CN114558610A - Limited-area Pd-based catalyst and preparation method and application thereof - Google Patents
Limited-area Pd-based catalyst and preparation method and application thereof Download PDFInfo
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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
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Abstract
The invention relates to the technical field of Pd-based catalyst preparation, in particular to a limited-area Pd-based catalyst and a preparation method and application thereof; the preparation method comprises the steps of carrying out cation exchange between a Pd precursor with positive electricity and an HY type molecular sieve framework so as to confine Pd particles in HY type molecular sieve pores, and inhibiting Pd agglomeration into large particles by utilizing the strict limitation of the HY type molecular sieve pores on the size of the Pd particles and the constraint effect of nanoscale pores, so that the particle size range is 2.2-3Pd particles of high dispersity in 1nm, and the generation of partially positively charged metallic Pd (Pd)n+) Further improving the catalytic efficiency of the 2,4, 6-trichloroanisole. Moreover, the Pd-based catalyst prepared by the method can avoid the problem of competition of humic acid molecules and 2,4, 6-trichloroanisole on Pd active sites in a humic acid environment, so that the resistance of the catalyst to humic acid is improved.
Description
Technical Field
The invention relates to the technical field of Pd-based catalyst preparation, in particular to a limited-area Pd-based catalyst and a preparation method and application thereof.
Background
The sensory quality (color, smell and taste) of drinking water is a water quality index which is most concerned by consumers and water supply institutions, and the smell is the most intuitive judgment of the quality of the drinking water for people. The earthy mildew smell is the most extensive and unpleasant peculiar smell in water, and the 2,4, 6-trichloroanisole as a typical disinfection by-product has strong earthy mildew smell and extremely low smell threshold, thereby not only influencing the water perception but also being more directly harmful to human health.
The 2,4, 6-trichloroanisole in the drinking water can be effectively removed by a liquid phase hydrogenation reduction method, and the Pd catalyst shows higher performance for dechlorination reaction, because the Pd has the capability of dissociating hydrogen under normal pressure and normal temperature and promoting the C-X bond to break. Currently commonly used Pd catalysts are supported, such as the ones listed below:
chinese patent CN201811556633.5 discloses a Pd-containing catalyst and a preparation method thereof, and the method adds Pd into a catalytic material by a fractional infiltration method, thereby improving the dispersion degree of Pd in the catalytic material and increasing the contact surface of Pd and the catalytic material.
Chinese patent CN200910304443.9 discloses a method for preparing eggshell type Pd catalyst by reaction deposition method, which comprises adding carrier into Pd metal salt solution, controlling Pd to deposit on the surface of carrier by rapid reduction reaction, filtering, washing, heating and drying in inert atmosphere to form stable eggshell type Pd catalyst.
In the above materials, no matter the Pd is loaded on the surface of the carrier by an impregnation method in multiple layers or by bulk deposition, the Pd is present on the surface of the carrier, the interaction between the Pd and the carrier is weak, the Pd is easy to drop after loading, and the actual natural water environment contains a large amount of humic acid which constitutes most of the organic matters in the source water, however, the reactant molecules compete with the humic acid molecules for the Pd active sites on the surface of the carrier, occupy the Pd surface, inhibit the dechlorination reaction of the chlorine-containing organic matters, reduce the catalytic activity of the catalyst, and are not favorable for the application of the catalyst in the actual water.
In order to solve the problems, the invention designs a limited-area Pd-based catalyst, a preparation method thereof and a hydrogenation reduction method for 2,4, 6-trichloroanisole based on the catalyst.
Disclosure of Invention
In order to achieve the above object, the present invention provides a domain-limited Pd-based catalyst and a preparation method thereof, wherein a positively charged Pd precursor is exchanged with cations in an HY-type molecular sieve framework to confine Pd particles in channels of the HY-type molecular sieve, and Pd is inhibited from agglomerating into large particles by using the strict limitation of the channels of the HY-type molecular sieve on the size of the Pd particles and the binding effect of nano-scale channels, so as to obtain Pd particles with smaller size and higher dispersity, and to generate a part of positively charged metal Pd (Pd) (Pd particles with smaller size and higher dispersity), and a preparation method thereofn+) Further improving the catalytic removal efficiency of the 2,4, 6-trichloroanisole.
The technical scheme of the invention is as follows:
a limited-area Pd-based catalyst comprising a catalyst support and a mass of active metal particles confined within the channels of the catalyst support;
the catalyst carrier is a molecular sieve which accounts for 100% of the mass of the catalyst carrier, and the content of the catalyst carrier in the catalyst is 98.27-99.6 wt.%;
the active metal particle groups account for 0.4-1.73 wt% of the mass of the catalyst.
Further, the molecular sieve is an HY type molecular sieve; in the HY type molecular sieve, the molar ratio is SiO2：Al2O3＝30：1。
Further, the active metal particles in the active metal particle groups are Pd particles.
Furthermore, the particle size range of the Pd particles in the HY type molecular sieve pore passage is 2.0-3.25 nm.
The invention also discloses a specific preparation method of the limited-area Pd-based catalyst, which comprises the following steps:
SA1, dispersing HY type molecular sieve in deionized water, and adding Pd (OAc)2Obtaining a mixed solution;
SA2, heating in a water bath and stirring the mixed solution prepared in the step SA1 to realize the exchange between the Pd precursor and the cations in the HY type molecular sieve pore channels;
SA3, filtering the mixed solution treated in the step SA2 to obtain filter residue, washing the filter residue with deionized water until the filtrate is neutral, and drying at 70 ℃;
SA4, drying the filter residue obtained in the step SA3 at the temperature of 300 ℃ in H2Reducing for 2h under the atmosphere to prepare the limited-area Pd-based catalyst.
Further, in the step SA1, the content of the HY type molecular sieve in the deionized water is 2 g/L.
Further, in the step SA2, the temperature of the water bath heating is 80 ℃, and the time of the water bath heating and stirring is 10 hours.
Further, the process conditions in the step SA2 are restricted to be unchanged by changing Pd (OAc) in the step SA12The addition of the solution enables the directional adjustment of the particle size of the Pd particles in the limited-area Pd-based catalyst obtained in step SA4, which is related to the following relationship:
when step SA1 is Pd (OAc)2When the addition amount of the solution is such that the content of Pd in the catalyst is in the range of 0.4 to 0.43 wt.%, the particle size of Pd particles in the limited-area Pd-based catalyst prepared in step SA4 is in the range of 2.21 to 2.3 nm;
when step SA1 is Pd (OAc)2When the addition amount of the solution is such that the content of Pd in the catalyst is in the range of 0.87 to 0.90 wt.%, the particle size of Pd particles in the limited-area Pd-based catalyst prepared in step SA4 is in the range of 2.92 to 3.01 nm;
when step SA1 is Pd (OAc)2When the amount of the solution added is such that the content of Pd in the catalyst is in the range of 1.7 to 1.73 wt.%, the particle size of the Pd particles in the limited-area Pd-based catalyst prepared in step SA4 is in the range of 3.11 to 3.21 nm.
The invention also discloses an application of the limited-area Pd-based catalyst in catalyzing 2,4, 6-trichloroanisole, and the application method comprises the following steps:
SB1, adding a limited-area Pd-based catalyst into deionized water with the pH value of 6 +/-0.1 at the temperature of 23 +/-5 ℃;
SB2, continuously and electromagnetically stirring the deionized water of the step SB1, and introducing H for 30min into the deionized water2Obtaining hydrogen saturated water;
SB3, adding 2,4, 6-trichloroanisole into the container containing the hydrogen saturated water prepared in the step SB2 in a closed environment, sampling and detecting at regular intervals until the 2,4, 6-trichloroanisole is completely converted into anisole.
Further, in the step SB1, the content of the limited-area Pd-based catalyst in the deionized water is 1/24 g/L; in the step SB2, the rotation speed of electromagnetic stirring is 1000-1500 rpm, and H is introduced2The flow rate of (A) is in the range of 150 to 200 mL/min.
Compared with the existing supported Pd-based catalyst, the invention has the beneficial effects that:
(1) according to the limited-area Pd-based catalyst prepared by the invention, the size of Pd particles in the HY type molecular sieve pore channel is limited within the range of 2.2-3.1 nm, namely, the agglomeration of the Pd particles is inhibited, the active metal Pd is stabilized, the loss of the metal Pd is reduced, and further, the interaction between the metal Pd and the HY type molecular sieve carrier is enhanced.
(2) The prepared limited-area Pd-based catalyst and the HY molecular sieve are used as an ordered porous material, so that the enrichment capacity of the catalyst on 2,4, 6-trichloroanisole can be enhanced, and the catalytic performance of the limited-area Pd-based catalyst is further synergistically improved.
(3) Compared with the traditional supported Pd-based catalyst, the domain-limited Pd-based catalyst prepared by the invention has the advantages that Pd particles are limited in HY molecular sieve pores, and the Pd is restrained from agglomerating into large particles by utilizing the strict limitation of the HY molecular sieve pores on the size of the Pd particles and the constraint effect of nanoscale pores, so that Pd particles with smaller size and higher dispersion degree and part of positively charged metal Pd are generated, and the catalytic efficiency of 2,4, 6-trichloroanisole is improved.
(4) Compared with the traditional supported Pd-based catalyst, the prepared confined Pd-based catalyst has the advantages that the HY molecular sieve has the screening effect, so that humic acid macromolecules can be prevented from entering pores of the confined Pd-based catalyst, the competition problem of the humic acid molecules and 2,4, 6-trichloroanisole on active sites is avoided, the resistance of the catalyst on the humic acid is improved, namely the stability of the confined Pd-based catalyst is improved, and the catalyst has potential for application in practical water bodies.
Drawings
FIG. 1 is a diagram showing humic acid resistance of a limited-range Pd-based catalyst in section 5 of an experimental example of the present invention;
FIG. 2 is a diagram showing humic acid resistance of the supported Pd-based catalyst in section 5 of the experimental example of the present invention;
FIG. 3 is an XPS spectrum of Pd @ Y and im-Pd/Y in section 2 of the experimental example of the present invention;
FIG. 4 is a graph showing the effect of Pd @ Y and im-Pd/Y on the catalytic degradation of 2,4, 6-trichloroanisole in section 4 of the experimental example of the present invention;
FIG. 5 is a graph showing the effect of Pd @ Y and im-Pd/Y on the catalytic degradation of 2,4, 6-trichloroanisole in humic acid environment in section 5 of the experimental example of the present invention;
FIG. 6 shows the data of the catalytic effect of Pd @ Y and im-Pd/Y on 2,4, 6-trichloroanisole in humic acid environment in section 5 of the experimental example of the present invention.
In fig. 1 and 2: 1-limited Pd-based catalyst, 2-supported Pd-based catalyst, 3-HY molecular sieve, 4-pore channels, 5-Pd particles, 6-2,4, 6-trichloroanisole molecules and 7-humic acid molecules.
Detailed Description
To further illustrate the manner in which the present invention is made and the effects achieved, the following description of the present invention will be made in detail and completely with reference to the accompanying drawings.
Example 1
Example 1 is primarily intended to illustrate the specific process of the present invention for preparing a limited-area Pd-based catalyst under specific process parameters, and the specific performance parameters of the prepared limited-area Pd-based catalyst, as follows.
1. Preparation method
In this example, all the experimental procedures described below were carried out in a laboratory environment at a laboratory temperature range of 23. + -. 5 ℃.
First, 1g of HY type molecular sieve was dispersed in 500mL of deionized water, followed by addition of Pd (OAc)2Obtaining a mixed solution; in the HY type molecular sieve, the molar ratio is SiO2：Al2O330: 1; heating and stirring the mixed solution for 10 hours in water bath at 80 ℃ to realize the exchange between Pd precursor and cations in HY type molecular sieve pore channels; filtering the mixed solution to obtain filter residue, washing the filter residue with deionized water until the filtrate is neutral, and drying at 70 ℃; drying the filter residue at 300 deg.C in H2Reducing for 2h under the atmosphere to prepare the limited-area Pd-based catalyst.
2. Component content of the Limited Pd-based catalyst
The content of Pd in the prepared limited-area Pd-based catalyst is 0.42 wt.%, and the content of HY molecular sieve is 99.58 wt.%, which is marked as Pd (0.42) @ Y.
Example 2
Example 2 is based on the scheme described in example 1, and is intended to illustrate specific performance parameters of the limited-area Pd-based catalyst prepared under different experimental parameters, which are as follows:
1. preparation method
Dispersing 1g HY type molecular sieve in 500mL deionized water, then adding Pd (OAc)2Obtaining a mixed solution; in the HY type molecular sieve, the molar ratio is SiO2：Al2O330: 1; heating and stirring the mixed solution for 10 hours in water bath at 80 ℃ to exchange cations in the existing Pd precursor and HY type molecular sieve pore channels; filtering the mixed solution to obtain filter residue, washing the filter residue with deionized water, and drying at 70 ℃; drying the filter residue at 300 deg.C in H2Reducing for 2h under the atmosphere to prepare the limited-area Pd-based catalyst.
2. Limited Pd-based catalyst
The preparation method is restricted to have the following process conditions unchanged:
change of Pd (OAc)2Amount of solution added, orientationThe particle size of the Pd particles in the prepared limited-area Pd-based catalyst is adjusted to obtain the following relational table.
TABLE 1 relation between Pd content in a limited-area Pd-based catalyst and Pd particle diameter
As can be seen from the data in table 1, due to the restriction effect of the channels in the HY-type molecular sieve on the Pd particles and the agglomeration phenomenon of the Pd particles themselves, in the channels of the domain-restricted Pd-based catalyst, the content and size of the Pd particles increase non-linearly at a uniform speed, but in a stepwise jumping manner, and there is an upper limit:
following Pd (OAc)2The added amount of the solution is increased, and the content of Pd particles in the pore channels of the limited-area Pd-based catalyst is divided into three distribution intervals: 0.4-0.43 wt.%, 0.87-0.90 wt.%, and 1.7-1.73 wt.%;
the size of the Pd particles in the pore channels of the limited-area Pd-based catalyst corresponding to the content of the Pd particles in the three distribution intervals is divided into three distribution intervals: 2.21 to 2.3nm, 2.92 to 3.01nm and 3.11 to 3.21 nm. It can be seen that the size range of the Pd particles in the pore channels of the limited-domain Pd-based catalyst is restricted to 2.2-3.1 nm, i.e. the agglomeration of the Pd particles is inhibited, and the interaction between the metal Pd and the HY type molecular sieve carrier is enhanced.
Examples of the experiments
The experimental example is based on the scheme described in example 2, and is intended to illustrate the difference in performance between the limited-area Pd-based catalyst prepared according to the present invention and the conventional supported Pd-based catalyst.
1. Design of experiments
In order to clarify the specific properties of the constrained-domain Pd-based catalysts prepared according to the present invention, the following experimental groups were designed:
control group 1:
for comparison, supported im-Pd/Y catalysts with different Pd loading amounts are synthesized by an impregnation method, and the specific catalyst preparation process comprises the following steps:
dispersing 1g of HY type molecular sieve in 100mL of deionized water, and then adding chloropalladite solution to obtain a mixed solution, wherein SiO in the HY type molecular sieve2：Al2O330: 1; dipping and stirring the mixed solution for 2 hours, evaporating the solution to dryness at 90 ℃ to obtain a product, and then baking the product at 70 ℃ until the weight of the product is not changed; drying the product at 300 deg.C in H2Reducing for 2h under the atmosphere to prepare the supported Pd-based catalyst.
The supported Pd-based catalyst was obtained with a Pd content of 0.86 wt.% and an HY-type molecular sieve content of 99.14 wt.%, which was designated im-Pd (0.86)/Y.
Control group 2: the control group 2 and the control group 1 have the same process parameters except that the addition amount of the chloropalladate solution is different.
The Pd content in the obtained supported Pd-based catalyst was 1.72 wt.%, and the HY-type molecular sieve content was 98.28 wt.%, which was denoted as im-Pd (1.72)/Y.
Experimental group 1: selecting the limited-area Pd-based catalyst with the Pd particle content of 0.4-0.43 wt.% of the median range in the embodiment 2 as an experimental object of an experimental group 1, and recording the limited-area Pd-based catalyst as Pd (0.42) @ Y;
experimental group 2: selecting the limited-area Pd-based catalyst with the Pd particle content of 0.87-0.9 wt.% in the interval median value in the embodiment 2 as an experimental object of an experimental group 2, and marking the limited-area Pd-based catalyst as Pd (0.89) @ Y;
experimental group 3: the limited-area Pd-based catalyst with the Pd particle content of 1.7-1.73 wt.% in the interval median value in example 2 was selected as the experimental object of experiment group 3, and is denoted as Pd (1.71) @ Y.
2. X-ray photoelectron spectroscopy (XPS)
The valence state of the sample elements was characterized by using an ESCALB 250 model X-ray photoelectron spectrometer (XPS) from Thermo Scientific, USA. The instrument was calibrated using Al K α as an excitation source (hv-1486.6 eV) and using C1 s-284.6 eV for the binding energy of other elements. XPS peak 4.1 software was used to analyze the XPS spectra of samples in the Pd 3d region. Using ShirleyBackground and% Lorentzian-Gaussian 80 to peak fit error (Σ x)2) Less than 6, the test results are shown in fig. 2.
FIG. 3 is XPS spectra of Pd 3d zones for prepared constrained-domain Pd @ Y catalysts of different Pd contents and supported im-Pd/Y catalysts of different Pd contents. As can be seen from the figure, Pd is successfully supported on HY molecular sieve, and the limited-domain catalyst Pd @ Y has higher Pdn+The content is beneficial to the activation of the C-Cl bond of the 2,4, 6-trichloroanisole and the promotion of the hydrodechlorination.
3. High Resolution Transmission Electron Microscope (HRTEM)
The supported Pd-based catalysts in the control group 1 and the control group 2, and the limited-area Pd-based catalysts in the experimental group 1, the experimental group 2, and the experimental group 3 were used as the experimental objects.
The morphology, crystal structure and particle size distribution of the active component of the catalyst are researched by adopting a high-resolution transmission electron microscope with the model of JEOL JEM-200 CX. And (3) placing a small amount of powder samples of the experimental objects in absolute ethyl alcohol, and carrying out ultrasonic treatment for 15-30 min at 200-350W to fully disperse the powder samples. A small amount of fully dispersed sample is dripped on the surface of the copper mesh, and the test is carried out after the ethanol is completely volatilized, and the test result is shown in table 2.
TABLE 2 Pd @ Y and im-Pd/Y for Pd particle size
As can be seen from the data in Table 2, the particle size of Pd particles in the limited-domain Pd-based catalyst Pd @ Y is smaller, the size range is restricted to 2.2-3.1 nm, and the particle size is far smaller than that of the supported Pd-based catalyst im-Pd/Y synthesized by an impregnation method. And when the active metal Pd particles are smaller, the surface area of the active metal Pd particles is larger (the contact area with a catalyzed object is larger), the content of exposed Pd active sites is higher, the catalytic activity is improved, and the inference is further obtained: the catalytic performance of the limited-area Pd-based catalyst Pd @ Y prepared by the invention is higher than that of the supported Pd-based catalyst Pd/Y.
4. Comparison of the catalytic degradation effects of Pd @ Y and im-Pd/Y on 2,4, 6-trichloroanisole.
In order to verify the inference that the catalytic performance of the limited-domain Pd-based catalyst Pd @ Y prepared by the invention is higher than that of the supported Pd-based catalyst Pd/Y in section 3, the following experiment is designed:
in view of the volatility of 2,4, 6-trichloroanisole, an experiment was undertaken with a hydrogen saturation reduction.
Adjusting the pH value of the deionized water to 6 +/-0.1 by using 0.1M HCl and 0.1M NaOH at the temperature of 23 +/-5 ℃; after adjusting the pH, adding a catalyst; stirring at 1000rpm, introducing H2The flow rate of the hydrogen-containing gas is 150mL/min, and the aeration time is 30min, so that hydrogen saturated water is obtained; then, tightly covering and sealing the glass reaction bottle by using a bottle cap filled with a polytetrafluoroethylene gasket; injecting 1 mg/L2, 4, 6-trichloroanisole into the bottle by using a trace sample injection needle, and starting catalytic hydrogenation reduction reaction; samples were taken at regular intervals during the reaction with a glass needle. To ensure the validity of the data, each set of experiments was repeated three times and the data results averaged.
The five groups of catalysts in the table 2 were used as the added catalysts, the catalyst contents were all 1/24g/L, and the test results after the hydrodechlorination reduction of 2,4, 6-trichloroanisole are shown in fig. 4.
FIG. 4 shows the catalytic degradation effect of Pd @ Y and im-Pd/Y on 2,4, 6-trichloroanisole within 120 min. When the reaction time is 30min, the removal rate of 2,4, 6-trichloroanisole by all supported limited-domain Pd-based catalysts Pd @ Y reaches over 95.5% (wherein Pd (0.42) @ Y is 95.5%, Pd (0.89) @ Y is 98.3%, and Pd (1.71) @ Y is 100%), while the supported catalysts im-Pd/Y are only 49.4% (im-Pd (0.86)/Y) and 68.7% (im-Pd (1.72)/Y), and Pd indicates that the activity of the limited-domain Pd-based catalyst im @ Y is obviously superior to that of the supported Pd-based catalysts im-Pd/Y, and the inference in section 3 of the experimental example is verified.
The principle of the above phenomenon is explained as follows: the limited-domain Pd-based catalyst Pd @ Y limits Pd particles in the pore channels of the HY molecular sieve, so that the active metal Pd particles are inhibited from agglomerating and growing, the particle size of the Pd particles is small and uniform, and the dispersity is high; and the limited-domain Pd-based catalyst Pd @ Y has higher Pdn+The content and the interaction between the metal Pd and the HY type molecular sieve carrier are stronger, which is beneficial to the activation of 2,4, 6-trichloroanisole and the hydrodechlorination thereof, thereby limitingThe catalytic activity of the domain type Pd-based catalyst Pd @ Y is obviously higher than that of the supported type Pd-based catalyst im-Pd/Y.
5. Influence of humic acid on catalytic reduction of 2,4, 6-trichloroanisole by Pd @ Y and im-Pd/Y
The experimental procedures referred to in experimental example section 4 were different in that: 5mgC/L Humic Acid (HA) was added to the reaction system, and the following control experiments were designed according to the catalyst:
im-Pd(0.86)/Y，im-Pd(0.86)/Y+HA，Pd(0.89)@Y，Pd(0.89)@Y+HA。
the test results of the above catalyst after the 2,4, 6-trichloroanisole is subjected to hydrogenation reduction dechlorination are shown in figure 5.
Referring to FIGS. 5 and 6, after 5mgC/L humic acid is added into the reaction system, the removal rate of 2,4, 6-trichloroanisole by the supported Pd-based catalyst im-Pd (0.86)/Y is reduced by 53.0% within 120min, and the removal rate of the limited-domain Pd-based catalyst Pd (0.89) @ Y is reduced by only 3.7%, which shows that the limited-domain Pd-based catalyst Pd @ Y has better humic acid resistance and stronger stability.
The reason for the above phenomenon is that, referring to fig. 1 and fig. 2, since the Pd active sites of the supported catalyst are located on the surface of the carrier, reactant molecules and humic acid molecules compete for limited active sites, thereby causing the catalytic activity to be reduced, while the Pd active particles are limited inside the carrier pore channels by the limited-area catalyst, and the sieving effect of the molecular sieve carrier can prevent humic acid macromolecules from entering the catalyst pore channels to occupy the active Pd sites, thereby avoiding the competition problem, protecting the active sites, and improving the resistance performance of the catalyst to humic acid, i.e. improving the stability of the catalyst.
Claims (10)
1. A limited-area Pd-based catalyst, characterized in that said catalyst comprises a catalyst support and a mass of active metal particles confined within the channels of said catalyst support;
the catalyst carrier is a molecular sieve with the mass ratio of 100%, and the content of the catalyst carrier in the catalyst is 98.27-99.6 wt.%;
the active metal particle groups account for 0.4-1.73 wt% of the mass of the catalyst.
2. The constrained-domain Pd-based catalyst according to claim 1, wherein said molecular sieve is an HY-type molecular sieve; in the HY type molecular sieve, the molar ratio is SiO2：Al2O3＝30：1。
3. A limited-area Pd-based catalyst according to claim 2, characterized in that the active metal particles of the mass of active metal particles are Pd-particles.
4. The confined Pd-based catalyst according to claim 3, wherein the Pd particles have a particle size in the HY type molecular sieve channel ranging from 2.0 to 3.2 nm.
5. The preparation method of the limited-area Pd-based catalyst as in any one of claims 1 to 4, wherein the particle size of Pd particles in the pore channels of the limited-area Pd-based catalyst can be directionally adjusted by changing the content of Pd in the limited-area Pd-based catalyst, and the specific method comprises the following steps:
SA1, dispersing HY type molecular sieve in deionized water, and adding Pd (OAc)2Obtaining a mixed solution;
SA2, heating in a water bath and stirring the mixed solution prepared in the step SA1 to realize the exchange between the Pd precursor and the cations in the HY type molecular sieve pore channels;
SA3, filtering the mixed solution treated in the step SA2 to obtain filter residue, washing the filter residue with deionized water until the filtrate is neutral, and drying at 70 ℃;
SA4, drying the filter residue obtained in the step SA3 at 300 ℃ H2Reducing for 2h under the atmosphere to prepare the limited-area Pd-based catalyst.
6. The method for preparing the limited-zone Pd-based catalyst as recited in claim 5, wherein in the step SA1, the content of HY-type molecular sieve in the deionized water is 2 g/L.
7. The method for preparing the limited-range Pd-based catalyst according to claim 5, wherein in the step SA2, the temperature of the water bath is 80 ℃, and the time of the water bath heating and stirring is 10 h.
8. The process for the preparation of a limited-range Pd-based catalyst as claimed in claim 5, wherein the process conditions in step SA2 are constrained to be constant by varying the Pd (OAc) in step SA12The addition of the solution enables the directional adjustment of the particle size of the Pd particles in the limited-area Pd-based catalyst obtained in step SA4, which is related to the following relationship:
when step SA1 is Pd (OAc)2When the addition amount of the solution is such that the content of Pd in the catalyst is in the range of 0.4 to 0.43 wt.%, the particle size of Pd particles in the limited-area Pd-based catalyst prepared in step SA4 is in the range of 2.21 to 2.3 nm;
when step SA1 is Pd (OAc)2When the addition amount of the solution is such that the content of Pd in the catalyst is in the range of 0.87 to 0.90 wt.%, the particle size of Pd particles in the limited-area Pd-based catalyst prepared in step SA4 is in the range of 2.92 to 3.01 nm;
when step SA1 is Pd (OAc)2When the amount of the solution added is such that the content of Pd in the catalyst is in the range of 1.7 to 1.73 wt.%, the particle size of the Pd particles in the limited-area Pd-based catalyst prepared in step SA4 is in the range of 3.11 to 3.21 nm.
9. The application of the limited-area Pd-based catalyst as set forth in any one of claims 1-4 in catalyzing 2,4, 6-trichloroanisole, wherein the application method comprises the following steps:
SB1, adding a limited-area Pd-based catalyst into deionized water with the pH value of 6 +/-0.1 at the temperature of 23 +/-5 ℃;
SB2, continuously and electromagnetically stirring the deionized water of the step SB1, and introducing H for 30min into the deionized water2Obtaining hydrogen saturated water;
SB3, adding 2,4, 6-trichloroanisole into the container containing the hydrogen saturated water prepared in the step SB2 in a closed environment, sampling and detecting at regular intervals until the 2,4, 6-trichloroanisole is completely converted into anisole.
10. The use according to claim 9, wherein in step SB1, the content of the limited-area Pd-based catalyst in deionized water is 1/24 g/L; in the step SB2, the rotation speed of electromagnetic stirring is 1000-1500 rpm, and H is introduced2The flow rate of (A) is in the range of 150 to 200 mL/min.
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