JP2001321673A - Molded microporous material catalyst for manufacturing dialkanol amine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a catalyst having excellent strength and selectivity of dialkanol amines. SOLUTION: The molded microporous materials catalyst for manufacturing a dialkanol amine is prepared by molding a composition containing microporous material powder and a laminar clay mineral and has 0.1-20% powdering degree. Excellent strength and excellent selectivity of dialkanol amines are attained and the production of impurities is reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a molded microporous material catalyst used for producing dialkanolamine by reacting ammonia and alkylene oxide, a method for producing the catalyst, and production of dialkanolamine using the catalyst. About the method.

[0002]

2. Description of the Related Art As a method for producing an alkanolamine by aminating an alkylene oxide with ammonia, industrially, ethylene oxide and a concentration of 20 to 40% by mass are used.
To produce ethanolamines by reacting with ammonia water.

[0003] In this method, three types of monoethanolamine, diethanolamine and triethanolamine are produced. However, as the demand for triethanolamine is decreasing, a production method for suppressing the production of triethanolamine is required. . For this reason, the amount of ammonia is adjusted to about 3 to 5 mol per mol of ethylene oxide, and the reaction is carried out under a condition of a large excess of ammonia to suppress the production of triethanolamine. However, the selectivity of triethanolamine is still high. 10 to 20% by mass or more,
The selectivity of diethanolamine is 40% by mass or less.
In addition, when water is used as a catalyst, such as ammonia water, a water recovery operation is required, which makes it difficult to produce ethanolamines at low cost.

On the other hand, in a system without water, the alkylene oxide hardly reacts with ammonia, and the presence of a catalyst is indispensable. As a catalyst for producing alkanolamines by amination of alkylene oxide with ammonia, for example, organic acids, inorganic acids, homogeneous catalysts such as ammonium salts, ion exchange resins in which sulfonic acid groups are fixed to the resin, or acid activation The use of clay catalysts, various zeolite catalysts, and also rare earth supported catalysts has been proposed. However, when a homogeneous catalyst such as an organic acid or an inorganic acid is used, a separation operation between the product alkanolamine and the catalyst is required, and in a homogeneous system in which the phase of the catalyst and the product is the same,
It is difficult to produce inexpensive and simple alkanolamines.

[0005] From such circumstances, as one of the methods for simplifying the operation of separating the product from the catalyst and improving the catalytic activity to improve the yield of alkanolamine, a homogeneous acid catalyst is immobilized. Methods have been developed for use.

[0006] For example, as a catalyst in which a homogeneous acid catalyst is immobilized, it is known that a microporous material in which ZSM-5, which is a kind of zeolite, is replaced with a rare earth metal provides high performance.

[0007] For example, Japanese Patent Application Laid-Open No. H11-322681 discloses an invention relating to a catalyst for dialkanolamine production using a catalyst comprising a microporous material and having excellent dialkanolamine selectivity.

The catalyst described in the publication is a microporous material having an effective pore diameter of 0.45 nm to 0.8 nm, or a catalyst obtained by ion-exchanging a microporous material with a rare earth element. It is said that dialkanolamine can be produced with high selectivity.

On the other hand, microporous material powders are generally used for various purposes such as paper fillers, soil conditioners, adsorbents, catalysts and their carriers, and are often used in powder form. In some cases, an appropriate shape such as spherical, columnar, granular, or honeycomb shape is required. In particular,
When used as a reaction catalyst in a fixed bed, it is necessary to form the catalyst into granular or honeycomb shapes.

[0010] However, the microporous material powder itself has no plasticity at all, and even if it is mixed with water, a plastic such as clay cannot be obtained.
Further, the microporous material powder does not have sinterability, and even if it is fired at a high temperature, a target zeolite sintered compact cannot be obtained. In the above publication, a zeolite molded article is manufactured in the examples, but the catalyst activity is evaluated, but there is no disclosure about the method for preparing the molded article, the moldability, and the strength of the molded article. Conventionally, in order to plastically mold a microporous material powder to prepare a target microporous material molded body, an inorganic binder such as an inorganic sol such as bentonite or kaolin, an inorganic sol such as colloidal silica, or a cellulosic organic material is used. A binder is blended to prepare a microporous material plastic molded article. However, a catalyst for producing dialkanolamine with a high selectivity without using a molding catalyst having sufficient strength for practical use, and the binder used for molding does not adversely affect the catalytic activity, and a method for producing the catalyst ,
It was not known until now.

[0011]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and has a practically sufficient strength, has a small amount of by-products, and has a small number of dialkanolamines. An object of the present invention is to provide a molded microporous material catalyst having excellent properties and a method for producing the catalyst.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by adding a layered clay mineral to a microporous material powder, a microporous material having plasticity in an aqueous system has been obtained. A molding mixture can be obtained, which can be molded into an arbitrary shape, and a molded catalyst obtained by drying and calcining at a specific temperature range is extremely useful as a catalyst for producing dialkanolamine by reacting ammonia with alkylene oxide. It shows excellent selectivity and low generation of impurities.
The present invention has been completed.

The above object is achieved by the following (1) to (5).

(1) A catalyst for producing a dialkanolamine represented by the following formula (II) by reacting ammonia with an alkylene oxide represented by the following formula (I):
The molding for producing dialkanolamine, wherein the catalyst is a catalyst obtained by molding a composition containing a microporous material powder and a layered clay mineral, and the degree of powdering of the catalyst is 0.1 to 20%. Microporous material catalyst.

[0015]

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[0016]

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(2) The molded microporous material catalyst for producing dialkanolamine according to the above (1), wherein the mass ratio between the microporous material powder and the layered clay mineral is 95/5 to 50/50.

(3) A composition containing the microporous material powder and the layered clay mineral is molded,
The method for producing a catalyst according to the above (1) or (2), which is obtained by performing a calcination treatment in a temperature range of from 1C to 1000C.

(4) The microporous material powder as described in (3) above, wherein the microporous material powder is obtained by supporting 0.1 to 10% by mass of a rare earth element on a metallosilicate and then heat-treating the same at 400 to 1000 ° C. A method for producing a catalyst.

(5) An alkylene oxide represented by the following general formula (I) and ammonia are reacted in a liquid phase in the presence of an inorganic catalyst in the presence of the catalyst described in the above (1) or (2). A method for producing a dialkanolamine represented by the following formula (II):

[0021]

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[0022]

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[0023]

DETAILED DESCRIPTION OF THE INVENTION A first aspect of the present invention is a catalyst for producing a dialkanolamine represented by the following formula (II) by reacting ammonia with an alkylene oxide represented by the following formula (I). Is a catalyst obtained by molding a composition containing a microporous material powder and a layered clay mineral, and the powdered degree of the catalyst is 0.1 to 20%. It is a material catalyst.

[0024]

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[0025]

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Here, α and β used in the present invention are defined as follows.

First, the reaction between ammonia and alkylene oxide is a sequential reaction, and the following reactions occur sequentially. In the formula, AO represents an alkylene oxide, MAA
Represents monoalkanolamine, DAA represents dialkanolamine, and TAA represents trialkanolamine.

[0028]

(Equation 1)

Assuming that the reactions (1), (2) and (3) are first-order with respect to the raw material concentrations of the alkylene oxide, ammonia and amine, the reaction rate constants of the respective reaction formulas are k ₁ and k ₁ Assuming that k ₂ and k ₃ , the respective reaction rates r ₁ , r ₂ and r ₃ are expressed as follows.
[] Is the concentration of the compound.

[0030]

(Equation 2)

Thus, assuming that the reaction rate constant between monoalkanolamine and alkylene oxide is 1, the reaction rate constant α between ammonia and alkylene oxide and the reaction rate constant β between dialkanolamine and alkylene oxide are α = k ₁ / k ₂ and β = k ₃ / k ₂ .

If the mole fractions of NH ₃ , MAA, DAA, and TAA in the reaction solution when the conversion of the alkylene oxide is 100% are x, y, z, and u, respectively, the reaction rate equation (4) To (6) and the material balance equation (x + y + z + u =
From 1), α and β are obtained as solutions of the following nonlinear equations (i) and (ii).

[0033]

(Equation 3)

[0034]

(Equation 4)

These non-linear equations can be solved by a usual numerical solution method, whereby the values of α and β can be obtained.

The present inventors have studied the reaction for producing dialkanolamine from an alkylene oxide and ammonia in the liquid phase in the presence of an inorganic catalyst. As a result, (i) the α was 0.10 or more, and Is 0.10 to 1.0, more preferably 0.10 to 0.5, and still more preferably 0.1 to 0.5.
10-0.30, and (ii) reacting under conditions such that the β is 0.5 or less, preferably 0.3 or less, more preferably 0.2 or less, so that the dialkanolamine can be efficiently produced. It has been found that it can be selectively manufactured.
If α is less than 0.10, the efficiency of the production of monoalkanolamine as the first product must be increased by increasing the molar ratio of ammonia to alkylene oxide as the raw material.

The reason why β is 0.5 or less is that β is preferably 0.5 or less in order to efficiently produce dialkanolamine by suppressing the by-product of triethanolamine. Because.

Further, it is difficult to separate impurities of glycol ethers in which one molecule of an alkylene oxide is added to a hydroxyl group of triethanolamine, and it is not preferable to produce impurities in a certain amount or more because the quality of trialkanolamine is deteriorated. In the present invention, the amount of production is set to 5% or less of trialkanolamine, more preferably 4% or less, and further preferably 3% or less. This achieves the production of high quality diethanolamine in combination with the improvement in diethanolamine selectivity.

The degree of pulverization of the catalyst of the present invention is 0.1 to 20%.
And more preferably 0.1 to 10%. If the degree of powdering exceeds 20%, the catalyst may collapse during the reaction and a continuous reaction may not be possible.
%, The presence of a large amount of an inorganic binder necessary for forming the microporous material is not preferable because the reaction activity is greatly reduced as compared with the original activity of the zeolite. Further, the selectivity of the target product may be significantly reduced in some cases.

The following catalyst and the second production method of the present invention are used as a catalyst and the production method for the production amount and the degree of pulverization of the alkylene oxide one molecule adduct of α, β, trialkanolamine. is there.

That is, the mass ratio between the microporous material powder and the layered clay mineral is 95/5 to 50/50.
The molded microporous material catalyst for dialkanolamine production according to claim 1, wherein the composition containing the microporous material powder and the layered clay mineral is molded, and then molded at a temperature in the range of 500 ° C to 1000 ° C. A method for producing the catalyst, which is obtained by calcining,
Alternatively, the microporous material powder allows the metallosilicate to support 0.1 to 10% by mass of a rare earth element,
Next, a method for producing the above catalyst, which is obtained by heat treatment at 400 to 1000 ° C.

The present invention relates to a microporous material which provides high performance as a catalyst used in the production of dialkanolamine by reacting ammonia with an alkylene oxide, and to a microporous material molded body without deteriorating its original catalytic performance. It is a manufacturing method obtained as.

The microporous material used in the present invention is a crystal having pores of a uniform diameter, and includes a metallosilicate type and an aluminophosphate type.

As the aluminophosphate type,
Aluminophosphate (ALP0), metalloaluminophosphate (MAPO), and silicoaluminophosphate (SAPO) are known, and any of them can be used.

Examples of the metallosilicate include those in which a metal atom (= T atom) other than silicon, such as aluminosilicate, gallosilicate, ferrisilicate, borosilicate, or zincosilicate, is Al, Ga, Fe, B, Zn, or the like. . The atomic ratio of silicon to T atoms (Si / T) is preferably in the range of 5 to 300, more preferably 7 to 20.
0, most preferably in the range of 10-100. T
If there are too many atoms, that is, the Si / T atomic ratio is small,
The structure becomes unstable, which is not preferable. Conversely, if the number of T atoms is too small, that is, if the Si / T atomic ratio is too large, the number of active sites is too small and sufficient activity cannot be obtained, which is not preferable. In the present invention, in order to secure a sufficient ion exchange rate, those exceeding 5 are particularly preferable.

As the types of metallosilicates, MFI, MEL, BEA, MOR, MT can be represented by a framework topology code showing the structure of the International Zeolite Society.
Although W and TON are mentioned, MFI or MEL is preferable from the viewpoint of the selectivity of dialkanolamine.

One having an MFI structure is ZSM-5, which is known as a synthetic high silica zeolite.
As a material having a MEL structure, there is ZSM-11, which is also known as a synthetic high silica zeolite.
MFI and MEL have very similar structures, and there are cases where both structures are included in one crystal due to intergrowth, but both can be used in the present invention.

The metallosilicate used in the present invention can be prepared by a known method. For example, it can be usually prepared by a so-called hydrothermal synthesis method in which a silica source / T atom source and a structure indicator are dispersed in water and heated in an autoclave. The gel obtained by concentrating and drying the silica source / T atom source and the structure indicator is brought into contact with water vapor in an autoclave,
It can also be prepared by a so-called dry gel method. Note that a commercially available zeolite such as ZSM-5 or ZSM-11 can be used.

Since the reaction between the alkylene oxide and the amine occurs mainly in the pores, the effective micropore diameter of the microporous material is preferably 0.45 to 0.8 nm in order to exhibit selectivity. Is 0.
5 to 0.7 nm.

As an example of such a microporous crystal, MFl, MEL, M can be expressed by a framework topology code showing the structure of the International Zeolite Society.
OR, TON, MTW, ATO, AFR, BEA and the like. Among them, from the viewpoint of the selectivity of diethanolamine, ZSM-5 (which belongs to MFl in the framework topology code showing the structure of the International Zeolite Society) and ZS
M-11 (a framework topology code representing the structure of the International Zeolite Society and belonging to MEL) is preferred.

The range of the effective micropore diameter is such that the reaction material does not easily diffuse into the pores and the activity does not decrease, and conversely trialkanolamine does not form in the pores. This is preferable because the selectivity of dialkanolamine does not decrease.

X-type and Y-type zeolites having large cavities inside (both belong to FAU when represented by the framework topology code showing the structure of the International Zeolite Society) have large pores because large cavities can be generated in these cavities. The shape selectivity expected from the pore diameter at the entrance and exit is rarely exhibited.

The reaction outside the pores is expected to have shape selectivity.
Since it is not possible to inactivate the outer surface of the primary crystal particles,
Is preferred. As a method of passivation,
Teaming treatment, silicon tetrachloride treatment, alkoxysilane treatment
And the like. For metallosilicate synthesis,
If the ion exchange site contains alkali metal ions,
I have. In that state, there is almost no acidity and the activity is low. So
Here, alkali metal ions are converted to protons and ammonium ions.
Ion exchange with cations, polyvalent cations, especially rare earth elements, etc.
It is desirable to increase the activity. In addition, usually in hydrothermal synthesis
Means that the alkali metal in the generated metallosilicate
Since it is included as ON, once NH _ThreeIon by Ion
Exchange and then firing at high temperature
Can be replaced with a mold.

In the catalyst of the present invention, it is preferable to use a catalyst obtained by heat-treating a microporous material with 0.1 to 10% by mass of a rare earth element supported thereon.
In particular, inorganic ion exchangers such as metallosilicates
The cation at the ion exchange site can be exchanged with another cation, which can be expressed by the ion exchange rate of the rare earth element to the ion exchangeable site of the metallosilicate, which is conventionally at most 5%. Met. Since this exchange rate is determined by the ion exchange equilibrium, it is necessary to use a large excess of the exchange metal-containing solution to achieve a high exchange rate in one operation, or to repeat the ion exchange operation several times. there were. However, exchange equilibrium is disadvantageous for multivalent metal ions having a large ionic radius such as rare earth elements.

The present inventors have conducted intensive studies on a method for increasing the ion exchange rate, which is usually difficult, and found that, surprisingly, the rare earth element and the metallosilicate were added in an amount of 0.1 to 10% by mass instead of ion exchange in a solution. % And then heat treatment at a high temperature of 400 ° C. to 1000 ° C., preferably 500 ° C. to 900 ° C., to obtain a high ion exchange rate or a high loading. Further, in a layered clay mineral such as montmorillonite, a rare earth element is easily entrapped in the layered structure to improve the loading rate, but increasing the loading rate does not improve the dialkanolamine selectivity. On the other hand, when a rare earth element is supported on a metallosilicate, it exhibits excellent selectivity as a catalyst for the dialkanolamine formation reaction by the reaction between ammonia and an alkylene oxide, and has a long life.

In the catalyst of the present invention, the method for heat-treating the microporous material with 0.1 to 10% by mass of a rare earth element supported thereon is not limited, but is generally performed in the following procedure.

For example, after mixing a microporous material with a solid rare earth or rare earth element-containing compound,
This is a method in which the mixture is pulverized and mixed with a pulverizer such as a mortar or a ball mill and heat-treated.

Further, a microporous material powder is charged into a solution in which a rare earth element or a rare earth element-containing compound is dissolved in a solvent such as water and dispersed, and the solvent is removed by evaporation and drying to allow the microporous material to carry the rare earth compound. Then, a heat treatment method may be used. The rare earth element to be supported in the present invention is preferably 0.1 to 10% by mass as a rare earth element,
Particularly preferably, it is 0.1 to 5% by mass. Depending on the content of the rare earth element, the selectivity of dialkanolamine is different. If it is less than 0.1% by mass, the selectivity of dialkanolamine is inferior. On the other hand, even if it exceeds 10% by mass, the selectivity does not change, and This is because preparation of the catalyst becomes difficult.

Rare earth elements preferable for use in the present invention include lanthanum, cerium, scandium, yttrium and alkaline earth metals. Among them, lanthanum and yttrium are preferred in terms of dialkanolamine selectivity. , Cerium, calcium and strontium are preferred.

Compounds that can be used to support rare earth elements include inorganic salts of rare earth elements such as halides, nitrates and sulfates, and oxides, hydroxides, oxalates and acetates of rare earth elements. And the like. Among these, compounds that can be decomposed or washed away by heat treatment and do not leave unnecessary components in the catalyst are preferable. Such compounds include lanthanum nitrate, lanthanum acetate, lanthanum oxalate, and the like.

In the present invention, the rare earth element or the rare earth element-containing compound which has been brought into contact with the microporous material in order to support the rare earth element on the microporous material, and which is left unsupported is a solvent such as water. By washing or by physical operation such as vibration.

The temperature of the heat treatment after supporting the rare earth element is preferably 400 to 1000 ° C., more preferably 500 to 1000 ° C., and particularly preferably 500 to 1000 ° C. because the rare earth element ions need to diffuse into the microporous material.
900 ° C. If the temperature is lower than 400 ° C., the diffusion of rare earth element ions is not sufficient. On the other hand, if the temperature is higher than 1000 ° C., the crystal structure of the catalyst is undesirably collapsed.

The time of the heat treatment is not particularly limited, but is usually 1 to 100 hours. If the treatment is performed at a high temperature for a long time, the crystal of the microporous material may be broken. Therefore, when the treatment temperature is relatively high, the treatment time is preferably shorter. In addition, at low temperatures, rare earth elements may not diffuse sufficiently. Therefore, when the processing temperature is relatively low, the processing time is preferably longer.

Generally, it is considered that the rare earth element is ion-exchanged at an exchangeable site in the microporous material by contact with the microporous material, but the possibility that the rare earth element is physically supported is undeniable. For this reason, in the present invention, the amount of the rare earth element carried is specified from the actual preparation of the catalyst. However,
When a rare earth element ion-exchanges only at exchangeable sites in a microporous material, this can be converted into an ion-exchange rate. For example, the ion exchange rate in the case of metallosilicate is defined by the following equation.

[0065]

(Equation 5)

Here, the number of exchangeable sites in the metallosilicate is generally proportional to the number of T atoms in the silicate × (valence of 4-T atoms) unless T atoms exist outside the lattice.
For example, the number of exchangeable sites of an H-ZSM-5 zeolite having an Si / Al atomic ratio of 28 is determined as follows.

In this case, the composition formula is (HAIO ₂ ) (Si
O ₂ ) ₂₈ and the formula weight is 1742.3. Therefore, the number of sites is 1 mol / 1742.3 g = 0.574 m
mol / g. An exchange rate of 10% with rare earth element lanthanum (trivalent) ions means that the valence of lanthanum is trivalent, so that 0.574 × (10/100) × (1/3) =
0.0191 mmol / g will be exchanged.

In the present invention, the above-mentioned microporous material powder is used, and the powder can be prepared by a conventionally known method.

The layered clay mineral used in the catalyst of the present invention is:
This is to add plastic moldability to the microporous material powder and to maintain strength even after molding. Various kinds of layered clay minerals can be used as long as they can impart plastic moldability in an aqueous system. For example, kaolinite group minerals as 1: 1 layered clay minerals,
Specific examples include kaolinite, halloysite, taitskite, lizardite, amesite, and the like. In addition, as the 2: 1 layered clay mineral, a pyrophyllite group mineral (eg, pyrophyllite), a smectite group mineral (eg, montmorillonite, saponite, bentonite, stevensite, hectorite, etc.), and a vermiculite group mineral (eg, vermiculite) are used. . These may be used alone or as a mixture of two or more. In the present invention, among these layered clay minerals, montmorillonite, which is a smectite group mineral, is preferable, and a salt exchanged with an arbitrary metal can be used. For example, H salt (acid clay, activated clay), Na salt (Na montmorillonite), Ca salt (Ca montmorillonite) and the like are commercially available and easily available.

The mixing ratio of the microporous material powder and the layered clay mineral can be set to an arbitrary amount, but the mass ratio of the microporous material powder to the layered clay mineral is 95.
/ 5 to 50/50 is preferable, and more preferably 1/50.
The range is 0/90 to 40/60. When the amount of the layered clay mineral is increased beyond this range, the presence of the layered clay mineral greatly reduces the properties of the microporous material per unit mass, for example, the reaction activity, compared to the activity of the single microporous material, and the desired production The selectivity of the product may be significantly reduced. Conversely, if the amount of the layered clay mineral is reduced below this range, the strength required for the catalyst cannot be secured.

Any method can be used for mixing the microporous material powder and the layered clay mineral to obtain a microporous material molding mixture having plastic moldability in an aqueous system. For example, a molding mixture can be obtained by putting a microporous material powder, a layered clay mineral, and a predetermined amount of water into an automatic mortar or kneader and mixing for a predetermined time.

When the microporous material powder and the layered clay mineral are mixed, an organic molding aid or an inorganic reinforcing material may be added. By adding an organic molding aid, it is possible to impart higher plastic moldability to the microporous material powder, and it is possible to obtain a microporous material molded body more easily by molding, drying, and firing. it can. The amount of these components is 0.1 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, per 100 parts by mass of the composition containing the microporous powder and the layered clay mineral.
Parts by weight.

As the organic molding aid, although it depends on the microporous material powder used, for example, a cellulosic compound, a polyvalent hydroxy compound, a polyvinyl polymer,
Highly water-absorbing resins and the like are preferably used. Further, a microporous material molded body having higher mechanical strength can be obtained by adding, reinforcing, and drying an inorganic reinforcing material, followed by drying and firing. As the inorganic reinforcing material, for example, an inorganic sol compound such as alumina sol, silica sol, titania sol, zirconia sol, glass fiber, carbon fiber, alumina fiber,
Inorganic fibers such as silica fibers, alumina silicate fibers, asbestos, zirconia fibers, silicate fibers, titanium fibers, boron fibers, and asbestos, and various metal whiskers.

The amount of water and the mixing time for mixing the composition containing the microporous material and the layered clay mineral are determined according to the type and mixing ratio of the microporous material, the layered clay mineral, the organic molding aid for the microporous material molded product, and the like. What is necessary is just to change arbitrarily according to the presence or absence and kind of an inorganic reinforcing material.

The mixture obtained as described above can be formed into an appropriate shape according to the type of reaction and the shape of the reactor, for example, a spherical shape, a columnar shape, a granular shape, a honeycomb shape and the like. As the molding method, a conventional extrusion molding may be performed by a conventionally known method using a molding machine according to the shape.

When the obtained molded product is dried and then fired, a microporous material molded product that can be used as a catalyst for producing alkanolamine by reacting ammonia and alkylene oxide is obtained.

The firing temperature is from 500 to 1000 ° C., more preferably from 600 to 1000 ° C. When the temperature is lower than 500 ° C., the strength cannot be ensured due to insufficient sintering, the properties of the layered clay mineral as the inorganic binder remain, and the selectivity of the target product may be significantly reduced. On the other hand, 1
If the temperature is higher than 000 ° C., the crystal structure of the microporous material is broken, and the selectivity inherent in the microporous material may not be exhibited. In the case where the microporous material is ZSM-5 or ZSM-11, the preferable firing temperature range is from 600 ° C to 1000 ° C, and more preferably from 650 ° C to 900 ° C.

As described above, when the composition containing the microporous material powder and the layered clay mineral is sintered, a catalyst having excellent strength can be obtained without lowering the original performance of the microporous material catalyst. This is because the layered clay mineral added to impart plastic moldability is dehydrated by firing at high temperature, the layers contract and the strength of the catalyst is secured, and only a weakly acidic outer surface has a catalytic effect. This is probably because the catalytic activity of the clay mineral is lost, so that only the original catalytic performance of the microporous material that provides high performance is exhibited.

The molded microporous material catalyst comprises:
It must have a shape and strength that can be provided to the reaction system. Although the shape of the catalyst can be arbitrarily set, the average catalyst particle diameter in the case of granulation is preferably in the range of 0.1 to 10 mm, more preferably in the range of 0.2 to 5 mm. In the “granular” of the present invention, when the catalyst shape is not spherical, the value is expressed by “equivalent diameter” which is six times the value obtained by dividing the volume by the outer surface area. Catalyst particle size 0.1
If it is less than 10 mm, it may not be strong enough to be used for the reaction. Conversely, if it is too large, it may be affected by diffusion, and the dialkanol may be reduced due to a decrease in catalytic activity or an increase in sequential products. The selectivity of the amine may be reduced.

The catalyst of the present invention has a degree of pulverization of 0.1 to 20%.
It is characterized in that, in the present invention, "degree of pulverization"
Was measured as follows. 0.30 of the obtained molded catalyst
A sample for measuring strength was prepared by adjusting the particle size to 0.71 mm. 14 g of this and a silica ball 3 of 12-14 mmφ
The pieces are placed in a sieve of 0.3 mm (50 mesh), and sieved using an automatic sieve (SIEVE SHAKER, manufactured by Iida Seisakusho).
Activated for minutes. The measurement of the degree of pulverization was in accordance with the following equation.

[0081]

(Equation 6)

The third aspect of the present invention is that, in the presence of the above-mentioned catalyst,
A method for producing a dialkanolamine represented by the following formula (II), comprising reacting an alkylene oxide represented by the following general formula (I) with ammonia in a liquid phase in the presence of an inorganic catalyst.

The starting alkylene oxide of the reaction system using the dialkanolamine production method and the dialkanolamine production catalyst of the present invention is an alkylene oxide represented by the above formula (I),
Illustrative are alkylene oxides having 2 to 4 carbon atoms, such as propylene oxide. The alkanolamine represented by the above formula (II) is obtained corresponding to these raw materials. Specific examples include monoethanolamine, diethanolamine, triethanolamine, and propanolamines.

Since the reaction must be carried out in the liquid phase, the reaction pressure generally needs to be kept higher than the vapor pressure of the reaction solution at the highest temperature in the reactor. If it is difficult, a part of the ammonia can be vaporized, and the latent heat of vaporization can remove the heat of reaction. In this case, the reaction pressure is preferably lower than the vapor pressure of the reaction solution at the highest temperature in the reaction system.

Usually, the production of alkanolamines is
It can be carried out in a temperature range of 0 to 300 ° C. The preferred range is 80-200 ° C. Operating pressure is 1-2
0 MPa.

Under the above conditions, the liquid hourly space velocity (L
HSV) is not particularly limited, but 1 hour ^-1The above conditions are usually
Used. The above LHSV is defined as follows.
You.

[0087]

(Equation 7)

By using the method of the present invention, dialkanolamine can be produced with high efficiency without particularly recycling monoalkanolamine. However, in the case of carrying out adiabatic single-stage reaction, for example, the alkylene oxide at the inlet of the reactor is used. If the concentration is limited or if there is no need to produce monoalkanolamine, it is possible to increase the amount of dialkanolamine by recycling part of the produced monoalkanolamine to the reactor. it can.

The molar ratio of the starting material ammonia to the alkylene oxide represented by the above formula (I) is not particularly limited as long as the above α and β can be used. 1
５０50 mol, more preferably 2 to 40 mol, particularly preferably 2 to 20 mol.

[0090]

The examples which follow show production examples of ethanolamines mainly from ethylene oxide and ammonia. The examples are intended for illustrative purposes and do not limit the invention.

Example 1 ZSM manufactured by Zeolyst, Inc.
-5 zeolite (Si / Al atomic ratio 28, proton type)
2 kg was added to 10 L of a 1 mol / L lanthanum nitrate aqueous solution heated to 60 ° C., and ion exchange was performed while maintaining the temperature at 60 ° C. while stirring for 12 hours. After filtration and washing with water, drying was performed at 120 ° C. for 12 hours, followed by baking in air at 550 ° C. for 3 hours. To the powder of the calcined lanthanum ion-exchanged ZSM-5, 700 g of Na salt of Montmorillonite (trade name: Knipia F) manufactured by Kunimine Kogyo Co., Ltd. was added, and the mixture was kneaded with a kneader to adjust the humidity. With 0.
It was extruded into a string having a diameter of 4 mmφ. The obtained molded body was once dried at 120 ° C for 2 hours, adjusted to a length of 2 to 5 mm with a sizing machine, and then dried at 120 ° C for 12 hours. The obtained dried molded body was calcined in air at 850 ° C. for 3 hours to obtain a catalyst.

The obtained catalyst was adjusted to a particle size of 0.30 to 0.71 mm to obtain a strength measurement sample. When the degree of pulverization of the obtained sample was measured with an automatic sieve, it was 2.2.
%Met.

The reaction for synthesizing diethanolamine from ethylene oxide and NH ₃ was carried out using the apparatus shown in FIG. The reaction tube 201 used was a tube made of stainless steel having an inner diameter of 15 mm and a length of 400 mm and having a heater for compensating heat radiation and kept warm. A protective tube into which a thermocouple can be inserted for measuring the temperature profile of the catalyst layer was provided inside the reactor. This reactor is charged with 50 mL of the catalyst, and the preheater 202
The raw material (ammonia / ethylene oxide molar ratio: 14) heated to 60 ° C. was passed through at an LHSV of 5 hr ⁻¹ to react.

The temperature rise due to the heat of reaction is initially caused by the inlet 10
The temperature becomes 150 ° C. at about 0 mm, and the reaction result at this time is an ethylene oxide conversion rate of 100%, and the production ratio of the produced ethanolamines is monoethanolamine / diethanolamine / triethanolamine = 69/30 by mass ratio.
However, diethanolamine was produced with a high selectivity, despite the low production of triethanolamine. The reaction rate constant ratio β is 0.14. Almost no triethanolamine EO adduct was found. After a lapse of 500 hours, the profile finally increased to a temperature of about 150 ° C. near the outlet of the catalyst layer, and deterioration of the catalyst was observed.
Although there was a change in β, selectivity of 0.20 or less was maintained. During the reaction up to the elapse of 500 hours, no turbidity of the reaction solution and no increase in pressure loss were observed, and the reaction could be performed stably.

After the reaction was stopped, the catalyst was removed from the reactor,
Upon observation, powdering of the catalyst was not observed as expected.

Comparative Example 1 Dry lanthanum ion-exchanged ZSM-5 powder was prepared under the same conditions as in Example 1. The obtained lanthanum ion-exchanged ZSM-5 powder was pulverized in a mortar and hardened into a disk shape using a pressure molding machine. The resulting mass was pulverized and sieved to a particle size of 30-50 mesh. The obtained molded body is fired in air at 550 ° C. for 3 hours,
The catalyst was used. A strength measurement sample was prepared in the same manner as in Example 1, and the particle size was adjusted to 0.30 to 0.71 mm. When the degree of powdering of the strength measurement sample was measured with an automatic sieve,
At 33%, it was extremely fragile.

The reaction for synthesizing diethanolamine from ethylene oxide and NH ₃ was carried out in the same reactor as in Example 1.
Performed under the same reaction conditions.

[0098] The temperature rise due to the heat of reaction is initially at the inlet 10
At about 0 mm, the temperature becomes 150 ° C. The reaction result at this time is an ethylene oxide conversion rate of 100%, and the production ratio of the produced ethanolamines is 70/29 by mass ratio of monoethanolamine / diethanolamine / triethanolamine.
However, diethanolamine was produced with a high selectivity, despite the low production of triethanolamine. The reaction rate constant ratio β is 0.15. Due to the low strength of the catalyst, the reaction liquid was slightly turbid after about 100 hours of the reaction, and powdering of the catalyst was confirmed.

Comparative Example 2 Under the same conditions as in Example 1, calcined lanthanum ion-exchanged ZSM-5 powder was prepared. 3.3 kg of Nissan Chemical's alumina sol (alumina content: 21 wt.%,
Trade name alumina sol 520) was added and mixed with a kneader. Further, 80 g of hydroxyethyl cellulose (product name: HEC Daicel, product number SP500) manufactured by Daicel Chemical Co., Ltd. was added thereto as an organic binder. After adjusting the humidity while heating the jacket of the kneader with steam, the extruder was extruded into a string having a diameter of 0.4 mmφ using a dome-shaped die. The obtained molded body was once dried at 120 ° C. for 2 hours, adjusted to a length of 2 to 5 mm with a granulator, and then dried.
Dry at 0 ° C. for 12 hours. The obtained molded body is placed in the air 85
It was calcined at 0 ° C. for 3 hours to obtain a catalyst.

A strength measurement sample was prepared in the same manner as in Example 1, and was adjusted to a particle size of 0.30 to 0.71 mm. The degree of powdering of the strength measurement sample was measured with an automatic sieve, and was 1.5%.

The reaction for synthesizing diethanolamine from ethylene oxide and NH ₃ was carried out in the same reactor as in Example 1,
Performed under the same reaction conditions. Initially, the temperature rise due to the heat of reaction is 160 ° C. at an inlet of about 100 mm, and the reaction result at this time is an ethylene oxide conversion rate of 100%, and the production ratio of the produced ethanolamines is monoethanolamine / diethanolamine / triethanol by mass ratio. Amine =
70/28/2, and β = 0.32. Generation of a plurality of impurities was observed in the product liquid, and among them, triethanolamine EO adducts were present at 7% of triethanolamine. After a lapse of 360 hours from the reaction, the temperature became close to 160 ° C. at the vicinity of the exit of the catalyst layer, and the catalyst was deteriorated. β = 0.56 and 0.5 or more, indicating that the selectivity was not maintained. Due to the high strength of the catalyst, the reaction was stable without any turbidity of the reaction solution and no increase in pressure drop during the reaction up to 360 hours.

Comparative Example 3 Under the same conditions as in Example 1, calcined lanthanum ion-exchanged ZSM-5 powder was prepared. 3.3 kg of Nissan Chemical's silica sol (silica content 20 wt.%, Trade name Snowtex N) was added to the calcined lanthanum ion-exchanged ZSM-5 powder and mixed with a kneader.
Further, as an organic binder, hydroxyethylcellulose manufactured by Daicel Chemical (product name: HEC Daicel, part number SP)
500) 80 g was added to this. After adjusting the humidity while heating the jacket of the kneader with steam, the extruder was extruded into a string having a diameter of 0.4 mmφ using a dome-shaped die. The obtained molded body was once dried at 120 ° C. for 2 hours, and was then adjusted to a length of 2 to 5 mm using a sizing machine. No viable catalyst was obtained.

(Example 2) Lanthanum ion exchange ZS of dried montmorillonite added with Na salt under the same conditions as in Example 1
An M-5 molded body was prepared. The obtained dried molded body was calcined in air at 650 ° C. for 3 hours to obtain a catalyst. A strength measurement sample was prepared in the same manner as in Example 1, and 0.30 to 0.71 mm
Particle size. The degree of powdering of the strength measurement sample was measured with an automatic sieve, and was 2.8%.

The reaction for synthesizing diethanolamine from ethylene oxide and NH ₃ was carried out in the same reactor as in Example 1.
Performed under the same reaction conditions.

The temperature rise due to the heat of reaction is initially caused at the inlet 10
The temperature becomes 150 ° C. at about 0 mm, and the reaction result at this time is an ethylene oxide conversion rate of 100%, and the production ratio of the produced ethanolamines is monoethanolamine / diethanolamine / triethanolamine = 73/26 by mass ratio.
/ 1 and β = 0.20. Diethanolamine was produced with high selectivity despite the low production of triethanolamine. Almost no triethanolamine EO adduct was found. During the reaction up to 300 hours, no turbidity of the reaction solution and no increase in pressure drop were observed, and the reaction could be performed stably.

(Example 3) ZSM manufactured by Zeolyst, Inc.
-5 zeolite (Si / Al atomic ratio 28, proton type)
2 kg was put into a 10-liter jacketed kneader, and 3 liters of water was added. 49.8 g of lanthanum nitrate nonahydrate was dissolved in 670 g of water, and the resulting lanthanum nitrate aqueous solution was subsequently added. Steam was introduced into the kneader jacket, and the lanthanum impregnated zeolite was kneaded with the kneader and concentrated. The amount of steam introduced was adjusted so that the temperature of the lanthanum impregnated zeolite was about 60 ° C. When the fluidity of the lanthanum-impregnated zeolite was lost, kneading and concentration of the kneader were completed. The obtained zeolite mixture was collected in a SUS vat, and then 12
Drying was performed at 0 ° C. for 12 hours, followed by baking in air at 550 ° C. for 3 hours. The obtained calcined lanthanum ion-supported ZS
The La / Al atomic ratio of M-5 is 0.1.

To the powder of the calcined lanthanum ion-supported ZSM-5, 700 g of Na salt of Montmorinite (trade name "Kunipia F", manufactured by Kunimine Industries) was added, and the mixture was humidified while being mixed with a kneader. It was extruded with a die into a cord with a diameter of 0.4 mmφ. The obtained molded body was once dried at 120 ° C. for 2 hours,
After adjusting to a length of 1 mm, it was dried at 120 ° C. for 12 hours. The obtained dried molded body was calcined in air at 850 ° C. for 3 hours to obtain a catalyst.

The obtained catalyst was adjusted to a particle size of 0.30 to 0.71 mm to prepare a sample for measuring the strength. When the degree of powdering of the obtained sample was measured with an automatic sieve, 1.8% was obtained.
Met.

The reaction for synthesizing diethanolamine from ethylene oxide and NH ₃ was carried out in the same reactor and under the same conditions as in Example 1.

The rise in temperature due to the heat of reaction is initially caused by the inlet 10
The temperature becomes 150 ° C. at about 0 mm, and the reaction result at this time is an ethylene oxide conversion rate of 100%, and the production ratio of the produced ethanolamines is monoethanolamine / diethanolamine / triethanolamine = 73/26 by mass ratio.
/ 1 and β = 0.20. Diethanolamine was produced with high selectivity despite the low production of triethanolamine. Almost no triethanolamine EO adduct was found. During the reaction up to 300 hours, no turbidity of the reaction solution and no increase in pressure drop were observed, and the reaction could be performed stably.

[0111]

According to the present invention, a catalyst containing a microporous material powder and a layered clay mineral formed into a composition and having a degree of pulverization of 0.1 to 20% is used. When producing an amine, the dialkanolamine can be produced stably because the strength is extremely excellent. Moreover,
The catalyst is extremely excellent in dialkanolamine selectivity.

[Brief description of the drawings]

FIG. 1 is a schematic view of a reaction apparatus used in Examples.

[Explanation of symbols]

 201: reaction tube, 202: preheater, 203, 204, 205: high pressure pump, 206: pressure control valve, 207: ammonia flash tower, 208: recovered ammonia tank, 210 ... Ammonia, 211 ... Ethylene oxide.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B01J 37/08 B01J 37/08 C07C 213/04 C07C 213/04 215/12 215/12 // C07B 61 / 00 300 C07B 61/00 300 (72) Inventor Hisakazu Shindo 5-8 Nishimitabicho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Hideaki Tsuneki 5-8 Nishimitabicho, Suita-shi, Osaka F-term (reference) in Nippon Shokubai Co., Ltd. CA71 CF90

Claims (5)

[Claims] 1. A catalyst for producing a dialkanolamine represented by the following formula (II) by reacting ammonia with an alkylene oxide represented by the following formula (I), the catalyst comprising a microporous material powder and a layered clay mineral And a powdered degree of the catalyst of from 0.1 to 20%. The molded microporous material catalyst for producing dialkanolamine. Embedded image Embedded image 2. The mass ratio of the microporous material powder to the layered clay mineral is from 95/5 to 50/50.
The shaped microporous material catalyst for producing dialkanolamine according to claim 1. 3. Molding a composition containing a microporous material powder and a layered clay mineral,
The method for producing a catalyst according to claim 1 or 2, which is obtained by calcining in a temperature range of 000 ° C. 4. The microporous material powder,
The method for producing a catalyst according to claim 3, wherein the metallosilicate is obtained by supporting 0.1 to 10% by mass of a rare earth element and then heat-treating the metallosilicate at 400 to 1000 ° C. 5. A method of reacting an alkylene oxide represented by the following general formula (I) with ammonia in the liquid phase in the presence of an inorganic catalyst in the presence of the catalyst according to claim 1 or 2. A method for producing a dialkanolamine represented by (II). Embedded image Embedded image