JPS58210072A - Manufacture of cyanuric chloride suspension in water or method and apparatus for reacting cyanuric chloride and ammonia or amine - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method and apparatus for producing a suspension of cyanuric chloride in water or reacting cyanuric chloride with ammonia or an amine as set forth in claims 1 and 7. Regarding.

Processes for producing suspensions of cyanuric chloride in water have been known for some time. That is, West German Patent Publication No. 1670
No. 731 discloses a method for introducing molten cyanuric chloride into water. This method is carried out, for example, as follows. A water stream is created on the inner wall of a vertical cylinder and the molten cyanuric chloride is blown into the head of the cylinder through a heatable nostle suitable for spray dispensing. However, this method has some drawbacks. For example, there are problems such as the fact that a layer of solid cyanuric chloride is easily formed on the surface of water and shattered, and that this method cannot obtain a cyanuric chloride suspension having an average particle size of 20 μm or less. Furthermore, in the known apparatus of this type, a portion of cyanuric chloride sublimates, which tends to cause nostle clogging.

German Patent Publication No. 2850242 describes a method for producing a suspension of cyanuric chloride in water, in which liquid cyanuric chloride is sprayed into a tubular container through a spray nozzle arranged at the top of the container. In this case, the tubular container is closed or can be closed at the top and tapers downwards into a thoracic shape with an opening. The water is ejected from 11 or more nostles located above the tapered area and forms a liquid layer that flows along the entire vessel wall up to the cyanuric chloride injection nostle. flows.

This method is also not completely satisfactory. The reason for this is that in practice the particle size of cyanuric chloride in the suspended suspension cannot reach the desired small particle size.

Furthermore, this method does not allow for the production of finely dispersed suspensions with high concentrations of cyanuric chloride, for example, 20% by weight or more. This is because if the concentration is higher than that, shell-like substances will be formed. The need for special reaction vessels is also a drawback of this method.

West German Patent Publication No. 2850331 also already describes the reaction of molten cyanuric chloride with amines. However, this process requires a special reactor, which is described in detail.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a new method which eliminates to the maximum extent the above-mentioned drawbacks of the previously known methods. In particular, the object of the present invention is to provide a new method capable of producing an aqueous suspension of cyanuric chloride having an average particle size of 20 μm or less and a concentration of cyanuric chloride of 20% by weight or more.

This objective was achieved by the method of the invention. That is, according to the present invention, it is possible to produce, for example, a 30% suspension of cyanuric chloride in water having a particle size of 0 to 20 μm. A preferred embodiment of the invention utilizes a specially adapted injector, which can be attached to a conventional reaction vessel. Furthermore, by employing the method of the present invention, it becomes possible to easily react cyanuric chloride directly with an ammonia solution or an aqueous solution or suspension of an amine.

Accordingly, the present invention provides a method for producing a suspension of cyanuric chloride in water by contacting molten cyanuric chloride with water or an aqueous solution or suspension of an ammonia or amine, or a method for producing a suspension of cyanuric chloride in water, or a mixture of cyanuric chloride and ammonia or an amine. The method is characterized in that molten cyanuric chloride is injected into water or into an aqueous solution or suspension of ammonia or amine through a nostle immersed in the liquid. shall be.

The temperature of the cyanuric chloride melt ranges from about 146°C to about 190°C below the melting point of cyanuric chloride, preferably from 155 to 180°C.

The temperature of the watery amine solution or suspension before the addition of cyanuric chloride is started is from 0 to 40°C, preferably from 0 to 25°C.

As amines in the process of the invention come into consideration aliphatic, aromatic or even heterocyclic amines, i.e. primary and secondary amines, as exemplified below, and also especially those containing primary or 27-mino groups. Dyes or fluorescent brighteners as well as their intermediate products come into consideration.

Examples include methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, n-methylamine, isomethylamine, tert
- Methylamine, 3-methoxypropylamine, α-aminoisophthyronitrile, aniline, n-ethylaniline, 2-13- or 4-aminopyridine, as well as naphthylaminesulfonic acid, aminonaphtholsulfonic acid, aminoanthraquinone, aminostyl Examples include hensulfonic acid or anthraquinone dyes having at least one unsubstituted or monosubstituted amine group.

The amine and cyanuric chloride are generally used in approximately stoichiometric amounts, although a small excess of one component, for example up to 10%, is acceptable.

The weight ratio of ammonia and amine to water can vary within a wide range. Generally 5 to 50%, preferably 10 to 40% solutions or suspensions are used.

If desired or necessary, conventional dispersants can be added to the aqueous suspension of the amine to improve the fine dispersion of the amine.

Spraying of molten cyanuric chloride is preferably carried out using a heated nostle, which is not submerged in the liquid;
I'm here. By using a spray nostle with the structure described in detail later, it is possible to start and stop the spray nostle while immersed in the d-liquid, and the heating system of the nostle prevents excessive heat from being applied to the reaction solution or suspended matter. The spraying conditions are such that the average particle size of cyanuric chloride after spraying is 0.5 to 200 μm, preferably 1 to 1 μm.
00/1m.

Particularly preferably, the thickness is selected to be 5 to 20 μm.

The method of the invention can be carried out either batchwise or continuously, the latter being preferred.

According to the method of the present invention, it is possible to produce a fine particle suspension containing cyanuric chloride in an amount of 50% by weight or more. Depending on the experimental conditions, the primary particles may aggregate to form loose agglomerates, but when a slight mechanical stress is applied, the agglomerates easily disintegrate and return to their original particle state. Long milling times, such as in the state of the art methods mentioned in the introduction, are not necessary. A suspension with a particle size of 5 to 20 μm is obtained which is virtually free of hydrolysis products.

Spraying cyanuric chloride, rather than water, into an aqueous solution or suspension of ammonia or an amine directly yields the reaction product of cyanuric chloride with 1'- or 2 moles of amine.

The molar ratio of the reaction products cyanuric chloride to amine depends on the ratio of the amounts used.

The method according to the invention is advantageously carried out by means of the apparatus according to the invention as defined in claim 7. An embodiment of the apparatus of the present invention will be described in detail below with reference to the drawings.

The illustrated device consists of two circuits.

namely, the melt circuit SMK and the suspension circuit SUK.

Melt circuit - 1 cyanuric chloride sump bath melting kettle 1, filter 2, feed (and circulation) pump 3, pressure holding valve 4 and various conduits not shown in details of the sump connecting these components. includes. The suspension circuit SUK includes a crystallizer (water tank) 5, an attritor 6, a circulation pump 7, a cooler 8 as well as various connecting pipes which are also not shown in detail. Furthermore, the apparatus includes an inlet pipe 9 for introducing the liquid phase (water or aqueous ammonia solution or amine solution or suspension) into the crystallizer 5, and an outlet pipe for removing the suspension from the suspension circuit SUK. 10 are provided. The device further includes an injector 11 as a central element. This injector 11 is connected to the melt circuit SMK and injects the melt (cyanuric chloride) into the liquid phase present in the crystallizer.

The construction of the injector 11 is shown in FIGS. 2 and 3.

That is, the injector 11 includes a bottle-shaped dip bell 21, open at the bottom, and a spray nostle 22 arranged concentrically within the dip bell. The spray nostle 22 is fixed by a cap nut 23 and a threaded collar 24 so that it can be immersed. The immersion bell 21 has two water inlet pipe connections 25 facing each other at approximately half its height.
has. Slightly above this connection there are two further pipe connections 26 and 27, which are used for introducing and discharging pressure gas (nitrogen), respectively. The introduction and discharge of this nitrogen are controlled by valves 46 and 47, respectively.

Furthermore, this immersion bell is provided with a connection 28 for a pressure line.

The injector-specific atomizing nostle 22, as can be seen in FIG. 3, consists essentially of three cylinders 31, 32, 33 between which two annular chambers 34, 35 are formed. ing. - The inner cylinder 33 forms the actual nozzle. That is, the cylinder 33 has a pipe connection port 36 for introducing the melt and a pipe connection port 37 for introducing heat at one end thereof, and one nozzle body 38 is screwed into the lower end thereof. ing.

The middle cylinder 32 forms a heating jacket 7 for the nostle. That is, the cylinder 32 has pipe connections 39.4 facing each other for reservoirs of heating medium (usually ?[+1).
0 is set.

The annular chamber 35 formed between this intermediate cylinder 32 and the innermost cylinder 33 is completely partitioned into two halves by a partition wall 41 that does not reach the lowermost part, and the ambiguous part is at the lower end. The heating medium can flow sufficiently uniformly through the heating jacket due to the mutual communication between the heating medium and the heating jacket.

The outermost cylinder 31 forms the thermally insulating jacket of the nostle reservoir. The presence of this insulating jacket prevents the liquid in which the injector is submerged during operation from being heated and shattered by the injector.

The outer annular chamber 34 is connected for this purpose via a connection 42 to a vacuum source (such as a vacuum network).

The entire injector 11 is held suspended by various conduits connected to it and is attached to the crystallizer 5 such that the spray nostle 22 is located below the liquid level 43 (FIG. 2), i.e. submerged in the liquid. Can be fixed.

”--The operation of the device described below will be explained below.

The molten cyanuric chloride is pumped through a p-filter in the melt circuit SMK. A partial stream in an amount regulated by the pressure holding valve 4 and the feed pump 3 enters the injector 11 and is sprayed into the aqueous solution or suspension of water or ammonia or amine in the crystallizer 5. be done.

The contents of the crystallizer 5 are circulated through the suspension circuit SUK and cooled in the process. Any agglomerates that may arise are ground up by the attritor 6. After the suspension has reached a predetermined solids concentration, or after the reaction of cyanuric chloride with ammonia or amine has ended, a partial stream is taken up continuously via the discharge conduit 10 and a corresponding volume of water is removed. Alternatively, an ammonia extract, an aqueous solution or a suspension of the amine is replenished via the feed line 9.

To start the injection, the nitrogen introduction valve 46 is opened and the immersion bell 21 is filled with nitrogen by kneading. Due to this nitrogen pressure, the liquid level inside the immersion bell is raised to the tip 1 of the spray nostle 22.
It is pushed down at the point where it is no longer immersed in the liquid.

In this state, the melt passage inside the spray nozzle and the nozzle tip 4N
(Nostle body 38) is heated. The cyanuric chloride melt is then supplied into the spray nostle, and at the same time the vent valve 47 is opened to release the nitrogen pressure. This causes the liquid level in the immersion bell to rise and the spray nostle to be immersed in the liquid. In this way sublimation of the melt and leakage of hydrolysis products (hydrochloric acid) are prevented.

By controlling the liquid level in the dip bell as described above, there is no need for a movable spray nostle. This is advantageous in several ways. - The liquid level control mentioned above and the vacuum insulation of the spray nostle simultaneously ensure that a large amount of undesired heat is not released into the liquid surrounding the nostle. This prevention of heat transfer is a prerequisite for the production of cyanuric chloride suspensions. This is because the nostle heating temperature is relatively high (
(160 DEG -190 DEG C.) and the tendency for hydrolysis increases sharply with increasing water temperature.

Fresh water or an aqueous solution of ammonia or amine can be fed into the dip bell 21 by means of the water inlet connection 25, so that the area directly surrounding the injection nostle 22 can additionally be cooled by the fresh supply liquid.

Control of the liquid level in the soaked ore can be carried out manually or by opening and closing valves 46 and 47 as appropriate using an automatic control device (not shown).

Examples are given below to further explain the present invention. All parts in the examples are parts by weight and temperatures are in degrees Celsius.

Example 1 108 parts of 2[(4-amino-2-ureidophenyl)-azo]-naphthalene-3,6,8-trisulfonic acid is fed as a 17% aqueous solution in a dispersion column, and its liquid level is 1 through the pressure spray nostle located lower.
36 parts of molten sheamer chloride at a temperature of 60° C. are blown in.

At this time, the temperature of the reaction solution rises from room temperature by about 30 to 40°C. This reaction solution is pumped into a reaction vessel, where the pH is adjusted to 4 to 4.5 by adding caustic soda.
The reaction is terminated while maintaining a constant value. The dichlorotriazine compound produced 10 minutes after the end of cyanuric chloride supply is reacted with ammonia to obtain a reactive dye of the following formula.

The resulting dye had a purity similar to that produced by conventional methods.

Example 2 1-amino-8- as a 30% aqueous slurry at a temperature of 0°C
35 parts of a cyanuric chloride solution at 160 DEG C. are blown into the dispersion column, which is fed with 60 parts of naphthol-3,6-disulfonic acid, through a pressure spray nostle located below the liquid level. At this time, the temperature of the reaction suspension is approximately 1
It rises at 0°C. This is pumped into a reaction kettle where the pl+ is adjusted to 1.5-2.
The reaction is terminated at a temperature of 5 to 10°C while maintaining a constant value of 0°C.

One hour after the end of the cyanuric chloride feed, free amine is no longer detected. As a result of a cup link test by titration with a cyasonium salt solution using a conventional method, the theoretical value of 95
It can be seen that the yield is less than 4%. The dichlorotriazinyl-amino-naphtholsulfonic acid thus prepared can be used directly in the preparation of reactive dyes.

Example 3 60 parts of a cyanuric chloride melt at 160° C. are blown into a dispersion column through a pressure spray nostle located below the liquid level. In this dispersion column, 10% of 4.4'-diaminostilhene-2,2'-disulfonic acid sodium salt at a temperature of 0°C was simultaneously added.
Stoichiometric amount of aqueous solution (1 mole of siamer chloride
/2 mol).

This reaction suspension is continuously pumped into the reaction vessel. In this reaction vessel, the temperature is protected to below 20°C with ice, and the pH is maintained at a constant value of 4.5 with caustic soda. The compound thus produced, N,N'-his-(4,
6-Cycloru1. , 3,5-triazin-2-yl)
-4゜4'-Diaminostilhene-2,2'-disulfonic acid-sodium salt can be directly subjected to the next step of fluorescent brightener production, and the yield and quality are the same as before. give.

Example 4 In the same manner as in Example 3, 60 parts of cyanuric chloride melt and 4,4'-diaminonutylhene-2,2'-
A 30% aqueous dispersion of disulfonic acid disodium salt was reacted. A fluorescent brightener was produced from this in almost quantitative yield.

Example 5 In the same manner as in Example 3, 45 parts of a cyanuric chloride melt at 160°C was reacted with 72 parts of a 20% aqueous isopropylamine solution at 0 to 5°C.

In the reaction vessel, the generated hydrochloric acid was neutralized with about 33 parts of 30% caustic soda while keeping the pH constant. After one hour, when virtually no more caustic soda has been consumed,
Analysis (nitrite titration) confirmed complete completion of the reaction.

The cyclo-isopropylamino-triacine thus prepared can be reacted with an amine such as ethylamine in a conventional manner to form a herbicide.

Example 6 45 parts of a trichlortriazine melt (160° C.) are blown into a dispersion column, which is fed with 21 parts of a 30% aqueous ammonia solution, through a pressure spray nostle located below the liquid level. The reaction mixture is continuously pumped into a reaction vessel where displacement is completed at a temperature of about 25° C. while maintaining the pH at a constant value between 8.5 and 90 with caustic soda. Amino-dichlorotriazine is obtained in a quantitative manner, which can be used directly for the preparation of reactive dyes.

Example 7 Trichlorotriazine melt (
160°C) was blown below the liquid surface. During this time, the temperature of the reaction mixture rises to about 10.degree. This is continuously pumped into a reaction vessel where it is plied with caustic soda.
The reaction is completed at a temperature of 10° C. while keeping H at a constant value of 50°C.

2.4-His-(3-amino-4-
Sulfoanilino-6-chloro-1.3,5-triazine is obtained, which can be used further for the preparation of reactive dyes.

Example 8 60 parts of a trichlortriazine melt (160° C.) are blown into a dispersion column, which is fed with 215 parts of water at 3° C., through a spray nostle located below the liquid level. The dispersion group prevents the liquid temperature from increasing due to external cooling.

This gives a 28% suspension of cyanuric chloride in water. The particle size of the obtained cyanuric chloride particles is between 0 and 201°C. Yield loss due to hydrolysis is less than 0.01%.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram illustrating an example of an apparatus for carrying out the method of the present invention. FIG. 2 is a detailed sectional view of the injector. FIG. 3 is a longitudinal sectional view of the specific spray nozzle shown in FIG. 2; FIG. 4 is a cross-sectional view of the spray nostle taken along line A--A in FIG. [Explanation of symbols of main parts] SMK...Melt circuit SUK...Suspension circuit 1...Melting pot 5...Crystallizer (tank) 6...Attritor 3...Supply-circulation Pump 9...Liquid phase (water or aqueous solution or suspension of ammonia or amine) supply conduit 10...Suspension removal conduit 11...Injector 22...Spray nostle 4 ... Pressure holding valve 7 ... Circulation pump 8 ... Cooler 21 ... Immersion bell 46.47 ... Pressure waste control valve 26 ... Pressure waste (nitrogen) introduction pipe connection port 27 ...・Pressure waste (nitrogen) outlet pipe connection ports 31, 32, 33...Three cylinders 35 arranged concentrically...An annular chamber (heating jacket) formed between the inner cylinder and the intermediate cylinder ) 39.40...Pipe connection port 34 for the heating medium (oil) reservoir...Annular chamber (thermal insulation jacket) formed between the intermediate cylinder and the outer cylinder 42...The annular chamber 34 is evacuated Application for connecting port to connect to source Person: Chiharikiakchenkesselschaft □1m Continued from page 1 Priority claim @May 24, 1982 ■Switzerland (CH)
■3184/82-4 0 Inventor Rudolf Büttaker Switzerland Lien 4125 Arnica Strasse 9

Claims (1)

[Claims] 1. Contacting molten cyanuric chloride with water or an aqueous solution or suspension of ammonia or an amine to produce a suspension of cyanuric chloride in water, or contacting cyanuric chloride with ammonia or an amine. A process characterized in that, in the reactor process, molten cyanuric chloride is injected into water or into an aqueous solution or suspension of ammonia or amine through a nozzle that is immersed in the liquid. 2. Process according to claim 1, characterized in that the molten cyanuric chloride has a temperature of 146 to 190°C, preferably 155 to 180°C. 3. Before addition of cyamel chloride, the temperature of the water or aqueous solution or suspension is 0 to 40°C, preferably 0 to 2°C.
2. Process according to claim 1, characterized in that it has a temperature of 5[deg.]C. 4. Process according to claim 1, characterized in that the ammonia or amine is used as a 5-50%, preferably 10-40% solution or suspension. 5. A method according to claim 1, characterized in that the nozzle is heated. 6. A patent characterized in that at the start of injection, the liquid level of the liquid surrounding the nozzle is lowered by a liquid level gauge that does not allow the tip of the nozzle to be immersed in the liquid, and immediately after the start of injection, the liquid level is raised again. A method according to claim 1. 7. A melting pot and a tank for the cold liquid (water or ammonia or an aqueous solution or suspension of the amine);
A device for carrying out the method according to claim 1, comprising a melt conduit extending from the melt kettle through the cold liquid tank and having an injector at its end towards the liquid tank. In the device, the injector is located below the level of the cold liquid and inside a dipping bell, the dipping bell being connected to a pressure source via a first opening/closing means and a second opening/closing means. and when the first opening/closing means is open and the second opening/closing means is closed, the level of the cold liquid in the dip bell is equal to the level of the injector. A device characterized by a descent below the level. 8. Device according to claim 7, characterized in that the injector is formed by an atomizing nostle and a pressure-supply pump is arranged in the melt conduit. 9. The melt conduit is configured as a circulation line and branches into two downstream of the pressure-supply pump, one branch extending to the nostle and the other branch extending to the melt 9. Device according to claim 8, characterized in that it is returned to the kettle and that an adjustable pressure-holding valve is preferably arranged in the latter branch. 10. Apparatus according to any one of claims 7 to 9, characterized in that the cold liquid tank is connected to an external circuit having a pump and a cooler. 11. Claim 10, characterized in that a grinder for crushing agglomerates is disposed in the external circulation path of the cold liquid tank upstream of the cold liquid pump. equipment. 12. Claims characterized in that, downstream of the attritor and preferably also downstream of the pump and cooler, a suspension removal channel is branched off from the external circuit of the cold liquid tank. 10. The device according to item 11. 13. Apparatus according to any one of claims 7 to 12, characterized in that at least the bowed part of the melt conduit that comes into contact with the cold liquid is thermally insulated on the outside thereof. 14. Apparatus according to claim 13, characterized in that the melt conduit section, which is thermally insulated towards the outside, can be heated effectively on the inside thereof. 15. Claim 13 or 1, characterized in that the nostle is inserted or screwed into the externally insulated and internally heatable conduit section.
The device according to item 4. 16. Apparatus according to any one of claims 13 to 15, characterized in that the insulated section of the melt conduit has an evacuated insulation jacket.