CN113398948A - Amorphous CoxMnyWO4Preparation method and application of/active carbon composite catalytic material - Google Patents
Amorphous CoxMnyWO4Preparation method and application of/active carbon composite catalytic material Download PDFInfo
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- CN113398948A CN113398948A CN202110491929.9A CN202110491929A CN113398948A CN 113398948 A CN113398948 A CN 113398948A CN 202110491929 A CN202110491929 A CN 202110491929A CN 113398948 A CN113398948 A CN 113398948A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses amorphous CoxMnyWO4The preparation method and the application of the/active carbon composite catalytic material are characterized in that the preparation method of the catalytic material comprises the following steps: s11: preparation of the dispersion: fully dissolving inorganic metal cobalt salt and manganese salt in water at room temperature, then adding activated carbon into the solution, and preparing a dispersion of the cobalt salt, the manganese salt and the activated carbon by adopting an ultrasonic treatment mode; s12: amorphous CoxMnyWO4Preparation of the/active carbon composite material: at room temperature, in S11Adding sodium tungstate solution into the dispersion liquid under the condition of stirring at the rotating speed of 200-500r/min to form mixed liquid, continuously stirring for 10-30min, filtering and cleaning the product after reaction, and obtaining amorphous Co after vacuum freeze dryingxMnyWO4Active carbon composite catalytic material. The invention can realize that the conversion rate of the ethylbenzene exceeds 80 percent, and the selectivity of the acetophenone product exceeds 90 percent, which is greatly higher than that of the traditional catalytic method.
Description
Technical Field
The invention relates to the technical field of acetophenone preparation, in particular to amorphous CoxMnyWO4A preparation method and application of an active carbon composite catalytic material.
Background
Acetophenone is an important intermediate for organic synthesis, and is widely applied to industries such as dye, spice, medicine and the like. Traditionally, acetophenone is produced by friedel-crafts acylation, i.e. it is synthesized from benzene and acetyl chloride in the presence of aluminium trichloride. However, the reaction conditions are harsh, and strong acid is generated after the reaction, which easily causes corrosion to production equipment and environmental pollution.
With the development of petrochemical industry and the development of selective oxidation catalysis technology, the synthesis of acetophenone by catalytic oxidation of ethylbenzene becomes a very active field. At present, aiming at a system for preparing acetophenone by ethylbenzene liquid phase oxidation, the related catalysts mainly comprise the following types, such as metalloporphyrin, transition metal complexes, metal phthalocyanine, molecular sieves, hydrotalcite, heteropoly compounds and the like. These catalysts generally have the following disadvantages and shortcomings, such as high raw material cost, complicated preparation process, etc., and the conversion rate of ethylbenzene is usually lower than 65%, and the selectivity of acetophenone is usually lower than 85%.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides amorphous CoxMnyWO4The catalyst has low raw material cost and simple synthesis process, and has good catalytic effect in the synthesis of acetophenone, thereby improving the conversion rate of ethylbenzene and the selectivity of acetophenone.
The amorphous Co provided by the inventionxMnyWO4The preparation method of the/active carbon composite catalytic material comprises the following steps:
s11: preparation of the Dispersion
Fully dissolving inorganic metal cobalt salt and manganese salt in water at room temperature, then adding activated carbon into the solution, and preparing a dispersion of the cobalt salt, the manganese salt and the activated carbon by adopting an ultrasonic treatment mode;
s12: amorphous CoxMnyWO4Preparation of/active carbon composite material
Adding sodium tungstate solution at room temperature under stirring at the rotation speed of 200-500r/min for the dispersion liquid in S11 to form a mixed solution, continuously stirring for 10-30min, filtering and cleaning the reaction product, and performing vacuum freeze drying to obtain amorphous CoxMnyWO4Active carbon composite catalytic material.
Preferably, x: y ranges from 0.5 to 2.5: 1.
Preferably, the molar concentration of the cobalt salt and manganese salt solution in the S11 is 0.5-5mol/L, and the molar ratio of the cobalt salt, manganese salt and activated carbon is 0.5-2.5:1: 0.01-0.3.
The specific surface area of the activated carbon is 1800 (+ -100) m2(ii)/g; the pore volume is 1.0-1.2cm3(ii)/g; the aperture is 2.0-2.2 nm; carbon content>95 percent; density 0.38-0.40 g/cc; iodine adsorption value 2000 (+ -100) mg/g.
Preferably, the conditions of the ultrasound in S11 are: ultrasonic frequency of 25-35KHz, power density of 0.3-0.5W/cm2And ultrasonic treatment is carried out for 5-15 min.
Preferably, the molar concentration of the sodium tungstate solution in the S12 is 0.5-5mol/L, and the molar ratio of the cobalt salt, the manganese salt and the sodium tungstate is 0.5-2.5:1: 0.5-1.5.
Preferably, the vacuum freeze-drying conditions in S12 are as follows: the vacuum pressure is-0.09 to-0.10 MPa, the temperature is-70 to-50 ℃, and the time is 12 to 36 hours.
The amorphous Co prepared by the method provided by the inventionxMnyWO4Active carbon composite catalytic material.
The present invention proposes the above amorphous CoxMnyWO4The application of the/active carbon composite catalytic material in preparing acetophenone by ethylbenzene oxidation.
Preferably, the method for preparing acetophenone comprises the following steps:
s21: amorphous CoxMnyWO4Adding the/active carbon composite catalytic material and ethylbenzene into a reactor, and continuously and uniformly introducing air or oxygen into the reactor;
s22: heating the materials in the reactor, distilling the reaction liquid at the temperature of 200-210 ℃ after the reaction is finished, and collecting the distillate to obtain the acetophenone.
Preferably, the amorphous CoxMnyWO4The dosage of the/active carbon composite material is 0.1-1.5 wt% of the dosage of the ethylbenzene.
Preferably, the aeration of air or oxygen in S21 is 5-50 times the initial volume of ethylbenzene per minute.
Preferably, the reaction conditions in S22 are: the heating temperature is 100 ℃ and 150 ℃, and the reaction time is 6-24 h.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) amorphous Co prepared by the inventionxMnyWO4The/active carbon composite catalytic material can change the chemical reaction rate without changing the amorphous substance of the total Gibbs free energy of the reaction, has larger specific surface area, more corresponding catalytic sites and higher catalytic efficiency.
(2) When the catalytic material prepared by the method is used for preparing acetophenone, the conversion rate of ethylbenzene can exceed 80%, and the selectivity of acetophenone products exceeds 90%, which is greatly higher than that of the traditional catalytic method.
(3) The catalyst of the invention can also be recycled. Experimental results show that the catalyst can be recycled for 10 times, the catalytic efficiency can still be maintained at 95%, and the catalyst has a wide industrial application prospect.
Drawings
FIG. 1 shows the amorphous Co proposed by the present inventionxMnyWO4XRD pattern of the/active carbon composite catalytic material;
FIG. 2 shows the amorphous Co proposed by the present inventionxMnyWO4TEM, SAED and Element mapping images of/activated carbon composite catalytic material;
FIG. 3 shows the amorphous Co proposed by the present inventionxMnyWO4HRTEM image of/active carbon composite catalytic material.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
The reagents in the invention are purchased from chemical reagents of national medicine group, Inc., and are directly used,
the method for detecting the ethylbenzene conversion rate and the acetophenone selectivity adopts a high-efficiency gas chromatography internal standard method (Agilent 6890N gas chromatograph) for quantification, and takes methylbenzene as an internal standard. The chromatographic analysis conditions were: the temperature of the gasification chamber is 280 ℃; FID detection, detector temperature 260 ℃; the column temperature was programmed to 80 ℃ initially and increased to 150 ℃ at a rate of 25 ℃/min. And (5) detecting results, quantitatively analyzing the characteristic peaks of the ethylbenzene and the acetophenone, and calculating to obtain the ethylbenzene conversion rate and the acetophenone selectivity.
Example 1
The amorphous CoxMnyWO4The specific preparation process of the/active carbon composite material comprises the following steps: firstly, preparing cobalt chloride and manganese chloride salt into solutions with the concentrations of 2.0mol/L and 3.0mol/L in 100mL of water; then adding 0.02mol of activated carbon, and fully performing ultrasonic treatment; then, 100mL of 5.0mol/L sodium tungstate solution is added rapidly (1min) under stirring to form a large amount of flocculent precipitate; finally, quickly (1min) moving the mixture into a freeze dryer, and freeze-drying the mixture for 12h to finally obtain amorphous Co0.4Mn0.6WO4An active carbon composite material.
The specific surface area of the activated carbon is 1900m2(ii)/g; pore volume of 1.0cm3(ii)/g; the aperture is 2.0 nm; the carbon content is 96%; density 0.38 g/cc; iodine adsorption value was 2100 mg/g.
Adding 0.5g of the catalyst and 100mL of ethylbenzene into a reflux device of a three-neck flask, and reacting for 24h at 120 ℃ under normal pressure by using air as an oxidant to obtain the target product acetophenone. The analysis by the high performance gas chromatography internal standard method shows that the conversion rate of the ethylbenzene is 82.6 percent, and the selectivity of the acetophenone is 90.3 percent.
Example 2
The amorphous CoxMnyWO4The specific preparation process of the/active carbon composite material comprises the following steps: firstly, preparing cobalt nitrate and manganese nitrate into solutions with the concentrations of 3.5mol/L and 2.0mol/L in 100mL of water; then adding 0.02mol of activated carbon, and fully performing ultrasonic treatment; then, 3.5mol/L of 100mL sodium tungstate solution is added rapidly (1min) under stirring to form a large amount of flocculent precipitate; finally, quickly (1min) moving the mixture into a freeze dryer, and freeze-drying the mixture for 24h to finally obtain amorphous Co1Mn0.57WO4An active carbon composite material.
The specific surface area of the activated carbon is 1800m2(ii)/g; pore volume of 1.1cm3(ii)/g; the aperture is 2.1 nm; carbon content 96.5%; density 0.39 g/cc; iodine adsorption value 2000 mg/g.
Adding 0.8g of the catalyst and 100mL of ethylbenzene into a reflux device of a three-neck flask, and reacting for 24h at 130 ℃ under normal pressure by using air as an oxidant to obtain the target product acetophenone. The analysis by the high performance gas chromatography internal standard method shows that the conversion rate of the ethylbenzene is 85.5 percent, and the selectivity of the acetophenone is 91.6 percent.
Example 3
The amorphous CoxMnyWO4The specific preparation process of the/active carbon composite material comprises the following steps: firstly, preparing cobalt acetate and manganese acetate salt into solutions with the concentrations of 2.5mol/L and 1.5mol/L in 100mL of water; then adding 0.03mol of activated carbon, and fully performing ultrasonic treatment; then, 5.0mol/L of 100mL sodium tungstate solution is added rapidly (1min) under stirring to form a large amount of flocculent precipitate; finally, quickly (1min) moving to a freeze drier, freezingAfter drying for 24h, amorphous Co is finally obtained0.5Mn0.3WO4An active carbon composite material.
The specific surface area of the activated carbon is 2000m2(ii)/g; pore volume is 1.2cm3(ii)/g; the aperture is 2.2 nm; carbon content>98 percent; density 0.40 g/cc; iodine adsorption value was 2100 mg/g.
Adding 1.4g of the catalyst and 100mL of ethylbenzene into a reflux device of a three-neck flask, and reacting for 24h at 120 ℃ under normal pressure by using air as an oxidant to obtain the target product acetophenone. The analysis by the high performance gas chromatography internal standard method shows that the conversion rate of the ethylbenzene is 92.2 percent, and the selectivity of the acetophenone is 93.8 percent.
Example 4
The amorphous CoxMnyWO4The specific preparation process of the/active carbon composite material comprises the following steps: firstly, preparing cobalt sulfate and manganese sulfate into solutions with the concentrations of 5.0mol/L and 3.0mol/L in 100mL of water; then adding 0.03mol of activated carbon, and fully performing ultrasonic treatment; then, adding 4.0 mol/L100 mL sodium tungstate solution rapidly (1min) under stirring to form a large amount of flocculent precipitate; finally, quickly (1min) moving the mixture into a freeze dryer, and freeze-drying the mixture for 24h to finally obtain amorphous Co1.25Mn0.75WO4An active carbon composite material.
The specific surface area of the activated carbon 1950m2(ii)/g; pore volume is 1.25cm3(ii)/g; the aperture is 2.15 nm; the carbon content was 97.5%; density 0.395 g/cc; iodine adsorption value 2050 mg/g.
Adding 1.2g of the catalyst and 100mL of ethylbenzene into a reflux device of a three-neck flask, and reacting for 24h at 120 ℃ under normal pressure by using oxygen as an oxidant to obtain the target product acetophenone. The analysis by the high performance gas chromatography internal standard method shows that the conversion rate of the ethylbenzene is 90.6 percent, and the selectivity of the acetophenone is 94.3 percent.
The Co-Mn-WOx/activated carbon composite material prepared in example 1 was subjected to relevant tests, wherein FIG. 1 shows CoxMnyWO4X-ray diffraction (XRD) pattern of the/activated carbon composite. It can be seen that within the 2 theta ranges of 5-20 deg., 20-40 deg., there are two low-intensity, broad ranges, respectivelyDiffraction peaks of (2) respectively corresponding to CoxMnyWO4Peak position of activated carbon, indicating CoxMnyWO4The/active carbon composite material has a structure with low crystallinity and long-range disorder.
FIG. 2 is CoxMnyWO4TEM, SAED and Element mapping of/activated carbon composites. TEM can see that the composite material is formed by loading Co on activated carbonxMnyWO4The structure is as follows; electron Diffraction (SAED) is selected to indicate that the composite material is in an amorphous state; the Element distribution (Element mapping) graph shows that the C, O, W, Co and Mn elements in the composite material are uniformly distributed.
FIG. 3 is CoxMnyWO4HRTEM image of/activated carbon composite. As can be seen, Co is present in the compositexMnyWO4The active carbon components are all in an amorphous state.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. Amorphous CoxMnyWO4The preparation method of the/active carbon composite catalytic material is characterized by comprising the following steps:
s11: preparation of the Dispersion
Fully dissolving inorganic metal cobalt salt and manganese salt in water at room temperature, then adding activated carbon into the solution, and preparing a dispersion of the cobalt salt, the manganese salt and the activated carbon by adopting an ultrasonic treatment mode;
s12: amorphous CoxMnyWO4Preparation of/active carbon composite material
Adding sodium tungstate solution at room temperature while stirring the dispersion liquid in S11 at the rotation speed of 200-500r/min to form a mixed liquid, continuously stirring for 10-30min, and reactingFiltering and cleaning the product, and obtaining amorphous Co after vacuum freeze dryingxMnyWO4An active carbon composite catalytic material;
preferably, x: y ranges from 0.5 to 2.5: 1.
2. The amorphous Co of claim 1xMnyWO4The preparation method of the/active carbon composite catalytic material is characterized in that the molar concentration of a cobalt salt solution and a manganese salt solution in S11 is 0.5-5mol/L, and the molar ratio of the cobalt salt solution to the manganese salt solution to the active carbon is 0.5-2.5:1: 0.01-0.3.
3. The amorphous Co of claim 1xMnyWO4The preparation method of the/active carbon composite catalytic material is characterized in that the ultrasonic conditions in the S11 are as follows: ultrasonic frequency of 25-35KHz, power density of 0.3-0.5W/cm2And ultrasonic treatment is carried out for 5-15 min.
4. The amorphous Co of claim 1xMnyWO4The preparation method of the/active carbon composite catalytic material is characterized in that the molar concentration of the sodium tungstate solution in the S12 is 0.5-5mol/L, and the molar ratio of the cobalt salt, the manganese salt and the sodium tungstate is 0.5-2.5:1: 0.5-1.5.
5. The amorphous Co of claim 1xMnyWO4The preparation method of the/active carbon composite catalytic material is characterized in that the vacuum freeze-drying conditions in the S12 are as follows: the vacuum pressure is-0.09 to-0.10 MPa, the temperature is-70 to-50 ℃, and the time is 12 to 36 hours.
6. Amorphous Co prepared by the method of any one of claims 1-5xMnyWO4Active carbon composite catalytic material.
7. The amorphous Co of claim 6xMnyWO4Active carbon composite catalytic materialThe application in preparing acetophenone by oxidizing ethylbenzene.
8. The amorphous Co of claim 7xMnyWO4The application of the/active carbon composite catalytic material in preparing acetophenone by oxidizing ethylbenzene is characterized in that the method for preparing the acetophenone comprises the following steps:
s21: amorphous CoxMnyWO4Adding the/active carbon composite catalytic material and ethylbenzene into a reactor, and continuously and uniformly introducing air or oxygen into the reactor;
s22: heating the materials in the reactor, distilling the reaction liquid at the temperature of 200-210 ℃ after the reaction is finished, and collecting the distillate to obtain the acetophenone;
preferably, the amorphous CoxMnyWO4The dosage of the/active carbon composite material is 0.1-1.5 wt% of the dosage of the ethylbenzene.
9. The amorphous Co of claim 8xMnyWO4The application of the/active carbon composite catalytic material in preparing acetophenone by oxidizing ethylbenzene is characterized in that the ventilation quantity of air or oxygen in S21 is 5-50 times of the initial volume of ethylbenzene per minute.
10. The amorphous Co of claim 8xMnyWO4The application of the/active carbon composite catalytic material in preparing acetophenone by oxidizing ethylbenzene is characterized in that the reaction conditions in S22 are as follows: the heating temperature is 100 ℃ and 150 ℃, and the reaction time is 6-24 h.
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