III US005187301A United States Patent 19) 11 Patent Number: 5,187,3019 9 Cullen et al. (45) Date of Patent: k Feb. 16, 1993 54 PREPARATION OF 3,412,137 11/1968 Stutts et al. ...................... 260/465.5 IMINODIACETONITRILE FROM 3,904,668 9/1975 Gaudette et al. ... 260/465.5. A GLYCOLONTRILE 3,988,360 10/1976 Gaudette et al. ............ 260/465.5. A 4,543,215 9/1985 Brunnmueller et al. ......... 260/465.5 75 Inventors: Barry A. Cullen, Lyndeboro; Brian 4,661,614 4/1987 Most et al. .......................... 558/346 A. Parker, Nashua, both of N.H. 4,895,971 1/1990 Su et al. .............................. 558/346 4,948,909 8/1990 K t al. ....................... 558/346 73) Assignee: W. R. Grace & Co.-Conn., New York, / oenge N.Y. FOREIGN PATENT DOCUMENTS * Notice: The portion of the term of this patent 3242.193 5/1984 Fed. Rep. of Germany . subsequent- - - to Jul. 16, 2009 has been o: 2. 3: Eleapan . disclaimed. 744675 2/1956 United Kingdom . (2) Appl. No. 97.27 OTHER PUBLICATIONS 22) Filed: Oct. 11, 1990 Eschweiler, Ann 278 (1894) pp. 232-243 (Translation of Related U.S. Application Data pp. 235-238 included). (63) continuation-in-partabandoned. of ser. No. 427,414, Oct. 26, 1989, Attorney,Primary ExaminerAgent, or Firm--KevinJoseph Paul S.Brust Lemack; William L. Baker 51) int. Cl. ............................................ C07C 253/30 52 U.S. C. ..................................... 558/.455; 558/346 (57) ABSTRACT 58) Field of Search ................................ 558/346,455 A process for producing iminodiacetonitrile (IDAN) 56) References Cited from glycolonitrile and ammonia or its salt is disclosed. In the batch process, pH is controlled with the addition U.S. PATENT DOCUMENTS of ammonia or suitable acids. In the continuous process, 2,442,547 6/1948 Mostek ................................ 260/464 glycolonitrile and ammonia are reacted in near stoichio 2,511,487 6/1950 Thompson ... 260/465.5 metric amounts at a temperature from about 90° C. to 2,731,490 1/1956 Barsky .......... ... 260/465.6 about 180° C. 2,752,383 6/1956 Belt ...... ... 260/465.6 2,794,044 5/1957 Miller ....... ... 260/465.5 3,167,580 1/1965 Saunders .......................... 260/465.5 11 Claims, 10 Drawing Sheets U.S. Patent Feb. 16, 1993 Sheet 1 of 10 5,187,301 k O U.S. Patent 5,187,301 y (i) 28, - - - - sesale - pc. 6 FG.2O 22 24 U.S. Patent Feb. 16, 1993 Sheet 3 of 10 5,187,301 FIG. 3 OO% 8O% 6 O % pH 5.3 e 90c 4O96 O OO 2OO TIME MNS. o 96/98 DAN 093/96 GLYCOLO 96/96 GLYCINO U.S. Patent Feb. 16, 1993 Sheet 4 of 10 5,187,301 FG. 4 pH 5.55 629O'C O 5O OO 5O 2OO 25 O TIME MNS o 96/98 DAN go 96/96 GLYCOLO 96/96 GLYCINO U.S. Patent Feb. 16, 1993 Sheet 5 of 10 5,187,301 F.G. 5 OO% 8O% 6O% pH 5.90 (P 90'C 4O% 2O% O 3O 6O 90 20 5O 8O 2 IO 24O TIME MINS O 96/98 DAN O 96/96 GLYCOLO a %/% GLYCINo U.S. Patent Feb. 16, 1993 Sheet 6 of 10 5,187,301 F.G. 6 OO96 6 O % pH 6.05 GP 90 C 4. O % 2O% O OO 2OO TIME MINS O 96/96. DAN 0 %/% GLYCOLO 96/96 GLYCINO U.S. Patent Feb. 16, 1993 Sheet 7 of 10 5,187,301 F.G. 7 OOO% 6 O O % pH 6.3 (0.90c OO% O 20 40 6O 8O OO2O 4O 6O 22024o TME MNS G 96/96. DAN 0%/% GLYCOLO 96/96 GLYCNO U.S. Patent Feb. 16, 1993 Sheet 8 of 10 5,187,301 FG. 8 80.00% / - DECREASE IN YELD DUE TO POLYMER FORMATION CORRESPONDING RISE IN pH NOTED 7OOO% O 2O 4O 6O 8O OO 2O TIME MNS O 96/96. DAN U.S. Patent Feb. 16, 1993 Sheet 9 of 10 5,187,301 FG. 9 96 EXACTLY 2 MOLE RATIO GLYCOLONTRILE TO NH3 EXAMPLES 6- 9 O 2 3 4. RETENTION TIME ( MNS) to 96 CONVERSION U.S. Patent Feb. 16, 1993 Sheet 10 of 10 5,187,301 FIG. O 93 EXACTLY 2 I MOLE RATIO GLYCOLONITRILE TO NH3 EXAMPLES 25-28 92 9 | 9 O 89 88 87 . 2 3. 4. RETENTION TIME ( MNS ) - G 96 CONVERSION 5,187,301 1. 2 FIG. 2 illustrates laboratory apparatus used to carry PREPARATION OF MINODIACETONTRLE out the continuous embodiment of the present inven FROM GLYCOLONTRLE tion; FIGS. 3-7 are graphs of the yield of IDAN and This application is a continuation-in-part of applica glycinonitrile and the conversion of glycolonitrile at tion Ser. No. 427,414, filed Oct. 26, 1989, now aban various PH's; doned. FIG. 8 is an exploded graph of the IDANyield curve of FIG. 7; and BACKGROUND OF THE INVENTION FIGS. 9-10 are plots of residence time vs. 76 conver 1. Field of the Invention 10 sion of glycolonitrile to IDAN This invention relates to the conversion of glycoloni trile to iminodiacetonitrile. DETAILED DESCRIPTION OF THE 2. Description of the Prior Art INVENTION Numerous methods for preparing iminodiacetonitrile On an industrial scale, the formation of IDAN from (IDAN) are disclosed in the prior art. For example, 15 hydrogen cyanide, formaldehyde and ammonia requires U.S. Pat. No. 2,511,487 to Thompson teaches reacting purified, commercial grade hydrogen cyanide and aminoacetonitrile with formaldehyde cyanhydrin at a formaldehyde in order to obtain product in high enough temperature of about 50' C. to 150° C. in the absence of yield t be economically feasible. Purification of crude alkali. HCN and formaldehyde adds substantial cost and time U.S. Pat. No. 2,794,044 to Miller discloses reacting 20 to the IDAN production process. ammonia, formaldehyde and hydrogen cyanide in a Accordingly, the instant invention is directed to a molar ratio of 2:3:3 at a pH of 5.5 to 6.5 and a tempera process for preparing IDAN by reacting preformed ture of from about O' C. to 50 C. for 10-24 hours. glycolonitrile with an ammonia source. The glycoloni U.S. Pat. No. 3,167,580 to Saunders, et. al. discloses trile can be formed by optionally using crude reaction reacting hydrogen cyanide, ammonia and formaldehyde 25 gases from an HCN reactor and a HCHO reactor as while critically controlling the mixing of the reactants, starting reactants without sacrificing reaction time or the mole ratio of each of the reactants, the temperature product yield. Specifically, crude (or purified) HCN and pH of the reaction, and the residence time of the and crude (or purified) formaldehyde are reacted to reactants. form glycolonitrile. This reaction removes heat in that U.S. Pat. No. 3,412,137 to Stutts discloses preparing 30 it is exothermic, releasing approx. 10 Kcal/g. Mole. In IDAN by reacting hexamethylenetetramine with about addition, the glycolonitrile so produced is a stable, non 6 molar equivalents of hydrogen cyanide in a buffered volatile product that can be stored at ambient tempera te. aqueous medium at a pH of from about 5 to 6.5 and a The reaction sequence is illustrated as follows: temperature of between about 0' and 75° C. 35 U.S. Pat. No. 4,661,614 to Most et. al. discloses pre paring IDAN by reacting formaldehyde, hydrogen HCN+CHO-CH2OHCN (l) cyanide and a source of ammonia under substantially stoichiometric conditions at a temperature between about 30' C. and 65' C. and a pH between about 1.5 and 40 In Reaction #1, glycolonitrile is formed in a process 5.5. (either batch or continuous) by maintaining the pH of However, each of the foregoing processes suffers the formaldehyde above about 3, preferably in a range from various drawbacks, such as the added burden of of about 5-7, most preferably about 5.5, with suitable forming complex starting reactants, poor yield, critical acids and bases, such as acetic acid or sulfuric acid and reaction conditions, etc. 45 sodium hydroxide or ammonia. It will be obvious to those skilled in the art that other acids and bases can be SUMMARY OF THE INVENTION used for pH adjustment. The exact pH used will depend The problems of the prior art have been overcome by on the particular configuration of the equipment. The the instant invention, which provides a novel process formaldehyde is then reacted with hydrogen cyanide in for producing iminodiacetonitrile by reacting pre 50 a temperature range of about 20-80 C., preferably formed glycolonitrile with an ammonia source. about 30 C. to form glycolonitrile. It is therefore an object of the invention to provide a Suitable sources of hydrogen cyanide and formalde new and improved process for the production of hyde to form the glycolonitrile can comprise crude, ininodiacetonitrile. unpurified product streams from hydrogen cyanide and It is a further object of the invention to provide a 55 formaldehyde production processes. For example, com process of producing iminodiacetonitrile in high yield mercially available hydroge cyanide is produced pri and low cost. marily by the ammoxidation of methane, the reaction of A still further object of the invention is to provide a ammonia and propane (alkane ammono-dehydrogena process for producing iminodiacetonitrile from a stable tion), the ammoxidation of methanol, the dehydration intermediate and without the requirement for storing of formamide, and the recovery of hydrogen cyanide as volatile and unstable HCN. the by-product in the preparation of acrylonitrile by the Another object of the invention is to provide a pro ammoxidation of propylene.