JP2014237620A - Method of producing indene, indene, coumarone-indene resin and product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing indene which comprises purifying indene from an indene-containing fraction obtained by distillation of tar and improves the yield of indene in the fraction after the purification to indene contained originally in raw tar.SOLUTION: A method of producing indene includes a step preheating tar after dehydration by heating means, a step pf heating the preheated tar in a heating furnace, a step of fractionating the heated tar to recover an indene-containing fraction and a step of purifying indene from the indene-containing fraction. In the preheating step, the preheating is carried out in a temperature atmosphere of 165°C or higher and lower than 182°C.

Description

  The present invention relates to a method for producing indene, indene, coumarone-indene resin and products.

  Tar, particularly coal tar produced from coal, contains several hundreds of hydrocarbons and other compounds, and the coal tar usually contains about 0.5 to 1.5% indene. . In view of this, indenes with increased purity are produced from the fraction obtained by distillation of tar by operations such as distillation and extraction.

Thus, indene is one component in the fraction obtained by distillation of tar, and the distillation of tar is generally performed according to the procedure shown in FIG. First, the raw material tar 101 is heated to about 150 ° C. by heat exchange using the heat exchanger 102 and then supplied to the dehydration tower 103, and water and light oil components 104 are distilled off in the dehydration tower 103. Next, the dehydrated tar is heated to about 300 to 330 ° C. by the heat exchanger 105 and the heating furnace 106 and then supplied to the distillation column 107, and the column top or column is supplied to the distillation column 107 according to each boiling point of the fraction. From the side, light oil 108, carboru oil 109, naphthalene oil 110, absorption oil 111, pitch 112, and the like are fractionally distilled.
Here, from the viewpoint of reducing the manufacturing cost by effectively using the exhaust heat (residual heat) in the distillation step, the pitch 112 fractionated from the distillation column 107 and the raw material tar in the heat exchanger 102 and the heat exchanger 105 In general, heat exchange is performed with 101 and tar after dehydration (for example, Patent Document 1).

JP 63-234089 A

  When inden is refined from the fraction containing indene obtained through the above-described steps (inden fraction containing inden), the yield of indene (in the fraction after purification with respect to the indene originally contained in the raw material tar) The problem was that the ratio of inden) was low.

  Therefore, the present invention, when purifying indene from the indene-containing fraction obtained by distillation of tar to produce indene, shows the yield of indene in the fraction after purification relative to indene originally contained in the raw material tar. It aims to provide a way to improve.

As described above, in the conventional tar distillation process, in order to reduce the manufacturing cost by effectively using exhaust heat such as pitch fractionated from the distillation column, raw tar and dehydrated tar and the like are subject to preheating. Is increased as much as possible to the temperature required in the next step.
On the other hand, the present inventors diligently studied that, in preheating during the distillation process, when preheating dehydrated tar, by performing the preheating in a specific temperature atmosphere, the yield of indene is improved. I found it.
The present invention is derived from the above findings, and the gist of the present invention is as follows.
(1) A step of preheating the dehydrated tar using a heating means, a step of heating the preheated tar in a heating furnace, and a step of fractionating the heated tar to recover an indene-containing fraction. And a step of purifying indene from the indene-containing fraction, and in the preheating step, preheating is performed in a temperature atmosphere of 165 ° C. or higher and lower than 182 ° C.

  (2) The method for producing indene according to (1), wherein the heating means is a heat exchanger.

  (3) An indene obtained by the method of (1) above.

  (4) A coumarone-indene resin characterized by using the indene of (3).

  (5) A product selected from the group consisting of a resin, a catalyst, a modifier, a pharmaceutical, and an agricultural chemical produced using the indene of (3).

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of indene which improved the yield of indene can be provided.

FIG. 1 is a schematic diagram showing a manufacturing flow of indene according to an embodiment of the present invention. FIG. 2 is a schematic diagram showing a production flow of indene according to another embodiment of the present invention. FIG. 3 is a schematic diagram showing a conventional general tar distillation flow.

Hereinafter, an indene production method according to an embodiment of the present invention will be described in detail with reference to the drawings. In addition, the following description and drawing are examples for demonstrating the manufacturing method of the indene based on this invention, and this invention is not limited to the form described and illustrated at all.
Hereinafter, for convenience of explanation, the preheating step of the indene production method according to the present invention may be referred to as a first step, the heating step as a second step, the fractionation step as a third step, and the purification step as a fourth step. .

In the present invention, “tar” means a tar capable of fractionating indene and is a concept including tar generated from petroleum, peat and wood in addition to coal tar generated from coal. The “tar” of the present invention is a concept including a low temperature tar and a high temperature tar as defined in JIS M 0104-1984. The tar of the present invention is preferably coal tar. The tar of the present invention is preferably a high temperature tar.
In the present invention, “fractional distillation” means fractional distillation and is a concept including rectification.
In this specification, carboru oil, naphthalene oil, washing oil, anthracene oil, and creosote oil are those defined in JIS M 0104-1984, respectively. Moreover, in this specification, a light oil means the gas light oil defined in JISM0104-1984.

(Indene production method)
FIG. 1 shows a flow of an example of the method for producing indene according to the present invention.
In the indene production method according to the present invention, the tar after dehydration in the dehydration tower 1 is preheated using the heating means 2 as the first step (preheating step).
As the second step (heating step), the preheated tar is heated in the heating furnace 3.
As the third step (fractionation step), the heated tar is fractionated in the distillation column 4 to recover the indene-containing fraction 5.
As the fourth step (purification step), indene 6 is purified from the indene-containing fraction 5.
In the indene production method according to the present invention, the preheating in the first step is performed in a temperature atmosphere of 165 ° C. or more and less than 182 ° C.

  As described above, the present inventor performs the preheating in the first step in a temperature atmosphere of 165 ° C. or higher and lower than 182 ° C., so that the indene in the fraction after purification with respect to the indene originally contained in the raw material tar. I found that the yield improved. The reason for this is that when preheating the tar after dehydration, the temperature of the heating furnace or the temperature atmosphere of the heating furnace is not directly raised to about 300 to 340 ° C., but the preheating is performed at the boiling point of indene (182 ° C.). When the temperature is lower than 165 ° C. or higher and lower than 182 ° C., indene in the tar after dehydration is stabilized, and conversion of indene to indane, a hydride of indene, and thermal polymerization or thermal decomposition of indene are suppressed. It is presumed that.

The heating means 2 for performing preheating in the first step is not particularly limited as long as the temperature atmosphere can be controlled to a temperature range of 165 ° C. or more and less than 182 ° C., and conventionally known heaters, heating furnaces, pipe stills Heating means such as a heat exchanger can be used. The temperature of tar in the heating means preheated at a temperature atmosphere of 165 ° C. or more and less than 182 ° C. is 165 ° C. or more and less than 182 ° C.
In the indene production method according to the present invention, the heating means 2 is preferably a heat exchanger. Thereby, the exhaust heat (residual heat) of a distillation process etc. can be used effectively and the manufacturing cost of indene can be reduced.

In the indene production method according to the present invention, for the reasons described above, preheating of the tar after dehydration in the first step is performed in a temperature atmosphere of 165 ° C. or more and less than 182 ° C. When the temperature is less than 165 ° C., There is a problem that the heating furnace load increases and the temperature in the furnace increases, and when the temperature is 182 ° C. or higher, the yield of indene is not sufficiently improved. From the viewpoint of increasing the yield of indene, it is more preferable to perform the preheating in a temperature atmosphere of 165 to 175 ° C.
In the first step, dehydrated tar is used. This is because tar usually contains about 3 to 10% of moisture, and the ammonium salt contained in the moisture causes corrosion of the apparatus. Also, bumping may occur during distillation, foaming may hinder rectification, etc. In order to cause problems, tar after dehydration is used from the viewpoint of preventing these problems. Even if heated to 165 ° C. to 175 ° C. before dehydration, the dehydration tower loses the latent heat of vaporization of the water, so the temperature of the dehydrated tar once decreases. For this reason, it is necessary to raise the temperature again.
The amount of water in the tar after dehydration can be appropriately changed or set, but is preferably 0.1% or less with respect to the mass of the tar.

  The preheating time in the first step is not particularly limited, and can be appropriately adjusted according to the amount of tar processed, the type of heating means, the scale, the desired indene purity, the fraction composition, and the like. The preheating time is preferably 30 seconds to 120 seconds from the viewpoint of increasing the yield of indene.

FIG. 2 is a flowchart of another example of the method for producing indene according to the present invention.
In this embodiment, the heat exchanger 7 is used as the heating means in the first step.
The heat exchanger 7 is not particularly limited as long as it can perform preheating of the tar after dehydration in a temperature atmosphere of 165 ° C. or more and less than 182 ° C., and a conventionally known one can be used. In FIG. 2, heat exchange is performed using the pitch 10 from the distillation column 4, but the present invention is not limited to this, and any exhaust heat or residual heat during the distillation process may be used.
There may be one heat exchanger 7 for preheating the dehydrated tar, or two or more. When two or more heat exchangers 7 are used, preheating may be performed in an atmosphere having a temperature of 165 ° C. or more and less than 182 ° C., which is the highest in the heat exchanger 7 immediately before being supplied to the heating furnace 3 in the second step.

  In the second step, the preheated tar is heated in the heating furnace 3. The temperature atmosphere (heating temperature) in the heating furnace 3 can be a conventionally known temperature atmosphere, for example, a temperature atmosphere of 300 to 340 ° C.

In the third step, the tar heated in the heating furnace 3 is fractionated to recover the indene-containing fraction 5. Examples of the indene-containing fraction 5 include conventional carbol oil and naphthalene oil. In addition, the indene fraction 5 may be a product obtained by deoxidizing at least one of carbol oil and naphthalene oil which are the indene fraction 5.
In the third step, at least the indene-containing fraction 5 may be recovered. In addition to the indene-containing fraction 5, for example, light oil 8, washing oil (tar absorbing oil) 9, heavy oil, anthracene oil, creosote oil, etc. These components may be recovered separately from the indene-containing fraction 5, and pitch 10 (soft pitch) may be recovered as a residue at that time.
The fractionation (distillation) method is not particularly limited. For example, a conventionally known fractionation method such as a continuous distillation method described in “Aromatic and Tar Industry Handbook” issued by the Japan Aromatic Industry Association is used. Can do.

  In the fourth step, indene 6 is purified from the indene-containing fraction 5. There is no restriction | limiting in particular as a purification method of indene from the indene containing fraction 5, A conventionally well-known purification method can be used. For example, methods such as distillation, extraction, and crystallization can be mentioned.

In the indene production method according to the present invention, for convenience of explanation, it is expressed as the first to fourth steps. However, a general tar distillation step other than the step is performed before or after the first to fourth steps. May be included. For example, before the first step, a step of removing sludge from the raw material tar (not shown), a step of heating the raw material tar 11 using heating means such as a heat exchanger 12 as shown in FIG. Including a step of supplying the raw material tar 11 from which water is removed to the dehydration tower 1 to dehydrate the raw material tar 11, a step of supplying the pitch 10 obtained from the bottom of the distillation tower 4 to the pitch manufacturing step 13, and the like. Good.
Each operation in each of the above steps may be either a batch type or a continuous type. However, since the continuous type is more advantageous from the viewpoint of cost, the continuous type is preferable.
In the indene production method according to the present invention, the dehydration tower 1, the heating furnace 3, and the distillation tower 4 are not particularly limited, and conventionally known ones can be used.

  In a preferred embodiment of the method for producing indene according to the present invention, the yield of indene can be improved by 5 to 10% as compared with the conventional method.

(Inden)
The indene according to the present invention is obtained by the above-described method for producing indene. By using the above method for producing indene, high-purity indene can be obtained.

(Coumaron-indene resin)
The coumarone-indene resin according to the present invention is characterized by using the above indene. By using the above indene production method, a highly pure coumarone-indene resin can be obtained. Further, the coumarone-indene resin of the present invention only needs to contain at least a coumarone unit and an indene unit, and may contain a constituent unit other than the coumarone unit and the indene unit (for example, a styrene unit).

(Product)
Applications of the product according to the present invention produced using the above indene are resins (for example, optical resins), catalysts (for example, metallocene catalysts), modifiers, pharmaceuticals (for example, aminoindanol derivatives, and pharmaceutical intermediates). ), And pesticides (including pesticide intermediates).

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

Example 1
Indene was produced using the flow shown in FIG. Specifically, the raw material tar (coal tar) 11 was preheated to 130 ° C. by the heat exchanger 12 and supplied to the dehydration tower 1. Next, preheating of the tar dehydrated in the dehydration tower 1 was performed using a heat exchanger 7 in a temperature atmosphere of 170 ° C. by exhaust heat recovery with the soft pitch 10 obtained from the bottom of the distillation tower 4. Next, the tar preheated in the heat exchanger 7 was heated to 320 ° C. in the heating furnace 3. Subsequently, the tar heated in the heating furnace 3 was subjected to fractional distillation in the distillation column 4, and an indene-containing fraction (carbol oil and naphthalene oil) 5 was recovered. The indene-containing fraction 5 was purified by distillation.
The yield of indene 6 in the fraction after purification was calculated from a gas chromatograph and a mass balance. Moreover, the ratio of indene and indane in the fraction after the purification was measured by a gas chromatograph.

(Comparative Examples 1-2)
In Example 1, except that the temperature atmosphere for preheating tar after dehydration was changed to the temperature shown in Table 1, the same operation as in Example 1 was carried out to fractionate indene-containing fraction 5, and the indene-containing fraction The fraction 5 was purified, and the yield of indene 6 and the ratio of indene to indane in the fraction after purification were measured in the same manner as in Example 1.

  Table 1 shows a summary of the indene yield and the ratio of indene to indane in Example 1 and Comparative Examples 1 and 2.

In Example 1 using the production method of the present invention, the yield of indene was high, the amount of indane in the fraction after purification was small (the ratio of indene to indane was high), and high-purity indene was obtained.
However, in Comparative Example 1 in which the temperature atmosphere of the heat exchanger 7 in the preheating process after dehydration was 215 ° C., the yield of indene and the purity of indene in the fraction after purification were lower than in Example 1.
In Comparative Example 2 in which the temperature atmosphere of the heat exchanger 7 in the preheating process after dehydration was 155 ° C., the yield of indene was lower than that in Example 1.

DESCRIPTION OF SYMBOLS 1 Dehydration tower 2 Heating means 3 Heating furnace 4 Distillation tower 5 Inden fraction containing 6 Inden 7 Heat exchanger 8 Light oil 9 Cleaning oil (tar absorption oil)
10 Pitch 11 Raw material tar 12 Heat exchanger 13 Pitch production process 101 Raw material tar 102 Heat exchanger 103 Dehydration tower 104 Water / light oil 105 Heat exchanger 106 Heating furnace 107 Distillation tower 108 Light oil 109 Carbol oil 110 Naphthalene oil 111 Absorbed oil 112 Pitch

Claims (5)

A step of preheating the dehydrated tar using a heating means;
Heating the preheated tar in a heating furnace;
A step of fractionating the heated tar to recover an indene-containing fraction, and a step of purifying indene from the indene-containing fraction.
In the preheating step, preheating is performed in a temperature atmosphere of 165 ° C. or higher and lower than 182 ° C.   The method for producing indene according to claim 1, wherein the heating means is a heat exchanger.   Inden, obtained by the method according to claim 1.   Coumarone-indene resin characterized by using the indene according to claim 3.   A product selected from the group consisting of resins, catalysts, modifiers, pharmaceuticals, and agricultural chemicals produced using the indene of claim 3.

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