JP2005314269A - Method for jointly producing dihydroxybenzene and diisopropenylbenzene - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To efficiently produce a dihydroxybenzene (DHB) and a diisopropenylbenzene (DST) simultaneously by using diisopropylbenzene (DIPB) as a starting material. <P>SOLUTION: The method for obtaining the DHB and the DST simultaneously comprises (1) an oxidation step for obtaining di(2-hydroperoxyisopropyl)benzene (DHPO) and 2-hydroxyisopropyl-2-hydroperoxyisopropylbenzene (CHPO) by subjecting the DIPB to an oxidation reaction, (2) a separation step for separating the DHPO and the CHPO into each compound, (3) an acidolysis step for obtaining dihydroxybenzene (DHB) by subjecting the DHPO to an acidolysis reaction, (4) a reduction step for obtaining di(2-hydroxyisopropyl)benzene (DCA) by subjecting the CHPO to a reduction reaction, and (5) a dehydration step for obtaining the DST by subjecting the DCA to a dehydration reaction. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for co-production of dihydroxybenzene (DHB) and diisopropenylbenzene (DST). More specifically, the present invention uses diisopropylbenzene (DHB) as a starting material, and dihydroxybenzene (DHB) having an excellent feature that dihydroxybenzene (DHB) and diisopropenylbenzene (DST) can be efficiently and simultaneously produced. ) And diisopropenylbenzene (DST). Dihydroxybenzene (DHB) is a compound useful as a raw material for adhesives, medical and agrochemical intermediates or dye intermediates, and diisopropenylbenzene (DST) is resistant to hydrolysis, weather resistance and low toxicity. It is a useful compound as an excellent urethane raw material.

As a method for producing dihydroxybenzene (DHB), diisopropylbenzene (DIPB) is converted to di (2-hydroperoxyisopropyl) benzene (DHPO) by subjecting it to air oxidation, and further di (2-hydroperoxyisopropyl) benzene. A method of decomposing (DHPO) in the presence of an acid catalyst is known (see Patent Document 1). Further, as a method for producing diisopropenylbenzene (DST), a method of dehydrogenating diisopropylbenzene (DIPB) in the presence of a dehydrogenation catalyst is known (see Patent Document 2).
However, dihydroxybenzene (DHB) and diisopropenylbenzene having excellent characteristics that dihydroxybenzene (DHB) and diisopropenylbenzene (DST) can be efficiently and simultaneously produced using diisopropylbenzene (DIPB) as a starting material. There is no disclosure about the method of co-production of (DST).
JP 49-72220 A JP 2000-327596 A

  In such a situation, the problem to be solved by the present invention is an excellent characteristic that dihydroxybenzene (DHB) and diisopropenylbenzene (DST) can be efficiently and simultaneously produced using diisopropylbenzene (DIPB) as a starting material. It is the point which provides the co-production method of dihydroxybenzene (DHB) and diisopropenylbenzene (DST) which have these.

That is, the present invention relates to a method for co-production of dihydroxybenzene (DHB) and diisopropenylbenzene (DST) having the following steps.
(1) Oxidation step: Step of obtaining di (2-hydroperoxyisopropyl) benzene (DHPO) and 2-hydroxyisopropyl-2-hydroperoxyisopropylbenzene (CHPO) by subjecting diisopropylbenzene (DIPB) to an oxidation reaction. ) Separation step: Di (2-hydroperoxyisopropyl) benzene (DHPO) and 2-hydroxyisopropyl-2-hydroperoxyisopropylbenzene (CHPO) obtained in the oxidation step are converted into di (2-hydroperoxyisopropyl) benzene (DHPO). ) And a solution containing 2-hydroxyisopropyl-2-hydroperoxyisopropylbenzene (CHPO) (3) Acid decomposition step: di (2-hydroperoxyisopropyl) benzene obtained in the separation step (DH Step of subjecting solution containing O) to acid decomposition reaction to obtain dihydroxybenzene (DHB) (4) Reduction step: Solution containing 2-hydroxyisopropyl-2-hydroperoxyisopropylbenzene (CHPO) obtained in separation step (5) Dehydration step: Di (2-hydroxyisopropyl) benzene (DCA) obtained in the reduction step is subjected to a dehydration reaction. Obtaining diisopropenylbenzene (DST)

  According to the present invention, using diisopropylbenzene (DIPB) as a starting material, dihydroxybenzene (DHB) and diisobenzene having an excellent feature that dihydroxybenzene (DHB) and diisopropenylbenzene (DST) can be efficiently and simultaneously produced. A method of co-production of propenylbenzene (DST) can be provided.

The compound names corresponding to the symbols are shown below.
DHB: dihydroxybenzene DST: diisopropenylbenzene DIPB: diisopropylbenzene DHPO: di (2-hydroperoxyisopropyl) benzene CHPO: 2-hydroxyisopropyl-2-hydroperoxyisopropylbenzene DCA: di (2-hydroxyisopropyl) benzene MHPO: Isopropyl-2-hydroperoxyisopropylbenzene MIBK: methyl isobutyl ketone

  The starting material of the present invention is DIPB. There is no particular limitation on the DIPB used. DIPB can be produced industrially by subjecting benzene and propylene to an alkylation reaction.

  The (1) oxidation step of the present invention is a step of subjecting DIPB to an oxidation reaction to obtain DHPO and CHPO.

  The oxidation reaction can be carried out under anhydrous non-alkaline conditions or in the presence of an aqueous alkali solution, but it is preferably carried out in the presence of an aqueous alkali solution from the viewpoint of reaction rate and reaction selectivity. In this case, the pH of the alkaline aqueous solution is preferably 8-11. Examples of the alkaline aqueous solution include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like, but an industrially inexpensive sodium hydroxide aqueous solution is preferable from the viewpoint of production cost. The alkali concentration is preferably 20% by weight or less. Moreover, it is preferable that the usage-amount of alkaline aqueous solution occupies 0.01-20 weight% of all the reaction liquids, and it is still more preferable to occupy 0.1-10 weight% of all the reaction liquids. If this ratio is too small, the reaction rate and the reaction selectivity may decrease. On the other hand, if this ratio is too large, the productivity will decrease due to the decrease in the reaction zone, and the active ingredient water in the reaction product will decrease. Loss to the layer can be an issue. The oxidation reaction is performed by blowing air into an oxidation raw material liquid containing DIPB. The reaction temperature is usually 70 to 120 ° C., and the reaction time is in the range of 0.1 to 20 hours. As a reaction mode, a batch method is possible, but a continuous method is preferred. The conversion rate of DIPB can be controlled by controlling the reaction conditions such as the pH and amount of the alkaline aqueous solution, the reaction temperature, and the reaction time. The lower the conversion rate, the higher the selectivity to the active ingredients DHPO, CHPO and their intermediate MHPO, while the higher the conversion rate, the higher the productivity. Here, productivity means the reactor unit capacity and the production rate of the active ingredient per unit time. Considering such circumstances, the conversion rate of DIPB in the continuous process is preferably 10 to 60%, more preferably 15 to 50%. And it is preferable to maintain the density | concentration of the unreacted DIPB and MHPO in an oxidation reaction liquid in the range of 20 to 50 weight%.

  The (2) separation step of the present invention is a step of separating DHPO and CHPO obtained in the oxidation step into a solution containing DHPO and a solution containing CHPO.

  The separation step is a step of separating DHPO and CHPO from each other by subjecting the oxidation reaction liquid obtained in the oxidation step to an extraction operation with an aqueous sodium hydroxide solution and an extraction operation with an organic solvent. The oxidation reaction solution obtained in the oxidation step contains unreacted DIPB, MHPO, DHPO, CHPO, and other by-products. Of these, DHPO and CHPO are extracted into aqueous sodium hydroxide. At this time, an appropriate amount of an aqueous sodium hydroxide solution and / or DIPB may be added to the oxidation reaction solution in order to improve the separation property and extraction efficiency of the oil water. The extraction temperature is usually in the range of 0 to 100 ° C. The organic solvent layer containing DIPB and MHPO that has not been extracted into the aqueous sodium hydroxide solution can be recycled to the oxidation step. The concentration of the aqueous sodium hydroxide solution when extracting DHPO and CHPO is preferably 2 to 20% by weight, and more preferably 4 to 15% by weight. If the concentration is too low, the extraction efficiency may decrease. On the other hand, if the concentration is too high, the amount of alkali used may increase and active ingredients such as DHPO and CHPO may deteriorate. The aqueous sodium hydroxide solution containing DHPO and CHPO obtained by the extraction operation with an aqueous sodium hydroxide solution is then subjected to an extraction operation with an organic solvent. Thereby, DHPO and CHPO can be separated from each other. As the organic solvent, ketones having 4 to 10 carbon atoms, ethers having 4 to 10 carbon atoms, and alcohols having 4 to 8 carbon atoms are preferable from the viewpoint of extraction efficiency and solvent recovery. MIBK is most preferable. A solvent may be used individually by 1 type, or may mix and use 2 or more types. The extraction with an organic solvent is preferably performed by combining extraction at a low temperature of about 0 to 50 ° C. and extraction at a high temperature that is performed at a temperature 5 to 50 ° C. higher than the extraction temperature. That is, CHPO is selectively transferred to the organic solvent layer by extraction at a low temperature, and then DHPO is transferred to the organic solvent layer by extraction at a high temperature. Thus, CHPO and DHPO are separately separated and recovered. A small amount of DHPO is also mixed in a solution containing CHPO obtained by extraction at a low temperature. A small amount of CHPO is also mixed in a solution containing DHPO obtained by extraction at a high temperature. The CHPO concentration in the solution obtained by extraction at a low temperature is preferably 2 to 20% by weight, and the DHPO concentration is preferably 1% by weight or less. The concentration of DHPO in the solution obtained by extraction at high temperature is preferably 5 to 30% by weight, and the concentration of CHPO is preferably 1% by weight or less.

  The (3) acid decomposition step of the present invention is a step of obtaining DHB by subjecting the solution containing DHPO obtained in the separation step to an acid decomposition reaction.

  The acid decomposition step is a step of obtaining DHB by subjecting DHPO obtained in the separation step to a decomposition reaction in the presence of an acid catalyst. Acid catalysts used include Lewis acids such as aluminum chloride, boron trifluoride, ferric chloride, stannic chloride, sulfuric acid, phosphoric acid, hydrochloric acid, perchloric acid, benzenesulfonic acid, p-toluenesulfonic acid, strong acid And protonic acids such as anionic ion exchange resin. Concentrated sulfuric acid and anhydrous sulfuric acid are preferable in terms of yield and ease of handling, and anhydrous sulfuric acid is more preferable. Since the liquid used for the acid decomposition reaction usually contains 1 to 10% by weight of water, the acid decomposition catalyst is adversely affected as it is. Therefore, usually, an operation of distilling off a part of water by distillation is performed before acid decomposition. It is preferable to reduce the water concentration removed to 1% by weight or less. The liquid thus obtained is subjected to an acid decomposition reaction. The acid decomposition reaction is usually carried out under normal pressure or reduced pressure at a reaction temperature of 30 to 150 ° C. and a reaction time of 1 to 200 minutes. The resulting acid decomposition reaction solution contains DHB, acetone, organic solvent, as well as acid catalyst and heavy substances. From this, acid catalyst removal by alkali neutralization / separation operation, removal of acetone and organic solvent by distillation Furthermore, DHB can be isolated by ordinary operations such as distillation, extraction, and crystallization.

  The (4) reduction step of the present invention is a step of obtaining DCA by subjecting the solution containing CHPO obtained in the separation step to a reduction reaction.

  The reduction step is a step of obtaining DCA by subjecting CHPO obtained in the separation step to a reduction reaction. The liquid to be subjected to the reduction step contains CHPO, DHPO and other impurities, and after performing the concentration operation to leave the liquid as it is or distill off a part of the organic solvent, It is subjected to a reduction reaction. The concentration of CHPO in the liquid or the liquid concentrate is preferably 2 to 30% by weight. As the reduction reaction, stoichiometric reduction using a reducing agent such as sodium sulfite or catalytic reduction using a hydrogenation catalyst can be applied. Note that the reduction reaction with hydrogen in the presence of a hydrogenation catalyst is more operable and inexpensive, and is industrially preferable. As the hydrogenation catalyst, a normal hydrogenation catalyst in which noble metals of Groups 8, 9 and 10 of the periodic table are supported on a support can be used. In particular, a palladium-supported catalyst can be preferably used from the viewpoint of activity and selectivity. . Examples of the carrier include alumina, silica, titania, magnesia and the like. The supported concentration of palladium on the support is usually 0.01 to 10% by weight as palladium metal. The hydrogen used for the reduction reaction does not need to be pure, and may contain an inert gas such as nitrogen, carbon dioxide, or methane. The reaction pressure is usually 0.1 to 10 MPa-A, and the reaction temperature is usually 20 to 150 ° C. The reaction time is usually 1 to 300 minutes. As a reaction form, it can be carried out by a fixed bed flow reaction in a liquid phase or a stirring tank slurry reaction. For example, in the case of a stirred tank slurry reaction, the catalyst concentration is usually in the range of 0.05 to 10% by weight.

  The (5) dehydration step of the present invention is a step for obtaining DST by subjecting the DCA obtained in the reduction step to a dehydration reaction.

  It is preferable to use an acid catalyst for the dehydration reaction. Any acid catalyst may be used as long as it causes a dehydration reaction of alcohols, such as inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as formic acid, acetic acid and p-toluenesulfonic acid, or alumina and strongly acidic ion exchange resins. Examples include solid acids. From the viewpoint of dehydration reaction activity, strong acids such as sulfuric acid, p-toluenesulfonic acid, and strongly acidic ion exchange resins are more preferable. The reaction pressure is usually about 0.01 to 1 MPa-A, and the reaction temperature is usually about 30 to 200 ° C. As a reaction form, a batch method is possible, but a continuous method is preferred.

By using the above series of steps, DHB and DST can be produced together.
In the present invention, steps other than the above steps may be added as long as the effects of the present invention are not impaired.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
(1) Oxidation process 80 parts by volume and 0.5% by weight of oxidizing raw material oil (including 37% by weight of DIPB (meta-substituted product) and 33% by weight of MHPO (meta-substituted product)) containing recycled components in the oxidation reactor The sodium hydroxide aqueous solution was continuously supplied at 5 parts by volume per hour, and air was passed through 20000 standard parts per hour at 95 ° C., 3 atm, and the residence time was 4 hours. In a steady state, a reaction solution containing 18% by weight of DIPB (meta-substituted product), 34% by weight of MHPO (meta-substituted product), 19% by weight of DHPO (meta-substituted product), and a small amount of CHPO (meta-substituted product) Obtained.

(2) Separation step Liquid mixture obtained by extracting an oxidation product of DIPB (meta-substituted product) with an 8% by weight sodium hydroxide aqueous solution and a recovery solution of DHPO (meta-substituted product) described later (DHPO (meta-substituted product) 100 parts) (containing 15% by weight and 2% by weight of CHPO (meta-substituted product)) were washed with 50 parts of MIBK at a temperature of 30 ° C. in a countercurrent. The aqueous layer after washing thus obtained contained 12% by weight of DHPO (meta-substituted product) and 0.1% by weight of CHPO (meta-substituted product). Also, by re-extracting the MIBK washing solution using 30 parts of an 8 wt% aqueous sodium hydroxide solution at a temperature of 30 ° C. and countercurrent, 98% of DHPO (meta-substituted product) in the MIBK washing solution is converted into the re-extraction solution. It was recovered. By extracting an aqueous layer containing these DHPO (meta-substituted product) with an excess of MIBK at 70 ° C., 12% by weight of DHPO (meta-substituted product), 0.1% by weight of CHPO (meta-substituted product), moisture A MIBK solution (X) containing 3% by weight was obtained. On the other hand, a MIBK solution (Y) containing 6% by weight of CHPO (meta-substituted product) and 0.2% by weight of DHPO (meta-substituted product) is obtained as the remainder of the recovery of DHPO (meta-substituted product) from the MIBK washing solution. It was.

(3) Acid decomposition step The MIBK solution (X) was concentrated under reduced pressure, and the concentrated solution having a DHPO (meta-substituted product) concentration of 20% by weight and a water concentration of 0.2% by weight was subjected to an acid decomposition reaction. The reaction was conducted in the presence of 0.1% by weight of anhydrous sulfuric acid as a catalyst at normal pressure, a reaction temperature of 60 ° C., and a reaction time of 10 minutes. The yield of DHB (meta-substituted product) from DHPO (meta-substituted product) was 94%. After neutralizing and removing the catalyst in the reaction solution, acetone (purity 99% or more) and DHB (meta-substituted product) (purity 99% or more) can be isolated by rectification and extraction, and the solvent MIBK can be recovered. It was.

(4) Reduction step In an autoclave equipped with a stirrer, a raw material MIBK solution (Y) and a palladium-alumina catalyst (supported by 1% by weight as palladium metal) are present in an amount of 0.5% by weight, and a hydrogen pressure of 6 Liquid phase hydrogen reduction reaction was performed at atmospheric pressure, reaction temperature 90 ° C., and reaction time 30 minutes. The conversion of CHPO (meta-substituted product) was substantially 100%, and the concentration of DCA (meta-substituted product) in the reaction solution was 6% by weight.

(5) Dehydration step Oil filled with silicon oil in a stainless steel cylindrical reactor (filling part inner diameter 5.9 cm × packing length 15 cm) filled with 318 g of strongly acidic ion exchange resin Duolite SC200 (manufactured by Sumika Chemtex Co., Ltd.) DCA (meta-substituted product) MIBK in which hydrogen is separated from the reaction solution obtained by hydrogen reduction reaction of CHPO (meta-substituted product) in the reactor in the presence of palladium / alumina catalyst. A solution (MIBK 88 wt%, DCA (meta-substituted product) 7 wt%) was supplied at 600 g / h to start dehydration reaction. From the compositional analysis of the dehydration reaction solution, after starting the feed of raw materials, the conversion rate of DCA (meta-substituted product) was 99.6% and the yield of DST (meta-substituted product) was 85% at 191h.

Claims (1)

A co-production method of dihydroxybenzene (DHB) and diisopropenylbenzene (DST) having the following steps.
(1) Oxidation step: Step of obtaining di (2-hydroperoxyisopropyl) benzene (DHPO) and 2-hydroxyisopropyl-2-hydroperoxyisopropylbenzene (CHPO) by subjecting diisopropylbenzene (DIPB) to an oxidation reaction. ) Separation step: Di (2-hydroperoxyisopropyl) benzene (DHPO) and 2-hydroxyisopropyl-2-hydroperoxyisopropylbenzene (CHPO) obtained in the oxidation step are converted into di (2-hydroperoxyisopropyl) benzene (DHPO). ) And a solution containing 2-hydroxyisopropyl-2-hydroperoxyisopropylbenzene (CHPO) (3) Acid decomposition step: di (2-hydroperoxyisopropyl) benzene obtained in the separation step (DH Step of subjecting solution containing O) to acid decomposition reaction to obtain dihydroxybenzene (DHB) (4) Reduction step: Solution containing 2-hydroxyisopropyl-2-hydroperoxyisopropylbenzene (CHPO) obtained in separation step (5) Dehydration step: Di (2-hydroxyisopropyl) benzene (DCA) obtained in the reduction step is subjected to a dehydration reaction. Obtaining diisopropenylbenzene (DST)