KR101222780B1 - Manufacturing Process for iodinated aromatic compounds - Google Patents

Abstract

The present invention relates to a method for producing an aromatic iodide compound, and more particularly, in the iodide reaction of an aromatic compound under an oxygen atmosphere using a zeolite catalyst, as a raw material, an aromatic substance and a mono iodine compound thereof, or a mono iodine compound It relates to a method for producing an aromatic iodide compound which is reacted.

Compared with the method using only aromatic compounds as raw materials without addition of mono iodine compounds, the method according to the present invention increases the productivity of diiodine compounds and selectivity of paradiiodine compounds, and at the same time prolongs the catalyst cycle by inhibiting side reactions. It shows the effect that can be done.

Benzene, naphthalene, iodide reaction, mono iodide benzene, mono iodide naphthalene, diiodine benzene, diiodine naphthalene

Description

Manufacturing Process for Aromatic Iodide Compounds {Manufacturing Process for iodinated aromatic compounds}

1 is a schematic view showing a process for producing an iodide reaction apparatus and an iodide compound according to Comparative Example 1.

2 is a schematic view showing the iodide reaction apparatus and the iodide compound production process according to Examples 1 to 3.

3 is a schematic view showing a process for producing an iodide reaction apparatus and an iodide compound according to Example 4;

Figure 4 is a schematic diagram showing the iodide reaction equipment and manufacturing process using the separation and recycling of mono iodine compound and iodine according to Example 6.

[Description of Symbols for Main Parts of Drawing]

R01: Iodide reactor (Na-13X zeolite catalyst 230ml packed with electric heater)

C10: distillation column 1, removing water and benzene from the reaction product

C20: distillation column 2, separating / recycling mono iodine benzene and iodine from the reaction product

C30: Distillation column 3, only diiodine benzene is separated into the top of the tower, and the bottom of the tower removes high-boiling substances, including triiodine compounds

Back Pressure Regulator: Control reaction pressure, enable pressurized reaction

Sample Handling System: Removes vapor contained in gas to protect the analyzer in post processing

Gas Chromatography (GC): Measurement of carbon dioxide contained in gases

The present invention relates to a method for producing an aromatic iodide compound, and more particularly, to an iodide reaction of an aromatic compound such as benzene, naphthalene, and biphenyl under an oxygen atmosphere using a zeolite catalyst, as an raw material thereof, an aromatic compound and its mono A method for producing an aromatic iodide compound by reacting an iodine compound or a mono iodine compound.

Techniques for preparing aromatic halogenated compounds by reacting halogen (bromine, chlorine, iodine, etc.) compounds with aromatic compounds such as benzene or naphthalene have been recognized for their commercial value.

Typically, paradichlorobenzene (p-dichlorobenzene) produced by reacting benzene and chlorine is used as a raw material for polyphenylene sulfide (PPS), an engineering plastic. A technique for preparing PPS by polymerizing paradichlorobenzene and sodium sulfide in N-methyl pyrrolidone solvent is known as the Macallum process and is currently commercially produced. PPS is made by this process. However, according to the MacColumm process, it is difficult to obtain a high molecular weight polymer, and thus a high molecular weight polymer is obtained through a post-process called curing, and the obtained PPS has a brittle disadvantage due to a crosslinking reaction. . In addition, metal salts such as sodium chloride (NaCl) are inevitably generated as reaction by-products in the polymerization process, which causes serious problems in economics and polymer properties of commercial processes.

In this way, the production of metal salts is essentially excluded and linear high molecular weight is obtained in US Pat. Nos. 4,746,758, 4,786713 and related patents directly using p-Diiodobenzene and sulfur. A method of melt polymerization has been proposed.

In addition, US Pat. Nos. 4,778,938, 4,746,758 and the like describe a method for preparing paradiiobenzene by reacting benzene with iodine under an oxygen atmosphere using a zeolite catalyst. According to these patents, not only high conversion and high selectivity of commercially preferred paradiode compounds can be minimized, but the oxidation of benzene or naphthalene, which is a raw material, can be minimized.

However, in order to use such iodination technology more commercially, it is desirable to further improve the productivity of the diiodine compound and the selectivity of the paradiiodine compound. The patent also mentions that carbon deposits are produced by the combustion of raw materials and the catalysts lose their activity. Moreover, the carbon deposits or multi-iodinated high molecular impurities thus produced not only lose the activity of the catalyst but also mix with the iodide products, which causes serious problems in the subsequent purification process.

In order to solve the above problems, the present inventors carry out iodide reaction using aromatic compounds such as benzene and naphthalene, mono-iodine compounds thereof, or mono-iodine compounds as raw materials, and thus the productivity of the diiodine compound and the selectivity of the paradiiodine compound. It has been found that it is possible to significantly increase the replacement cycle of the catalyst, and the present invention has been completed based on this.

Accordingly, an object of the present invention is to provide a method for producing an aromatic iodide compound which minimizes deactivation of the catalyst and increases productivity of the diiodine compound and selectivity of the paradiiodine compound of the aromatic compound and at the same time suppresses side reactions. There is.

Method for producing an aromatic iodide compound according to the present invention for achieving the above object,

A method of iodideing an aromatic compound in an oxygen atmosphere using a zeolite catalyst, characterized in that the raw material is reacted with an aromatic compound and its mono iodine compound or a mono iodine compound.

Hereinafter, the present invention will be described in detail.

As described above, the present invention is a method for iodideing an aromatic compound under an oxygen atmosphere using a zeolite catalyst, wherein the deactivation of the catalyst using an aromatic material and its mono-iodine compound, or a mono-iodine compound as a raw material The present invention relates to a method for preparing an aromatic iodide compound which can prolong the life of the catalyst by minimizing and increasing the productivity of the diiodine compound and the selectivity of the paradiiodine compound and at the same time suppressing side reactions.

In addition, in the present invention, it was possible to separate and purify the reaction product obtained by the above production method by distillation to reuse the mono iodine compound and iodine.

In the present invention, the most widely used Na-13X zeolite catalyst was used as a catalyst for the iodization reaction. Although the iodide reaction of aromatics was carried out using various catalysts such as Y-type, ZSM5, K-13X, Na-13X catalyst was found to be the most useful. The K-13X zeolite catalyst was found to have a low solubility that the conversion rate of the aromatics and iodine was not more than 50%, and the other catalysts did not reach the Na-13X catalyst.

It is known that the iodide reaction of an aromatic substance using a zeolite catalyst occurs over a wide range of 200 to 400 ° C. As a result of examining the iodide reaction characteristics of the aromatic compounds according to the reaction temperature in the present invention, the higher the reaction temperature, the higher the conversion rate of the raw material (aromatic and iodine), while the selectivity and diiodine compound of the most highly regarded commercially available paradiiodine compound The production rate of was lowered. On the other hand, the reaction pressure can also be carried out in various areas, the higher the reaction pressure was found to increase the efficiency of the iodide reaction.

On the other hand, hydrogen iodide (Hydroiodic acid) generated during the iodide reaction should be oxidized back to the iodine molecule (Iodine) to participate in the reaction. The presence of oxygen during the reaction is essential. When no oxygen is present or the amount is less than hydrogen iodide, hydrogen iodide forms azeotropes with water generated during the oxidation reaction, which not only adversely affects the purification process after the reaction, but also causes severe corrosion of the equipment due to strong oxidation. Done. Therefore, it can be seen that oxygen is required as much as or more than the number of moles of iodine molecules used in the reaction.

The molar ratio of the aromatic compound and iodine used as a raw material can be used in various ways. The higher the iodine content, the higher the production rate of multi-iodinated aromatics, while the lower the conversion rate of iodine. However, if the ratio of the aromatic compound to the iodine compound is increased in order to increase the conversion rate of iodine, the conversion rate of the iodine can be increased, but since the productivity of the diiodine compound is reduced, the reaction should be appropriately adjusted according to the purpose.

Aromatic compounds, such as benzene or naphthalene, are converted into oxide materials such as carbon dioxide through oxidation, when high temperature conditions are met in the presence of oxygen, which causes raw material loss. At this time, the carbon dioxide produced is a material produced by a complete oxidation reaction, and may form carbon deposits through incomplete oxidation or carbonization. The carbon deposits thus formed lose the activity of the catalyst and shorten the replacement cycle of the catalyst.

The present invention describes that the productivity of the diiodine compound and the selectivity of the double paradiiodine compound can be increased by using the aromatic compound and its mono iodine compound or mono iodine compound as raw materials. In addition, according to the method of the present invention, it is possible to minimize the production of carbon dioxide and carbon deposits, which can significantly extend the catalyst replacement cycle and obtain a high quality iodide compound.

According to the present invention, the aromatic compound is preferably selected from the group consisting of benzene, naphthalene, and biphenyl, and the mono iodine compound is selected from the group consisting of mono iodine benzene, mono iodine naphthalene, and mono iodine biphenyl It is preferred, but not necessarily limited thereto.

In addition, the mono iodine compound may be manufactured or purchased and used, but as shown in FIG. 4, a method of separating and purifying the mono iodine compound by distillation is more efficient. That is, as shown in Figure 4 in distillation column 1 (C10) to remove the benzene and water, and distillation column 2 (C20) to separate the mono-iodine benzene and iodine to the top of the tower and then re-introduced into the reactor (R01) of the present invention The method can be implemented efficiently.

Concepts of terms used in Comparative Examples and Examples to be described below to demonstrate the utility of the present invention will be described. First, in the reaction conditions, the ratio of aromatic / iodine (Aromatic / I) represents the molar ratio of the aromatic compound and iodine used. When preparing a diiodine compound, benzene reacts with one mole of iodine molecules (two iodine atoms). shall. Therefore, the ratio of aromatic / iodine is defined as in Equation 1 below:

Aromatic / iodine = (moles of benzene x 2) + (moles of mono-iodine benzene) / moles of iodine molecule x 2

Next, we define the concept of terminology to determine the efficiency of reaction products and reaction processes. First of all, the productivity of p-DIB is defined as the production rate of paradiiodine benzene produced per unit time and per unit volume of the catalyst. The unit is expressed as g / l · hr. Conversion of iodine and benzene is obtained by dividing the amount of iodine and benzene reacted and converted to the product by the amount of iodine and benzene added, and then expressing the ratio as a percentage.

The type of iodide benzene produced by the iodide reaction is mono-iodobenzene reacted with one iodine atom, di-iodobenzene reacted with two iodine atoms, and tri-iodine benzene reacted with three iodine atoms It can be divided into tri-iodobenzene, and diiodine benzene (DIB) and triiodine benzene (TIB) may each have three isomers. That is, as isoiodine benzene, three isomers of para (p-), ortho (o-), and meta (m-) diiodine benzene are produced by iodide reaction. Here, the total amount of diiodobenzene produced (Total DIB, diiodobenzene) refers to the sum of the weight percentage of para, ortho, and meta diiodine benzene contained in the product, which is represented by Equation 2 below.

Total DIB  = (p + m + o DIB ) / ( Product ) x 100

On the other hand, selectivity is the concentration of paraisomers in the three diiodine benzene contained in the product expressed as a weight percentage, which is represented by the following equation (3).

Selectivity = (p- DIB ) / (p + m + o DIB ) x 100

According to the present invention, a commercially valuable paradiode compound can be produced with high efficiency, which is possible when the sum of the amount of diiodine compound produced and the selectivity of the paradiode compound are high.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

Comparative Example 1

Using the apparatus shown in FIG. 1, benzene (26.4 g per hour) and iodine (42.9 g per hour) were added to the reactor without addition of mono-iodine benzene, and the reaction was carried out in a continuous process at a reaction temperature of 280 ° C. and atmospheric pressure. After reaching 24 hours, sampling and analysis were performed. Each experimental condition and the results are shown in Table 1 below.

Example 1

In carrying out the iodization reaction under the same conditions as in Comparative Example 1 using the apparatus shown in Figure 2, benzene (6.6g per hour), mono iodine benzene (48.4g per hour) and iodine (25.8g per hour) were added. Each experimental condition and the results are shown in Table 1 below.

Example 2

In carrying out the iodization reaction under the same conditions as in Comparative Example 1 using the apparatus shown in Figure 2, benzene (16.5 g per hour), mono iodine benzene (38.5 g per hour) and iodine (38.8 g per hour) were added. Each experimental condition and the results are shown in Table 1 below.

Example 3

In performing the iodization reaction under the same conditions as in Comparative Example 1 using the apparatus shown in FIG. 2, benzene (27.5 g per hour), mono iodine benzene (27.5 g per hour) and iodine (53.2 g per hour) were added thereto. Each experimental condition and the results are shown in Table 1 below.

Example 4

In carrying out the iodization reaction under the same conditions as in Comparative Example 1 using the apparatus shown in FIG. 3, mono-iodine benzene (55 g per hour) and iodine (17.1 g per hour) were added without adding benzene. Each experimental condition and the results are shown in Table 1 below.

Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Input condition benzene g / hr 26.4 6.6 16.5 27.5 0 Iodine Benzene g / hr 0.0 48.4 38.5 27.5 55 iodine g / hr 42.9 25.8 38.8 53.2 17.1 Aromatic / iodine Mole ratio 2.0 2.0 2.0 2.0 2.0 O ₂ Ml / min 220.0 100.0 120.0 200.0 80 Product composition benzene wt% 9.84 3.63 7.71 9.78 0 Iodine Benzene wt% 44.31 38.53 44.01 44.25 45 p-DIB wt% 22.99 40.47 33.96 30.78 38.97 m-DIB wt% 9.21 6.76 6.21 6.88 7.84 o-DIB wt% 2.92 1.88 1.98 2.54 2.12 TIB wt% 3.11 5.19 3.49 3.24 5.65 characteristic  p-DIB productivity g / ℓhr 69.97 123.17 103.36 93.68 118.60 I ₂ conversion rate % 91.38 88.41 90.20 90.50 92.44 Benzene conversion rate % 73.96 61.50 67.29 75.11 - Full DIB wt% 35.12 49.11 42.15 40.20 48.93 Selectivity % 66.00 83.00 80.57 77.00 80.00 CO ₂ % 2.54 0.78 0.88 1.16 0.05

As can be seen from Table 1, iodine reaction was performed by adding benzene and mono-iodine benzene together in comparison with Comparative Example 1 using only benzene as a raw material in terms of total DIB and selectivity of paradiode benzene. Examples 1 to 3 having these results show excellent results. Similar results were confirmed in Example 4 using only mono-iodine benzene as a raw material without the addition of benzene, and the productivity of p-DIB of paradiiodine benzene also used mono-iodine benzene as the raw material, or benzene and mono-iodine When benzene was added together, a high value could be obtained, thereby confirming that paraisomers were efficiently generated per unit volume of the catalyst.

Comparative Example 2

The iodide reaction was carried out in the same manner as in Comparative Example 1 and the product was analyzed after 200 hours and 400 hours.

Example 5

In performing the iodide reaction in the same manner as in Example 3, the product was analyzed after 200 hours and 400 hours after the start of the reaction.

I ₂ conversion rate (%) Black impurity (g) 200 hr 400 hr 200 hr 400 hr Comparative Example 2 80 65 One 3 Example 5 87 82 0.13 0.38

As shown in Table 2, in Comparative Example 2, the conversion rate of iodine was 80% after 200 hours, and the conversion rate of iodine was 65% after 400 hours, and the amount of black impurities detected in the product increased over time. It became. On the contrary, in Example 5, the iodine conversion was 87% and 82% after 200 hours and 400 hours, respectively, and a much smaller amount of black impurities were detected than in Comparative Example 2. This black impurity is a mixture of carbon deposits in the product, and it can be considered that the activity of the catalyst is reduced by the carbon deposits.

This can be confirmed by the carbon dioxide generation amount of Comparative Example 1 and Examples 1 to 4 as shown in Table 1. When the mono-iodine benzene was added together, the concentration of carbon dioxide contained in the gas was significantly reduced than when only benzene was added as a raw material.

Example 6

Example 6 was carried out in the apparatus shown in FIG. 4. At this time, the melting temperatures of para, meta and ortho diiodine benzene were 131 ° C, 36 ° C and 27 ° C, respectively. Thus, it can be considered that all of the diiodine benzene exists as a solid at room temperature (25 ° C.), but in fact, the diiodine benzene obtained from the top of the third distillation column (CO 3) coexisted with the solid and the liquid. The crystallization and solid-liquid separation resulted in the separation of pure paraisomer solid and mother liquor consisting of 13.1% para, 71.5% meta, and 15.4% ortho. there was. It was also confirmed that the three (para, meta, ortho) isomers could be present as liquids by forming eutectic at temperatures below their respective melting temperatures.

As described above, according to the present invention, an iodine reaction is carried out using an aromatic compound and a mono iodine compound or a mono iodine compound as a desired raw material to increase the productivity of the diiodine compound and the selectivity of the paradiiodine compound and to suppress side reactions. The catalyst life can be extended.

Claims (4)

As a method for producing a diiodinated aromatic compound, (I) aromatic compounds and monoiodine compounds thereof or (ii) aromatic compounds as initial aromatic reactants to selectively form p-diiodated aromatic compounds under a temperature condition of 200 to 400 DEG C and an oxygen atmosphere using a zeolite catalyst Reacting the mono iodine compound with iodine in the gas phase, Wherein the aromatic compound is benzene or biphenyl, The mono iodine compound is mono iodine benzene or mono iodine biphenyl, and A method for producing a diiodinated aromatic compound, characterized in that at least 50% by weight of the mono iodine compound of the aromatic compound in the initial aromatic reactant (i). delete delete delete

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