KR20130122617A - Continuous batch reaction method for producing polychloropropane - Google Patents

Abstract

The present invention relates to an addition reaction in which a polychloropropane is obtained by adding carbon tetrachloride to ethylene unsubstituted or chlorine in a liquid phase reaction system, and ethylene unsubstituted or chlorine substituted in a batch reactor in which a liquid phase and a gaseous phase exist. 2nd batch when carrying out by a batch system, supplying the raw material for next batch reaction from a reactor after completion | finish of a batch reaction, supplying the raw material for next batch reaction to the said reactor continuously, and performing said addition reaction repeatedly by a batch system. Thereafter, the partial pressure of ethylene substituted with unsubstituted or chlorine present in the gas phase is adjusted to 0.11 to 0.52 MPa (abs) at 25 ° C. to perform the addition reaction. All.

Description

Continuous batch reaction method for producing polychloropropane {CONTINUOUS BATCH REACTION METHOD FOR PRODUCING POLYCHLOROPROPANE}

The present invention relates to a continuous batch reaction process for producing polychloropropane. More specifically, the present invention relates to a method capable of stably controlling the reaction rate and selectivity of each batch when polychloropropane is produced by a method of repeatedly performing the batch reaction.

Chlorinated hydrocarbons are important as raw materials or intermediates for producing various products such as pesticides, pharmaceuticals, and Freon substitutes. For example, trichloroallyldiisopropylthiocarbamate useful as a herbicide can be prepared starting from 1,1,1,2,3-pentachloropropane and going through 1,1,2,3-tetrachloropropene. Can be.

As a manufacturing method of such chlorinated hydrocarbon, For example, the 1st reaction which adds carbon tetrachloride to a C2 unsaturated compound (unsubstituted or chlorine substituted ethylene), and obtains chloropropane,

A second reaction of dehydrochlorination of the chloropropane to obtain chloropropene;

Three-step reaction is known which consists of the 3rd reaction which further adds chlorine to the said chloropropene and obtains the target chloropropane. Among these, as the first reaction, for example, Japanese Patent Application Laid-Open No. 2-47969 carries out an addition reaction of ethylene and carbon tetrachloride in the presence of a phase transfer catalyst composed of a metal iron and a phosphoryl compound, thereby providing 1,1,1, An example of 3-tetrachloropropane is described.

Such a 1st reaction is often performed by the batch system in the reaction system which consists of a liquid phase which consists of carbon tetrachloride, and a gaseous phase which mainly consists of a C2 unsaturated compound.

When performing this batch reaction industrially, after completion of the reaction of each batch, after discharging the reaction mixture from the reactor, new carbon tetrachloride is introduced without washing the reactor, a catalyst and an unsaturated compound having 2 carbon atoms are supplied, and It is more efficient to perform a batch reaction. However, according to the inventors' study, it was found that when such a batch reaction is repeatedly performed, the addition reaction activity may decrease or the reaction selectivity may change as the batch number passes.

This invention is made | formed in view that the above-mentioned problem existed in the prior art, and the objective is when manufacturing a polychloropropane by the method of performing a batch reaction repeatedly, and the reaction rate of each batch, The present invention provides a method for stably controlling the selectivity.

New objects and advantages of the invention will be apparent from the following description.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said problem, when the addition reaction of carbon tetrachloride and an unsaturated compound of C2 is carried out by the method which performs a batch reaction repeatedly, the composition of a gaseous-phase part goes through a batch number. I found it gradually changing. That is, air dissolved in carbon tetrachloride as a raw material, impurities contained in a small amount in the raw material, etc. remain in the gas phase without being completely removed after completion of the batch. The absolute amount of the compound is attenuated.

It is not known so far to cause such a situation when polychloropropane is produced by the method of performing a batch reaction repeatedly, and it was revealed by the present inventors' examination.

This invention was completed based on the above knowledge.

According to the present invention, the above problems in the prior art,

In a liquid phase reaction system, an addition reaction in which polychloropropane is obtained by adding carbon tetrachloride to ethylene substituted with unsubstituted or chlorine is placed while supplying ethylene substituted with unsubstituted or chlorine in a batch reactor in which a liquid phase and a gaseous phase exist. After the second batch when the reaction mixture is discharged from the reactor after the completion of the batch reaction, the raw material for the next batch reaction is continuously supplied to the reactor, and the addition reaction is repeatedly performed in the batch method. To

The partial pressure of the unsubstituted or chlorine-substituted ethylene present in the gas phase is adjusted to 0.11 to 0.52 MPa (abs) at 25 ° C. to perform the above addition reaction.

1 is a graph showing the results of continuous batch reactions in Experimental Example A-1 and Example B-1.
2 is a graph showing the results of continuous batch reactions in Experimental Example A-2 and Example C-1.
3 is a graph showing the ethylene partial pressure before the start of each batch reaction in Experimental Example A-2 and Example C-1.

The method of the present invention as described above can be realized by, for example, the following two specific methods.

The first method for practicing the present invention,

When the reaction mixture is discharged from the reactor after the completion of the reaction of the previous batch, and subsequently the raw material for the next batch reaction is supplied to the reactor,

First, carbon tetrachloride was put into the reactor,

After supplying and pressurizing the ethylene unsubstituted or substituted with chlorine to the gaseous phase, and performing the pressurization / decompression operation for reducing the gas phase pressure by evacuating one or more times, the ethylene unsubstituted or substituted with chlorine is further added to the gaseous phase. After supplying and pressurizing and adjusting the partial pressure of ethylene substituted by unsubstituted or chlorine which exists in a gaseous-phase part to the said range, the next batch reaction is performed (henceforth "the method 1").

The second method for practicing the present invention,

When the reaction mixture is discharged from the reactor after the completion of the reaction of the previous batch, and subsequently the raw material for the next batch reaction is supplied to the reactor,

First, carbon tetrachloride was put into the reactor,

The partial pressure of unsubstituted or chlorine substituted ethylene present in the gaseous phase is adjusted to the above-mentioned range by supplying and pressurizing ethylene substituted with unsubstituted or chlorine to the gaseous phase, and the voltage of the gaseous phase is adjusted to the above range. It is a method (hereinafter also referred to as "method 2") which is set to the total pressure of the partial pressure of ethylene substituted with ring or chlorine and the partial pressure of gases other than ethylene substituted with unsubstituted or chlorine present in the gas phase portion.

Hereinafter, after describing reaction of the 1st batch common to each said method, the matter of each method individual in a 2nd batch or more is demonstrated in detail.

<First batch>

Ethylene (hereinafter referred to as an "unsaturated compound having 2 carbon atoms") substituted with unsubstituted or chlorine used as a raw material in the present invention includes ethylene, vinyl chloride, 1,1-dichloroethylene, 1,2-dichloroethylene, 1 Although 1, 2- trichloroethylene and perchloroethylene are included, ethylene or vinyl chloride which is gas at normal temperature and normal pressure is preferable at the point which is easy to implement this method. As a product obtained by adding carbon tetrachloride to such a raw material compound, it is obvious to a person skilled in the art what kind of polychloropropane is obtained according to the raw material compound to be used, for example, when ethylene is used as a raw material compound, 1,1,1,3 When tetrachloropropane uses vinyl chloride, 1,1,1,3,3-pentachloropropane is obtained, respectively.

Each batch reaction of the continuous batch reaction in the present invention proceeds in a liquid phase reaction system in a batch reactor in which a liquid phase and a gas phase exist. At this time, the unsaturated compound having 2 carbon atoms, which is a raw material compound, is supplied to the reaction system, and then dissolved in a liquid phase to be provided for addition reaction with carbon tetrachloride. It is preferable that the raw material compound corresponding to the consumed amount is added to the gas phase at any time, so that the pressure in the gas phase part is kept substantially constant during the batch reaction.

When supplying a C2 unsaturated compound to a reaction system, the said unsaturated compound may be supplied to a gas phase part, for example, may be supplied to a liquid part by bubbling, or both may be performed simultaneously. However, it is preferable to supply an unsaturated compound having 2 carbon atoms to the gas phase part because of the fact that the stable progress of the reaction is ensured, and the bubbling in the liquid requires a larger pressure than that supplied to the gas phase part.

It is preferable that addition reaction in this invention is performed in presence of a suitable catalyst. As a catalyst which can be used here, an iron-phosphate ester catalyst, an iron- aprotic polar solvent catalyst, a copper-amine catalyst etc. are mentioned, for example, Among these, an iron-phosphate ester catalyst is preferable.

The addition reaction is preferably performed in a state where an iron-phosphate ester catalyst is present in the liquid phase. This iron-phosphate ester catalyst is prepared by contacting a predetermined amount of iron and a predetermined amount of phosphate ester in a liquid reaction system (that is, in liquid carbon tetrachloride). The contact of iron and phosphate ester is carried out by a method in which all the amounts of iron and phosphate ester are added to the reaction system at one time before the start of the reaction,

Or it can carry out by adding whole quantity of iron and a part of phosphate ester before reaction start, and adding phosphate ester further in progress of addition reaction. Here, "before reaction start" refers to the time before raising the temperature of a reaction system to the temperature (henceforth "minimum reaction temperature") with which carbon tetrachloride and a C2 unsaturated compound react substantially. For example, when a C2 unsaturated compound is ethylene, the minimum reaction temperature at the time of using the said iron-phosphate ester catalyst is 90 degreeC. Therefore, it is preferable that all or part of the whole quantity of iron and phosphate ester is added when reaction system is less than 90 degreeC, and it is more preferable to add when it is normal temperature.

As iron used here, metal iron, pure iron, soft iron, carbon steel, ferro silicon steel, alloy containing iron (for example, stainless steel etc.) etc. are mentioned, for example. The shape of iron may be any shape such as powder, granular, bulk, rod, spherical, plate, fibrous, or the like, as well as a metal piece or a distillation filler which is optionally processed using them. Examples of the processed metal pieces include coils, meshes, steel wool, and other irregular shaped pieces; As said distillate packing, Raschig ring, helix, etc. are mentioned, for example. Although any form of these can be used, it is preferable that it is powder form or fibrous form from a viewpoint of ensuring sufficient contact area with a phosphate ester and a reactant. From the same viewpoint, it is preferable that the specific surface area of iron measured by BET method using nitrogen as an adsorbate is 0.001-5 m <2> / g.

As the amount of iron used in the case of adding phosphate ester collectively before the start of the reaction, from the viewpoint of achieving both a high reaction conversion ratio and a high selectivity, it should be 0.001 mol or more with respect to 1 mol of carbon tetrachloride to be used. It is preferable to set it as 0.005 mol or more, and it is preferable to set it as 0.01 mol or more especially. The upper limit of the amount of iron used is not particularly limited. Increasing the amount of iron hardly affects the activity and selectivity, but the amount of raw material that can be introduced into the reactor is reduced by the amount corresponding to the volume of iron, resulting in a decrease in the reaction efficiency, and not involving in the reaction. It is also disadvantageous economically in that there are many irons. From such a viewpoint, the amount of iron used is preferably 10 mol or less, more preferably 5 mol or less, even more preferably 1 mol or less, particularly 0.1 mol or less, per 1 mol of carbon tetrachloride to be used. It is preferable to set it as.

As said phosphate ester, it is following General formula (1), for example

(In formula (1), R <^1> is a phenyl group or a C1-C4 alkyl group, and R <^2> and R <^3> is a hydrogen atom, a phenyl group, or a C1-C4 alkyl group each independently.)

The compound represented by these is mentioned, As a specific example, a trimethyl phosphate, a triethyl phosphate, a tripropyl phosphate, a tributyl phosphate, diethyl phosphate, a dibutyl phosphate, a monophenyl phosphate, a monobutyl phosphate, a dimethylphenyl phosphate And diethyl phenyl phosphate, dimethyl ethyl phosphate, phenyl ethyl phosphate and the like. Among these, trialkyl phosphates in which all of R ¹ , R ² and R ³ are alkyl groups having 1 to 4 carbon atoms in the general formula (1) are preferable, and trimethyl phosphate, triethyl phosphate, and tripropyl phosphate are particularly preferred. Tributyl phosphate is preferred.

It is preferable to make it into 0.001 mol or more with respect to 1 mol of carbon tetrachloride used from a viewpoint of ensuring high conversion rate and high selectivity, and it is especially preferable to set it as 0.002 mol or more. Although the upper limit of the usage-amount of phosphate ester is not specifically limited, When the usage-amount is excessively large, it becomes difficult to control reaction by exotherm, and it becomes economically disadvantageous because there are many waste phosphate esters which do not participate in reaction. From such a viewpoint, the amount of phosphate ester used is preferably 1 mol or less, more preferably 0.1 mol or less, and even 0.05 mol or less with respect to 1 mol of carbon tetrachloride.

In order to reliably advance the reaction, the reaction temperature of the addition reaction is preferably set to a temperature higher than the minimum reaction temperature, more preferably 90 to 160 ° C in order to achieve high conversion and high selectivity, and to be 105 to 130 ° C. More preferred.

The reaction pressure may be a pressure at which the reaction system can maintain a liquid phase at the reaction temperature. As reaction pressure converted at 25 degreeC, it is preferable that it is 0.13-0.54 Mpa (abs), and it is more preferable that it is 0.17-0.37 Mpa (abs). For example, at 110 ° C, considering that the vapor pressure of carbon tetrachloride is 0.25 MPa, the reaction pressure can be 0.40 to 0.90 MPa (abs), and preferably 0.45 to 0.70 MPa (abs).

As a partial pressure of a C2 unsaturated compound in a gaseous-phase part, it is preferable to set it as 0.11-0.52 Mpa (abs) as a value converted at 25 degreeC, and it is more preferable to set it as 0.15-0.35 Mpa (abs). When this value sets reaction temperature to 110 degreeC, for example, the said preferable range becomes 0.15-0.65 MPa (abs), and a more preferable range becomes 0.20-0.45 MPa (abs). When the partial pressure of the unsaturated compound having 2 carbon atoms converted to 25 ° C. is less than 0.11 MPa, the concentration of the raw material compound (unsaturated compound having 2 carbon atoms) in the liquid phase may be too low, and the reaction addition rate may be insufficient. At excess pressures, the rate at which the multimers are produced increases and the selectivity may be impaired.

Said reaction pressure is the value which totaled the partial pressure of a C2 unsaturated compound, and the partial pressure of other gas. At this time, it should be noted that carbon tetrachloride, which is a liquid having only a small vapor pressure, has a significant vapor pressure at the reaction temperature at 25 ° C. The vapor pressure of carbon tetrachloride is only about 0.02 MPa at 25 ° C, but is significantly higher at 0.25 MPa at 110 ° C. The partial pressure of the unsaturated compound having 2 carbon atoms and the partial pressure of other gases can be obtained from the analysis results by gas chromatography of the gas phase part and the voltage of the gas phase part. In addition, all the said pressures are absolute pressures in the temperature which was set or mentioned.

In each batch of the continuous batch reaction in the present invention, in the first reaction as described above, adding the entire amount of iron and a part of the phosphate ester before the start of the reaction, and further adding the phosphate ester during the progress of the addition reaction It is preferable at the point which can improve controllability of reaction, raises a conversion ratio and a selectivity, and can reduce the quantity of iron and phosphate ester to be used.

The amount of iron collectively added before the start of the reaction can be less than the above-mentioned value as the lower limit of the amount of iron used when the phosphate ester is added collectively before the start of the reaction. In this case, the amount of iron used is more preferably 0.0005 mol or more, more preferably 0.001 mol or more, and particularly 0.005 mol or more with respect to 1 mol of carbon tetrachloride to be used. The upper limit of the amount of iron used is set from an economic point of view. In this case, the amount of iron used is preferably 1 mol or less, more preferably 0.1 mol or less, and even more preferably 0.05 mol or less with respect to 1 mol of carbon tetrachloride to be used.

In addition reaction in this invention, it is preferable that a part of phosphate ester is added before reaction start, and further addition of phosphate ester is carried out during addition reaction progress. The addition of the phosphate ester may be performed only once, may be performed by dividing several times, or may be performed continuously. As a frequency | count of the addition in the case of dividing into several times, it is preferable to use 2-10 times, and it is preferable to carry out 2-6 times.

It is preferable to make all the usage-amount (the total amount in 1 batch of addition amount and addition amount before reaction start) of phosphate ester into 0.001 mol or more with respect to 1 mol of carbon tetrachloride to be used, Especially 0.002 mol It is preferable to make it the above. The total addition amount of the phosphate ester in the case of adding further is not specifically limited. However, also in this case, when the total addition amount of phosphate ester is excessively large, it will become economically disadvantageous in that it will increase waste phosphate ester which is not involved in reaction. From such a viewpoint, the total addition amount of the phosphate ester in the case of further addition is preferably 1 mol or less, more preferably 0.1 mol or less, and even 0.01 mol or less with respect to 1 mol of carbon tetrachloride.

In the method of further adding phosphate ester, even if the usage-amount of phosphate ester is smaller than the method of the prior art, for example, Unexamined-Japanese-Patent No. 2-47969, the target compound has higher conversion ratio and stable It has the advantage of being able to manufacture efficiently at reaction rate.

In the present invention, even when phosphate ester is added after the temperature of the reaction system is raised to the lowest reaction temperature, the addition reaction proceeds. However, in order to start reaction stably, it is preferable to add at least a part of phosphate ester before temperature rising (before reaction start). As addition amount of the phosphate ester before reaction start, it is preferable to set it as 0.0001 mol or more with respect to 1 mol of carbon tetrachloride to use, and it is more preferable to set it as 0.0005 mol or more. The upper limit of the phosphate ester added before the start of the reaction is irrespective of the aspect of the additional addition (whether the addition is performed only once, divided into several times, or continuously). Regardless of the number of times of addition, the amount is preferably 80% or less, more preferably 70% or less of the total amount of phosphate ester used. By setting the addition amount of the phosphate ester before the start of the reaction in the above range, the reaction can be started stably, the control of the reaction becomes easy, and as a result, a high conversion ratio can be achieved.

It is preferable to perform the addition reaction disclosed in this way, continuously monitoring the consumption rate of a C2 unsaturated compound. Continuous monitoring of the consumption rate of this unsaturated compound can be performed, for example, by investigating the quantity of the unsaturated compound supplied to a gaseous phase in order to maintain moderate reaction pressure in liquid phase batch reaction in presence of a gaseous phase.

When adding phosphate ester only once, when the consumption rate of an unsaturated compound becomes 5-50% of the average consumption rate in 60 minutes after the start of reaction, More preferably, it is 10-40%, The whole amount of the remainder of a phosphate ester is further added. By this additional addition, the consumption rate of the unsaturated compound once reduced is restored, and then the remaining addition reaction proceeds while the consumption rate decreases again.

In the case where the addition of the phosphate ester is performed by dividing in several times, the consumption rate is preferably 5 to 50%, more preferably 10 to 40% of the average consumption rate in 60 minutes after the start of the reaction. Further addition of the first phosphate ester is performed. By this first additional addition, the consumption rate of the unsaturated compound once reduced is recovered, and then the consumption rate decreases again. And when the consumption rate of an unsaturated compound becomes 5-50% of the average consumption rate in 60 minutes after the start of reaction again, More preferably, it is 10-40%, The addition of the phosphate ester after the 2nd time is added. Addition is done. By this further addition, the consumption rate of the unsaturated compound is restored again. Thereafter, the consumption rate of the unsaturated compound having 2 carbon atoms can be continuously monitored to further add phosphate ester by a predetermined number of times.

It is preferable that each divided addition amount in the case of dividing addition of phosphate ester into several times sets the addition amount for every time equally, or to make it gradually add a large amount every time the number of times is repeated.

When additional addition of phosphate ester is performed continuously, you may carry out immediately after reaction start, and the consumption rate becomes like this. Preferably it is 5-50% of the average consumption rate in 60 minutes after the start of reaction, More preferably, it is 10-40 When it becomes%, you may start additional addition of phosphate ester. The continuous addition of this phosphoric acid is difficult to control the reaction when the addition rate is high, and the amount of phosphate esters that are wasted without being involved in the reaction becomes economically disadvantageous. In addition, a slow addition speeds up the reaction. From this viewpoint, it is preferable to carry out at the speed | rate of 1.3 * 10 <^-6> -6.6 * 10 <^-3> mol / min with respect to 1 mol of carbon tetrachloride, and the rate of 6.6 * 10 <^-6> -6.6 * 10 <^-4> mol / min It is more preferable to carry out. Here, when the consumption rate of the unsaturated compound of carbon number 2 is slowed to 5 to 50% of the average consumption rate in 60 minutes after the start of the reaction, phosphate ester 1.3 × 10 ^{−6 to} 6.6 per mole of carbon tetrachloride In the range of the rate of * 10 <^-3> mol / min, More preferably, it is 6.6 * 10 <^-6> -6.6 * 10 <^-4> mol / min, you may make the said speed of continuous addition addition accelerate from the middle. This continuous addition, What is necessary is just to continue until the conversion rate of carbon tetrachloride becomes 30 to 100%, More preferably, it may continue until it becomes 80 to 98%. The conversion rate of carbon tetrachloride can be judged from the consumption amount of an unsaturated compound having 2 carbon atoms.

As an aspect of the addition of phosphate ester, it is preferable to carry out only once or continuously. Here, when the addition of the phosphate ester is performed only once, there is an advantage that the operation becomes simple, and when this is continuously performed, there is an advantage that the control of the reaction becomes easy.

It is preferable to make reaction time of the sum total into 1-12 hours, and, as for addition reaction performed as mentioned above, it is more preferable to set it as 2-10 hours.

Since the reaction mixture obtained by such a method contains a target substance converted into the target substance at a high conversion rate and a high selectivity, the unreacted carbon tetrachloride (the content rate is slight) contained therein and the iron-phosphate ester catalyst residue Iv), by-products and excess C2 unsaturated compounds can be separated and used in most cases as they are as products. Although refinement | purification can be performed after addition reaction as desired, the said refinement | purification method may be extremely simple, and it can be made into a high purity product by the simple distillation purification of about 2-10 grades of theoretical stages, for example.

After carrying out the first batch of the addition reaction according to the batch method in this way, the reaction mixture is discharged from the reactor, and then the carbon tetrachloride and an unsaturated compound having 2 carbon atoms and optionally a suitable catalyst are supplied to the reactor to prepare the addition reaction. 2 After the batch is repeated.

Examples of the discharge of the reaction liquid mixture include a method of opening a discharge port attached to the reactor and dropping it by gravity, a method of introducing a gas into the reactor and pressurizing it out. At this time, the liquid phase portion decreases and the gas phase portion increases with the discharge of the reaction mixture, but at this time, it is preferable to maintain the pressure in the gas phase portion by supplying an unsaturated compound having 2 carbon atoms. Moreover, it is preferable to use a C2 unsaturated compound as gas introduce | transduced for pressurized discharge | release.

When an iron-phosphate ester catalyst is used as the catalyst, although the amount of iron in the first batch is also used, usually unreacted iron remains in the reactor. Since this unreacted iron can be used as a catalyst component after the 2nd batch as it is, it does not need to be taken out. (Instead, since such unreacted solid iron has higher surface activity than new iron, it is a reactive reactor. Preferably left). Therefore, in the reaction after the second batch, after considering the amount of iron remaining in the reactor, the amount of iron to be added may be reduced.

In the case where the iron-phosphate ester catalyst is used as the catalyst, the reaction mixture of all the batches is not discharged in its entirety, and the amount thereof is 0.5 to 20% by volume, preferably 2 to 10% by volume, more preferably 3 to 5% by volume. It is preferable to leave about% in a reactor in the point which can make the initial reaction rate after a next batch favorable. It is assumed that this is because the iron-phosphate ester catalyst is dissolved in the reaction mixture of the previous batch, and therefore this acts effectively as a catalyst at the beginning of the reaction.

<After the second batch>

(1) In the case of method 1

When the method of the present invention is carried out according to Method 1, after the second batch of the continuous batch reaction, the reaction mixture is discharged from the reactor after the completion of the addition reaction of the previous batch, and the raw materials for the next batch reaction are subsequently fed to the reactor. When supplying

First, carbon tetrachloride was put into the reactor,

After supplying and pressurizing the unsaturated compound having 2 carbon atoms to pressurize the gaseous phase, and then performing the pressurization / decompression operation to reduce the gas phase pressure by evacuating one or more times, further supplying the unsaturated compound having 2 carbon atoms to the gas phase portion and pressurizing it Each batch reaction is performed after adjusting the partial pressure of ethylene substituted with unsubstituted or chlorine present in the above range, that is, from 0.11 to 0.52 MPa (abs).

The maximum characteristic point of the method 1 is that after discharging the reaction mixture, when feeding the raw material for the next batch reaction to the reactor, carbon tetrachloride is first introduced into the reactor, and then, the carbon dioxide unsaturated compound is supplied to the gas phase part and pressurized. Next, after performing the pressurization / decompression operation which exhausts and depresses gaseous-phase pressure 1 or more times, a C2 unsaturated compound is supplied and pressurized to a gaseous-phase part, and each batch reaction is further performed. By performing such an operation, the reaction rate of the addition reaction after the second batch is maintained at the same level or higher than that of the first batch.

That is, in the gas phase part after the second batch, as described above, impurities contained in a small amount of air (nitrogen, oxygen, carbon dioxide, etc.) dissolved in carbon tetrachloride, which is a raw material, and unsaturated compounds having 2 carbon atoms, as well as unsaturated compounds having 2 carbon atoms The lamp remains and accumulates after completion of placement without being completely removed. Therefore, the partial pressure of the unsaturated compound having 2 carbon atoms as the raw material compound is lower than the voltage of the gas phase part, and thus the concentration of the raw material compound in the liquid phase part is lowered. The reaction rate in the case gradually decreases as the batch water passes. Here, as an impurity contained in a small amount in a C2 unsaturated compound, ethane, methane, etc. are mentioned, for example, when a C2 unsaturated compound is ethylene.

Therefore, by the above-mentioned pressurization / decompression operation, by substituting one or more times of the gaseous phase part with an unsaturated compound having 2 carbon atoms, the partial pressure of the gaseous part of the unsaturated compound having 2 carbon atoms (and hence the concentration in the liquid phase) is the same between the batches. This aims to maintain the reaction rate.

This substitution operation aims to introduce a raw material compound (unsaturated compound having 2 carbon atoms) into the gas phase part at room temperature (25 ° C.) until it exceeds the desired voltage, and then exhausts it to replace the gas phase part with the raw material compound. Since the temperature at the time of substitution, the pressurized pressure, and the pressure after the exhaust gas do not need to be strictly controlled, respectively. However, excessive pressurization and depressurization lead to insignificant consumption of raw compound. Therefore, from the viewpoint of avoiding such waste, the pressure at the time of supplying and pressurizing the unsaturated compound having 2 carbon atoms to the gas phase part is preferably 0.11 to 2.1 MPa (abs), and is preferably 0.15 to 1.0 MPa (abs). It is more preferable. From the same point of view, the pressure after exhaust is preferably 0.10 to 0.3 MPa (asb), and more preferably 0.10 to 0.15 MPa (abs). In this pressurization / decompression operation, the time for keeping the system in a pressurized state is arbitrary, but can be, for example, 1 to 120 seconds, preferably 2 to 30 seconds.

Although this pressurization / decompression operation is performed one or more times, the frequency is preferably 1 to 10 times, more preferably 1 to 2 times.

Thereafter, the raw material compound is supplied again, and the voltage of the gas phase part is set in the range of the preferred reaction pressure described above with respect to the first batch to start the addition reaction.

As a partial pressure of a C2 unsaturated compound in a gaseous-phase part at the time of the addition reaction after a 2nd batch, it is suitable to set it as the preferable range mentioned above about a 1st batch. That is, it is preferable to set it as 0.11-0.52 MPa (abs) as 25 degreeC conversion value, and it is preferable to set it as 0.15-0.35 MPa (abs).

Moreover, addition of the catalyst component (especially phosphate ester) for after a 2nd batch may be performed before the pressurization / decompression operation by said C2 unsaturated compound, and may be performed after this operation.

The continuous arrangement method according to this method 1 can be repeatedly performed a plurality of times, for example, 2 to 300 times.

According to the method 1 as described above, when polychloropropane is produced by the method of repeatedly performing the batch reaction, the reaction rate and the selectivity of each batch can be stably controlled.

Moreover, the same effect is acquired even if supply and exhaust of a C2 unsaturated compound are performed before injecting carbon tetrachloride into a reactor. However, since the amount of the unsaturated compound having 2 carbon atoms required for substitution of the gas phase part is at least reduced, the above operation is preferably performed after the addition of carbon tetrachloride.

(2) In the case of method 2

When the method of the present invention is carried out according to Method 2, after the second batch of the continuous batch reaction, the reaction mixture is discharged from the reactor after the completion of the reaction of the previous batch, and the raw material for the next batch reaction is subsequently supplied to the reactor. When,

First, carbon tetrachloride was put into the reactor,

By supplying ethylene substituted with unsubstituted or chlorine to the gas phase part, the partial pressure of ethylene substituted with unsubstituted or chlorine present in the gaseous part is adjusted to the above-mentioned range, that is, 0.11 to 0.52 MPa (abs), Each batch reaction is performed by setting a voltage to the total pressure of the partial pressure of the said ethylene substituted with the said unsubstituted or chlorine, and the partial pressure of gases other than the ethylene substituted with the unsubstituted or chlorine which exists in a gaseous-phase part.

The maximum characteristic point of the method 2 is that after the 2nd batch of continuous batch reaction, the voltage of a gaseous-phase part is made into the desired partial pressure of the unsaturated compound of C2, and the partial pressure of gas other than the C2 unsaturated compound which exists in a gaseous-phase part. To set the total pressure. By making such a setting, the reaction rate of the addition reaction after the second batch is maintained at the same level as the first batch.

That is, in the gas phase part after the second batch, as described above, impurities contained in a small amount of air (nitrogen, oxygen, carbon dioxide, etc.) dissolved in carbon tetrachloride as a raw material, and unsaturated compounds having 2 carbon atoms, in addition to the unsaturated compounds having 2 carbon atoms After the arrangement is completed, the back is not completely removed but remains accumulated. Therefore, the partial pressure of the unsaturated compound having 2 carbon atoms as the raw material compound is lower than the voltage of the gas phase part, and thus the concentration of the raw material compound in the liquid phase part is lowered. The reaction rate in the case gradually decreases as the batch water passes.

Therefore, the gas phase part partial pressure of a C2 unsaturated compound is set by setting the voltage of a gas phase part to the total pressure of the desired partial pressure of a C2 unsaturated compound and the partial pressure of gas other than the C2 unsaturated compound which exists in a gas phase part. (There is also the concentration in the liquid phase) to be the same between the batches, whereby the reaction temperature is maintained.

The kind of components other than a C2 unsaturated compound and each partial pressure in a gaseous-phase part can be easily understood by gas chromatography. The partial pressure of these components accumulates gradually in the gas phase part as the batch reaction is repeated, and gradually increases, and at some point, the gas phase part composition and the exhaust gas composition coincide with each other to reach equilibrium. Here, the kind of components other than the C2 unsaturated compound and each partial pressure which accumulate for each batch or after reaching equilibrium depend on the filling rate of carbon tetrachloride, the purity of the raw material compound to be used, and the like.

In carrying out the method of the present invention, after each batch reaction, the gas phase part component is analyzed to find the sum of the partial pressures of gases other than the C2 unsaturated compound, and then the desired partial pressure of the C2 unsaturated compound is added to the gas phase. You may set a negative voltage. However, when performing a series (one series) batch reaction repeatedly on the same conditions, the sum of the partial pressures of gases other than a C2 unsaturated compound in a gaseous-phase part for each batch is between series depending on a repeat batch number. Can be assumed to be the same. Therefore, you may set the gas phase part voltage using the value measured after completion | finish of each batch in the repetitive reaction of a certain series as an estimated value in each batch of another series.

As a partial pressure of a C2 unsaturated compound in a gaseous-phase part at the time of addition reaction after a 2nd batch, it is suitable to set it as the preferable range mentioned above about a 1st batch. That is, it is preferable to set it as 0.11-0.52 MPa (abs) as 25 degreeC conversion value, and it is preferable to set it as 0.15-0.35 MPa (abs).

The continuous arrangement method according to this method 2 can be repeatedly performed a plurality of times, for example, 2 to 300 times.

Method 2 as described above is capable of stably controlling the reaction rate and selectivity of each batch when polychloropropane is produced by a method of repeating the batch reaction.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples.

Reference example (addition reaction of the first batch)

An SUS autoclave (internal volume 1,500 ml) with a stirrer, a gas inlet and gas outlet for ethylene, an addition of carbon tetrachloride and iron and an additional addition of phosphate ester and a liquid outlet was filled with ethylene. In the autoclave, 1,560 g of carbon tetrachloride, 2.0 g of triethyl phosphate, and 4.0 g of K100 (manufactured by JFE Steel Co., Ltd., coke reduced iron powder) were charged, and the temperature was set to 110 ° C, and the gas phase voltage was 0.5 MPa (abs). Ethylene was supplied so as to perform addition reaction. The ethylene partial pressure in the gas phase immediately after the voltage of the gas phase became 0.5 MPa (abs) was 0.25 MPa.

When the temperature of 110 degreeC and the gas phase voltage became 0.5 MPa (abs), triethyl phosphate was continuously added at 0.02 ml / min until completion | finish of reaction.

During the reaction, ethylene is supplied while the voltage in the gas phase is maintained at 0.5 MPa (abs), and the consumption rate (additional feed rate) of ethylene is 0.1 mol% / min (200 ml / min) relative to the initial amount of carbon tetrachloride. It was judged that the reaction was completed at this point, and the addition reaction of the 1st batch was complete | finished.

The reaction time was 600 minutes, the triethyl phosphate used was 14.5 g, the conversion rate of carbon tetrachloride was 94%, and the selectivity of 1,1,1,3-tetrachloropropane was 97%.

Experimental example A-1 (comparative example which shows the method of a prior art)

The addition reaction of the 1st batch was performed like the said reference example.

After completion of the first reaction in the first batch, the gaseous phase was pressurized with ethylene to discharge 95% by volume of the liquid reaction mixture from the liquid outlet and remain as it is (5 vol% in the reactor without washing the autoclave). 1,560 g of carbon tetrachloride, 2.0 g of triethyl phosphate, and 3.0 g of K100 were added again, leaving the mixture solution, and the temperature was set at 110 ° C., and ethylene was supplied so that the gas phase voltage was 0.5 MPa (abs) to start the addition reaction. did. During the reaction, in the same manner as in the first batch, ethylene supply and further continuous addition of triethyl phosphate were performed, and the reaction was terminated based on the same criteria as in the first batch.

The above operation was repeated and reaction of up to a 5th batch was performed.

The 1st, 5th, and 2nd, 3rd, and 5th batches showed the partial pressure of ethylene before reaction start, the reaction time determined by the said reference | standard, and reaction conversion ratio in FIG. In addition, the pressure composition of the gaseous-phase part before reaction start of a 5th batch (at normal temperature) was as showing in following Table 1. In Table 1, although the sum total of carbon tetrachloride, ethylene, and other composition does not become 100%, this is because of rounding off three decimal places of a calculation result.

[Table 1]

Experimental Example B-1 (Example of Method 1)

This experimental example is an Example showing the case where pressurization / decompression operation by a C2 unsaturated compound is performed before starting reaction of each batch, in addition to making 95 volume% of the reaction mixture of all the batches. This experiment example was performed as the addition reaction after the 6th batch following the said experiment example A-1.

After completion of the addition reaction in the fifth batch in Experimental Example A-1, the gaseous phase was pressurized with ethylene to discharge 95% by volume of the liquid reaction mixture from the liquid outlet, as it is (without washing the autoclave, 1,560 g of carbon tetrachloride, 2.0 g of triethyl phosphate, and 3.0 g of K100 were added again while leaving 5 vol% of the reaction mixture in the reactor. Thereafter, ethylene was supplied and pressurized so that the gas phase voltage was 0.5 MPa (abs), and the pressure was maintained for 60 seconds, and then the ethylene was exhausted to set the gas phase voltage to 0.11 MPa (abs). Next, the temperature was set to 110 ° C and ethylene was supplied again to start the addition reaction so that the gas phase voltage was 0.5 MPa (abs). The ethylene partial pressure in the gas phase at the start of the reaction was 0.25 MPa. Triethyl phosphate was further added continuously at the time of 110 degreeC and the gas phase voltage became 0.5 Mpa (abs) until the completion | finish of reaction at the rate of 0.02 ml / min. During the reaction, ethylene was supplied while supplying ethylene so that the voltage in the gas phase was maintained at 0.5 MPa (abs). Triethyl phosphate was further added continuously in the same manner as in the first batch, and the reaction was terminated based on the same criteria as in the first batch.

The above operation was repeated and reaction of up to a 15th batch was performed.

In the sixth, ninth and fifteenth batches of each of the sixth to fifteenth batches, the ethylene partial pressure before the start of the reaction and the reaction time and the reaction conversion rate determined based on the above criteria are shown in FIG. 1 as a result of Experimental Example A-1. Shown in succession.

From the results of Experimental Examples A-1 and B-1, in the case of producing polychloropropane by the method of repeating the batch reaction, the batch number was determined according to the method of Experimental Example A-1 (the conventional technique). Although reaction time required until completion | finish of reaction increases with roughness, reaction selectivity is unstable, but according to the method of Experimental Example B-1 (method 1 of this invention), even if batch reaction is repeated continuously, it is related to batch number. It is understood that the reaction rate and selectivity can be controlled stably without.

In the following Experimental Examples B-2 to B-5, the relationship between the gas phase part pressure (reaction pressure) and the reaction result during the reaction was investigated.

Experimental Example B-2 (Example of Method 1)

The addition reaction of the 1st batch was performed like the said reference example.

Subsequently, as in the sixth batch of Experimental Example B-1, after the completion of the previous batch, the next batch of raw materials and the like are added without washing the autoclave, and the batch reaction is performed after the pressurization / decompression operation with ethylene is performed. The addition reaction of the 2nd batch and the 3rd batch was performed sequentially. The reaction pressure in the second batch and the third batch is 0.50 MPa (abs) at the reaction temperature. However, the reaction pressure corresponds to 0.21 MPa (abs) in terms of the pressure at 25 ° C.

The reaction time, reaction conversion ratio, and selectivity of 1,1,1,3-tetrachloropropane in the third batch are shown in Table 2, respectively.

Experimental Example B-3 (Example of Method 1)

The addition reaction of the 1st batch was performed like the said reference example.

Subsequently, as in the sixth batch of Experimental Example B-1, after the completion of the previous batch, the next batch of raw materials and the like are added without washing the autoclave, and the batch reaction is performed after the pressurization / decompression operation with ethylene is performed. The addition reaction of the 3rd batch and the 4th batch was performed sequentially. The reaction pressure is 0.40 MPa (abs) (25 ° C. conversion value = 0.13 MPa (abs)) in the third batch, and 0.45 MPa (abs) (25 ° C. conversion value = 0.17 MPa (abs)) in the fourth batch. did.

The reaction time, reaction conversion ratio, and selectivity of 1,1,1,3-tetrachloropropane in the third and fourth batches are shown in Table 2, respectively.

Experimental Example B-4 (Example of Method 1)

The addition reaction of the 1st batch was performed like the said reference example.

Subsequently, similarly to the 6th batch of Experimental example B-1, the addition reaction of the 2nd batch was performed as a batch reaction after performing the pressurization / decompression operation by ethylene.

Next, except that the reaction pressure was changed, as in the sixth batch of Experimental Example B-1, after the completion of the previous batch, the raw material for the next batch was added without washing the autoclave, and the pressurization / decompression operation with ethylene was performed. As a subsequent batch reaction, the addition reactions of the third batch and the fourth batch were performed sequentially. The reaction pressure is 0.70 MPa (abs) (25 ° C. conversion value = 0.37 MPa (abs)) in the third batch and 0.35 MPa (abs) (25 ° C. conversion value = 0.09 MPa (abs)) in the fourth batch. did.

The reaction time, reaction conversion ratio, and selectivity of 1,1,1,3-tetrachloropropane in the third and fourth batches are shown in Table 2, respectively.

Experimental Example B-5 (Example of Method 1)

The addition reaction of the 1st batch was performed like the said reference example.

Subsequently, as in the sixth batch of Experimental Example B-1, after the completion of the previous batch, the next batch of raw materials and the like are added without washing the autoclave, and the batch reaction is performed after the pressurization / decompression operation with ethylene is performed. The addition reaction of the 2nd batch was performed.

Next, except for changing the reaction pressure to 0.90 MPa (abs) (25 ° C. conversion value = 0.52 MPa (abs)), similarly to the sixth batch of Experimental Example 2, the batch reaction after performing the pressurization / decompression operation with ethylene As an addition, the addition reaction of the 3rd batch was performed.

The reaction time, reaction conversion ratio, and selectivity of 1,1,1,3-tetrachloropropane in this third batch are shown in Table 2, respectively.

[Table 2]

Experimental example A-2 (comparative example which shows the method of a prior art)

The addition reaction of the 1st batch was performed like the said reference example.

After completion of the first reaction in the first batch, the gaseous phase was pressurized with ethylene, and 95 vol% of the liquid reaction mixture was discharged from the liquid outlet, as it is (without washing the autoclave, 5 vol% of the reaction mixture in the reactor). 1,560 g of carbon tetrachloride, 2.0 g of triethyl phosphate, and 3.0 g of K100 were added again, the temperature was set at 110 ° C., and ethylene was supplied so that the gas phase voltage was 0.5 MPa (abs). .

During the reaction, ethylene supply and further addition of triethyl phosphate were performed in the same manner as in the first batch, and the reaction was completed on the same basis as in the first batch.

The above operation was repeated and reaction of the 7th batch was performed.

2 and 3 show the reaction time, reaction conversion rate and ethylene partial pressure before the start of the reaction determined for the first, second, third, fifth and seventh batches in the first to seventh batches. . In the seventh batch, ethylene was supplied to the reaction system, and the result of measuring the gas phase part immediately after the gas phase pressure became 0.5 MPa by gas chromatography (GC) was as shown in Table 3 below. Mole% .Also, since carbon tetrachloride condenses when cooled sample is cooled to room temperature, the correct value is not obtained in GC, so it was calculated without this).

[Table 3]

Experimental Example C-1 (Example of Method 2)

The addition reaction of the 1st batch was performed like the said reference example.

This experiment example was performed as the addition reaction after the 8th batch following the said experiment example A-2.

After completion of the addition reaction in the seventh batch in Experimental Example A-2, the gaseous phase was pressurized with ethylene to discharge 95% by volume of the liquid reaction mixture from the liquid outlet, as it is (without washing the autoclave, Leaving 5% by volume of the reaction mixture in the reactor), 1,560 g of carbon tetrachloride, 2.0 g of triethyl phosphate, and 3.0 g of K100 were added thereto, and the temperature was set to 110 ° C., and the gas phase voltage was 0.6 MPa (abs). Ethylene was fed as possible to initiate the addition reaction.

During the reaction, ethylene was supplied while supplying ethylene so that the voltage in the gas phase was maintained at 0.6 MPa (abs). In the same manner as in the first batch in Experimental Example 1, further continuous addition of triethyl phosphate was performed, and the reaction was terminated based on the same criteria as in the first batch.

The above operation was repeated and reaction of up to a 30th batch was performed.

Reaction time and reaction determined based on the above criteria for the 8th, 12th, 15th, 18th, 20th, 23rd, 26th, 29th, and 30th batches of the 8th to 30th batches. The conversion ratio and the ethylene partial pressure before the start of the reaction are shown in Figs. 2 and 3 successively in the results of Experimental Example A-2. In the thirtieth batch, ethylene was supplied to the reaction system, and the gas phase portion immediately after the gas phase pressure became 0.6 MPa was measured by GC. The results are as shown in Table 4 below (unit is mole%. For the same as in Table 3).

[Table 4]

From the results of Experimental Example A-2 and Experimental Example C-1, in the case of producing polychloropropane by the method of repeating the batch reaction, the batch according to the method of Experimental Example A-2 (the conventional technique) As the number of reactions increases, the reaction time required until the end of the reaction increases and the reaction selectivity is unstable. However, according to the method of Experimental Example C-1 (method 2 of the present invention), even if the batch reaction is repeated continuously, It is understood that regardless of the reaction rate and selectivity can be controlled stably.

Claims (8)

In a liquid phase reaction system, an addition reaction in which polychloropropane is obtained by adding carbon tetrachloride to ethylene substituted with unsubstituted or chlorine is placed while supplying ethylene substituted with unsubstituted or chlorine in a batch reactor in which a liquid phase and a gaseous phase exist. After the second batch when the reaction mixture is discharged from the reactor after the completion of the batch reaction, the raw material for the next batch reaction is continuously supplied to the reactor, and the addition reaction is repeatedly performed in the batch method. To
Said addition reaction is performed by adjusting the partial pressure of the ethylene substituted by unsubstituted or chlorine which exists in the said gaseous-phase part to 0.11-0.52 Mpa (abs) at 25 degreeC. The method of claim 1,
When the reaction mixture is discharged from the reactor after the completion of the reaction of the previous batch, and subsequently the raw material for the next batch reaction is supplied to the reactor,
First, carbon tetrachloride was put into the reactor,
After supplying and pressurizing the ethylene unsubstituted or substituted with chlorine to the gaseous phase, and performing the pressurization / decompression operation for reducing the gas phase pressure by evacuating one or more times, the ethylene unsubstituted or substituted with chlorine is further added to the gaseous phase. The continuous batch reaction method of performing a next batch reaction after supplying and pressurizing and adjusting the partial pressure of the unsubstituted or chlorine substituted chlorine which exists in a gaseous-phase part to said pressure. 3. The method of claim 2,
The pressurized pressure in the said pressurization / decompression operation is 0.11-2.1 MPa (abs), and the gas phase pressure after a fall is 0.1-0.3 MPa (abs), The continuous batch reaction method. 3. The method of claim 2,
And the addition reaction is carried out in the presence of an iron-phosphate ester catalyst. The method of claim 1,
When the reaction mixture is discharged from the reactor after the completion of the reaction of the previous batch, and subsequently the raw material for the next batch reaction is supplied to the reactor,
First, carbon tetrachloride was put into the reactor,
The partial pressure of unsubstituted or chlorine substituted ethylene present in the gaseous phase is adjusted to the above-mentioned range by supplying and pressurizing ethylene substituted with unsubstituted or chlorine to the gaseous phase, and the voltage of the gaseous phase is adjusted to the above range. The continuous batch reaction method performed by setting to the total pressure of the partial pressure of ethylene substituted by ring or chlorine, and the partial pressure of gases other than ethylene substituted with chlorine which are not present in a gaseous-phase part. The method of claim 5,
Gas other than ethylene substituted with unsubstituted or chlorine present in the gas phase portion contains at least one member selected from the group consisting of carbon tetrachloride, gas dissolved in carbon tetrachloride and impurity gas of ethylene substituted with unsubstituted or chlorine. Continuous batch reaction method. The method of claim 5,
And the addition reaction is carried out in the presence of an iron-phosphate ester catalyst. 8. The method according to any one of claims 1 to 7,
The unsubstituted or chlorine-substituted ethylene is ethylene or vinyl chloride.

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