JP2570903B2 - Method for producing double metal cyanide complex catalyst - Google Patents

Description

The present invention relates to a method for producing a double metal cyanide complex catalyst.

[Prior Art] Conventionally, double metal cyanide complexes have been known as catalysts for ring-opening reactions of monoepoxides such as alkylene oxides (US 3278457, US 3278458, US 3278459). The production method of the double metal cyanide complex catalyst used at this time is proposed in US Pat. No. 3,427,256, US Pat. No. 3,418,491, US Pat. No. 4,472,560, US Pat.

[Problems to be Solved by the Invention] In the above-mentioned method for producing a double metal cyanide complex catalyst, after synthesizing from an aqueous metal halide solution, an aqueous alkali metal cyanometalate solution and an organic ligand, the organic ligand is batch-processed. The complex metal cyanide complex catalyst is manufactured by adding a washing operation of mixing and filtering with the ligand, but this catalyst is very difficult to filter and the filtration operation time is long, and the filtration efficiency fluctuates due to batch operation. Therefore, the catalyst cannot be synthesized stably, and further, the yield of the catalyst deteriorates in the filtration operation, and the continuous synthesis of the double metal cyanide complex catalyst cannot be performed.

[Means for Solving the Problems] The present invention is the following invention which has been made to solve the above problems.

In a method for producing a double metal cyanide complexing catalyst using a metal halide aqueous solution, an alkali metal cyanometalate aqueous solution and an organic ligand, the reaction, the catalyst after aging is washed with a washing liquid to separate the washing liquid, A method for producing a double metal cyanide complex catalyst, wherein a rotating cylindrical filter or a rotating disk filter is used.

As the metal of the metal halide salt used in the present invention,
Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Mo
(IV), Mo (VI), Al (III), V (V), Sr (II), W (I
V), W (VI), Mn (II) and Cr (III) are selected from one type or two or more types, preferably Zn (II) and Fe (II).

Fe (II), Fe (III), Co as gold metal constituting cyanometalate anion of alkali metal cyanometalate
(II), Co (III), Cr (III), Mn (II), Mn (III), V (I
V), select one or more than two from the group of V (V),
Preferably, Co (III) or Fe (II) is used.

Ethers, esters, alcohols as organic ligands,
Use one kind of organic ligand selected from aldehydes, ketones, amides, nitriles, sulfides, or two or more kinds of mixed organic ligands. Used.

The organic ligand is also used as a washing solution. The washing liquid may be composed of only the organic ligand, or may be a mixture with another inert solvent. Since the washing should not cause decoordination of the coordinated organic ligand, it is preferable that the washing liquid is composed only of the organic ligand. However, it is possible to use an organic ligand different from the coordinated organic ligand as the washing liquid.

In the washing step, it is preferable in terms of productivity to continuously perform washing and solid-liquid separation using a rotary cylindrical (or disk) filter. At this time, the cleaning liquid can be circulated.
By using this filter, filtration can be easily performed in a short time. Further, by performing the continuous operation, it is possible to stably produce a large amount of a catalyst of a constant quality with high production efficiency.

Example 1 A slurry solution is obtained by reacting zinc chloride, potassium cobalt cyanate and diethylene glycol dimethyl ether. The obtained slurry solution is subjected to solid-liquid separation using a rotary cylindrical filter to obtain a filter cake. This filter cake is put into an aqueous solution of diethylene glycol dimethyl ether, stirred for 30 minutes, and then subjected to solid-liquid separation using a rotary cylindrical filter to obtain a filter cake. This filter cake is put into diethylene glycol dimethyl ether, stirred for 30 minutes, and then subjected to solid-liquid decomposition using a rotary cylindrical filter to obtain a substance. The solid substance was dried and pulverized to obtain a double metal cyanide complex catalyst. In this way, a double metal cyanide complex catalyst is
Samples are synthesized, and Samples 1 to 3 are obtained.

Example 2 A composite metal cyanide complex catalyst was prepared using a synthesis apparatus in which a reaction tank, a rotary cylindrical filter 1, a washing tank 1, a rotary cylindrical filter 2, a washing tank 2, and a rotary cylindrical filter 3 were connected in series. Was continuously synthesized.

In a reaction vessel, zinc chloride, potassium potassium cyanate, and diethylene glycol dimethyl ether are reacted to obtain a slurry solution. The obtained slurry solution is subjected to solid-liquid separation using a rotary cylindrical filter 1 to obtain a filter cake.
The filtrate is continuously supplied to the washing tank 1 with an aqueous solution of diethylene glycol dimethyl ether. The slurry-like substance from the washing tank 1 is subjected to solid-liquid separation using a rotary cylindrical filter 2,
The obtained filter cake and diethylene glycol methyl ether are continuously supplied to the washing tank 2. The slurry-like substance from the washing tank 2 is subjected to solid-liquid separation using a rotary cylindrical filter 3 to obtain a filter cake. The filter cake was dried and pulverized to obtain a double metal cyanide complex catalyst. With this method, three samples of the composite metal cyanide complex catalyst are synthesized, and are referred to as samples 4 to 6, respectively.

Example 3 A continuous synthesis of a double metal cyanide complex catalyst was carried out using a synthesis apparatus in which a reaction tank and a rotary cylindrical filter equipped with two spray nozzles for supplying a cleaning liquid were connected in series.

In a reaction tank, zinc chloride, potassium potassium cyanate,
Diethylene glycol dimethyl ether is reacted to obtain a slurry solution. While supplying the obtained slurry solution to the rotary cylindrical filter, the aqueous solution of diethylene glycol dimethyl ether and diethylene glycol dimethyl ether are sprayed onto the solid on the rotary cylindrical filter from two washing liquid supply spray nozzles to wash the filter mass. obtain. The filter cake was dried and pulverized to obtain a double metal cyanide complex catalyst. In this manner, two samples of the double metal cyanide complex catalyst are synthesized, and are referred to as samples 7 to 8, respectively.

Comparative Example 1 Zinc chloride, potassium potassium cyanate and diethylene glycol dimethyl ether are reacted to obtain a slurry solution. The obtained slurry solution is centrifuged at a centrifugal force of 1000 G for 5 minutes, and the supernatant is separated by decantation to obtain a solid. This solid substance is put into an aqueous solution of diethylene glycol dimethyl ether, stirred for 3 minutes, centrifuged at 500 G for 5 minutes, and the supernatant is separated by decantation to obtain a solid substance. This solid substance is put into diethylene glycol dimethyl ether, stirred for 30 minutes, centrifuged at 1,000 G for 5 minutes, and the supernatant is separated by decantation to obtain a solid substance. The solid substance was dried and pulverized to obtain a double metal cyanide complex catalyst. According to this method, three samples of the composite metal cyanide complex catalyst are synthesized, and the respective samples are referred to as samples 9 to 11.

Comparative Example 2 A slurry solution was obtained by reacting zinc chloride, potassium cobalt cyanate, and diethylene glycol dimethyl ether. The obtained slurry solution is separated by suction filtration to obtain a solid. This solid substance is poured into an aqueous solution of diethylene glycol dimethyl ether having the obtained catalyst weight, stirred for 30 minutes, and then separated by suction filtration to obtain a solid substance. This solid substance is put into diethylene glycol dimethyl ether, stirred for 30 minutes, and then separated by suction filtration to obtain a solid substance. The solid substance was dried and pulverized to obtain a double metal cyanide complex catalyst. Three samples of the composite metal cyanide complex synthesized by this method were synthesized, and these were designated as Samples 12 to 14, respectively.

For the double metal cyanide complex catalysts of Samples 1 to 14 synthesized by the above method, the yields of the catalysts and the results of the propylene oxide ring-opening polymerization reaction are shown below.

Samples 1 to 7 and Sample 8 are experiments performed in accordance with the conditions of the present invention, and both the catalyst yield and the attained molecular weight of ring-opening polymerization of propylene side are high and stable.

Example 2 and Example 3 are apparatuses for continuously synthesizing a double metal cyanide complex catalyst. In particular, Example 3 uses one rotating cylindrical filtration device to improve the stable synthesis of a double metal cyanide complex catalyst, as well as to improve the production capacity of a continuous synthesis device and to reduce labor costs by automation. The effect is large.

On the other hand, in Comparative Example 1 by centrifugation, the yield of the catalyst was low, the dispersion of the performance was large, and the ability as a catalyst was low.

In Comparative Example 2 in which solid-liquid separation is performed by suction filtration, it is also recognized that the yield of the catalyst is lower than that of Samples 1 to 5, and the ability as a catalyst is low. In addition, suction filtration requires 2 to 8 hours per process, and the processing time is longer than that of the centrifugation method.

[Effects of the Invention] The present invention provides a method capable of efficiently producing a double metal cyanide complex catalyst, and has a feature that the activity of the obtained catalyst is uniform and high.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C07F 9/00 9450-4H C07F 9/00 Z 11/00 9450-4H 11/00 Z 13/00 9450-4H 13/00 Z 15/00 9450-4H 15/00 Z C08G 65/04 NQE C08G 65/04 NQE

Claims (3)

(57) [Claims] 1. A method for producing a double metal cyanide complex catalyst using a metal halide aqueous solution, an alkali metal cyanometalate aqueous solution and an organic ligand, wherein the catalyst after the reaction and aging is washed with a washing liquid. , Wherein a rotary cylindrical filter or a rotary disk filter is used. 2. The method for producing a double metal cyanide complex catalyst according to claim 1, wherein the washing liquid is an organic ligand. 3. The method for producing a double metal cyanide complex catalyst according to claim 1, wherein the catalyst is continuously washed.