CN109675625B - Catalytic hydrogenation Pd/AC-P catalyst for catalyzing halogenated aromatic hydrocarbon and preparation method and application thereof - Google Patents
Catalytic hydrogenation Pd/AC-P catalyst for catalyzing halogenated aromatic hydrocarbon and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalytic hydrogenation Pd/AC-P catalyst for catalyzing halogenated aromatic hydrocarbon, a preparation method and application thereof, belonging to the technical field of wastewater treatment. In order to solve the problems of poor catalytic activity and difficult separation in the prior art, the method provides a catalytic hydrogenation Pd/AC-P catalyst for catalyzing halogenated aromatic hydrocarbon and a preparation method and application thereof, and the method comprises the steps of weighing corresponding chloropalladate according to the loading amount, and dropwise adding the chloropalladate into ordered mesoporous carbon to obtain a mixture; after drying, roasting in the atmosphere of hydrogen to obtain a solid substance; weighing corresponding ionic liquid, polysiloxane and anhydrous methanol, and uniformly mixing to obtain corresponding mixed liquor; and mixing and drying to obtain the corresponding catalytic hydrogenation Pd/AC-P catalyst. The invention has the characteristics of heat resistance, cold resistance, small viscosity change along with temperature, water resistance and small surface tension, can reduce palladium particles formed in the preparation process, and is more favorable for further improving the capability of catalytic activity.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a catalytic hydrogenation Pd/AC-P catalyst for catalyzing halogenated aromatic hydrocarbon, and a preparation method and application thereof.
Background
The halogenated phenol compound is an important chemical raw material and an organic solvent, and is widely applied to the industries of medicine, leather making, electronics, pesticide and the like. However, the compounds have strong chemical stability, are not easy to decompose in natural environment, and cause persistent harm to the environment, and meanwhile, the halogenated phenol compounds are easy to bioaccumulate and finally harm animals and human beings after bioaccumulation. Since the organic substance contains chlorine, which has a great influence on environmental pollution, the removal of chlorine from the compound can effectively reduce the toxic effect. The priority control pollutants published by the U.S. EPA and the European Union are organic chlorides in the first place and nearly in half, and governments around the world have stated prohibition on discharging organic chlorides into rivers, lakes and shallow landfills.
Catalytic Hydrodechlorination (HDC) belongs to one of chemical reduction technologies, which uses active hydrogen provided by a catalyst to replace chlorine atoms in halogenated phenol to dechlorinate phenol. HDC is the reduction of chlorophenols by catalytic hydrogenation and the production of pollution-free recoverable compounds that not only remove halogenated organics, but also recover the products for collection for use therein. In order to effectively remove pollutants, the preparation of catalysts with excellent performances such as high stability, strong catalytic performance, good selectivity and the like is very important, but the activity and the catalytic capability of the existing catalysts for halogenated aromatic compounds are poor.
The ordered activated carbon has more active sites on the surface because the pore channels are arranged in order, the pore volume and the specific surface area are larger than those of the common activated carbon, and the ordered activated carbon has very important value in the fields of adsorption separation, super capacitance, energy storage materials, catalyst carriers, drug delivery, slow release and the like, and can be used as a load material to improve the catalytic capability.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a catalytic hydrogenation Pd/AC-P catalyst for catalyzing halogenated aromatic hydrocarbon and a preparation method and application thereof, and solves the problem of how to improve the catalytic activity of a palladium-based catalyst and the effect of easy separation.
One of the purposes of the invention is realized by the following technical scheme that the catalyst for catalyzing and hydrogenating the halogenated aromatic hydrocarbon adopts a mesoporous molecular sieve as a carrier, and is loaded with a first component of metal palladium, and also loaded with a second component of separating molecular liquid and a third component of polysiloxane.
The invention uses the carrier of the mesoporous molecular sieve and the Ionic Liquid (IL) which has unique solvent performance, catalytic performance and structure designability and can be used as a solvent, a catalytic active center, a stabilizer, a dispersant and the like in a catalytic system, and the introduction of the ionic liquid not only ensures that the reaction system is easy to separate and the reaction condition is reduced, but also can improve the activity and the selectivity of the catalyst. Meanwhile, by loading the third component polysiloxane, compared with the catalyst Pd/AC without adding the third component polysiloxane, the palladium particles of the prepared dechlorination hydrogenation catalyst become smaller by adding the polysiloxane, so that the activity of the palladium-based catalyst can be higher, and a good synergistic effect is realized through the combined action of the components, wherein the polysiloxane can adopt Polydimethylsiloxane (PDMS). The halogenated aromatic hydrocarbon can be mono-substituted or multi-substituted, such as chlorinated aromatic hydrocarbon or dichloro aromatic hydrocarbon.
In the Pd/AC-P catalyst for catalytic hydrogenation of the halogenated aromatic hydrocarbon, the ionic liquid is preferably 1-butyl-3-methylimidazole trichloroacetate. The ionic liquid enables a reaction system to be easily separated, reaction conditions are mild, and a catalyst is easier to load uniformly. Preferably, the mesoporous molecular sieve is ordered mesoporous carbon.
In the Pd/AC-P catalyst for catalytic hydrogenation of the halogenated aromatic hydrocarbon, the loading capacity of palladium is 0.8-1.5 wt%, the loading capacity of ionic liquid is 0.5-2 wt% and the loading capacity of polydimethylsiloxane is 0.5-2 wt% based on the mass of carbon.
The second purpose of the invention is realized by the following technical scheme, and the preparation method of the Pd/AC-P catalyst for catalytic hydrogenation of the halogenated aromatic hydrocarbon comprises the following steps:
A. weighing corresponding chloropalladic acid according to the loading amount, and dropwise adding the chloropalladic acid into the ordered mesoporous carbon to obtain a mixture;
B. drying the mixture obtained in the step A, and roasting in the atmosphere of hydrogen to obtain a solid substance;
C. weighing corresponding ionic liquid, polysiloxane and anhydrous methanol according to different loading amounts, and uniformly mixing to obtain corresponding mixed liquor;
D. and C, dropwise adding the mixed liquid obtained in the step C into the solid substance obtained in the step B, and drying after dropwise adding is finished to obtain the corresponding catalytic hydrogenation Pd/AC-P catalyst.
The method for preparing the corresponding catalytic hydrogenation Pd/AC-P catalyst by adopting the isometric impregnation method has the advantages of simple method operation and easy synthesis, and can effectively load the ionic liquid and the polysiloxane on the active carbon so as to better improve the performance of catalytic activity.
In the preparation method of the Pd/AC-P catalyst for catalytic hydrogenation of the halogenated aromatic hydrocarbon, the drying temperature in the step B and the drying temperature in the step D are respectively 60-140 ℃ and the drying time is 4-13 h.
In the preparation method of the Pd/AC-P catalyst for catalytic hydrogenation of halogenated aromatic compounds, the roasting temperature in the step B under the hydrogen atmosphere is preferably 250 ℃, and the roasting time is preferably 2 hours.
The third purpose of the invention is realized by the following technical scheme that the application of the catalytic hydrogenation Pd/AC-P catalyst for catalyzing halogenated aromatic hydrocarbon is adopted for catalytic hydrogenation dechlorination, and the hydrogen source for catalytic hydrogenation dechlorination is selected from hydrogen, formic acid-sodium formate, methanol, ethanol or ethylene glycol. These sources of hydrogen carry only few impurities and can be separated relatively easily and completely from the catalyst after hydrogenation.
In summary, compared with the prior art, the invention has the following advantages:
1. the invention adopts polysiloxane such as Polydimethylsiloxane (PDMS), has the characteristics of heat resistance, cold resistance, small viscosity change along with temperature, water resistance and small surface tension, can reduce palladium particles formed in the preparation process, and is more favorable for further improving the capability of catalytic activity.
2. In the catalyst prepared by loading polyion liquid, the actually measured loading capacity of palladium is higher.
Drawings
FIG. 1 is a TEM image of the Pd/AC and Pd/AC-P catalysts of the present invention.
FIG. 2 is an XRD pattern of the Pd/AC and Pd/AC-P catalysts of the present invention.
FIG. 3 is an XPS broad scan and Pd3d orbital plot of a Pd/AC-P catalyst of the present invention.
Detailed Description
The technical solutions of the present invention will be further specifically described below with reference to specific examples and drawings, but the present invention is not limited to these examples.
Example one
1. About 2 g of ordered activated carbon was weighed and 1.67 ml of chloropalladate (H) was additionally measured2PdCl41g/100ml), 5 ml of deionized water, mixed and added to the ordered activated carbon.
2. Dried in an oven at 100 ℃ for 4 h.
3. The dried sample was ground for 40 min.
4. And (3) putting the ground sample into a hydrogen atmosphere at 250 ℃ (the heating rate is 2 ℃/min) to continuously reduce for 2h to obtain a solid substance.
5. 0.2 g of ionic liquid (1-butyl-3-methylimidazole trichloroacetate) and 0.5 g of polydimethylsiloxane were weighed out, and 1.67 ml of chloropalladate (H)2PdCl41g/100ml) and 6 ml of anhydrous methanol, and magnetically stirred at 30 ℃ for 1 hour to obtain a mixture.
6. Weighing 1g of the solid matter obtained in the step 4, weighing 1g of the mixture obtained in the step 5, mixing, drying at 100 ℃ for 8h, and grinding to finally obtain the palladium supported ionic liquid catalyst added with polysiloxane, which is named as Pd/AC-P catalyst.
7. 2.3 g of formic acid and 5.4 g of sodium formate were weighed out and dissolved in 100ml of deionized water and poured into a volumetric flask as hydrogen source.
8. 0.8 g of the substrate 4-chlorophenol (4-CP) was weighed out and dissolved in 100ml of deionized water and poured into a volumetric flask.
9. 10ml of water is taken in a clean three-neck flask, and 10ml of prepared hydrogen source (0.5mol/L HCOOH +0.8mol/L NaCOOH), substrate (8g/L) and 50mg of prepared Pd/AC-P catalyst are added at the same time.
10. The reaction conditions are as follows: an oil bath at 25 ℃ was run and stirring was turned on while timing was started.
11. The reaction time was 240min, samples were taken every 30min and the composition of the samples was analysed by gas chromatography. 12. The degradation rate of the dichlorophen is 100 percent, the product phenol is 90 percent, the cyclohexanone is 8 percent, and the cyclohexanol is 2 percent.
Example two
1. About 1g of ordered activated carbon was weighed, and 1.67 ml of chloropalladate (H) was further measured2PdCl41g/100ml), 5 ml of deionized water, mixed and added to the ordered activated carbon.
2. Dried in an oven at 100 ℃ for 8 h.
3. The dried sample was ground for 40 min.
4. And putting the ground sample into a hydrogen atmosphere at 250 ℃ (the heating rate is 1 ℃/min) to continue to reduce for 2h to obtain a solid substance.
5. 0.1 g of ionic liquid (1-butyl-3-methylimidazole trichloroacetate) and 0.05 g of polydimethylsiloxane were weighed out, and 1.67 ml of chloropalladate (H) was measured2PdCl41g/100ml) and 6 ml of anhydrous methanol, and magnetically stirred at 30 ℃ for 1 hour to obtain a mixture.
6. 0.5 g of the solid material obtained in step 4 was weighed, 0.5 g of the mixture obtained in step 5 was additionally weighed, mixed, dried at 100 ℃ for 8h, and finally ground to obtain a polysiloxane-added palladium-supported ionic liquid catalyst, named Pd/AC-P catalyst.
7. 4.6 g of formic acid and 5.4 g of sodium formate were weighed out and dissolved in 100ml of deionized water and poured into a volumetric flask as a hydrogen source.
8. 0.4 g of the substrate 4-chlorophenol (4-CP) was weighed out and dissolved in 100ml of deionized water and poured into a volumetric flask.
9. 10ml of water is taken in a clean three-neck flask, and 10ml of prepared hydrogen source (1mol/L HCOOH +0.8mol/L NaCOOH) and substrate (4g/L) and 50mg of prepared Pd/AC-P catalyst are added at the same time.
10. The reaction conditions are as follows: an oil bath at 25 ℃ was run and stirring was turned on while timing was started.
11. The reaction time was 240min, samples were taken every 30min and the composition of the samples was analysed by gas chromatography.
12. The degradation rate of the dichlorophen is 100 percent, the product phenol is 95 percent, the cyclohexanone is 2 percent, and the cyclohexanol is 3 percent.
EXAMPLE III
1. About 1g of ordered activated carbon was weighed and an additional 0.84 ml of chloropalladate (H) was measured2PdCl41g/100ml), 5 ml of deionized water, mixed and added to the ordered activated carbon.
2. Dried in an oven at 100 ℃ for 8 h.
3. The dried sample was ground for 40 min.
4. And putting the ground sample into a hydrogen atmosphere at 300 ℃ (the heating rate is 1 ℃/min) to continue to reduce for 2h to obtain a solid substance.
5. 0.05 g of ionic liquid (1-butyl-3-methylimidazole trichloroacetate) and 0.05 g of polydimethylsiloxane were weighed out, and 0.84 ml of chloropalladate (H) was measured2PdCl41g/100ml) and 5 ml of anhydrous methanol, and magnetically stirred at 30 ℃ for 1 hour to obtain a mixture.
6. 0.5 g of the solid material obtained in step 4 was weighed and 0.5 g of the mixture obtained in step 5 was additionally weighed and mixed, dried at 90 ℃ for 8h and ground to finally obtain a polysiloxane-added palladium supported ionic liquid catalyst, named Pd/AC-P catalyst.
7. 4.6 g of formic acid and 2.7 g of sodium formate were weighed out and dissolved in 100ml of deionized water and poured into a volumetric flask as hydrogen source.
8. 0.4 g of the substrate 4-chlorophenol (4-CP) was weighed out and dissolved in 100ml of deionized water and poured into a volumetric flask.
9. 10ml of water is taken in a clean three-neck flask, and 10ml of prepared hydrogen source (1mol/L HCOOH +0.8mol/L NaCOOH) and substrate (4g/L) and 50mg of prepared Pd/AC-P catalyst are added at the same time.
10. The reaction conditions are as follows: an oil bath at 25 ℃ was run and stirring was turned on while timing was started.
11. The reaction time was 240min, samples were taken every 30min and the composition of the samples was analysed by gas chromatography.
12. The degradation rate of the dichlorophen is 98 percent, the product phenol is 98 percent, the cyclohexanone is 1 percent, and the cyclohexanol is 1 percent.
Example four
1. About 1g of ordered activated carbon was weighed, and 1.67 ml of chloropalladate (H) was further measured2PdCl41g/100ml), 5 ml of deionized water, mixed and added to the ordered activated carbon.
2. Dried in an oven at 100 ℃ for 8 h.
3. The dried sample was ground for 40 min.
4. And putting the ground sample into a hydrogen atmosphere at 300 ℃ (the heating rate is 1 ℃/min) to continue to reduce for 2h to obtain a solid substance.
5. 0.05 g of ionic liquid (1-butyl-3-methylimidazole trichloroacetate) and 0.1 g of polydimethylsiloxane were weighed out, and 1.67 ml of chloropalladate (H) was measured2PdCl41g/100ml) and 5 ml of anhydrous methanol, and magnetically stirred at 30 ℃ for 1 hour to obtain a mixture.
6. 0.5 g of the solid material obtained in step 4 was weighed and 0.5 g of the mixture obtained in step 5 was additionally weighed and mixed, dried at 90 ℃ for 8h and ground to finally obtain a polysiloxane-added palladium supported ionic liquid catalyst, named Pd/AC-P catalyst.
7. 4.6 g of formic acid and 2.7 g of sodium formate were weighed out and dissolved in 100ml of deionized water and poured into a volumetric flask as hydrogen source.
8. 0.8 g of the substrate 4-chlorophenol (4-CP) was weighed out and dissolved in 100ml of deionized water and poured into a volumetric flask.
9. 10ml of water is taken in a clean three-neck flask, and 10ml of prepared hydrogen source (1mol/L HCOOH +0.8mol/L NaCOOH) and substrate (8g/L) and 50mg of prepared Pd/AC-P catalyst are added at the same time.
10. The reaction conditions are as follows: an oil bath at 25 ℃ was run and stirring was turned on while timing was started.
11. The reaction time was 240min, samples were taken every 30min and the composition of the samples was analysed by gas chromatography.
12. The degradation rate of the dichlorophen is 95 percent, the product phenol is 93 percent, the cyclohexanone is 5 percent, and the cyclohexanol is 2 percent.
EXAMPLE five
1. About 1g of ordered activated carbon was weighed, and 1.67 ml of chloropalladate (H) was further measured2PdCl41g/100ml), 5 ml of deionized water, mixed and added to the ordered activated carbon.
2. Dried in an oven at 100 ℃ for 8 h.
3. The dried sample was ground for 40 min.
4. And putting the ground sample into a hydrogen atmosphere at 300 ℃ (the heating rate is 1 ℃/min) to continue to reduce for 2h to obtain a solid substance.
5. 0.1 g of ionic liquid (1-butyl-3-methylimidazole trichloroacetate) and 0.2 g of polydimethylsiloxane were weighed out, and 1.67 ml of chloropalladate (H) was measured2PdCl41g/100ml) and 3 ml of anhydrous methanol, and magnetically stirred at 30 ℃ for 1 hour to obtain a mixture.
6. Weighing 1g of the solid substance obtained in the step 4, weighing 1g of the mixture obtained in the step 5, mixing, drying at 90 ℃ for 8h, and grinding to finally obtain the palladium supported ionic liquid catalyst added with polysiloxane, which is named as Pd/AC-P catalyst.
7. 4.6 g of formic acid and 2.7 g of sodium formate were weighed out and dissolved in 100ml of deionized water and poured into a volumetric flask as hydrogen source.
8. 0.8 g of the substrate 4-chlorophenol (4-CP) was weighed out and dissolved in 100ml of deionized water and poured into a volumetric flask.
9. 10ml of water is taken in a clean three-neck flask, and 10ml of prepared hydrogen source (1mol/L HCOOH +0.8mol/L NaCOOH) and substrate (8g/L) and 50mg of prepared Pd/AC-P catalyst are added at the same time.
10. The reaction conditions are as follows: an oil bath at 25 ℃ was run and stirring was turned on while timing was started.
11. The reaction time was 240min, samples were taken every 30min and the composition of the samples was analysed by gas chromatography.
12. The degradation rate of the dichlorophen is 92 percent, the product phenol is 97 percent, the cyclohexanone is 1 percent, and the cyclohexanol is 2 percent.
The halogenated aromatic hydrocarbon may be dibromophenol, chlorophenol, or the like. The catalyst can achieve the equivalent level when degrading the dichlorophen, and the degradation rate reaches more than 91 percent.
The corresponding catalysts obtained above were randomly selected for analysis, and from the results of FIGS. 1 to 3, FIGS. 1(a-1) and (a-2) are TEM images of Pd/AC as the catalysts, and FIGS. 1 (b-1) and (b-2) are TEM images of Pd/AC-P as the catalysts, and the TEM images clearly reveal the morphological changes of the two catalysts. In Pd/AC-P, it can be clearly seen that the dispersion of Pd particles becomes higher and the diameter of Pd particles is smaller, compared to Pd/AC.
The XRD patterns of the Pd/AC catalyst and the Pd/AC-P catalyst in the figure 2 can obtain that the diameter of the Pd particles in the Pd/AC-P catalyst is smaller.
FIG. 3(a) is XPS broad scan of Pd/AC catalyst and (b) is Pd3d orbital map of XPS of Pd/AC-P catalyst. The load of Pd in the catalyst is 1 percent which can be obtained from a wide-scanning chart of the catalyst, and the Pd in the catalyst can be obtained from an orbital chart0And Pd2+The ratio between is 1: 1.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (5)
1. A catalytic hydrogenation Pd/AC-P catalyst for catalyzing halogenated aromatic hydrocarbon is characterized in that the catalyst takes ordered mesoporous carbon as a carrier, a first component of metal palladium is loaded, and a second component of ion liquid and a third component of polysiloxane are also loaded;
the preparation method of the catalyst comprises the following steps:
A. weighing corresponding chloropalladic acid according to the loading amount, and dropwise adding the chloropalladic acid into the ordered mesoporous carbon to obtain a mixture;
B. drying the mixture obtained in the step A, and roasting in the atmosphere of hydrogen to obtain a solid substance;
C. weighing corresponding ionic liquid, polysiloxane and anhydrous methanol according to different loading amounts, and uniformly mixing to obtain corresponding mixed liquor;
D. dripping the mixed solution obtained in the step C into the solid substance obtained in the step B, and drying after the dripping is finished to obtain a corresponding catalytic hydrogenation Pd/AC-P catalyst;
the ionic liquid is 1-butyl-3-methylimidazole trichloroacetate.
2. A process for the preparation of a Pd/AC-P catalyst for the catalytic hydrogenation of halogenated aromatic compounds according to claim 1, characterized in that it comprises the following steps:
A. weighing corresponding chloropalladic acid according to the loading amount, and dropwise adding the chloropalladic acid into the ordered mesoporous carbon to obtain a mixture;
B. drying the mixture obtained in the step A, and roasting in the atmosphere of hydrogen to obtain a solid substance;
C. weighing corresponding ionic liquid, polysiloxane and anhydrous methanol according to different loading amounts, and uniformly mixing to obtain corresponding mixed liquor;
D. and C, dropwise adding the mixed liquid obtained in the step C into the solid substance obtained in the step B, and drying after dropwise adding is finished to obtain the corresponding catalytic hydrogenation Pd/AC-P catalyst.
3. The method for preparing Pd/AC-P catalyst for catalytic hydrogenation of halogenated aromatic compounds according to claim 2, wherein the drying temperature in step B and the drying temperature in step D are respectively 60-140 ℃ and the drying time is 4-13 h.
4. The method for preparing Pd/AC-P catalyst for catalytic hydrogenation of halogenated aromatic substances according to claim 2, wherein the calcination temperature in the hydrogen atmosphere in the step B is 250 ℃ and the calcination time is 2 h.
5. Use of a Pd/AC-P catalyst for catalytic hydrogenation of halogenated aromatic compounds, characterized in that the Pd/AC-P catalyst of claim 1 is used for catalytic hydrodechlorination, the source of hydrogen being selected from hydrogen, formic acid-sodium formate, methanol, ethanol or ethylene glycol.
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