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Continuous Production of Oxamide by the Catalytic Oxidation of HCN

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Continuous Production of Oxamide by the Catalytic Oxidation of HCN Europaisches Patentamt European Patent Office © Publication number: 0 571 041 A1 Office europeen des brevets EUROPEAN PATENT APPLICATION © Application number: 93201408.7408.7 © int. Ci.5; C07C 231/00, C07C 233/56 @ Date of filing: 18.05.93 ® Priority: 22.05.92 IT MI921248 © Applicant: Enichem Anic S.r.l. Via Ruggero Settimo 55 @ Date of publication of application: 1-90139 Palermo(IT) 24.11.93 Bulletin 93/47 @ Inventor: Messina, Giuseppe © Designated Contracting States: Via Perpignan 27, AT BE CH DE DK ES FR GB GR IE IT LI LU MC 1-07041, Alghero (Sassari)(IT) NL PT SE Inventor: Sechi, Giovanni Matteo Via Alessandro Volta 4 1-07014, Ozieri (Sassari)(IT) Inventor: De Micheli, Silvio Via Roma 112 I-20024, Garbagnate Milanese (Milan)(IT) © Representative: Roggero, Sergio Ing. Barzano & Zanardo Milano S.p.A. Via Borgonuovo 10 1-20121 Milano (IT) © Continuous production of oxamide by the catalytic oxidation of HCN. © A continuous process for the production of ox- ng.3 amide is based on the catalytic oxidation of hy- drogen cyanide with oxygen or air in a strong excess in a solution of copper nitrate in water-acetic acid. The process is carried out in a vertical tubular SR reactor, with continuous recycling of part of the V suspension of oxamides from the bottom to the top of the reactor. L5 < "•3 I- 6 5 Rank Xerox (UK) Business Services (3. 10/3.6/3.3. 1) 1 EP 0 571 041 A1 2 The present invention relates to a procedure 2 HCN + 1/2 02 -> (CN)2 + H20 for the preparation in continuous of oxamide. (CN)2 + 2 H20 - ■> H2N-CO-CO-NH2 Oxamide is an organic compound which is used in the synthesis of the widest variety of pro- 2 HCN + 1/2 02 + H20 --> H2N-CO-CO-NH2 ducts ranging from esters, dialkylamides and 5 hydrazides of oxalic acid, to copolyoxamides or The scheme of the reaction zone of the copolymers of a bicarboxylic acid with the oxamide Hoechst process is shown in figure 1 . of an aliphatic or aromatic diamine; these com- The Hoechst process, as described in the pounds are described for example in Italian patent above patents and article, is carried out by feeding applications 20121 A/86, 20274 A/88 and 20276 10 in continuous, in the lower part of a tubolar bubble A/88 filed by the present applicant. reactor (T) containing the aqueous acid solution of The use of oxamide as a slow release fertilizer the catalyst, HCN together with oxygen. The ox- is just as well-known [Development in Plant and amide which is continuously formed precipitates in Soil Sci., 15, Fertilizer Manual, Ed. T.P. Higne; W. a crystalline form and is collected at the bottom of Junk Publishers (1985), page 279]; it is based on 15 the reactor (F), which has a conical shape, in the the slow release of nitrogen by the oxamide. so-called thickening zone, from which it is trans- In spite of the affirmed and increasing use of ferred as a suspension to a centrifuge, where the oxamide, this compound is still not produced on a oxamide is separated from the catalytic solution wide scale because of the relatively high costs and which is recycled to the tubular bubble reactor (T); complicated synthesis methods. There are basi- 20 the latter solution is regenerated by adding copper cally three of these methods: the Degussa process nitrate and the quantity of water consumed accord- (GB 1.251.721), which is based on the oxidation of ing to the stoichiometry of the reaction. The thick- HCN with hydrogen peroxide, the Sagami process ening zone of the solid (F) is situated below the (DE 2034208), which is based on the use of N02 inlet of the oxygen and HCN. instead of hydrogen peroxide, and the Hoechst 25 In the upper part of the reactor there is an process (DEO 2308941, DE 2403120) which is exchanger which cools the off-gases and con- based on the oxidation of HCN with oxygen and air. denses the vapours of water and acetic acid. Of the three above processes, the first two are The excess oxygen, hydrogen cyanide and un- rather expensive, both for the type of oxidant used converted cyanogen, nitrogen oxides (NyOx), CO, and for the necessity of isolating cyanogen (N=C- 30 C02, N2, deriving from the secondary reactions, C=N) as an intermediate product to be hydrolized leave the head of the tubolar reactor together with in a subsequent step. water and acetic acid. The Hoechst process on the other hand is The results of this process are still not satisfac- considered the most accessible and economical of tory however from the point of view of production the three, both for the low cost of the oxidant used 35 on an industrial scale because: (oxygen and air), and for the synthesis procedure - there is a heterogeneous distribution of the which consists of a single step; in addition all the reagents; in fact the oxygen tends to be products can be recycled, catalyst included. distributed preferentially in the upper part of The catalyst used is an aqueous solution of the reactor whereas the hydrogen cyanide, copper nitrate which is used in the presence of an 40 owing to its solubility in the catalyst, tends to aliphatic carboxylic acid (acetic acid). A subse- move both upwards and downwards with re- quent patent (DE 2402354) emphasizes, in the spect to the feeding point, economy of the process, the role of the oxidant - oxygen is never present in the suspension (oxygen or air), which must be advantageously taken from the thickening zone (F) of the used in great excess with respect to the 45 reactor whereas the gases contained therein stoichiometric quantity. are basically composed of N2, NO, CO and The relative reaction scheme as defined by the C02, authors (W. Riemenschneider, Chemtech., October - the recycled catalytic solution always con- 1976, pages 658-661) is specified below whereas tains reasonable quantities of formamide and the scheme of the Hoechst plant is specified in the 50 acetamide which are destroyed (by oxidation) same article. when re-fed into the reactor as such a quan- tity does not increase with time. 2 Cu(N03)2 + 4 HCN -- > (CN)2 + 2 CuCN + 4 The presence of NO in the suspension continu- HN03 ously removed from the thickening zone (F) of the 2 CuCN + 6 HNO3 - > 2 Cu(N03)2 + 2 HCN + 2 55 reactor, together with the lack of oxygen therein, H20 + 2 N02 indicates insufficient re-oxidation of this gas; infact, 2 N02 + 1/2 02 + H20 -- > 2 HNO3 in the oxidative process for the formation of ox- amide, the nitrates can be reduced to products 2 3 EP 0 571 041 A1 4 having a lower oxidation level (NO and NO2) which however, if there is a strong excess of oxygen, as 2 HCN + 1/2 02 + H20 -- > H2N-OC-CO-NH2 is also recommended in German patent application DE 2402354, should be reoxidized to nitric acid. and including the following operations: In addition, the lack of oxygen in the thickening 5 - feeding in continuous into a tubular vertical zone (F) of the reactor favours the accumulation of reactor: reduced products (e.g. HNO2) which can attack the i) the catalytic solution of copper nitrate Cu- oxamide, oxidizing it exhaustively with the forma- (N03)2, which also contains acetic acid, nitric tion of gaseous products such as those specified acid and the stoichiometric quantity of water above, in the suspension at the bottom; for exam- 10 consumed in the reaction, ple: ii) hydrogen cyanide (HCN), iii) oxygen or air which, bubbling through the H2N-CO-CO-NH2 + 2HN02 -- > 2 N2 + CO + tubular reactor, causes the stirring of the sus- C02 + 3 H20 pension of oxamide inside, 15 - continuously removing the suspension of ox- The carbon monoxide which is formed accord- amide from the bottom of the tubular reactor ing to this reaction, as it is also flammable, in- and the quantity of oxygen in excess of the creases the concentration of combustible products stoichiometric quantity from the head of the (hydrogen cyanide, acetic acid, cyanogen) in the reactor together with any other gases pro- gaseous phase and makes more critical the control 20 duced in secondary reactions, of the explosivity of the gaseous mixture both in - continuously separating the oxamide from a the head of the reactor and in the bubbling-bed. part of the suspension removed from the The present invention therefore relates to a bottom of the reactor, process for the production of oxamide which, al- - recycling the catalyst solution, containing though using the same reagents and same catalytic 25 copper nitrate, acetic acid and nitric acid, system of the Hoechst process mentioned above, after adding the stoichiometric quantity of wa- overcomes the above disadvantages of the known ter consumed in the synthesis reaction, art. this process being characterized in that: In fact, as mentioned before, the applicant has a) the suspension of oxamide is continuously discovered that the disadvantages of the known art 30 removed from the lowest point of the reactor, can mainly be attributed to the bad distribution of b) a great quantity of the suspension of oxamide the reagents and, among these, above all oxygen, removed from the lowest point of the reactor is both inside the reactor where the synthesis of the recycled, re-introducing it into the highest part oxamide takes place and on the bottom (thickening of the reactor, after cooling it in a heat ex- zone F) and outside the reactor before the oxamide 35 changer at a temperature which is sufficient to in suspension is separated from the catalytic solu- maintain the established reaction temperature tion.
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