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Process for the Preparation of Iminodiacetonitrile and Iminodiacetic Acid

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Process for the Preparation of Iminodiacetonitrile and Iminodiacetic Acid Europaisches Patentamt 3 European Patent Office © Publication number: 0 413 673 A2 Office europeen des brevets © EUROPEAN PATENT APPLICATION © Application number: 90870125.3125.3 © int. ci A C07C 255/25, C07C 229/16 © Date of filing: 13.08.90 © Priority: 14.08.89 US 394039 © Applicant: MONSANTO COMPANY Patent Department 800 North Lindbergh @ Date of publication of application: Boulevard 20.02.91 Bulletin 91/08 St. Louis, Missouri 63167(US) © Designated Contracting States: @ Inventor: Koenig, Karl Eric AT BE CH DE DK ES FR GB GR IT LI LU NL SE 1912 Gastorf Pointe Court Ballwin, Missouri 63011 (US) Inventor: Morrison, Paul Arthur 852 Hyde Park Drive Arnold, Missouri 6301 0(US) Inventor: Lanser, Gary Allen 1704 Falcon Ridge Blvd. Friendswood, Texas 77456(US) Inventor: Weisenfeid, Robert Beller 915 La Cherie Drive Manchester, Missouri 63021 (US) © Representative: Bosch, Henry A G et al Monsanto Services International S.A. Patent Department, Avenue de Tervuren 270/272, Letter Box No. 21 B-1150 Brussels(BE) © Process for the preparation of iminodiacetonitrile and iminodiacetic acid. © An improved process is provided for producing iminodiacetonitrile by contacting ammonia, formal- dehyde and hydrogen cyanide, or hex- amethylenetetramine, formaldehyde and hydrogen <^ cyanide in a reaction medium, the improvement ^ which comprises the further steps of thereafter ad- justing the pH of the reaction medium to a pH ^ between about 5.5 and about pH 10 and heating the CO reaction medium to an elevated temperature for a (Y) sufficient time to convert by-products in the reaction ^ medium to iminodiacetonitrile. <fr O Q. LU Xerox Copy Centre 1 EP0 413 673 A2 2 PROCESS FOR THE PREPARATION OF IMINODIACETONITRILE AND IMINODIACETIC ACID BACKGROUND OF THE INVENTION nide at a temperature between about 20° and ° 90 C and at a pH between 5.5 and 6.5. Although satisfactory results can be achieved The present invention is directed to a process by these prior art processes, all of them suffer from for the preparation of iminodiacetonitrile (IDAN) and 5 one or more disadvantages. All of the prior art iminodiacetic acid (IDA) and derivatives thereof. processes produce unwanted by-products such as It is well known that IDAN is a valuable inter- glycolonitrile, aminoacetonitrile, ammonium salts, mediate to prepare compounds such as IDA. It is and the like. Now, there is provided an improve- also well known that IDA is a valuable intermediate ment to the prior art processes which converts for the preparation of other compounds. In fact, IDA w most of the by-products to the desired IDAN, IDA, is produced in commercial quantities in the United and derivatives thereof, and increases the overall States for use as an intermediate in the preparation yields. Because the quantity of the by-products is of numerous other compounds. Numerous methods reduced, disposal of these by-products is signifi- are known in the art to prepare both IDAN and IDA. cantly simplified. For example, U.S. Patent 3,886,198 to Phil- 75 brook, et al., discloses a process for preparing IDAN by preparing an aqueous mixture of hex- SUMMARY OF THE INVENTION amethylenetetramine, hydrogen cyanide and a strong acid such as sulfuric acid, hydrochloric acid and nitric acid, the aqueous mixture having a pH of 20 These and other advantages are achieved in a 3 to 5 and a mole ratio of hexamethylenetetramine process for producing iminodiacetonitrile by con- to hydrogen cyanide of 1 to 5-7. The aqueous tacting ammonia, formaldehyde and hydrogen cya- mixture is passed through a tubular reactor reaction nide or hexamethylenetetramine, formaldehyde and zone at a temperature between 50° C and 120° C. hydrogen cyanide in a reaction medium, the im- U.S. Patent 3,988,360 to Gaudette, et al., dis- 25 provement which comprises the further steps of closes a continuous process for preparing IDAN by thereafter adjusting the pH of the reaction medium continuously preparing an aqueous reaction mix- to a pH between about pH 5.5 and about pH 10.0 ture of hexamethylenetetramine, formaldehyde and and heating the reaction medium to an elevated hydrogen cyanide having a mole ratio of hex- temperature for a sufficient time to convert by- amethylenetetramine to formaldehyde to hydrogen 30 products in the reaction medium to im- cyanide of 1 to 1-2.2 to 6.9-8.6 in a continuous inodiacetonitrile. reaction zone by continuously feeding an aqueous hexamethylenetetramine solution having a tempera- ° ture of 0-80 C, an aqueous formaldehyde solution DESCRIPTION OF THE PREFERRED EMBODI- having a temperature of 0-80 °C, and hydrogen 35 MENTS cyanide having a temperature of 0-25 °C into a continuous reaction zone at a temperature between ° ° 50 and 250 C. The pH of the resulting aqueous As noted above, numerous methods are known reaction mixture is between 5 and 1 0. The resulting to those skilled in the art on the preparation of IDAN can be recovered, or it can be hydrolyzed to 40 IDAN and IDA. Generally, this involves the reaction form an alkali metal salt of IDA, which can be at a pH between about 3-7 of ammonia, formal- recovered or converted to IDA by acidification. dehyde, and hydrogen cyanide at temperatures up U.S. Patent 4,307,037 to Suchsland, et al., dis- to about 120° C. On the other hand, an aqueous closes a process for the production of IDAN by reaction mixture of hexamethylenetetramine, form- reaction of hexamethylenetetramine with hydrogen 45 aldehyde and hydrogen cyanide can be reacted at cyanide in acidic aqueous mediums. In the pro- temperatures up to 250 °C. The actual process cess, the pH during the reaction is between 5.5 used to prepare the IDAN and IDA is not critical in and 7.5 at the beginning, and is progressively the improved process of the present invention. lowered during the reaction by about 0.5 to 3.5 However, we have found that the process of units by the addition of acid. so the present invention is particularly applicable to a United States Statutory Invention Registration process for producing IDAN, or its hydrolyzable H4 to Cullen discloses a process for preparing products, and IDA by reacting 2 mole equivalents IDAN by the reaction of 1 mole equivalent of hex- of formaldehyde with 1 mole equivalent of hex- amethylenetetramine, 2 mole equivalents of formal- amethylenetetramine and 8 mole equivalents of dehyde, and 8 mole equivalents of hydrogen cya- hydrogen cyanide in the presence of a strong 2 3 EP 0 413 673 A2 4 mineral acid, such as hydrochloric acid, sulfuric As will occur to those skilled in the art, any acid, nitric acid and the like, to produce 4 mole number of means can be used to adjust the pH of equivalents of IDAN. This reaction is typically run the reaction medium. Suitable materials to adjust ° at modest temperatures, say between about 20 C the pH include the alkali metal hydroxides, such as ° and 60 C at a pH between about 5 and about 6. 5 sodium hydroxide, potassium hydroxide, lithium hy- This process reduces the amount of unwanted by- droxide and the like, or the addition of an alkali products, such as glycolonitrile, aminoacetonitrile metal carbonate, such as sodium carbonate, potas- and ammonium salts. Hydrochloric acid or sulfuric sium carbonate and the like. Alkaline earth hydrox- acid are preferred as the strong mineral acid, which ides, such as calcium hydroxide or alkaline earth produces an ammonium salt as a by-product. w carbonates, such as calcium carbonate can also be Regardless of the method by which the IDAN used to adjust the pH of the reaction medium. As and IDA is produced from hexamethylenetetramine, will occur to those skilled in the art, ammonium or its precursors, ammonia and formaldehyde, by hydroxide and ammonium carbonate should be reacting the hexamethylenetetramine with formal- avoided. The alkali metal hydroxides are preferred. dehyde and hydrogen cyanide, the improvement 75 Sodium hydroxide is especially preferred because according to the present process converts unwan- of its ready availability and inexpensive price. ted by-products such as glycolonitrile, In the process of the present invention, the aminoacetonitrile and the ammonium salts to the temperatures can vary within wide ranges. At tem- desired IDAN, salts of IDA, and derivatives thereof. peratures much over 100° C, side reaction that It is not important in the process of the present 20 form color bodies occur. Preferably, the reaction invention whether the IDAN or its derivatives is medium containing a molar excess of glycolonitrile produced in a continuous or in a batch process. to aminoacetonitrile and ammonium salt is heated The improved process comprises the additional to a tempera ture between about 50 °C and about steps of adjusting the pH of the reaction medium to 80° C. At temperatures below about 50° C, the con- a pH between about pH 5.5 and about pH 10.0, 25 version of the by-products to the desired IDAN or and heating the reaction medium to an elevated its derivatives is quite slow. It is especially pre- temperature for a sufficient time to convert the by- ferred to heat the reaction medium to temperatures ° ° products in the reaction medium to IDAN or its between about 60 C and about 80 C. ° ° derivatives. At the temperatures of 50 to 1 00 C and at a The IDAN goes through a series of derivatives 30 pH between about 5.5 and about 10.0, the reaction to end at the disalts of IDA, depending on the is completed within about 5 hours. At temperatures temperature and the pH of the reaction medium. between about 60° C and 80° C at the preferred pH These derivatives can be prepared through routine between about pH 6 and pH 8, the reaction accord- experimentation in view of the present disclosure ing to the process of the present invention is com- by those skilled in the art.
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