mounted a distilled-water reservoir comprising a flow regulating valve in the connecting tube; a spherical receiver flask 18 disposed below the column 15 and connected to the upper
  • distilled water is introduced into the reservoir 16 and into the flask 17, the bath is adjusted to a temperature of 50 C. and, while a light current of propylene is passed into the reactor to avoid any admission of liquid into the chamber 2, 539.8 g. of 72.2% nitric acid (i.e. 6.20 mol. of HNO are introduced into the reactor through the dropping funnel 9.
  • the rate of supply of propylene is adjusted to 1.4 litre per hour (0 C./760 mm. Hg).
  • Oxygen is simultaneously admitted to the outlet of the coiled condenser at a rate of 5.3 litres per hour to ensure oxidation of the nitrous vapours emanating from the reactor; part of the vapours is condensed by the condenser 11, the coil of which is cooled by a current of ice-cold water, and returns to the reactor; the remainder of the vapours enters the absorption system consisting of the column 13 sprinkled with liquid taken from 17 by the recycling pump 14 and on the other hand through the column 15 which is sprinkled dropwise by water coming from 16.
  • the reaction mass is then cooled to 25 C., and there is passed through the reactor, above the level of the liquid, for about 20 minutes, a current of oxygen at a rate of 10 litres per hour to ensure the degassing of the apparatus and the oxidation of the nitrous vapours.
  • the reaction mixture is then weighed and a test is made to determine the nitric acid concentration of the reaction mass, and another to determine the oxalic acid formed.
  • the weight of the reaction mass is 616.1 g.
  • the mass is introduced into a three-necked, round-bottomed onelitre flask equipped with a stirring system and a thermometer, and this flask is placed in the preceding apparatus in place of the reactor.
  • the temperature of the products is raised to 50 C. and a current of oxygen is simultaneously admitted (rate of flow 2.3 litres per hour) to the outlet of the coiled condenser.
  • a test is made to determine the oxalic acid formed, and the finishing is then continued for 19 hours at 50 C.
  • the contents of the flask are cooled to 25 C. and degassed as before.
  • the weight of the mixture is 578.8 g., i.e. a loss of 84.4 g. during the finishing phase.
  • Two tests are made, one to determine the oxalic acid and the other to determine the nitric acid concentration in the reaction mass.
  • Determination of the oxalic acid is effected in the conventional manner after it has been isolated by precipitation as calcium oxalate.
  • the nitric acid balance is established by nitrometric determination by means of the Lunge volumenometer, on the one hand on the reaction mixture after finishing, and on the other hand on the nitric acid liquors resulting from the oxidation of the nitrous vapours in the course of the reaction and in the course of the finishing.
  • Recoverable nitrogen in the reactor expressed in mol. of HINO after finishing, 5.62.
  • the reaction medium is left for 16 hours at 5-10" C.
  • Dihydrated oxalic acid precipitates as white crystals.
  • the precipitate is filtered off, washed with cc. of ice-cold water on a filter and then dried at 40 C. to constant weight, 25.8 g. of 100%. pure product are recovered.
  • Oxygen rate of flow: 5.3 l./h.
  • Nitric acid added 150 g. at 93.5%
  • nitric acid In to the reactor are charged 392 g. of 75% nitric acid, the temperature of which is raised to 50 C. by circulation of water through the double jacket. Propylene containing 8% of propane is then passed into the reactor at a rate of fiow of 4.94 litres per hour, i.e. 4.54 litres per hour 100% propylene. Gas extractions are effected every 90 minutes at the outlet of the column for the recovery of the nitrous vapours, and chromatographically analysed. Extractions are simultaneously made from the reactor to determine the nitric acid concentration.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US876220A 1965-04-07 1969-12-01 Preparation of oxalic acid Expired - Lifetime US3651135A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR12311A FR1528569A (fr) 1965-04-07 1965-04-07 Préparation d'acide oxalique

Publications (1)

Publication Number Publication Date
US3651135A true US3651135A (en) 1972-03-21

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ID=8575862

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US876220A Expired - Lifetime US3651135A (en) 1965-04-07 1969-12-01 Preparation of oxalic acid

Country Status (7)

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US (1) US3651135A (fr)
BE (1) BE679159A (fr)
DE (1) DE1593296A1 (fr)
FR (1) FR1528569A (fr)
GB (1) GB1110474A (fr)
LU (1) LU50838A1 (fr)
NL (1) NL152841B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2714201C1 (ru) * 2016-09-12 2020-02-13 Тал Ор Еколоджй Лтд. Извлечение щавелевой кислоты из промышленного оксалата железа

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2714201C1 (ru) * 2016-09-12 2020-02-13 Тал Ор Еколоджй Лтд. Извлечение щавелевой кислоты из промышленного оксалата железа
US10843994B2 (en) 2016-09-12 2020-11-24 Tal Or Ecology Ltd. Recovery of oxalic acid from industrial ferrous oxalate

Also Published As

Publication number Publication date
FR1528569A (fr) 1968-06-14
BE679159A (fr) 1966-10-06
DE1593296A1 (de) 1971-09-16
GB1110474A (en) 1968-04-18
NL6603748A (fr) 1966-10-10
NL152841B (nl) 1977-04-15
LU50838A1 (fr) 1966-06-06

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