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United States Patent [191 [111 3,799,993 Hill Et Al United States Patent [191 [111 3,799,993 Hill et al. [45] Mar. 26, 1974 [54] PROCESS FOR THE MANUFACTURE OF 2,475,095 7/1949 Hoek ................................ .. 260/645 TRINITROTOLUENE 2,934,571 4/1960 Bonetti . .. 260/645 [75] Inventors: Marion E. Hill, Palo Alto; Wesley E. 3,708,546 1/1973 Coon et al. ....................... .. 260/645 Towel-g, Atherton; Gerald J_ FOREIGN PATENTS OR APPLICATIONS McDonald, Menlo Park, all of Calif. 752,608 7/1956 Great Britain .................... .. 260/645 [73] Assignee: The United States of America as 1,054,571 1 / 1967 G rem B mam' ' .................... .. 260 / 645 rAegrlesewzghlg ‘t2: slejclémry of the Primary Examiner-Leland A. Sebastian y’ g ’ ' ' Attorney, Agent, or Firm-Edward J. Kelly; Herbert [22] Filed: Aug. 25, 1972 Berl; A. Victor Erkkila '[21] Appl. No.1 283,694 [57] ABSTRACT [52] 0.5. CI. ............................... .. 260/645, 260/688 Process for Preparing TNT comprises nitrating toluene [51] Int. Cl. .......................................... .. C07c 79/10 with an anhydrous nitraiing agent NOZHSO4 obtained {58] Field of Search ................................... .. 260/645 by mixing HNOQ and oleum- The Process eliminates pollution problems associated with conventional man [ 56] References Cited ufacturing processes and produces TNT in high yields UNITED STATES PATENTS and rapid reaction rates. 2,297,733 10/1942 Wyler et a1. ...................... .. 260/645 14 Claims, 1 Drawing Figure TOLUENE HNO3+ 803 l DNT + H 2 504 l 80% TNT DINITRATOR r TRINITRATOR ——> To ‘r WORKUP NITRATING ACID ONT 20% ' RECYCLE ACIDS SOLVENT I EXTRACTION ,.___> SURPLUS H2 so4ro ACID RECOVERY PMENTEDHARZS m4 3799.993 TOLUENE HNO3+ 803 l DNI+ H2 304 80% l TNT DINITRATOR + TRINITRATOR ->T° A WORKUP NITRATING ACID MT 20% v RECYCLE ACIDS SOLVENT , EXTRACTION ‘_____> SURPLUS H2 504 TO ACID RECOVERY 3,799,993 1 2 PROCESS FOR THE MANUFACTURE OF by ?ltration and washed with water to remove adhering TRINITROTOLUENE acid. The concentrated nitric acid-sulfuric acid mother liquors have a high capacity for retaining impurities in The invention described herein may be manufac solution so that a TNT product of excellent purity is tured, used and licensed by or for the Government for 5 thus obtained directly. If desired, a TNT product of governmental purposes without the payment to us of greater purity can be obtained by washing the TNT any royalties thereon. crystals, prior to washing with water, with concentrated sulfuric acid and/or nitric acid. BACKGROUND OF THE INVENTION The invention relates to a process for producing TNT BRIEF DESCRIPTION OF THE DRAWING (2,4,6-trinitrotoluene). In particular the invention re The drawing shows a schematic flow diagram of a lates to a process for nitrating toluene to produce TNT. continuous closed-loop process for manufacturing TNT is conventionally manufactured by a multistep TNT from toluene according to this invention. process, wherein toluene is ?rst nitrated with a mixture of nitric acid and sulfuric acid to produce MNT "oEscRiRrIoN 0? THE PREFERRED (mononitrotoluene), the MNT is then nitrated to DNT EMBODIMENTS (dinitrotoluene) and the DNT is ?nally nitrated to We consider that the high reactivity of the anhydrous TNT, the acid strength and temperature being in nitrating mixture of HNO3 and oleum is due in part to creased for each nitro group introduced. The TNT ob the formation of nitronium bisulfate (NO2HSO4) from tained contains small amounts of other TNT isomers in 20 HNO3 and S031 addition to the desired 2,4,6-isomer as well as DNT iso mers, which must be removed in order to produce a TNT of sufficient purity for use as a military explosive. The stoichiometric conversion of HNO3 to this nitro Such purification is usually accomplished by a selliting nium salt provides a high concentration of nitronium process, which involves treating the crude TNT with 25 ion, which is recognized as the reactive species in most aqueous sodium bisulfite solution, which selectively ex aromatic nitration reactions. The favorable solvation tacts the undesired TNT isomers from the desired effect provided by anhydrous H2804 also contributes to 2,4,6~isomer. The waste liquors resulting from such sel the high reactivity of the system. liting operations, called “red water," cannot be eco US. Pat. No. 2934571 discloses a process for pro nomically puri?ed without creating a serious pollution ducing DNT substantially instantaneously and in nearly problem. In addition, large amounts of nitrogen oxide quantitative yield by contacting toluene with a mixture fumes are evolved from the nitration reactors and cre of l-INOa and oleum at a temperature between —50° C ate a serious atmospheric pollution problem, which is and 60° C. However, the process of this patent is lim costly to alleviate. ited to the production of DNT and other aromatic com 35 pounds containing not more than 2 nitro groups. SUMMARY OF THE INVENTION We have now found that TNT can be obtained in An object of the present invention is to provide a pro over 9Q% yield and rapid reaction rate by nitrating cess for nitrating toluene to TNT in high yields and DNT with a mixture of HNO3 and oleum at a tempera rapid reaction rates. ture of about 70° C or higher. We have also unexpect Another object is to provide a novel process for ni 40 edly found that the nitration of toluene in the aforesaid trating DNT to TNT in high yields. manner produces a DNT containing less than 2% of A further object is to provide a process for nitrating meta isomers, which is only half as much as in the cur toluene to TNT, which produces TNT of military speci rent TNT process of manufacture; and that by nitrating fication grade, eliminates the polluting nitrogen oxide the DNT further with a nitrating mixture of l-INO3 and fumes emanated from the conventional nitration reac oleum, a TNT product can be directly obtained having tions and eliminates the sellite process with its atten a purity suf?cient for military use. dant red water disposal problem. In carrying out the nitration of toluene to DNT with A still further object is to provide a process for nitrat an anhydrous mixture of HNO; and oleum according to ing toluene which minimizes the formation of metal iso the present invention, two moles of l-INO3 are theoreti mers, maximizes the ratio of 2,4- to 2,6-DNT isomers cally required to introduce two nitro groups into each produced and maximizes the yield of desired 2,4,6 mole of toluene; however, it is preferable to employ a TNT isomer. small molar excess of I-INO3, e.g. about 5%, over the Another object is to provide a continuous, closed theoretical amount required so as to maximize the yield loop process for nitrating toluene to TNT. of DNT produced. Considerably higher molar ratios of 55 These and other objects and advantages are achieved HNOg to toluene, e.g. 3 to 8 moles of l-INOa per mole by the process of this invention, which is based on the of toluene, can be employed to accomplish the dinitra use of an extremely active anhydrous nitrating mixture tion reaction at the low temperatures employed in the prepared from HNO3 and oleum. In accordance with present process, but provide no technical advantage. the process ofthis invention, toluene is nitrated to DNT Further, it is preferable to employ a small, e.g. about a by reacting it at temperatures below about 40° C with 10% molar excess of I-INOQ relative to free S03, since an anhydrous mixture of I-INOa and oleum, and the an excess of SO; over HNO3 is undesirable due to the DNT thus produced is nitrated to TNT, without isola competing sulfonation reaction with toluene. The ratio tion from the dinitration reaction mixture, by treatment of free 30;, to H280, in the oleum employed is rela at a temperature of at least about 70° C with an anhy 65 tively less important and is conveniently about I part drous mixture of l-INOa and oleum. When the trinitra by weight per 4 parts H2804. The nitration of toluene tion reaction is complete, the reaction mixture is to DNT can be carried out at minus 40°-50° C or lower; cooled to precipitate the TNT, which is separated, as but it is preferably carried out at a temperature not ex 3,799,993 3 4 ceeding about +l0° C and especially at between about A nitrating mixture of 25.1 g (398 mmoles) of abso —l0° C and —20° C. At these preferred temperatures lute nitric acid and 143.9 g of 20% oleum consisting of the dinitration is rapid and the production of undesired 29.6 g (370 mmoles) free 80;, and I 14.3 g H280, was meta isomers is minimized. Reaction temperatures placed in a two-piece glass reactor provided with a above about 40° C. are undesirable, since they promote thermometer and a glass agitator shaft with a Te?on the formation of undesired meta isomers. blade. The bottom part of the reactor was a 100 ml After the dinitration reaction is complete, the reac ?ask, which was joined to the top by a ground glass tion mixture containing the DNT and spent acid liquor ?ange and was ?tted with an internal glass coil for heat can be charged with fresh HNO; and S03, as required, ing the contents with steam or cooling with water; and and the resulting mixture is heated to a temperature of H) the top part was ?tted with a thermometer port and about 70° C or higher, preferably between 70° and 100° three other ground glass joints. l 7.3 g (188 mmoles) of C., and especially about 90° C., to effect the nitration toluene (re?ned grade) were added dropwise during of DNT to TNT.
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