JP2017137263A - Method for producing 1,1,1,3-tetrachloropropane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing 1,1,1,3-tetrachloropropane by adding carbon tetrachloride to ethylene in a liquid phase in which a metal complex is dissolved and by efficiently removing the metal complex from a reaction mixture obtained without decomposing the target 1,1,1,3-tetrachloropropane.SOLUTION: The method for producing 1,1,1,3-tetrachloropropane comprises: applying centrifugal force to a reaction mixture obtained by carrying out the addition reaction for phase separation; and separating and removing a light phase containing the metal complex.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a process for producing 1,1,1,3-tetrachloropropane. More specifically, the present invention relates to a production technique for efficiently removing a metal complex that is produced when 1,1,1,3-tetrachloropropane is produced.

  Chlorinated hydrocarbons are important as raw materials or intermediates for producing various products such as agricultural chemicals, pharmaceuticals, and CFC substitute materials. For example, by chlorinating 1,1,3-trichloro-1-propene produced by dehydrochlorination starting from 1,1,1,3-tetrachloropropane, an important chlorine compound intermediate in various industrial products 1,1,1,2,3-pentachloropropane can be synthesized.

  As a method for producing 1,1,1,3-tetrachloropropane mentioned above, a reaction obtained by adding carbon tetrachloride to ethylene (hereinafter also referred to as an addition reaction) is known.

  This reaction is often carried out batchwise in a reaction system consisting of a liquid phase composed of carbon tetrachloride and a gas phase composed mainly of ethylene. Specifically, Patent Document 1 discloses a production method in which an addition reaction between ethylene and carbon tetrachloride is performed in the presence of metallic iron and a phosphoryl group-containing phosphorus compound to obtain 1,1,1,3-tetrachloropropane. It is disclosed.

  Patent Document 2 discloses a method for producing 1,1,1,3-tetrachloropropane in which the above reaction is performed in the presence of an iron-phosphate ester catalyst, and phosphoric acids used as catalyst components are divided into multiple stages. A method of additional addition is disclosed.

  As disclosed in Patent Documents 1 and 2, all of the reactions are liquid phase reactions, and a metal complex dissolved in the liquid phase acts as a catalyst. By the way, if the metal complex remains in the obtained reaction solution, thermal decomposition of 1,1,1,3-tetrachloropropane, which is the target product, may occur in subsequent steps such as the distillation purification step and the next reaction step. In addition to a decrease in the progress yield, there is a risk that operation troubles may occur due to device corrosion or scaling in the device.

  Specifically, scale adhesion reduces the heat transfer capability of the heat exchanger and may lead to blockage of the liquid supply piping. From the 1,1,1,3-tetrachloropropane solution after the reaction, the metal complex The process of separating and removing is also indispensable for improving productivity in an industrial scale process.

  As a means for separating and removing the metal complex, it is considered to separate and remove a light phase containing a large amount of the metal complex using the specific gravity difference between the metal complex and the target 1,1,1,3-tetrachloropropane. It is done. However, the reaction solution obtained after the reaction is in a state in which the metal complex is finely dispersed in the solution, and it took a long time to advantageously separate into the light phase and the heavy phase, and problems remained. .

  In Patent Document 3, carbon tetrachloride and vinyl chloride are reacted in the presence of an iron-amide complex to obtain a similar 1,1,1,3,3-pentachloropropane, and the resulting chloropropane is fluorinated. A production method for obtaining 1-chloro-3,3,3-trifluoropropane by reacting with hydrogen is disclosed. Further, after the production of 1,1,1,3,3-pentachloropropane, By restricting the iron-amide complex to a certain concentration or less, problems such as shortening of catalyst life, reaction suppression, equipment scaling and corrosion in the production process of 1-chloro-3,3,3-trifluoropropane Is described as improving. As a means for limiting the catalyst component composed of the metal complex to a certain concentration or less, it is described that the catalyst component is separated and removed by an adsorption method, a water washing method, a membrane separation method, a distillation method, or the like.

  However, when these separation and removal means are applied, the adsorption method requires a running cost of an adsorbent such as activated alumina and silica gel, and the water washing method decomposes the target product due to contact with water and causes a decrease in yield. It is necessary to provide a dehydration step. Further, in the membrane separation method, since the processing flux is small, the processing cost becomes large, and there are still problems such as the necessity of dealing with membrane contamination, cleaning due to clogging, and replacement.

Japanese Examined Patent Publication No. 02-47969 JP 2012-36190 A JP 2013-139414 A

  Therefore, the object of the present invention is to remove the metal complex efficiently from the reaction solution obtained after the addition reaction without decomposing the target 1,1,1,3-tetrachloropropane. It is to provide a method for producing 1,1,3-tetrachloropropane.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors applied a centrifugal force to the reaction solution obtained after the addition reaction, whereby the light phase containing the metal complex and the target 1,1,1 It has been found that it is efficiently separated into a heavy phase mainly composed of 1,3-tetrachloropropane. That is, a light phase containing the metal complex is separated and removed from a reaction solution to which a centrifugal force is applied, thereby achieving the above object.

  That is, the present invention applies an addition reaction of ethylene to carbon tetrachloride in a liquid phase in which the metal complex is dissolved, and applies centrifugal force to the resulting reaction liquid containing 1,1,1,3-tetrachloropropane. In this process, 1,1,1,3-tetrachloropropane is produced by separating and removing the light phase containing the metal complex.

  By applying centrifugal force to the reaction solution obtained from the addition reaction to efficiently separate and remove the contained metal complex, corrosion in pipes, equipment in the subsequent process, scaling, and 1,1, The decomposition of 1,3-tetrachloropropane can be reduced. Moreover, since the process can be constructed in a non-aqueous system, the introduction of a dehydration step after washing with water can be omitted, the equipment cost can be reduced, and this is extremely useful industrially.

FIG. 1 shows an example of an apparatus for carrying out the method of the present invention. FIG. 2 shows the relationship between the metal complex concentration and the decomposition rate of chloropropane by a simulation experiment. FIG. 3 shows the relationship between the metal complex concentration and the corrosion rate of stainless steel “SUS304” by a simulation experiment. FIG. 4 shows the relationship between the application of centrifugal force, the standing time, and the metal complex concentration in the heavy phase reaction solution.

  In the liquid phase in which the metal complex is dissolved, the present invention is obtained by adding carbon tetrachloride to ethylene and applying centrifugal force to the resulting reaction liquid containing 1,1,1,3-tetrachloropropane. It is a method for producing 1,1,1,3-tetrachloropropane characterized by causing phase separation and separating and removing the light phase containing the metal complex.

  First, the addition reaction will be described. In the present invention, the addition reaction for adding carbon tetrachloride to ethylene in a liquid phase is performed in a liquid phase in which the metal complex is dissolved.

  The metal complex only needs to be dissolved in the liquid phase of carbon tetrachloride, and the origin thereof is not particularly limited. Generally, however, the metal complex is obtained by using a metal solubilizer and carbon tetrachloride. It is adjusted to the said state by dissolving in the liquid phase. That is, the metal solubilizer binds to a metal as a ligand to form the metal complex and dissolves in the liquid phase of carbon tetrachloride.

  In this invention, iron, copper, aluminum etc. are mentioned as a metal which forms a metal complex, Since iron is rich in reactivity and can be procured cheaply, it can be preferably used. The iron is not particularly limited, and examples thereof include metallic iron, pure iron, soft iron, carbon steel, ferrosilicon steel, and an alloy containing iron (for example, stainless steel). Although it does not specifically limit about copper and aluminum, Specifically, pure copper, a copper alloy, brass, pure aluminum, an aluminum alloy etc. can be mentioned.

The shape of the metal used when the metal is dissolved in the liquid phase of carbon tetrachloride is, for example, any shape such as powder, granule, lump, rod, sphere, plate, and fiber. In addition, a metal piece, a distilled packing, and the like that are further processed using these may be used. From the viewpoint of ensuring a sufficient contact area between the metal and the metal solubilizer and carbon tetrachloride, the shape is preferably powder or fiber. From the same viewpoint, it is preferable that the specific surface area of the metal measured by the BET method using nitrogen as an adsorbate is 0.001 to ⁵ m ² / g.

  In the present invention, the metal solubilizer is not particularly limited as long as the metal used is dissolved. For example, polar solvents, such as a protic polar solvent or an aprotic polar solvent, are mentioned.

  Specific examples of the protic polar solvent include 1-butanol, 1-propanol, isopropyl alcohol, amine solvents, etc. Among the amine solvents, monoethanolamine, diethanolamine, triethanolamine and the like. Can be preferably used.

  Specific examples of the aprotic polar solvent include acetone, acetylacetone, methyl ethyl ketone, diethyl ether, ethyl acetate, acetonitrile, dimethyl sulfoxide, amide solvents, phosphate ester solvents, and the like. Specific examples of the amide solvent include N-ethylformamide, N, N-dimethylformamide (DMF), N-methylacetamide, N, N-dimethylacetamide (DMAC) and the like. Specific examples of the phosphate ester solvent include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, diethyl phosphate, dibutyl phosphate, monophenyl phosphate, monobutyl phosphate, phosphorus And dimethylphenyl phosphate, diethylphenyl phosphate, dimethylethyl phosphate, and phenylethylmethyl phosphate. Of these, amide solvents and phosphate esters can be preferably used. If it is an amide solvent, N, N-dimethylacetamide is particularly preferable, and if it is a phosphate ester solvent, it is preferably a trialkyl phosphate, specifically, trimethyl phosphate, triethyl phosphate, Tripropyl phosphate or tributyl phosphate is particularly preferred.

  The combination of the metal and the metal solubilizer is not particularly limited as long as the metal forms a complex and dissolves in the reaction solution, and the metal-aprotic polar solvent is not limited. In particular, an iron-amide catalyst or an iron-phosphate ester catalyst is preferable because a high conversion can be obtained. As a catalyst system for other metal-metal solubilizers, a copper-amine catalyst is also a suitable example.

  The amount of the metal used is preferably 0.001 mol or more, and 0.005 mol or more with respect to 1 mol of carbon tetrachloride to be used from the viewpoint of achieving both a high reaction conversion rate and a high selectivity. It is more preferable that the amount be 0.01 mol or more. The upper limit of the amount of metal used is not particularly limited, but even if the amount of metal used is increased, the activity and selectivity are hardly affected, but the absolute amount of the raw material that can be introduced into the reactor is equivalent to the volume of the metal. It is economically disadvantageous in that it is reduced and more metal is wasted without being involved in the reaction. From this viewpoint, the amount of metal used is preferably 10 mol or less, preferably 5 mol or less, more preferably 1 mol or less, particularly 1 mol of carbon tetrachloride used. The amount is preferably 0.1 mol or less.

  The use amount of the metal solubilizer is formed from the combination of the metal and the metal solubilizer with respect to 1 mole of the metal used in terms of ensuring high conversion and high selectivity. It is preferable that the theoretical coordination quantity necessary for the metal complex is at least equimolar, more preferably at least 1.5 molar. The amount of the metal solubilizer used is usually selected so as to satisfy the above relationship in a range of 0.001 mol or more, and further 0.002 mol or more with respect to 1 mol of carbon tetrachloride. The

  The upper limit of the amount of metal solubilizer used is not particularly limited. However, if the amount used is excessively large, it becomes difficult to control the reaction due to heat generation, and more metal solubilizer is wasted without being involved in the reaction. This is economically disadvantageous. From this viewpoint, the amount of the metal solubilizer used is preferably 100 mol or less, more preferably 10 mol or less, and may be 5 mol or less, relative to 1 mol of the metal used. The amount of the metal solubilizer used is 1 mol or less, 0.1 mol or less, and 0.05 mol or less with respect to 1 mol of carbon tetrachloride. Preferably it is done.

  Addition of the above catalyst species to the reaction system is carried out by adding each amount in the reaction system all at once before starting the reaction, or adding all of the iron and a part of the metal solubilizer before starting the reaction. In addition, the metal solubilizer can be added by a method of additionally adding during the progress of the addition reaction. During the addition reaction, the amount of the metal complex formed by the catalyst often occupies approximately 0.5 to 1% by mass of the entire reaction solution on average. However, it is not limited to this range because it is largely proportional to the amount of the metal solubilizer used as the catalyst.

  The reaction temperature of the addition reaction is preferably 70 to 180 ° C, and more preferably 90 to 150 ° C in order to achieve both a high conversion rate and a high selectivity. The reaction pressure may be any pressure as long as the reaction system can maintain a liquid phase at the above reaction temperature, and can be generally 0.05 to 3 MPaG, preferably 0.1 to 2 MPaG. If the reaction pressure is less than 0.05 MPa, the ethylene concentration in the liquid phase becomes too low, and the reaction addition rate may be insufficient. On the other hand, when the pressure exceeds 3 MPa, the ratio of multimer formation increases and the selectivity may be impaired.

  The addition reaction may be continued until the conversion rate of carbon tetrachloride reaches 30 to 100%, more preferably 80 to 98%. The conversion rate of carbon tetrachloride can be determined from the consumption of unsaturated compounds, and can be grasped by directly analyzing the reaction mixture by gas chromatography or the like.

  Further, the reaction time is not particularly limited, but under the conditions as described above, the total reaction time is often 1 to 12 hours, and generally 2 to 10 hours. In the case of significantly deviating from this range, it is desirable to appropriately change the supply rate of the unsaturated compound and the reaction temperature.

  The reaction liquid after completion of the reaction is a single-phase liquid in which the metal complex is finely dispersed in the liquid. The most characteristic feature of the present invention is that a centrifugal force is applied to the reaction solution, so that a light phase solution containing a large amount of metal complex and a 1,1,1,3-tetrachloropropane, which is the target product, are the main components. Phase separation into phase reaction solution.

  That is, by applying centrifugal force, it is possible to accelerate the aggregation rate of the metal complex in the phase separation and efficiently reduce the concentration of the metal complex contained in the heavy phase reaction liquid. Therefore, a reaction solution with a reduced metal complex concentration can be obtained by separating and removing the liquid component forming the light phase.

  In the present invention, the magnitude of the centrifugal force to be applied is not particularly limited as long as the concentration of the metal complex contained in the heavy phase reaction solution finally becomes a desired concentration. Preferably it is 400 G or more. The greater the centrifugal acceleration applied to the reaction solution, the more the effect of the present invention can be obtained, but about 4000 G is practical at most. The treatment time for applying the centrifugal force may be determined in consideration of the magnitude of the centrifugal force, but is preferably 5 seconds or more, and more preferably 10 seconds or more. The longer the processing time for applying the centrifugal force, the better. However, not only the effect reaches a peak, but also the time efficiency is lowered, and about 300 seconds is sufficient.

  The centrifuge may be either a batch type or a distribution type. If the centrifugal acceleration is too low or the treatment time is too short, there may be cases where sufficient coagulation effect of the metal complex cannot be obtained.In actual operation, the centrifugal force should be set appropriately depending on the amount of reaction liquid treated. Multiply it.

  Moreover, when the liquid temperature of the reaction liquid at the time of the centrifugal treatment is high (80 ° C. or higher), there is a concern about corrosion of the piping and equipment by the metal complex, and therefore the temperature of the reaction liquid is preferably 60 ° C. or lower, more preferably. Is preferably lowered to 40 ° C. or less, more preferably to room temperature, and then transferred to a centrifuge.

  The liquid after applying the centrifugal force is once transferred to a container and the light phase liquid is separated and removed. However, as a preferred embodiment, after the liquid is once transferred to the container, a standing time can be further provided. Since the liquid after applying centrifugal force is rapidly separated, it is effective to provide a standing time to effectively reduce the metal complex concentration in the heavy phase reaction liquid even for a short time. is there.

  The standing time may be set so that the concentration of the metal complex finally contained in the heavy phase reaction solution becomes a desired concentration in consideration of the magnitude of the centrifugal force to be applied. Although the said standing time is not specifically limited, It is preferable to set it as 30 minutes or more, and it is more preferable to set it as 60 minutes or more. The longer the standing time is, the more preferable, but the effect obtained even if it is set too long not only reaches a peak, but the processing time becomes enormous and inefficient, so it is preferably 5 hours or less, and 3 hours or less. More preferably.

  By the phase separation, the concentration of the metal complex contained in the heavy phase reaction liquid is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and 0.001% by mass or less. It is particularly preferable to do this. By making the concentration of the metal complex contained in the heavy phase reaction liquid within the above range, corrosion of pipes and equipment in the post-process, scaling, and decomposition of 1,1,1,3-tetrachloropropane in the purification process are efficient. Can be suppressed.

  In the present invention, the method for separating and removing the light phase containing the metal complex from the reaction solution containing 1,1,1,3-tetrachloropropane is not particularly limited. For example, the liquid after applying centrifugal force is transferred to a container and separated into two phases, and then the light phase liquid is sucked and removed, adsorbed on a mat, or removed to reduce the heavy phase. For example, it is possible to easily and efficiently separate and remove the metal complex from the reaction solution.

  When performing the suction removal, the suction device is not particularly limited. For example, a light phase may be sucked by appropriately using a dropper, an aspirator, a suction device, or the like.

  When the light phase is made to adsorb the mat, there is no particular limitation as long as the light phase can adsorb the light phase preferentially. As a material of the adsorption mat, for example, natural fibers (cotton etc.) and synthetic fibers (polypropylene, polyethylene) can be used. The used mat can be easily regenerated by washing and drying with a polar solvent such as acetone.

  Next, when extracting the heavy phase from the lower part of the container, an extraction port is provided in the lower part of the container, and the heavy phase reaction liquid is extracted from the extraction port. At this time, since the light phase descends according to the amount of extraction, the extraction is stopped before the light phase reaches the extraction port. The light phase gradually accumulates and increases as the above operation (transferring the reaction solution with centrifugal force to the vessel and extracting the heavy phase reaction solution) is repeated, so the light phase solution overflows from the top of the vessel. Alternatively, a discharge port for discharging the light phase liquid may be provided at the top of the container.

  A plurality of such containers can be installed in consideration of reaction time, distillation time, and standing time. Further, in order to increase the separation speed, it is also preferable to use a container having a lower height even with the same capacity.

  The reaction liquid (heavy phase) from which the light phase containing the metal complex has been separated and removed in this manner is subjected to a purification step and distilled to obtain 1,1,1,3-tetrachloropropane having a higher purity. It is suitable to use for the next reaction. Therefore, it is preferable to provide a step of separating and removing the light phase liquid by applying centrifugal force to separate and remove the light phase liquid until the reaction is completed and then supplied to the purification step.

  When a metal complex is contained in the reaction solution, problems of scale adhesion and corrosion to the apparatus wall material become more apparent in a severe environment under heating in distillation. Subjecting the liquid (heavy phase) to distillation in this way is a particularly preferred embodiment because the effects of the present invention are more remarkably exhibited.

  The conditions for performing distillation are not particularly limited. The reaction can be performed at normal pressure (101 kPa) and near the boiling point of 1,1,1,3-tetrapropane from which the temperature at the top of the distillation column was obtained, but if the temperature at the top of the distillation column is too high (at the bottom of the column) (The temperature also increases) 1,1,1,3-tetrapropane is likely to be decomposed, and if the temperature at the top of the distillation column is too low, the energy for cooling the top of the distillation column increases during distillation, or the pressure is greatly increased. Since it must be reduced, the cost of the equipment and the operating cost become high. Therefore, the temperature range at the bottom of the column during distillation is preferably 20 ° C to 200 ° C, more preferably 50 ° C to 150 ° C, and particularly preferably 70 ° C to 120 ° C. The pressure at the time of distillation is not particularly limited as long as 1,1,1,3-tetrapropane is vaporized at the above temperature and reaches the top of the distillation column, but is preferably 1 kPa to 110 kPa. The pressure here is an absolute pressure.

  FIG. 4 is a schematic diagram showing an example of a manufacturing apparatus for carrying out the present invention. That is, a reactor (1) for storing raw materials and the generated reaction mixture, a liquid extraction pipe (2) for extracting the reaction mixture generated in the reactor, and a centrifuge for applying centrifugal force to the extracted post-reaction liquid ( 3) The liquid extraction tube (4) for transferring the centrifuged post-reaction liquid to the static separation tank, the metal complex and the reaction liquid contained in the post-reaction liquid are statically separated into two phases A static tank (5) for separation, a light-phase liquid extraction pipe (6) for transporting the metal complex that has been separated into two phases by static separation, and a reaction liquid that has also been statically separated to remove the metal complex. A heavy phase extraction pipe (7).

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

In the following examples, the amount of metal complex in the reaction solution is converted to the amount of metal complex expected from the amount of metal obtained by quantifying the amount of metal by emission spectroscopy using an ICP (inductively coupled plasma) apparatus. did. In addition, the structure of the assumed metal complex is [Cu · (C ₂ H ₅ O) ₃ PO] in the copper-triethyl phosphate system, and [Fe · (C ₂ H ₅ O) in the iron-triethyl phosphate system. ) ₃ PO], iron -N, in a system of N- dimethylacetamide (DMAc) is _{[FeCl 2 · 2FeCl 3 · 6} (C 4 H 9 NO)]. The composition of the reaction solution was analyzed by gas chromatography (FID detection).
Example 1
(Synthesis of 1,1,1,3-tetrachloropropane)
In a 1 L glass autoclave equipped with a stirrer, 5.5 mol of carbon tetrachloride, 0.03 mol of iron (0.55 mol% with respect to 100 mol% of carbon tetrachloride), 0.005 mol of N, N-dimethylacetamide (tetrachloride) Carbon was added as 100 mol% and 0.1 mol%) was charged and sealed.

  After the air in the autoclave was purged with nitrogen, it was subsequently purged with ethylene, and the temperature was raised to 130 ° C. while stirring at 400 rpm. Addition reaction was started by supplying ethylene into the system so that the pressure in the gas phase was 0.6 MPaG.

During the reaction, ethylene is continuously supplied so that the total pressure in the gas phase is maintained at 130 ° C. and 0.6 MPaG, and N, N-dimethylacetamide (DMAc) is continuously supplied at 0.0002 mol / min. Supplied into the system. The total amount of N, N-dimethylacetamide (DMAc) added was 0.035 mol in total with the amount charged. After 5 hours, the reaction was completed and the temperature was lowered to room temperature. Then, the reaction solution was extracted from the autoclave and filled into a PP container (capacity 1 L). The composition of the obtained reaction solution was the conversion rate of carbon tetrachloride. The selectivity for the target 1,1,1,3-tetrachloropropane was 94%, and the concentration of iron-N, N-dimethylacetamide (DMAc) complex in the liquid immediately after the reaction was 0.6. It was mass%.
(Separation and removal of light phase liquid)
The obtained reaction solution was kept at 2000 rpm (equivalent to 400 G) for 3 min in a centrifuge, then taken out and left to stand for 3 hours. The reaction solution is separated into two phases. When the light phase solution is sucked with a poly dropper and collected in a PP container (capacity 50 ml), it is 0.6% by mass with respect to the total amount of the reaction solution. Was 99.4% by mass. Further, the concentration of iron-N, N-dimethylacetamide (DMAc) complex in the heavy phase reaction solution was 0.01% by mass.
(Simulation experiment)
Subsequently, in order to create a simulated state in the tower when distillation was performed continuously for a long period of time, the following experiment was conducted to evaluate the stability when a continuous operation was performed for a long period of time.

A 500 cc glass round bottom flask was charged with 500 g of the above heavy phase reaction solution, and a SUS304 test piece measuring 19 × 15 × 1.5 mm in thickness was immersed in the solution. A glass serpentine condenser was attached to the opening of the round bottom flask, and the vaporized heavy phase reaction liquid was returned to the round bottom flask by refluxing and kept in an oil bath heated to 110 ° C. for 16 hours. After completion of the simulation experiment, the composition of the heavy phase reaction solution was analyzed before and after the simulation experiment, and the difference in 1,1,1,3-tetrachloropropane purity change was calculated as the chloropropane decomposition rate. As a result, the chloropropane decomposition rate was 0.8%. Met. Moreover, when the weight change of the test piece before and behind a simulation experiment was measured and the amount of scale adhesion was calculated | required, it was 0.9 mg.
Comparative Example 1
In addition to synthesizing 1,1,1,3-tetrachloropropane in the same procedure as in Example 1, the reaction liquid extracted from the autoclave immediately after the completion of the reaction was charged into a round bottom flask without the operation of separating and removing the light phase liquid. The same procedure as in Example 1 was performed. At this time, the concentration of iron-N, N-dimethylacetamide (DMAc) complex in the reaction solution was 0.7% by mass, and the decomposition rate of the chloropropane solution after the simulation experiment was 2.34%. Moreover, the amount of scale adhesion was 54.3 mg.
Example 2 and Reference Examples 1-3
1,1,1,3-tetrachloropropane was synthesized in the same procedure as in Example 1. The composition of the obtained reaction solution was 94% conversion of carbon tetrachloride and 98% selectivity of 1,1,1,3-tetrachloropropane as the target product. Moreover, the iron-N, N-dimethylacetamide (DMAc) complex concentration in the liquid immediately after the reaction was 0.6% by mass.

  Subsequently, the light phase liquid was recovered from the obtained reaction liquid in the same procedure as in Example 1. The recovered light phase liquid was 0.6 mass% with respect to the total amount of the reaction liquid, and the heavy phase reaction liquid from which the light phase was separated and removed was 99.4 mass%. The metal complex concentration in the heavy phase reaction solution was 0.01% by mass.

The recovered light phase reaction solution was used as a metal complex simulation solution in a simulation experiment described later.
(Simulation experiment)
Four 100 cc glass eggplant flasks were prepared, and each was filled with 80 g of a SUS304 test piece of length 19 × width 15 × thickness 1.5 mm and the heavy phase reaction liquid from which the light phase had been removed. About 1-3, the said metal complex pseudo | simulation liquid was further added so that a metal complex density | concentration might be the quantity described in Table 1, respectively. Subsequently, a glass snake tube cooler was attached to the opening of each eggplant flask, and the vaporized heavy phase reaction liquid was refluxed and returned to the eggplant flask, and held in an oil bath heated to 130 ° C. for 1 week. After completion of the simulation experiment, the weight change of the test piece before and after each simulation experiment was measured to determine the amount of scale adhesion and the corrosion rate. In addition, the composition of the heavy phase reaction solution was analyzed before and after the simulation experiment, and the chloropropane decomposition rate was calculated from the difference in 1,1,1,3-tetrachloropropane purity change. Each result is shown in Table 1, FIG. 2, and FIG.
From the results, the chloropropane decomposition rate, the corrosion rate, and the scale adhesion amount with respect to the metal complex concentration increased in almost linear proportion.

Example 3
In a 2 L SUS316 autoclave equipped with a stirrer, 11 mol of carbon tetrachloride, 0.07 mol of iron (0.65 mol% of carbon tetrachloride as 100 mol%), 0.01 mol of triethyl phosphate (100 mol% of carbon tetrachloride) 0.1 mol%) was charged and sealed. After the air in the autoclave was purged with nitrogen, it was subsequently purged with ethylene, and the temperature was raised to 110 ° C. while stirring at 350 rpm. The addition reaction was started by supplying ethylene into the system so that the total pressure in the gas phase was 0.5 MPaG.

  During the reaction, ethylene was continuously supplied so that the total pressure in the gas phase at 110 ° C. was maintained at 0.5 MPaG, and triethyl phosphate was continuously supplied into the system at 0.0001 mol / min. The total amount of triethyl phosphate added together with the amount charged was 0.052 mol. After 7 hours, the reaction was completed and the temperature was lowered to room temperature, and then the reaction solution was extracted from the autoclave and filled into a PP container. As a result, a reaction liquid having a carbon tetrachloride conversion rate of 95% and a 1,1,1,3-tetrachloropropane selectivity of 96% was obtained.

Subsequently, the reaction solution was held for 3 min at 2000 rpm (equivalent to 400 G) in a centrifuge. The reaction solution taken out from the centrifuge was allowed to stand for 0.25 hours. The reaction liquid after standing was separated into two phases, and the concentration of the iron-triethyl phosphate complex in the heavy phase reaction liquid was 0.11% by mass.
Example 4
The same procedure as in Example 1 was performed except that the reaction solution was allowed to stand for 1 hour after centrifugation. The reaction solution after standing was separated into two phases, and the concentration of iron-triethyl phosphate complex in the heavy phase reaction solution was 0.03% by mass.
Example 5
The same procedure as in Example 1 was performed except that the reaction solution was allowed to stand for 3 hours after centrifugation. The reaction liquid after standing was separated into two phases, and the concentration of the iron-triethyl phosphate complex in the heavy phase reaction liquid was 0.02% by mass.
Comparative Example 2
The reaction solution taken out from the autoclave was subjected to the same procedure as in Example 3 except that it was not subjected to a centrifuge and allowed to stand for 1 hour. The reaction liquid after standing for 1 hour was separated into two phases, and the concentration of iron-triethyl phosphate complex in the heavy phase reaction liquid was 0.47% by mass.
Comparative Example 3
The same procedure as in Comparative Example 1 was performed except that the standing time was 3 hours. The reaction liquid after standing was separated into two phases, and the concentration of the iron-triethyl phosphate complex in the heavy phase reaction liquid was 0.28% by mass.
Comparative Example 4
The procedure was the same as in Comparative Example 1 except that the standing time was 6 hours. The reaction liquid after standing was separated into two phases, and the concentration of iron-triethyl phosphate complex in the heavy phase reaction liquid was 0.09% by mass.
Comparative Example 5
The procedure was the same as in Comparative Example 1 except that the standing time was 15 hours. The reaction solution after standing was separated into two phases, and the concentration of the iron-triethyl phosphate complex in the heavy phase reaction solution was 0.01% by mass.

The results of Examples 3 to 5 and Comparative Examples 2 to 5 are shown in FIG.
Example 6
In a 120 cc SUS316 autoclave equipped with a stirrer, 0.5 mol of carbon tetrachloride, 0.012 mol of copper powder (2.4 mol% with respect to 100 mol% of carbon tetrachloride), 0.003 mol of triethyl phosphate (carbon tetrachloride was added) 100 mol% as 0.6 mol%) was charged and sealed.

  After the air in the autoclave was purged with nitrogen, it was subsequently purged with ethylene, and the temperature was raised to 110 ° C. while stirring at 350 rpm. The addition reaction was started by supplying ethylene into the system so that the total pressure in the gas phase was 0.3 MPaG.

  During the reaction, ethylene was continuously supplied so that the total pressure in the gas phase at 110 ° C. was maintained at 0.3 MPaG. After 6 hours, the reaction was completed and the temperature was lowered to room temperature, and then the reaction solution was extracted from the autoclave into a PP container. As a result, a reaction solution having a carbon tetrachloride conversion rate of 12% and a target 1,1,1,3-tetrachloropropane selectivity of 25% was obtained, and the concentration of the copper-triethyl phosphate complex in the solution was 0. It was 0.62% by mass.

  Subsequently, the obtained reaction solution was held at 2000 rpm (equivalent to 400 G) for 3 min by a centrifuge, then taken out and allowed to stand for 3 hours. The reaction solution was separated into two phases, and the concentration of the copper-triethyl phosphate complex in the heavy phase reaction solution was 0.01% by mass.

(1) Reactor (2) Liquid extraction tube (3) Centrifuge (4) Liquid extraction tube after centrifugation (5) Static settling tank (6) Light phase extraction tube (7) Heavy phase extraction tube

Claims (6)

In the liquid phase in which the metal complex is dissolved, carbon tetrachloride is added to ethylene and the resulting reaction solution containing 1,1,1,3-tetrachloropropane is subjected to centrifugal force to cause phase separation. And a process for producing 1,1,1,3-tetrachloropropane characterized by separating and removing the light phase containing the metal complex. The method for producing 1,1,1,3-tetrachloropropane according to claim 1, wherein the magnitude of the centrifugal force is 200 G or more, and the treatment time for applying the centrifugal force is 5 seconds or more. The amount of the metal complex contained in the reaction solution after separating and removing the light phase containing the metal complex is 0.01% by mass or less, of 1,1,1,3-tetrachloropropane according to claim 1 or 2. Production method. The method for producing 1,1,1,3-tetrachloropropane according to any one of claims 1 to 3, wherein the metal complex has a structure in which a metal solubilizer is bonded to a metal as a ligand. 5. The metal complex according to claim 1, wherein the metal complex is at least one selected from the group consisting of an iron-phosphate ester complex, a copper-phosphate ester complex, and an iron-amide complex. A method for producing 1,1,1,3-tetrachloropropane. The reaction solution obtained by separating and removing the light phase containing the metal complex obtained by the method according to any one of claims 1 to 4 is further subjected to distillation to obtain 1,1,1,3-tetrachloropropane. The said manufacturing method which raises the purity of.

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