CN112724038B - Production method of cyclic ketoxime - Google Patents
Production method of cyclic ketoxime Download PDFInfo
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Abstract
The invention relates to the field of synthesis of cyclic ketoxime, and discloses a production method of cyclic ketoxime, which comprises the following steps: (I) Mixing a catalyst, cyclic ketone, ammonia and a solvent to obtain a mixed material; (II) contacting the mixed material obtained in the step (I) with peroxide under the condition of cyclic ketone oxidation reaction; wherein the catalyst comprises a metal-containing mesoporous molecular sieve, and the metal-containing mesoporous molecular sieve comprises: a mesoporous molecular sieve, fluorine elements, and metal elements selected from at least one of group IVB metal elements and group IVA metal elements; the molar ratio of the metal element to the fluorine element to the mesoporous molecular sieve is 1: (0.1-10): (10-100), wherein the mesoporous molecular sieve is SiO 2 And (6) counting. The method is environment-friendly, and has the characteristics of high reactant conversion rate and high selectivity of the product cyclic ketoxime.
Description
Technical Field
The invention relates to the field of synthesis of cyclic ketoxime, and in particular relates to a production method of cyclic ketoxime.
Background
Currently, cyclohexanone oxime is mainly synthesized by the reaction of hydroxylamine salt and cyclohexanone. This process has two major disadvantages: (1) high dosage of hydroxylamine salt; (2) A large amount of by-product inorganic salts such as ammonium sulfate (Gerd d. Catalysis reviews,2001,43 (4): 381-441.) are produced and the process is not environmentally friendly.
US4745221a discloses a method for synthesizing cyclohexanone oxime using titanium silicalite molecular sieve or a mixture of silica and titanium silicalite molecular sieve as a catalyst, but the selectivity of the product oxime is low, only 79.45%, and the utilization rate of hydrogen peroxide is only 68.7%. US4794198a and US5227525a disclose processes for synthesizing cyclohexanone oxime by liquid phase ammoxidation using titanium silicalite molecular sieve as catalyst and tert-butanol-water as solvent, respectively, wherein the conversion rate of cyclohexanone can reach 98.3%, and the selectivity of cyclohexanone oxime can reach 99.6%, but the processes have the disadvantages of complex post-reaction treatment and difficult treatment of the separation process of the product cyclohexanone oxime. EP0496385A1 discloses a method for synthesizing oxime by liquid-phase ammoxidation, which adopts multi-step treatment, i.e. a method of two-kettle or three-kettle series connection and hydrogen peroxide multi-point feeding, and although the high conversion rate of cyclohexanone and the high selectivity of cyclohexanone oxime are ensured, the utilization rate of hydrogen peroxide is only 89% at most. US06462235B1 discloses a liquid phase method for producing oxime using titanium silicalite TS-1 as a catalyst and aldehyde or ketone, ammonia and hydrogen peroxide as raw materials under the coexistence of ammonium salt or substituted ammonium salt, which is very effective for macromolecular cyclic ketones, but requires the addition of a cocatalyst ammonium salt or substituted ammonium salt in the reaction to obtain high conversion and selectivity, which increases the cost of the reaction and the difficulty of product separation. CN1432560A discloses a method for synthesizing cyclohexanone oxime by using 0.1-0.3 μm titanium silicalite TS-1 as a catalyst, which solves the problem of catalyst separation, but the reaction system still uses tert-butyl alcohol-water as a solvent, and has the defect of complex post-reaction treatment. Therefore, many difficulties still exist in the ammoxidation reaction of the macromolecular cyclic ketone at present.
In order to solve the above problems, it is necessary to develop a novel synthesis process of an environment-friendly cyclic ketoxime.
Disclosure of Invention
The invention aims to overcome the defects of the ammoxidation reaction of cyclic ketone in the prior art, and provides a production method of cyclic ketoxime, which is environment-friendly and has the characteristics of high reactant conversion rate and high selectivity of the product cyclic ketoxime.
In order to achieve the above object, the present invention provides a process for producing a cyclic ketoxime, which comprises:
(I) Mixing a catalyst, cyclic ketone, ammonia and a solvent to obtain a mixed material;
(II) contacting the mixed material obtained in the step (I) with peroxide under the condition of cyclic ketone oxidation reaction;
wherein the catalyst comprises a metal-containing mesoporous molecular sieve comprising: a mesoporous molecular sieve, fluorine elements, and metal elements selected from at least one of group IVB metal elements and group IVA metal elements; the molar ratio of the metal element to the fluorine element to the mesoporous molecular sieve is 1: (0.1-10): (10-100), wherein the mesoporous molecular sieve is SiO 2 And (6) counting.
Preferably, the preparation method of the metal-containing mesoporous molecular sieve comprises the following steps:
(1) Mixing a metal source, a fluorine source and a silicon source to obtain a first material;
(2) Mixing the first material with a mesoporous molecular sieve to obtain a second material;
(3) Aging the second material;
(4) And drying and roasting the aged product.
The production method of the cyclic ketoxime provided by the invention is environment-friendly and simple and convenient in post-treatment, can realize the ammoxidation reaction of macromolecular cyclic ketone, and has the advantages of high cyclic ketone conversion rate, high cyclic ketoxime selectivity and high hydrogen peroxide utilization rate. The results of the examples show that in the production method of the cyclic ketoxime, the conversion rate of the reactant and the selectivity of the target product are high, wherein the highest utilization rate of the hydrogen peroxide can reach 99.9%, the highest conversion rate of the reactant cyclohexanone can reach 99.8%, and the highest selectivity of the product cyclohexanone oxime can reach 99.8%, and the effect is remarkable.
Drawings
FIG. 1 is a UV-Vis characterization spectrum of Ti-SBA-15 mesoporous molecular sieve C-1 prepared in preparation example 1 and Ti-SBA-15 mesoporous molecular sieve X prepared in preparation comparative example 1;
FIG. 2 is a SEM representation of the Ti-SBA-15 mesoporous molecular sieve X prepared in comparative example 1;
FIG. 3 is a SEM representation spectrum of Ti-SBA-15 mesoporous molecular sieve C-1 prepared in preparation example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for producing cyclohexanone oxime, which comprises the following steps:
(I) Mixing a catalyst, cyclic ketone, ammonia and a solvent to obtain a mixed material;
(II) contacting the mixed material obtained in the step (I) with peroxide under the condition of cyclic ketone oxidation reaction;
wherein the catalyst comprises a metal-containing mesoporous molecular sieve, and the metal-containing mesoporous molecular sieve comprises: a mesoporous molecular sieve, fluorine and a metal element selected from at least one of group IVB metal elements and group IVA metal elements; the molar ratio of the metal element to the fluorine element to the mesoporous molecular sieve is 1: (0.1-10): (10-100), wherein the mesoporous molecular sieve is SiO 2 And (6) counting.
According to the present invention, it is preferable that the content of the metal-containing mesoporous molecular sieve in the catalyst is 50 to 100% by weight. Besides the metal-containing mesoporous molecular sieve, the catalyst can also contain silicon dioxide and/or other titanium-containing molecular sieves. That is, the catalyst may be an assembly of the metal-containing mesoporous molecular sieve and silica, an assembly of the metal-containing mesoporous molecular sieve and other titanium-containing molecular sieves, or an assembly of the metal-containing mesoporous molecular sieve, other titanium-containing molecular sieves, and silica.
According to a preferred embodiment of the present invention, the catalyst is a metal-containing mesoporous molecular sieve, i.e. the content of the metal-containing mesoporous molecular sieve in the catalyst is 100%.
According to the present invention, the XRF method can be used to determine the molar ratio of the metal element, the fluorine element and the mesoporous molecular sieve in the metal-containing mesoporous molecular sieve.
According to the present invention, preferably, the mass ratio of the cyclic ketone, the catalyst and the solvent is 1: (0.01-0.2): (0.5-15), preferably 1: (0.03-0.15): (1-10).
Preferably, the molar ratio of cyclic ketone to ammonia is 1: (0.5-5), preferably 1: (1-3).
In the present invention, in the step (1), ammonia may be introduced in the form of gaseous ammonia or liquid ammonia. Preferably, in step (1), the ammonia is introduced in the form of aqueous ammonia. The concentration of the aqueous ammonia in the present invention is selected in a wide range, and the concentration of the aqueous ammonia is preferably 20 to 30% by weight.
In the step (1), the mixing is not particularly limited, and preferably, the mixing is under stirring conditions.
According to the invention, the molar ratio of cyclic ketone to peroxide is preferably 1: (0.5-3), preferably 1: (1-2).
In the present invention, the peroxide is selected from a wide range as long as it is a compound containing a peroxy group, and specifically, it may be an inorganic peroxide or an organic peroxide. Preferably, the peroxide is selected from at least one of hydrogen peroxide, peroxyacetic acid, peroxypropionic acid and trifluoroperoxyacetic acid. Further preferably, the peroxide is hydrogen peroxide.
Preferably, the hydrogen peroxide is introduced in the form of an aqueous hydrogen peroxide solution, preferably in a concentration of 1 to 50 wt.%, more preferably 5 to 45 wt.%, more preferably 20 to 40 wt.%.
According to the present invention, preferably, the cyclic ketone oxidation reaction conditions include: the temperature is 30-150 ℃, preferably 60-90 ℃; the pressure is 1-5atm, preferably 1-2atm; the time is 0.1 to 10 hours, preferably 0.5 to 3 hours.
According to one embodiment of the invention, it may be that peroxide is introduced into the mixed mass. The above-mentioned times of the present invention do not include the peroxide addition time.
The feeding method of the peroxide is not particularly limited in the present invention, and the peroxide can be introduced in a dropwise manner in order to avoid decomposition of the peroxide by a conventional technical means in the art. The dropping speed is selected in a wide range and can be determined by a person skilled in the art according to the test scale. For example, the dropping time may be 1 to 8 hours, preferably 1 to 2 hours.
Preferably, after step (II), the process further comprises separating the catalyst from the reaction product. The separation in the present invention is not particularly limited, and may be carried out by a conventional operation in the art, for example, filtration, as long as the object of solid-liquid separation can be achieved. The separated liquid can be separated into the target product by adopting a common distillation or rectification method, and the distillation or rectification is a conventional choice in the field and is not described again.
According to the invention, the method provided by the invention is particularly suitable for ammoxidation of macromolecular cyclic ketone, preferably the cyclic ketone has 5-9C atoms, and more preferably cyclohexanone.
The solvent used in the process for producing a cyclic ketoxime of the present invention is not particularly limited, and preferably, the solvent is selected from the group consisting of water and C 1 -C 6 Alcohol of (1), C 2 -C 6 Acid and C 2 -C 8 One or more of (a) nitrile(s). In the present invention, the term "C" is used 1 -C 6 The alcohol of (1) represents an alcohol having a total number of carbon atoms of 1 to 6, including a linear alcohol, a branched alcohol or a cyclic alcohol, and the "C" is 2 -C 6 The expression "acid" denotes an acid having a total number of carbon atoms of 2 to 6, including a straight chain acid, a branched chain acid or a cyclic acid, said "C" being 2 -C 8 The "nitrile" of (a) means a nitrile having a total number of carbon atoms of 2 to 8, and includes a straight chain nitrile, a branched chain ketone or a cyclic nitrile. Further preferably, the solvent is at least one selected from the group consisting of water, methanol, ethanol, tert-butanol, n-propanol, isopropanol and sec-butanol, and more preferably water.
According to a preferred embodiment of the present invention, in the metal-containing mesoporous molecular sieve, the mesoporous molecular sieve is selected from at least one of SBA-15, MCM-41, MCM-48, HMS, KIT-6 and MSU, more preferably from at least one of SBA-15, MCM-41, MCM-48, HMS and KIT-6. The adoption of the optimal mode is more beneficial to improving the catalytic performance of the metal-containing mesoporous molecular sieve.
In the invention, the mesoporous molecular sieve can be obtained by commercial products or can be prepared by the existing method.
According to the present invention, the metal element is selected from at least one of a group IVB metal element and a group IVA metal element, preferably, the metal element is selected from at least one of a Ti element, a Zr element, a Sn element and a Ge element, more preferably, at least one of a Ti element, a Zr element and a Sn element, and most preferably, a Ti element.
According to the present invention, it is preferable that the molar ratio of the metal element, the fluorine element and the mesoporous molecular sieve is 1: (0.2-5): (40-75). At such a preferable ratio, it is more advantageous in the production of the cyclic ketoxime to improve the reaction conversion and the product selectivity.
Preferably, the metal-containing mesoporous molecular sieve has a characteristic peak at a wavelength of 220-230nm, characterized by UV-Vis. The characteristic peak indicates that the metal element in the metal mesoporous molecular sieve of the invention has a specific occurrence state.
Preferably, the average radial diameter of the metal-containing mesoporous molecular sieve is 5 to 35 μm, and more preferably 5 to 28 μm. The average radial diameter of the metal-containing mesoporous molecular sieve is measured by a TEM method.
According to the method for producing a cyclic ketoxime provided by the invention, the object of the invention can be achieved as long as the metal-containing mesoporous molecular sieve is adopted, the selection range of the preparation method of the metal-containing mesoporous molecular sieve is wide, and preferably, the preparation method of the metal-containing mesoporous molecular sieve comprises the following steps:
(1) Mixing a metal source, a fluorine source and a silicon source to obtain a first material;
(2) Mixing the first material with a mesoporous molecular sieve to obtain a second material;
(3) Aging the second material;
(4) And drying and roasting the aged product.
According to the present invention, the selection of the metal may be as described above, and will not be described herein.
The metal source can be selected from a wide range of sources as long as the metal source can provide the metal, and the metal source is, for example, a soluble salt containing the metal. Preferably, the metal source is selected from TiCl 4 、TiOSO 4 、TiCl 3 、TiF 4 、H 2 TiF 6 、(NH 4 ) 2 TiF 6 、SnCl 4 、ZrCl 4 And ZrF 4 At least one of (1).
In the present invention, the fluorine source may be selected from a wide range as long as it can provide fluorine, for example, hydrofluoric acid and/or a fluorine-containing soluble salt. Preferably, the fluorine source is selected from NH 4 F. At least one of NaF, KF and HF.
In the present invention, the term "soluble" refers to the fact that the solvent can be dissolved directly or by the aid of a cosolvent.
The silicon source selection range of the invention is wide, and the silicon source can be various silicon sources conventionally used in the field. Specifically, the silicon source is an organic silicon source and/or an inorganic silicon source. Preferably, the silicon source is selected from H 2 SiF 6 、SiF 4 、SiCl 4 、(NH 4 ) 2 SiF 6 And ethyl orthosilicate. The adoption of the preferred embodiment is more beneficial to improving the catalytic performance of the prepared molecular sieve.
According to the present invention, the fluorine source and the silicon source may be introduced in the form of a solution (e.g., an aqueous solution).
According to the present invention, the mixing process in step (1) may optionally further include a solvent, if the metal source, the fluorine source and the silicon source can satisfy the requirement of uniform mixing, i.e. the solvent does not need to be introduced, and the solvent (preferably water) needs to be introduced otherwise. In the present invention, the amount of the solvent to be introduced is not particularly limited, and may be appropriately selected depending on the amounts of the metal source, the fluorine source and the silicon source to be introduced, as long as the mixing is sufficient.
According to a preferred embodiment of the present invention, the step (1) comprises: and mixing a metal source, a fluorine source, a solvent and a silicon source to obtain the first material.
In the present invention, the mixing in the step (1) is not particularly limited, and may be performed under stirring conditions or ultrasonic conditions. Preferably, the mixing in step (1) is carried out under ultrasound, which is more favorable for material mixing.
According to a preferred embodiment of the present invention, the metal source, the fluorine source and the mesoporous molecular sieve are used in amounts such that the molar ratio of the modified metal element, the fluorine element and the mesoporous molecular sieve in the obtained metal-containing mesoporous molecular sieve is 1: (0.1-10): (10-100), preferably 1: (0.2-5): (40-75). It should be noted that, if the metal source and the silicon source contain F element during the preparation process, which can provide part of F element, the amount of the fluorine source can be reduced accordingly. The person skilled in the art knows how to select the metal source, the fluorine source and the ratio of the amount of mesoporous molecular sieve based on the above disclosure.
According to the present invention, it is preferable that the molar ratio of the metal source, the fluorine source, and the silicon source is 1: (0.1-10): (0.1-10), preferably 1: (0.2-5): (0.2-5), the silicon source is SiO 2 And (6) counting.
According to the method provided by the invention, the selection of the mesoporous molecular sieve is as described above, and details are not repeated here.
According to the present invention, preferably, the molar ratio of the metal source to the mesoporous molecular sieve is 1: (10-100), more preferably 1: (20-60), wherein the mesoporous molecular sieve is SiO 2 And (6) counting.
In the present invention, the mixing in the step (2) is not particularly limited, and may be performed under stirring conditions as long as the mesoporous molecular sieve and the first material are uniformly mixed.
According to the invention, the temperature of the ageing is preferably 20 to 100 ℃ and the ageing time can be 0.5 to 24 hours. In order to further optimize the aging effect, it is preferable that the aging in step (3) is performed under stirring conditions. The stirring is preferably carried out using a magnetic stirrer.
Preferably, the aging conditions include: the aging temperature is 20-80 ℃, and the aging time is 0.5-18h.
Further preferably, the aging conditions include: the aging temperature is 25-70 ℃, and the aging time is 1-12h. In the preferable case, the prepared metal-containing mesoporous molecular sieve is more favorable for obtaining high material conversion rate and product selectivity.
According to an embodiment of the present invention, the method may further include: filtering and washing the aged product to obtain an aged product before the drying in the step (4). The filtration and washing are all operations well known to those skilled in the art, and the present invention is not particularly limited.
The conditions for the drying in step (4) are particularly limited in the present invention, and may be those well known to those skilled in the art. For example, the drying conditions may include: the temperature is 80-180 ℃ and the time is 1-20 hours.
Preferably, the calcination in step (4) is carried out at a temperature of 300 to 880 ℃, preferably 300 to 700 ℃, more preferably 400 to 600 ℃. The selection range of the roasting time is wide, and the roasting time is preferably 1 to 10 hours, more preferably 2 to 6 hours.
According to the present invention, preferably, the method further comprises: acid is introduced in the step (1) and/or the step (2) to adjust the pH. It should be noted that, in this preferred embodiment, the acid may be introduced separately in step (1) to adjust the pH of the first material, may be introduced separately in step (2) to adjust the pH of the second material, or may be introduced in both step (1) and step (2) to adjust the pH of the first material and the second material. As long as the pH of the material to be aged (the second material) can be adjusted. Preferably, the method further comprises: acid is introduced in the step (2) to adjust the pH.
The acid may be various acids conventionally used in the art as long as it can function to adjust the pH, and for example, the acid may be at least one of nitric acid, hydrochloric acid, acetic acid, and carbonic acid.
In the conventional preparation method, the hydrolysis rate of the metal source is higher than that of the silicon source under acidic conditions, and the metal source is hydrolyzed into corresponding metal oxide before being combined with the mesoporous molecular sieve, so that the metal source cannot be inserted into the molecular sieve framework. The preparation method of the preferable metal-containing mesoporous molecular sieve provided by the invention overcomes the defects, the addition of the fluorine source influences the occurrence state of the metal atoms, the formation of chemical bonds between the metal atoms and oxygen atoms is reduced, and the generation of metal oxides is avoided. Preferably, the pH of the second material is 1 to 7, more preferably 3 to 6.5. In such a preferred case, it is more advantageous to improve the reaction conversion rate and the product selectivity of the obtained metal-containing mesoporous molecular sieve in the production of the cyclic ketoxime.
The present invention will be described in detail below by way of examples.
The reagents used in the following examples are all commercially available chemically pure reagents.
Hydrochloric acid, silicon tetrachloride, tetraethoxysilane (TEOS) and titanium tetrachloride are analytically pure and purchased from chemical reagents of national drug group, inc.;
the SBA-15 mesoporous molecular sieve is produced by Hunan Jianchang petrochemical company; MCM-41, HMS, KIT-6 and MCM-48 all-silicon mesoporous molecular sieves were synthesized according to the monograph (Zhao Dongyuan, et al, ordered mesoporous molecular sieve materials [ M ]. Higher education publishers, 2012).
The UV-Vis characterization map of the metal-containing mesoporous molecular sieve prepared in the preparation example is obtained by characterization of an instrument with the model of UV-visble550 purchased from JASCO company; the average radial diameter of the particles is measured by a TEM method; the molar ratio of the metal element, the fluorine element and the mesoporous molecular sieve is measured by an XRF method.
The room temperature refers to 25 ℃ without special limitation; atm is a unit of pressure, and 1atm represents 1 standard atmosphere.
In the following preparation examples, the silicon source and the molecular sieve are both used in SiO 2 And (6) counting.
Preparation example 1
(1) Mixing a metal source, a fluorine source and a silicon source in an ultrasonic environment to form a colorless transparent solution;
(2) Adding the colorless transparent solution into a suspension containing the SBA-15 molecular sieve which is continuously stirred, and then adding 0.1mol/L hydrochloric acid to adjust the pH value to 6.1-6.2; the proportion and the types of the metal source, the fluorine source, the silicon source and the mesoporous molecular sieve are listed in table 1;
(3) Continuously stirring and aging the suspension obtained in the step (2) for 2 hours at the temperature of 40 ℃;
(4) And (4) sequentially filtering and washing the product obtained in the step (3) to obtain an aged product, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 3 hours to obtain the Ti-SBA-15 mesoporous molecular sieve C-1.
FIG. 1 shows a UV-Vis characterization spectrum of Ti-SBA-15 mesoporous molecular sieve C-1, and as can be seen from FIG. 1, the molecular sieve has a characteristic peak at a wavelength of 220-230 nm. The characteristic peak positions of the metal-containing mesoporous molecular sieve, characterized by UV-Vis, are listed in Table 2.
FIG. 3 is a SEM characteristic chromatogram of the Ti-SBA-15 mesoporous molecular sieve C-1, from which it can be seen that the Ti-SBA-15 mesoporous molecular sieve C-1 has a smaller average radial diameter, and the average radial diameters of the metal-containing mesoporous molecular sieves are listed in Table 2.
Preparation examples 2 to 12
According to the method of preparation example 1, metal-containing mesoporous molecular sieves C-2 to C-12 were prepared respectively, except that the ratios and kinds of the metal source, the fluorine source, the silicon source and the mesoporous molecular sieve used in step (1) and the aging conditions in step (3) were different, and the details of the respective preparation examples are shown in Table 1.
Characteristic peak positions, average radial diameters of metal mesoporous molecular sieves C-2 to C-12, and mesoporous molecular sieves (in the form of SiO) 2 Calculated), the molar ratio of fluorine and the modifying metal element are listed in table 2.
TABLE 1
TABLE 2
Preparation of comparative example 1
The Ti-SBA-15 mesoporous molecular sieve material is directly synthesized according to the method reported by the Applied Catalysis A, general,2004,273 (1-2): 185-191. TEOS and titanium trichloride are respectively used as a silicon source and a metal titanium source, a triblock copolymer P123 (molecular weight = 5800) is used as a structure directing agent, a concentrated hydrochloric acid aqueous solution is used as an acid source, and the specific synthesis steps are as follows:
(1) Dissolving 2g P123 in 60ml of hydrochloric acid solution with pH 5;
(2) After 4.25g of tetraethyl orthosilicate (TEOS) had been prehydrolyzed at 40 ℃ for a period of time, 0.02g of TiCl was added to the acidic solution with vigorous stirring 3 Mixing with 2ml hydrogen peroxide solution, and stirring for 24 hours;
(3) The resulting mixture was statically aged at 60 ℃ for 24 hours;
(4) The resulting aged product was recovered, washed, and dried at 100 ℃ overnight. Calcining for 6h at 550 ℃ in the air to obtain the Ti-SBA-15 mesoporous molecular sieve X.
The UV-Vis characterization spectrogram of the Ti-SBA-15 mesoporous molecular sieve X is shown in figure 1, and the molecular sieve does not have a characteristic peak at the wavelength of 220-230nm as can be seen from figure 1. The characteristic peak positions of the metal-containing mesoporous molecular sieve characterized by UV-Vis are shown in Table 2.
FIG. 2 is a SEM characterization of the Ti-SBA-15 mesoporous molecular sieve X, and a comparison of FIGS. 2 and 3 shows that the Ti-SBA-15 mesoporous molecular sieve X has a larger average radial diameter and that the average radial diameter of the metal-containing mesoporous molecular sieve is shown in Table 2.
Preparation of comparative example 2
Ti-MCM-41 was synthesized by microwave hydrothermal method according to the method reported in Journal of Environmental Sciences,2016, 44. Cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is used as template agent. Titanium isopropoxide and sodium silicate (Na) 2 SiO 3 ) The method is used as a metal titanium source and a silicon source respectively, and comprises the following specific synthesis steps:
(1) 4.25g CTAB and 5.32g Na were added 2 SiO 3 Dissolving the two solutions in 30mL and 15mL of deionized water respectively, mixing the two solutions, and then stirring vigorously for 30 minutes at room temperature;
(2) Adding 0.45g of titanium isopropoxide into the mixture, stirring for 180min, and adjusting the pH value of the mixed solution to 9.5-10.0 by using 0.1mol/L hydrochloric acid;
(3) Heating the mixed solution at 100 ℃ for 180 minutes under the 120W microwave hydrothermal condition, then washing with deionized water and drying;
(4) And sintering the obtained product at 823K for 6 hours to obtain the Ti-MCM-41 molecular sieve Y.
The characteristic peak positions of Ti-MCM-41 molecular sieve Y are shown in Table 2 by the characterization of UV-Vis. The average radial diameter of the metal-containing mesoporous molecular sieve is shown in table 2.
Preparation of comparative example 3
Neutral S was used according to the method reported in the Journal of Molecular Catalysis A: chemical,2015,397 0 I 0 Synthesizing the HMS-Ti molecular sieve material by a template method. The process is based on a neutral primary amine surfactant S 0 (dodecylamine) with a neutral inorganic precursor I 0 (tetraethoxysilane: TEOS) hydrogen bond and self-assembly, and mesitylene and tetrabutyl orthotitanate are respectively used as Ti 4+ Cationic swelling agent and precursor, filtering the product obtained by the reaction and washing the product with distilled water. Then dried at room temperature for 24h and dried at 100 ℃ for 2h, and then calcined in air at 550 ℃ for 3.5h to obtain the HMS-Ti molecular sieve Z.
The characteristic peak positions of the HMS-Ti molecular sieve Z characterized by UV-Vis are listed in Table 2. The average radial diameter of the metal-containing mesoporous molecular sieve is shown in table 2.
Example 1
This example is used to illustrate the cyclic ketoxime production method provided by the present invention, and the specific steps include:
(1) Adding the catalyst C-1 obtained in preparation example 1, cyclohexanone, ammonia water (with the concentration of 30 wt%) and water into a reactor, and mixing under stirring to obtain a mixed material; the weight ratio of cyclohexanone, catalyst and water is 1.03; the specific material ratios and conditions are shown in Table 3.
(2) Introducing 30 wt% aqueous hydrogen peroxide solution into the mixture at a reaction temperature of 60 ℃ for 1h, wherein the molar ratio of cyclohexanone to hydrogen peroxide is 1:1; continuously reacting for 0.5h after the hydrogen peroxide is added, and controlling the reaction pressure to be 3atm; the specific material ratios and conditions are listed in table 3.
The reactants and products are analyzed by gas chromatography (Agilent 6890N, HP-5 capillary column 30m 0.25mm 0.25 μm), toluene is used as an internal standard, an internal standard method is adopted for quantification, the content of hydrogen peroxide, cyclohexanone and cyclohexanone oxime in the reaction products is measured and obtained, and the data of the hydrogen peroxide utilization rate, the cyclohexanone conversion rate and the cyclohexanone oxime selectivity are respectively obtained by calculation. The data results are shown in Table 4.
Wherein: cyclohexanone conversion = (amount of raw material cyclohexanone substances-amount of cyclohexanone substances remaining after reaction)/amount of raw material cyclohexanone substances × 100%;
cyclohexanone oxime product selectivity = amount of cyclohexanone oxime substance/(amount of raw material cyclohexanone substance-amount of cyclohexanone substance remaining after reaction) × 100%;
H 2 O 2 utilization rate = (initial H) 2 O 2 Amount of substance-remaining H after reaction 2 O 2 Amount of material)/initial H 2 O 2 Amount of substance × 100%.
Examples 2 to 22
The process according to example 1 was followed except that the specific material ratios and conditions were varied, the specific material ratios and conditions are shown in Table 3, and the results of the calculated data on hydrogen peroxide utilization, cyclohexanone conversion and cyclohexanone oxime selectivity are shown in Table 4.
Examples 23 to 33
The procedure of example 1 was followed, except that the catalyst C-1 was replaced with the catalysts C-2 to C-12, respectively. The results of the data on hydrogen peroxide utilization, cyclohexanone conversion and cyclohexanone oxime selectivity are shown in table 4.
Comparative examples 1 to 3
The procedure of example 1 was followed except that the catalysts were replaced with X, Y and Z, respectively, prepared in comparative examples 1-3, and the data calculated for hydrogen peroxide utilization, cyclohexanone conversion and cyclohexanone oxime selectivity are shown in table 4.
TABLE 3
TABLE 4
The production of the cyclic ketoxime provided by the invention can realize the ammoxidation of macromolecular cyclic ketone, and the method is environment-friendly and has simple and convenient post-treatment. The results of the examples show that when cyclohexanone oxime is produced by oxidizing cyclohexanone in the method provided by the invention, the conversion rate of the reactant and the selectivity of the target product are higher, and the effect is remarkable, wherein the utilization rate of hydrogen peroxide can reach 99.9% at most, the conversion rate of the reactant cyclohexanone can reach 99.8% at most, and the selectivity of the product cyclohexanone oxime can reach 99.8% at most.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (38)
1. A process for producing a cyclic ketoxime, which comprises:
(I) Mixing a catalyst, cyclic ketone, ammonia and a solvent to obtain a mixed material;
(II) contacting the mixed material obtained in the step (I) with peroxide under the condition of cyclic ketone oxidation reaction;
wherein the catalyst comprises a metal-containing mesoporous molecular sieve, and the metal-containing mesoporous molecular sieve comprises: mesoporous molecular sieve, fluorine element and metal element, and a method for producing the sameThe metal element is at least one selected from group IVB metal elements and group IVA metal elements; the molar ratio of the metal element to the fluorine element to the mesoporous molecular sieve is 1: (0.1-10): (10-100), wherein the mesoporous molecular sieve is SiO 2 Counting;
characterized by UV-Vis, the metal-containing mesoporous molecular sieve has a characteristic peak at the wavelength of 220-230 nm;
wherein, the preparation method of the metal-containing mesoporous molecular sieve comprises the following steps:
(1) Mixing a metal source, a fluorine source and a silicon source to obtain a first material;
(2) Mixing the first material with a mesoporous molecular sieve to obtain a second material;
(3) Aging the second material;
(4) And drying and roasting the aged product.
2. The production method according to claim 1, wherein the mass ratio of the cyclic ketone, the catalyst and the solvent is 1: (0.01-0.2): (0.5-15).
3. The production method according to claim 2, wherein the mass ratio of the cyclic ketone, the catalyst and the solvent is 1: (0.03-0.15): (1-10).
4. The production method according to claim 1, wherein,
the molar ratio of the cyclic ketone to the ammonia is 1: (0.5-5).
5. The production method according to claim 4,
the molar ratio of cyclic ketone to ammonia is 1: (1-3).
6. The production method according to claim 1,
in the step (1), the ammonia is introduced in the form of aqueous ammonia, the concentration of which is 20 to 30% by weight.
7. The production process according to claim 1, wherein the molar ratio of the cyclic ketone to the peroxide is 1: (0.5-3).
8. The production method according to claim 7, wherein,
the molar ratio of the cyclic ketone to the peroxide is 1: (1-2).
9. The production method according to claim 8, wherein,
the peroxide is hydrogen peroxide.
10. The production method according to claim 9, wherein,
in step (II), the hydrogen peroxide is introduced in the form of an aqueous hydrogen peroxide solution having a concentration of 1 to 50% by weight.
11. The production method according to any one of claims 1 to 10, wherein the cyclic ketone oxidation reaction conditions include: the temperature is 30-150 ℃; the pressure is 1-5atm; the time is 0.1-10 hours.
12. The production method according to claim 11, wherein the cyclic ketone oxidation reaction conditions include: the temperature is 60-90 ℃; the pressure is 1-2atm; the time is 0.5-3 hours.
13. The production method according to any one of claims 1 to 10, wherein the cyclic ketone is a cyclic ketone having 5 to 9 carbon atoms.
14. The production method according to claim 13, wherein,
the cyclic ketone is cyclohexanone.
15. The production method according to any one of claims 1 to 10,
the solvent is water and C 1 -C 6 Alcohol of (1), C 2 -C 6 Acid and C 2 -C 8 At least one ofAnd (4) seed preparation.
16. The production method according to claim 15, wherein,
the solvent is water.
17. The production method according to any one of claims 1 to 10, wherein, in the metal-containing mesoporous molecular sieve, the mesoporous molecular sieve is selected from at least one of SBA-15, MCM-41, MCM-48, HMS, KIT-6, and MSU.
18. The production method according to claim 17,
the metal element is at least one selected from the group consisting of a Ti element, a Zr element, a Sn element and a Ge element.
19. The production method according to any one of claims 1 to 10,
the molar ratio of the metal element to the fluorine element to the mesoporous molecular sieve is 1: (0.2-5): (40-75).
20. The production method according to any one of claims 1 to 10,
the average radial diameter of the metal-containing mesoporous molecular sieve is 5-35 mu m.
21. The production method according to claim 20,
the average radial diameter of the metal-containing mesoporous molecular sieve is 5-28 mu m.
22. The production process according to any one of claims 1 to 10, wherein the metal source is selected from TiCl 4 、TiOSO 4 、TiCl 3 、TiF 4 、H 2 TiF 6 、(NH 4 ) 2 TiF 6 、SnCl 4 、ZrCl 4 And ZrF 4 At least one of (1).
23. The production method according to any one of claims 1 to 10,
the fluorine source is selected from NH 4 F. At least one of NaF, KF and HF.
24. The production method according to any one of claims 1 to 10,
the silicon source is an organic silicon source and/or an inorganic silicon source.
25. The production method according to claim 24,
the silicon source is selected from H 2 SiF 6 、SiF 4 、SiCl 4 、(NH 4 ) 2 SiF 6 And ethyl orthosilicate.
26. The production method according to any one of claims 1 to 10, wherein the molar ratio of the metal source, the fluorine source, and the silicon source is 1: (0.1-10): (0.1-10), the silicon source is SiO 2 And (6) counting.
27. The production method according to claim 26,
the molar ratio of the metal source to the fluorine source to the silicon source is 1: (0.2-5): (0.2-5).
28. The production method according to any one of claims 1 to 10,
the molar ratio of the metal source to the mesoporous molecular sieve is 1: (10-100), wherein the mesoporous molecular sieve is SiO 2 And (6) counting.
29. The production method according to claim 28,
the molar ratio of the metal source to the mesoporous molecular sieve is 1: (20-60).
30. The production method according to any one of claims 1 to 10, wherein the aging condition of step (3) includes: under the condition of stirring, the aging temperature is 20-100 ℃, and the aging time is 0.5-24h.
31. The production method according to claim 30, wherein,
the aging conditions include: the aging temperature is 20-80 ℃, and the aging time is 0.5-18h.
32. The production method according to claim 31,
the aging conditions include: the aging temperature is 25-70 ℃, and the aging time is 1-12h.
33. The production method according to any one of claims 1 to 10,
the roasting in the step (4) is carried out at the temperature of 300-880 ℃.
34. The production method according to claim 33,
the roasting in the step (4) is carried out at the temperature of 300-700 ℃.
35. The production method according to claim 34,
the roasting in the step (4) is carried out at the temperature of 400-600 ℃.
36. The production method according to any one of claims 1 to 10, wherein the method further comprises: introducing acid to adjust the pH in the step (2).
37. The production method according to claim 36,
the acid is introduced in an amount such that the pH of the second material is between 1 and 7.
38. The production method according to claim 37,
the acid is introduced in an amount such that the pH of the second material is between 3 and 6.5.
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| CN1683323A (en) * | 2005-03-17 | 2005-10-19 | 华东师范大学 | Process for producing cyclohexanone-oxime |
| CN101928231A (en) * | 2009-06-18 | 2010-12-29 | 住友化学株式会社 | Be used to prepare the method for oxime |
| CN102627291A (en) * | 2012-04-09 | 2012-08-08 | 华东师范大学 | Fluorine-containing titanium-silicon molecular sieve with MWW (Manual Wire Wrap) structure and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1683323A (en) * | 2005-03-17 | 2005-10-19 | 华东师范大学 | Process for producing cyclohexanone-oxime |
| CN101928231A (en) * | 2009-06-18 | 2010-12-29 | 住友化学株式会社 | Be used to prepare the method for oxime |
| CN102627291A (en) * | 2012-04-09 | 2012-08-08 | 华东师范大学 | Fluorine-containing titanium-silicon molecular sieve with MWW (Manual Wire Wrap) structure and preparation method and application thereof |
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