The method of liquid-phase chlorination of 1,3-butadiene

 

(57) Abstract:

Usage: dichlorobutene-3, 4-dichlorobutene-1 and TRANS -1, 4-dichlorobutene-2 is a valuable intermediate products in the production of polyamides, chloroprene; reagent 1: 1, 3-butadiene, the reagent is 2-chloro. The synthesis conditions: liquid-phase chlorination in a solvent inert to reaction with elemental chlorine in the synthesis conditions, which are selected from the group butane, pentane or fluorinated hydrocarbons of the formula

< / BR>
where R is independently hydrogen, fluorine or bromine, R is hydrogen, R is independently fluorine, chlorine or bromine, m and n is 0 to 3, provided that the terminal carbon atoms independently perhalocarbon or fully hydrogencarbon, and the boiling point of the solvent is from 15 to 40oC at atmospheric pressure, the process is conducted at 25 - 100oAnd pressure sufficient to provide the resulting reaction mixture boiling point not lower than prerna 25 - 100oWhen the mass ratio of solvent to dichlorobutene of 2.5 - 10 : 1, in the presence of a chlorination catalyst, separating unreacted 1 : 3-butadiene and solvent and returned to the reactor, remove dichlorobutene.

The invention relates to an improved ability, the m output very good selectivity, low operating temperature and ensure rapid and economical removal of unreacted 1,3-butadiene and solvent for re-use them in the system.

1,4-dichlorobutene-2 is a valuable intermediate product used in the production of some important polyamides, such as nylon 66, 3,4-dichlorobutene-1, in turn, is also an important intermediate used in the manufacture of chloroprene, which serves as the main monomer when receiving a whole class of important synthetic rubber known under the name "neoprene".

There is a method of liquid-phase chlorination of 1,3-butadiene in the presence of halogenated solvents, for example, in systems catalyzed by soluble Quaternary ammonium chlorides, pyridinium, phosphonium and sulfone (1), with the aim of obtaining 3,4-dichlorobutene-1 and 1.4-dichlorobutene-2. There are also known methods of chlorination in the vapor phase, which for many years used on an industrial scale. Methods of chlorination in the vapor phase are associated with the use of excess amounts of 1,3-butadiene, which requires recycling. This reaction has a low output, poor selective temperature of about 225-300aboutC. Despite the fact that the liquid-phase chlorination characterized by a higher yield of the target product, i.e., 3,4-dichlorobutene-1 and TRANS-1,4-dichlorobutene-2 compared with the processes in the vapor phase, it has not found industrial application. This is primarily due to high operational costs and the need for large investments in equipment designed to remove solvent from the low-boiling products, dichlorobutenes and high-boiling products in several distillation columns.

The purpose of this invention is to provide a method of low-temperature liquid-phase chlorination of 1,3-butadiene, in which the solvent is easily separated from the products of chlorination. In particular, the method relates to liquid-phase chlorination of 1,3-butadiene with the aim of obtaining a mixture of 3,4-dichlorobutene-1 and TRANS-1,4-dichlorobutene-2, comprising contacting the cooled due to the evaporation of the reactor 1,3-butadiene with elemental chlorine in a solvent and in the atmosphere, essentially not containing oxygen, in the presence of a chlorination catalyst at a temperature of about 25-100aboutWith the specified solvent is a butane or pentane, or is a fluorinated RA is rum, R' is hydrogen, R", independently, fluorine, chlorine or bromine, m and n is 0-3, provided that limit carbon atoms, independently, pre galogenirovannyie or fully hydrogencarbon, and the final boiling point of the solvent at atmospheric pressure is from -15 to 40aboutWith, and the ratio of solvent and dichlorobutene from 2.5:1 to 10:1, and the solvent is practically inert against elemental chlorine in the reaction conditions; separating Napareuli - rovavshego 1,3-butadiene and solvent from dichlorobutenes, subsequent recirculation of unreacted 1,3-butadiene and solvent to the reactor for re-use and recovery of dichlorobutenes.

Offer in accordance with the invention, the method includes the supply of elemental chlorine and 1,3-butadiene in a cooled due to evaporation reactor containing a specific solvent. To reduce or prevent free radical reactions and the formation of excess amounts of hydrogen chloride in the reactor add small amounts of inhibitors of free radicals (in addition to free of oxygen or air). The catalyst or similar material for the formation of chlorination catalyst neposredstvennom at a temperature of about 25-100aboutWith 1,3-butadiene and elemental chlorine react in the liquid phase with the formation of dichlorobutene. The heat formed during the reaction, take away, evaporating part of the solvent and unreacted 1,3-butadiene. A couple of solvent and 1,3-butadiene is then condensed in the partial condenser and returned to the reactor. The remains from the bottom of the reactor, which represents a product stream containing dichlorobutene, unreacted 1,3-butadiene and the solvent is sent to a Stripping column or an evaporator, where the raw dichlorobutene separated by distillation of the low-boiling solvent and 1,3-butadiene (about 2 wt.) the top straps. Raw dichlorobutene containing minor amounts of low - and high-boiling by-products, is served in a treatment column for purification. A couple of solvent and unreacted 1,3-butadiene from the top of Stripping tower condense and return to the reactor for reuse.

The reaction of elemental chlorine, for example, gaseous, with 1,3-butadiene is vysokoergonomichnoy. The solution used in the process, acts as a diluent, which increases output and used for reactor cooling through evaporation. Up until steaming to be a reaction heat.

The reaction is carried out practically in the absence of oxygen. The presence of oxygen, such as air will lead to the formation of unstable peroxides butadiene, to avoid this, the air must be eliminated.

An important condition for achieving these goals is the use of certain solvents.

The solvents used in accordance with the proposed method, are hydrocarbons, namely, butane or pentane, or fluorinated solvents of the formula (CR3)(CR2')m(CR2")nR, where R is, independently, hydrogen, fluorine, chlorine or bromine, R' is hydrogen, R", independently, fluorine, chlorine or bromine, m and n is 0-3, provided that limit carbon atoms, independently, pre galogenirovannyie or fully hydrogencarbon, while the boiling point of the solvent at atmospheric pressure is (-15aboutC)-40aboutAnd they are essentially inert with respect to elemental chlorine under the reaction conditions and the ratio of solvent and dichlorobutanes product ranges from 2.5:1 to 10:1.

The solvents used in the chlorination process, have values of the boiling temperature close to the temperature is orites allows you to ensure separation of the solvent, and unreacted 1,3-butadiene from dichlorobutane by single-stage steam. The fluorinated solvent may be represented by the formula (CR3)(CR2')m(CR2")nR, where R, R', R", m, n are defined above. In a preferred embodiment, R and R" in the above formula represent fluorine, chlorine or bromine and m is 0. Pre-fluorinated solvents, where R and R" is represented by fluorine and m 0 are particularly effective, but their use is limited for environmental reasons. If the boiling point of the solvent above the 40aboutWith, it will be difficult to separate from low-boiling by-products and dichlorobutenes without distillation equipment, the use of which requires large investments. On the other hand, if the boiling point of the solvent is too low, i.e. below -15aboutSince, it is difficult condensation and its implementation requires low-temperature cooling and compression under high pressure in order to avoid excessive losses due to leakage of gas. The solvents used in accordance with the proposed method, are hydrocarbons, namely, butane and pentane, or fluorinated restoratiion, 1,1,1, 2,2 - pentafluoropropane, pepernoten, 2,2-dichlorotrifluoroethane and 2,2,3,3-tetrafluroethane. Among the preferred solvents are butane, pentane, 1,1-dichloro-1-foraten and 1,2-dichlorotetrafluoroethane the latter is especially preferred because the temperature of its boiling point is very close to the boiling temperature of butadiene and, in addition, it is produced on an industrial scale. The weight ratio of solvent and crude dichlorobutene in the reactor is from 2.5:1 to 10:1, preferably at least 6. At smaller values of this ratio decreases output at shorter stay of the material in the reactor. For example, when the weight ratio equal to 8, a sufficient residence time in the reactor is 20 minutes

The chlorination is carried out at 25-100aboutWith, preferably 40-46aboutWith, and under sufficient pressure so that the boiling temperature of the solution in the reactor, consisting of 1,3-butadiene, dichlorobutenes and solvent was 25-100aboutWith, preferably 40-60aboutC. the Pressure at which carry out the reaction varies depending on the boiling point of the used solvent. In any case, this pressure should be sufficient to ensure that in the range of about 25-100aboutC. reaction Heat dissipate through evaporation of the solvent and 1,3-butadiene, which condense and return to the reactor. The residence time of material in the reactor in a continuous process typically varies in the range of about 1.5 to 10 minutes when the residence time of the mixture in the reactor is less than 1.5 min decreases the output dichlorobutenes, and when it exceeds 10 minutes, the implementation of the process on an industrial scale becomes uneconomic.

In order to accelerate the reaction of ionic chlorine in the reaction mixture was added the catalyst. These catalysts are well known in this field. Among the suitable catalysts are materials that are sources of chloride ions. They can be added to the reaction mixture in the form of chloride salts or in the form of materials that can react with components of the reaction mixture with the formation of chloride salts on the spot, i.e., which is the raw material for the preparation of the catalyst. Representative examples of acceptable compounds that can act as catalysts are the Quaternary ammonium chloride, Quaternary chlorides of phosphonium and tertiary chlorides of sulfone. Can isometrically as examples of compounds added to the reaction mixture for the formation of catalysts directly on the site, include amines, primary, secondary, or tertiary, or similar phosphides or sulfides. These compounds are capable of reacting with one or more chlorine substituted by materials in the reaction mixture, or hydrogen chloride with the formation of source of chloride ions. Among other materials that act as a source of raw materials for the formation of ion sources of chloride include salts in which the anion is a chloride ion, but which can come in ion-exchange reaction in the reaction medium with the formation of chloride ions. The preferred catalysts are the Quaternary ammonium chlorides, because they are produced on an industrial scale, as surface-active substances. Representative - tion Quaternary ammonium compounds are chloride of butyldiethanolamine, chloride of dilaudidtramadol, chloride of amitrityline, chloride of tetraoctylammonium, chloride of hexyltrimethoxysilane, etc. To the number of suitable Quaternary phosphonium compounds include, for example, chloride tetrabutylphosphonium, chloride methyltrichlorosilane, chloride trimethyloctadecylammonium, hortatory, include chloride trimethylsilane, chloride Vexillology, chloride methyldichlorosilane, chloride propyltrimethoxysilane and chloride, dimethyltin - logicalmulti. Usually it is more convenient to obtain the catalyst directly in the reaction mixture, for example, by adding the amine as the free base, which can react with the formation of source of chloride ions. It is particularly convenient to use as source material for the formation of the catalyst is pyridine. Other compounds that can form the catalyst directly in the reaction medium include amides of carboxylic acids, such as formamide, ndimethylacetamide, 2-pyrrolidone, 2-piperidone, 1-butylacetamide. The concentration of material that serves as the raw material for the formation of the catalyst, is typically 20-200 hours/million calculated on the total amount of solvent present. If the concentration is less than 20 hours/million, reduced output, and at concentrations above 200 hours/million process becomes uneconomic due to the high cost.

In the preferred embodiment, but not necessarily, the process is carried out in the presence of inhibitors of free radicals. Traditional inhibit-alpha-naphtylamine, phenothiazines and N-nitrosodiphenylamine and other substances, such as sulfur. The oxygen in the proposed method should not be used as an inhibitor of free radicals, because in this case the formation of unstable peroxide compounds butadiene. It is established that practically acceptable concentration of the inhibitor is about 20-80 hours/million calculated on the total amount of solvent present. If the concentration is below 20 hours/million, it leads to reduction of yield and concentrations above 80 hours/million are uneconomic.

The reaction mixture or the flow coming from the chlorination reactor, is directed to the treatment column for separation of unreacted 1,3-butadiene and solvent from 3,4-dichlorobutene-1 and TRANS-1,4-dichlorobutene-2. Physical separation of the reaction mixture into two main streams, one of which consists of a 1,3-butadiene/solvent, and the other from dichlorobutene may be carried out using suitable devices well known in this field. Physical separation of the reaction mixture can be carried out, for example, in the Stripping column. The heat supplied to the bottom of the column, causing evaporation of the reaction components. The low-boiling corrode one thread, in the reactor, and more high-boiling components, which include dichlorobutene, removed from the bottom of the column and sent for further purification. For separation of the reaction mixture flows, one of which contains sent for recycling and returned to the reactor 1,3-butadiene/solvent and other recoverable dichlorobutene, you can use single-stage evaporators. It is also possible to use conventional distillation columns. Preferred is the separation in the Stripping column.

In the examples illustrating the invention, all parts and percentages given in the calculation of the weight, except in those cases where there are special instructions.

P R I m e R 1. In the Nickel reactor high pressure, which has a cylindrical shape and is cooled by evaporation, provided with mixing means and having an internal height and diameter of 23 and 7, 8 mm, respectively, was continuously applied to the flow of chlorine gas and a second stream comprising 1,3-butadiene in the solvent 1,2-dichlorotetrafluoroethane. The boiling point of this fluorinated solvent at atmospheric pressure is 4aboutC. Chlorine was introduced with the speed of 0.17 g/C. the feed Rate of the stream containing the s butadiene reached 99.3% of the working liquid level in the reactor was 15 cm, when these flow rates of the material corresponded to stay in the reactor for a 3.2 minutes In the reactor also added inhibitor phenylethanolamine dissolved in pyridine (starting material for the catalyst chlorination), so that their concentration in the calculation of the amount of solvent (1,2-dichlorotetrafluoroethane) was 50 and 100 hours/million respectively. The ratio of solvent/dichlorobutene reached 10. The operating temperature of the reactor was 323 K (50aboutC) and pressure 445 kPa. Then the reaction mixture containing 3,4-dichlorobutene-1 and TRANS-1,4-dichlorobutene-2, unreacted 1,3-butadiene and solvent, was sent to the Stripping column. Unreacted 1,3-butadiene and the solvent was separated by evaporation and took from the top of the column, and then are condensed and returned to the reactor for reuse in the system. Dichlorobutene were taken from the bottom of the column. The output of dichlorobutenes determined by gas chromatography with a capillary of the molten oxide and dimensions of 60 m x 0.25 mm (inner diameter), with one associated layer of 95% dimethyl - 5% diphenylsiloxane, the maximum operating temperature which does not exceed 250aboutWith amounted to 96.3% of the Product had the following visionofhumanity 0,6 other 0,5

P R I m m e R 2. Repeated the procedure described in example 1, but the solvent used n-pentane. Into the reactor were introduced chlorine gas and a second stream comprising 1,3-butadiene in the solvent n-pentane, which had a purity of 99.3% of the boiling Temperature of the solvent was 36aboutC. the feed Rate of chlorine was 0,22 g/S. the Speed of flow, consisting of butadiene and solvent, reaching 1.5 g/C (0.27 g/with butadiene and 1,2 g/n-pentane). The degree of purity butadiene was 99.8% working liquid level in the reactor was 14 cm, which when used flow rates of the material corresponded to stay in the reactor for 3 minutes In the reactor was added inhibitor, phenyl-alpha-naphtylamine, dissolved in pyridine (starting material for catalyst chlorination), so that their concentration in the calculation of the amount of the pentane solvent was 100 and 200 hours /million respectively. The operating temperature of the reactor reached 330 K (57aboutC) and pressure of 310 kPa.

The ratio of solvent/dichlorobutene was 3. Then the reaction mixture containing dichlorobutene, unreacted 1,3-butadiene and solvent, was sent to the Stripping column. Unreacted is in the reactor for reuse in the system. Dichlorobutene were taken from the bottom of the column. The output of dichlorobutenes determined by gas chromatography using a column having capillaries of the molten silicon oxide and dimensions of 60 m x 0.25 mm (inner diameter) associated with one layer of 95% dimethyl-5% diphenylsiloxane, the maximum operating temperature which NPE exceeded 250aboutWith, were 96.7%

The product had the following weight composition, Monochlorotoluene 1,0 3,4-Dichlorobutene-1 48 CIS-1,4-dichlorobutene-2 1,3, TRANS-1,4-dichlorobutene-2 45 Trichlorobutene 0.8 Tetrachlorobutane other 3,5 0,4

P R I m e R 3. The reactor, cooled by evaporation and having a diameter of 5 cm and a length of 15 cm, equipped with a magnetic stirrer and a partial condenser hot irrigation area of 0.1 m2. Into the reactor was introduced gaseous chlorine, liquid 1,3-butadiene and solvent n-butane, the degree of purity was 99.7% of the boiling Temperature of the solvent was -4aboutC. Chlorine was applied with a speed of 0.1 g/s feedrate butadiene reached 0.12 g/C. the Rate of introduction of the solvent containing the source material for the formation of chlorination catalyst (pyridine) and inhibitor (phenyl-alpha-naphtylamine) was 0,46 g/C. the Degree of purity butadiene reached 99.3% of the operating level of serebyaniy in the reactor for 2.5 minutes In the solvent is added inhibitor (phenyl-alpha-naphthyl-amine) dissolved in pyridine (starting material for catalyst chlorination), so that their concentration in the calculation of the amount of the solvent n-butane, respectively 40 and 170 hours/million Ratio of solvent and dichlorobutenes reached 2.5. The operating temperature of the reactor was 320 (48aboutC) and pressure of 448 kPa, then the reaction mixture consisting of 3,4-dichlorobutene-1 and TRANS-1,4-dichlorobutene-2, unreacted 1,3-butadiene and solvent, was sent to the Stripping column. Unreacted 1,3-butadiene and the solvent was separated by evaporation and took from the top of the Stripping column, and then are condensed and returned to the reactor for reuse in the system. Dichlorobutene were taken from the bottom of the column. The output of dichlorobutenes determined by gas chromatography using a column having capillaries of the molten silicon oxide and dimensions of 60 m x 0.25 mm (inner diameter) associated with one layer of 95% dimethyl-5% diphenylsiloxane, the maximum operating temperature which does not exceed 250aboutWith 98% of the Product had the following weight composition, Monochlorotoluene 1,8 3,4-Dichlorobutadiene-1 54 CIS-1,4-dichlorobutene the procedure of example 3, except the flow of gaseous chlorine was applied to the reactor with a speed of 3.6 g/min, and 1,3-butadiene was injected with a speed of 4.1 g/min as solvent used is 1,1-dichloro-2 - foraten, having a boiling point of 32aboutWith, which was filed in the reactor with a speed of 64 g/min operating level of liquid in the reactor was 7.6 cm, which when used flow rates of the material corresponded to his stay in the reactor for 2.5 minutes In the reactor was added inhibitor (phenyl-alpha-naphtylamine) dissolved in pyridine (starting material for catalyst), so that their concentration in the calculation of the amount of solvent (1,1-dichloro-1-floridana) were 40 and 10 hours/million respectively. The ratio of solvent and dichlorobutene was 10. The operating temperature of the reactor reached 318 K (45aboutC) and pressure of 172 kPa. Then the reaction mixture containing dichlorobutene, unreacted 1,3-butadiene and solvent, was sent to the Stripping column. Unreacted 1,3-butadiene and the solvent was separated by evaporation and took from the top of the Stripping column, and then are condensed and returned to the reactor for reuse in the system. Dichlorobutene were taken from the bottom of the column. The output of dichlorobutenes, certain mesmeri 60 m x 0.25 mm (inner diameter), the maximum operating temperature was 250aboutWith reached 96,3% of the Product had the following weight composition, 3,4-Dichlorobutene-1 45,37 CIS-1,4-dichlorobutene-2 0,99 TRANS-1,4-dichlorobutene-2 47,19 Trichlorobutene 0.75 Tetrachlorobutane 3.73 Monochlorotoluene 1,2 other 0,76

P R I m e R s 5-15. Repeating the procedure described in example 1, but instead of the parameters specified in example 1, and used the settings shown in the table.

The METHOD of LIQUID-phase CHLORINATION of 1,3-BUTADIENE from a mixture of 3,4-dichlorobutene-1 and TRANS-1,4-dichlorobutene-2, comprising contacting 1,3-butadiene and elemental chlorine in a solvent, generally inert to reaction with elemental chlorine under the reaction conditions, in an atmosphere essentially devoid of oxygen, in the presence of a chlorination catalyst at 25 - 100oC and at a pressure sufficient to provide the resulting reaction mixture boiling point not lower than about 25 - 100oWhen the mass ratio of the solvent and dichlorobutene 2.5 to 100 : 1, the separation of unreacted 1,3-butadiene and solvent from dichlorobutenes and removing dichlorobutenes, characterized in that, to facilitate separation of the target product and reduce energy costs, Gloria is on, pentane or fluorinated hydrocarbons of the General formula

< / BR>
where R is independently hydrogen, fluorine, chlorine or bromine;

R is hydrogen;

R is independently fluorine, chlorine or bromine;

m and n = 0 - 3,

provided that the terminal carbon atoms independently perhalocarbon or fully hydrogencarbon, and the boiling point of the solvent is from -15 to 40oC at atmospheric pressure, while the unreacted 1,3-butadiene and the solvent is returned to the reactor.

 

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