CN111250116A - Catalyst, and preparation method and application thereof - Google Patents
Catalyst, and preparation method and application thereof Download PDFInfo
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- CN111250116A CN111250116A CN201811458105.6A CN201811458105A CN111250116A CN 111250116 A CN111250116 A CN 111250116A CN 201811458105 A CN201811458105 A CN 201811458105A CN 111250116 A CN111250116 A CN 111250116A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The application discloses a catalyst, which comprises an open tubular capillary column and an active component loaded on the inner wall of the open tubular capillary column. The catalyst can be applied to the process of preparing p-methoxybenzaldehyde by high-flow-rate catalytic oxidation of p-methoxytoluene, and the selectivity of aldehyde products can reach more than 80%. Compared with the traditional heterogeneous catalyst, the catalyst has high selectivity on the reacted aldehyde product, the active components are not easy to lose, and the service life of the catalyst is long.
Description
Technical Field
The application relates to a catalyst, a preparation method and application thereof, and belongs to the technical field of chemical preparation.
Background
P-methoxybenzaldehyde is also called anisaldehyde, is colorless or light yellow liquid at normal temperature, has lasting hawthorn fragrance, is a perfume with high economic value, is an important organic chemical synthesis intermediate, and is also an intermediate for preparing porphyrin photosensitizer, amino-carbapenem and the like.
The synthesis method of p-methoxybenzaldehyde mainly comprises the following methods: (1) prepared by oxidizing p-methoxy toluene; (2) prepared by alkylation reaction of p-hydroxybenzaldehyde and dimethyl sulfate under alkaline condition; (3) prepared by oxidizing p-propenyl anisole; (4) prepared by oxidizing p-methoxy benzyl alcohol; (5) the phenol is methylated by dimethyl sulfate, and then is prepared by chloromethylation and hydrolysis reaction; (6) is prepared from p-methylphenol through methylating and oxidizing.
In the process of preparing p-methoxybenzaldehyde by oxidizing p-methoxytoluene, molecular oxygen is used as an oxidant, so that the process is a relatively green oxidation process. For example, patent CN102070382A reports that porphyrin metal salt and porphyrin metal salt supported on a carrier are used as catalysts to catalyze the oxidation of toluene and substituted toluene, the reaction conditions are harsh, and the yield of p-methoxybenzaldehyde is low.
Disclosure of Invention
According to one aspect of the application, the catalyst can be applied to the process of preparing p-methoxybenzaldehyde by catalytically oxidizing p-methoxytoluene at a high flow rate, and the selectivity of aldehyde products can reach more than 80%. Compared with the traditional heterogeneous catalyst, the catalyst has high selectivity on the reacted aldehyde product, the active components are not easy to lose, and the service life of the catalyst is long.
A catalyst comprising an open tubular capillary column and an active component supported on the inner wall of the open tubular capillary column.
In the application, the catalyst takes a capillary column as a substrate, and an active component with a certain thickness is loaded on the inner surface of the capillary column to form the open-tube catalyst.
Open-tubular capillary columns refer to: an open tubular capillary column refers to a hollow capillary column without packing material in the middle.
Optionally, the open-tubular capillary column not loaded with active component has an inner diameter of 100 and 500 microns; the active component has a thickness within the open tubular capillary column of 10-200 microns.
The upper limit of the internal diameter of the open tubular capillary column is independently selected from 200 μm, 300 μm, 500 μm; the lower limits of the internal diameter of the open tubular capillary column are independently selected from 100 μm, 200 μm, 300 μm.
Optionally, the active component comprises a compound containing an active element.
Specifically, the active element may be at least one of Co, Mn, V, Pd.
Preferably, the active element comprises Co.
Optionally, the number of the open tubular capillary columns is 1 to 50, and a plurality of the open tubular capillary columns are connected in parallel.
In particular, a plurality of capillary columns are secured together in a bundle. The liquid inlet ends of the capillary columns are flush, and the liquid outlet ends of the capillary columns are also flush, namely, the capillary columns are arranged side by side to form a capillary tube bundle. Of course, the number of open tubular capillary columns is not limited to 1-50 provided in the present application, and those skilled in the art can select an appropriate number according to actual production needs.
Optionally, the loading capacity of the active component in the open tubular capillary column is 0.1-5 mmol/m2。
According to another aspect of the present application, there is also provided a method for preparing the above catalyst, comprising the steps of:
(a) activating the open tubular capillary column with an alkali solution;
(b) injecting a solution A containing a nitrogen-containing silane compound into the open tubular capillary column activated in the step (a), reacting in an alkaline environment, and then calcining the open tubular capillary column;
(c) and (c) injecting the solution containing the active elements into the open tubular capillary column subjected to the calcination treatment in the step (b), and drying to obtain the catalyst.
Specifically, in the step (a), alkali liquor is injected into the capillary column by using an injector, the end of the capillary column is sealed by using a rubber plug, the capillary column is activated in water bath, then the capillary column is washed to be neutral by using deionized water, finally the capillary column is washed by using absolute ethyl alcohol, and the capillary column is dried, so that the activation of the capillary column is completed.
Optionally, the temperature of the water bath is 50-70 ℃, and the activation time is 1-5 h. Preferably, the temperature of the water bath is 60 ℃, and the activation time is 2-4 h.
Optionally, the alkali solution in step (a) comprises at least one of a sodium hydroxide solution, a potassium hydroxide solution and a lithium hydroxide solution.
Specifically, in the step (b), the solution A containing the nitrogenous silane compound is injected into the activated open tubular capillary column by using an injector, water bath reaction is carried out in an alkaline environment, then the open tubular capillary column is placed into an oven to be dried, and the open tubular capillary column is placed into a muffle furnace to be calcined after the drying.
Alternatively, the nitrogen-containing silane compound of step (b) includes at least one of 3-aminopropyltrimethoxysilane, pyridyltrimethoxysilane, pyrimidyltrimethoxysilane and imidazolyltrimethoxysilane.
Optionally, the solution a in step (b) further comprises anhydrous ethanol, ethyl orthosilicate, cetyltrimethylammonium bromide;
the volume part ratio of the absolute ethyl alcohol, the ethyl orthosilicate, the nitrogen-containing silane compound and the hexadecyl trimethyl ammonium bromide is 10: 0.5-2: 0.1-1: 0.1 to 2.
In the present application, the preparation method of solution a is: mixing absolute ethyl alcohol, tetraethoxysilane, nitrogen-containing silane compound and CTAB according to the volume parts; and (3) putting the mixed solution into an ice water bath at 0 ℃, adding ammonia water into the mixed solution under magnetic stirring, and continuously stirring to form the solution A containing the nitrogenous silane compound.
CTAB refers to cetyltrimethylammonium bromide.
In the present application, the active component may be supported (immobilized) within the capillary column by the nitrogen-containing silane compound. Modified with a nitrogen-containing silane compound to function as a fixing agent for the active ingredient.
Optionally, the reaction temperature in the step (b) is 50-90 ℃, and the reaction time is 2-7 h.
Specifically, the capillary column is placed in a water bath at 50-90 ℃ for reaction, and the reaction time is 2-7 h. Preferably, the temperature of the water bath is 60-80 ℃, and the reaction time in the water bath is 3-6 h.
The upper limit of the reaction temperature of the capillary column in the water bath is independently selected from 60 ℃, 80 ℃, 90 ℃ and the lower limit of the reaction temperature of the capillary column in the water bath is independently selected from 50 ℃, 60 ℃, 80 ℃.
The upper limit of the reaction time of the capillary column in the water bath is independently selected from 3h, 6h, 7h, and the lower limit of the reaction time of the capillary column in the water bath is independently selected from 2h, 3h, 6 h.
The drying temperature and the drying time in the drying oven are not strictly limited, and the skilled person in the art can select the appropriate drying temperature and drying time according to the actual production needs. Preferably, in the step (b), the drying temperature in the oven is 110-130 ℃, and the drying time is 2-4 h. Preferably, the drying temperature is 120 ℃ and the drying time is 3 h.
Optionally, the calcining temperature in the step (b) is 400-800 ℃, and the calcining time is 1-7 h.
The upper limit of the calcination temperature is independently selected from 500 deg.C, 600 deg.C, 700 deg.C, 800 deg.C, and the lower limit of the calcination temperature is independently selected from 400 deg.C, 500 deg.C, 600 deg.C, 700 deg.C.
The upper limit of the calcination time is independently selected from 2h, 3h, 6h, 7h, and the lower limit of the calcination time is independently selected from 1h, 2h, 3h, 6 h.
Preferably, the calcination temperature is 500-700 ℃, and the calcination time is 2-6 h.
Specifically, in the step (c), a solution containing an active element is injected into the obtained capillary column by using an injector, the injection is repeated for 4-9 times, and the active component can be loaded on the inner wall of the open-tubular capillary column after drying.
Alternatively, the solution containing the active element may be a solution formed of a salt compound containing the active element.
The salt compound containing the active element comprises Co salt, and the Co salt is selected from at least one of cobalt nitrate, cobalt chloride, cobalt acetate, cobalt sulfate, cobalt naphthenate and cobalt isooctanoate.
Optionally, the salt compound of the active element is a Mn salt selected from manganese nitrate, manganese chloride, manganese acetate and manganese sulfate.
Optionally, the salt compound of the active element is a V salt, and the V salt is selected from vanadyl sulfate and vanadium nitrate.
Optionally, the salt compound of the active element is a Pd salt selected from palladium nitrate, palladium chloride and palladium acetate.
Optionally, the salt compound of the active element is 0.5-2% by mass of the solution. For example, the mass percentage of the aqueous solution of Co salt is 0.5-2%.
In another aspect of the present application, there is provided the above catalyst, and the use of the catalyst prepared by the above method in the preparation of p-methoxybenzaldehyde by oxidation of p-methoxytoluene, wherein a p-methoxytoluene-containing solution B is mixed with oxygen and then injected into the catalyst, and the mixture is subjected to oxidation reaction with the active component to obtain the p-methoxybenzaldehyde.
Optionally, the solvent in the solution B is acetic acid, and the mass percentage of the p-methoxytoluene in the solution B is 1-30%.
Optionally, the flow rate of the mixture of the solution B and oxygen injected into the catalyst is 0.1-5 m/s, the pressure of the oxygen is 0.1-0.5 MPa, and the reaction temperature is 60-120 ℃. The pressure of oxygen refers to the pressure of oxygen at the time of reaction.
In the present application, the preparation of p-methoxybenzaldehyde from p-methoxytoluene is a high flow oxidation.
In the application, the structural formula of the p-methoxytoluene is shown as a formula I, and the structural formula of the p-methoxybenzaldehyde is shown as a formula II;
the beneficial effects that this application can produce include:
1) compared with the traditional catalytic reaction process, the catalyst can obtain p-methoxybenzaldehyde with high selectivity, and the selectivity can reach more than 80%.
2) The catalyst has long service life and does not deactivate after continuous reaction for 72 hours.
Drawings
FIG. 1 is a scanning electron micrograph of sample No. 1.
Figure 2 is a graph of conversion and selectivity over time for sample # 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The conversion, selectivity, in the examples of the present application were calculated as follows:
conversion of p-methoxytoluene ═ p-methoxytoluene mole in gas-liquid mixture) - (p-methoxytoluene mole in product) ]/(p-methoxytoluene mole in gas-liquid mixture) × (100%)
Selectivity to p-methoxybenzaldehyde ═ p-methoxybenzaldehyde moles ÷ total of all product moles × 100%.
In the examples of the present application, the conversion of p-methoxytoluene and the selectivity to p-methoxybenzaldehyde were calculated on a molar basis.
EXAMPLE 1 preparation of catalyst samples
Preparation of sample No. 1
1) Taking a capillary column with the inner diameter of 200 microns, injecting 1mol/L NaOH solution by using an injector, sealing by using a rubber plug, activating for 2 hours in water bath at 60 ℃, washing to be neutral by using deionized water, washing by using absolute ethyl alcohol, and drying;
2) adding 10ml of absolute ethyl alcohol, 2ml of ethyl orthosilicate, 0.3ml of pyridyl trimethoxy silane and 1ml of CTAB into a beaker, and uniformly stirring; putting into ice water bath at 0 deg.C, adding 0.2ml ammonia water into the solution under magnetic stirring, and stirring for 20min to obtain uniform and transparent solution A;
3) injecting the solution A into an activated capillary column by using an injector, sealing the end by using a rubber plug, putting the capillary column into a water bath at 60 ℃ for reacting for 6 hours, and then putting the capillary column into a drying box at 120 ℃ for drying and drying for 3 hours; placing the prepared capillary column into a muffle furnace for calcination at 600 ℃ for 2 h;
4) injecting 1 wt% cobalt chloride aqueous solution into the capillary column with an injector, repeatedly injecting for 6 times, and drying to obtain the catalytic device, and recording as sample No. 1.
Preparation of sample No. 2
1) Taking a capillary column with the inner diameter of 500 micrometers, injecting 2mol/L NaOH solution by using an injector, sealing by using a rubber plug, activating for 4 hours in water bath at 60 ℃, washing to be neutral by using deionized water, washing by using absolute ethyl alcohol, and drying;
2) adding 10ml of absolute ethyl alcohol, 1ml of ethyl orthosilicate, 0.3ml of pyridyl trimethoxy silane and 0.5ml of CTAB into a beaker, and uniformly stirring; putting into ice water bath at 0 deg.C, adding 0.4ml ammonia water into the solution under magnetic stirring, and stirring for 30min to obtain uniform and transparent solution A;
3) injecting the solution A into an activated capillary column by using an injector, sealing the end by using a rubber plug, putting the capillary column into a water bath at 60 ℃ for reaction for 3 hours, and then putting the capillary column into a drying box at 120 ℃ for drying and drying for 3 hours; placing the prepared capillary column into a muffle furnace for calcination at 500 ℃ for 2 h;
4) injecting 1 wt% cobalt nitrate water solution into the capillary column with an injector, repeatedly injecting for 8 times, and drying to obtain the catalytic device, and recording as sample No. 2.
Preparation of sample No. 3
1) Taking a capillary column with the inner diameter of 300 microns, injecting 1mol/L NaOH solution by using an injector, sealing by using a rubber plug, activating for 4 hours in water bath at 60 ℃, washing to be neutral by using deionized water, washing by using absolute ethyl alcohol, and drying;
2) adding 10ml of absolute ethyl alcohol, 1ml of ethyl orthosilicate, 0.5ml of imidazolyl trimethoxy silane and 0.5ml of CTAB into a beaker, and uniformly stirring; putting into ice water bath at 0 deg.C, adding 0.4ml ammonia water into the solution under magnetic stirring, and stirring for 30min to obtain uniform and transparent solution A;
3) injecting the solution A into an activated capillary column by using an injector, sealing the end by using a rubber plug, putting the capillary column into a water bath at 80 ℃ for reaction for 3 hours, and then putting the capillary column into a drying box at 120 ℃ for drying and drying for 3 hours; placing the prepared capillary column into a muffle furnace for calcination at 700 ℃ for 6 h;
4) injecting 0.8 wt% cobalt sulfate aqueous solution into the capillary column with an injector, repeatedly injecting for 8 times, and oven drying to obtain the catalytic device, and recording as sample # 3.
Preparation of sample No. 4
1) Taking a capillary column with the inner diameter of 500 micrometers, injecting 1mol/L NaOH solution by using an injector, sealing by using a rubber plug, activating for 4 hours in a water bath at 60 ℃, washing to be neutral by using deionized water, washing by using absolute ethyl alcohol, and drying;
2) adding 10ml of absolute ethyl alcohol, 1ml of ethyl orthosilicate, 0.1ml of imidazolyl trimethoxy silane and 0.5ml of CTAB into a beaker, and uniformly stirring; putting into ice water bath at 0 deg.C, adding 0.2ml ammonia water into the solution under magnetic stirring, and stirring for 30min to obtain uniform and transparent solution A;
3) injecting the solution A into an activated capillary column by using an injector, sealing the end by using a rubber plug, putting the capillary column into a water bath at 80 ℃ for reaction for 3 hours, and then putting the capillary column into a drying box at 120 ℃ for drying and drying for 3 hours; placing the prepared capillary column into a muffle furnace for calcination at 500 ℃ for 3 h;
4) injecting 2 wt% cobalt nitrate water solution into the capillary column with an injector, repeatedly injecting for 5 times, and drying to obtain the catalytic device and recording the sample No. 4.
Example 2 morphology testing of catalyst samples
SEM morphology tests were performed on samples No. 1# to No. 4# respectively using a Hitachi (SU8020) type scanning electron microscope. Representatively designated as sample No. 1, FIG. 1 is a scanning electron micrograph of sample No. 1. As can be seen from FIG. 1, the active ingredient has a thickness of 50 μm inside the open tubular capillary column.
The scanning electron micrographs of other samples are similar to sample No. 1, and the inner diameter of the open tubular capillary column after loading the active component is 10-490 μm.
Example 3 Performance testing of catalyst samples
Respectively connecting samples 1# to 4# to a catalytic oxidation fixed bed reaction system, mixing 20% of solution B containing p-methoxytoluene with oxygen, controlling the pressure of the oxygen to be 0.3MPa by using a back pressure valve, pumping the gas-liquid mixture into the sample 1# by using a pump, wherein the flow rate is 4m/s, the reaction temperature is 80 ℃, detecting products at an outlet by using a gas chromatography, and calculating the conversion rate of the p-methoxytoluene and the selectivity of the p-methoxybenzaldehyde.
The sample # 1 is typically represented, and the specific test data is shown in fig. 2. FIG. 2 is a graph showing the conversion and selectivity of sample No. 1 as a function of time, and it can be seen from FIG. 2 that the conversion of p-methoxytoluene of sample No. 1 is 35-50%, the selectivity of p-methoxybenzaldehyde of sample No. 1 is > 80%, and it can also be seen from FIG. 2 that the service life of sample No. 1 is long and the reaction is not deactivated for 72 hours continuously.
The other samples are similar to the performance data of sample # 1, and it can be seen that the selectivity of the catalyst sample to anisaldehyde is more than 80%, the service life of the sample is long, and the reaction is not deactivated after 72 hours.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A catalyst comprising an open tubular capillary column and an active component supported on the inner wall of the open tubular capillary column.
2. The catalyst of claim 1, wherein the open-tube capillary column not loaded with active component has an internal diameter of 100 to 500 μm.
3. The catalyst of claim 1, wherein the active component comprises a compound containing an active element;
the active element comprises Co.
4. The catalyst according to claim 1, wherein the number of the open-tube capillary columns is 1 to 50, and a plurality of the open-tube capillary columns are connected in parallel.
5. The catalyst according to claim 1, wherein the loading amount of the active component in the open tubular capillary column is 0.1 to 5mmol/m2。
6. A method for preparing the catalyst according to any one of claims 1 to 5, comprising the steps of:
(a) activating the open tubular capillary column with an alkali solution;
(b) injecting a solution A containing a nitrogen-containing silane compound into the open tubular capillary column activated in the step (a), reacting in an alkaline environment, and then calcining the open tubular capillary column;
(c) and (c) injecting the solution containing the active elements into the open tubular capillary column subjected to the calcination treatment in the step (b), and drying to obtain the catalyst.
7. The method according to claim 6, wherein the nitrogen-containing silane compound in the step (b) comprises at least one of 3-aminopropyltrimethoxysilane, pyridyltrimethoxysilane, pyrimidyltrimethoxysilane and imidazolyltrimethoxysilane.
8. The method according to claim 6, wherein the solution A in step (b) further comprises anhydrous ethanol, ethyl orthosilicate, cetyltrimethylammonium bromide;
the volume part ratio of the absolute ethyl alcohol, the ethyl orthosilicate, the nitrogen-containing silane compound and the hexadecyl trimethyl ammonium bromide is 10: 0.5-2: 0.1-1: 0.1 to 2.
9. The method according to claim 6, wherein the solution containing the active element in the step (c) is a solution formed by a salt compound containing the active element;
the salt compound of the active element accounts for 0.5-2% of the solution.
10. The catalyst of any one of claims 1 to 6 and the catalyst prepared by the method of any one of claims 7 to 9, which are used for preparing p-methoxybenzaldehyde by oxidizing p-methoxytoluene, are characterized in that a p-methoxytoluene-containing solution B and oxygen are mixed and then injected into the catalyst, and the mixture and the active components are subjected to oxidation reaction to obtain the p-methoxybenzaldehyde.
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| CN1485131A (en) * | 2002-09-26 | 2004-03-31 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing benzaldehyde and benzyl alcohol from toluol, the preparation process and application thereof |
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