KR20060069273A - Manufacturing method of oxime - Google Patents

Abstract

The present invention provides a method for producing an oxime by subjecting ketones to darkening reactions with peroxides and ammonia in the presence of titanosilicates exhibiting an X-ray diffraction pattern having peaks at the following positions as the lattice spacing display.

Grid spacing d (Å):

13.2 ± 0.6,

12.3 ± 0.3,

11.0 ± 0.3,

9.0 ± 0.3,

6.8 ± 0.3,

3.9 ± 0.2,

3.5 ± 0.1, and

3.4 ± 0.1.

Description

Production method of oxime {PROCESS FOR PRODUCING OXIME}

1 is a chart showing an X-ray diffraction pattern of titanosilicate (Ti-MWW precursor) prepared and used in Example 1. FIG.

FIG. 2 is a chart showing an X-ray diffraction pattern of titanosilicate (Ti-MWW) obtained by firing the titanosilicate prepared in Example 1. FIG.

3 is a chart showing an X-ray diffraction pattern of titanosilicate (TS-1) used in Comparative Example 1. FIG.

[Patent Document 1] Japanese Patent Application Laid-Open No. 62-59256

[Patent Document 2] International Publication No. 03/074421 Pamphlet

The present invention relates to a process for preparing oximes by ammoximation reaction of ketones. Oxime is useful as a raw material of amide or lactam, for example.

As one of the methods for producing an oxime, a method is known in which a ketone is subjected to a deepening reaction using a titanosilicate as a catalyst. For example, Japanese Laid-Open Patent Publication No. 62-59256 (Patent Document 1) discloses using the titanosilicate having a MFI structure (titanium silicalite TS-1) as a catalyst to carry out the darkening reaction. In addition, International Publication No. 03/074421 pamphlet (Patent Document 2) discloses using the titanosilicate having a MWW structure as a catalyst to perform the above-described deepening reaction.

However, in the method disclosed in Patent Document 1, since the performance of the catalyst is not sufficient, it may not be satisfactory in view of the conversion ratio of ketone and the selectivity of oxime. Moreover, in the method disclosed by patent document 2, since the preparation process of a catalyst is long and complicated, it may not be satisfied in terms of cost. Accordingly, an object of the present invention is to provide a method for producing an oxime at low cost with high yield by performing the above-described deepening reaction using a catalyst which has excellent performance and can be advantageously prepared in a cost-effective manner. There is.

The present invention provides a method for producing an oxime characterized in that the ketones are subjected to darkening reaction with peroxide and ammonia in the presence of a titanosilicate showing an X-ray diffraction pattern having a peak at the following positions with a lattice spacing display:

Grid spacing d (Å):

13.2 ± 0.6,

12.3 ± 0.3,

11.0 ± 0.3,

9.0 ± 0.3,

6.8 ± 0.3,

3.9 ± 0.2,

3.5 ± 0.1, and

3.4 ± 0.1.

To practice the invention  Best form for

In the present invention, the titanosilicate used in the catalyst for the deepening reaction is a crystalline titanosilicate containing titanium, silicon, and oxygen as the constituent elements of the skeleton, and the skeleton may consist essentially of titanium, silicon, and oxygen. And an element other than titanium, silicon, and oxygen, such as boron, aluminum, gallium, iron, and chromium, may also be included as an element which comprises a skeleton. In addition, this titanosilicate may be used, molded or pelletized, with or without a binder, or supported on a carrier.

In the said titanosilicate, content of titanium is represented by the atomic ratio (Ti / Si) with respect to silicon, Preferably it is 0.0001 or more, More preferably, it is 0.005 or more, More preferably, it is 0.1 or less, More preferably, 0.05 It is as follows. In addition, when this titanosilicate contains elements other than titanium, silicon, and oxygen, content of the element is represented by the atomic ratio with respect to silicon, and is 0.05 or less normally, Preferably it is 0.02 or less. In addition, oxygen may exist corresponding to content of each element other than oxygen, and oxidation number. A typical composition of such titanosilicate can be represented by the following formula on the basis of silicon (= 1).

SiO ₂ xTiO ₂ yM ⁿ O _{n / 2}

(Wherein, M represents at least one element other than silicon, titanium and oxygen, n is the oxidation number of the element, x is 0.0001 to 0.1 and y is 0 to 0.05.)

In addition, in the X-ray diffraction pattern, the titanosilicate used in the present invention has a peak at the following position by the lattice plane spacing d [Å (angstrom)]. Titanosilicates exhibiting this particular X-ray diffraction pattern are excellent in terms of activity and selectivity as catalysts in the deepening reaction of ketones, that is, conversion of ketones and selectivity of oximes.

Grid spacing d (Å):

13.2 ± 0.6,

12.3 ± 0.3,

11.0 ± 0.3,

9.0 ± 0.3,

6.8 ± 0.3,

3.9 ± 0.2,

3.5 ± 0.1, and

3.4 ± 0.1.

This X-ray diffraction pattern can be obtained by a general X-ray diffraction apparatus using copper K-alpha radiation. That is, when copper K-alpha radiation was used, the peak of d = 13.2 ± 0.6 Hz was 2θ (θ is the Bragg angle; the same below) = 6.7 ° (nearly 6.4 to 7.0 °); the peak of d = 12.3 ± 0.3 Hz is around 2θ = 7.2 ° (7.0-7.4 °); the peak of d = 11.0 ± 0.3 Hz is around 2θ = 8.0 (7.8∼8.3 °); the peak of d = 9.0 ± 0.3 Hz is around 2θ = 9.8 ° (9.5-10.2 °); the peak of d = 6.8 ± 0.3 Hz is around 2θ = 13.0 ° (12.5-13.6 °); the peak of d = 3.9 ± 0.2 Hz is around 2θ = 22.8 ° (21.6-24.0 °); a peak of d = 3.5 ± 0.1 Hz is around 2θ = 25.4 ° (24.7-26.2 °); the peak of d = 3.4 ± 0.1 Hz is around 2θ = 26.2 ° (25.4-27.0 °); Are observed respectively.

Moreover, in this X-ray diffraction pattern, presence of the peak of that excepting the above is arbitrary. In addition, although each said peak usually shows the maximum value in the lattice spacing, it overlaps with other peak and may be detected as a shoulder peak.

The titanosilicate showing the above-mentioned specific X-ray diffraction pattern can be obtained as a precursor when preparing titanosilicate (hereinafter sometimes referred to as Ti-MWW) having an MWW structure. That is, for example, Chemistry Letters, 2000, p.774-775, Japanese Unexamined Patent Application Publication No. 2002-102709, and the like, as a preparation method of Ti-MWW by a direct synthesis method, a structural regulator (Template), a titanium compound, a boron compound, a silicon compound and water are mixed and heated, followed by acid treatment as needed, and the obtained precursor is calcined to prepare Ti-MWW, which is described in the present invention. It corresponds to the said specific titanosilicate used. In addition, Chemical Communications, (UK), 2002, p. 1026-1027, Japanese Unexamined Patent Publication No. 2003-327425, International Publication No. 03/074421 pamphlet (Patent Document 2), etc. As a method for preparing Ti-MWW by the method, a structural regulator, a boron compound, a silicon compound, and water are mixed and heated, and then fired as necessary, followed by acid treatment to obtain a silicate. It is described to prepare Ti-MWW by mixing the titanium compound and water, heating and then acid treatment as necessary to calcinate the obtained precursor, which precursor corresponds to the specific titanosilicate used in the present invention. . As described above, the titanosilicate (Ti-MWW precursor) used in the present invention is obtained as a precursor before firing when Ti-MWW is prepared, and compared to Ti-MWW, the equipment, energy and time required for the firing are reduced. We can do it and can prepare at low cost. Therefore, the deepening reaction using the Ti-MW precursor according to the present invention as a catalyst is advantageous from the viewpoint of the preparation cost of the catalyst as compared with the deepening reaction using Ti-MWW for the catalyst as disclosed in Patent Document 2. Oximes can be made cheaper.

Here, as a structural regulator used in the said preparation method, a piperidine, a hexamethylene imine, etc. are mentioned, As a titanium compound, tetraalkyl ortho titanate like tetra- n-butyl ortho titanate, and tetra titanate peroxide are mentioned. Titanium peroxide, such as propyl ammonium, a titanium halide, etc. are mentioned, As a boron compound, boric acid etc. are mentioned, As a silicon compound, tetraalkyl orthosilicate like tetraethyl orthosilicate, fumed silica, etc. are mentioned.

In addition, the heating conditions of each mixture in the said preparation method are a heating temperature of 100-200 degreeC normally, a heating time is 2 to 240 hours normally, and the temperature increase rate to a heating temperature is 0.01-2 degreeC / min normally. As this heating method, the hydrothermal synthesis method carried out under the pressure of the mixture is generally employed, and may be a batch method or a circulation method. In addition, during heating, a zeolite having a MWW structure or the like is added as seed crystal or hydrofluoric acid is added. You may do it.

In addition, in the said preparation method, acid treatment is performed in order to remove a structural regulator, boron, extra-skeletal titanium, etc., and nitric acid and sulfuric acid are used suitably for this acid.

The Ti-MWW precursor obtained by the said preparation method is used after washing with water, if necessary, after drying, As this drying method, the method of heating with a dryer, the method of blowing the heated gas, the method of using a spray dryer, etc. are mentioned. . Especially, the method of using a spray dryer is preferable because it can also shape into particle | grains of about 1-1000 micrometers of particle sizes at the same time as drying.

If the drying temperature is too high, the energy cost is high, and the temperature conversion of the Ti-MWW precursor to the Ti-MWW takes place in the firing temperature range. On the other hand, if the drying temperature is too low, drying takes time, resulting in low production efficiency. Adjusted accordingly. In the above-mentioned Japanese Patent Application Laid-Open No. 2002-102709 or Japanese Patent Laid-Open No. 2003-327425 or the like, the firing temperature for performing a structural conversion from Ti-MWW precursor to Ti-MWW is preferably 200 to 700 ° C, more preferably. Preferably, considering that it is described as 300 to 650 ° C, most preferably 400 to 600 ° C, the drying temperature is preferably lower than 200 ° C for a lower energy cost, and is usually 20 ° C in view of production efficiency. That's it.

The structure conversion from the Ti-MWW precursor to the Ti-MWW by firing is specifically caused by the dehydration and condensation of the interlayer of the Ti-MWW precursor, which is a layered titanosilicate, to crystallize into the MWW structure, which is an X-ray diffraction pattern. This can be confirmed by the change of. That is, FIG. 1 is a chart of the X-ray diffraction pattern by the copper K-alpha radiation of the Ti-MWW precursor prepared and used in Example 1 described later, and FIG. 2 is fired at 530 ° C. for 6 hours by firing the Ti-MWW precursor. It is a chart of the X-ray diffraction pattern by the obtained copper K-alpha radiation of Ti-MWW, The lattice spacing which is one of the peaks prescribed | regulated by this invention as a result of the structural conversion from Ti-MWW precursor to Ti-MWW by this baking. It can be seen that d = 13.2 ± 0.6 Hz (near 2θ = 6.7 °) is lost. This peak is, for example, a peak derived from plane 002, as described in Catalyst, 2001, Vol. 43, p.158, and is specific to the layer structure of the Ti-MWW precursor in terms of contrast with Ti-MWW. Will.

An oxime can be produced in high yield by using the titanosilicate of the Ti-MWW precursor described above in a catalyst and subjecting ketone to peroxide and ammonia in the presence of the catalyst. In this deepening reaction, the titanosilicate of the catalyst is preferably suspended in the liquid phase of the reaction mixture and is present as a solid phase. The ratio is appropriately adjusted in consideration of catalyst activity, dispersibility, etc., but is usually 0.1 to 10% by weight relative to the liquid phase. About%. Moreover, you may make silicon compounds other than titanosilicates, such as a silica gel, silicic acid, and crystalline silica, coexist for the purpose of suppressing the fall of the catalyst activity of titanosilicate.

The ketone as a raw material may be an aliphatic ketone, an alicyclic ketone, an aromatic ketone, or two or more of them may be used if necessary. Specific examples of the ketones include dialkyl ketones such as acetone, methyl ethyl ketone and isobutyl methyl ketone; Alkyl alkenyl ketones such as mesityl oxide; Alkylaryl ketones such as acetophenone; Diaryl ketones such as benzophenone; Cycloalkanones such as cyclopentanone, cyclohexanone, cyclooctanone, and cyclododecanone; Cycloalkenone, such as cyclopentenone and cyclohexenone, etc. are mentioned. Especially, cycloalkanone becomes a preferable object of this invention.

The ketone which is a raw material may be, for example, one obtained by oxidation of an alkane, one obtained by oxidation (dehydrogenation) of a secondary alcohol, or one obtained by hydration and oxidation (dehydrogenation) of an alkene.

Examples of the peroxide include, besides hydrogen peroxide, organic peroxides such as t-butyl hydroperoxide, di-t-butyl peroxide and cumene hydroperoxide. Among them, hydrogen peroxide is preferably used. Hydrogen peroxide is usually produced by the so-called anthraquinone method and generally marketed as an aqueous solution having a concentration of 10 to 70% by weight, and thus it can be used. In addition, hydrogen peroxide may be prepared by reacting hydrogen and oxygen in an organic solvent in the presence of a solid catalyst supporting metal palladium, and when hydrogen peroxide according to this method is used, hydrogen peroxide obtained by separating the catalyst from the reaction mixture. What is necessary is just to use the organic solvent solution instead of the said hydrogen peroxide aqueous solution.

The use amount of peroxide is 0.5-3 mol normally with respect to 1 mol of ketones, Preferably it is 0.5-1.5 mol. Examples of peroxides include, for example, phosphates such as sodium phosphate, polyphosphates such as sodium pyrophosphate and sodium tripolyphosphate, pyrophosphate, ascorbic acid, ethylenediaminetetraacetic acid, nitrotriacetic acid, aminotriacetic acid and diethylenetriaminepenta. Acetic acid or the like may be added.

The ammonia may be a gaseous one, a liquid one, or may be used as a solution of water or an organic solvent. The amount of ammonia used is preferably adjusted so that the concentration of ammonia in the liquid phase of the reaction mixture is 1% by weight or more. Thus, by making the ammonia concentration in the reaction mixture liquid phase more than a predetermined value, it is possible to increase the conversion rate of the ketone as the raw material and the selectivity of the oxime as the target, and further increase the yield of the oxime as the target. The concentration of this ammonia is preferably 1.5% by weight or more, and usually 10% by weight or less, preferably 5% by weight or less. Moreover, the reference | standard of the ammonia usage-amount is 1 mol or more normally with respect to 1 mol of ketones, More preferably, it is 1.5 mol or more.

The deepening reaction may be carried out in a solvent. Examples of the reaction solvent include aromatic compounds such as benzene and toluene, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and s-butyl alcohol. and alcohols such as t-butyl alcohol and t-amyl alcohol, water and the like. Especially, alcohol and water are preferable, and the mixed solvent of alcohol and water is especially used preferably.

Although the deepening reaction may be carried out batchwise or continuously, it is possible to carry out continuously by extracting the liquid phase of the reaction mixture from the reaction system while supplying ketone, peroxide and ammonia into the reaction system for productivity and operability. It is also preferable from the viewpoint of.

Batch reaction may be performed, for example, by putting a ketone, ammonia, a catalyst, and a solvent in a reactor, and stirring, and supplying a peroxide in this, and putting a ketone, a catalyst, and a solvent in a reactor, stirring, and a peroxide and You may carry out by supplying ammonia, and you may carry out by adding a catalyst and a solvent to a reactor, and supplying a ketone, a peroxide, and ammonia in it under stirring.

The continuous reaction is preferably performed by, for example, leaving a reaction mixture in which the catalyst is suspended in the reactor, drawing the liquid phase of the reaction mixture from the reactor through a filter while supplying ketone, peroxide, ammonia and a solvent therein. Can be. Moreover, from the viewpoint of preventing decomposition of the peroxide, the reactor is preferably glass lined or stainless steel.

The reaction temperature of a deepening reaction is 50-120 degreeC normally, Preferably it is 70-100 degreeC. In addition, although the reaction pressure may be atmospheric pressure, in order to make it easy to melt | dissolve ammonia in the liquid phase of a reaction mixture, it is preferable to carry out reaction normally under the pressure of 0.2-1 MPa, Preferably 0.2-0.5 MPa in absolute pressure, In this case, nitrogen You may adjust pressure using inert gas, such as helium or helium.

The post-treatment operation of the obtained reaction mixture is appropriately selected. For example, the oxime can be separated by separating the catalyst from the reaction mixture by filtration or decantation and then distilling the liquid phase.

EXAMPLE

Hereinafter, although the Example of this invention is shown, this invention is not limited by this.

Example 1

(Preparation of Catalyst)

Autoclave 9.1 kg piperidine, 25.6 kg pure water, 6.2 kg boric acid, 0.54 kg tetra-n-butylortho titanate, and fumed silica (“CAB-O-SIL M-7D” manufactured by CABOT) 4.5 kg was added, the mixture was stirred at room temperature under an air atmosphere to prepare a gel, and aged for 1.5 hours. The autoclave was sealed, heated to 170 ° C. over 10 hours with stirring, and then maintained at 168 hours at the same temperature to undergo hydrothermal synthesis to obtain a suspension. This suspension was filtered, and the filtration residue was washed with water until the pH of the washing | cleaning liquid became about 10, and it dried at 50 degreeC, and obtained the white powder which still contains water.

To 350 g of this hydrous white powder, 3.5 L of 13 wt% nitric acid was added and refluxed for 20 hours. Subsequently, the filtrate was washed with water, and the residue was washed with water until the cleaning liquid became neutral, and then dried sufficiently at 50 ° C. to give 98 g of titanosilicate (Ti-MWW precursor) having a Ti / Si (atomic ratio) of 0.0139. Obtained as. About this titanosilicate, as a result of measuring the X-ray diffraction pattern by the X-ray diffraction apparatus using copper K-alpha radiation, the peak of the following table | surface was observed as shown in FIG.

2θ (°) Grid spacing d (Å) 6.82 13.0 7.23 12.2 7.97 11.1 9.78 9.0 12.9 6.8 22.7 3.9 25.2 3.5 26.2 3.4

(Deepening reaction)

The titanosilicate obtained above was used for a catalyst, and the deepening reaction was performed. That is, a 1 liter autoclave was used as a reactor, in which 13.4 g / hour of cyclohexanone, 52 g / hour of hydrous t-butyl alcohol (12 weight% of water), and 8.9 of 60 weight% hydrogen peroxide solution were used. by feeding the ammonia at a concentration of 2% by weight in the liquid phase of the reaction mixture, withdrawing the liquid phase of the reaction mixture from the reactor through a filter, at a temperature of 85 ° C. and a pressure of 0.35 MPa ( Absolute pressure), and the continuous reaction was performed on conditions of 6 hours of residence time. In the meantime, the said titanosilicate was present in the reaction mixture in a reactor in the ratio of 0.2 weight% with respect to a liquid phase.

As a result of analyzing the liquid phase extracted 1.5 hours after the start of reaction, the conversion rate of cyclohexanone was 95.7%, the selectivity of cyclohexanone oxime was 99.0%, and the yield of cyclohexanone oxime was 94.7%. Moreover, as a result of analyzing the liquid phase extracted 52 hours after the start of reaction, the conversion rate of cyclohexanone was 99.8%, the selectivity of cyclohexanone oxime was 99.4%, and the yield of cyclohexanone oxime was 99.2%. The reaction was terminated because the oxygen concentration in the autoclave rapidly increased after 106 hours from the start of the reaction.

Comparative Example 1

The deepening reaction was performed similarly to Example 1 using TS-1 (commercially available product) which is a titanosilicate having an MFI structure as a catalyst. In addition, the X-ray diffraction pattern of TS-1 used here is as shown in FIG. 3, and d = 13.2 ± 0.6 kW (near 2θ = 6.7 °) or d = 12.3 ± 0.3 kW (2θ = 7.2 °) specified in the present invention. Peaks) are not observed.

As a result of analyzing the liquid phase extracted after 1.5 hours from the start of reaction, the conversion rate of cyclohexanone was 70.9%, the selectivity of cyclohexanone oxime was 98.7%, and the yield of cyclohexanone oxime was 70.0%. After 3 hours from the start of the reaction, the reaction was terminated because the oxygen concentration in the autoclave rapidly increased.

According to the present invention, oximes can be produced inexpensively and at high yields by the deepening reaction of ketones.

Claims (5)

In the presence of a titanosilicate exhibiting an X-ray diffraction pattern having a peak at the following position as the lattice spacing display, ketones are subjected to a deepening reaction with peroxide and ammonia, wherein the oxime is produced. Grid spacing d (Å): 13.2 ± 0.6, 12.3 ± 0.3, 11.0 ± 0.3, 9.0 ± 0.3, 6.8 ± 0.3, 3.9 ± 0.2, 3.5 ± 0.1, and 3.4 ± 0.1. The production method according to claim 1, wherein the atomic ratio of titanium to silicon in titanosilicate is 0.0001 to 0.1. The method of claim 1 wherein the peroxide is hydrogen peroxide. The process according to claim 1, wherein the deepening reaction is carried out in a mixed solvent of alcohol and water. The process according to claim 1, wherein the ketone is cycloalkane.

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