JP2003096074A - Method for producing alkylene carbonate - Google Patents

Abstract

(57) [Summary] An alkylene carbonate is efficiently produced by a reaction between alkylene oxide and carbon dioxide in an industrially advantageous manner. SOLUTION: An alkylene obtained by reacting alkylene oxide with carbon dioxide using 3-octahedral smectite or alkali metal-containing 3-octahedral smectite as a catalyst to obtain a highly selective and high yield alkylene. Method for producing carbonate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing alkylene carbonate. More specifically, it relates to a method for producing an alkylene carbonate by reacting alkylene oxide and carbon dioxide in the presence of a 3-octahedral smectite and / or an alkali metal-containing 3-octahedral smectite. Propylene carbonate and ethylene carbonate are industrially very important substances as organic solvents, acrylic fiber processing agents, hydroxylethylating agent substances and the like.

[0002]

2. Description of the Related Art Conventionally, a homogeneous catalyst has been mainly known as a method for producing alkylene carbonate by reacting alkylene oxide with carbon dioxide. However, when a homogeneous catalyst is used, it is necessary to separate the reaction mixture and the catalyst, which not only complicates the process but also causes the catalyst to be precipitated during the separation operation and mixed in the product,
There is a problem that a by-product is generated. on the other hand,
A method of using an ion exchange resin as a heterogeneous catalyst is known. U.S. Pat. No. 2,773,070 discloses the use of a quaternary ammonium halide as a catalyst, and a method using a carboxylic acid type cation exchange resin having an alkyl group-substituted ammonium cation as a counter cation as a catalyst. Kaihei 7-206847) is also known. On the other hand, a method using magnesium oxide as a catalyst (T.Yano
et al., Chem. Commun., 1997, 1129-113.
In 0), it is reported that dimethylformamide is used as an organic solvent to increase the activity.

[0003]

As described above, the method for producing alkylene carbonate by reacting alkylene oxide and carbon dioxide is an environmentally friendly method as a method for producing alkylene carbonate, but when a homogeneous catalyst is used. Has a problem in separation of the catalyst, and in a heterogeneous catalyst, when an ion exchange resin is used, the heat resistance is low and it decomposes during the reaction, or the activity is low at a heat resistant temperature or lower. there were. Further, in the case of the magnesium oxide catalyst, it is necessary to use a harmful organic solvent in order to improve the reaction efficiency, and further there is a problem that the step of separating the used organic solvent from the product or the raw material is increased. In the present invention, as a result of intensive studies for many years to solve these problems, a high heat resistance, it is not necessary to use an organic solvent, and an extremely highly active catalyst has been found, leading to the completion of the present invention. It was

[0004]

Means for Solving the Problems That is, the present invention is
A method for producing alkylene carbonate by reacting alkylene oxide with carbon dioxide, comprising: 3-octahedral smectite and / or alkyl metal-containing 3-octahedral smectite and / or 3-octahedral smectite or alkali metal-containing 3 -A method for producing an alkylene carbonate, which comprises reacting in the presence of a synthetic porous body composed of octahedral smectite. By carrying out the present invention, it has become possible to produce alkylene carbonate with extremely high efficiency.

Hereinafter, the method for producing alkylene carbonate according to the present invention will be described in detail. The alkylene oxide used as a raw material in the present invention is represented by the general formula (1)

[0006]

[Chemical 1] (1) (In the above formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different groups, and each of them may be hydrogen or a substituted or unsubstituted alkyl group having 15 or less carbon atoms, aryl Represents a group, an alkenyl group, a cycloalkyl group, an arylalkyl group, and the substituents mentioned here include an amino group, a nitro group, a carbonyl group, a carboxyl group, an alkoxy group,
An acetoxy group, a hydroxyl group, a mercapto group, a sulfone group, a halogen atom and the like. ) Is an alkylene oxide.

Specific examples thereof include alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, and fatty acids such as cyclic oxides having a substituent, cyclohexylene oxide, and cyclohexylene oxides having a substituent. Examples thereof include arylalkyl oxides such as cyclic oxides, styrene oxides, and styrene oxides having a substituent. However, the present invention is not limited to these alkylene oxides, and includes 2 carbon atoms and 1 oxygen atom. A three-membered ring formed of two compounds having at least one in its structural formula, that is, a so-called epoxy compound, can be used for the reaction. In the present invention, one or more of these may be subjected to the reaction. Therefore, the alkylene carbonate produced in the present invention is a carbonate produced from the alkylene oxide, and has the general formula (2)

[0008]

[Chemical 2] (2) (In the above formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different groups, and each have hydrogen or a substituent or an unsubstituted alkyl group having 15 or less carbon atoms, aryl Represents a group, an alkenyl group, a cycloalkyl group, an arylalkyl group, and the substituents mentioned here include an amino group, a nitro group, a carbonyl group, a carboxyl group, an alkoxy group,
An acetoxy group, a hydroxyl group, a mercapto group, a sulfone group, a halogen atom and the like. ) Is a carbonate represented by.

Specific examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, vinyl ethylene carbonate, chloromethyl ethylene carbonate, cyclohexane carbonate, cyclopentane carbonate and styrene carbonate.

The heterogeneous catalyst used in the present invention is 3-
A synthetic porous body composed of octahedral smectite and / or alkali metal-containing 3-octahedral smectite and / or 3-octahedral smectite or alkali metal-containing 3-octahedral smectite.

The 3-octahedral smectite is a known substance, and is classified into hectorite, saponite, and stevensite represented by the following formulas (3) to (5).
W Brindley and G Brown (GWBr
indley and G. Brown), Mineralogica Society Monograph Number Five (Mineralogica)
l Society Monograph No.5), page 170, Mineralogical Societ
y), 1980].

[0012]

Embedded image Hectorite: (M ⁺ _y · nH ₂ O) (Mg _3-y Li _y ) Si ₄ O ₁₀ (OH) ₂ (3)

[0013]

Embedded image saponite ^{_{:( M + xy · nH 2 O}} ) [Mg 3-y (Al, Fe) y]] (Si 4-x Al x) O 10 (OH) 2 (4)

[0014]

[Chemical 5] Stephen Sight: (M ⁺ _2y・ nH ₂ O) (Mg _3-y □ _y ) Si ₄ O ₁₀ (OH) ₂ (5)

[In the above formulas (3) to (5), M, □
And n represent the number of water molecules between the alkali metal, the atom deficiency and the layer, respectively. Hectorite develops a negative charge in the silicate layer by substituting monovalent lithium for divalent magnesium in the octahedral sheet, and develops a negative charge in stevensite due to a partial lack of magnesium. Or, in saponite, it is considered that a negative charge is developed by replacing tetravalent silicon in the tetrahedral sheet with trivalent aluminum. In order to compensate for the negative charge of these silicate layers, cations such as alkali metals enter between the layers, and the structure is electrically neutral. It is believed that water molecules are distributed around the alkali metal between the layers. Moreover, the value of y in the formula (3) is usually 0.2 to 0.5, and is 0.
33, and the value of y in equation (4) is usually
It is near 0, and when the value of y is 0, the value of x is 0.2 to 0.5.
And the ideal composition is 0.33, and the value of y in the formula (5) is usually 0.1 to 0.3, and the ideal composition is 0.17. There is.

Methods for synthesizing these smectites are also known, and hectorite is disclosed in Japanese Examined Patent Publication No. 61-128.
Japanese Patent Publication No. 6-62 regarding saponites
As for the 290 publication and the like, and the site, the Japanese Examined Patent Publication No. 63-6485 publication can be exemplified.
Compounds obtained by substituting the hydroxyl groups of the compounds of formulas (3) to (5) with fluorine have also been synthesized. These hectorites, saponites and stevensites are used in paints, cosmetics, pharmaceuticals,
It is also known that it can be used as a gelling agent and the like.

When hydrothermally synthesizing the above-mentioned 3-octahedral smectite, an alkali metal which forms a smectite structure existing as an exchangeable cation between layers by allowing excess alkali metal to exist in the slurry is Apart from
Alkali metal added in excess enters the interlayer and hydroxide,
It has been found that 3-octahedral smectites obtained between layers in the form of compounds such as chlorides, nitrates, sulphates, phosphates, polyphosphates, halides, oxides are obtained. In the present invention, this substance is simply referred to as alkali metal-containing 3-octahedral smectite.

In the above formulas (3) to (5), Ni, Co, Fe, Zn and C are used instead of magnesium in the octahedral sheet.
It is also possible to synthesize an alkali metal-containing 3-octahedral smectite in which at least one heavy metal ion selected from divalent heavy metal ions such as u, Mn, Pb, and Cd is partially or entirely substituted.

Further, the above divalent heavy metal ion or Mg
The alkali metal-containing 3-octahedral smectite containing ions in the octahedral sheet shows porosity when dried at 50 ° C. or higher, and gives a specific surface area of 100 to 800 m ² / g, and the alkali metal-containing 3-octahedral type. It is also possible to manufacture a porous body or a porous material made of smectite.

Alkali metal-containing 3-octahedral smectite has the same X content as ordinary 3-octahedral smectite.
It can be identified by a linear diffraction method. The value of d (06) is in the range of 1.51 to 1.54Å, and it is recognized that the value of d is further increased when iron is added. In the case of alkali metal-containing 3-octahedral smectite, broad (001) reflection is often observed around 15Å. When it becomes a porous body, the (001) reflection is often observed in the case of delamination. For hk reflection (02,
The peak of (11) is near 4.55Å, and (13,2)
The peak of 0) is recognized around 2.60Å.

However, the above-mentioned 3-octahedral smectite, alkali metal-containing 3-octahedral smectite, or the porous body or porous material composed of the above-mentioned two types of 3-octahedral smectite is used as a catalyst in the production of alkylene carbonate. Little is known about the technology used.

When 3-octahedral smectite or alkali metal-containing 3-octahedral smectite is used as a catalyst and, for example, propylene oxide is reacted with carbon dioxide, the conversion is higher than that of the magnesium oxide catalyst, and the selectivity is further increased. Of the propylene carbonate and the yield of propylene carbonate are increased.

It is recognized that high catalytic activity can be obtained when the amount of alkali metal contained in the catalyst is large. The value of the total alkali metal amount of the sample is obtained by chemical analysis or fluorescent X-ray analysis, and then the cation exchange amount is obtained by measuring the amount of adsorbed methylene blue, and the value of the exchangeable alkali metal amount is calculated. The alkali metal content is easily calculated by subtracting the value of the exchangeable alkali metal amount from the value of the total alkali metal amount of the sample.

It has been confirmed that a catalyst containing a large amount of alkali metal in the catalyst can obtain high catalytic activity. In the present invention, the amount of alkali metal contained between layers is Si = 8.
In the range of 0 to 10, it can be usually used as a catalyst, preferably in the range of 0 to 8, and more preferably 0.
It is preferred to use a catalyst in the range of ~ 6, and most preferably in the range of 0.1-4.

As the alkali metal contained in the catalyst, sodium, lithium, potassium, cesium, ammonium and the like are used. These alkali metals may be used alone or as a mixture of a plurality of the above alkali metals. In addition, Mg, Ni, Co, Fe, Zn, Cu, Mn, Pb, C
d, divalent metals such as Ca, trivalent metals such as Al, or Si
Even if it contains a small amount of a tetravalent metal such as the above, it can be used as the catalyst of the present invention as long as an alkali metal other than the exchangeable alkali metal is included between the layers of the 3-octahedral smectite.

In the present invention, the shape of the catalyst is not particularly limited, but it is desirable that the catalyst is molded in order to facilitate liquid permeability during the reaction and separation of the catalyst after the reaction. Even if it is molded by a general method such as granulation or tableting,
Alternatively, powder of about 100 μm can also be used.

In preparing the catalyst used in the present invention, a suitable binder may be used. The binder is used for the purpose of binding solids to enhance the mechanical strength of the catalyst, and any inorganic or organic substance can be used as long as it does not inhibit the reaction according to the present invention or the catalytic activity. . Further, the binder is not particularly limited as long as it exhibits catalytic activity to the reaction to some extent. Specific examples of the binder used in the present invention include kibushi clay, kaolin, talc, bentonite, silica sol, alumina sol, zirconia sol, and organic polymer.

In preparing the catalyst used in the present invention, 3-octahedral smectite and alkali metal inclusion 3-
The octahedral smectite often exhibits porosity and gives a large specific surface area, so that it is not necessary to use a carrier, but an appropriate carrier may be used for the catalyst. The carrier is used for the purpose of dispersing catalytic active points on the surface thereof to form a catalyst having a high surface area and increasing the mechanical strength of the catalyst.
The carrier is not particularly limited as long as it does not inhibit the reaction or the catalytic activity, and a carrier that exhibits some catalytic activity to the reaction can also be used.

In addition, it is preferable to use a catalyst having a large specific surface area as a catalyst used in the present invention, since a porous material having a large specific surface area tends to obtain high catalytic activity. A catalyst having a specific surface area of 10 to 800 m ² / g is usually used, but it is preferable to use a catalyst of 50 to 700 m ² / g, and more preferably 50 to 600 m.
Desirable to use ² / g of catalyst, and most preferably desirable to use a catalyst in the range of 100 to 500 m ² / g. When the specific surface area is less than 10 m ² / g, sufficient catalytic activity cannot be obtained, which is not preferable. On the other hand, if the specific surface area exceeds 800 m ² / g, the strength of the catalyst will decrease and problems will occur in terms of durability, such being undesirable.

The catalyst used in the present invention does not need to be particularly activated, but it is activated by heat treatment in a gas stream of hydrogen, nitrogen or the like for the purpose of removing surface adsorbates such as water before use. You can also do it. The treatment temperature at that time is usually in the range of 50 ° C to 700 ° C, more preferably in the range of 50 to 200 ° C, and most preferably 5 ° C.
It is in the range of 0 to 150 ° C. When the treatment temperature is lower than 80 ° C, desorption of the adsorbed substance becomes insufficient, which is not preferable. Further, when the treatment temperature exceeds 700 ° C., the catalyst is contained in the 3-
It is not preferable because the structure of octahedral smectite is broken and the surface area is reduced. The activation treatment time is not particularly limited because it depends on the amount of adsorbed substances on the surface and the treatment temperature, but a treatment time of 0.1 to 100 hours is usually used.

Next, an embodiment of the present invention will be described.
In carrying out the present invention, the reaction method can be carried out in any of a batch type, a semibatch type and a continuous flow type. The reaction form is a liquid phase with the catalyst in the solid state,
It can be carried out in any form of a gas phase and a liquid-gas mixed phase. Further, it can be carried out under any condition of normal pressure, increased pressure and reduced pressure. From the viewpoint of reaction efficiency, it is recommended to carry out the liquid phase reaction, but the present invention is not limited thereto. In carrying out the present invention in a liquid state,
When carrying out the reaction at a reaction temperature higher than the boiling point of the raw material or product used, the reaction should be performed under pressure with a gas (eg, argon, nitrogen or helium) that is inert to the reaction raw material and reaction product. You can also

The reaction temperature is not particularly limited, but is preferably 0 ° to 250 ° C., more preferably 30 to 20.
0 ° C. range, and most preferably 50-180 ° C.
Is the range. If the reaction temperature is too low, the reaction rate will be extremely reduced, which will not be an efficient production method.
Extremely high temperatures produce undesired by-products which reduce the selectivity of the desired product and are not economical.

When carrying out the present invention, for example, when carrying out a batch reaction, the reaction time is not particularly limited, but it is preferably several minutes to 30 hours, and more preferably 0.5 to 30 hours. It takes about 20 hours. or,
Fixed bed, if carried out in a continuous flow reaction
The contact time with the catalyst is not particularly limited, but is preferably about 0.1 second to 10 hours, more preferably 1 second to 1 hour. If the contact time is too short, the reaction will not proceed sufficiently, and if the contact time is too long, unnecessary retention will occur and the products, raw materials, etc. may be decomposed.

When carrying out the reaction, the composition of the starting materials alkylene oxide and carbon dioxide is not particularly limited, but for example, in order to achieve a high conversion of alkylene oxide, the molar ratio of carbon dioxide to alkylene oxide is increased. Is preferred (theoretical equivalent is 1 equivalent of carbon dioxide to alkylene oxide). Further, in order to increase the conversion rate of carbon dioxide, it is possible to carry out the reaction by charging alkylene oxide in excess of the theoretical equivalent. In the present invention, the molar ratio of carbon dioxide to alkylene oxide is preferably in the range of 0.05 to 50, and more preferably 0.5 to 25. Of course, the present invention is not limited to these ranges.

In the present invention, when these alkylene oxide and carbon dioxide are charged, alkylene oxide and carbon dioxide are used as raw materials, and no solvent is particularly required, but a solvent (for example, benzene, toluene, xylene, hexane, alcohol) is used. It is safe to use it after diluting it with a solvent, a ketone, etc.). Further, in the present invention, the case where the alkylene oxide is ethylene oxide or propylene oxide is preferable.

In the present invention, the amount of the catalyst used is not particularly limited, but when it is carried out in a batch reaction, for example, it is preferably 0.1 to 0.1% by weight based on the total weight of the alkylene oxide and carbon dioxide as the raw materials. 200%,
More preferably, it is 1.0 to 50%. When the amount of catalyst used is too small, the progress of the reaction is substantially reduced,
If the amount is large, problems such as reduction in efficiency of stirring and contact may occur. After carrying out the present invention, the alkylene carbonate as a product is isolated and purified from the unreacted raw material by a conventional separation, production method such as distillation, extraction, crystallization and the like.

[0037]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present embodiment specifically describes the present invention, and the present invention is not limited to these embodiments.

[0038]

Example 1 400 ml of water was placed in a 1000 ml beaker, and No. 3 water glass (SiO ₂ : 28%, Na ₂ O: 9).
%, Molar ratio 3.22) 86 g is dissolved, and 24 ml of 16N nitric acid solution is added at once with stirring to obtain a silicic acid solution. Then, a solution of 61.6 g of magnesium chloride hexahydrate primary reagent (purity 98%) dissolved in 200 ml of water was added to the silicic acid solution to prepare 2 homogeneous solutions of silicic acid-magnesium salt.
It is added dropwise to 400 ml of a specified aqueous sodium hydroxide solution over 5 minutes while stirring. Immediately after the reaction precipitate obtained was filtered and washed thoroughly with water, 20 ml of an aqueous solution in which 3.1 g of sodium hydroxide was dissolved was added to form a slurry, which was transferred to an autoclave. The reaction was performed at 1.66 MPa and 200 ° C. for 3 hours. After cooling, the reaction product was taken out and dried at 80 ° C, and then crushed with a crusher to obtain Mg containing a large amount of sodium.
A system 3-octahedral smectite sample was obtained. The chemical composition obtained from the chemical analysis values is Si-Mg-Na-K = 8-6.44-2.
It was 81-0.13. The amount of methylene blue adsorbed was 0.
It was 68 meq / g. The value of the cation exchange capacity calculated from the adsorption amount of methylene blue of this sample is (Na + K) = (0.54 + 0.03) = 0.5 for Si = 8.
The value of inclusion (Na + K) between layers is (2.27+
Calculated as 0.10) = 2.37. The number of cations present in the octahedron sheet is 6, so an excess of 0.44
It is considered that Mg exists between the layers in the form of hydroxide, oxide or cation. In addition, the X-ray powder diffraction pattern is similar to that of ordinary smectite, and (35,0
6) The d value of the reflection peak was 1.523Å. The 2% aqueous solution formed a solid gel having strong thixotropy after standing for one day. This sample was dried in a dryer at 110 ° C. for 15 hours and used as a catalyst. The specific surface area obtained from the nitrogen adsorption amount was 110 m ² / g. An attempt was made to produce propylene carbonate from propylene oxide and carbon dioxide using the above catalyst using a stainless steel autoclave having a volume of 50 ml. Propylene oxide 57mmol
(3.31 g) and 0.9 g of catalyst were placed in an autoclave,
Carbon dioxide was introduced at 1 MPa. The mixture was heated to 150 ° C., liquefied carbon dioxide was further introduced to adjust the pressure to 8 MPa, and the reaction was carried out for 15 hours while stirring. After the reaction was completed, the pressure was lowered by cooling to 0 ° C. with ice water. The obtained reaction product mixture was examined by a gas chromatograph measuring device and a mass spectrometer. The value of propylene oxide in the reaction product was 8.2 mmol and the value of propylene carbonate was 46 mmol. The conversion of propylene oxide calculated from the analytical values was 85.6% and the selectivity of propylene carbonate was 94.3%. Therefore, the yield of propylene carbonate was 80.7%.

[0039]

Example 2 Propylene carbonate was produced under the same operating conditions as in Example 1. However, the catalyst amount was 0.2 g. The value of propylene oxide in the obtained reaction product was 27.6 mmol and the value of propylene carbonate was 26.3 mmol. The propylene oxide conversion calculated from the analytical values was 51.6%, and the propylene carbonate selectivity was 89.5%. Therefore, the yield of propylene carbonate was 46.2%. Even if the amount of catalyst was reduced to about 22%, the selectivity to propylene carbonate showed a high value, and the conversion rate also gave a relatively high value.

[0040]

Example 3 Using 57 mmol of ethylene oxide as a raw material instead of 57 mmol of propylene oxide, ethylene carbonate was produced under the same operating conditions as in Example 1. The value of ethylene oxide in the obtained reaction product was 3.2 mmol and the value of ethylene carbonate was 52.
It was 1 mmol. The ethylene oxide conversion calculated from the analytical values was 94.4%, and the ethylene carbonate selectivity was 96.8%. Therefore, the yield of ethylene carbonate was 91.4%.

[0041]

Example 4 400 ml of water was placed in a beaker of 1000 ml, and No. 3 water glass (SiO ₂ : 28%, Na ₂ O: 9).
%, Molar ratio 3.22) 86 g is dissolved, and 24 ml of 16N nitric acid solution is added at once with stirring to obtain a silicic acid solution. Then, a solution of 61.6 g of magnesium chloride hexahydrate primary reagent (purity 98%) dissolved in 200 ml of water was added to the silicic acid solution to prepare 2 homogeneous solutions of silicic acid-magnesium salt.
It is added dropwise to 400 ml of a specified aqueous sodium hydroxide solution over 5 minutes while stirring. Immediately after the reaction precipitate obtained is filtered and washed thoroughly with water, 20 ml of an aqueous solution in which 1.4 g of sodium hydroxide is dissolved is added to form a slurry, and the slurry is transferred to an autoclave. The reaction was performed at 1.66 MPa and 200 ° C. for 3 hours. After cooling, the reaction product was taken out, dried at 80 ° C, and then pulverized with a crusher to obtain Mg containing a large amount of sodium.
A system 3-octahedral smectite sample was obtained. The chemical composition obtained from the chemical analysis values is Si-Mg-Na-K = 8-6.44-2.
It was 28-0.12. The amount of methylene blue adsorbed was 0.
It was 74 meq / g. The value of the cation exchange capacity calculated from the adsorption amount of methylene blue of this sample is (Na + K) = (0.57 + 0.03) = 0.60 for Si = 8.
And the value of inclusion (Na + K) between layers is (1.71+
0.09) = 1.80 is calculated. The number of cations present in the octahedron sheet is 6, so an excess of 0.44
It is considered that Mg exists between the layers in the form of hydroxide, oxide or cation. In addition, the X-ray powder diffraction pattern is similar to the pattern of ordinary smectite, and the (35,0
6) The d value of the reflection peak was 1.523Å. The 2% aqueous solution formed a solid gel having strong thixotropy after standing for one day. The specific surface area of the catalyst obtained by drying this sample at 90 ° C. for 1 hour was 186 m ² / g. Using this catalyst, an attempt was made to synthesize propylene carbonate from propylene oxide and carbon dioxide under the same conditions as in Example 1.
Propylene oxide in the reaction product was 22.3 mmol and propylene carbonate was 29.6 mmol.
The conversion rate of propylene oxide obtained from the chemical composition of the reaction product was 60.9%, the selectivity of propylene carbonate was 85.3%, and the yield of propylene carbonate was 51.9%.

[0042]

Example 5 400 ml of water was put into a beaker of 1000 ml, and No. 3 water glass (SiO ₂ : 28%, Na ₂ O: 9).
%, Molar ratio 3.22) 86 g is dissolved, and 25 ml of 12N hydrochloric acid solution is added at once with stirring to obtain a silicic acid solution. Then, a solution of 61.6 g of magnesium chloride hexahydrate primary reagent (purity 98%) dissolved in 100 ml of water was added to the silicic acid solution to prepare 2 homogeneous solutions of silicic acid-magnesium salt.
It is added dropwise to 320 ml of 0% ammonia water over 5 minutes while stirring. Immediately after the reaction precipitate obtained was filtered and washed thoroughly with water, 20 ml of an aqueous solution in which 1.4 g of sodium hydroxide was dissolved was added to form a slurry and transferred to an autoclave.
The reaction was carried out at 1.66 MPa and 200 ° C. for 3 hours. After cooling, the reaction product was taken out, dried at 80 ° C., and then pulverized with a crusher to obtain a Mg-based 3-octahedral smectite sample.
The chemical composition obtained from the chemical analysis values is Si-Mg-Na-K = 8-
It was 6.17-0.63-0.02. The amount of methylene blue adsorbed was 0.84 meq / g. The cation exchange capacity calculated from the amount of methylene blue adsorbed in this sample is as follows: Si = 8 (Na + K) = (0.62 + 0.0
2) = 0.64, the value of inclusion (Na + K) between layers was calculated to be 0.01, and it is considered that most of the alkali metals are not included in the layers. The number of cations present in the octahedron sheet is 6, so an excess of 0.49
It is considered that Mg exists between the layers in the form of hydroxide, oxide or cation. The X-ray powder diffraction pattern was similar to that of ordinary smectite, and the d value of the (35,06) reflection peak was 1.523Å. The 2% aqueous solution formed a solid gel having strong thixotropy after standing for one day. This sample was dried at 110 ° C. for 15 hours to obtain a catalyst. The specific surface area obtained from the nitrogen adsorption amount was 372 m ² / g. Using this catalyst, an attempt was made to synthesize propylene carbonate from propylene oxide and carbon dioxide under the same conditions as in Example 1. 20.4 ml of propylene oxide and 20.4 ml of propylene carbonate in the reaction product
Met. The conversion rate of propylene oxide obtained from the chemical composition of the reaction product was 64.2%, the selectivity of propylene carbonate was 55.7%, and the yield of propylene carbonate was 35.8%.

[0043]

Comparative Example 1 An attempt was made to synthesize propylene carbonate from propylene oxide and carbon dioxide in the same manner as in Example 1 except that commercially available magnesium dioxide was used as a catalyst. The specific surface area of this catalyst was 14 m ² / g. It was 39.5 mmol of propylene oxide and 15.3 mmol of propylene carbonate in the reaction product. From the chemical composition of the reaction product, the conversion of propylene oxide was 30.
7%, the selectivity of propylene carbonate was 87.4%, and the yield of propylene carbonate was 26.8%.

[0044]

Example 6 86 g of No. 3 water glass was dissolved in 200 ml of distilled water, and 180 ml of a 2N aqueous sodium hydroxide solution was added to obtain an alkaline solution A. An acidic solution B was prepared by dissolving 64.2 g of nickel chloride hexahydrate primary reagent in 300 ml of distilled water. While stirring Solution B in Solution A, 5
The mixture was added dropwise over 1 minute and stirred for 1 hour. The obtained reaction complex precipitate was filtered, washed thoroughly with water, transferred to a beaker, and 20 ml of water in which 0.72 g of lithium hydroxide primary reagent was dissolved was added to obtain a slurry. This slurry was transferred to an autoclave having an internal volume of 1 liter, and the slurry was 1.66 MPa,
The reaction was carried out at 200 ° C. for 2 hours. After cooling, the reaction product was taken out, dried at 80 ° C., and then pulverized to obtain Ni-containing hectorite. The chemical composition obtained from the chemical analysis values is Si-Ni-Li-Na.
= 8-5.61-0.39-0.97. The amount of methylene blue adsorbed was 0.76 meq / g. The cation exchange capacity calculated from the amount of methylene blue adsorbed in this sample is Si
= 8 for 0.71 and the value of Na included between layers is 0.
Calculated as 26. The X-ray powder diffraction pattern was similar to the pattern of ordinary hectorite, and the d value of the (35,06) reflection peak was 1.522Å. This sample dispersed in water to form a thixotropic green translucent solid gel. This sample was dried in a dryer at 80 ° C. for 1 hour to obtain a catalyst. The specific surface area of the catalyst obtained from the nitrogen adsorption measurement was 302 m ² / g. Example 1 using this catalyst
An attempt was made to synthesize propylene carbonate from propylene oxide and carbon dioxide under the same conditions as in. It was 34.6 mmol of propylene oxide and 21.7 mmol of propylene carbonate in the reaction product. Propylene oxide conversion obtained from chemical composition of reaction product 39.3
%, The propylene carbonate selectivity was 96.9%, and the propylene carbonate yield was 38.1%.

[0045]

Example 7 200 ml of water was placed in a 1000 ml beaker and water glass No. 3 (SiO ₂ : 28%, Na ₂ O: 9) was added.
%, Molar ratio 3.22) 86 g was dissolved, and 200 ml of 2N aqueous sodium hydroxide solution was further added to obtain an alkaline solution A. Further, an acidic liquid B was prepared by dissolving 71.3 g of nickel chloride hexahydrate primary reagent in 200 ml of distilled water.
The solution B was added dropwise to the solution A with stirring for 5 minutes and further stirred for 1 hour. The resulting reaction complex precipitate is filtered,
After thoroughly washing with water, 30 ml of 10% hydrofluoric acid solution was added to obtain a slurry. This slurry was transferred to an autoclave with an internal volume of 1000 ml, 1.66 MPa, 200 ° C.
And reacted for 2 hours. After cooling, the reaction product is taken out, and 5
After drying at 0 ° C., it was pulverized to obtain a fluorine-containing Ni3-octahedral smectite porous body. The chemical composition obtained from the chemical analysis values was Si-Ni-Na-F = 8-6.17-0.75-3.
The amount of methylene blue adsorbed was 0.08 meq / g. The value of cation exchange capacity calculated from the amount of methylene blue adsorbed in this sample is 0.09 for Si = 8, and the value of Na contained between layers is calculated to be 0.66. Further, the X-ray diffraction pattern was similar to that of smectite, but (001) was delaminated and was not clearly observed, and the d value of the (35,06) reflection peak was 1.524Å. This sample did not disperse in water but precipitated. This sample is placed in a drier at 50 ° C for 5
The specific surface area of the catalyst obtained by drying for 3 hours is 305 m ² / g
Met. Using this catalyst, an attempt was made to synthesize propylene carbonate from propylene oxide and carbon dioxide under the same conditions as in Example 1. 25.9 mmol of propylene oxide and 28.0 propylene carbonate in the reaction product
It was mmol. The propylene oxide conversion rate obtained from the chemical composition of the reaction product was 54.6%, the propylene carbonate selectivity was 90.0%, and the propylene carbonate yield was 49.1%.

[0046]

Example 8 86 g of No. 3 water glass in 200 ml of distilled water
Was dissolved and 200 ml of a 2N aqueous sodium hydroxide solution was added to obtain a solution A. Further, a solution B was obtained by dissolving 71.3 g of nickel chloride hexahydrate primary reagent in 300 ml of distilled water.
The solution B was added dropwise to the solution A with stirring for 10 minutes and further stirred for 1 hour. The reaction complex precipitate obtained was filtered, washed thoroughly with water, then transferred to a beaker, and 20 ml of water was added.
Was added to form a slurry. This slurry was transferred to an autoclave having an internal volume of 1 liter, and the volume was 1.66 MPa, 200
The reaction was carried out at 0 ° C for 2 hours. After cooling, the reaction product was taken out, dried at 80 ° C., and then pulverized to obtain a Ni-based synthetic porous body having a high Na content. The chemical composition obtained from the chemical analysis values is Si-Ni.
-Na = 8-5.90-1.40, and the X-ray powder diffraction diagram shows that when measured using a copper tube and a nickel filter, it was broad at around 2θ = 20 °, 35 ° and 60 °. Diffraction was observed. These were similar to the diffraction pattern of smectite having a similar composition, but the diffraction line of 001 reflection observed in smectite was not observed, and it was recognized as a low crystalline smectite-like substance. Considering the chemical composition together, N consisting of Ni-based stevensite-like substances
It is considered to be a synthetic porous material having a high a content. The pore characteristics obtained from nitrogen adsorption were a specific surface area of 400 m ² / g, a pore volume of 0.239 ml and an average pore diameter of 2.4 nm. The amount of methylene blue adsorbed on this sample was 0.64 meq / g, and it was not dispersed at all in water. The value of the cation exchange capacity calculated from the amount of methylene blue adsorbed in this sample is 0.62 for Si = 8, and the value of Na contained between layers is calculated to be 0.78. Place the synthetic porous body in a dryer 1
It was dried at 10 ° C. for 15 hours to obtain a catalyst. Using this catalyst, an attempt was made to synthesize propylene carbonate from propylene oxide and carbon dioxide under the same conditions as in Example 1. The amount of propylene oxide in the reaction product was 31.8 mmol and the amount of propylene carbonate was 21.3 mmol. The conversion rate of propylene oxide obtained from the chemical composition of the reaction product was 44.2%, and the selectivity of propylene carbonate was 84.
The yield was 5% and the yield of propylene carbonate was 37.4%.

[0047]

According to the present invention, alkylene carbonate can be produced in high yield from alkylene oxide and carbon dioxide by using 3-octahedral smectite or alkali metal-containing 3-octahedral smectite as a catalyst. it can. Since the catalyst used in the reaction is a solid, it can be easily separated from the product, and the alkylene carbonate can be purified by distillation or solvent extraction. Therefore, industrially important alkylene carbonate can be efficiently produced from carbon dioxide by an environmentally friendly process and is extremely useful.

Continued front page    (72) Inventor Balchandra Mahadeo Banague             Hokkaido, Sapporo, Kita-ku, Kita 13-jo Nishi 8-chome, Hokkaido             Department of Materials Engineering, Graduate School of Engineering, University (72) Inventor Masayuki Shirai             3-16-10, Saiwaicho, Miyagino-ku, Sendai City, Miyagi Prefecture             No. 103 (72) Inventor Kazuo Torii             1-19-13 Nishi-Nakada, Taihaku-ku, Sendai City, Miyagi Prefecture

Claims (6)

[Claims] 1. A compound represented by the general formula (1): (1) (In the above formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different groups, and each of them may be hydrogen or a substituted or unsubstituted alkyl group having 15 or less carbon atoms, aryl Represents a group, an alkenyl group, a cycloalkyl group, an arylalkyl group, and the substituents mentioned here include an amino group, a nitro group, a carbonyl group, a carboxyl group, an alkoxy group,
An acetoxy group, a hydroxyl group, a mercapto group, a sulfone group, a halogen atom and the like. ) Is reacted with an alkylene oxide represented by the general formula (2) to give a compound represented by the general formula (2): (2) (In the above formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different groups, and each have hydrogen or a substituent or an unsubstituted alkyl group having 15 or less carbon atoms, aryl Represents a group, an alkenyl group, a cycloalkyl group, an arylalkyl group, and the substituents mentioned here include an amino group, a nitro group, a carbonyl group, a carboxyl group, an alkoxy group,
An acetoxy group, a hydroxyl group, a mercapto group, a sulfone group, a halogen atom and the like. ) In the method for producing an alkylene carbonate represented by the formula (3), at least one of a 3-octahedral smectite and / or an alkali metal-containing 3-octahedral smectite is used as a catalyst. 2. The method for producing an alkylene carbonate according to claim 1, wherein hectorite and / or stymbunsite is used as the 3-octahedral smectite. 3. The method for producing an alkylene carbonate according to claim 1, wherein an alkali metal-containing hectorite and / or an alkali metal-containing stimbunsite is used as the alkali metal-containing 3-octahedral smectite. 4. The method for producing an alkylene carbonate according to claim 1, wherein a synthetic porous body comprising 3-octahedral smectite and / or alkali metal-containing 3-octahedral smectite is used. 5. A part or all of magnesium in the octahedral sheet is replaced with at least one heavy metal selected from divalent heavy metal ions such as Ni, Co, Fe, Zn, Cu, Mn, Pb and Cd 3. -A octahedral smectite and / or an alkali metal-containing 3-octahedral smectite and / or a synthetic porous body comprising the above 3-octahedral smectite or an alkali metal-containing 3-octahedral smectite The method for producing an alkylene carbonate according to any one of claims 1 to 4. 6. The production of alkylene carbonate according to claim 1, wherein the alkylene oxide is propylene oxide and / or ethylene oxide and the alkylene carbonate is propylene carbonate and / or ethylene carbonate. Method.