DE1109182B - Process for the production of high molecular weight secondary amines suitable for hydrometallurgical purposes - Google Patents

Description

Method of manufacture suitable for hydrometallurgical purposes High molecular weight secondary amines The invention relates to a process for Production of high molar secondary amines. These amines have valuable properties which they use for hydrometallurgical uses involving metals from aqueous Solutions of their salts are to be separated, and for the extraction of mineral acids make particularly valuable from aqueous systems.

The secondary amines according to the invention have the following structural formula: in which R1 is an alkyl radical containing 9 to 15 carbon atoms with a branched chain, R2 is either hydrogen or CH, and R3, R4 and R5 are alkyl radicals. Examples of the connections of this type are: *) The latter compound is made from commercially available technically pure amines, which consist of a mixture of alkylamines with 18 to 24 carbon atoms. Accordingly, the sum of the carbon atoms (R3, R4 and R5) in this formula can be different, as indicated. The new compounds can be prepared by a process which gives very satisfactory yields. This process essentially consists of the following process steps: First, benzene is alkylated with a compound that is selected so that it has the properties required for R1 in the above formula and not be greater than 23. Liche number of carbon atoms supplies. For example, trimeric propylene or nonene is used to make the benzyl compound used in Examples 1 and 2 below. The compound is then chloromethylated in the usual way, for example with chloromethyl ether and zinc chloride. The product obtained (e.g. nonylbenzyl chloride) is reacted with an alkylamine (e.g. tert-octylamine) in the presence of an alcohol (e.g. isopropanol) to give the high molar amine of the present invention. This manufacturing process is detailed and illustrated in the examples below.

The new products are viscous, oily, mostly amber-colored liquids. They are all insoluble in water and soluble in kerosene and other petroleum hydrocarbons as well as in benzene, xylene and toluene, common organic solvents and light and heavy mineral oils. The new amines have many hydrometallurgical uses useful in which a solution of any of the above amines in kerosene or a Similar solvent is stirred with an aqueous phase that is to be obtained Contains metal ions or the metals to be separated. Own the present products have an extremely low tendency to emulsify and have high extraction coefficients in many of these hydrometallurgical systems. In the above way one can from hydrometallurgical systems by using the new amines niobium from tantalum, Separate niobium from protactinium, zinc from cobalt, etc. One of their most important hydrometallurgical Possible uses is the separation of uranium from sulfuric acid solutions, obtained when the acid is used to leach uranium from its ores. A number of examples of this use are given below.

The present amines are also very valuable in removing mineral acids such as hydrochloric acid and sulfuric acid from protein hydrolyzates. They can also be used to remove mineral acids such as hydrochloric acid and nitric acid from aqueous phases. For example, a 0.1N solution of the amine (here nonylbenzyl-tert-dodecylamine) in kerosene, applied in an aqueous system containing 0.098N hydrochloric acid, effectively removes 95% of the acid when a ratio of two parts Amine to one part acid is used. If an amine to acid ratio of 3: 1 is used, 97.10% of the acid is removed. If the same amine is used in the same concentration in an aqueous phase containing 0.97 n-nitric acid, 98.3 % of the acid using an acid ratio of 2: 1 and 99.10% of the acid using one Amine-acid ratio of 3: 1 removed. Similar results are obtained using the other amines of the invention. After the amines have been used to remove the acids from aqueous systems, they can easily be recovered by regeneration with sodium hydroxide, sodium carbonate, ammonium hydroxide or the like.

Other uses of the secondary amines are use along with lubricating oils, in which they work well as ashless detergents. They are also used as anti-sludge agents in fuel oils, fuel oils, diesel oils and other cracked or untreated normally sludge prone Distillation valuable.

The use of amines in the hydrometallurgy of uranium.

The following procedure was used with each of the amines described in in the table below. About 1 milliequivalent of each amine was made weighed, diluted to 10 cc with commercial kerosene and poured into a 60 cc Separating funnel done. 40 cc of a leaching liquid was added to each funnel, which essentially consisted of: 0.79 g U30 $ per liter 2.5 g Fe +++ per liter 40.0 g S 04- per liter (This caustic solution is typical for the composition of leaching liquids, which are obtained when using sulfuric acid as in industrial uranium processing processes used to extract uranium from its ores using ion exchange resins The remaining components of the caustic solution include Mn ++ -, A1 +++ _ and H + ions. The pH of this solution is 1.5.

Each separatory funnel was stopped with a stopper and the contents stirred gently to ensure complete mix. After the deposition the lower, aqueous phase was drawn off and poured away from the phases. Every funnel Another 40 cc of fresh liquor was added and the above procedure repeated. Finally a third fresh caustic solution was added, stirred, Waited for the divorce and withdrawn the aqueous phase.

At this point, 10 cc of 10% (weight to volume) NaCO 3 solution was added to each separatory funnel. After careful stirring, the phases were allowed to separate. The aqueous phase with a high uranium content was drawn off and analyzed for uranium by conventional methods. This procedure was repeated one more time. The uranium extraction coefficient of each amine was obtained by taking the weight of uranium extracted and relating it to the weight of the amine used for extraction. The following results were obtained: Extracted Amine U used in mg (ver Amin turned it around Amine in g mg Nonylbenzyl tert-octal amine ................ 370 57.5 Nonylbenzyl tert-dodecyl amine ................ 427 64.2 Dodecylbenzyl-tert-octyl- amine ................ 405 49.1 Dodecylbenzyl tert- dodecylamine *) ........ 475 61.9 Dodecylbenzyl tert- dodecylamine **) ....... 447 57.0 Pentadecylbenzyl tert. octylamine ............ 464 55.6 Methyldodecylbenzyl-tert: octadecylamine. . . . . . . . . 514 58.0 Methyldodecylbenzyl-tert.- dodecylamine .......... 442 41.2 *) Manufactured according to the first method described in Example 4 travel. **) Manufactured according to the second described in Example 4 Procedure. In the following, the dodecylbenzyl-tert-dodecylamine obtained according to the invention is compared with the benzyl-tert-octylamine obtained by known processes with regard to their ability to extract uranium from sulfuric acid leaching liquid.

About 1 milliequivalent of each amine was diluted to 10 cc with kerosene and placed in a 60 cc separatory funnel. 40 cc was added to each funnel sulfuric acid leaching liquid (West Rand 36-15 C) added.

The separating funnels were plugged and gently agitated. After the phase separation, the aqueous phase was drawn off and discarded. The process was repeated twice with the addition of 40 cm3 of leaching liquid each time. Then 10 cm3 of a 10% (w / v) Na2CO3 solution were added, shaken gently and, after separation, the uranium-containing aqueous phase was drawn off. After another extraction with 10 cubic meters of 10% (w / v) Na2CO3 solution, the aqueous solution drawn off was combined with the first aqueous extract. The combined extracts were diluted to 100 cm3. Equal parts of each of these extraction solutions were analyzed for uranium and gave the following results: The above experiment shows that no significant amounts of uranium can be extracted with the aid of the known amine, while the product according to the invention has an approximately 30-fold extraction efficiency.

Example 1 Nonylbenzyl-tert-octylamine 202 g (0.8 mol) of nonylbenzyl chloride (15.020 / ° Cl) were within 40 minutes at reflux temperature (105 to 115 ° C) while stirring vigorously a mixture of 15 g of 99a / ° isopropanol and 206.4 g of tert-octylamine (1.6 mol) were added. (The nonylbenzyl chloride was obtained by alkylation of benzene with trimeric propylene (nonene) and subsequent chloromethylation). The reaction mixture was heated and refluxed for 7 hours (115 to 120 ° C) stirred. During the first part of this time an additional 35 g became 99% Isopropanol added to solubilize the tert-octylamine hydrochloride, the began to crystallize out.

The reaction mixture was then cooled to about 80.degree. C., then neutralized by adding 70 g of 50% strength sodium hydroxide solution (0.876 mol) and stirred at 80.degree. C. for 1 hour. The aqueous layer was discarded and the organic layer was washed and the remaining water and excess tert-octylamine were driven off by heating under vacuum until a vessel temperature of 210 ° C. and a vacuum of 5 mm were finally reached. The deposited crude product weighed 242 g and had a neutral equivalent of 356 (non-aqueous titration with perchloric acid). Part of this residue was distilled under vacuum. 141.3 g of distillate were collected from a sample weighing 156.1 g, which boiled between 175 and 200 ° C. at 5 mm and had a neutral equivalent of 353 (non-aqueous titration).

Example 2 Nonylbenzyl-tert-dodecylamine 101 g (0.4 mol) of nonylbenzyl chloride (15.02 ° / a C1) were added within a quarter of an hour at 110 to 115 ° C to a mixture of 15 g of 99% isopropanol and 152 g ( 0.8 mol) of tert-dodecylamine (a commercially available technically pure compound consisting of a mixture of primary aliphatic amines having 12 to 15 carbon atoms) was added. The reaction is carried out at reflux temperature for 12 hours. A sample of the reaction mixture was heated and stirred with 35 g of 40% strength sodium hydroxide solution at 80 ° C. for 1 hour. The organic layer was washed with water and deposited at 5 mm until a vessel temperature of 190 ° C. was reached. The deposited product weighed 130 g and had a neutral equivalent of 416 (non-aqueous titration). A 65.5 g sample of the product was distilled to give 54.8 g of distillate which boiled at 201 to 230 ° C and 5 mm and had a neutral equivalent of 407 (non-aqueous titration).

Example 3 Dodecylbenzyl-tert-octylamine 219.2 g (0.8 mol) of dodecylbenzyl chloride (12.95% Cl) were added within 40 minutes at 105 to 115 ° C to a mixture of 206.4 g (1.6 Mol) tert-octylamine and 15 g of 99% isopropanol were added. The reaction mixture was then heated and refluxed for 8 hours with stirring and then neutralized with 50% sodium hydroxide solution, washed and freed from all moisture. The excess amine was removed by vacuum distillation at 5 mm until a vessel temperature of 165.degree. C. was reached. This crude product (235.1 g) had a neutral equivalent of 406 (non-aqueous titration with n / 10 perchloric acid). Half of the crude product was distilled at 5 mm and gave a fraction of 82.6 g which boiled at 200 to 210 ° C. and had a neutral equivalent of 393.1 (non-aqueous titration).

Example 4 Dodecylbenzyl-tert-dodecylamine Dodecylbenzene was chloromethylated with a mixture of chloromethyl ether and zinc chloride to form a product which consisted mainly of monochloromethyldodecylbenzene. This product boiled at 170 to 190 ° C. and had a chlorine content of 12.250% (theory 12.0411 / J. 290 parts of this product (one equivalent) were added to 380 parts (2 equivalents) of a technical tert-dodecylamine (an im Commercially available mixture of primary aliphatic amines, mainly with 11 to 14 carbon atoms) was added The mixture was heated to 170 ° C. and held at this temperature for 2 hours together with 80 parts of 50% sodium hydroxide solution (1 mol) the sodium chloride sludge was decanted and washed with 200 parts of hot water The organic layer was then dried and deposited at a pressure of 5 mm Hg until a vessel temperature of 190 ° C. The distillate consisted of 185 parts of tert-dodecylamine with a neutral equivalent of 198. The residue consisted of 430 parts of a dark amber colored liquid with a neutral equivalent of 450. The theoretical value is 442.

In a further preparation of the same compound, chloromethylated Dodecylbenzene (1 mol), tert-dodecylamine (1.25 mol), 50% sodium hydroxide solution (1 mol) and isopropyl alcohol (50 parts) heated with stirring at 85 ° C for 10 hours. To At the end of this time, the reaction mixture was poured into a separatory funnel. the aqueous layer was drained. The organic layer was up to the attainment a vessel temperature of 220 ° C at a pressure of 5 mm. The residue, 285 parts by weight with a neutral equivalent of 465 consisted mainly from dodecylbenzyl-tert-dodecylamine.

Example 5 Pentadecylbenzyl tert: octylamine 67.1 g (0.2 mole) pentadecylbenzyl chloride were within 30 minutes to 77.4 g (0.6 M01) tert-octylamine and 15 g isopropanol added at 112 ° C. The pentadecylbenzyl chloride used was by alkylation made of benzene with pentameric propylene and subsequent chloromethylation been. The reaction mixture was left on for 8 hours after the addition was complete Heated 110 to 115 ° C. The reaction mixture was made by adding 10 g of sodium hydroxide, 40 g of water and 40 cc of 99% isopropanol and stirring for 1 hour at 80 "C neutralized. The organic layer was washed and the remaining water was removed in vacuo. The crude product was distilled and yielded 44.4 g which boiled at 216-228 ° C and had a neutral equivalent of 450 (non-aqueous titration).

Example 6 (methyldodecylbenzyl) -tert-octadecylamine Dodecyltoluene was chloromethylated with a mixture of chloromethyl ether and zinc chloride to give a product which consisted mainly of monochloromethyldodecyltoluenes. 280 parts of this product were reacted with 630 parts of a commercially available technical amine which consists of a mixture of primary aliphatic amines in which tert.-octadecylamine predominates, but which also contains some higher homologues up to tert: C "H" NH2. After 2 hours at 230 ° C resulted in a titration of hydrogen chloride, that the reaction was about 960, finished /. 40 parts of sodium hydroxide, dissolved in 200 parts of water, were added. After stirring for 30 minutes and heating to 80 ° C., the organic layer was removed and the excess amine mixture (tert.-C "H37 N H2 to tert.-Cg4 H" N H2) was driven off. The amine obtained (boiling point 120 to 154 ° C. and 0.7 mm) made up 369 parts. The residue, 482 parts by weight, had a neutral equivalent of 513 (theory 558.5) and contained no chlorine.

Claims (1)

PATENT CLAIM: Process for the production of high molecular weight secondary amines of the general formula I suitable for hydrometallurgical purposes in which R1 is an alkyl radical containing 9 to 15 carbon atoms with a branched chain, R2 is hydrogen or CH, and R3, R4 and R5 are alkyl radicals whose sum of carbon atoms is between 7 and 23, characterized in that an alkylbenzyl chloride of the general formula II in which R1 and R2 have the above meaning, with an alkylamine of the general formula III in which R3, R4 and R5 have the above meaning. Documents considered: French Patent No. 1,159,968; U.S. Patent No. 2,613,226.