JP2002201151A - Method for producing alkylene oxide adduct - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an alkylene oxide(AO) adduct, which enables the control of the collapse and micronization of a solid catalyst on an AO addition reaction, the maintenance of the filtration recovery of the catalyst, the recycle of the catalyst, and the production of the AO adduct at a low cost and in a state reduced in the amount of the waste catalyst. SOLUTION: This method for producing the alkylene oxide adduct, comprises adding the alkylene oxide to an active hydrogen-containing compound in the presence of a solid catalyst, is characterized by controlling the gas phase partial pressure of the alkylene oxide in the reaction system to 0.001 to 0.19 MPa absolute pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an alkylene oxide adduct using a solid catalyst.

[0002]

2. Description of the Related Art As a technique for adding an alkylene oxide (hereinafter abbreviated as AO) to an active hydrogen-containing compound such as alcohol or phenol, a solid catalyst used in an addition reaction and a method using the same are disclosed. A method for producing an adduct is known.

Hitherto, in the AO addition reaction using a solid catalyst, it has been considered that it is extremely difficult to carry out a filtration treatment for separating the solid catalyst and the product after the reaction, and a technical development intended to improve the filtration has been carried out. . However, the technology disclosed for the purpose of improving the filterability of the catalyst is a technology for reducing the amount of catalyst used by providing a catalyst with improved reaction activity (Japanese Patent Application Laid-Open (JP-A) No)
8-268919), technology to reduce the viscosity of by-products by adding water to the product (JP-A-5-505986), use of other widely known filter aids, and catalyst granulation Only a technique for improving performance has been disclosed.

[0004] On the other hand, the present inventors have found that disintegration and micronization of a solid catalyst are greatly promoted by an AO addition reaction. Under the conditions where such micronization occurs, even if the improvement technology described in JP-A-8-268919 is used,
As the filtration process is repeated with the generated fine particles, the fine particles are clogged in the filter medium, and there is a problem that the recovery and reuse of the catalyst becomes extremely difficult or the filtration cannot be performed. Further, if these fine particles are to be captured using a filter aid or the like, there is a problem that the catalyst cannot be reused and the advantages of a solid catalyst cannot be effectively used. In addition, the method of adding water to the product has a similar problem in that the problem of micronization of the catalyst itself cannot be overcome.

[0005] An object of the present invention is to reduce the amount of waste catalyst by reducing the amount of waste catalyst by suppressing the disintegration and fine particles of the solid catalyst during the AO addition reaction and maintaining the filtration and recovery of the catalyst. An object of the present invention is to provide a method for producing an AO adduct at low cost.

[0006]

Means for Solving the Problems The present inventors have found that the AO pressure in the gas phase in the reaction system at the time of adding AO has a great effect on the fine-particle formation of the solid catalyst, It has been found that when the content is within a certain range, the fine particles of the solid catalyst are extremely unlikely to occur, so that even if the catalyst is reused, the filtration of the catalyst after the addition reaction can be maintained in a very good state. Until now, the AO pressure has been set as high as possible within the range where safety can be ensured from the viewpoint of catalytic activity and the like, but this cannot be said to sufficiently consider the subsequent filtration step. .

The present invention relates to a method for producing an AO adduct by adding AO to an active hydrogen-containing compound in the presence of a solid catalyst.
This is a method for producing an AO adduct in which the partial pressure of the gas phase of AO in the reaction system is set to 0.001 to 0.19 MPa absolute pressure.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the term "catalyst fine-graining" means that when the catalyst is a powder catalyst, the average particle diameter of the catalyst after the reaction is smaller than that before the reaction in each reaction process after the first reaction. 5% or more of the weight per molded article in the molded catalyst is disintegrated,
This refers to the phenomenon that the generation of fine powder occurs.

As the solid catalyst used in the present invention, for example,
A composite oxide catalyst comprising at least one kind of divalent metal selected from Zn ²⁺ , Ca ²⁺ and Ba ²⁺ and Al ³⁺ (JP-A-11-31955)
6), calcined hydrotalcite (JP-A-2-718441), aluminum hydroxide / magnesium calcined product (JP-A-8-2689)
No. 19), calcined hydrotalcite stone (Japanese Unexamined Patent Publication No. 2-7184)
1) and the like.

[0010] Such fine particles of the catalyst are caused by mechanically disintegrating the catalyst at the active point in the pores of the catalyst by a high molecular weight substance such as polyalkylene glycol by-produced during the reaction. That is, the generation of fine by-products in a highly active catalyst causes a rapid growth / reaction of the by-products, thereby promoting the formation of fine particles. Therefore, among the catalysts, particularly when a magnesium oxide-based catalyst which is a solid catalyst having a high by-product amount of a high molecular weight substance such as polyalkylene glycol and a high reaction activity is used, the effect of the present invention becomes more remarkable. preferable. As such a magnesium oxide-based catalyst, Mg described in JP-A-8-268919
/ Al catalyst is exemplified.

The type of the AO addition reaction is not particularly limited, and any type such as a stirred tank type batch type, a stirred tank type flow type, and a fixed bed flow type can be used.

Examples of the active hydrogen-containing compound used in the AO addition reaction include alcohols, phenols, polyols, carboxylic acids, thiols, amines, and amides. Are preferred.

Examples of the alcohols include saturated or unsaturated ones having 2 to 30 carbon atoms, and may be any of primary, secondary and tertiary alcohols. In particular,
Examples thereof include lower alcohols such as ethanol and propanol, higher alcohols such as lauryl alcohol and stearyl alcohol, and aromatic alcohols such as benzyl alcohol.

The AO may be any as long as it can react with an active hydrogen-containing compound to form an adduct, but those having 2 to 8 carbon atoms and epoxidized adjacent carbon atoms are preferred. Preferred are ethylene oxide, propylene oxide and mixtures thereof.

The partial pressure of the gas phase of AO in the reaction system is 0.001 to 0.19 MPa absolute pressure, and preferably 0.01 to 0.19 MPa, because if it is too high, the fine particles of the catalyst cannot be suppressed, and if it is too low, the reaction activity decreases. 0.15 MPa absolute pressure, more preferably 0.01 to 0.1
It is 3 MPa absolute pressure, most preferably 0.01 to 0.09 MPa absolute pressure.

On the other hand, increasing the total pressure in the reaction system using an inert gas such as nitrogen gas does not significantly affect the pulverization of the catalyst.

When the AO addition reaction is carried out batchwise, the amount of the solid catalyst used is usually 0.05 to 20% by weight, preferably 0.1 to 8% by weight based on the active hydrogen-containing compound, although it depends on the activity of the solid catalyst used. % Is more preferred. When the reaction temperature is too low, the reaction rate is slow, and when the reaction temperature is too high, the product is decomposed.
180 ° C, most preferably 120-160 ° C.

When the catalyst is used in the form of a powder, for example, an active hydrogen-containing compound and a catalyst are charged into a reactor, the atmosphere is replaced with nitrogen, the temperature is raised to a predetermined temperature, and the amount of AO in the reactor is reduced. After introducing and reacting AO while keeping the gaseous phase partial pressure within the above-mentioned fixed range, the reaction can be carried out by cooling and filtering off the catalyst.

When the catalyst is used in a molded article, the molded catalyst is put into a stirring blade having a basket made of, for example, a stainless steel wire, and this and an active hydrogen-containing compound are charged into a reactor, and nitrogen replacement is performed. Then, after the temperature is raised to a predetermined temperature, AO is introduced and reacted while keeping the gaseous phase partial pressure of AO in the reactor within the above-mentioned fixed range, then cooled, and the catalyst is filtered off. It can be done by doing.

When the production of the AO adduct is carried out in a fixed bed flow type, the catalyst is filled in a fixed bed flow type reactor, while the gas phase partial pressure of AO is kept within the above-mentioned fixed range. AO and the active hydrogen-containing compound are passed. The liquid passing speed when passing AO and the active hydrogen-containing compound is preferably 0.1 to 100 h ^-1 , more preferably 0.2 to 70 h ^-1 , and particularly preferably ¹ to 50 h ^-1 in terms of liquid hourly space velocity. Reaction temperature is 50 ~ 300 ℃
Is preferably 80 to 250 ° C, and particularly preferably 100 to 230 ° C. When lower AO, particularly ethylene oxide, is used as AO, it is preferable to carry out the reaction in a nitrogen atmosphere in order to avoid the risk of explosion.

[0021]

EXAMPLES Example 1 <Preparation of solid catalyst> Zn (NO ₃ ) ₂ .6H ₂ O 67.0 g, Al (NO ₃ ) ₃ .9H
96.5 g of ₂ O and 173.0 g of Mg (NO ₃ ) ₂・ 6H ₂ O were ion-exchanged with 1560
g solution of 0.24 mol / L Na ₂ CO ₃ aqueous solution and 4N
Along with the aqueous NaOH solution, a liquid volume of 12.5 ml / min, 9 ml / min and 5 to 7.5 ml / min was supplied to a 5 L reactor.
Put 500 g of water in the reaction tank in advance and use a constant-speed stirrer for 250 r
Stirred at pm. The temperature of the reaction solution is controlled so that the solution temperature becomes 15 ± 2 ° C., and NaOH is further adjusted so that the pH becomes 9.7 to 10.3.
After adjusting the addition amount of the aqueous solution and performing a precipitation reaction for 2 hours,
The supply of each aqueous solution was stopped, and the suspension was aged for 1 hour with stirring. This suspension was filtered, and the obtained white solid was sufficiently washed with ion-exchanged water. After washing, 11
It was dried in a hot air dryer at 0 ° C. for 12 hours. The dried white solid was calcined in a nitrogen stream at 550 ° C. for 2 hours.

<Production of AO adduct> 500 g of lauryl alcohol (Kalcol 2098, manufactured by Kao Corporation) in a 3.5 L autoclave
And 0.75% by weight of the above solid catalyst with respect to the alcohol, and the system was purged with nitrogen, and then heated to 160 ° C. while stirring at a constant speed of 400 rpm. At the same temperature, the total pressure in the system is 0.02M
Pressurize with nitrogen to obtain Pa-G, then 355 g of ethylene oxide (hereinafter abbreviated as EO) with internal pressure of 0.08 to 0.10MP
a The reaction was carried out while maintaining the absolute pressure. Predetermined amount of E
After introducing O, the mixture was aged at the same temperature for 30 minutes, and then cooled to 110 ° C., and the product slurry was discharged from the reactor.

<Catalyst Filtration Experiment> The filtration experiment was performed with an ID of 28 mm ×
40cm cylindrical pressure filter and filter cloth (Shikishima Campus FT7501
SS) at 110 ° C. under constant pressure filtration conditions. That is, about 80 g of the extracted slurry was heated to 110 ° C.
The mixture was charged into a pressure filter maintained at 0 ° C., pressurized to a constant pressure of 0.1 MPa-G with nitrogen, and the weight of the filtrate was measured at regular intervals. The obtained filtrate and data of the filtration time were applied to the Ruth equation shown below, whereby the filter cake specific resistance α was used as an index of filterability.
I asked. Table 1 shows the results.

[0024]

(Equation 1)

(Wherein, V: filtrate volume [m ³ ], A: filtration area
[m ² ], V ₀ : virtual filtrate volume [m ³ ], P: filtration pressure [kgf / m ² ],
θ: filtration time [h], m: wet-dry mass ratio of cake, θ ₀ : time to obtain V ₀ [h], s: solid content concentration, K: Ruth constant pressure filtration constant [m ⁶ /
h], μ ': Filtrate viscosity [kg · s / m ² ], α: Cake average specific resistance
[m / kg], ρ: Filtrate density [kg / m ³ ]. ) Modified Ruth's constant pressure filtration

[0026]

(Equation 2)

With respect to (V / A), dθ / d (V / A)
Was plotted, and the cake specific resistance α was calculated from the slope of the obtained straight line.

<Measurement of catalyst particle size> The catalyst particle size distribution after the reaction was measured by using a slurry before and after the reaction by a light scattering method (LA700 manufactured by HORIBA) using ethanol as a solvent. From the obtained data, a volume-based average particle diameter (dp) was determined.
Table 1 shows the results.

<Catalyst Recovery Experiment> The new catalyst and lauryl alcohol were added to the catalyst cake filtered off from the AO adduct, and the AO adduct was produced again using the same catalyst slurry concentration of 0.75% by weight as the raw material as in the first reaction. went. The amount of the new catalyst added at this time was 10% by weight of the total catalyst amount. After reaction 1
The same catalyst filtration experiment and catalyst particle size measurement as the first time were performed.
This collection experiment was performed 12 times in total. Table 1 summarizes the results
Shown in

Example 2 A total of three reaction recovery evaluations were performed in the same manner as in Example 1 except that the EO partial pressure was changed to 0.15 MPa absolute pressure. Table 1 shows the results.

Example 3 A total of 3 were prepared in the same manner as in Example 1 except that a Mg / Al catalyst (KW300 manufactured by Kyowa Chemical Co., Ltd.) calcined at 500 ° C. for 2 hours was used as a catalyst.
A collection evaluation was performed. Table 1 shows the results.

Example 4 A total of three recovery evaluations were performed in the same manner as in Example 1 except that the total pressure in the system at the beginning of the reaction was changed to 0.27 MPa-G using nitrogen (partial pressure of EO was 0.08 MPa). Absolute pressure). Table 1 shows the results.

Comparative Example 1 A total of three recovery evaluations were performed in the same manner as in Example 1 except that the EO partial pressure was changed to 0.27 MPa absolute pressure. Table 1 shows the results.

Comparative Example 2 A total of two recovery evaluations were performed in the same manner as in Example 3 except that the EO partial pressure was set to 0.2 MPa absolute pressure. Table 1 shows the results.

[0035]

[Table 1]

As is clear from Table 1, the catalyst particle size after the reaction is more affected by the partial pressure of the gas phase of AO than by the total pressure in the reaction system.

[0037]

According to the present invention, the disintegration and fine particle formation of the solid catalyst are suppressed, and the AO adduct can be produced very efficiently as compared with the prior art.

Continued on the front page F term (reference) 4H006 AA02 AC41 AC43 BA06 BA09 BA30 BA68 BC10 BC11 BC18 GN06 GP01 GP10 4H039 CA60 CA61 CF90

Claims (1)

[Claims] When an alkylene oxide is added to an active hydrogen-containing compound in the presence of a solid catalyst to produce an alkylene oxide adduct, the gas phase partial pressure of the alkylene oxide in the reaction system is set to 0.001 to 0.19 MPa absolute pressure. To produce an alkylene oxide adduct.