The method of obtaining alcohol solvate of chlorides of rare earth elements

 

(57) Abstract:

The invention relates to methods of producing alcohol solvate of chlorides of rare earth elements ( REE ), which are used to prepare catalysts for the polymerization of dienes in the form of a dispersion in the hydrocarbon. The essence of the invention: an alcohol solvate of chlorides REE receive when interacting REE oxides with hydrochloridum agent in the environment monohydroxy aliphatic alcohol followed by distillation of the excess alcohol. The distillation of alcohol is carried out in the presence of 20 to 100 wt. petroleum oils or liquid paraffin having a boiling range 220-270C With simultaneous formation of the dispersion alcohol solvate of chlorides of rare earth elements. table 1.

The invention relates to methods of producing alcohol solvate of metal chlorides.

The proposed method can find application in the synthetic rubber industry, because alcohol solvate of chlorides of rare earth elements (REE) are used to prepare catalysts for the polymerization of dienes [1]

A method of obtaining the solvate of REE chlorides with alcohols, in particular ethanol, through the cooperation of REE oxides with hydrochloridum agent chloride is Vashego of hydrated chloride REE monohydroxy aliphatic alcohol is ethanol at a mass ratio of ethanol to chloride REE 8, adding benzene in a volume ratio of ethanol 1: 2, the distillation of water in the composition of the ternary azeotropic mixture with benzene and ethanol with periodic addition of benzene and evaporation of a solution of MES in dry ethanol [2]

In this way we can distinguish the following stages:

1) obtaining an aqueous solution of chloride of REE from the corresponding oxide,

2) selection of crystallohydrate 1HCl36H2On evaporation to dryness of the aqueous solution of chloride REE, 3) dissolution of hydrated in ethanol,

4) distillation of water in the composition of the ternary azeotrope with ethanol and benzene,

5) selection of MES 1Cl33C2H5OH by the process of evaporation of the alcoholic solution to dryness.

Selected MES dispersed in a hydrocarbon and the resulting dispersion is used as a component for the preparation of a catalyst for the polymerization of dienes.

The disadvantage of this method is the complexity of its implementation, in particular a multi-stage.

Also known is a method of obtaining alcohol solvate of REE chlorides by reacting oxides of rare-earth elements with hydrochloridum agent (AHC) hydrogen chloride or hydrochloride piperylene or isoprene in the environment of the monatomic Alitalia powder [3] Then MES dispersed in a hydrocarbon, and cooked dispersion is used to obtain the catalyst for the polymerization of dienes.

This method has certain advantages, as it reduces the number of technological operations, however, has several disadvantages: eye-catching in the sediment during the distillation of alcohol MES is characterized by heterogeneity in alcohol content and a significant dispersion of particles. The process of distillation of alcohol is accompanied by the reaction of formation of by-product oxychloride REE MOCl

MCl3+ H2O ->> MOCl + 2HCl

In this reaction involved the water that is released during the interaction of REE oxide with hydrochloridum agent. All of these factors: strong heterogeneity of particle size, the diverse composition of the product according to the alcohol content, and the presence of oxychlorides REE adversely affect the catalytic activity of MES.

The aim of the invention is to improve the uniformity in composition and particle size alcohol solvate of REE chlorides and lower content of oxychlorides REE.

This objective is achieved in that in the method of obtaining the solvate of chlorides of rare-earth elements, used in the form of a dispersion in the hydrocarbon component of the cat is a lot of aliphatic alcohol followed by distillation of the excess alcohol, the distillation of alcohol is carried out in the presence of 20-100 wt. petroleum oils or liquid paraffin with an initial boiling point 220-270aboutWith the simultaneous formation of the dispersion alcohol solvate of chlorides of rare-earth elements.

The essence of the method consists in the following.

The oxide of neodymium, praseodymium or their technical mixtures "Didyma" beyond HELL 11.46-89 (Ln2O3) is poured into the machine, equipped with a stirrer and a heating jacket, then the apparatus is filled with monohydroxy aliphatic alcohol at a mass ratio of alcohol to the oxide from 5 to 80 and is added with stirring a solution of hydrochloride agent (AHC) in alcohol at a molar ratio of AHC to REE from 2.8 to 3.3. As a monohydroxy aliphatic alcohol used is ethanol (ES), isopropanol (IPA), n-butanol (BS), Isobutanol (CHD), n-octanol (OS), cyclohexanol (CGS) or mixtures thereof. As hydro - glorieuses agent applied hydrogen chloride (in the form of a solution in a monohydroxy aliphatic alcohol), hydrochloride piperylene or hydrochloride of isoprene. The interaction is carried out with stirring and at a temperature of 25-80aboutC for 1-24 h, forming a solution of chlorides of rare-earth elements in alcohol. Then to the solution 38.101998-84 in the amount of 20-100 wt. Distillation of the excess alcohol is carried out in the evaporator, for example in evaporation unit with mixer or rotary film evaporator (EPI). In the process of distillation of the excess alcohol leads to the formation of a dispersion of chloride solvate REE in petroleum oil or liquid paraffin. Dispersion flexible and convenient for packaging and use as a catalyst component.

P R I m e R 1. In the apparatus load 48 kg oxide neodymium (Nd2O3), pour 3755 kg of isopropyl alcohol (IPA) and serves 116 kg 27%-aqueous solution of hydrogen chloride (HCl) in isopropyl alcohol. When the mass ratio of the alcohol to the oxide is 80, the molar ratio of HCl to REE 3. The reaction mass was stirred at 60aboutC for 4 h after which the resulting solution is mixed with 783 kg (20 wt.) liquid paraffin on THE 38.101531-85. The prepared solution is metered in EPI. Formed during the distillation of the alcohol dispersion of MES of neodymium chloride in paraffin flows into the lower part of the device.

For clarity, the conditions of the syntheses and characterization of the obtained dispersions from this example and all subsequent information in the table.

P R I m m e R 2. In the apparatus of the load 24 kg oxide praseodymium (Pr2O3), 80 kg of isopropyl alcohol and serves 54 kg 27% rest the UB> 2,8. The reaction is carried out under stirring for 1 h at 80aboutC. After the reaction solution is mixed with liquid paraffin in number to 79.3 kg (50 wt.) and the excess alcohol is distilled off in an evaporator unit with mixer.

P R I m e R 3. In the apparatus of the load 24 kg oxide Didyma (Ln2O3), 600 kg n-butanol, include mixing and serves 45,1 kg of the hydrochloride piperylene (GHP). The mass ratio BS/Ln2O325, the molar ratio GHP/Ln 3. The reaction mass was stirred at 25aboutC for 24 h the resulting solution is mixed with 401 kg of liquid paraffin (60 wt.) and the excess alcohol is distilled off in the FIR.

P R I m e R 4. In the apparatus of the load 24 kg Nd2O3pour 480 kg of Isobutanol and 47 kg of the hydrochloride of isoprene (GHEE). The mass ratio of CHD/Nd2O320, the molar ratio of GHEE/Nd 3,2. The reaction mixture was stirred for 5 h at 40aboutWith, and then mixed with 551 kg of liquid paraffin (100 wt.). This is followed by a distillation of the excess CHD in evaporation apparatus with stirrer.

P R I m e R 5. In the apparatus load 48 kg of neodymium oxide, 638 kg of cyclohexanol (CGS) and 112 kg 27% solution of HCl in CGS. The mass ratio CGS/Nd2O315, the molar ratio of HCl/Nd of 2.9. The reaction mass is stirred in tonko excess CGS in the FIR.

P R I m e R 6. In the apparatus load 48 kg Ln2O3, 387 kg absolute ethanol and 127,4 kg 27% HCl solution in ES. The mass ratio ES/Ln2O310, the molar ratio of HCl/3,3 Ln. The reaction mass is stirred for 3 h at 55aboutWith, and then mixed with 169 kg oil (30 wt). This is followed by a distillation of the excess of the ES in the FIR.

P R I m e R 7. In the apparatus of the load 24 kg Ln2O3, 199 kg n-octanol and 56 kg 27% HCl solution in the OS. When the mass ratio of OC/Ln2O310, the molar ratio of HCl/Ln 2,9. The reaction mass is stirred for 4 h at 50aboutWith, and then mixed with 139,5 kg oil (50 wt.). This is followed by a distillation of the excess of the OS in the FIR.

P R I m e R 8. In the apparatus of the load 24 kg Pr2O3, 120 kg CGS, 480 kg of isopropyl alcohol and 46 kg GHEE. The mass ratio CGS/Pr2O35, the mass ratio of IPA/Pr2O320, the molar ratio of GHEE/Pr 3,1. The reaction mass is stirred for 4 h at 50aboutC, then mixed with the oil oil in the amount of 670 kg (100 wt.). This is followed by a distillation of the excess CGS and IPS in the FIR.

P R I m e R 9 (control). In the apparatus load 48 kg Nd2O3, 3755 kg of isopropyl alcohol and 116 kg 27% solution of HCl in isopropyl alcohol. When this mass relationship, the donkey which the excess isopropyl alcohol is distilled off in the FIR. Received MES neodymium chloride with isopropyl alcohol is a powder, dusting during unloading and packaging. In powder samples are placed UGT RPS and aluminium A7 to determine the rate of corrosion of these materials.

P R I m e R 10 (control). In the apparatus of the load 24 kg Ln2O3, 240 kg CGS include mixing and serves 48 kg GHP. The mass ratio CGS/Ln2O325, the molar ratio GHP/3,2 Ln. The reaction mass was stirred at 60aboutC for 4 h Then the solution is mixed with 156 kg of toluene (50 wt.) and the excess alcohol is distilled off in the FIR. The product is a rapidly stratifying the variance of the MES chloride Didyma in toluene. The dispersion is placed samples of steel UGT RPS and aluminium A7 to determine the rate of corrosion of these materials.

The examples show that the proposed method allows to obtain a dispersion of the solvate of chlorides of rare-earth elements that can be directly used as a component for the preparation of a catalyst for the polymerization of dienes. The product is characterized by high purity in respect of by-products, uniformity of content of alcohol, melkodyspersnoho and uniformity of particle size. In addition to CHOGM. Organization of the synthesis of the solvate of chlorides of rare earth in the form of a dispersion in oil or paraffin eliminates the contact of staff with a dusting product during operations of loading and unloading of product.

Thus, the proposed method due to the fact that the distillation of the excess alcohol is carried out in the presence of 20-100 wt. petroleum oils or liquid paraffin with an initial boiling point 220-270aboutWith the simultaneous formation of a dispersion therein of alcohol solvate of chlorides of rare-earth elements, allows to obtain the chloride solvate REE uniform composition and particle size, as well as to reduce the content of oxychlorides REE.

The METHOD of OBTAINING ALCOHOL SOLVATE of CHLORIDES of RARE earth ELEMENTS, used in the form of a dispersion in the hydrocarbon as a component of catalyst for the polymerization of dienes, by reacting the oxide of rare earth element with hydrochloridum agent in the environment monohydroxy aliphatic alcohol followed by distillation of the excess alcohol, characterized in that the distillation of the excess alcohol is carried out in the presence of 20 to 100 wt. petroleum oils or liquid paraffin with an initial boiling point of 220 270oWith the simultaneous formation of a dispersion of an alcohol solvate PI is

 

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