CN107398299B - Preparation method and application of modified TS-1 catalyst - Google Patents
Preparation method and application of modified TS-1 catalyst Download PDFInfo
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Abstract
A preparation method and application of a modified TS-1 catalyst are provided, 0.2g TS-1 catalyst is loaded into a ceramic crucible and placed in a heating cavity of an ultraviolet high-temperature reactor; vacuumizing the cavity to 2Pa, and heating to 425 ℃ within 2 min; and irradiating the sample for 10min by using ultraviolet to obtain the modified TS-1 catalyst. The modified TS-1 catalyst is applied to the reaction of preparing cyclohexanone oxime by cyclohexanone ammoximation. The modified TS-1 catalyst shows higher catalytic activity and higher selectivity to a target product cyclohexanone oxime in the cyclohexanone ammoximation reaction.
Description
Technical Field
The invention relates to the field of zeolite molecular sieves and industrial catalysis, in particular to a preparation method and application of a modified TS-1 catalyst.
Background
The synthesis of the titanium silicalite TS-1 and the successful application of the titanium silicalite TS-1 as an organic selective oxidation catalyst are considered as important milestones in the field of zeolite molecular sieve catalysis in the 80 th of the 20 th century. TS-1 is a zeolite molecular sieve with MFI structure, it is formed from straight channels (pore diameter is about 0.57nm x 0.51nm), Z-shaped channels (pore diameter is about 0.54nm) and cross channels (pores diameter is about 0.90nm) connected with them, and it is characterized by that it uses Ti to make the molecular sieve have MFI structure4+Substituting part of Si in the skeleton of the all-silicon molecular sieve4+. Due to Ti4+The ion has the characteristic of six coordination, the energy of the titanium-oxygen tetrahedron is higher, the structure has electron defects, and the titanium-oxygen tetrahedron has the potential of accepting electron pairs, and is used for H2O2Or the organic peroxide compound has unique adsorption activation performance. At present, the number of the current day,the main reactions in which selective oxidation of organic compounds has been carried out using TS-1 as a catalyst are olefin epoxidation, aromatic hydroxylation, ketone ammoxidation, alkane oxidation, alcohol oxidation, and the like. Wherein, the production process for synthesizing cyclohexanone oxime by one step by taking TS-1 as a catalyst and taking cyclohexanone, ammonia and hydrogen peroxide as reaction raw materials successfully realizes industrial large-scale production.
Cyclohexanone oxime is a key intermediate for producing nylon-6 monomer epsilon-caprolactam, and the traditional production process flow is as follows: cyclohexanone and hydroxylamine are subjected to non-catalytic oxidation reaction to generate cyclohexanone oxime, and the cyclohexanone oxime is subjected to liquid-phase Beckmann rearrangement reaction under the catalytic action of oleum to prepare epsilon-caprolactam. The production process uses toxic hydroxylamine and strongly corrosive fuming sulfuric acid, and produces a large amount of by-products ammonium sulfate (about 2.8 tons of ammonium sulfate per ton of epsilon-caprolactam) and nitrogen oxides, thereby causing serious environmental pollution.
The company Montedipe S.p.A (now EniChem S.p.A) in Italy in the 80 th century succeeded in developing a cyclohexanone ammoximation process from cyclohexanone, ammonia and H2O2The cyclohexanone oxime is directly prepared by the ammoximation reaction of the titanium silicalite TS-1 as the raw material. Subsequently, Sumitomo Chemical company, japan, developed a process for producing epsilon-caprolactam by subjecting cyclohexanone oxime to a gas phase Beckmann rearrangement reaction in which concentrated sulfuric acid is replaced with a high-silicon MFI-type molecular sieve catalyst, thereby avoiding the production of ammonium sulfate as a by-product. Compared with the traditional process, the production process for preparing the epsilon-caprolactam by combining cyclohexanone ammoximation and gas-phase Beckmann rearrangement reaction has the following advantages: the intermediate steps are few, hydroxylamine synthesis is not needed, and the process flow is shortened; the reaction temperature is low, and the energy consumption is reduced; the catalyst can be repeatedly used; the method has no by-product ammonium sulfate, and the generated by-product only contains water (shown as the following formula), thereby improving the economic benefit and the social benefit of the epsilon-caprolactam production, realizing zero emission and meeting the requirements of green chemical development.
Cyclohexanone ammoximation and cyclohexanone oxime gas phase Beckmann rearrangement reaction for producing epsilon-caprolactam
However, researches show that in the production process of preparing cyclohexanone oxime by ammoxizing cyclohexanone under the catalytic action of TS-1, the catalytic activity of TS-1 is limited by intragranular mass transfer, the catalytic activity is gradually reduced along with the increase of the crystal size of TS-1, and the catalytic activity is obviously reduced when the crystal size is larger than 0.5 um.
In order to improve the mass transfer performance of the TS-1 catalyst, scientists synthesize nano-scale TS-1 small crystals, but the method not only causes the problem that molecular sieve crystals and synthetic liquid are difficult to separate in the synthesis process, but also causes the catalyst and reaction liquid to be difficult to separate in the reaction process, thereby causing high energy consumption. At present, in the technology of synthesizing cyclohexanone oxime by a single-kettle continuous slurry bed developed by medium petrifaction, a membrane microfiltration separation technology is used for separating TS-1 microcrystals and reaction media, however, a membrane is easy to be polluted in the using process, and needs to be cleaned and replaced at irregular time, which causes great inconvenience to the separation process.
Disclosure of Invention
The invention provides a preparation method and application of a modified TS-1 catalyst.
Synthesizing a TS-1 catalyst: as tetraethyl orthosilicate (TEOS): tetrabutyl titanate (TBOT): tetrapropylammonium hydroxide (TPAOH): h2The molar ratio of O is 1: 0.03: 0.45: 15.5; adding a mixed solution of 24.19g of TEOS and 1.19g of TBOT into 42.98g of 25 wt.% aqueous solution of TPAOH, stirring for 3h at 60 ℃, discharging alcohol for 1h at 80 ℃, transferring the obtained colloidal solution into a 100ml stainless steel reaction kettle, dynamically crystallizing for 24h (rotation speed is 25-120 r/min) in a homogeneous reactor, centrifuging, washing and drying, and finally roasting solid powder for 6h at 550 ℃ in an air atmosphere at a heating rate of 5 ℃/min to obtain the TS-1 catalyst. Synthetic methods are described in the literature references (M.G. Clerici et al, J.Catal.,1991,129: 157-167).
A preparation method of a modified TS-1 catalyst comprises the following steps: 0.2g of TS-1 catalyst is loaded into a ceramic crucible and placed in a heating cavity of an ultraviolet high-temperature reactor; vacuumizing the cavity to 2Pa, and heating to 425 ℃ within 2 min; and (3) irradiating the sample for 10min by ultraviolet (with the wavelength of 200-400nm) to obtain the modified TS-1 catalyst.
The application of the modified TS-1 catalyst in the reaction for preparing cyclohexanone oxime by cyclohexanone ammoximation comprises the following steps:
1) adding the modified TS-1 catalyst, solvent and cyclohexanone into a three-port glass reactor provided with a reflux condensing device at one time, heating in a constant-temperature water bath at 78 ℃, and magnetically stirring a reaction mixture; wherein the dosage ratio of the TS-1 catalyst to the cyclohexanone is 8 g/mol; the solvent is equimolar mixed solution of tert-butyl alcohol and distilled water;
2) and then continuously adding 30 wt.% of hydrogen peroxide by using a constant-current sample injection pump, wherein the molar ratio of hydrogen peroxide to cyclohexanone is 1.2: 1, the continuous feeding rate of hydrogen peroxide is 0.04 ml/min; and simultaneously adding 25 wt.% of ammonia water in a batch manner, wherein the molar ratio of the ammonia water to the cyclohexanone is 2: 1, intermittently adding ammonia water for 10 min;
3) after the mixture reacts for 3 hours, methanol is added for mixing and stirring, centrifugal separation is carried out, a liquid sample is taken, and then the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime are analyzed on a gas chromatograph by an internal standard method.
On a gas chromatography Agilent 7890B provided with a FID detector and an HP-5 capillary column, the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime are calculated by taking toluene as an internal standard substance and adopting an internal standard method according to the following formulas:
in the formula C0、C1And C2The concentration of cyclohexanone before reaction, the concentration of cyclohexanone after reaction and the concentration of cyclohexanone oxime are respectively.
The invention adopts a method of ultraviolet high-temperature treatment to modify TS-1 catalyst, applies the catalyst before and after modification to the reaction of cyclohexanone ammoximation synthesis of cyclohexanone oxime, and performs XRD and SEM representation on the catalyst. The result shows that compared with the traditional TS-1 catalyst, the modified TS-1 catalyst shows higher catalytic activity and higher selectivity to the target product cyclohexanone oxime in the cyclohexanone ammoximation reaction, and the crystal structure and the morphology of the modified TS-1 catalyst are not changed before and after modification.
Drawings
FIG. 1 is a schematic view of an ultraviolet high-temperature reactor apparatus
FIG. 2 is an XRD spectrum of the catalyst of example 1
FIG. 3 is an SEM image of the catalyst of example 1
FIG. 4 is an XRD spectrum of the catalyst of example 2
FIG. 5 is an SEM image of the catalyst of example 2
FIG. 6 is an XRD spectrum of the catalyst of example 3
FIG. 7 is an SEM image of the catalyst of example 3
Detailed Description
The present invention will be further described below by way of specific examples, but the present invention is not limited to the following examples.
Example 1
Preparation of TS-1 catalyst: according to the following ratio of TEOS: TBOT: TPAOH: h2The molar ratio of O is 1: 0.03: 0.45: 15.5; adding a mixed solution of 24.19g TEOS and 1.19g TBOT into 42.98g of 25 wt.% aqueous solution of TPAOH, stirring for 3h at 60 ℃, discharging alcohol for 1h at 80 ℃, transferring the obtained colloidal solution into a 100ml stainless steel reaction kettle, dynamically crystallizing for 24h (rotation speed is 25 rpm) in a homogeneous reactor, centrifuging, washing and drying, and finally roasting the solid powder for 6h at 550 ℃ in an air atmosphere at the temperature rise rate of 5 ℃/min to obtain the TS-1 catalyst.
Modification of TS-1 catalyst: taking 0.2g of TS-1 catalyst, loading the catalyst into a ceramic crucible, and placing the ceramic crucible into a heating cavity of an ultraviolet high-temperature reactor; vacuumizing the cavity to 2Pa, and heating to 425 ℃ within 2 min; and (3) irradiating the sample for 10min by using ultraviolet with the wavelength of 200-400nm to obtain the modified TS-1 catalyst.
The ultraviolet high-temperature reactor is shown in figure 1 and consists of an ultraviolet light source, a temperature control system and a vacuum system. The xenon lamp 1 is arranged on the support frame 3, and ultraviolet light obtained after light generated by the xenon lamp passes through the optical filter is irradiated on the powder sample through the window 2; the sample is placed in the crucible 8 and is fed into the heating chamber 4 through the quick opening door 11. the quartz crucible cover 7 prevents the powder sample from being drawn away by the vacuum pump 14. The temperature control system comprises a resistance-type heating platform 5, a vacuum electric through flange 10 (integrating a pair of K-type thermocouples and a pair of power connectors) and a PID temperature control power supply, and the temperature control precision is +/-1 ℃. The vacuum system includes a pirani vacuum gauge 6, a KF16 bellows 12, a KF16 manual angle valve 13, and a vacuum pump 14. In addition, the bellows valve 9 is connected with a protective gas circuit, so that the ultraviolet high-temperature treatment of the sample in the protective atmosphere can be realized. The cavity of the ultraviolet high-temperature reaction system and the temperature control power supply are arranged on the stand 15.
The XRD characterization result of the TS-1 catalyst before and after modification is shown in figure 2, the SEM characterization result is shown in figure 3, and the crystal structure and the morphology of the catalyst before and after modification are not changed.
The modified TS-1 catalyst is applied to the reaction of synthesizing cyclohexanone oxime by ammoximation of cyclohexanone:
according to the dosage ratio of the TS-1 catalyst to the cyclohexanone being 8g/mol, 0.128g of the TS-1 catalyst, 1.571g of the cyclohexanone and 5.910g of the solvent are added into a 100ml three-mouth glass flask provided with a reflux condensing device, then the three-mouth glass flask is placed into a constant temperature water bath at 78 ℃ for heating, and the reaction mixture is magnetically stirred.
Continuously feeding the mixture into the three-neck flask by using a peristaltic pump at a flow rate of 0.04ml/min, wherein the molar ratio of hydrogen peroxide to cyclohexanone is 1.2: 1, 2.177g of 30 wt.% hydrogen peroxide is added; simultaneously, 2.40ml of 25 wt% ammonia water is added every 10min, wherein the molar ratio of ammonia water to cyclohexanone is 2: 1.
adding hydrogen peroxide into a reactor to start timing, after reacting for 3 hours, adding methanol for mixing and stirring, performing centrifugal separation, taking a liquid sample, and calculating the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime by adopting an internal standard method on a gas chromatography Agilent 7890B provided with an FID detector and an HP-5 capillary column and taking toluene as an internal standard substance according to the following formulas:
in the formula C0、C1And C2The concentration of cyclohexanone before reaction, the concentration of cyclohexanone after reaction and the concentration of cyclohexanone oxime are respectively.
Catalyst activity evaluation results: the conversion of cyclohexanone was 81.8% and the selectivity to cyclohexanone oxime was 83.9%.
Comparative example 1
The TS-1 catalyst was prepared as in example 1.
The TS-1 catalyst is applied to the reaction of synthesizing cyclohexanone oxime by cyclohexanone ammoximation:
according to the dosage ratio of the TS-1 catalyst to the cyclohexanone being 8g/mol, 0.128g of the TS-1 catalyst, 1.571g of the cyclohexanone and 5.910g of the solvent are added into a 100ml three-mouth glass flask provided with a reflux condensing device, then the three-mouth glass flask is placed into a constant temperature water bath at 78 ℃ for heating, and the reaction mixture is magnetically stirred.
Continuously feeding the mixture into the three-neck flask by using a peristaltic pump at a flow rate of 0.04ml/min, wherein the molar ratio of hydrogen peroxide to cyclohexanone is 1.2: 1, 2.177g of 30 wt.% hydrogen peroxide is added; simultaneously, 2.40ml of 25 wt% ammonia water is added every 10min, wherein the molar ratio of ammonia water to cyclohexanone is 2: 1.
adding hydrogen peroxide into a reactor to start timing, after reacting for 3 hours, adding methanol for mixing and stirring, performing centrifugal separation, taking a liquid sample, and calculating the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime by adopting an internal standard method on a gas chromatography Agilent 7890B provided with an FID detector and an HP-5 capillary column and taking toluene as an internal standard substance according to the following formulas:
in the formula C0、C1And C2The concentration of cyclohexanone before reaction, the concentration of cyclohexanone after reaction and the concentration of cyclohexanone oxime are respectively.
Catalyst activity evaluation results: the conversion of cyclohexanone was 71.1% and the selectivity to cyclohexanone oxime was 74.1%.
Example 2
Preparation of TS-1 catalyst: according to the following ratio of TEOS: TBOT: TPAOH: h2The molar ratio of O is 1: 0.03: 0.45: 15.5; adding a mixed solution of 24.19g TEOS and 1.19g TBOT into 42.98g of 25 wt.% aqueous solution of TPAOH, stirring for 3h at 60 ℃, discharging alcohol for 1h at 80 ℃, transferring the obtained colloidal solution into a 100ml stainless steel reaction kettle, dynamically crystallizing for 24h in a homogeneous reactor (the rotation speed is 80 rpm), centrifuging, washing and drying, and finally roasting the solid powder for 6h at the temperature rise rate of 5 ℃/min in an air atmosphere at 550 ℃ to obtain the TS-1 catalyst.
Modification of TS-1 catalyst: taking 0.2g of TS-1 catalyst, loading the catalyst into a ceramic crucible, and placing the ceramic crucible into a heating cavity of an ultraviolet high-temperature reactor; vacuumizing the cavity to 2Pa, and heating to 425 ℃ within 2 min; and (3) irradiating the sample for 10min by using ultraviolet with the wavelength of 200-400nm to obtain the modified TS-1 catalyst.
The XRD characterization result of the TS-1 catalyst before and after modification is shown in figure 4, the SEM characterization result is shown in figure 5, and the crystal structure and the morphology of the catalyst before and after modification are not changed.
The modified TS-1 catalyst is applied to the reaction of synthesizing cyclohexanone oxime by ammoximation of cyclohexanone:
according to the dosage ratio of the TS-1 catalyst to the cyclohexanone being 8g/mol, 0.128g of the TS-1 catalyst, 1.571g of the cyclohexanone and 5.910g of the solvent are added into a 100ml three-mouth glass flask provided with a reflux condensing device, then the three-mouth glass flask is placed into a constant temperature water bath at 78 ℃ for heating, and the reaction mixture is magnetically stirred.
Continuously feeding the mixture into the three-neck flask by using a peristaltic pump at a flow rate of 0.04ml/min, wherein the molar ratio of hydrogen peroxide to cyclohexanone is 1.2: 1, 2.177g of 30 wt.% hydrogen peroxide is added; simultaneously, 2.40ml of 25 wt% ammonia water is added every 10min, wherein the molar ratio of ammonia water to cyclohexanone is 2: 1.
adding hydrogen peroxide into a reactor to start timing, after reacting for 3 hours, adding methanol for mixing and stirring, performing centrifugal separation, taking a liquid sample, and calculating the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime by adopting an internal standard method on a gas chromatography Agilent 7890B provided with an FID detector and an HP-5 capillary column and taking toluene as an internal standard substance according to the following formulas:
in the formula C0、C1And C2The concentration of cyclohexanone before reaction, the concentration of cyclohexanone after reaction and the concentration of cyclohexanone oxime are respectively.
Catalyst activity evaluation results: the conversion of cyclohexanone was 96.4% and the selectivity to cyclohexanone oxime was 99.9%.
Comparative example 2
The TS-1 catalyst was prepared as in example 2.
The TS-1 catalyst is applied to the reaction of synthesizing cyclohexanone oxime by cyclohexanone ammoximation:
according to the dosage ratio of the TS-1 catalyst to the cyclohexanone being 8g/mol, 0.128g of the TS-1 catalyst, 1.571g of the cyclohexanone and 5.910g of the solvent are added into a 100ml three-mouth glass flask provided with a reflux condensing device, then the three-mouth glass flask is placed into a constant temperature water bath at 78 ℃ for heating, and the reaction mixture is magnetically stirred.
Continuously feeding the mixture into the three-neck flask by using a peristaltic pump at a flow rate of 0.04ml/min, wherein the molar ratio of hydrogen peroxide to cyclohexanone is 1.2: 1, 2.177g of 30 wt.% hydrogen peroxide is added; simultaneously, 2.40ml of 25 wt% ammonia water is added every 10min, wherein the molar ratio of ammonia water to cyclohexanone is 2: 1.
adding hydrogen peroxide into a reactor to start timing, after reacting for 3 hours, adding methanol for mixing and stirring, performing centrifugal separation, taking a liquid sample, and calculating the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime by adopting an internal standard method on a gas chromatography Agilent 7890B provided with an FID detector and an HP-5 capillary column and taking toluene as an internal standard substance according to the following formulas:
in the formula C0、C1And C2The concentration of cyclohexanone before reaction, the concentration of cyclohexanone after reaction and the concentration of cyclohexanone oxime are respectively.
Catalyst activity evaluation results: the conversion of cyclohexanone was 76.6% and the selectivity to cyclohexanone oxime was 99.9%.
Example 3
Preparation of TS-1 catalyst: according to the following ratio of TEOS: TBOT: TPAOH: h2The molar ratio of O is 1: 0.03: 0.45: 15.5; adding a mixed solution of 24.19g TEOS and 1.19g TBOT into 42.98g of 25 wt.% aqueous solution of TPAOH, stirring for 3h at 60 ℃, discharging alcohol for 1h at 80 ℃, transferring the obtained colloidal solution into a 100ml stainless steel reaction kettle, dynamically crystallizing for 24h (rotation speed of 120 rpm) in a homogeneous reactor, centrifuging, washing and drying, and finally roasting the solid powder for 6h at 550 ℃ in an air atmosphere at the temperature rising rate of 5 ℃/min to obtain the TS-1 catalyst.
Modification of TS-1 catalyst: taking 0.2g of TS-1 catalyst, loading the catalyst into a ceramic crucible, and placing the ceramic crucible into a heating cavity of an ultraviolet high-temperature reactor; vacuumizing the cavity to 2Pa, and heating to 425 ℃ within 2 min; and (3) irradiating the sample for 10min by using ultraviolet with the wavelength of 200-400nm to obtain the modified TS-1 catalyst.
The XRD characterization result of the TS-1 catalyst before and after modification is shown in figure 6, and the SEM characterization result is shown in figure 7, and the crystal structure and the morphology of the catalyst before and after modification are not changed.
The modified TS-1 catalyst is applied to the reaction of synthesizing cyclohexanone oxime by ammoximation of cyclohexanone:
according to the dosage ratio of the TS-1 catalyst to the cyclohexanone being 8g/mol, 0.128g of the TS-1 catalyst, 1.571g of the cyclohexanone and 5.910g of the solvent are added into a 100ml three-mouth glass flask provided with a reflux condensing device, then the three-mouth glass flask is placed into a constant temperature water bath at 78 ℃ for heating, and the reaction mixture is magnetically stirred.
Continuously feeding the mixture into the three-neck flask by using a peristaltic pump at a flow rate of 0.04ml/min, wherein the molar ratio of hydrogen peroxide to cyclohexanone is 1.2: 1, 2.177g of 30 wt.% hydrogen peroxide is added; simultaneously, 2.40ml of 25 wt% ammonia water is added every 10min, wherein the molar ratio of ammonia water to cyclohexanone is 2: 1.
adding hydrogen peroxide into a reactor to start timing, after reacting for 3 hours, adding methanol for mixing and stirring, performing centrifugal separation, taking a liquid sample, and calculating the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime by adopting an internal standard method on a gas chromatography Agilent 7890B provided with an FID detector and an HP-5 capillary column and taking toluene as an internal standard substance according to the following formulas:
in the formula C0、C1And C2The concentration of cyclohexanone before reaction, the concentration of cyclohexanone after reaction and the concentration of cyclohexanone oxime are respectively.
Catalyst activity evaluation results: the conversion of cyclohexanone was 99.1% and the selectivity to cyclohexanone oxime was 99.9%.
Comparative example 3
The TS-1 catalyst was prepared as in example 3.
The TS-1 catalyst is applied to the reaction of synthesizing cyclohexanone oxime by cyclohexanone ammoximation:
according to the dosage ratio of the TS-1 catalyst to the cyclohexanone being 8g/mol, 0.128g of the TS-1 catalyst, 1.571g of the cyclohexanone and 5.910g of the solvent are added into a 100ml three-mouth glass flask provided with a reflux condensing device, then the three-mouth glass flask is placed into a constant temperature water bath at 78 ℃ for heating, and the reaction mixture is magnetically stirred.
Continuously feeding the mixture into the three-neck flask by using a peristaltic pump at a flow rate of 0.04ml/min, wherein the molar ratio of hydrogen peroxide to cyclohexanone is 1.2: 1, 2.177g of 30 wt.% hydrogen peroxide is added; simultaneously, 2.40ml of 25 wt% ammonia water is added every 10min, wherein the molar ratio of ammonia water to cyclohexanone is 2: 1.
adding hydrogen peroxide into a reactor to start timing, after reacting for 3 hours, adding methanol for mixing and stirring, performing centrifugal separation, taking a liquid sample, and calculating the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime by adopting an internal standard method on a gas chromatography Agilent 7890B provided with an FID detector and an HP-5 capillary column and taking toluene as an internal standard substance according to the following formulas:
in the formula C0、C1And C2The concentration of cyclohexanone before reaction, the concentration of cyclohexanone after reaction and the concentration of cyclohexanone oxime are respectively.
Catalyst activity evaluation results: the conversion of cyclohexanone was 88.5% and the selectivity to cyclohexanone oxime was 99.9%.
Claims (3)
1. A preparation method of a modified TS-1 catalyst is characterized by comprising the following steps: 0.2g of TS-1 catalyst is loaded into a ceramic crucible and placed in a heating cavity of an ultraviolet high-temperature reactor; vacuumizing the cavity to 2Pa, and heating to 425 ℃ within 2 min; and irradiating the sample for 10min by using ultraviolet to obtain the modified TS-1 catalyst.
2. The use of the modified TS-1 catalyst prepared by the process of claim 1 in the reaction of preparing cyclohexanone oxime by ammoximation of cyclohexanone.
3. Use according to claim 2, characterized in that it comprises the following steps:
1) adding the modified TS-1 catalyst, a solvent and cyclohexanone into a three-port glass reactor provided with a reflux condensing device at one time, heating in a constant-temperature water bath at 78 ℃, and magnetically stirring a reaction mixture; wherein the dosage ratio of the modified TS-1 catalyst to cyclohexanone is 8g/mol, and the solvent is an equimolar mixed solution of tert-butyl alcohol and distilled water;
2) and then continuously adding 30 wt.% of hydrogen peroxide by using a constant-current sample injection pump, wherein the molar ratio of hydrogen peroxide to cyclohexanone is 1.2: 1, the continuous feeding rate of hydrogen peroxide is 0.04 ml/min; and simultaneously adding 25 wt.% of ammonia water in a batch manner, wherein the molar ratio of the ammonia water to the cyclohexanone is 2: 1, intermittently adding ammonia water for 10 min;
3) after the mixture reacts for 3 hours, methanol is added for mixing and stirring, centrifugal separation is carried out, a liquid sample is taken, and then the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime are analyzed on a gas chromatograph by an internal standard method.
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