Disclosure of Invention
The invention solves the problems that the noble metal homogeneous palladium catalysis technology in the prior art is difficult to recover and has at least one aspect of heavy metal residue.
In order to solve the problems, the invention provides a precious metal-supported polyaniline catalyst, which is prepared by dissolving aniline or aniline derivatives and polyvinyl alcohol in hydrobromic acid, adding a solution of precious metal salt and hydrogen peroxide to react, and then carrying out post-treatment, wherein the metal loading of the precious metal-supported polyaniline catalyst is 0.001-1 wt%.
Preferably, the aniline derivative comprises one or more of aromatic amines such as o-phenylenediamine, m-phenylenediamine, p-anisidine, p-trifluoromethylaniline and 1-naphthylamine.
Preferably, the polyvinyl alcohol is used in an equivalent weight range comprised between 2 and 2000ppm with respect to the aniline or aniline derivative.
Preferably, the noble metal salt comprises a palladium salt comprising palladium chloride, palladium acetate or palladium bis (acetylacetonate).
Preferably, the concentration of the hydrogen peroxide is less than 6%.
Preferably, the reaction time range includes 8 to 120 hours.
Compared with the prior art, the polyaniline supported noble metal catalyst has the advantages that: in the invention, hydrobromic acid and polyvinyl alcohol are used in the preparation process of the polyaniline-supported noble metal catalyst, and the radius of bromide ions is far greater than that of chloride ions and fluoride ions, so compared with hydrochloric acid and hydrofluoric acid, the catalyst is more likely to have solvation effect, and the elementary reaction rate is higher in the catalyst transmetalization process, so that the overall reaction rate is higher, the catalytic activity is higher, and the polyvinyl alcohol can serve as a 'soft template' in the catalyst preparation process to accelerate the growth of a polyaniline carrier. In addition, the polyaniline-supported noble metal catalyst has low metal loading, high TON number, high catalytic activity and low catalyst cost.
In order to solve the problems, the invention also provides a continuous flow reactor, which comprises a base body, a filtering component, a sealing component, a feeding hole and a discharging hole which are oppositely arranged at the two ends of the base body, the sealing component is sleeved outside the base body, the filtering component is arranged at the end part of the base body and is arranged inside the sealing component, the filtering components comprise a first filtering component and a second filtering component which are respectively arranged at two ends of the base body, the sealing assembly comprises a first sealing element and a second sealing element, the first sealing element and the second sealing element are respectively arranged at two ends of the base body, the first sealing element is provided with the feed inlet, the second sealing element is provided with the discharge outlet, and the base body is filled with the polyaniline loaded noble metal catalyst.
Preferably, the first filter assembly and/or the second filter assembly comprises a filter element and a filter membrane, and the filter membrane is arranged at the end part close to the base body relative to the filter element.
Preferably, the matrix is filled with glass beads and absorbent cotton, and the absorbent cotton is suitable for filling the gap between the glass beads and the filter assembly.
The continuous flow reactor can realize the continuous separation of the catalyst and the product, and the arrangement of the filtering component ensures that stirring is not needed in the process of realizing the continuous separation of the catalyst and the product, so that the structure is simpler and the separation effect is good.
In order to solve the problems, the invention also provides a continuous flow reaction device which comprises a reaction pump, a fraction collector and the continuous flow reactor, wherein the reaction pump is communicated with the feeding hole of the continuous flow reactor, and the fraction collector is communicated with the discharging hole of the continuous flow reactor.
The advantages of the continuous flow reactor and the continuous flow reactor of the present invention over the prior art are the same and will not be described herein.
Detailed Description
The technical solutions in the embodiments of the present application will be described in detail and clearly with reference to the accompanying drawings.
In the description of the embodiments of the present application, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
The description of the term "some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The invention provides a precious metal catalyst 8 supported by polyaniline, the precious metal catalyst 8 supported by polyaniline is prepared by dissolving aniline or aniline derivatives and polyvinyl alcohol in hydrobromic acid, adding a solution of precious metal salt in hydrobromic acid and hydrogen peroxide for reaction and then carrying out post-treatment, and the metal loading capacity of the precious metal catalyst 8 supported by polyaniline is 0.001-1 wt%.
Therefore, hydrobromic acid and polyvinyl alcohol are used in the preparation process of the polyaniline-supported noble metal catalyst 8, and as the radius of bromide ions is far greater than that of chloride ions and fluoride ions, compared with hydrochloric acid and hydrofluoric acid, the polyaniline-supported noble metal catalyst is more likely to have solvation effect, and the elementary reaction rate is higher in the catalyst transmetalization process, so that the overall reaction rate is higher, the catalytic activity is higher, and the polyvinyl alcohol can serve as a 'soft template' in the catalyst preparation process to accelerate the growth of a polyaniline carrier. In addition, in the embodiment, the precious metal catalyst 8 supported by polyaniline has low metal loading, high TON number, high catalytic activity and low catalyst cost. The catalyst is stable to air and moisture, and can be stably stored for one year under the conditions of air and room temperature without obvious reduction of catalytic activity.
In some preferred embodiments, the aniline derivative includes one or more of o-phenylenediamine, m-phenylenediamine, p-anisidine, p-trifluoromethylaniline, and 1-naphthylamine. The raw material source is wide.
In some preferred embodiments, the polyvinyl alcohol has an average molecular weight in the range of 1000-1000000 and a degree of alcoholysis in the range of 40-98% relative to the equivalent weight of aniline or aniline derivative used in the range of 2-2000ppm, whereby the polyvinyl alcohol cooperates with aniline or aniline derivative to increase the activity of the catalyst.
In the present embodiment, the noble metal salt is preferably a palladium salt, and in some preferred embodiments, the palladium salt includes commercial palladium salts such as palladium chloride, palladium acetate, palladium bis (acetylacetonate), and the like. In some specific embodiments, the palladium salt is palladium chloride. Low cost, low toxicity and good catalytic performance.
In the embodiment, the concentration of the hydrogen peroxide is less than 6%, in some preferable embodiments, 3% of medical hydrogen peroxide is selected, and compared with the prior art that 30% of hydrogen peroxide (explosive agent) is adopted, the material is easier to obtain.
In some embodiments, the reaction time range includes 8-120 hours. In some preferred embodiments, the reaction time is 24 hours, which ensures low cost while also allowing for increased activity of the resulting catalyst.
In some embodiments, the post-treatment comprises adjusting the pH to neutral, centrifuging and vacuum drying, whereby the purity of the catalyst can be ensured.
In some embodiments, the vacuum drying temperature range includes room temperature to 80 ℃, preferably 60 ℃, and the vacuum drying time is 2-24 hours, preferably 12 hours. Therefore, the drying effect is better.
In some preferred embodiments, the water retention agent is added to the centrifuged product before vacuum drying, and the equivalent range of the water retention agent used corresponding to the centrifuged product includes 1-1000ppm, which can effectively enhance the catalyst stability.
In some embodiments, the water retaining agent is a copolymer comprising acrylamide-acrylate, such as polyacrylamide, sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, and the like.
As shown in fig. 1 and 2, another embodiment of the present invention provides a continuous flow reactor, which includes a base 3, a filter assembly, a seal assembly, and a feed inlet 1 and a discharge outlet 2 oppositely disposed at two ends of the base 3, wherein the seal assembly is sleeved outside the base 3, the filter assembly is disposed at an end of the base 3 and disposed inside the seal assembly, the filter assembly includes a first filter assembly 4 and a second filter assembly 5, the first filter assembly 4 and the second filter assembly 5 are respectively disposed at two ends of the base 3, the seal assembly includes a first seal member 61 and a second seal member 62, the first seal member 61 and the second seal member 62 are respectively disposed at two ends of the base 3, the first seal member 61 is provided with the feed inlet 1, the second seal member 62 is provided with the discharge outlet 2, and the base 3 is filled with a polyaniline-loaded noble metal catalyst 8.
From this, can realize the continuous separation of catalyst and result, and filtering component's setting for need not the stirring at the in-process of realizing the continuous separation of catalyst and result, the structure is simpler, and separation effect is good.
The shape of the base body 3 is not limited in this embodiment, and in some preferred embodiments, the base body 3 is cylindrical, and has a simple structure and an attractive appearance.
Preferably, the first filter assembly 4 and/or the second filter assembly 5 comprise a filter cartridge and a filter membrane, the filter membrane being arranged close to the end of the base body 3 with respect to the filter cartridge.
Thus, the filter cartridge provides support for the combination of the filter membrane and the cartridge body.
In some preferred embodiments, the filter membrane has a molecular weight cut-off in the range of 100-10000, which enables efficient separation of catalyst from product.
In some specific embodiments, the first filter assembly 4 comprises a first filter element 41 and a first filter membrane 42, the second filter assembly 5 comprises a second filter element and a second filter membrane, and the first filter membrane 42 can prevent the catalyst from leaking and mixing back to the upstream pipeline; the second filter membrane can realize the separation of the catalyst and the product.
In some preferred embodiments, the first filter 42 and the second filter are of the same pore size, and thus, the installation direction is not considered, and even if the installation direction is reversed, no influence is caused, and the installation is easier.
In some preferred embodiments, the matrix 3 is further filled with glass beads and absorbent cotton, and the absorbent cotton is suitable for filling the gap between the glass beads and the filter assembly.
In some preferred embodiments, in order to avoid the catalyst from being concentrated in a certain section of the reactor cylinder to block the flow path, the glass beads are filled in the matrix 3, which can help the polyaniline-supported noble metal catalyst 8 to be ground, so that the catalyst is uniformly distributed in the reactor, and in addition, the porosity is increased, and the pressure drop is prevented from being too high.
In some embodiments, the diameter of the glass beads is in the range of 0.1 to 5mm, and in some preferred embodiments, the diameter of the glass beads is 0.3mm, so that the polyaniline can be dispersed more effectively.
In some preferred embodiments, the gap between the glass bead and the filter assembly is filled with absorbent cotton, which not only can prevent the glass bead from rushing to one side of the second filter element, but also can generate a smaller pressure drop relative to the glass bead. In addition, the absorbent cotton is added as a pre-filter, so that the possibility that the catalyst and the degradation products thereof are adsorbed on the filter membrane can be reduced, and the service life of the filter membrane is prolonged.
In this embodiment, the filling manner of the polyaniline-supported noble metal catalyst 8 is as follows: put into filter membrane, filter core in proper order at the feed end or the discharge end of base member 3, screwed up the sealing member to fill in appropriate amount absorbent cotton, weigh polyaniline load noble metal catalyst 8 and glass pearl, use the mortar porphyrization back, add to base member 3 from discharge end or feed end, fill in absorbent cotton and fill surplus space, put into another filter membrane and another filter core in proper order again, screwed up another sealing member, accomplish loading of polyaniline load noble metal catalyst 8.
In some embodiments, the outer portion of the base body 3 is provided with a jacket 7 around, and the jacket 7 is provided with an oil inlet and an oil outlet for providing a carrier for heat exchange, and the structure is simple.
As shown in fig. 3, another embodiment of the present invention further provides a continuous flow reaction apparatus, which comprises a reaction pump 9, a fraction collector 10 and a continuous flow reactor, wherein the reaction pump 9 is communicated with the feed inlet 1 of the continuous flow reactor, and the fraction collector 10 is communicated with the discharge outlet 2 of the continuous flow reactor. Therefore, the reaction solvent is pumped out by the reaction pump 9 and enters the feeding port 1 of the continuous flow reactor for reaction, and the product flows to the fraction collector 10 through the discharging port 2 of the continuous flow reactor for collection.
In some preferred embodiments, a one-way valve 11 and a pressure gauge 12 are arranged on a connecting pipeline between the reaction pump 9 and the continuous flow reactor, the flow rate of the reaction solvent is controlled through the one-way valve 11, and the pressure drop in the continuous flow reactor is monitored through the pressure gauge 12, so that the structure is simple.
In some preferred embodiments, a back pressure valve 13 is disposed on the connection pipeline between the continuous flow reactor and the fraction collector 10, and when the reaction temperature is close to or exceeds the boiling point of the reaction solvent, the back pressure valve 13 can maintain a certain pressure (pressure) in the system, prevent the solvent from evaporating in a large amount, and can maintain the pressure of the system stable and reduce the influence of flow fluctuation of the reaction pump 9.
In addition, in this embodiment, before pumping the reaction solvent into the continuous flow reactor, the polyaniline-supported noble metal catalyst 8 needs to be activated, and the activation method includes: activating the reaction solvent at the flow rate of 0.01-1ml/min at the activation temperature of 40-75 ℃ for 2-12 hours.
In some embodiments, the solvent comprises one or more of water, ethanol, n-propanol, isopropanol, and methoxyethanol. In some embodiments, the flow rate of the reaction solvent is preferably 0.1ml/min, the activation temperature is preferably 50 ℃ and the activation time is preferably 8 hours. Thus, the better the activation effect, the higher the reactivity of the catalyst.
The advantages of the continuous flow reaction device and the continuous flow reactor of the embodiment of the invention relative to the prior art are the same, and are not described in detail herein.
Example 1
The embodiment provides a preparation method of a polyaniline supported palladium catalyst, which comprises the following steps: 10mmol of aniline and 0.0023mmol of polyvinyl alcohol are dissolved in 100ml of hydrobromic acid (1mol/L), 160. mu.L of palladium chloride solution (0.1mol/L dissolved in 1mol/L hydrobromic acid) are added, and 20.8ml of hydrogen peroxide are added within 1 hour. After stirring at room temperature for 24 hours, the reaction mixture was neutralized to pH 7 with 1mol/L sodium hydroxide solution. After centrifugal separation, the mixture is dried for 12 hours at 60 ℃ by using a vacuum drying oven to obtain the polyaniline supported palladium catalyst.
In this example, according to the above method, the influence of the reaction time on the catalytic activity of the polyaniline-supported palladium catalyst was examined by changing the reaction time, i.e., the stirring time at room temperature.
In this example, the activity of the polyaniline-supported palladium catalyst was examined by the following method, which specifically includes:
p-methylphenylboronic acid (67.98mg, 0.5mmol), potassium carbonate (69.11mg, 0.5mmol) and a polyaniline-supported palladium catalyst (1.5mg) were weighed, transferred to a 15ml clean, dried, pressure-resistant sealed tube, evacuated and purged with nitrogen three times. Iodobenzene (102mg, 56. mu.L), solvent (EtOH/H) were measured2O1: 1, 2.0mL) was put into a pressure-tight tube, stirred at normal temperature for 10min, and then heated to 100 ℃. After 12h, the reaction was stopped and cooled to room temperature, 60 μ L of n-dodecane was added and quenched using MTBE (3ml) -citric acid (0.5M,3ml) system to give a gas phase yield.
The results are given in the following table:
Entry
|
catalyst and process for preparing same
|
Catalyst preparation time/h
|
Yield/%)
|
1
|
Pd/PANI-1
|
8
|
2
|
2
|
Pd/PANI-2
|
16
|
18
|
3
|
Pd/PANI-3
|
24
|
99
|
4
|
Pd/PANI-4
|
32
|
99
|
5
|
Pd/PANI-5
|
40
|
99
|
6
|
Pd/PANI-6
|
48
|
99
|
7
|
Pd/PANI-7
|
56
|
99
|
8
|
Pd/PANI-8
|
64
|
99
|
8
|
Pd/PANI-9
|
120
|
99 |
As can be seen from the above table, the preparation time of the catalyst is preferably 24 hours in view of the catalytic effect and the time cost. Not only ensures low cost, but also increases the activity of the prepared catalyst.
In this example, the Pd/PANI-3 obtained was tested in series, and the test results are shown in FIG. 4-FIG. 7. Fig. 4 is a scanning electron microscope image of the polyaniline-supported palladium catalyst Pd/PANI-3 obtained in this example, where the catalyst is fibrous and has a typical polyaniline morphology. FIG. 5 is a scanning electron microscope-X-ray energy spectrum analysis diagram of "carbon element" in the polyaniline supported palladium catalyst. FIG. 6 is a scanning electron microscope-X-ray energy spectrum analysis diagram of "nitrogen element" in the polyaniline supported palladium catalyst. FIG. 7 is a scanning electron microscope-X-ray energy spectrum analysis diagram of "palladium element" in the polyaniline-supported palladium catalyst. And as can be seen from fig. 5-7, the polyaniline-supported palladium catalyst has uniform distribution of the carbon, nitrogen and palladium main elements, thereby providing a guarantee for the stability of the catalyst performance.
Example 2
This example provides a method for preparing a polyaniline supported palladium catalyst, which is different from that in example 1 in that a water retention agent is added to a product after centrifugal separation before vacuum drying, and specifically includes: 10mmol of aniline and 0.0023mmol of polyvinyl alcohol are dissolved in 100ml of hydrobromic acid (1mol/L), 160. mu.L of palladium chloride solution (0.1mol/L dissolved in 1mol/L hydrobromic acid) are added, and 20.8ml of hydrogen peroxide are added within 1 hour. After stirring at room temperature for 24 hours, the reaction mixture was neutralized to pH 7 with 1mol/L sodium hydroxide solution. After centrifugal separation, 0.001mmol of polyacrylamide was added, and the mixture was dried at 60 ℃ for 12 hours using a vacuum oven to obtain a polyaniline-supported palladium catalyst.
Example 3
The embodiment provides a preparation method of a polyaniline supported palladium catalyst, which comprises the following steps: 10mmol of aniline and 0.02mmol of polyvinyl alcohol were dissolved in 100ml of hydrobromic acid (1mol/L), 160. mu.L of a palladium chloride solution (0.1mol/L dissolved in 1mol/L of hydrobromic acid) were added, and 31.2ml of hydrogen peroxide were added over 1 hour. After stirring at room temperature for 120 hours, the reaction mixture was neutralized to pH 7 with a 0.2mol/L sodium tripolyphosphate solution. After centrifugal separation, drying for 24 hours at room temperature by using a vacuum drying oven to obtain the polyaniline supported palladium catalyst.
Example 4
The embodiment provides a preparation method of a polyaniline supported palladium catalyst, which comprises the following steps: 10mmol of 4-methoxyaniline and 0.02mmol of polyvinyl alcohol were dissolved in 200ml of hydrobromic acid (1mol/L), 1600. mu.L of a palladium chloride solution (0.1mol/L dissolved in 1mol/L of hydrobromic acid) were added, and 20.8ml of hydrogen peroxide were added over 1 hour. After stirring at room temperature for 48 hours, the reaction mixture was neutralized to pH 7 with a 0.33mol/L sodium phosphate solution. After centrifugal separation, the mixture is dried for 2 hours at 80 ℃ by using a vacuum drying oven to obtain the polyaniline supported palladium catalyst.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.