DE1568584A1 - Process for the production of azines and / or isohydrazones or hydrazine - Google Patents

Description

dr. w. Schalk dipl.-ing. Peter Wirth

DIPL-tNG.G.E.M.DANNENBERG DR. V. SCH MI ED-KOWARZI K

6 FRANKFURT AM MAIN

GRi ESCHENHEIMER STR. 39

Boa. 38 884/65 September 8, 1966 SK / Pr.

PISONS Industrial Chemicals Limited Willows Works
Derby Road

Louchborough / Leicestershire / England

¹¹ Process for the production of azines and / or isohydrazones or hydrazine "

The present invention relates to improved processes for the preparation of azines and isohydrazones which lead to hydrazine, Hydrazine hydrate or hydrazine salts can be converted.

The production of azines and isohydrazones is based on the reaction of chloramine and ammonia with carbonyl compounds in the presence or absence of a strong base. In the presence of a strong base the subsequent reaction leads to the azine, and in the absence of a strong base the subsequent reaction leads to the isohydrazone. If an insufficiently strong base is present, a mixture of azine and isohydrazone is formed. The chloramine used in the reaction can be produced "in situ" during the reaction or else in a separate process stage. In general, the chloramine Ü098U / 182S __ ^ _

BATH ORIGINAL

by converting clay to chlorine or a hypochlorite (usually bleach) and ammonia in liquid or gaseous form Phase established.

According to the invention it has now been found that improved results and particular advantages can be achieved if the reaction τοη chloramine with dta aqueous ammonia and a Carries out carbonyl compound in two or more stages.

Thus, the present invention relates to a process for the production of azines and / or isohydrazones, which is characterized in that aqueous ammonia and a carbonyl compound with chloramine in a series of two or more Reacting reaction vessels arranged as a cascade system »This system preferably consists of three or four cascaded reaction * vessels

The reaction can be carried out in the presence of a strong base, e.g. sodium hydroxide, which is added either per se or as Result of using τοη hypochlorite Torhanden 1st, carried out · In this case the resulting product is the azine corresponding to the carbonyl compound used »Should an azine are produced, the p & VYert of the reaction mixture is preferably "as" hen 12.8 and 13 * 5 · Otherwise the reaction can take place in the complete absence of a strong base or in In the absence of a sufficiently strong base, so that the resulting product is either an isohydrazone or a mixture of azine and isohydrazone.

8 ^ / 1626

The chloramine may in situ, for example by the reaction of chlorine and aqueous ammonia, or can be made separately, for B _o, by the reaction of gaseous chlorine, and gaseous ammonia or aqueous hypochlorite and aqueous ammonia ·

Studies of chloramine formation show that it is actually instantaneous, even at the lower temperatures. However, Ks decomposes very quickly, especially when it is produced in aqueous solution (with 8 jo bleaching liquor and 20 % ammonia, for example, the decomposition of chloramine can be determined after about θ indications) Since the chloramine is produced in a separate process step, it is important to add the chloramine to the aqueous ionic acid and the carbonyl compound as quickly as possible. The residence time depends, of course, on the flow rate of the durometer, but it must be measured in such a way that complete chloramine formation is possible without decomposition can occur

The application of the cascade system according to the invention offers the Advantage that only a simple technical system is required, and high molar ratios of the participants in the individual Process stages are given while very low total moles Ratios are required. Besides, there is such a thing System «very easy to use.

0 0 9814/182 6 bad original

If the chloramine is made in situ, it will two times by the implementation τοη gaseous chlorine with aqueous ammonia.

When producing τοη chloramine in a separate process » stage, this is done in two ways by reacting τοη aqueous ammonia and lead hydroxide (i.e. aqueous vatriumhrpoehlorit) or by implementing τοη gaseous chlorine and gaseous Ammonia «In the case mentioned last, the reaction takes place occasionally when it enters the reaction vessel, for example by introducing the gaseous ammonia and the gaseous chlorine through concentric double nozzles.

The reaction according to the invention is carried out by adding the chloramine or the chloramine-forming reaction * to each participant individual vessel of the series are added while the largest part and τ. or say the total amount of carbonyl bond can only be added to the first reaction vessel · Me required amount of aqueous ammonia is torsugly total ■ given the first reaction vessel, while only the aqueous x ^ ixak, which (if necessary) is required for chloramine formation, is added to the following reaction vessels.

You use th carboxyl compounds can be a Ke tea or Aldehyde of the cowardly formula

E ¹

- Q

in which R is hydrogen or an alkyl group with tor preferentially

009814/1826

1 to 4 carbon atoms, such as methyl »ethyl _ε propyl or

Butyl ι 1st! R represents an alkyl group with preferably 1 to 4 Carbon atoms such as methyl «ethyl» propyl © or _{butyl β or}

1 2 is an aryl group, like phenyl ₉ , οά · τ in ό. & Ν R and 1 together with the carbon dioxide of the carbonyl group Form eyeloaliphatic ring · Suitable carbonyl compounds Examples include acetaldehyde »propionaldehyde, methyl isobutylene ketone, diethyl ketone» benzaldehyde and gyelohexanone · Preferably acetone or methyl ethyl ketone is used as the carbonyl compound «. Preferably at least 2 UoI will be achieved Carbonyl compound used per mole of hydrazine formed *

An agent such as gelatin or ethylene diamine tetra acid can be used acid can be used to remove any ions that may be present Might interfere with reaction »remove · This action is jadooh. not an essential part of the procedure

The method according to the invention can be carried out at atmospheric pressure or also, with increased. Pressure carried out, are · Venn with increased. Druok is worked, »so this should preferably not more than 20 At above atmospheric pressure

The temperature at which the individual stages of the process according to the invention are carried out «is. not essential.) ea can, for example, with any temperature between. Q ⁰ G or below and the boiling point of the carbonyl compound aei dem. The pressure applied is worked out when carrying out the process in the absence of a sufficiently strong base

0098 U / 1826 ^B * o original

** ■ Isohjrdrason ohn · Starting in is formed, it is sweekaäfiig- • th _t both stages dea traversed at a temperature "wieohen 25 tmd 45 ° C to perform · When performing muddled dee in the presence of a sufficiently strong base, so Dafi haupteäohlioh or aueeohliefllioh that azine is formed, the slower reaction is the formation of azine from hydrasos, and the rate of this reaction increases with increasing temperature, so that preferably the higher temperatures, ζ · Β · 40-55 ° C, are used will·

The practical effect of the present invention is explained in more detail, for example, in the enclosed Figures 1, 2 and 3, and they show processes in which chloramine is produced in a separate process stage from bleaching liquor and ammonia. These figures illustrate a reaction in which chloramine is produced from 2 moles of ammonia and 1 mole of lead hydroxide. The chloramine can, however, if necessary, also be produced using other proportions of ammonia to lead liquor. In the processes shown in Figures 1, 2 and 3, the molar ratio of ammonia to lead liquor in each reaction vessel is a total of 30t 1 »In the two-stage process (Figure 1) the total molar ratio is Ammonia lead liquor I6s1 / ~ (28 + 2 + 2) (1 + 1) J 1 the sesamtmol never receives Ia dea broad level experience (figmr 2) τοη ammonia lead liquor. 11.3 * 1 / ~ ( ²⁸ + 2 + 2 + 2) (1 + 1 + 1) _7, while, it is in the tiers tufenrfahrea (figure 3) 9i1 / ~ (2β + 2 + 2 + 2+ 2) + (1 + 1 + 1 + 1) J is.

0098U / 1826

tin lower deasminrrehaltniii Aaa @ aiak au. Bl®ishla «g © see below

can a small amount of dee Hefcktioaßproifakt »» «ms the final stage bu of the first stage Eurüok led w®sdea _s lhareh diase Suokftthrung it is possible to keep the molar ratio in &« n uni & en levels high »while simultaneously the fieesmtronhalt is kept low» read Yerhäl1aai8 ₉ alt dem the It & tage susiielo

is led, bestinat ä & a in j®der level Torhfiaasae Molir @ rMlt-Ailg «i®i» it is «trwüneoht, the iJ5E; oniakkoss © m; T9.tlon la

the fieEktisn. © o hock like mSglioli aa hold ₉ «at should also di @ Konssentratiom" des Irnmmleke ^ that of the watery healings a «a Aamoniek BBi _a S ₀ B * 35 $ & «i Ιλήμ» 'ssoporetus "« Ed aaraalea jfereeikg) © feglsiiali iJie with ®iaer Briuiliuag ■ des Breiake-e #besfaile © rköht wtMea

Sas tob. Is © bydr * s © a is TOstatliekea, - feoio AaIa ₀ I buttocks man "fees? ¥ ®rw9Bdnsg eines? Eteasfe © ®. 3ί% β® kesgescaü'fe tifeHa Isqsä & ® ä> € äs ^ .T5 su ü- io ^ siLrassi
gewaadalt w © adeis <>. Soalt feSasöa. ülo wassigGB- Asia © leicht sm hydrassin salts uagewanäelt wesäesj) iasLsa susel si® EdLt treated with an acid * such as hydrochloric acid® or sulfuric acid | However, they can also be converted directly to hydrate, such as by distillation * which is carried out twice under pressure. This embodiment of the invention is a very effective and economical process for the production of hydrazine, since the carbonyl compound is obtained as a different product in the hydrolysis and can be fed back into the process.

009814/1826

The isohydrazone or the hybrid of azine and isohydrazone, the be obtained by the process according to the invention in the absence of a sufficiently strong base, can also hydrazine salts, such as hydrazine sulfate, by hydrolysis with a strong Acid can be converted · By appropriate treatment of the hydrazine salt · hydrazine hydrate can be produced «Azine and isohydrazone can also be converted to hydrasine hydrate by treatment with cation exchange resins

The following examples explain the present invention example 1

The procedure of this example was carried out using an apparatus as shown in Figure 4.

Using the apparatus illustrated, 30 moles / hour were obtained. aqueous ammonia (30 wt .- ^ b) and 7 mol / h. Methyl ethyl ketone fed to the first reaction vessel | the mixture arrived at this point Duroh overflow into the second and then into the third reaction vessel · After all three reaction vessels have been filled, were given 1 mole / hour to each jar. Chlorine and 50 w / w - # aqueous Sodium hydroxide added so that at 35 ° C the pHA value in each Fieaktionsgefäß was between 12.8 and 13.5. The Seaktionsgefäß provided with a stirring gate also contained dust and water. Locking devices to ensure good mixing and a balanced

0098U / 1826 bad original

to enable sufficient dispersion of the chlorine gas · With a residence time of 15 minutes in each reaction vessel and a temperature of 35 ° C, the yield of methylethylketonazine was 90 $. The total _{molar ratio Cl 2} iNH to iMethylethylketoniNaOH was 1110 * 2.33 / 2.

Example 2

The procedure described in this example was carried out using the method described in S ¹ Ig. 5 performed Vorriohtung shown.

using the device shown, 30 moles / hour were obtained. aqueous ammonia (30 wt .- ^) and 7 mol / h. Methyl ethyl ketone fed to the first heating vessel} the mixture reached this point by overflowing into the wide and then into the third reaction vessel, after all three reaction vessels were filled each reaction vessel at a rate of 2 moles / hour. 30 wt .- ^ aqueous sodium hydroxide added, and at the same time were fed through the concentric double nozzles to each reaction vessel Ammonia and chlorine added, namely the gaseous ammonia at a rate of 2 mol / hour. through the outer nozzle and gaseous chlorine at a rate of 1 mole / hour. through the inner nozzle. At a reaction temperature of 33 0 and a residence time of 15 minutes in the reaction vessel the yield of methylethylketonazine 92 $ 6.

0098U / 1826 bad o « _e , NAL

Example 5

Chloramine was produced in three separate Y-shaped reaction vessels which opened into three tank-shaped reaction vessels arranged one behind the other with a stirrer, as shown in FIG a 6% lead liquor solution is prepared and continuously fed to each tank-shaped reaction vessel provided with a stirrer at a rate of 1 mol / hour. fed. At the same time, 6 hauls / hour were carried out. Methyl ethyl ketone and 38 moles / hour. 35 ⁰ Mg ** aqueous ammonia fed to the first reaction vessel. Thus the total molar ratio of ammonia bleach in each tank-shaped reaction vessel provided with a stirrer was 40 »1» and the total ammonia / bleach ratio was about 15 <1 ». The yield of azine was 96 $.

Example. 4th

The procedure according to Example 3 was repeated, but with the 35 ^ ige aqueous Amaoni ak by the with a stirring device equipped, tank-shaped reaction vessel at a speed of 24 fetch / hour was performed, being in each reaction vessel a total ammonia / lead liquor ratio of 2611 and an ammonia / lead liquor ratio of 10% in total were achieved. The asim yield was 94 ji.

0098U / 1826

example 5

The process according to Example 3 was repeated, except that acetone was used instead of methyl ethyl ketone. The acetone azine was obtained in a yield of 93 % .

Example 6

The procedure of Example 1 was repeated, except that no sodium hydroxide was added. The product consisted of a mixture of azine and isohydrazone from methyl ethyl ketone. Hydrolysis of a sample with dilute sulfuric acid and the subsequent titration of the hydra & insulphate with potassium iodate showed that “a S2 ßä.gB yield aa Hyäraasia had been achieved. The addition of a sample of the products followed by a solution of potassium iodine 2 M-Sahwefoleic acid followed by the addition of the released. Iodine with sodium thiosialfate s © igtQ _a tsS 73 $ ^ -®s hydrazine as Iaohydrazone TorhuLden. was «

Example 7

The procedure according to Example 2 was repeated, except that no * Hatriunhydroxyd was added. A 92% yield was obtained and 75 % of the hydrazine was obtained as leohydrazone.

0098U / 1826

Claims (1)

Claims 1. Process for the preparation of azines and / or Ieohydrazones, characterized in that aqueous ammonia and a carbonyl compound with chloramine in two or more in Row and arranged in a cascade system reacted reaction vessels. 2 «Method according to claim 1 * characterized in that the total carbonyl bond serving as reactant is only added to the first reaction vessel. and 2 5 · The method according to claim 1, characterized in that the The reaction is carried out in 3 or 4 reaction vessels arranged in a cascade system. 4. Method according to claims 1-5, characterized in that the reaction is carried out in the presence of a strong base, if the product is that of the carbonyl compound used corresponding azine is to be obtained 5. The method according to claim 1-5, characterized in that the reaction is carried out in the absence of a strong base when the product is isohydraeon or a mixture Isohydrazone and azine, according to the carbonyl compound used, is to be obtained. 0098H / 1826 6. The method according to claim 1-5 »characterized) that the Chloramine is produced in situ by reacting gaseous chlorine and aqueous ammonia in each reaction vessel. 7. The method according to claim 1 - 5t daduroh characterized in that the Chloramine, is produced in a separate process step from aqueous ammonia and lead hydroxide. 8. The method according to claim 1-5 »daduroh characterized in that the Chloramine in a separate process stage from gaseous Ammonia and gaseous chlorine is produced. 9. Procedure according to. Claim. 8th,. daduroh marked that the Chloramine is formed upon entry into the reaction vessel. 10. The method according to claim. 9 % characterized in that the gaseous Α ^ τηοη τ ^ V and the gaseous chlorine are introduced through concentric double nozzles .. 11 »Procedure, according to claim. 1 - 1Q, daduroh marked ^ that the total required amount of aqueous · «. Ammonia the first Reaction vessel is added. 12. The method according to claim 1-10, characterized in that only which may be necessary for the formation of chloramine · aqueous · Ammonia of the second and the subsequent reaction vessels and the remainder of the required aqueous ammonia the first Reaction vessel is supplied. 009814/1 £ 26 ^ßÄD original 13. The method according to claim 1-12, characterized in that as the carbonyl compound, a ketone or aldehyde of the following formula Is used in which B is hydrogen or an alkyl group 2 is, R represents an alkyl or aryl group, or in which 1 2 £ and E together with the carbon atom of the carbonyl group form an oyoloaliphatic sing. 14 »Method according to claim 13» characterized in that acetone or methyl ethyl ketone is used as the carbonyl compound. 15. The method according to claim 1 - I4 *. characterized in that at least 2 moles: Caxbonyl-Yerhverbindungen per mole of that formed Hydrazines are used " 16. The method, naoh claim 4, characterized in that it at a temperature of 40 - 55 ° G is carried out. 17 * The method according to claim 5i is characterized in that it »At a temperature τοη 20 - 45 ° G is carried out * The patent attorney! 009614/1926 AB blank page