Method for producing organic amines

 

(57) Abstract:

The inventive organic amines obtained by condensation of hydroxiapatite with ammonia or an amine in the presence of a hydrogenating catalyst is a mixture of oxides of Nickel and titanium, promotianal palladium and copper oxide. The catalyst formed in the form of Raschig rings with a diameter of 5 to 10 mm and a wall thickness of 1,5 - 2 mm, 1 table.

The invention relates to methods of producing amines by condensation of hydroxyl-containing organic compounds with ammonia or amines in the presence of a hydrogenating catalyst with getting as cyclic and aliphatic amines used as catalysts obtaining polyurethane foam (PUF) as reagents in flotation of ores, the manufacture of bandages for orthopedic and other purposes.

Cyclic amines, such as formalin (IOE), piperazine (PIP) and their derivatives, are used as chemicals for rubber, corrosion inhibitors, emulsifiers, antigelmintnyj drugs to combat ascariasis, etc.

A method of obtaining a wide range of amines as aliphatic and cyclic on the catalysts, representing the phosphates of rare earth elements (cerium, neodymium, lanthanum). The process wasp is by the necessity of using high temperatures, which leads to excessive energy consumption, and the use of rare earth elements.

The objective of the invention is to devise a method of obtaining amines with high selectivity.

To solve this problem it is suggested to conduct the process of obtaining amines on the catalyst composition is Nickel oxide, titanium dioxide, promoted copper oxide and palladium, are molded in the form of Raschig rings with a diameter of 5-10 mm and wall thickness of the rings of 1.5-2 mm

The study of the process of obtaining amines at the example of a PESTILENCE, Amor, DMDA showed that the number of products decreases as crushing the tablets of the catalyst. Apparently this is due to the reaction at a major catalyst grain in interdiffuse region and the deletion of the diffusion inhibition by crushing of the catalyst.

Thus, optimum results are achieved with the implementation of the process on the catalyst in the form of Raschig rings with wall thickness of 1,5-2 mm and a diameter of 5-6 mm With increasing wall thickness more than 2 mm comes diffusion braking, and when the thickness is smaller, the catalyst becomes fragile. The diameter of 5-6 mm is optimal for the hydrodynamics of the process.

To obtain amino is Kehl and copper, as well as titanium dioxide, followed by evaporation, drying and calcining the resulting mixture, and processing the catalyst mass with a solution of palladium chloride, drying and forming of the catalyst in the form of Raschig rings. The reaction between the hydroxyl-containing compound and the amino group takes place on the catalyst in the gas phase at atmospheric pressure (0.01 to 0.05 MPa) and relatively low temperature (180-250aboutC).

Reaction conditions, in particular the ratio of components may vary depending on the volatility of the parent compounds. In the case of high volatility of amino compounds, such as methylamine, these compounds are taken in great abundance, reaching 5-10 moles per 1 mole of hydroxyl compounds. Conversely, when using a high-boiling amine, and gidroksosoedinenii volatile, the excess is taken last. In all cases, the reaction mixture should be in the gaseous state, contact with the catalyst of the reactants in the liquid state is invalid.

P R I m e R 1 (comparative). In the contact tube 20 mm in diameter load 100 cm3the catalyst obtained as described in the prototype and having the following composition, % : (NiO 70; NiO225; CuO 0,2; Pd 0,2). The catalyst is heated to 200-210aboutWith the ACI hydrogen 18 l/H. Receive produce the following composition, % : Amor 22; ethanol 29; 31 MOR; MOR 1,5, 2-methoxyethanol 2,5; 3 methylmorpholin 1,5; water the rest. Produce share, as described in example 5.

P R I m m e R 2. 530 wt. including basic Nickel carbonate 2.24 wt. including basic copper carbonate are stirred in 1380 wt. including aqueous ammonia and then make 230 wt. including titanium dioxide. The mixture is evaporated, dried and calcined at 380-400aboutC.

The calcined powder is suspended in a solution of 1.61 wt. including palladium chloride in 900 wt. including water, acidified with 2 wt. including an aqueous solution of hydrochloric acid. To the suspension, add 7 wt. including an aqueous solution of ammonia and 15 wt. including 40% solution of formaldehyde in water. The mixture is heated with stirring to 95aboutC, kept at this temperature for 0.5 h, evaporated and dried. The dried catalyst mass is loaded into the mixer, add 100 wt. including water, 15 wt. including graphite and mix thoroughly to obtain a homogeneous mass, which granularit in the form of Raschig rings with a diameter of 5 mm and a wall thickness of 1.5 mm, dried at 90-150aboutC. Obtain a catalyst of the following composition, % : NiO 57; TiO238; CuO Is 0.3; Pd 0,18; graphite else.

This catalyst conduct process as follows.

aboutC. Daggett served with a speed of 18 g/H. the reaction Products are condensed in a receiver cooled with water and analyzed on the GC. The results of the analysis on the content side 2-methoxyethanol and 3-methylmorpholine presented in the table.

P R I m e R 3. The reaction is carried out under the conditions of example 2, but instead of ammonia take methylamine. MOR of catalyzate allocate rectification. Conversion of deg in MOR is 85% , unreacted deg returns in the process of contacting, the output of MOR on reacted deg is 75% .

P R I m e R 4. The catalyst obtained according to example 2, but differing composition, % : NiO 71,5; TiO224,6; CuO - 0,2; Pd 0,3) when the diameter of the ring 10 mm and wall thickness 2 mm get MOR of the research and methanol. The reaction is carried out under the conditions of example 2, but in a stream of hydrogen (without ammonia) vapor mixture of the research and methanol were taken in a molar ratio of 1: 2. 18 g/h of a mixture serves 9-18 l/h of hydrogen. Conversion of the research leaves 90-95% , the output of MMAR 87% .

P R I m e R 5. The reaction is carried out under the conditions of example 4, but use a catalyst with a diameter of 8 mm and a wall thickness of 1.5 mm instead of methanol take ethanol. The floor is real

The resulting mixture is subjected to separation: distilled alcohol and azeotrope Amor with water. Alcohol and unreacted morpholine return in the process, and the azeotropic mixture Amor with water, dehydrated with benzene and allocate Amor high efficiency distillation column with a yield of 73% morpholine and purity 99.8% .

P R I m e R 6. The reaction is carried out under the conditions of example 5, but in a stream of hydrogen is vaporized mixture of deg and research, taken in a molar ratio of 1: 2, the hydrogen is supplied in the amount of 15 moles per one mole deg. Get a mixture of the following composition, % : DMDA 26,0 MDEA 3.4 Amor 3.6 MMOL 1,3 MOR 52,0 deg 9,6

The mixture is subjected to separation. At atmospheric pressure of distilled MOR, Amor, PESTILENCE and water and share obtained zipper in terms of the allocation of Amor described in example 5 and the resulting morpholine return in the process.

Of the remaining cubed mixture under vacuum distilled unreacted deg content MMDAA to 10% and return this wrap in the process of contacting.

The mixture MDEA and DMDA share on rectification column with obtaining commercial DMDA 97% purity. MDEA can be returned into the process of contacting or used as a catalyst in the production of polyurethane foam. The output of the sum M is the conditions of example 6, but in a stream of hydrogen is vaporized mixture of ethylene glycol and PESTILENCE, taken in a molar ratio of 1: (3-5). Get catalysate, containing 30% of demoralisation (DME), which is marked by distillation. Unreacted ethylene glycol, MOR, 2-hydroxyethyl MOR and 2-amino-ethyl MOR return in the process. The output of the DME on the reacted ethylene glycol 73% .

P R I m e R 8. The reaction is carried out under the conditions of example 7, but in a stream of hydrogen is vaporized mixture of ethylene glycol and piperazine (PIP), taken in a molar ratio of 1: (3-5). Given the low volatility of the resulting piperazineethanol, the process is carried out in a large excess of hydrogen from 15 to 39 moles per mole of glycol. Get catalysate, containing 35% of piperazineethanol, which is marked by distillation.

Unreacted ethylene glycol and intermediate products 2-hydroxyethylpiperazine and 2-AMINOETHYLPIPERAZINE return on engagement. So Kip. piperazineethanol 164-165aboutWith 15 mm RT. Art. , so pl. 97aboutWith, yield 68% .

P R I m e R 9. The reaction is carried out, using as raw material amerosport - ethanolamine, vaporizing it in a stream of hydrogen supplied in an amount of 5 to 15 moles per 1 mole of ethanolamine. When submitting 10 moles of hydrogen per 1 mol of ethanolamine and a load of 0.3 m 11 Piperazine 9 2-Hydroxyethyl - piperazine 21 Triethylenediamine 31 Ethanolamine 7 Water the Rest

Effective rectification of a mixture allocate morpholine, piperazine, triethylenediamine with a total yield of 69% came in the reaction of ethanolamine.

2-Hydroxyethylpiperazine return to the contacts, an intermediate fraction by repeated rectification.

Thus the proposed method allows to obtain a wide range of amines limited; to provide a high selectivity to the target product; to simplify the extraction technology of the target product from the reaction mixture; get a range of useful products at the same time.

The reaction between Dagon and ammonia (56) U.S. Patent N 4582907, CL 547-194, 1984.

METHOD for producing ORGANIC AMINES by condensation of hydroxiapatite with ammonia or an amine in the presence of a hydrogenating catalyst, characterized in that as the catalyst, a mixture of oxides of Nickel and titanium, promoted palladium and copper oxide formed in the form of Raschig rings with a diameter of 5 to 10 mm and a wall thickness of 1.5 - 2 mm.

 

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