JP2008308389A - Method for producing titanosilicate and method for producing oxime - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a titanosilicate which exhibits excellent performances as a catalyst in an ammoximation reaction of a ketone in terms of the conversion rate of the ketone, the selectivity of an oxime and catalyst life, and to provide a method for producing an oxime with good selectivity while maintaining catalyst life over a prolonged period of time by bringing a ketone into an ammoximation reaction at a high conversion rate. <P>SOLUTION: The method for producing the titanosilicate having MWW structure includes: mixing a silicon compound, a titanium compound, a boron compound, water and a structure directing agent; bringing a prepared mixture into a hydrothermal synthesis reaction by temperature rising to 150-200°C; and firing obtained crystals, wherein a temperature rising rate in the temperature range from 50°C to 150°C is ≤45°C/h. The method for producing an oxime includes bringing a ketone into an ammoximation reaction with a peroxide and ammonia in the presence of the titanosilicate having MWW structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a titanosilicate having an MWW structure and an ammoximation reaction of a ketone with a peroxide and ammonia in the presence of the titanosilicate having an MWW structure obtained by the production method. And a method of manufacturing. Oxime is useful, for example, as a raw material for amides and lactams.

Conventionally, a titanosilicate having an MWW structure has been used as one of catalysts in a method for producing an oxime by an ammoximation reaction of a ketone with a peroxide and ammonia.
As a method for producing titanosilicate having such an MWW structure, a method is proposed in which a silicon compound, a titanium compound, a boron compound, water and a structure directing agent are mixed at room temperature and then heated to a hydrothermal synthesis reaction. (Refer nonpatent literature 1).

Chemistry Letters, (Japan), 2000, p. 774-775

  However, when the titanosilicate produced by the above method is used as a catalyst in the production of an oxime in which a ketone is ammoximation-reacted with a peroxide and ammonia, the conversion of the ketone and the selectivity of the oxime are sufficient. In some cases, satisfactory performance was not exhibited. Further, it was not always sufficient in terms of catalyst life.

  Accordingly, an object of the present invention is to provide a method for producing a titanosilicate that exhibits excellent performance in terms of ketone conversion, oxime selectivity and catalyst life as a catalyst in the ketone ammoximation reaction, Another object of the present invention is to provide a method for producing an oxime with a good selectivity while allowing a ketone to undergo an ammoximation reaction at a high conversion rate and maintaining a catalyst life over a long period of time.

  As a result of intensive studies to solve the above problems, the present inventors have mixed a silicon compound, a titanium compound, a boron compound, water, and a structure directing agent, and then raised the temperature to a predetermined temperature to perform a hydrothermal synthesis reaction. In carrying out the process, it was found that a desired titanosilicate can be produced by performing the temperature increase at a temperature increase rate (temperature increase rate) between a specific temperature and a specific temperature below a certain level, and the present invention has been completed. It came to do.

  That is, the method for producing the titanosilicate of the present invention is obtained by mixing a silicon compound, a titanium compound, a boron compound, water, and a structure directing agent, then raising the temperature to 150 to 200 ° C. and subjecting it to a hydrothermal synthesis reaction. A method for producing a titanosilicate having an MWW structure by firing the obtained crystal, wherein the temperature rise rate in the temperature range from 50 ° C. to 150 ° C. is 45 ° C./hour or less.

  The oxime production method of the present invention is a method in which a ketone is ammoximation-reacted with a peroxide and ammonia in the presence of a titanosilicate having an MWW structure obtained by the method of producing the titanosilicate of the present invention. It is.

  According to the present invention, as a catalyst in the ammoximation reaction of ketone, it is possible to produce a titanosilicate that exhibits excellent performance in terms of conversion rate of ketone, selectivity of oxime, and catalyst life. It is done. Then, in the presence of such titanosilicate, an oxime can be produced with a good selectivity while maintaining the catalyst life over a long period of time by causing the ketone to undergo an ammoximation reaction at a high conversion rate.

  In the method for producing a titanosilicate according to the present invention, a silicon compound, a titanium compound, a boron compound, water and a structure directing agent are mixed and subjected to a hydrothermal synthesis reaction, and the obtained crystal is fired.

Examples of the silicon compound include tetraalkyl orthosilicate such as tetraethyl orthosilicate, silica (fumed silica), and the like.
Examples of the titanium compound include tetraalkyl orthotitanates such as tetra-n-butyl orthotitanate, peroxy titanates such as tetra-n-butyl ammonium peroxytitanate, and titanium halides.
Examples of the boron compound include boric acid and anhydrous boric acid.
The structure directing agent is used as a template for forming a layered structure. For example, conventionally known structure directing agents such as piperidine and hexamethyleneimine can be used.

  The use ratio of each raw material is based on silicon in the silicon compound, the titanium compound is 0.01 to 0.1 mol times as titanium, the boron compound is 0.1 to 2 mol times as boron, Water is preferably 3 to 50 mole times, and the structure directing agent is preferably 0.3 to 3 mole times.

It is preferable to mix each said raw material (a silicon compound, a titanium compound, a boron compound, water, and a structure directing agent) at the temperature of 50 degrees C or less, More preferably, it is 0-50 degreeC, More preferably, it is 10-50 degreeC. Mix at temperature. When the temperature at the time of mixing each raw material exceeds 50 degreeC, there exists a possibility that the production amount of an inactive titanium oxide particle may increase.
In addition, when the mixing of each raw material starts at a temperature of 50 ° C. or lower (for example, room temperature) and the temperature of the mixture exceeds 50 ° C. due to heat generated by the heat of dissolution at the time of raw material charging, 50 ° C. or higher As long as the temperature increase rate in the range described later is satisfied from that point, the temperature increase described later may be started from that temperature without particularly taking measures such as cooling.

  The method for mixing the raw materials is not particularly limited. For example, all the raw materials may be mixed together or the raw materials may be mixed sequentially. In particular, it is preferable to mix the raw material that is a liquid after mixing the raw material that is a liquid first, in that it can be uniformly stirred and, in turn, can prevent uneven distribution of titanium in the obtained titanosilicate.

The mixture of the raw materials is heated to 150 to 200 ° C. and subjected to a hydrothermal synthesis reaction. In general, hydrothermal synthesis refers to the synthesis and crystal growth method of substances performed in the presence of high-temperature water, particularly high-temperature and high-pressure water ("Iwanami Rikagaku Dictionary", 4th edition, Iwanami Shoten Co., Ltd., 1987). Specifically, the raw materials are mixed, heated in an autoclave at a temperature of about 100 to 200 ° C. under a self-pressure, and stirred for several hours to several days. Is called.
In the present invention, the conditions for the general hydrothermal synthesis reaction are the same except that the heating temperature of the hydrothermal synthesis reaction is set to 150 to 200 ° C. and the temperature rise rate during the temperature rise is controlled as described later. Can be adopted.

  When the temperature of the mixture of raw materials is increased, the rate of temperature increase (temperature increase rate) during the temperature increase from 50 ° C. to 150 ° C. is 45 ° C./hour or less, preferably 40 ° C./hour or less. When a rapid temperature increase exceeding 45 ° C./hour occurs in a specific temperature range from 50 ° C. to 150 ° C., the catalytic activity of the resulting titanosilicate is significantly reduced. In the temperature range below 50 ° C. or the temperature range exceeding 150 ° C., even if the rate of temperature increase exceeds 45 ° C./hour, there is no significant adverse effect on the catalytic activity of titanosilicate. However, not only in the specific temperature range (temperature range from 50 ° C. to 150 ° C.), but also in which period the temperature rises from the time when the raw materials are mixed to the time when hydrothermal synthesis is finished. Even if it exists, it is preferable to make temperature rise rate into the said range.

  In the present invention, the temperature rise rate indicates a temperature change per hour, that is, an average temperature change per hour. The temperature change per hour is obtained from the temperature difference between the beginning and end of one hour. When determining the rate of temperature rise in the specific temperature range (temperature range from 50 ° C. to 150 ° C.), the temperature change per hour continues every hour starting from the time of mixing or the start of temperature rise. It is preferable to measure it.

  The specific temperature range (temperature range from 50 ° C. to 150 ° C.) and the lower limit of the temperature increase rate outside the temperature range are not particularly limited, but catalytic activity is considered in view of industrial productivity. It is desirable that the internal temperature reach the target temperature quickly within the range of the temperature increase rate that does not cause a significant decrease in the temperature. The temperature increase rate is preferably 1.5 ° C./hour or more, more preferably 6 ° C./hour. It should be more than hours. However, immediately after the start of temperature increase or immediately before the internal temperature reaches the target temperature, the preferable range of the lower limit mentioned above may be exceeded due to the characteristics of the heating operation.

  The heating means in the hydrothermal synthesis reaction is not particularly limited. For example, using a reactor with a jacket on the outside of the reactor and heating a mixture in the reactor by circulating a high-temperature fluid through the jacket, contacting a solid heating device such as a band heater on the outside of the reactor A method of heating the mixture in the reactor by installing a pipe capable of circulating a fluid inside the reactor, and a method of heating the mixture in the reactor by circulating a high-temperature fluid through the pipe. be able to.

  The rate of temperature rise is usually determined by gradually increasing the temperature of the heating medium (for example, the temperature of the high-temperature fluid or the set temperature of the solid heating device) at a constant rate (linear method), heating The temperature of the working medium can be appropriately adjusted by a method of increasing the temperature of the medium every certain time (stepped method). At this time, a temperature difference generally occurs between the temperature of the heating medium and the internal temperature (the temperature of the mixture in the reactor), and even if the temperature rise of the heating medium is stopped and maintained at a constant temperature, the internal temperature There is a time lag before the temperature reaches a certain temperature. Therefore, normally, when the internal temperature reaches a temperature that is 10-20 ° C. lower than the target temperature, the temperature of the heating medium is kept constant, and after confirming that the internal temperature stops rising and becomes constant Then, a method is adopted in which the temperature of the heating medium is adjusted again so that the internal temperature finally becomes a desired temperature. If the temperature of the reactor surface in contact with the reaction liquid (mixed liquid) is high, the temperature of the reaction liquid rises locally, and the catalytic activity of the obtained titanosilicate may be reduced. The temperature is preferably 240 ° C. or lower.

  The crystal obtained by the hydrothermal synthesis reaction is a layered titanosilicate. Specifically, the layer structure of the layered titanosilicate can be confirmed by the presence of a peak on the 001 plane to the 002 plane in the X-ray diffraction pattern (for example, the 33rd in addition to Non-Patent Document 1). Summary of Petroleum and Petrochemical Discussion Meeting; Catalyst, 2001, 43, p158-160; Chemical Communications (UK), 2002, p1026-1027; Catalyst, 2002, 44, p468 -470; etc.). Then, the layer structure of the layered titanosilicate is converted into an MWW structure by firing the interlayer dehydration condensation of the crystal sheet to form a three-dimensional crystal structure. Specifically, this structural conversion can be confirmed by the disappearance of the 001 to 002 plane peaks in the X-ray diffraction pattern (see the above-mentioned documents).

  If necessary, the crystals obtained by the hydrothermal synthesis reaction may be subjected to an acid treatment before being subjected to firing described later. By performing acid treatment, boron introduced into the titanosilicate skeleton and titanium outside the skeleton can be removed, and the catalytic activity of the obtained titanosilicate can be improved.

  When the acid treatment is performed, the acid treatment is usually performed for 1 to 48 hours under heating and reflux. Examples of acids that can be used for the acid treatment include inorganic acids such as nitric acid, sulfuric acid, carbonic acid, and phosphoric acid, and organic acids such as formic acid and acetic acid. Of these, nitric acid and sulfuric acid are particularly preferable. The amount of acid used is not particularly limited, and may be set as appropriate as long as boron introduced into the titanosilicate skeleton and titanium outside the skeleton can be sufficiently removed.

  The crystals (layered titanosilicate) obtained by the hydrothermal synthesis reaction are calcined. The firing conditions are not particularly limited, and may be heated at a temperature of about 200 to 700 ° C. for about 1 to 24 hours.

  The calcination is usually performed after separating the crystals from the reaction solution containing the crystals (layered titanosilicate) and, if necessary, washing and drying. At this time, the conditions and methods of separation, washing and drying are not particularly limited, and can be performed according to ordinary conditions and methods. For example, it may be separated by filtration, and the filter residue may be washed with water until the pH of the washing solution is in the range of 4 to 10, and dried at 50 to 150 ° C. for about 1 to 24 hours. Further, when drying is performed using a spray dryer, it is advantageous in that it can be formed into particles having a particle diameter of about 1 to 1000 μm simultaneously with drying. Such separation, washing and drying can be performed on the crystals obtained by the hydrothermal synthesis reaction before the acid treatment, if necessary.

  The titanosilicate obtained by the production method of the present invention is a crystalline titanosilicate having an MWW structure (hereinafter, the crystalline titanosilicate having an MWW structure may be referred to as “Ti-MWW”). MWW is one of the structure codes of zeolite defined by the International Zeolite Association (IZA). Specific examples of the compound having an MWW structure include MCM-22, SSZ-25, ITQ-1, ERB-1, and PSH-3.

  As used herein, titanosilicate includes titanium, silicon, and oxygen as elements constituting the skeleton, and the skeleton may be substantially composed of only titanium, silicon, and oxygen. In addition, elements other than titanium, silicon, and oxygen, such as boron, aluminum, gallium, iron, and chromium, may be included as elements constituting the skeleton.

  In the Ti-MWW obtained by the production method of the present invention, the atomic ratio of titanium to silicon (Ti / Si) is usually 0.005 to 0.1, preferably 0.01 or more. In addition, when this titanosilicate contains elements other than titanium, silicon, and oxygen, the atomic ratio of the contained element with respect to silicon is 0.05 or less normally, Preferably it is 0.02 or less. Moreover, oxygen can exist corresponding to the atomic ratio and oxidation number of each element other than oxygen. A typical composition of such titanosilicate can be represented by the following formula with silicon as the reference (= 1).

SiO ₂ xTiO ₂ yMO _{n / 2}
(In the formula, M represents at least one element other than silicon, titanium, and oxygen, n is the oxidation number of the element, x is 0.005 to 0.1, and y is 0 to 0.05. .)

  The content ratio (Ti content) of titanium contained in Ti-MWW obtained by the production method of the present invention in titanosilicate is usually 0.4% or more, preferably 1% or more.

  Thus, a titanosilicate having an MWW structure can be obtained. In the presence of this titanosilicate, the ammoximation reaction of the ketone with peroxide and ammonia allows the ketone to be ammoximeated at a high conversion rate while maintaining the catalyst life for a long time. Oxime can be produced at a rate. Such titanosilicate is expected to have excellent catalytic activity as a catalyst in oxidation reactions such as epoxidation and oximation other than the above reaction.

Ti-MWW used as a catalyst may be used in the form of particles or pellets with or without a binder, or may be used by being supported on a carrier.
Ti-MWW used as a catalyst is preferably suspended in the liquid phase of the reaction mixture and present as a solid phase, and the ratio is usually about 0.1 to 10% by weight with respect to the liquid phase. . In addition, for the purpose of suppressing a decrease in the catalytic activity of Ti-MWW, silicon compounds other than titanosilicates such as silica gel, silicic acid, and crystalline silica may coexist.

  The ketone may be an aliphatic ketone, an alicyclic ketone, or an aromatic ketone, and two or more of them may be used as necessary. The ketone may be obtained by, for example, oxidation of alkane, may be obtained by oxidation (dehydrogenation) of secondary alcohol, or hydration and oxidation of alkene. It may be obtained by (dehydrogenation).

  Specific examples of the ketone include dialkyl ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; alkyl alkenyl ketones such as mesityl oxide; alkyl aryl ketones such as acetophenone; diaryl ketones such as benzophenone; Examples include cycloalkanones such as nonone, cyclohexanone, cyclooctanone and cyclododecanone; cycloalkenones such as cyclopentenone and cyclohexenone. Among these, cycloalkanone is preferable.

Specific examples of the peroxide include hydrogen peroxide, and organic peroxides such as t-butyl hydroperoxide, di-t-butyl peroxide, and cumene hydroperoxide. Among these, hydrogen peroxide is preferable in terms of reactivity.
Hydrogen peroxide is usually produced by the so-called anthraquinone method, and is generally marketed as an aqueous solution having a concentration of 10 to 70% by weight. Therefore, this aqueous hydrogen peroxide solution can be used. Hydrogen peroxide can also be produced by reacting hydrogen and oxygen in an organic solvent in the presence of a solid catalyst supporting metal palladium. An organic solvent solution of hydrogen peroxide obtained by separating the catalyst from the mixture can be used.

  The amount of the peroxide used is usually 0.5 to 3 moles, preferably 0.5 to 1.5 moles per mole of ketone. Examples of the peroxide include phosphates such as sodium phosphate, polyphosphates such as sodium pyrophosphate and sodium tripolyphosphate, pyrophosphate, ascorbic acid, ethylenediaminetetraacetic acid, nitrotriacetic acid, aminotriacetic acid. Diethylenetriaminepentaacetic acid or the like may be added.

  The ammonia may be a gaseous one, a liquid one, or a solution of water or an organic solvent.

  The amount of ammonia used is preferably adjusted so that the ammonia concentration in the liquid phase of the reaction mixture is 1% by weight or more. Thus, by setting the ammonia concentration in the liquid phase of the reaction mixture to 1% by weight or more, it is possible to increase the conversion rate of the raw material ketone and the selectivity of the target oxime, and thus the yield of the target oxime. The rate can be increased. The ammonia concentration in the liquid phase of the reaction mixture is preferably 1.5% by weight or more, while the upper limit is usually 10% by weight or less, preferably 5% by weight or less. It is good. In addition, the standard of the usage-amount of ammonia is 1 mol or more normally with respect to 1 mol of ketones, Preferably it is 1.5 mol or more.

  The ammoximation reaction can also be performed in a solvent. Examples of the reaction solvent at this time include aromatic compounds such as benzene and toluene, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, t -Alcohols such as amyl alcohol, water and the like. Among these, alcohol and water are preferable, and a mixed solvent of alcohol and water is more preferable in terms of reactivity.

  The ammoximation reaction may be performed batchwise or continuously. In particular, it is desirable from the viewpoint of productivity and operability that the reaction system is continuously extracted by supplying a reaction mixture from the reaction system while supplying ketone, peroxide and ammonia into the reaction system.

  The batch reaction may be performed, for example, by adding a ketone, ammonia, a catalyst, and a solvent to a reactor, and supplying a peroxide to the reactor with stirring, or by adding a ketone, a catalyst, and a solvent to the reactor. It may be carried out by supplying peroxide and ammonia into this under stirring, or by adding a catalyst and solvent into the reactor and supplying ketone, peroxide and ammonia into this under stirring. You may go.

In the continuous reaction, for example, a reaction mixture in which a catalyst is suspended is present in the reactor, and a ketone, peroxide, ammonia and a solvent are supplied to the reaction mixture through a filter or the like from the reactor. It can be suitably carried out by extracting the liquid phase of the reaction mixture.
In either case of batch type or continuous type, the reactor is preferably glass-lined or stainless steel from the viewpoint of preventing decomposition of peroxide.

The reaction temperature of the ammoximation reaction is usually 50 to 120 ° C, preferably 70 to 100 ° C. The reaction pressure may be normal pressure, but in order to easily dissolve ammonia in the liquid phase of the reaction mixture, the absolute pressure is usually 0.2 to 1 MPa, preferably 0.2 to 0.5 MPa. It is preferable to carry out the reaction. When performing under pressure, you may adjust a pressure using inert gas, such as nitrogen and helium.
The post-treatment operation for recovering the oxime from the reaction mixture obtained by the ammoximation reaction is not particularly limited and may be appropriately performed according to a normal method. For example, after separating the catalyst from the reaction mixture by filtration or decantation, the oxime can be separated and recovered by subjecting the liquid phase to distillation.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
Here, the Ti content (content ratio of the amount of titanium in Ti-MWW) of the titanosilicate (Ti-MWW) obtained in each Example and Comparative Example was measured by ICP analysis. Moreover, the analysis of the liquid phase in the production of oxime was performed by gas chromatography.
The catalyst life of Ti-MWW in oxime production was judged based on the oxygen concentration in the autoclave. In other words, when hydrogen peroxide is used as a peroxide, if the catalytic activity decreases, the amount of oxygen generated due to thermal decomposition of hydrogen peroxide increases, and the oxygen concentration in the system increases rapidly. It can be said that the longer the reaction time until the oxygen concentration rapidly increases, the longer the catalyst life.

<ICP analysis>
Weigh the sample in a platinum dish, add hydrofluoric acid and nitric acid, heat and evaporate to dryness, add sodium carbonate and boric acid, melt with a burner, and add diluted hydrochloric acid to the resulting melt. In addition, the mixture was heated to obtain a test solution as a constant volume. The Ti in this test solution was subjected to ICP analysis with an ICP emission analyzer (“SPS4000” manufactured by Seiko Denshi Kogyo Co., Ltd.), and the Ti content in the sample was determined.

Example 1
[Manufacture of titanosilicate]
In a beaker, 445.87 g of pure water, 77.53 g of piperidine, and 11.07 g of tetra-n-butyl orthotitanate were placed, and the same was applied to room temperature (20 ± 10 ° C .; “room temperature” described below) in an air atmosphere. ), And the mixture was stirred until it became uniform after adding 53.93 g of boric acid at room temperature. 39.20 g of fumed silica (“CAB-O-SIL M-7D” manufactured by CABOT) was added to the obtained aqueous solution at room temperature and stirred for 1 hour, and then the mixture was transferred to an autoclave and the autoclave was sealed.

  The mixture was heated from 29.5 ° C. to 170 ° C. over 5 hours by heating the autoclave with a heater while stirring. During this time, the internal temperature of the autoclave is constantly monitored, and it is confirmed that the temperature continues to rise at least in the temperature range from 50 ° C to 150 ° C. At the same time, the temperature rise rate from the internal temperature every hour (temperature rise rate) Asked. Then, the heater temperature was manually raised stepwise every hour so that the temperature increase rate did not exceed 45 ° C./hour between 50 ° C. and 150 ° C. Specifically, the internal temperature, the heating rate and the heater temperature every hour in the temperature range from 50 ° C. to 150 ° C. are as shown in Table 1, and the heating rate is 39.1 ° C./hour at the maximum. there were.

  After the internal temperature of the autoclave reached 170 ° C., hydrothermal synthesis was performed by heating at the same temperature for 7.5 days. The obtained suspension was filtered, and the residue was washed until the pH of the washing solution became 10 or less, and then dried at 110 ° C. for 16 hours to obtain 44.40 g of a white powder. 30 g of this white powder was heated to reflux in 900 g of 2M nitric acid for 16 hours and then filtered, and the residue was washed until the pH of the washing solution reached 4 or higher. The obtained white powder was dried and then calcined at 530 ° C. for 10 hours to obtain Ti-MWW (1) having a Ti content of 2.1%.

[Oxime production]
A 1 liter autoclave was used as a reactor, in which cyclohexanone was 19.63 g / hour, hydrous t-butyl alcohol (water 12 wt%) was 34 g / hour, and 50 wt% hydrogen peroxide was 15.64 g. By extracting the liquid phase of the reaction mixture from the reactor through a filter while supplying ammonia at a rate of / hour and supplying ammonia in a concentration of 2% by weight in the liquid phase of the reaction mixture. The continuous reaction was performed under the conditions of 95 ° C., pressure 0.35 MPa (absolute pressure), and residence time 6 hours. During this period, the Ti-MWW (1) was present in the reaction mixture in the reactor at a ratio of 0.2 wt% with respect to the liquid phase.

  As a result of analyzing the liquid phase extracted 5.5 hours after the start of the reaction, the conversion of cyclohexanone was 99.3%, the selectivity of cyclohexanone oxime was 99.6%, and the yield of cyclohexanone oxime was 98.8%. Met. As a result of analyzing the liquid phase extracted 96 hours after the start of the reaction, the conversion of cyclohexanone was 99.5%, the selectivity of cyclohexanone oxime was 99.4%, and the yield of cyclohexanone oxime was 99.0%. Met. Furthermore, when the reaction was continued, the oxygen concentration in the autoclave increased rapidly after 155 hours from the start of the reaction, so the reaction was terminated at this point.

(Example 2)
[Manufacture of titanosilicate]
In a beaker, 445.20 g of pure water, 77.83 g of piperidine and 11.20 g of tetra-n-butyl orthotitanate were added and stirred in an air atmosphere until it became uniform at room temperature, and then 53.68 g of boric acid was added at room temperature. And stirred until uniform. After 39.70 g of fumed silica (“CAB-O-SIL M-7D” manufactured by CABOT) was added to the obtained aqueous solution at room temperature and stirred for 1 hour, the mixture was transferred to an autoclave and the autoclave was sealed.

  The mixture was heated from 28.9 ° C. to 173 ° C. over 10 hours by heating the autoclave with a heater while stirring. During this time, the internal temperature of the autoclave is constantly monitored, and it is confirmed that the temperature continues to rise at least in the temperature range from 50 ° C to 150 ° C. At the same time, the temperature rise rate from the internal temperature every hour (temperature rise rate) Asked. Then, the heater temperature was manually raised stepwise every hour so that the temperature increase rate did not exceed 45 ° C./hour between 50 ° C. and 150 ° C. Specifically, the internal temperature, the heating rate and the heater temperature for each hour in the temperature range from 50 ° C. to 150 ° C. are as shown in Table 2, and the heating rate is 28.2 ° C./hour at the maximum. there were.

  After the internal temperature of the autoclave reached 173 ° C., hydrothermal synthesis was performed by heating at the same temperature for 7 days. The obtained suspension was filtered, and the residue was washed until the pH of the washing solution was 10 or less, and then dried at 110 ° C. for 16 hours to obtain 43.83 g of a white powder. 30 g of this white powder was heated to reflux in 900 g of 2M nitric acid for 16 hours and then filtered, and the residue was washed until the pH of the washing solution reached 4 or higher. The obtained white powder was dried and then calcined at 530 ° C. for 10 hours to obtain Ti-MWW (2) having a Ti content of 2.4%.

[Oxime production]
A continuous reaction was carried out under the same conditions as in Example 1 except that the above Ti-MWW (2) was used instead of Ti-MWW (1).
As a result of analyzing the liquid phase extracted 17 hours after the start of the reaction, the conversion of cyclohexanone was 99.8%, the selectivity of cyclohexanone oxime was 99.6%, and the yield of cyclohexanone oxime was 99.4%. It was. As a result of analyzing the liquid phase extracted 125 hours after the start of the reaction, the conversion of cyclohexanone was 99.1%, the selectivity of cyclohexanone oxime was 99.2%, and the yield of cyclohexanone oxime was 98.3%. Met. Furthermore, when the reaction was continued, the oxygen concentration in the autoclave increased rapidly after 138 hours from the start of the reaction, so the reaction was terminated at this point.

(Example 3)
[Manufacture of titanosilicate]
In a beaker, 445.50 g of pure water, 77.48 g of piperidine and 9.01 g of tetra-n-butyl orthotitanate were added and stirred in an air atmosphere until it became uniform at room temperature, and then 53.65 g of boric acid was added at room temperature. And stirred until uniform. 39.85 g of fumed silica (“CAB-O-SIL M-7D” manufactured by CABOT) was added to the obtained aqueous solution at room temperature and stirred for 1 hour, and then Ti-MWW (1) obtained in Example 1 was used. 0.50 g was added as a seed crystal to the mixed solution, and the mixed solution was transferred to an autoclave to seal the autoclave.

  The mixture was heated from 27.2 ° C. to 154 ° C. over 7 hours by heating the autoclave with a heater while stirring. During this time, the internal temperature of the autoclave is constantly monitored, and it is confirmed that the temperature continues to rise at least in the temperature range from 50 ° C to 150 ° C. At the same time, the temperature rise rate from the internal temperature every hour (temperature rise rate) Asked. And it heated by the method of raising a heater temperature linearly so that the temperature increase rate may not exceed 45 degreeC / hour between 50 degreeC and 150 degreeC. Specifically, the internal temperature, the heating rate and the heater temperature every hour in the temperature range from 50 ° C. to 150 ° C. are as shown in Table 3, and the heating rate is 33.5 ° C./hour at the maximum. there were.

  After the internal temperature of the autoclave reached 154 ° C., hydrothermal synthesis was performed by heating at the same temperature for 12 hours. Then, after heating up again from 154 degreeC to 170 degreeC over 10 hours, it heated for 6.5 days at the same temperature and hydrothermal synthesis was performed. The obtained suspension was filtered, and the residue was washed until the pH of the wash became 10 or less, and then dried at 110 ° C. for 16 hours to obtain 76.50 g of a white powder. 30 g of this white powder was heated to reflux in 900 g of 2M nitric acid for 16 hours and then filtered, and the residue was washed until the pH of the washing solution reached 4 or higher. The obtained white powder was dried and then calcined at 530 ° C. for 10 hours to obtain Ti-MWW (3) having a Ti content of 1.1%.

[Oxime production]
A continuous reaction was carried out under the same conditions as in Example 1 except that the above Ti-MWW (3) was used instead of Ti-MWW (1).
As a result of analyzing the liquid phase extracted 5.5 hours after the start of the reaction, the conversion of cyclohexanone was 99.2%, the selectivity of cyclohexanone oxime was 99.5%, and the yield of cyclohexanone oxime was 98.7%. Met. As a result of analyzing the liquid phase extracted 127 hours after the start of the reaction, the conversion of cyclohexanone was 95.9%, the selectivity of cyclohexanone oxime was 98.1%, and the yield of cyclohexanone oxime was 94.1%. Met. Furthermore, when the reaction was continued, since the oxygen concentration in the autoclave rapidly increased 131 hours after the start of the reaction, the reaction was terminated at this point.

Example 4
[Manufacture of titanosilicate]
In a beaker, 450.16 g of pure water, 77.63 g of piperidine, and 8.80 g of tetra-n-butyl orthotitanate were added and stirred in an air atmosphere until uniform at room temperature, and then 53.86 g of boric acid was added at room temperature. And stirred until uniform. After adding 39.20 g of fumed silica (“CAB-O-SIL M-7D” manufactured by CABOT) to the obtained aqueous solution at room temperature and stirring for 1 hour, Ti-MWW (1) obtained in Example 1 was used. 0.35 g was added as a seed crystal to the mixed solution, and the mixed solution was transferred to an autoclave to seal the autoclave.

  The mixture was heated from 24.5 ° C. to 175 ° C. over 7 hours by heating the autoclave with a heater while stirring. During this time, the internal temperature of the autoclave is constantly monitored, and it is confirmed that the temperature continues to rise at least in the temperature range from 50 ° C to 150 ° C. At the same time, the temperature rise rate from the internal temperature every hour (temperature rise rate) Asked. And it heated by the method of raising a heater temperature linearly so that the temperature increase rate may not exceed 45 degreeC / hour between 50 degreeC and 150 degreeC. Specifically, the internal temperature, the heating rate and the heater temperature every hour in the temperature range from 50 ° C. to 150 ° C. are as shown in Table 4, and the heating rate is 33.9 ° C./hour at the maximum. there were.

  After the internal temperature of the autoclave reached 175 ° C., hydrothermal synthesis was performed by heating at the same temperature for 7 days. The obtained suspension was filtered, and the residue was washed until the pH of the washing solution was 10 or less, and then dried at 110 ° C. for 16 hours to obtain 44.90 g of a white powder. 7 g of this white powder was heated to reflux in 210 g of 2M nitric acid for 8 hours and then filtered. The residue was washed until the pH of the washing solution was 4 or higher. The obtained white powder was dried and then calcined at 530 ° C. for 10 hours to obtain Ti-MWW (4) having a Ti content of 1.6%.

[Oxime production]
A continuous reaction was carried out under the same conditions as in Example 1 except that the above Ti-MWW (4) was used instead of Ti-MWW (1).
As a result of analyzing the liquid phase extracted 6.5 hours after the start of the reaction, the conversion of cyclohexanone was 99.7%, the selectivity of cyclohexanone oxime was 99.7%, and the yield of cyclohexanone oxime was 99.4%. Met. As a result of analyzing the liquid phase extracted after 70 hours from the start of the reaction, the conversion of cyclohexanone was 99.9%, the selectivity of cyclohexanone oxime was 99.7%, and the yield of cyclohexanone oxime was 99.6%. Met. Furthermore, when the reaction was continued, the oxygen concentration in the autoclave rapidly increased 89 hours after the start of the reaction, so the reaction was terminated at this point.

(Comparative Example 1)
[Manufacture of titanosilicate]
In a beaker, 379.03 g of pure water, 120.05 g of piperidine, and 13.95 g of tetra-n-butyl orthotitanate were added and stirred in an air atmosphere until it became uniform at room temperature, and then 82.82 g of boric acid was added at room temperature. And stirred until uniform. After adding 60.23 g of fumed silica (“CAB-O-SIL M-7D” manufactured by CABOT) at room temperature and stirring for 1 hour, the mixture was transferred to an autoclave and the autoclave was sealed.

  The mixture was heated from 22.3 ° C. to 184 ° C. over 7 hours by heating the autoclave with a heater while stirring. During this time, the internal temperature of the autoclave is constantly monitored, and it is confirmed that the temperature continues to rise at least in the temperature range from 50 ° C to 150 ° C. At the same time, the temperature rise rate from the internal temperature every hour (temperature rise rate) Asked. Heating was performed by manually raising the heater temperature step by step every hour. Specifically, the internal temperature, the heating rate and the heater temperature for each hour in the temperature range from 50 ° C. to 150 ° C. are as shown in Table 5, and the heating rate is 49.0 ° C./hour at the maximum. There was a time.

  After the internal temperature of the autoclave reached 184 ° C., hydrothermal synthesis was performed by heating at the same temperature for 7 days. The obtained suspension was filtered, and the residue was washed until the pH of the washing solution became 10 or less, and then dried at 110 ° C. for 16 hours to obtain 43.21 g of a white powder. 30 g of this white powder was heated and refluxed in 900 g of 2M nitric acid for 8 hours and then filtered, and the residue was washed until the pH of the washing solution became 4 or higher. The obtained white powder was dried and then calcined at 530 ° C. for 10 hours to obtain Ti-MWW (C1) having a Ti content of 2.6%.

[Oxime production]
A continuous reaction was performed under the same conditions as in Example 1 except that the above Ti-MWW (C1) was used instead of Ti-MWW (1).
However, since the oxygen concentration in the autoclave rapidly increased immediately after the start of the reaction, the reaction was terminated after 30 minutes.

(Comparative Example 2)
[Manufacture of titanosilicate]
In a beaker, 446.35 g of pure water, 77.93 g of piperidine and 8.86 g of tetra-n-butyl orthotitanate were added and stirred in an air atmosphere until it became uniform at room temperature, and then 54.81 g of boric acid was added at room temperature. And stirred until uniform. After 39.40 g of fumed silica (“CAB-O-SIL M-7D” manufactured by CABOT) was added to the obtained aqueous solution at room temperature and stirred for 1 hour, the mixture was transferred to an autoclave and the autoclave was sealed.

  The mixture was heated from 24.6 ° C. to 163 ° C. over 7 hours by heating the autoclave with a heater while stirring. During this time, the internal temperature of the autoclave is constantly monitored, and it is confirmed that the temperature continues to rise at least in the temperature range from 50 ° C to 150 ° C. At the same time, the temperature rise rate from the internal temperature every hour (temperature rise rate) Asked. Heating was performed by raising the heater temperature linearly. Specifically, the internal temperature, the heating rate and the heater temperature for each hour in the temperature range from 50 ° C. to 150 ° C. are as shown in Table 6, and the heating rate is 47.6 ° C./hour at the maximum. There was a time.

  After the internal temperature of the autoclave reached 163 ° C., hydrothermal synthesis was performed by heating at the same temperature for 14 hours. Then, after heating up again from 163 degreeC to 176 degreeC over 4 hours, it heated at the same temperature for 7 days and hydrothermal synthesis was performed. The obtained suspension was filtered, and the residue was washed until the pH of the washing solution was 10 or less, and then dried at 110 ° C. for 16 hours to obtain 41.05 g of a white powder. 30 g of this white powder was heated and refluxed in 900 g of 2M nitric acid for 8 hours and then filtered, and the residue was washed until the pH of the washing solution became 4 or higher. The obtained white powder was dried and then calcined at 530 ° C. for 10 hours to obtain Ti-MWW (C2) having a Ti content of 1.8%.

[Oxime production]
A continuous reaction was performed under the same conditions as in Example 1 except that the above Ti-MWW (C2) was used instead of Ti-MWW (1).
However, since the oxygen concentration in the autoclave rapidly increased immediately after the start of the reaction, the reaction was terminated after 30 minutes.

(Comparative Example 3)
[Manufacture of titanosilicate]
In a beaker, 446.04 g of pure water, 77.58 g of piperidine, and 8.88 g of tetra-n-butyl orthotitanate were added and stirred in an air atmosphere until uniform at room temperature, and then 53.77 g of boric acid was added at room temperature. And stirred until uniform. After 39.59 g of fumed silica (“CAB-O-SIL M-7D” manufactured by CABOT) was added to the obtained aqueous solution at room temperature and stirred for 1 hour, the mixture was transferred to an autoclave and the autoclave was sealed.

  The mixture was heated from 25.9 ° C. to 165 ° C. over 7 hours by heating the autoclave with a heater while stirring. During this time, the internal temperature of the autoclave is constantly monitored, and it is confirmed that the temperature continues to rise at least in the temperature range from 50 ° C to 150 ° C. At the same time, the temperature rise rate from the internal temperature every hour (temperature rise rate) Asked. Heating was performed by raising the heater temperature linearly. Specifically, the internal temperature, the heating rate and the heater temperature for each hour in the temperature range from 50 ° C. to 150 ° C. are as shown in Table 7, and the heating rate is 48.2 ° C./hour at the maximum. There was a time.

  After the internal temperature of the autoclave reached 165 ° C., hydrothermal synthesis was performed by heating at the same temperature for 12 hours. Then, after heating up again from 165 degreeC to 178 degreeC over 3 hours, it heated at the same temperature for 6 days and hydrothermal synthesis was performed. The obtained suspension was filtered, and the residue was washed until the pH of the washing solution became 10 or less, and then dried at 110 ° C. for 16 hours to obtain 40.85 g of a white powder. 30 g of this white powder was heated and refluxed in 900 g of 2M nitric acid for 8 hours and then filtered, and the residue was washed until the pH of the washing solution became 4 or higher. The obtained white powder was dried and then calcined at 530 ° C. for 10 hours to obtain Ti-MWW (C3) having a Ti content of 1.5%.

[Oxime production]
A continuous reaction was performed under the same conditions as in Example 1 except that the above Ti-MWW (C3) was used instead of Ti-MWW (1).
However, since the oxygen concentration in the autoclave rapidly increased immediately after the start of the reaction, the reaction was terminated after 1 hour. As a result of analyzing the liquid phase extracted after completion of the reaction, the conversion of cyclohexanone was 58.9%, the selectivity of cyclohexanone oxime was 95.7%, and the yield of cyclohexanone oxime was 56.4%.

(Comparative Example 4)
[Manufacture of titanosilicate]
In a beaker, 450.16 g of pure water, 77.63 g of piperidine, and 8.80 g of tetra-n-butyl orthotitanate were added and stirred in an air atmosphere until uniform at room temperature, and then 53.86 g of boric acid was added at room temperature. And stirred until uniform. After adding 39.20 g of fumed silica (“CAB-O-SIL M-7D” manufactured by CABOT) to the obtained aqueous solution at room temperature and stirring for 1 hour, Ti-MWW (1) obtained in Example 1 was used. 0.35 g was added as a seed crystal to the mixed solution, and the mixed solution was transferred to an autoclave to seal the autoclave.

  The mixture was heated from 27.9 ° C. to 163 ° C. over 5 hours by heating the autoclave with a heater while stirring. During this time, the internal temperature of the autoclave is constantly monitored, and it is confirmed that the temperature continues to rise at least in the temperature range from 50 ° C to 150 ° C. At the same time, the temperature rise rate from the internal temperature every hour (temperature rise rate) Asked. Heating was performed by raising the heater temperature linearly. Specifically, the internal temperature, the heating rate and the heater temperature for each hour in the temperature range from 50 ° C. to 150 ° C. are as shown in Table 8, and the heating rate is 45.5 ° C./hour at the maximum. There was a time.

  After the internal temperature of the autoclave reached 163 ° C., hydrothermal synthesis was performed by heating at the same temperature for 16 hours. Then, after heating up again from 163 degreeC to 174 degreeC over 3 hours, it heated at the same temperature for 7 days and hydrothermal synthesis was performed. The obtained suspension was filtered, and the residue was washed until the pH of the washing solution was 10 or less, and then dried at 110 ° C. for 16 hours to obtain 44.90 g of a white powder. 7 g of this white powder was heated to reflux in 210 g of 2M nitric acid for 8 hours and then filtered. The residue was washed until the pH of the washing solution was 4 or higher. The obtained white powder was dried and then calcined at 530 ° C. for 10 hours to obtain Ti-MWW (C4) having a Ti content of 1.6%.

[Oxime production]
A continuous reaction was performed under the same conditions as in Example 1 except that the above Ti-MWW (C4) was used instead of Ti-MWW (1).
However, since the oxygen concentration in the autoclave rapidly increased immediately after the start of the reaction, the reaction was terminated after 1.5 hours. As a result of analyzing the liquid phase extracted after completion of the reaction, the conversion of cyclohexanone was 62.2%, the selectivity of cyclohexanone oxime was 85.4%, and the yield of cyclohexanone oxime was 53.1%.

Claims (5)

  After mixing a silicon compound, a titanium compound, a boron compound, water, and a structure-directing agent, the temperature is raised to 150 to 200 ° C., subjected to a hydrothermal synthesis reaction, and the resulting crystal is fired to obtain a tita having an MWW structure. A method for producing a titanosilicate, wherein the temperature rise rate in a temperature range from 50 ° C to 150 ° C is 45 ° C / hour or less.   A method for producing an oxime, wherein a ketone is subjected to an ammoximation reaction with a peroxide and ammonia in the presence of a titanosilicate having an MWW structure obtained by the method for producing a titanosilicate according to claim 1.   The method for producing an oxime according to claim 2, wherein the ammoximation reaction is carried out in a mixed solvent of alcohol and water.   The method for producing an oxime according to claim 2 or 3, wherein the peroxide is hydrogen peroxide.   The method for producing an oxime according to any one of claims 2 to 4, wherein the ketone is a cycloalkanone.