PROCESS FOR PRODUCING NITRILOTRIACETONITRILE

Abstract: A process for producing nitrilotriacetonitrile from an ammonia derivative, formaldehyde, and hydrogen cyanide, in which hydrogen cyanide is scrubbed from a gas stream (14, 28) containing hydrogen cyanide with a solution (15, 29) containing nitrilotriacetonitrile mother liquor which is used directly in the nitrilotriacetonitrile production without the purification process normally used to produce hydrogen cyanide.

Description: PROCESS FOR PRODUCING NITRILOTRIACETONITRILE Background of the Invention Field of the Invention This invention relates to the production of nitrilotriacetonitrile, and more particularly to the source and manner of addition of hydrogen cyanide to the reaction mixture to produce nitrilo triaceonitri le.- Background It is well known that ammonia, an ammonium salt, or an ammonia-formaldehyde condensation product will react with formaldehyde and hydrogen cyanide to produce nitrilotriacetonitrile. A common ammonia-formaldehyde condensation product is hexamethylenetetramine (HMTA). These recations have been generally defined in the following U.S. Patents to J. J. Singer, et al: 2,855,428, and 3,061,628 and to organ, et al: 3,463,805 Nitrilotriacetonitrile can be produced from hexamethylenetetramine by the following reaction: pH' 1 N4(CH2)616 CH2O + 12 HCN 4N(CX2CNY3+6H20 (1) If the hexamethylenetetramine is replaced by equivalent amounts of ammonia or ammonium and formaldehyde, nitrilotriacetonitrite can be produced from ammonia or an ammonium salt by the following reaction: : pH f 1 EMI2.1 <tb> NH3(or <SEP> HN4+) <SEP> + <SEP> 3CH20 <SEP> + <SEP> 3HCN <tb> <SEP> N(CH2CN)3C+H+ <SEP> if <SEP> NH4+ <SEP> is <SEP> used <SEP> (2) <tb> The effect of many factors on these reactions h-as been studied, including dilution ratios, temperature ranges, order of addition of reactants, order of reaction steps, and otters. But, current processes use hydrogen cyanide as commercially available, which is anhydrous or substantially anhydrous form. Hydrogen cyanide is most commonly produced commercially by reaction of ammonia with methane, methanol or other suitable volatile hydrocarbon, at elevated temperatures to produce hydrogen cyanide, hydrog-en, and other inert gases. Hydrogen cyanide is normally purified to greater than 98% purity and liquified prior to use. This purification process typically comprises cooling the product gas stream; removing ammonia with a sulfuric acid solution or a monoammonium phosphate solution; absorbing hydrogen cyanide from the resulting gas stream in an acidic aqueous solution stripping the hydrogen cyanide from the resulting solution; condensing the stripped hpdro- gen cyanide and water mixture; fractionating to produce hydrogen cyanide; liquifying the hydrogen cyanide, and stabilizing the liquifled hydrogen cyanide to prevent polymerization. Purification of hydrogen cyanide to the comme-rcia-l grade anhydrous hydrogen cyanide as outlined above, is a complex 'process requiring large expenditures for equipment, energy, and material handling. Additionally, cyan-;de-containing waste streams are produced- that must be treated and disposed of. Tt would be an advancement in the art to be able to use hydrogen cyanide to produce nitrilo triacetonitrile without the costty and waste producing purification steps. It is an advantage of this invention that nitrilotriacetonitrile can be produced using hydrogen cyanide without undergoing the usual purification. It is a further advantage of this in vention that mother liquor produced in production of nitrilotriacetonitrile can be recycled to extract hydrogen cyanide from the reactor product gas stream reducing the amount of waste in the nitrilotriacetonitrile and hydrogen cyanide production processes. Further advantages can be seen from the following description and example-s. Summary of the Invention This invention provides a process for producing nitrilotriacetonitrile comprising: a. producing a gas stream containing hydrogen cyanide; b. scrubbing said gas stream with an aqueous solution containing nitrilotriacetonitrile mother liquor, to produce a hydrogen cyanide-containing solution; ce adding formaldehyde and an ammonia derRvat-ive selected from the group consisting of ammonia, an ammonium salt and hexamethylenetetramine, t said hydrogen cyanide containing solution, to produce a reaction mixture; and d. reacting said reaction mixture to produce nitrilotriacetonitrile. Description of the Preferred Embodiment Hydrogen cyanide can be produced by the reaction of methane, methanol, or other volatile hydrocarbon with ammonia in the presence z nce of a catalyst or In a fluidized bed at a temperature in excess of 1000 C. The gas stream produced contains nitrogen, methane, ammonia, hydrogen, hydrogen cyanide, and other gas components. Unless otherwise specified, all parts and percents are by weight. Hydrogen cyanide is produced commercially primarily by the Andrussow Process, the Degussa Process, also called the SMA Process, and the Fluohmic Process, and ammoxidation of methanol or other hydrocarbons. All of these processes use ammonia as the source of nitrogen, and the product gas stream will contain some unreacted ammonia. Since ammonia will react with hydrogen cyanide, removal of this unreacted ammonia is an important step in the purification process. The Andrussow- Process produces hydrogen cyanide by the following theoretical reaction: EMI5.1 at about llOD C, with heat being supplied by combustion of methane Metal catalysts from Group VIII of the Periodic Table are normally used, preferably a Plattnum-Rhodlum gauze. The oxygen is normally supplied by mixing an appropriate amount of air with the other reactants. A typical product gas stream produced by the Andrussow Process has the following composition: nitrogen 64Z, water 13X, hydrogen cyanide 11%, carbon monoxide 7%, hydrogen 2%, ammonia 2X, carbon dioxide 1X, methane 0.4X. The Degussa Process produces hydrogen cyanide by the following theoretical reaction: EMI5.2 in a tubular reactor impregnated with a platinum catalyst at 1200 C, with heat being supplied by indirectly heating the tubes with gas or electri- city. A typical product gas stream contains: hydrogen cyanide 71Z, hydrogen 17X, nitrogen 7%, methane 4%, ammonia 2X. Other processes for production of hydrogen cyanide include the Fluohmic Process; by reacting ammonia apdpropane in an electrically heated fluidized carbon bed; ammoxidation of methanol or other hydrocarbons; and a decomposition of formamide, which is produced from ammonia and carbon monoxide. Any process that produces hydrogen cyanide in suff-icient quantities can be used with this invention. Under the process of this invention, an unpurified hydrogen cyanide-containing gas stream is scrubbed with nitrilotriacetonitrile mother liquor. Preferred is mother liquor containing sulfuric acid, and preferably about 10X to about 25X apparent sulfuric acid concentration. Apparant sulfuric acid concentration is determined by titration against a standard sodium hydroxide solution. Additional sulfuric acid and additional water can be added to the mother liquor to form the scrubbing solution and to adjust the apparent sulfuric acid concentration to the desired concentration. The unpurified gas stream may be c-ooled prior to scrubbing, preferably to about 800C to about 1000C, or may be both cooled and treated to remove the unreacted ammonia. The resulting solution preferably contains about 10X t about 60X, more preferably about 20% to about 40%, hydrogen cyanide. This hydrogen cyanidecontaining solution can be used without further purification to produce nitrilotriacetonitrile, using any suitable process for synthesizing nitrilotriacetonitrile. Production of nitrilotriacetonitrile involves crystallization of the product from the reactant solution resulting in production of mother liquor containing an inorganic acid. This mother liquor can be used for scrubbing the hydrogen cyanide from the reactor stream. Additional acid and additional water can be added as necessary to make up a suitable scrubbing solution. Example 1 A typical sample of nitrilotriacetonitrile mother liquor was analyzed to contain about 10X apparent sulfuric acid, about 1X-ammonia, and about 10X organic components comprising un reacted organic reactant, nitrile intermediates, and dissolved nitrilotriacetonitrile. A mixture of the mother liquor and hydrogen cyanide at a ratio of 1 to 2 was homogeneous. Upon cooling to about 7 C, the mixture formed two layers, an upper hydrogen cyanide layer and a lower mother liquor layer. Upon warming above about 70C, a homogeneous solution again formed. Because the solubility of the hydrogen cyanide in the mother liquor below about 70C decreases significantly, hydrogen cyanide scrubbing with nitri1otriacetonitrile mother liquor must be done at temperatures above about 7 C. Example 2 The scrubbing efficiency of hydrogen cyanide by a dilute sulfuric acid solution and by a dilute sulfuric' acid solution containing nitrilotriacetonitrile mother liquor were determined at about 440C and at about 320C. Five percent hydro gen cyanide in an inert gas was bubbled at a rate of about 10 milliliters per minute into 100 mitli- liters of solution, through 5.5 centimeters of the solution, in a constant temperature water bath, until the scrubbed gas contained about 1X hydrogen cyanide. By these tests, the dilute sulfuric acid solution and the nitrilotriacetonitrile mother liquor' showed similar scrubbing efficiencies, even though theoretically the hydrogen cyanide should be somewhat more s-oluble in the dilute sulfuric acid solution than in the mother liquor. At about 440C, the hydrogen cyanide concentration of the scrubbing solution reached about 25X, and at about 320C, the hydrogen cyanide concentration of the solution reached about- 57%. Examole 3 An apparatus was constructed for continuous production, of nitrilotriacetonitrile, as described below The components were constructed using stainless steel. A dual feed syste-m was constructed consisting of two feed tanks each with a feed pump. The feed from the two pumps joined at a tee. A small gear pump and mixing loop premixed the reactants to form the reaction mixture just prior to its introduction to the reactor system. The first stage of the reactor system was a circulating loop reactor. The circulating loop reactor consisted of a pump, two shell and tube heat exchangers, and connecting lines to form a continuous loop, an inlet for introduction of the reaction mixture to then loop and an outlet through which the reaction mixture can be withdrawn. One heat exchanger was 5 inches (lZ.7 cm) in length, and the other was 7 inches tut7.8 cm) in length. Both were constructed of lf4" (6.35 mm) Or tubing that was jacketed for heat transfer fluid. Flow of the heat transfer fluid was thermostatically controlled to maintain the desired temperature. The volume of the circulating loop reactor was 10 ml. A plug-flow tubular reactor was connected to the outlet from the circulating loop reactor as the second stage of the reactor system. The plugflow tubular reactor consisted of two sections, a packed section and a heated return section. The packed section was a shell and tube heat exchanger made using 2 feet (61.0 cm) of 1/2" (12.7 mm) OD tubing packed with glass beads and jacketed for heat transfer fluid. The volume of the packed section was 30 ml. The heated return connected the end of the plug-flow tubular reactor to the product receiver The heated return was another shell and tube heat exchanger constructed of 1/8" C3.2 mm) OD tubing with a jacket. The volume of the,,heated return was 5 ml, for a total reactor system volume of 45 ml. The packed section and the heated return section were both supplied with a heat transfer fluid the flow of which was thermostatically controlled to maintain the temperature. The connection between the packed section, the heated return, and the product receiver were wrapped with heating tape to insure that the temperature remained above 950C to prevent pluggage caus-ed by crystallized nitrilotriacetonitrile. The product receiver was stirred, was cooled by a bucket of ice and water to crystallize the niRrilotriacetonitrile,wand was fitted with a valve at the bottom to remove the nitrilotriacetoni trill slurry produced. Crystalline nitrilotriacetonitrile was separated by filtration. The reactor system and the receiver were all maintained at a pressure of about 75 psig (about 620 KPa) with pressurized nitrogen. The two feed tanks contained reactant solutions consisting of: Feed No. 1 Feed No. 2 56 9 99.7% HMTA 23 g 96.4X H2S04 211 9 35.9% CH20 131 g mother liquor (containing 9.23% H2S04) 9 g H20 36 g H20 138 g 99Z HCN Feed No. 2 contained 42% hydrogen cyanide, equivalent to a solution produced by scrubbing a hydrogen cyanide-containing gas stream at about 35 C. Feed No. 2 contained about 10.4Z apparent sulfuric acid The feed rates were adjusted to produce the amount of excess hydrogen cyanide indicated. Formaldehyde was present in about 5X excess as indicated. Sojourn times were calculated by dividing the reactor volume by the total feed rate. Since the volume of the circulating loop reactor was approximately 22Z of the volume of the complete reactor system, the reaction mixture on the average spent about 22% of the sojourn time in the circulating loop reactor. The reaction conditions and the yield of nitrilotriacetonitrile (NTAN) for each of the reaction runs is shown in Table I. TABLE I 1 2 3 4 5 6 % excess CH2O 5 5 5 5.2 5 5. % excess HCN 11 0.85 4.7 10.6 10.4 16.5 Reactor Temp. C 115 115 115 115 115 115 Sojourn Time, Min. 10.2 10.0 10.0 10.3 10.4 10.6 % Yield NTAN 91.6 88.0 91.5 92.6 91.3 97.5 Melting Range NTAN C 125.5- 125.0- 125.5- 125.0- 125.3- 125.4 127.2 126.8 127.3 126.8 127.9 127.0 Example 4 Nitrilotriacetonitrile was produced in three runs with the first using recycled mother liquor from stock and the second and third using recycled mother liquor from the previous run. About 50X of the mother liquor produced was recycled to the next run. The mother liquor was mixed with ammonium sulfate, sulfuric acid, and liquid hydrogen cyanide. This simulated -a solution obtained by scrubbing a product gas stream containing hydrogen cyanide and ammonia with the nitrilotriacetonitr;Te mother liquor. Solutions of hexamethylenetetramine and formaldehyde were added to give a reaction mixture as shown in Table II. The "organics" were primarily intermediates from the nitrilotriacetonitrile reaction and dissolved nitrilotriacetonitrile from the mother liquor. The reaction mixture was reacted at a temperature of 75-80 C for about one hour. The mixture was cooled below about ZOOC to crystallize nitrilotriacetonitrile. The crystalline nitrilotriacetonitrile was separated by filtration and the crystals washed. The amount of nitrilotriacetonitrile and mother liquor produced, and analysis of the motber liquor are shown in Tabl-e 11. TABLE II Runs 1 2 3 Source of Recycled Stock Run l Run 2 Mother Liquor Reactant Mixture, g. Apparent H2S04 22.0 26.6 22.6 NH3 4.4 3.8 3.8 HCN 68.0 72.5 69.9 HMTA 28.4 28.4 28.4 CH2O 37.0 37.0 37.0 Organics 3.9 10.2 8.3 HO 138.3 158.3 166.3 Total 306.0 336.6 336.6 Products 9. NTAN 98.6 102.2 100.8 Mother Liquor 207.4 234.4 235.8 NTAN Yield 90.8X 94.1X 92.9X (based on HMTA) Analysis of Mother Liquor. Apparent H2SO4 21.6 24.9 22.6 NH3 3.7 3.4 2.6 Organics and Unreacted 26.4 10.6 10.6 HCN and CH2O In each run some ammonia was consumed, and the amount of ammonia did not build up in the mother liquor as it was recycled. These data show that ammonium salts will not build up through a series of runs with mother liquor continuously recycled. Example 5 This example describes the process of this invention with the Degussa Process for production of hydrogen cyanide. This example follows the scheme outtined in Figure 1. Ammonia (11) and methane (12) are fed into an indirectly heated tubular reactor. The product gas steam (13) is then cooled to 800C to lOQ C. This cooled gas stream (14)- contains about 71Z hydrogen cyanide, with the remainder being methane, ammonia, hydrogen, and nitrogen. This cooled gas stream is then scrubbed with a solution (15) made up of recycled mother liquor from crystallization of nitrilotriacetonitrite CIS) together with added sulfuric acid (19) to adjust the apparent sulfuric acid concentration of the scrubbing solution to about 18.5X. The hydro gen-cyanide-free gas stream (16) is removed, and the hydrogen cyanide-containing solution (17), with about 33Z hydrogen cyanide is then used in the reaction with hexamethylenetetramine and formaldehyde or with ammonia and formaldehyde to produce nitrilotriacetonitrile. Example 6 This example describes the process of this invention with the Andrussow Process, with ammonia scrubbing prior to the hydrogen cyanide scrubbing. This example follows the scheme outlined in Figure 2. Methane (21), ammonia (22), and air (23) are fed into a reactor containing platinum-rhodium catalyst. The product gas stream (24) is then cooled to 800C to 1000c. This cooled gas stream (25) is then scrubbed with a solution containing about 30X monoammonium phosphate. The ammonium-containing solution (27) could be treated to recover the ammonia, or could be used directly as diammonium phosphate. The ammonia-free gas stream (28) is then scrubbed with a solution (29) made up of recycled mother liquor from crystallization of nitrilotriacetonitrile (32) together with added sulfuric acid (33) sufficient to adjust the apparent sulfuric acid concentration of the scrubbing-solution to about 18.5%. The hdyrogen free cyanide-containing gas stream (30) is removed, and the hydrogen cyanide-containing solution C31), with about 33% hydrogen cyanide is then used in the reactin with hexamethylenetetramine and formaldehyde or with ammonia and formaldehyde to produce nitrilotriacetonitrile. Those skilled in the art will recognize many possible variations on the examples. Any process producing a gas stream containing hydrogen cyanide can be used as the source of hydrogen cyanide. Ammonia may be scrubbed out of the gas stream or this step may be omitted as desired. Many variations of the reactions to produce nitrilotriacetonitrile from the hydrogen cyanidecontaining solution are also known. In addiction, other variations will be recognized by one skilled in the art. It is intended that this invention include all of these variations. These examples are intended to i 1 lus- trate and explain the process of this invention and are not intended to in any way limit the process of this invention.

Claims: What is claimed is: la A process for producing nitrilotriacetonitrile comprising: a. producing a gas stream containing hydrogen cyanide; be scrubbing said gas stream with an aqueous solution containing nitrilo triacetonitrile mother liquor, to produce a hydrogen cyanide-contain ing solution; c. adding formaldehyde and an ammonia derivative selected from the group consisting of ammonia, an ammonium salt, and hexamethylenetet-anine, to said hydrogen cyanide-. containing solution, to produce a reaction mixture; and d. reacting said reaction mixture to produce nitrilotriacetonitrile. 2. The process of Claim 1 wherein the ammonia derivative is hexamethylenetetramine. 3 The process of Claim 1 wherein the ammonia derivative is ammonia or an ammonium salt. 4. The process of Claim 1 wherein the gas stream containing hydrogen cyanide is produced by reacting methane, ammonia, and oxygen in the presence of a metal catalyst from Group VIII of the Periodic Table. 5. The process of Claim 1 wherein the gas stream containing hydrogen cyanide is produced by reacting methane and ammonia in an indirectly heated reactor. 6. The process of Claim 1 wherein the gas stream containing hydrogen cyanide is produced by reacting ammonia and propane in an electrically heated fluidized carbon bed. 7. The process of Claim 1 wherein the aqueous scrubbing solution contains sulfuric acid. 8. The process of Claim 7 wherein the apparent concentration: of sulfuric acid is about 10% to about 25%. 9. The process of Claim 1 wherein the hydrogen cyanide-containing solution contains about 10% to about 60X hydrogen cyanide. 10. The process of Claim 1 wherein the hydrogen cyanide-containing solution contains about 20% to about 40% hydrogen cyanide. Ii. The process of Claim 1, further comprising treating the gas stream containing hydrogen cyanide to remove ammonia, prior to scrubbing of (b).

Inventors: SHEN, CHUNG YU
Applicants: MONSANTO COMPANY
Application year: 1983
Main classification: C07C121
IPC codes: C07C253, C07C67, C07C255