US2294849A - Manufacture of nitric acid esters - Google Patents

Manufacture of nitric acid esters Download PDF

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Publication number
US2294849A
US2294849A US225908A US22590838A US2294849A US 2294849 A US2294849 A US 2294849A US 225908 A US225908 A US 225908A US 22590838 A US22590838 A US 22590838A US 2294849 A US2294849 A US 2294849A
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United States
Prior art keywords
nitric acid
alcohol
water
nitrate
reaction
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Expired - Lifetime
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US225908A
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English (en)
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John F Olin
Frederick P Fritsch
Joseph J Schaefer
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Sharples Chemicals Inc
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Sharples Chemicals Inc
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Priority to US225908A priority Critical patent/US2294849A/en
Priority to GB5722/40A priority patent/GB540050A/en
Priority to NL97876A priority patent/NL65504C/xx
Priority to FR867145D priority patent/FR867145A/fr
Priority to CH237619D priority patent/CH237619A/de
Priority to BE440425D priority patent/BE440425A/xx
Application granted granted Critical
Publication of US2294849A publication Critical patent/US2294849A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/02—Preparation of esters of nitric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C203/00—Esters of nitric or nitrous acid
    • C07C203/02—Esters of nitric acid
    • C07C203/04—Esters of nitric acid having nitrate groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C203/00—Esters of nitric or nitrous acid
    • C07C203/02—Esters of nitric acid
    • C07C203/08—Esters of nitric acid having nitrate groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • This invention relates to a process for the preparation of nitrate esters from aliphatic alcohols.
  • the nitration of aliphatic alcohols to obtain esters of nitric acid has long presented a problem of considerable commercial importance.
  • the potential importance of such esters is very great since they are useful as intermediates in the preparation of a wide variety of organic chemicals in addition to possessing properties that render them suitable for many purposes as ultimate products.
  • that of ignition promotion in Diesel engines is believed to be highly important. For example, a relatively small quantity of an alkyl nitrate improves the combustion characteristics of Diesel fuel to a remarkable degree.
  • nitrates from methyl, ethyl, propyl, butyl and amyl alcohols Two procedures for the preparation of nitrates from methyl, ethyl, propyl, butyl and amyl alcohols have been described.
  • One method which has been used to prepare nitrates from monohydric alcohols containing less than three carbon atoms, consists essentially in the distillation of a mixture of nitric acid and alcohol in the presence of urea.
  • the nitrate formed is readily volatilized and may be distilled from the reaction zone to prevent accumulation of the ester in the nitrating vessel which might otherwise result in explosions. Since the presence of even small amounts of nitrous acid tends to initiate a vigorous auto-oxidation of explosive violence, urea is added to decompose nitrous acid as formed in accordance with the following equation:
  • the methyl and ethyl nitrates may be prepared with fairly good results, but the method is not suitable for the nitration of alcohols containing three or more carbon atoms.
  • higher temperatures are required to obtain the esterifcation reaction than when the lower alcohols are nitrated.
  • Higher reaction occurring incident to nitration of the alcohol and therefore preventing the successful practice of the nitration process.
  • the oxidation of the alcohol can be to some eX- tent prevented by the addition of urea to the reaction mixture, but even when this precaution is taken the yield of the desired nitrate is still very low.
  • An object of this invention has been the provision of a process for reacting an aliphaticl
  • Experimental determinations indicate that amyl nitrate and water form a constant boiling mixture at 20 mm. absolute pressure containing 1.8'parts of water to 1 part of ester and that mixed amyl alcohols distilled with water at the same pressure give a constant boiling mixture in which Water and alcohol are present in the approxi mate ratio of 125:1. On this basis it was calculated that -a 40% nitric acid solution should give satisfactory results at 20 mm. of mercury absolute pressure. In actual practice under such conditions it was found that the ratio of water to ester in the distillate was unexpectedly high.
  • esterication of an aliphatic alcohol proceeds through the formation of an oxonium derivative of very low vapor pressure. From that intermediate compound, the ester is formed by loss of water, but in the presence of concentrated nitric acid, the oxonium derivative is oxidized to form undesired by-products.
  • the concentrated nitric acid When concentrated nitric acid is used, the concentrated nitric acid also causes auto-oxida- Cil tion of the alkyl nitrate formed in accordance with Equation 2 above, with the result that the contents of the reaction vessel frequently explode.
  • the operator desiring to produce amyl nitrate, for example, is on .the horns of a dilemma when attempting to operate in acocrdance with the prior art procedure for producing methyl and ethyl nitrates. If he initiates the reaction with the use of a concentrated nitric acid, the initial reaction involves undesired production of valeraldehyde and reduction of the nitric acid as indicated in Equation 3.
  • Equation 2 water formed incident to the esterication reaction as indicated in Equation 2 rapidly dilutes the reaction mixture and reduces the nitric acid to a concentration at which it will not efficiently perform its nitrating function.
  • the applicants conceived the present invention and solved the difficulties of the prior art procedures by developing nitration technique whereby the concentration of the nitric acid in the esterication vessel may be maintained substantially constant, and may be maintained at such point as to effectively accomplish the nitration function while minimizing the occurrence of the undesired reaction of Equation 3, and minimizing the occurrence of auto-oxidation of the alkyl nitrate formed in accordance with Equation 2.
  • autooxidation in the esterication vessel is prevented by removing the alkyl nitrate from the esterication vessel promptly after the formation thereof and water is removed with the alkyl nitrate in the form of an azeotropic mixture.
  • the amount of water necessary to maintain the desired dilution of the nitric acid in the esterication vessel may be added to the esterication vessel, when necessary, in the form of a diluent for the nitric acid and/or alcohol added to the esterication vessel from vtime to time and a.
  • part of the water required for such dilution may be returned to the esterication vessel from the azeo- Vtropic mixture removed from the vessel by condensing and decanting this azeotropic mixture and returning the water so decanted to the esterification vessel.
  • the azeotropic distillation of the mixture of water, alkyl nitrate, alcohol and nitric acid from the esterication vessel is accomplished in accordance with the preferred embodiment of the invention by maintaining a sub-atmospheric pressurein that vessel.
  • the maintenance of such sub-atmospheric pressure enables the operator to remove the azeotropic mixture from the vessel without the application of excessive heat, and thus to maintain'the reaction mixture at a lower temperature than could be maintained if distillation were attempted at atmospheric pressure.
  • the reaction of Equations 1 and '2 is favored, the reaction of Equation 3 is suppressed, and auto-oxidation of the alkyl nitrate is suppressed.
  • urea Since there is usually a tendency toward formation of nitrous acid in the reaction mass which will initiate oxidation if permitted to accumuiate, it is preferred that a small proportion of urea be added to the vessel in which the present process is practiced. As a general rule the proportion of urea added is less than that employed in the process of the prior art, but as a precaution against decreased yields, inferior grade ester, and explosion it is always well to follow the practice of adding 'at least a small amount of urea.
  • I, 2 and 3 designate storage tanks for alcohol, 50% urea solution and 70% nitric acid, respectively, each connected by a valved pipe to reaction vessel 4.
  • the reaction vessel is equipped with a condenser 6.
  • a pipe to convey distillate connects condenser 6 to a decanter l, adapted to separate the distillate into two layers of substantially immiscible liquids of different specific gravity.
  • the draw-oir lines for the decanter are preferably adapted to be transposed in order that either the lighter or heavier liquid can be passed to storage vessel 8, While the other layer is recycled, at least in part, to reaction vessel 4, through a line having an outlet controlled by valve 9 to permit withdrawal of water from the system.
  • nitric acid of the desired concentration is supplied to reaction vessel 5, together with a. small quantity of vurea, the pressure reduced in the system to the desired point and heat applied to vessel until rapid boiling of the acid is begun.
  • Molecular equivalents of aliphatic alcohol and nitric acid from tanks l and 3 are slowly run into vessel 0 at a xed rate and enough urea solution is added from tank 2 continuously or intermittently to substantially inhibit oxidation due to the presence of nitrous acid.
  • the vapors rising from the reaction mass pass through the column 5 to condenser 6 from which a distillate containing alkyl nitrate, alcohol, water and a little nitric acid is conducted to decanter 1.
  • the distillate separates into two layers.
  • the upper layer in most instances contains alkyl nitrate and alcohol which is passed continuously to storage vessel 8, from which it is Withdrawn for purification.
  • the water layer may be used in part to dilute the 70% nitric acid to the desired degree, but since Water is obtained as a result of the reaction, it is necessary to continuously withdraw a part thereof from the system through valve 9 in order to maintain the quantity of water in the vessel i substantially constant. Ester is withdrawn from storage vessel 8 and purified.
  • ester-alcohol layer in the decanter is generally lighter than the water layer, it must be borne in mind that some esters such as 2- chloroethyl nitrate, are heavier than water, and the decanter connections must be interchanged in such esterication operations.
  • EXAMPLE 1 n-Butyl nitrate-Using the apparatus described above n-butyl nitrate was prepared by the reaction of nitric acid on n-butanol. The reactor was initially charged with 10 mols of a 50% aqueous solution of nitric acid which was then vigorously boiled at a pressure of about 400 mm. of mercury absolute, which pressure was maintained substantially constant throughout the run. 20 mols of n-butyl alcohol and 22 mols of nitric acid in the form of .a 70% solution were added during the course of the experiment. The average temperature in the reaction vessel was approximately 97 C. Small quantities of 50% urea solution were added from time to time in order to inhibit oxidation.
  • the crude ester was washed, neutralized, dried and fractionated at reduced pressure to obtain 17.3 mols of butyl nltrate and 1.23 mols of butyl alcohol. Approximately grams of material was lost in the process of purifying the crude ester.
  • the normal butyl nitrate was obtained in a state of high purity as a clear water-white liquid of mild ethereal odor, having a specific gravity of 1.032 at 20 C. and a boiling point of 133 C. at a pressure of 29.62 inches of mercury.
  • the conversion of butanol to butyl nitrate was 86.5% of the original charge With a yield of 92.2% based on the alcohol consumed during the process.
  • EXAMPLE 3 Methyl nitrates-A mixture of isomeric primary and secondary amyl' alcohols was nitrated. The original charge was 15.5 mols of nitric acid as a 50% solution under an absolute pressure of 300 mm., 48 mols of the mixed amyl alcohols were added to the boiling acid in the reactor together With 40 mols of nitric and 154.2o c.r
  • the milicia was a colorless liquid boiling at 52 C. under 2 mm. 'pressure and atfl'lfi C. under rpressure vwith 50% nitricr acid gave a good yield mol per-,mol of ester) wheny considered withl thev vsame data in 'connection' with 'the nitration of -oi the .present type. y acid as used in this disclosure and in the claims y -use of'concentrated acids, thatis.
  • nitric acid conf taining substantiallyA more than y'10%' HNO:y is possible under very closely controlled conditions but should be avoided in most nltration reactions f
  • the lterm dilute nitric appended hereto isto be understood as referring vto an acid containing HNOinot substantially in excess of ,70%. f It has beeninoted that extremely nizraieQ-Nirrauon of ynormal hexyl nitrate yas a light colored liquid: 40
  • the acid in storage tank 3 has contained 30% of water (specic gravity of 1.42).
  • water preferably that decanted from the raw product in order to conserve the acid content thereof, is added to the 70% acid in such ratio as to dilute the strong acid to the desired concentration.
  • a nitric acid solution is placed in the reaction vessel and heated to vigcrous boiling under reduced pressure. Alcohol and nitric acid are then continuously added to the heated mass in substantially molecular proportions.
  • a portion of the water in the distillate (containing some nitric acid) is decanted therefrom and used to dilute the acid supplied to the reaction.
  • water equivalent to that formed by the nitration plus the amount used to dilute the acid as added is Withdrawn from the system as a lay-product inthe form of dilute nitric acid.
  • the absolute pressure permissible may be any subatmospheric pressure although it is highly desirable to operate at pressures above 20 mm. of mercury. In general, it has been determined that a-bsolute pressures within the range of 50 mm. to 650 mm. of mercury give good results although much better results are obtained by maintaining the pressure at 250-400 mm. abso ⁇ lute. As the pressure is reduced below 250 mm. the conversion of alcohol to nitrate is decreased. Pressures above the preferred range result in low yields, due to the increased tendency toward oxidation.
  • aliphatic hydroxy compound is to be understood as ⁇ contemplating those compounds in which an hydroxy radical is attached to a carbon atom of an aliphatic compound or group.
  • the invention includes nitration of alkyl, alicyclic and heterocyclic alcohols, except in the case of heterocyclic compounds, those in which an hydroxyl radical is joined to an aryl grou-p.
  • the invention may be practiced by continuously or intermittently returning ester from the decanter to the esteriiication vessel instead of returning water to the esterni-cation vessel as described in the albove illustrative examples.
  • it will be desirable to return methyl nitrate to the esterification vessel in order that the ratio of methyl nitrate to water in the esteriiication vessel may be suihcient to eiect removal of the water fromthe esterication vessel in the form of an azeotropic mixture.
  • Such return of ester to carry off the water as formed in the form of an azeotropic mixture enables the operator to remove the Water as formed,
  • an entraimng liquid such as benzene, can be intermittently or continuously added to the esterification vessel to increase the ratio of Water to ester in the distillate.
  • alcohol from the tank I may be vaporized and passed into the space above the .boiling nitric acid in the reactor 4, instead of adding this alcohol in the liquid phase.
  • alcohol from the tank I may be vaporized and passed into the space above the .boiling nitric acid in the reactor 4, instead of adding this alcohol in the liquid phase.
  • EXAMPLE l2.-Isopropyl nitrate.l0 mols of nitric acid in the form of a 50% aqueous solution are brought to boiling temperature in the reaction vessel under an absolute pressure of 275 mm. of mercury.
  • nitric acid and iso-propyl alcohol are then added in molecular equivalents, the isopropyl alcohol ibeing preheated and -passed in the vapor phase into the space above the yboiling nitric acid in the reactor 4.
  • the, invention is not necessarily limited to the practice of esterication by a continuous process. tion can be partially realized by returning water or ester to the esterication vessel in such proportions as to reduce the degree of concentration or dilution of the acid in the esterication vessel and thereby avoid the alternative defects of the prior art of over-concentration or overdilution of the acid.
  • the advantages of the invention may also be partially realized in the esterication of some alcohols without the use of vacuum in the practice of the azeotropic distillation.
  • the features of reducing the temperature in the esteriiication vessel by the employment of azeotropic distillation and avoiding or reducing the tendency of the nitric acid to become more dilute or more concentrated as the case may be, as the esterication reaction proceeds have an advantage independent of the advantage obtained by the use of sub-atmospheric pressures in the
  • the advantages of the invenesterication vessel, and these features may be used per se to obtain such advantage.
  • the invention includes the addition of water whether in the form of diluent for the nitric acid, alcohol or urea added during the course of the reaction, in the form of dilute acid decanted from the decanter 1 or in the form of separately added water.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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US225908A 1938-08-20 1938-08-20 Manufacture of nitric acid esters Expired - Lifetime US2294849A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US225908A US2294849A (en) 1938-08-20 1938-08-20 Manufacture of nitric acid esters
GB5722/40A GB540050A (en) 1938-08-20 1940-03-29 Improvements in or relating to manufacture of nitric acid esters
NL97876A NL65504C (xx) 1938-08-20 1940-05-06
FR867145D FR867145A (fr) 1938-08-20 1940-05-15 Perfectionnements à la fabrication des esters nitriques
CH237619D CH237619A (de) 1938-08-20 1940-05-24 Verfahren zur Herstellung aliphatischer Nitrate.
BE440425D BE440425A (xx) 1938-08-20 1941-01-30

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US225908A US2294849A (en) 1938-08-20 1938-08-20 Manufacture of nitric acid esters
GB5722/40A GB540050A (en) 1938-08-20 1940-03-29 Improvements in or relating to manufacture of nitric acid esters
NL97876A NL65504C (xx) 1938-08-20 1940-05-06
FR867145T 1940-05-15
CH237619T 1940-05-24
BE440425T 1941-01-30

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US (1) US2294849A (xx)
BE (1) BE440425A (xx)
CH (1) CH237619A (xx)
FR (1) FR867145A (xx)
GB (1) GB540050A (xx)
NL (1) NL65504C (xx)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647914A (en) * 1950-07-24 1953-08-04 Ici Ltd Manufacture of an alkyl nitrate
US2736742A (en) * 1954-07-08 1956-02-28 Nitroglycerin Ab Method of processing acid nitrated organic products
US2750415A (en) * 1952-07-25 1956-06-12 Du Pont Separation and oxidation of cyclohexyl nitrate and related compounds
US2768964A (en) * 1953-05-27 1956-10-30 Du Pont Production of alkyl nitrates
US2977384A (en) * 1953-07-10 1961-03-28 Ici Ltd Production of alkyl nitrates
US3409620A (en) * 1967-02-06 1968-11-05 Mario Biazzi Sa Dr Ing Continuous manufacture in vacuum of nitric esters and/or organic nitro compounds
US4251455A (en) * 1978-05-12 1981-02-17 Josef Meissner Gmbh & Co. Continuous closed loop nitration of polyhydric alcohols
US4536190A (en) * 1984-04-02 1985-08-20 Ethyl Corporation Cetane improver composition
EP0359335A2 (en) * 1988-09-15 1990-03-21 Cedona Pharmaceuticals B.V. Pharmaceutical composition having relaxing activity which contains a nitrate ester as active substance
US5162568A (en) * 1983-11-21 1992-11-10 E. I. Du Pont De Nemours And Company Nitration of alkanols
US20060128983A1 (en) * 2002-11-14 2006-06-15 Nevio Francescutti Process for the mononitration of alkanediols
CN102557953A (zh) * 2011-12-29 2012-07-11 北京理工大学 一种制备c4～c10烷基直链烃一元醇硝酸酯的方法
WO2021102542A1 (pt) 2019-11-28 2021-06-03 Petróleo Brasileiro S.A. - Petrobras Nitratos de éteres de glicerol e etanol como melhoradores de cetano do diesel e processo de produção dos mesmos
CN113651698A (zh) * 2021-08-17 2021-11-16 西安万德能源化学股份有限公司 一种提高硝酸异丙酯合成后废酸安定性的处理方法
RU2780865C1 (ru) * 2022-04-14 2022-10-04 Общество с ограниченной ответственностью "ГЕНХИМСНАБ" Способ получения цетаноповышающей присадки н-бутилнитрат

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL89497C (xx) * 1953-09-16 1900-01-01
DE1046007B (de) * 1954-07-02 1958-12-11 Nynaes Petroleum Ab Verfahren zur Herstellung von Isopropylnitrat

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647914A (en) * 1950-07-24 1953-08-04 Ici Ltd Manufacture of an alkyl nitrate
US2750415A (en) * 1952-07-25 1956-06-12 Du Pont Separation and oxidation of cyclohexyl nitrate and related compounds
US2768964A (en) * 1953-05-27 1956-10-30 Du Pont Production of alkyl nitrates
US2977384A (en) * 1953-07-10 1961-03-28 Ici Ltd Production of alkyl nitrates
US2736742A (en) * 1954-07-08 1956-02-28 Nitroglycerin Ab Method of processing acid nitrated organic products
US3409620A (en) * 1967-02-06 1968-11-05 Mario Biazzi Sa Dr Ing Continuous manufacture in vacuum of nitric esters and/or organic nitro compounds
US4251455A (en) * 1978-05-12 1981-02-17 Josef Meissner Gmbh & Co. Continuous closed loop nitration of polyhydric alcohols
US5162568A (en) * 1983-11-21 1992-11-10 E. I. Du Pont De Nemours And Company Nitration of alkanols
US4536190A (en) * 1984-04-02 1985-08-20 Ethyl Corporation Cetane improver composition
EP0359335A2 (en) * 1988-09-15 1990-03-21 Cedona Pharmaceuticals B.V. Pharmaceutical composition having relaxing activity which contains a nitrate ester as active substance
EP0359335A3 (en) * 1988-09-15 1991-03-06 Cedona Pharmaceuticals B.V. Pharmaceutical composition having relaxing activity which contains a nitrate ester as active substance
US7851649B2 (en) 2002-11-14 2010-12-14 Dipharma S.P.A. Process for the mononitration of alkanediols
US7335789B2 (en) * 2002-11-14 2008-02-26 Dipharma S.P.A. Process for the mononitration of alkanediols
US20080146830A1 (en) * 2002-11-14 2008-06-19 Dipharma S.P.A. process for the mononitration of alkanediols
US20060128983A1 (en) * 2002-11-14 2006-06-15 Nevio Francescutti Process for the mononitration of alkanediols
CN102557953A (zh) * 2011-12-29 2012-07-11 北京理工大学 一种制备c4～c10烷基直链烃一元醇硝酸酯的方法
CN102557953B (zh) * 2011-12-29 2013-11-06 北京理工大学 一种制备c4～c10烷基直链烃一元醇硝酸酯的方法
WO2021102542A1 (pt) 2019-11-28 2021-06-03 Petróleo Brasileiro S.A. - Petrobras Nitratos de éteres de glicerol e etanol como melhoradores de cetano do diesel e processo de produção dos mesmos
CN113651698A (zh) * 2021-08-17 2021-11-16 西安万德能源化学股份有限公司 一种提高硝酸异丙酯合成后废酸安定性的处理方法
CN113651698B (zh) * 2021-08-17 2024-01-12 西安万德能源化学股份有限公司 一种提高硝酸异丙酯合成后废酸安定性的处理方法
RU2780865C1 (ru) * 2022-04-14 2022-10-04 Общество с ограниченной ответственностью "ГЕНХИМСНАБ" Способ получения цетаноповышающей присадки н-бутилнитрат

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BE440425A (xx) 1941-02-28
NL65504C (xx) 1950-04-15
FR867145A (fr) 1941-10-02
GB540050A (en) 1941-10-03
CH237619A (de) 1945-05-15

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