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United States Patent (19) (11) 4,056,469 Eichenhofer Et Al

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United States Patent (19) (11) 4,056,469 Eichenhofer Et Al United States Patent (19) (11) 4,056,469 Eichenhofer et al. 45) Nov. 1, 1977 (54) PURIFICATION OF WASTE WATER FROM (56) References Cited HYDRAZINE PRODUCTION U.S. PATENT DOCUMENTS 75 Inventors: Kurt-Wilhelm Eichenhofer, 3,767,572 10/1973 Bober et al. ........................... 210/62 Leverkusen; Reinhard Schliebs, 3,923,648 12/1975 Lashley .................................. 210/59 Cologne, both of Germany Primary Examiner-Thomas G. Wyse Attorney, Agent, or Firm-Burgess, Dinklage & Sprung (73) Assignee: Bayer Aktiengesellschaft, (57) ABSTRACT Leverkusen, Germany A process for the purification of waste water produced in hydrazine production by the oxidation of ammonia or (21) Appl. No.: 696,253 an amine with an oxidizing agent in the presence of an aldehyde or ketone, comprising intensively mixing the 22) Filed: June 15, 1976 . waste water with chlorine or a hypochlorite at a tem perature of about 10°C to 110° C and a pH of about 5 (30) Foreign Application Priority Data to 10 until the treated waste water reaches a redox July 3, 1975 Germany ............................. 2529647 potential to platinum, relative to Ag/AgCl, of about -400 mV to +800 mV. Advantageously a small (51) Int. C.’................................................ CO2C5/04 amount of waste water is distilled off both before and (52) U.S. C. ................ ..................... 210/62 after the chlorine or hypochlorite treatment. (58) Field of Search ............................. 210/50, 59, 62; 260/DIG. 2; 423/407,408 9 Claims, 1 Drawing Figure 4,056,469 1. 2 tion at the acid pH of approximately 1.5 necessary when PURIFICATION OF WASTE WATER FROM using sodium chlorite, represents a greater consumption HYDRAZINE PRODUCTION of acid and base. The object of the present invention is a quick and The present invention relates to a process for the 5 economic process for the removal of the disruptive purification of waste water resulting during the produc- . components in waste waters containing hydrazine. tion of hydrazine from aldehydes or ketones. There are This object is realized by the present invention in a number of known processes for the production of volving a process for the purification of waste water, hydrazines using aldehydes or ketones, in which ammo such as that arising in hydrazine production by the nia (or primary amines) is reacted with aldehydes or 10 oxidation of ammonia (or amines) with oxidizing agents ketones in the presence of specific oxidizing agents, in the presence of aldehydes or ketones, which is char such as chlorine or HO, in most cases by way of the acterized in that the waste water is treated at tempera intermediate products hydrazone and ketazine or tures of about 10 C to 110C and at pH values of about diaziridine, to form hydrazine (U.S. Pat. Nos. 2,993,758, 5 to 10 by intensively mixing with chlorine or hypo 3,077,383; German Offenlegungsschrift No. 2,127,229, 15 chlorite, until a redox potential, relative to Ag/AgCl, of U.S. Pat. Nos. 3,869,541, 3,892,805, 3,803,071). about -400 mV to --800 mV has been reached in the The organic hydrazine derivatives, such as hydra treated waste water. zones, aldazines, ketazines or diaziridines are usually It has been found that, according to the process of the removed from the reaction mixture by distillation (U.S. application, at specific temperatures, specific pH values Pat. No. 3,494,737 German Offenlegungsschrift No. 20 and specific redox potentials a practically quantitative 2,361,932) and subsequently converted hydrolytically elimination of organic hydrazine derivatives and hydra into hydrazine hydrate and aldehyde or ketone (Ger zine takes place using practically stoichiometric quanti man Pat. No. 1259,859, U.S. Pat. No. 3,481,701, British ties of chlorine or hypochlorite, which for example in Pat. No. 1,129,613) or converted by the addition of an the case of dimethyl ketazine as the waste water constit acid into hydrazine salts (U.S. Pat. No. 3,010,790). 25 The waste water occurring in these known processes uent can be described by the following formal equation as a rule still contains small quantities of compounds of (1): hydrazine with the aldehydes or ketones, for example hydrazones, ketazines or diaziridines, and in small quan HC eH, (1) tities hydrazine itself. When acetone is reacted with 30 c=N-N=c + 2 NaOCl - G ammonia (or amine) and oxidizing agents, the waste HC CH, water contains, for example, dimethyl hydrazone and HC Aor dimethyl ketazine and/or 3,3-dimethyl diaziridine. N 2 C=O + 2 NaCl + Nat The waste waters also contain, in smaller quantities, a / number of partially unidentifiable organic compounds. 35 HC Depending on the embodiment of the hydrazine pro duction process the waste waters can contain salts, such For the implementation of the waste water treatment as chlorides, sulfates, carbonates, hydrogen carbonates, process according to the invention an extensive separa acetates, formates, hydroxides, cyanates, cyanides, etc. tion beforehand of organic acid radicals, e.g. acetate of sodium, potassium, calcium or ammonium, and other and formate down to low concentrations of approxi organic compounds, such as alcohols or amines. mately 0.1% by weight is advantageous, since in their Owing to its toxicity it has only been possible to intro presence there occurs a corresponding increased con duce industrial waste water resulting during hydrazine sumption of chlorine or hypochlorite. This separation production into biological purification installations by can for example take place by distillation or ion ex diluting it heavily with other waste waters. 45 change, and in the case of distillation the organic acid It is therefore of great interest to subject waste waters radicals remain in the distillation residue. Ammonium resulting during hydrazine production to a purification salts, which are present in the waste water, are usefully which quantitatively removes the hydrazine and the converted by the addition of lyes, releasing ammonia, organic hydrazine derviatives. If the waste water con into potassium, sodium or calcium salts. The quantity of tains large quantities of sodium chloride as a by-product 50 ammonia in the waste water should not exceed about of hydrazine production it is necessary to remove these 0.1% by weight. solutions of organic compounds containing sodium The pH value to be maintained according to the pro chloride, according to a hitherto unknown and particu cess of the invention can be adjusted by the addition of larly useful proposal; chlorine can be produced from the acids, such as sulfuric acid or hydrochloric acid, or sodium chloride in a subsequent chlorine-alkali-electrol 55 bases, such as caustic soda or caustic potash solution. In ysis and used as an oxidizing agent for the production of the case of waste water containing sodium chloride, hydrazines (recycling). Purified waste waters contain hydrochloric acid or caustic soda in concentrated state ing sodium chloride can also be used for the regenera (hydrochloric acid approximately 35%, caustic soda tion of ion exchangers, as cooling sols or in dye produc approximately 40%) are preferred as the agents regulat tion. ing the pH value. Chlorine can be used in gaseous or The purification of dimethylhydrazine containing liquid form or dissolved in water. Hypochlorite is pref. waste waters by means of sodium chlorite is known erably used in the form of aqueous solutions (bleaching (German Auslegeschrift No. 1,242,515). However, the lye) of the sodium, potassium or calcium salts ("bleach 'use of sodium hypochlorite only apparently led to the ing powder'). Since the waste water from hydrazine desired elimination of dimethylhydrazine. The reaction 65 production is as a rule alkaline owing to its hydroxide or time of 24 hours specified for dimethylhydrazine re carbonate content, chlorine is preferred as the oxidizing moval is however uneconomic for large scale waste agent, because it exploits the natural basicity of the water purification. In addition, a waste water purifica waste water and thus the pH range of 5 to 10 according 4,056,469 3 4. to the invention can be maintained particularly econom a constant content of organic hydrazine derivatives and ically. The introduction of chlorine or hypochlorite can hydrazine, of about 0.01 to 0.1% by weight (calculated be controlled by means of a redox potential measure as hydrazine and in relation to waste water). Waste ment, for example by a potential measurement using water having such a hydrazine content of organic hy platinum against a silver-silver chloride electrode. The drazine derivatives and hydrazine is especially suitable redox potential of the waste water to be treated using for the process according to the application. To obtain platinum, relative to the comparative electrode silver a waste water of this type, it is generally sufficient to silver chloride in 3.5 molar potassium chloride solution distill off up to 10% by volume of the waste water origi (-|-200 mV against Standard-Hydrogen electrode) nally present. A reduction of the chlorine or hypochlo should be from approximately -400 to --800 mV, and 10 rite consumption in the subsequent waste water treat preferably between about -200 and -- 700 mV, particu ment is achieved by reducing the content of organic larly preferably between about -- 100 mV and --600 hydrazine derivatives and optionally hydrazine. Possi mV. A very small quantity of hydrazine or waste water ble chlorination of the organic compounds is avoided containing organic hydrazine derivatives corresponds by a reduction of the content of organc compounds in to the negative limit value of the redox potential, and a 15 the waste water- a means of measuring this is the total small quantity of waste water containing chlorine or organic carbon (TOC = total organic carbon values). hypochlorite corresponds to the positive limit value of The distillation causes a TOC reduction of up to about the redox potential.
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