PROCESS FOR PREPARING A HYDRAZINE HYDROHALIDE

Abstract: A process for preparing a hydrazine hydrohalide compris­ ing the steps of: (a) oxiding a benzophenone-imine with molecular oxygen in the presence of a copper halide catalyst to produce benzo­ phenone-azine; (b) contacting the oxidation reaction mixture with an aqueous solution containing a hydrohalic acid thereby hydro­ lyzing the benzophenone-azines to produce a hydrazine hydro­ halide and, simultaneously extracting and removing the cata­ lyst with the hydrohalide acid-containing aqueous solution to obtain an aqueous solution containing the hydrazine hydro­ halide and the catalyst; (c) separating the aqueous solution and adjusting the so­ lution to a pH of from 3 to 7 with an alkali; (d) contacting the aqueous solution with a benzophe­ none-imine to extract the catalyst; (e) separating the catalyst-containing benzophenone-­ imines solution from the aqueous solution containing the hy­ drazine hydrohalide to recover the hydrazine hydrohalide and to recycle the catalyst-containing benzophenone-imine solu­ tion to step (a). The process is advantageous in that the catalyst is easily recovered for reuse.

Description: PROCESS FOR PREPARING .A HYDRAZINE HYDROHALIDE L This invention relates to a process for preparing hydrazine hydrohalides comprising oxidizing benzophenone-imines with molecular oxygen in the presence of a copper halide catalyst and hydrolyzing the resulting benzo phenone-azines. Hydrazine hydrohalogides are industrially useful for a wide variety of applications, for example, as foaming agents or - intermediates for producing bydrazine, and the like, and, therefore, it is desirable to be able to prepare them inexpensively. It is known that benzophenone-imines are contacted with molecular oxygen in the presence of a copper halide catalyst to obtain benzophenone-azines as described in U.S. Patent 2,870,206 and that azines are hydrolyzed with an aqueous solution of a hydrohalic acid to obtain hydrazine hydrohalides as described in Japanese Patent Application (OPI) No. 97600/76 (the term "OPI" as used herein means an unexamined published patent application ). Production of hydrazine hydrohalides by combining these processes is industrially advantageous but inevitably demands a simple and easy process for the removal and reuse of the copper catalyst used. Known processes for recovering the copper halide catalyst comprise adding water, aqueous ammonia or an aqueous salt solution to the reaction mixture containing the benzophenone-azines produced by oxidation with molecular oxygen to thereby precipitating the copper halide catalyst, and reusing the thus recovered catalyst as disclosed in Japanese Patent Applications(OPI) Nos. 71045/78 and 38346/ 80. These processes, however, cannot be considered industrially advantageous because of poor workability resulting from handling of a solid. The present inventors have conducted extensive in vestigetions on processes for preparing hydrazine hydrohalides - by hydrolysis of a benzophenone-azine obtained by oxidation of a benzophenone-imine with molecular oxygen. As a result, it has now been found that, when benzophenoneazines are hydrolyzed by a specific process, the catalyst can not only easily be extracted and removed from the reaction mixture simultaneously with the hydrolysis but also simply and effectively be recovered from the resulting aqueous solution of hydrazine hydrohaZi-oe containing the catalyst and reused. The present invention is based on this finding. The present invention relates to a process for pre paring a hydrazine hydrohalide , comprising the steps of: (a) oxidizing a benzophenone- imine with molecular oxygen in the presence of a copper halide catalyst to pre pare Åa benzophenone- azine (b) contacting the oxidation reaction mixture obtained in step (a) with an aqueous solution containing a hydrohalogenic acid at a concentration of from 10 to 60% by weight, thereby hydrolyzing the benzophenone azine to produce a hydrazine hydrohalide and, at the same time, extracting and removing the catalyst with the hydrohalic acid-containing aqueous solution from the reaction mixture, to obtain an aqueous solution containing the hydrazine hydrohalide and the catalyst; ; (c) separating the aqueous solution containing the hy drazine hydrohalide and catalyst which is ob tained in step (b) and adjusting the solution to a pH of from 3 to 7 with an alkali; (d) contacting the aqueous solution having a pH of 3 to 7 obtained in step (c) with benzophenone-imine- to extract the catalyst with the benzophenone-imine from said aqueous solution; (e) separating the catalyst-containing benzophenone imine solution obtained in step (d) from the aque ous solution containing the hydrazine hydrohalogen ide, thereby to recover the hydrazine hydrohalogen ide as an aqueous solution and to recycle the catalyst-containing benzophenone-imines solution to step (a). According to the present invention, hydrazine hydrohalogenides can be produced with industrial advantages in terms of easiness to recover and reuse the catalyst. In the accompanying drawing: The figure-is a flow - sheet of the reaction used in Example 2. The elements are: supply pipe for benzophenoneimine 1, pipes for discharging air 2 and 8, first reactor 3, pipes for introducing air 4 and 10, pipes for discharging reaction solution 5 and 11, pump 6, pipe for introducing reaction solution 7, and second reactor 9. The benzophenone-imines which can be used in the present invention can be represented by the formula (I): EMI4.1 wherein R1 and R2, which may be the same or different, each represents an acyclic, alicyclic or aromatic hydrocarbon group having from 1 to 10 carbon atoms, an ether, acyl, acyloxy, alkoxycarbonyl, carboxylic acid amido or di-substituted amino group derived from these hydrocarbon groups, a halogen atom, a hydroxyl group, a nitro group or a cyano group, or R1 and R may -together form a single 1 2 bond or a ring; and m and n each represents 0 or an integer of from 1 to 5. Specific examples of the benzophenone-imines represented by the formula (I) include benzophenone-imine, 2-, 3or 4-methylbenzophenone-imine, 2-, 3- or 4-ethylbenzophenone-imine, 2-, 3- or 4-n- and/or isopropylbenzophenoneimine, 2-, 3- or 4-n- and/or iso- and/or tert-butylbenzophenone-imine, 2-, 3- or 4-amylbenzophenone-imine, 2-, 3- or 4decylbenzophenone-imine, 2-, 3- or 4-methoxybenzophenoneimine1 4-cyclohexylbenzophenone-imine, 4-phenylbenzophenoneimine, 2,4-dimethylbenzophenone-imine, 2, 3-dimethylbenzophe- none-imine, 3,4-dimethylbenzophenone-imine, 2,4-diethylbenzophenone-imine, 2, 3-diethylbenzophenone-imine, 3,4-diethylbenzophenone-imine, 2-methyl-4-ethylbenzophenone-imine, 2methyl-4-butylbenzophenone-imine, 2,2'-, 3,3'-, 4,4'-, 2,3'-, 2,4'- or 3,4'-dimethylbenzophenone-imine, 2-, 3- or 4-chlorobenzophenone-imine, 2-chioro-4-methylbenzophenoneimine, 4-chloro-4'-methylbenzophenone-imine, 4,4' -dichloro- benzophenone-imine, 4-nitrobenzophenone-imine, 2,4-dinitrobenzophenone-imine, 4-hydroxybenzophenone-imine, 4-N, N- dimethylaminobenzophenone-imine, 4-acetylbenzophenone-imine, 4-methoxybenzophenone-imine, 4-N,N-dimethylcarbamoylbenzophenone-imine, 4-cyanobenzophenone-imine, fluorenone-imine, xanthone-imine, anthrone-imine and acridone-imine. Other imine compounds may also be used. Methods for preparing these and other imines include, for example, a method of reacting corresponding benzophenones with ammonia, a method of reacting benzonitriles with an aryl magnesium bromide, i.e., a Grignard reagent, a method of dehydrating a diarylamino alcohol, and the like. All imines prepared by any of these methods can be employed in the present invention. The benzophenone-imines that can be used in the present invention, except for unsubstituted benzophenoneimine of the formula (I) wherein m and n are 0, are those containing various substituents or with substituents jointly forming a single bond or a ring. In carrying out the process of the invention on an industrial scale, unsubstituted benzophenone-imine and 1- or 2-mono- or 1,2-di-substituted benzophenone-imine are preferred. Among them, unsubstituted benzophenone-imine is particularly preferred. The copper halide which is used as a catalyst in the present invention preferably is cuprous chloride, cuprous bromide br cuprous iodide, with cuprous chloride being more preferred. Solvents are not particularly required in the present invention. It is possible, however, to use solvents for the purpose of maintaining the reaction system in a solution state or facilitating oil-water separation in the extraction, hydrolysis or back extraction. Such being the case, solvents that are not easily oxidized in the oxidation of benzophenone-imines and, in particular, have poor affinity for water and a low viscosity are preferred. Examples of such solvents are benzene, toluene, o-, m- or p-xylene, ethylbenzene, mesitylene, cumene, pseudocumene, amylbenzene, aromatic hydrocarbons having from 6 to 16 carbon atoms, and mixtures thereof, chlorobenzene, o-, m- or p-dichlorobenzene, nitrobenzene, o-, m- or p-dinitrobenzene, o-, m- or pchlorotoluene, diphenyl, phenanthrene, anisole, diphenyl ether, acetophenone, dibenzyl, benzophenone, hexane, heptane, cyclohexane, cyclooctane, ethylcyclohexane, ethylene dichloride, tetrachloroethylene, diisopropyl ether, dipropyl ether, diisobutyl ketone, butyl acetate, butyl benzoate, phenyl benzoate and dimethyl phthalate. Of these, benzophenone is most preferred. It is usually preferable in the present invention to use an imination reaction mixture of benzophenones as the starting benzophenoneimines, and reaction mixtures having benzophenone-imine concentrations of from 1 to 90% by weight, and preferably from 5 to 508 by weight, are usually employed. In case of using the imination reaction mixture, solvent is not always necessary since the unreacted benzophenones remaining in the reaction mixture serves as a solvent. Each step of the process of the present invention will now be described in detail. Step (a): Conditions for the oxidation of benzophenone-imine are not definitely specified as they vary depending on the activity and amount of the catalyst added to the reaction system, and the like, but usually, the copper halide catalyst is used in an amount ranging from 10 2 to 2xl01 mols, and preferably from 2x10 2 to 10 1 mols, per liter of the total volume of the reaction solution. The reaction temperature usually is from 60 to 2500 C, and preferably from 70" to 2300C. The molecular oxygen which can be used includes pure oxygen, air, and other oxygen-containing mixed gases, and the reaction can be carried out either under atmospheric pressure or under elevated pressure. The oxygen partial pressure is preferably from 0.01 to 20 atm., and more preferably from 0.05 to 10 atm., but wider ranges may also be used. In order to minimize side reactions or sedimentation of the catalyst, it is desirable to control the oxidation reaction so that the conversion of the benzophenone-imine falls within the range of from 85% to 99%. In this step (a), the reaction can preferably be carried out according to an embodiment hereinafter described in order to prevent sedimentation of the catalyst and to stably conduct the reaction. Such a preferred embodiment of step (a) comprises conducting the reaction in a multistage system under an oxygen partial pressure gradually decreasing from the former stage to the latter stage and at a conversion gradually decreasing from the former stage to the latter stage, while controlling the conversion so that the molar ratio of benzenephenone-imines to the copper halide in the final stage is maintained at 1 or more. According to this embodiment, since the former stage having a higher ratio of the benzophenone-imine to the copper halide catalyst has a higher permissible water partial pressure of the gaseous phase, it is possible to conduct the reaction under pressure, or to conduct the reaction at a high reaction rate by raising the oxygen concentration in the introduced gas. Further, the reaction can be effected using a small-sized reactor. Furthermore, since the permissible water concentration in the reaction mixture is high, the amount of the gas to be introduced for removal of water needs not to be increased. On the contrary, in the latter stage in which conversion of the benzophenone-imine has proceeded to a certain extent, the molar ratio of the benzophenone-imine to the copper halide and the permissible water partial pressure become smaller. Therefore, the reaction is effected at a rate lower than that of the former stage by reducing the reaction pressure or the oxygen concentration of the introduced gas. The water partial pressure can easily be reduced below the permissible level with a small amount of gas introduced. The reaction rate does not depend on the concentration of benzophenone-imine and becomes lower towards the latter stages by reducing the oxygen partial pressure. The reduction of the reaction rate in the latter stage does not give rise to a serious barrier if a high conversion of benzophenone-imine is provided in the former stage wherein the catalyst has high solubility. In this embodiment, the reaction is carried out in a multistage system wherein the conversion of imines (on the basis of benzophenone-imines introduced into the first stage') is higher in the former stage than in the latter stage, preferably in such a manner that the conversion in the final stage is from 5 to 30%. Further, since the copper halide is apt to get sedimented if the molar ratio of the benzophenone-imines to the copper halide is less than 1, conversion of the benzophenone-imine should be stopped before the benzophenoneimine /copper halide molar ratio falls to less than 1. It is preferable that the benzophenone-imine /copper halide molar ratio be adjusted to 1 to 5, and preferably 1 to 3, in the final stage and 2 to 20, and preferably 3 to 10, in the stage or stages before the final stage. The above-described embodiment of step (a) overcomes various disadvantages resulting from insolubilization and sedimentation of the catalyst, thus making it possible not only to achieve stable continuous reaction at a high conversion of benzophenone-imines but also to reduce the requisite amount of the gas to be introduced. In addition, this embodiment eliminates the necessity to use a large-sized apparatus. Thus, by the above-described embodiment, benzophenone-azines can be prepared with an economic advantage. The term "multistage reaction system" as used herein means a reaction system composed of two or more reaction chambers through which the oxidation reaction mixture successively passes and each of which maintains a different oxygen pressure. Such a reaction system may comprise a plurality of reaction vessels connected in a series, or a plurality of reaction chambers united in one column. The number of stages is not particularly restricted as long as it is 2 or more, but too many stages make operation com plicated. Usually,-2 or 3 stages, and preferably 2 stages, are employed. In this embodiment, large amounts of the copper halide catalyst bring about high reaction rates but in order to control the molar ratio of benzophenone-imines to copper halide within the above-recited range of from 1 to 5 in the final stage, the finally achieved conversion of benzophenone-imines has to be lowered. In turn, small amounts of the catalyst reduce the reaction rate. Accordingly, the amount of the copper halide catalyst to be used should be determined taking into account the factors affecting the reaction rate, such as temperature, oxygen partial pressure, reaction time, etc., and is usually selected from the above-recited range. The molecular oxygen may be pure oxygen or a mixed gas comprising oxygen and an inert gas , e.g., nitrogen, namely air. The partial oxygen pressure is lower in the latter stage than in the former stage within such a range that the oxygen partial pressure in the final stage ranges from 0.1 to 1 atm. and that in the former stage or stages ranges from 0.3 to 10 atm. Oxygen or an oxygen-containing mixed gas is continuously introduced into the reaction system, which is preferably dried. According to this embodiment, the amount of gas to be introduced should be large enough such that the partial water pressure in each reaction stage should be less than the permissible level in agreement with the benzophenoneimine /copper halide molar ratio of the respective reaction stage. Such an amount varies depending upon the reaction temperature, total pressure, oxygen partial pressure, catalyst concentration, retention time, benzophenone-imine cop- per halide molar ratio and the like and, therefore, cannot be definitely determined. However, the total requisite amount of gas to be introduced can greatly be lessened as compared to when the reaction is conducted in one step, because the continuous reaction according to this embodiment can be effected in a multistage system in which different reaction conditions can be applied in conformity with the conversion of benzophenone-imine , i.e., the benzophenoneimines/copper halide molar ratio. Step (b): In step (b), the oxidation reaction mixture obtained in step (a) is brought into contact with an aqueous solution containing a hydrohalogenic acid to thereby hydrolyze the benzophenone-azine to produce a hydrazine hydrohalide-- and, at the same time, to extract and remove the catalyst from the oxidation reaction mixture. The hydrohalic acid used herein can be hydrochloric acid, hydrobromic acid or hydroiodic acid, with hydrochloric acid being preferred. The concentration of the hydrohalic acid in the aqueous solution usually is from 10 to 60t by weight, and preferably from 20 to 40% by weight. The amount of the hydrohalic acid to be used is usually in the range of from 0.8 to 2 mols per mol of the benzophenone-azines subjected to the reaction. Too low amounts of the hydrohalic acid result in unfavorably low conversions of benzophenone-azines. On the other hand, too high amounts of the hydrohalic acid cause a large amount of the hydrohalic acid to remain unreacted in the hydrolysis reaction mixture, which leads to by-production of a large amount of salts after the subsequent neutralization. In cases where the oxidation mixture contains unreacted benzophenone-imines, extraction and removal of the catalyst and hydrolysis of benzophenone-azines are sometimes hindered. Such being the case, it is necessary to use a hydrohalogenic acid in an amount equimolar to the unreacted benzophenone-imines to be supplied in addition to the abovedescribed amount. The temperature, pressure and oil-water contact time employed in step (b) are not particularly restricted, but usually, the temperature is from 60C to 2000C; the pressure is from 0.1 to 10 atm.; and the contact time is from 0.1 to 10 hours. This step can be carried out either in the presence or absence of air, and either in a batch system or in a continuous system. A counter-current multistage operation may also be employed. Step (c): The aqueous solution containing the hydrazine hydrohalide and the catalyst obtained in step (b) is separated from the hydrolysis mixture, and adjusted to a pH of from 3 to 7. If the separated aqueous solution to be subjected to the subsequent extraction step has a pH value less than 3.0, benzophenones-imine supplied in the subsequent step are conspicuously hydrolyzed to reduce the extraction efficiency. Therefore, it is necessary to increase the pH value of the aqueous solution up to 3 to 7 with an alkali, e.g., ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, etc. , preferably sodium hydroxide, prior to step (d). The atmosphere for the pH-adjustment is not particularly restricted, but pH-adjustment is preferably effected in the absence of oxygen in order to avoid decomposition of hydrazines in the aqueous solution as possible. An oxygenfree atmosphere can be achieved by displacing the system with inert gas, e.g., nitrogen, helium, hydrogen, methane, ethane, carbon dioxide, etc., or steam, or by sealing the system. Step (d): This step comprises contacting the aqueous solution at pH 3 to 7 obtained in step (c) with benzophenone-imines to extract the catalyst. The copper halide catalyst can easily be extracted upon contact with benzophenone-imines, and the extract is to be separated in the subsequent step (e) and recycled as a catalyst for oxidation of benzophenone-imines. Conditions for extraction of the catalyst cannot be definitely specified, as they vary depending- upon the concentration of the catalyst in the aqueous solution to be extracted, the type of benzophenone-imines, whether or not an organic solvent is used, the type of the aqueous solution, the mode of extraction, and the like. However, extraction can usually be conducted at a temperature of from 0 to 200"C, and preferably from 30 to 150"C, and for a period of from 1 second to 1 hour. The atmosphere employed for the extraction is the same as described in step (c). The amount of the benzophenone-imines to be used as an extracting solvent in this step may be the whole or a part of the benzophenone-imines which are subjected to the oxidation reaction for obtaining benzophenone-azines. In the latter case, it is also possible that the concentration of the copper halide catalyst present in the benzophenoneimines which have been subjected to extraction is adjusted by addition of the benzophenone-imines which are not subjected to extraction, and the resulting benzophenone-imines solution containing the catalyst is recycled to step (a) for oxidation. The extraction can be effected in either a batch system or a continuous system. In order to improve the extraction efficiency, counter-current multistage extraction can be appropriately adopted. Step (e): In this step, the extracted solution obtained in step (d) is separated into a solution of benzophenone-imines containing the catalyst and an aqueous solution containing the produced hydrazine hydrohalogenide to thereby recover the hydrazine hydrohalogenide as an aqueous solution and, at the same time, the solution of the benzophenone-imines containing the catalyst is recycled to step (a). The hydrazine hydrohalogenide can be obtained as an aqueous solution by this step. It is also possible for the hydrazine hydrohal y bide to be converted to hydrazine hydrate by addition of an alkali, followed by distillation to obtain hydrazine hydrate. The copper halide catalyst thus recovered in an oily layer composed of the benzophenone-imines can be reused as a catalyst for the oxidation of benzophenone-imines with molecular oxygen with no need of any additional treatment. As described above, the present invention makes it possible to recover and reuse the copper halide catalyst by easy liquid-liquid extraction without requiring any extra treatment. Thus, the present invention provides a highly rationalized process for preparing hydrazine hydrohalides with great industrial advantages. The present invention will now be illustrated in greater detail with reference to examples Wherein percentages are by weight unless otherwise indicated. G designates gauge pressures. EXAMPLE 1 (1) Preparation of Benzophenone-azine by Oxidation of Ben zophenone-imine To 300 g of benzophenone-imine solution (benzophenone-imine content: 25.09; benzophenone content: 75; imine: 0.414 mol) was added 1.31 g (13.2 mmol) of a cuprous chloride catalyst, and the resulting mixture was stirred at 1200C under atmospheric pressure for 2 hours while blowing oxygen gas thereinto at a rate of 0.5 NR/min. After the reaction, the reaction mixture was analyzed by gas chromatography and was found to contain benzophenone-imine and benzophenone-azine at concentrations of 1.5% and 23.0%, respectively. (2) Preparation of Hydrazine Hydrqchloride by Hydrolysis of Benzophenone-azine, and Extraction of Catalyst from Oxidation Mixture of Benzophenone-imine Two hundreds grams of the reaction mixture obtained in (1) above and 30.6 g of a 25% aqueous solution of hydrochloric acid (0.210 mol) were contacted at 100"C for 2 hours under stirring to hydrolyze benzophenone-azine and, at the same time, to extract and remove the catalyst. The rate of hydrolysis of benzophenone-azine was 92% (decomposed azine: 0.118 mol). After the reaction, the aqueous layer was analyzed and was found to contain 8.7 mmols of cuprous chloride (extractability: 99.0%) and 0.118 mol of hydrazine hydrochloride (yield: 92.0%). (3) pH-Adjustment of Aqueous Solution Containing Hydrazine Hydrochloride and Catalyst A 40% aqueous solution of sodium hydroxide was added to the aqueous solution containing hydrazine hydrochloride and the catalyst obtained in (2) above under a nitrogen gas stream to adjust to a pH of 5. (4) Extraction of Catalyst with Benzophenone-Imine The aqueous solution having been adjusted to a pH of 5 was contacted with 30 g of benzophenone-imine solution having the same composition as used in (1) above under a nitrogen gas stream at 700C for 20 seconds, to thereby extract cuprous chloride with the benzophenone-imine solution. This extraction operation was repeated twice. (5) Separation of Hydrazine Hydrochloride Aqueous Solution and Preparation of Benzophenone-azine Using Catalyst Extract (Benzophenone-imine Splution) Liquid-liquid separation after the extraction of the step (4) above gave an aqueous solution of hydrazine hydrochloride containing 0.118 mol of hydrazine hydrochloride (yield: 92.0%). The separated catalyst extract (i.e., a benzophenone-imine solution) was adjusted so as to contain 0.85 g (8.6 mmols) of cuprous chloride in 194 g of benzophenoneimine solution (benzophenone-imine content: 25.0%; benzophenone content: 75%; imine: 0.268 mol) by supplying benzophenone-imine and benzophenone. The thus adjusted solution was stirred at 1200C under atmospheric pressure for 2 hours while blowing oxygen gas at a rate of 0.3 NRlmin. The reaction mixture was analyzed by gas chromatography and was found to contain 1.7% of benzophenone-imine and 23.1t of benzophenone-azine EXAMPLE 2 Benzophenone-azine was produced using the apparatus as shown in Figure. In each of 2-liter reactors (3) and (9) each equipped with a gas sparger and stirring wings was charged 1,000 g of benzophenone-imine solution (benzophenone-imine: 25.0%; CuCI: 0.4%; the remainder was benzophenone) as a raw material. The reaction was continuously carried out in the two reactors at 1200C and at 4 Kg/cm2G in reactor (3) and 0 Kg/ cm2G in reactor (9). Benzophenone-imine solution was supplied into reactor (3) through pipe (1) at a rate of 500 g/hr, and air was supplied into reactor (3) through pipe (4) at a rate of 0.85 NQ/min. The reaction mixture was withdrawn from pipe (5). The reaction was continuously carried out so that the raw material resides in reactor (3) for 2 hours in average. The reaction mixture discharged from reactor (3) was supplied into reactor (9) through pipe (7), and air was supplied therein through pipe (10) at a rate of 0.11 NZ/min. The reaction mixture was discharged through pipe (11). The reaction was continuously carried out so that the raw material resides in reactor (9) for 2 hours. After 48-hour continuous reaction, the reaction mixture discharged from pipe (5) contained 3.8% of benzophenone-imine and 21.2% of benzophenone-azine (yield: 85%) and had a benzophenoneimine/copper molar ratio of 5.0. The reaction mixture discharged from pipe (11) contained 0.9% of benzophenone-imine and 24.2% of benzophenone-azine (yield: 96%) and had a benzophenone-imine/copper molar ratio of 1.2. The water concentrations at pipes for discharging air (2) and (8) were 12 mol% and 13 mol%, respectively. The resulting reaction mixture was a clear reddish brown solution, and no sedimentation of copper chloride was observed in either of reactors (3) and (9). COMPARATIVE EXAMPLE 1 The reaction was carried out using only reactor (3) 2 at a pressure of 4 Kg/cm2G. The same procedure as described in Example 2 was repeated except that 2,000 g of the starting benzophenone imine solution was charged in reactor (3) and retained therein for 4 hours in average while introducing air at a rate of 1.40 NQ/min. After 48-hour continuous reaction, the reaction mixture withdrawn through pipe (5) contained 2.3t of benzophenone-imine and 22.5% of benzophenone-azine (yield: 90%) and had a benzophenone-imine/copper molar ratio of 3.1. The water concentration in the pipe (2) was 8.0 mol%. The resulting reaction mixture was opaque and greenish black. Sedimentation of the catalyst was observed in reactor (3), and a part of the sedimented catalyst attached to the wall of reactor (3). COMPARATIVE EXAMPLE 2 The reaction was continuously conducted using only reactor (3) having a volume of 10 liters at a pressure of O Kg/cm2G. The same procedure as described in Example 2 was repeated except that 5,000 g of the starting benzophenoneimine solution was charged in reactor (3) and retained therein for 10 hours on average while supplying air at a rate of 1.0 Ng/ min. After 48-hour continuous reaction, the reaction mixture from pipe (5) contained 1.2% of benzophenone-imine and 23.8% of benzophenone-azine (yield: 95%) and had an imine/ copper molar ratio of 1.6. The water concentration in pipe (2) was 12 mol%. The resulting reaction mixture was a clear reddish brown solution. No sedimentation of the catalyst was observed, but the reaction required a long time and a large-sized reactor. COMPARATIVE EXAMPLE 3 The reaction was continuously performed using only reactor (3) having a volume of 4 liters at a pressure of 2 O Kg/cm2G. G. The same procedure as described in Example 2 was repeated except that 2000 g of the starting benzophenoneimine solution was charged in the reactor and retained therein for 4 hours in average while introducing air at a rate of 1.0 NQ/ min. After the reaction was continued for 48 hours, the reaction mixture withdrawn from pipe (5) contained 15.5% of benzophenone-imine and 9.5% of benzophenone-azine (yield: 38%) and had an imine/copper molar ratio of 21.2. The water concentration in pipe (2) was 4.8 mol%. The resulting reaction mixture was a clear reddish brown solution, and no sedimentation of the catalyst was observed.

Claims: CLAIMS 1. A process for preparing a hydrazine hydronali'de which comprises the steps of: (a) oxidizing a bOnzophenone-imine with molecular oxygen in the presence of a copper halide catalyst to pre pare a -benzophenone-azine (b) contacting the oxidation reaction mixture obtained in step (a) with an aqueous solution containing a hydrohalogenic acid at a concentration of from 10 to 60% by weight, thereby hydrolyzing the benzophenone- azine to produce a hydrazine hydrohalide and, at the same time, extracting and removing the cata lyst with the hydrohalide-containing aqueous solution from the reaction mixture, to obtain an aqueous solution containing the hydrazine hydrohalide and the catalyst; ; (c) separating the aqueous solution containing the hy drazine hydrohalide and catalyst which is ob tained in step (b) and adjusting the solution to a pH of from 3 to 7 with an alkali; (d) contacting the aqueous solution having a pH of 3 to 7 obtained in step (c) with benzophenone-imine to extract the catalyst with the benzophenone-imine from said aqueous solution; (e) separating the catalyst-containing benzophenone imine solution obtained in step (d) from the aque ous solution containing the hydrazine hydrohalogen ide, thereby to recover the hydrazine hydrohal ide as an aqueous solution and to recycle the cata lyst-containing benzophenone-imine solution to step (a). 2. A process as claimed in Claim 1, wherein step (a) is continuously carried out in a multistage system under an oxygen partial pressure gradually decreasing from the former stage to the latter stage and at a conversion gradually decreasing from the former stage to the latter stage, while controlling the conversion so that the molar ratio of benzophenone-imine- to the copper halide in the final stage be maintained at 1 or more. 3. A process as claimed in Claim 1 or 2, wherein the copper halide in step (a) is cuprous chloride. 4. A process as claimed in Claim 1, 2 or 3, wherein the benzophenone-imine in step (a), (d) or (e) is benzophenone-imine, and the benzophenone-azine in step (a) or (b) is benzophenone-azine. 5. A process as claimed in any preceding claim, wherein step (a) is carried out in the presence of benzophenone as a solvent. 6. A process as claimed in any preceding claim, wherein the aqueous solution in step (b) contains a hydrohalic acid at a concentration of from 20 to 40% by weight. 7. A process as claimed in any preceding claim, wherein the hydrohalic acid in step (b) is used in an amount of from 0.8 to 2 mols per mole of the benzophenoneazine 8. A process as claimed in any preceding claim, wherein the oxidation reaction mixture obtained in step (a) contains the unreacted benzophenone-imine and the hydrohalogenic acid in step (b) is used in a total amount of an equimole to the unreacted benzophenone-imine and from 0.8 to 2 mols per mole of the benzophenoneazine 9. A process as claimed in any preceding claim, wherein the hydrohalic acid in step (b) is hydrochloric acid. 10. A process as claimed in any preceding claim, wherein the alkali in step (c) is ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide or sodium carbonate.

Inventors: AOKI, OSAMU, AOKI, YOSHIYUKI, KOHZAKI, TOSHIAKI, NAWATA, TAKANARI, SAKAGUCHI, SHUZABU, SHIMPO, MASAFUMI, TAKEDA, NORIO
Applicants: MITSUBISHI GAS CHEMICAL COMPANY, INC.
Application year: 1985
Main classification: C01B21
IPC codes: C01B21