Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds

Definitions

• the present invention relates to a method for producing an acetate ester. More specifically, the present invention relates to a method for producing an acetate ester that can obtain an acetate ester useful as a solvent or a fragrance, such as isopropyl acetate or butyl acetate, with excellent selectivity and reaction efficiency using a specific catalyst.
• styrene sulfonic acid type cation exchange resin or a phenolic sulfonic acid type cation exchange resin has been conventionally used (Patent Documents 1 to 6).
• the styrene sulfonic acid type cation exchange resin is obtained by sulfonating a crosslinked resin obtained by copolymerizing styrene and a compound having a plurality of unsaturated side chains such as divinylbenzene.
• the phenolic sulfonic acid type cation exchange resin is usually obtained by condensing phenolsulfonic acid with formaldehyde or the like.
• styrene sulfonic acid type cation exchange resin or phenolic sulfonic acid type cation exchange resin used for the production of acetate ester by addition reaction of olefin and acetic acid the amount of sulfonic acid group added to benzene ring The ion exchange capacity was small.
• acetic anhydride and water by-product due to acetic acid dehydration reaction are unavoidable due to the use at high temperature, and side reactions such as hydration reaction of olefin also occur, and olefin oligomerization and polymerization reaction are also added.
• the effective utilization rate decreases.
• a benzenesulfonic acid type cation exchange resin catalyst having a large ion exchange capacity is also known.
• the use of a catalyst having a large ion exchange capacity may cause oligomerization of the olefin.
• An object of the present invention is to provide a method for producing an acetate ester with a high selectivity with a long catalyst life by suppressing a decrease in the olefin polymerization reaction and the catalyst life resulting therefrom or a reduction in the effective utilization of olefins derived from side reactions. Is to provide.
• the present inventors have obtained a porous specific structure ion exchange resin, In addition, by using a resin having an ion exchange capacity of 4.8 mmol / g or more, the activity of the addition reaction of olefin and acetic acid is remarkably increased, and the degree of the increase is more than estimated from the magnitude of the ion exchange capacity. The present inventors discovered a new fact that it is much larger and the selectivity of the acetate ester in the addition reaction is not decreased in spite of the increased activity.
• the present inventors use an ion exchange resin having the above-described specific structure and an ion exchange capacity of 4.8 mmol / g or more to perform an ester formation reaction by addition reaction of olefin and acetic acid. Further, by maintaining the olefin conversion rate under specific conditions, it was found that an acetic acid ester was obtained with high selectivity and a decrease in catalyst activity could be suppressed, and the present invention was achieved. That is, for the first time, the present invention makes it possible to produce an ester from olefin and acetic acid in a high yield with a long catalyst life.
• the catalyst in a method for producing an acetate ester by reacting an olefin such as propylene with acetic acid, has a structure in which a sulfonic acid group is added to a copolymer of styrene and divinylbenzene, and is porous.
• a method for producing an acetate ester characterized by using a porous cation exchange resin having an ion exchange capacity of 4.8 mmol / g or more.
• the manufacturing method of acetate ester characterized by performing esterification reaction on specific reaction conditions using the said ion exchange resin is provided.
• the production method of the present invention uses a specific porous cation exchange resin, it suppresses side reactions such as polymerization reaction of olefin, and has a long catalyst life and high selectivity from olefin and acetic acid even under mild conditions.
• the acetate can be produced with When the resulting acetate is isopropyl acetate or butyl acetate, it is useful as a solvent for ink, a solvent for paint, or a solvent for adhesives. It is also useful as a perfume raw material.
• isopropyl acetate obtained by the production method of the present invention is an environmentally superior solvent with a low content of acetaldehyde that causes odor and sick house disease and ethanol that becomes acetaldehyde by oxidation.
• the present invention uses a specific ion exchange resin as a catalyst in a method for producing an acetate ester by reacting an olefin and acetic acid.
• the catalyst used in the present invention is a porous cation exchange resin that has a structure in which a sulfonic acid group is added to a copolymer of styrene and divinylbenzene, is porous, and has a specific ion exchange capacity.
• the porous cation exchange resin has a large number of macropores in its polymer matrix and usually exhibits a large surface area of about 20 m 2 / g or more. The surface area can be determined by the BET method.
• a cation exchange resin having a structure in which a sulfonic acid group is added to a copolymer of styrene and divinylbenzene in addition to those used in the present invention, so-called gel ion exchange resins having different production methods are well known.
• the gel type ion exchange resin has few effective macropores in its polymer matrix and has a very small surface area. When such an ion exchange resin is used as a catalyst, even if it has the same chemical structure and the ion exchange capacity is 4.8 mmol / g or more, the desired effect of the present invention cannot be obtained.
• the ion exchange capacity of the porous cation exchange resin used in the present invention is 4.8 mmol / g or more.
• the ion exchange capacity is less than 4.8 mmol / g, the addition reaction activity of olefin and acetic acid is greatly reduced. Further, even when the ion exchange capacity is large, when the gel ion exchange resin is used, the activity of the addition reaction of olefin with acetic acid is low, and a desired effect cannot be obtained.
• the reaction temperature is increased in order to achieve a sufficient reaction rate, an olefin polymerization reaction also occurs, and the selectivity for the formation of acetate to the olefin is reduced. As a result, the polymer is deposited on the catalyst surface. There is a possibility that the catalytic activity may be lowered, and furthermore, since the temperature is high, a dehydration reaction of acetic acid is likely to occur.
• the ion exchange capacity is a value obtained by an ion exchange reaction using a sodium chloride solution, by exchanging protons of sodium sulfonate groups and sodium ions, and neutralizing titrating the amount of hydrogen chloride produced. Desired.
• the ion exchange reaction is represented by the following formula. R-SO 3 H + NaCl ⁇ R-SO 3 Na + HCl
• R shows the residue except the sulfonic acid group part of the ion exchange resin.
• porous cation exchange resin used in the present invention.
• examples thereof include, but are not limited to, “Levacit K2620” and “Levacit K2420” (registered trademark) manufactured by LANXESS, and “Amberlist 36” and “Amberlist 35” (registered trademark) manufactured by Rohm and Haas.
• the olefin used in the esterification reaction of the present invention is not particularly limited and may be linear, branched or cyclic, and an aliphatic olefin having 2 to 5 carbon atoms is preferably used. More preferably, olefins having 3 or 4 carbon atoms, specifically, propylene, 1-butene, 2-butene, and isobutene are used. As these olefins, it is natural that high-purity olefins can be used, but low-purity olefins can also be used as long as they do not inhibit the esterification reaction.
• a butane-butene fraction is used, various butyl acetate mixtures are obtained.
• acetic acid used in the esterification reaction of the present invention.
• acetic acid produced by direct oxidation of light hydrocarbons or acetic acid produced by methanol carbonylation reaction can be used.
• esterification reaction conditions reaction method
• a general method practiced in the chemical industry can be adopted. That is, either a stationary phase flow type using a catalyst layer filled with an ion exchange resin or a batch reaction method in which an ion exchange resin is suspended and reacted in a tank reactor equipped with a stirrer can be employed.
• a stationary phase flow system is desirable, and a stationary phase flow system in which olefin and acetic acid are continuously supplied is a preferred system.
• the reaction mixture obtained from the reactor outlet is circulated to the reactor inlet, and a new raw material (hereinafter referred to as “feedstock”) supplied to the reactor is diluted.
• feedstock a new raw material supplied to the reactor is diluted.
• a so-called local recycling method can also be used. Local recycling is a preferred method that is effective in preventing local heating in the reactor due to the heat of reaction of acetic acid and olefin addition, and suppressing olefin oligomerization reaction or polymerization reaction by reducing the olefin concentration at the reactor inlet. .
• the recycle liquid In addition to returning the recycled liquid to the inlet of the reactor, it is also possible to return it to the middle stage of the reactor. Furthermore, it is possible to divide the recycle liquid back to each part of the reactor.
• the ratio of acetic acid and olefin in the production method of the present invention is not substantially different from the case of using a conventional benzenesulfonic acid type ion exchange resin. That is, the preferred ratio is 1.0 to 3.0 as the molar ratio of acetic acid / olefin. Note that this figure in the stationary phase flow system represents the molar ratio of acetic acid / olefin in the feedstock.
• the amount of unreacted acetic acid increases and the burden on recovery such as distillation may increase.
• the oligomerization reaction and polymerization reaction of the olefin tend to be reduced by local recycling.
• the ratio is desirably 1.0 or more.
• reaction temperature is preferably 60 to 150 ° C, more preferably 60 to 130 ° C, still more preferably 65 ° C to 110 ° C. If it is less than 60 ° C., the rate of addition reaction between acetic acid and olefin is small, and an acetate ester cannot be obtained efficiently. Moreover, when it exceeds 150 degreeC, the heat deterioration of an ion exchange resin will occur easily.
• oligomerization reaction or polymerization reaction of olefin is likely to occur, the selectivity for the formation of acetate to olefin is reduced, and deposition of the polymer on the catalyst surface may occur and the catalyst life may be reduced. is there.
• the acetate formation reaction by the addition reaction of olefin and acetic acid is an exothermic reaction.
• the reaction takes place over time, and in the case of a stationary phase flow reactor, the reaction takes place from the inlet to the outlet of the reactor.
• the temperature changes. In any case, it is preferable that the minimum temperature and the maximum temperature in the reactor are within the above-mentioned range.
• the stationary phase flow type if local recycling is adopted, the degree of temperature distribution change from the inlet to the outlet of the reactor is alleviated.
• the reaction rate is preferably 80% or more.
• the reaction rate is less than 80%, since the concentration of olefin in the reactor is high, propylene oligomerization tends to proceed, and the selectivity of acetate ester to propylene may decrease. Therefore, in the present invention, when propylene is used as the olefin, it is desirable to carry out the reaction under the conditions of a reaction temperature of 110 ° C. or lower and a propylene reaction rate of 80% or higher.
• the selectivity of acetate to propylene is high, and the decrease in catalytic activity due to olefin oligomerization and polymerization reaction is also suppressed.
• setting the reaction rate to 80% or more also contributes to suppressing the cost for facilities and operations necessary for separation and recovery of unreacted propylene downstream of the reactor.
• Such control of the reaction rate can be appropriately performed by adjusting, for example, the reaction temperature, the supply amount of the feedstock, and the like.
• the reaction temperature is 60 ° C.
• the activity of addition reaction of olefin to acetic acid was low and there was a problem in practical use, by using the above-mentioned porous cation exchange resin in the present invention, oligomerization of olefin even at a low temperature of 60 ° C. It is possible to produce an acetate ester with high catalytic activity while suppressing polymerization.
• an acetate ester can be produced from a temperature as low as 60 ° C. or more, which is advantageous in terms of chemical equilibrium, and suppresses the generation of side reactions such as olefin oligomerization and polymerization reaction, Acetic acid esters can be produced with a long catalyst life.
• reaction time varies depending on the reaction temperature, molar ratio of acetic acid / olefin, catalyst / reaction raw material, etc., but is generally 0.5 to 10 hours.
• the preferred liquid hourly space velocity (LHSV) is 0.5 to 20 (Feed-ml / Cat-ml / h) for the feedstock.
• reaction pressure in the reactor may be sufficient to keep the reaction system in a liquid phase, preferably 1.5 to 5.0 MPa for propylene, and 0.5 for butenes. ⁇ 5.0 MPa is preferred.
• the catalyst / reaction raw material ratio in the case of using a stirred tank type batch reactor is preferably 0.005 to 0.2 in terms of mass ratio.
• it is less than 0.005
• the contact efficiency between the catalyst and the reaction raw material is poor, and the conversion rate of the addition reaction of acetic acid and olefin may be small.
• stirring efficiency falls and there exists a possibility that the production efficiency of the acetate per catalyst may fall.
• the acetate obtained by the production method of the present invention can be easily purified from the reaction product by a known method such as distillation as appropriate.
• the ion exchange capacity of the cation exchange resin used in each example was measured by the following method. The results are shown in Table 1. 0.1 g of the cation exchange resin used in each example was placed in a glass container, 50 g of a 1 mol / L NaCl solution was added thereto, and the mixture was stirred for 30 minutes. After stirring, only the solution was transferred to a glass beaker and titrated with a 0.1 mol / L KOH solution to determine the ion exchange capacity.
• Example 1 As a porous cation exchange resin having a structure in which a sulfonic acid group is added to a copolymer of styrene and divinylbenzene, “Levacit K2620” (registered trademark) (surface area by BET method 33 m 2 / g) manufactured by LANXESS is used. It was. To a 100 cc autoclave equipped with a stirrer, 36 g of acetic acid (purity 99.8%), 0.5 g of the porous cation exchange resin, and 16.8 g of propylene (purity 99.8%) were introduced. Subsequently, the pressure in the autoclave was increased to 2 MPa using nitrogen.
• the temperature in the autoclave was raised to 80 ° C. using an electric furnace while stirring at a rotation speed of 500 rpm.
• the reaction was continued for 4 hours after reaching 80 ° C.
• the reaction solution was collected in a sampling tube, and the product was analyzed by gas chromatography using a hydrogen ion detector. The results are shown in Table 1.
• Examples 2 and 3 and Comparative Examples 1 and 2 As a porous cation exchange resin having a structure in which a sulfonic acid group is added to a copolymer of styrene and divinylbenzene, “Amberlyst 36” (registered trademark) manufactured by Rohm and Haas (surface area of 33 m 2 / g by BET method) (Example 2), “Amberlyst 35” (registered trademark) manufactured by Rohm and Haas (surface area 50 m 2 / g by BET method) (Example 3), “Levacit K2629” (registered trademark) manufactured by LANXESS (BET method surface area of 40 m 2 / g by) (Comparative example 1), or Rohm and Haas Co.
• Comparative Examples 3 and 4 As a cation exchange resin having a structure in which a sulfonic acid group is added to a copolymer of styrene and divinylbenzene, "Levacite K1461” (registered trademark) manufactured by LANXESS of gel type (surface area by BET method is below detection limit) ( Comparative Example 3) or “Amberlyst 31” (registered trademark) manufactured by Rohm and Haas (registered trademark) (surface area by BET method is below detection limit) (Comparative Example 4) was used. The reaction of propylene and acetic acid was carried out by the method. The results are shown in Table 1.
• Examples 4 to 9 As the ion exchange resin, the same ion exchange resin as in Example 3 was used as a catalyst, and the reaction temperature was changed to carry out the reaction between propylene and acetic acid. Acetic acid (purity 99.8%) 0.86 g / min and propylene (purity 99.8%) 0.4 g / min were introduced into a fixed bed flow reactor filled with 50 ml of the porous cation exchange resin. The recycling amount was set to 700 g / h. When a steady state was reached, a sample was taken and the product was analyzed by gas chromatography with a hydrogen ion detector. The results are shown in Table 2.
• Example 8 is an example in which the reaction was carried out at a temperature of 60 ° C. In this case, the propylene reaction rate was slightly lowered, and the selectivity for acetate was also slightly lowered. In addition, 36% of propylene remained unreacted.
• Example 9 where the reaction temperature was 120 ° C., the reaction rate of propylene was as high as 87%, but the selectivity of acetate was slightly lowered. Further, as will be described later, under the condition where the reaction temperature exceeds 110 ° C., the decrease in the catalyst activity with time was slightly larger than when the reaction temperature was 110 ° C. or less.
• Example 10 Using the same ion exchange resin as in Example 3, a life test for catalytic activity was conducted. In a fixed bed flow reactor filled with 33 ml of the porous cation exchange resin, acetic acid (purity 99.8%) 0.28 g / min, propane-propylene fraction obtained from petroleum fluid catalytic cracker (propylene purity) 76.5%) 0.13 g / min was introduced, and the recycling amount was set to 700 g / h. When a steady state was reached, a sample was taken and the product was analyzed by gas chromatography with a hydrogen ion detector. The reaction temperature was set so that the propylene reaction rate at the start of oil passing was about 90%, and the reaction was started.
• acetic acid purity 99.8%
• propane-propylene fraction obtained from petroleum fluid catalytic cracker propane-propylene fraction obtained from petroleum fluid catalytic cracker (propylene purity) 76.5%) 0.13 g / min was introduced, and the recycling amount was set to 700 g /
• Comparative Example 5 Using the same ion exchange resin as in Comparative Example 2, a life test for catalytic activity was performed under the same conditions as in Example 10. However, in order to obtain a propylene reaction rate of 90%, the reaction temperature needs to be 80 ° C. Therefore, the reaction temperature at the start of oil passing was set to 80 ° C. The results are also shown in Table 3. In the case of Comparative Example 7 using an ion exchange resin having an ion exchange capacity of less than 4.8 mmol / g, since the catalytic activity is small, the temperature at the start of oil passage must be 10 ° C.
• Example 10 As a result, the aging of the activity was remarkably reduced, and when the oil was passed for 2500 hours, the value fell below 80%, and it was necessary to raise the reaction temperature in order to recover 80% or more. Moreover, after raising the reaction temperature, the selectivity for isopropyl acetate was 95%, which was lower than in Example 10.
• Example 11 A life test of the catalyst activity was performed under the same conditions as in Example 10 except that the reaction temperature at the start of oil passing was 115 ° C.
• the propylene reaction rate at the start of oil passing was 90%, and the propylene reaction rate was almost the same even though the reaction temperature was increased by 45 ° C.
• the selectivity for isopropyl acetate was 88%, which was lower than that of Example 10.
• the propylene reaction rate decreased to 78% when the oil flowed for 1000 hours, and it was necessary to raise the reaction temperature in order to maintain the reaction rate above 80%. , Activity decreased.
• the selectivity for isopropyl acetate was 87%.
• the ion exchange capacity is 4.8 mmol / g or more and a porous ion exchange resin is used, compared with the case where the ion exchange capacity is less than 4.8 mmol / g or the gel type ion exchange resin is used, It can be seen that since the acetate ester can be produced at a low reaction temperature, the decrease in the catalytic activity is small and the acetate ester can be produced with high efficiency. It is also clear that when propylene is used as the olefin, isopropyl acetate can be produced with a high selectivity and a reduction in catalytic activity by setting the propylene reaction rate to 80% or more and the reaction temperature to 110 ° C. or less. Became.

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• 2009
  • 2009-11-26 CN CN2009801504101A patent/CN102264685A/zh active Pending
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