CN110508290B - High-dispersion palladium/cobalt hydroxide catalyst and preparation method and application thereof - Google Patents
High-dispersion palladium/cobalt hydroxide catalyst and preparation method and application thereof Download PDFInfo
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- CN110508290B CN110508290B CN201910814713.4A CN201910814713A CN110508290B CN 110508290 B CN110508290 B CN 110508290B CN 201910814713 A CN201910814713 A CN 201910814713A CN 110508290 B CN110508290 B CN 110508290B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
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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
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- 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
Abstract
The invention provides a high-dispersion Pd/Co (OH)2The invention firstly prepares Co (OH) with higher specific surface area by a simple method2Then calcining to make the surface of said carrier have more defect sites, then loading the palladium impregnating solution on Co (OH)2On the carrier, high dispersion Pd/Co (OH) with better performance is prepared2A catalyst; highly dispersed Pd/Co (OH) of the invention2The preparation of the catalyst is applied to the selective hydrogenation reaction of acetylene, and the catalyst not only has high catalytic activity and high ethylene selectivity, but also has the advantages of excellent stability, high atom utilization rate and the like.
Description
(I) technical field
The invention relates to a high-dispersion Pd/Co (OH)2A catalyst and a preparation method thereof, and application in selective hydrogenation reaction of acetylene.
(II) background of the invention
Ethylene is one of the most important chemical products in the world, and is widely applied to various fields such as synthetic plastics, rubber, fibers, medicines, pesticides and dyes. Industrial ethylene is mainly produced by cracking naphtha, diesel oil and other raw materials, but about 0.3 to 3 percent of acetylene is often generated in the process of preparing ethylene gas; these traces of acetylene poison the Ziegler-Natta catalysts of downstream polyethylene processes, not only reducing the activity and lifetime of the catalyst, but also severely affecting the product quality of the polyethylene process. Therefore, the method has important industrial significance for removing trace acetylene in the raw material gas.
The method for removing acetylene commonly used in industry is a selective hydrogenation method, which has the advantages of no pollution, low energy consumption, simple process and the like and is widely applied. However, the palladium-based catalyst conventionally used in industry has a poor ethylene selectivity although it has a good catalytic activity, and may be excessively hydrogenated to ethane or oligomerized to green oil, thereby affecting the service life of the catalyst. Thus, the ethylene selectivity of palladium-based catalysts in acetylene hydrogenation is of great importance to the ethylene industry, and therefore, it is necessary to modify the catalysts to prevent the excessive hydrogenation of ethylene to ethane, thereby further improving the ethylene selectivity.
The synthesized carrier surface has more abundant defect sites, thereby being capable of being combined with metal more highly. And the abundant-OH functional groups on the surface can effectively anchor metal atoms, so that the metal atoms are highly dispersed on the surface of the carrier. Compared with common alumina, the synthesized carrier has weaker acidity of defect sites, and the selectivity and stability of the catalyst are further improved.
Based on the background, the invention provides a high-dispersion Pd/Co (OH)2The preparation of the catalyst is used for improving the selectivity of the palladium-based catalyst in the acetylene hydrogenation reaction.
Disclosure of the invention
The invention provides a high-dispersion Pd/Co (OH)2A catalyst and a preparation method thereof, and application in selective hydrogenation reaction of acetylene. The preparation method has simple process, and the prepared catalyst can greatly improve the ethylene selectivity in the selective hydrogenation reaction of acetylene.
The technical scheme of the invention is as follows:
high-dispersion Pd/Co (OH)2The catalyst is prepared by the following method:
(1) preparing a palladium impregnation solution: dissolving a palladium compound in a solvent to prepare a palladium impregnation solution;
in the palladium impregnation liquid, the concentration of the palladium compound is 0.001-0.01g/mL calculated by palladium;
the palladium compound is palladium acetate, palladium acetylacetonate, dichlorodiammine palladium, ammonium tetrachloropalladate, sodium chloropalladate or tetraamminepalladium nitrate, preferably palladium acetate;
the solvent is determined according to the kind of the palladium compound, and can be water, hydrochloric acid, ethanol, acetone and the like, and the invention has no special requirement for the solvent;
(2)Co(OH)2synthesis of the carrier: dissolving cobalt chloride hexahydrate and a precipitator in deionized water, stirring for 0.5h, then adding propylene oxide, stirring for 0.5-5 h at room temperature (20-30 ℃), precipitating, then drying for 12h at 80 ℃, washing a solid product with methanol and deionized water, drying for 8-12 h at 110 ℃, finally placing the solid product in a muffle furnace, roasting for 2-6h at 350-700 ℃, and obtaining Co (OH)2A carrier;
the weight ratio of the cobalt chloride hexahydrate, the precipitator and the propylene oxide is 1: 1-5: 1-10, preferably 1: 2: 10;
the precipitant is sodium dodecyl sulfate, hexamethylenetetramine, ammonium nitrate, ammonium fluoride or ammonium chloride, preferably ammonium chloride;
(3) high dispersion Pd/Co (O)H)2Preparation of the catalyst: mixing Co (OH)2Immersing the carrier in a palladium impregnation solution, uniformly dispersing, impregnating for 9-12h at room temperature, drying for 9-12h at the temperature of 110-2A catalyst;
in the invention, after the cobalt hydroxide in the step (3) is immersed in the palladium immersion liquid and is immersed for 9-12h, the system can be placed in a microwave reactor, the microwave is carried out for 20-80min at the temperature of 110-130 ℃, the dispersion of the metal components on the carrier can be further promoted, then the sample is placed in a drying oven at the temperature of 110-130 ℃ for drying for 9-12h, and then the final catalyst is obtained by calcining.
In the catalyst obtained in the present invention, the supported amount of the palladium compound in terms of palladium is 0.01 to 0.5% by weight, preferably 0.01 to 0.1% by weight, more preferably 0.01 to 0.03% by weight, based on the mass of the carrier.
In the preparation method of the catalyst of the present invention, the palladium compound can be regarded as being supported completely, and the addition amount of the palladium compound and the carrier can be selected by those skilled in the art according to the required loading amount.
The high-dispersion Pd/Co (OH) of the invention2The catalyst can be applied to acetylene hydrogenation reaction. Specifically, the application method comprises the following steps:
before the selective hydrogenation reaction of acetylene, hydrogen is needed to reduce the catalyst, wherein the reduction temperature is 130-230 ℃ and the time is 1-4 h; and then the reduced catalyst is used for acetylene selective hydrogenation reaction, and the reaction conditions are as follows: the temperature is 60-210 ℃ (preferably 60-150 ℃), the pressure is 0.1-1MPa (preferably 0.1-0.3MPa, more preferably normal pressure), the space velocity is 1000--1(preferably 4000--1)；
In the acetylene selective hydrogenation reaction, the gas composition at the initial reaction is as follows (volume fraction): 0.33% C2H2、0.66％H2、33.3％C2H4The balance N2。
Compared with the prior art, the invention has the beneficial effects that:
(1) highly dispersed Pd/Co (OH) of the invention2The catalyst is prepared by a simple methodCo (OH) with a high specific surface area is prepared2Then calcining and the like to make the surface of the carrier have more defect sites. Then, the palladium impregnation liquid was supported on Co (OH)2On the carrier, high dispersion Pd/Co (OH) with better performance is prepared2A catalyst. On the one hand, a higher degree of dispersion of palladium on the support is obtained, which is advantageous for the acetylene hydrogenation reaction; on the other hand, the acidity of the carrier surface is lower than that of alumina, that is, the carrier surface has almost no medium-strong acid sites, and less green oil is generated in the acetylene hydrogenation reaction, so that the prepared high-dispersion Pd/Co (OH)2The catalyst has higher stability; finally, high dispersion Pd/Co (OH)2The catalyst surface contains a large number of hydroxyl groups, and the hydroxyl groups can better stably anchor the existence of palladium, so that the palladium is further highly dispersed and exists on the catalyst. In addition, the anchoring between the hydroxyl and the palladium is in a chemical form, and the hydroxyl can provide electron transfer to the palladium active site, so that the palladium active center presents an electron-rich state, and high ethylene selectivity is obtained.
(2) Highly dispersed Pd/Co (OH) of the invention2The preparation method of the catalyst has simple process.
(3) Highly dispersed Pd/Co (OH) of the invention2The preparation of the catalyst is applied to the selective hydrogenation reaction of acetylene, and the catalyst not only has high catalytic activity and high ethylene selectivity, but also has the advantages of excellent stability, high atom utilization rate and the like.
(IV) detailed description of the preferred embodiments
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.
In the following examples, Co (OH)2The carrier is synthesized by the following method:
placing 0.01mol of cobalt chloride hexahydrate and 0.02mol of precipitator ammonium chloride in a small beaker, adding a certain amount of deionized water to dissolve, stirring for 0.5h, then adding 0.1mol of propylene oxide, stirring for 5h at room temperature, precipitating, then placing at 80 ℃ for drying for 12h, washing a solid product with methanol and deionized water for 3-5 times, and cooling to 110 DEG CDrying overnight, finally placing into a muffle furnace, roasting for 6h at 600 ℃ to obtain Co (OH)2And (3) a carrier.
Examples 1 to 5
Weighing a certain amount of palladium acetate, dissolving the palladium acetate in concentrated hydrochloric acid, transferring the solution to a volumetric flask, and adding a certain amount of deionized water to corresponding scales to prepare palladium chloride palladate solution with the mass concentration of palladium of 0.001 g/mL. According to the loading amount and the proportion listed in the table 2, the metered chloropalladate solution is mixed with a certain amount of deionized water, and after the mixture is uniformly stirred, the high-dispersion Co (OH) is uniformly mixed2Support (specific surface area about 150-250 m)2/g) pouring into the impregnation liquid, and performing ultrasonic treatment to uniformly disperse the impregnation liquid. Wetting Co (OH)2Soaking the carrier at room temperature for 12h, drying at 110 ℃ for 12h, taking out a sample, calcining the sample at 350-700 ℃ for 6h to obtain high-dispersion Pd/Co (OH)2The catalyst of (1).
Example 4 Co (OH)2The texture properties of the support before and after loading Pd are compared in table 1:
TABLE 1 comparison of the texture Properties of Pd-loaded carriers before and after loading
Example 6
With reference to the operation of example 5, the only difference is that the support is replaced by a support having a specific surface area of 60m2Alumina in a/g ratio to produce simple Pd/Al2O3A catalyst.
Example 7
With reference to the operation of example 5, the only difference is that the support is replaced by a support having a specific surface area of 420m2Alumina in a/g ratio to produce simple Pd/Al2O3A catalyst.
Example 8
The highly dispersed Pd/Co (OH) prepared in example 22The catalyst reacts for 80min at 100 ℃ in a microwave reactor to obtain the finished product catalyst.
Example 9
The highly dispersed Pd/Co (OH) prepared in example 52The catalyst reacts in a microwave reactor at 120 ℃ for 60min to obtain the finished catalyst.
The catalyst activity and selectivity of the prepared catalyst were evaluated according to the following methods:
0.3g of catalyst is placed in a small quartz tube reactor, the quartz tube is placed in a temperature-controllable heating jacket, and the catalyst needs to be in pure H before the evaluation of the selective hydrogenation reaction of acetylene2Reducing for 1h at 180 ℃ in the atmosphere, wherein the flow rate of the reducing gas is 10 mL/min; after the reduction, the reaction was carried out at the temperature shown in Table 2. The reaction gas composition (volume fraction): 0.33 percent of acetylene, 33.3 percent of ethylene, 0.66 percent of hydrogen and the balance of nitrogen, wherein the flow rate of reaction gas is 50mL/min, and the reaction pressure is normal pressure. The reaction gas outlet is connected with a gas chromatography for on-line detection, and the evaluation result of the catalyst is shown in the following table 2.
TABLE 2 high dispersion Pd/Co (OH)2Evaluation results of acetylene selective hydrogenation reaction of catalyst
Examples 10 to 15
Referring to the preparation methods of the catalysts of examples 1 to 5, the loading amounts of the palladium impregnation liquids are shown in Table 3, and highly dispersed Pd/Co (OH) was prepared2A catalyst.
The catalyst activity and selectivity evaluation methods were the same as above, while the calcination temperature for preparing the catalyst and the reaction temperature in the acetylene hydrogenation reaction were varied, and the catalyst evaluation results are shown in table 3 below.
TABLE 3 high dispersion Pd/Co (OH)2Evaluation results of acetylene selective hydrogenation reaction of catalyst
Claims (3)
1. High-dispersion Pd/Co (OH)2The application of the catalyst in the selective hydrogenation reaction of acetylene is characterized in that the application method comprises the following steps：
Before the selective hydrogenation reaction of acetylene, hydrogen is firstly used for reducing the catalyst, the reduction temperature is 130-230 ℃, and the reduction time is 1-4 h; and then the reduced catalyst is used for acetylene selective hydrogenation reaction, and the reaction conditions are as follows: the temperature is 60-210 ℃, the pressure is 0.1-1MPa, and the space velocity is 1000--1(ii) a In the acetylene selective hydrogenation reaction, the initial gas volume fraction of the reaction is as follows: 0.33% C2H2、0.66% H2、33.3% C2H4The balance N2；
The preparation method of the catalyst comprises the following steps:
(1) preparing a palladium impregnation solution: dissolving a palladium compound in a solvent to prepare a palladium impregnation solution;
the palladium compound is palladium acetate, palladium acetylacetonate, dichlorodiammine palladium, ammonium tetrachloropalladate, sodium chloropalladate or tetraamminepalladium nitrate;
（2）Co(OH)2synthesis of the carrier: dissolving cobalt chloride hexahydrate and a precipitator in deionized water, stirring for 0.5h, then adding propylene oxide, stirring for 0.5-5 h at room temperature, precipitating, then drying at 80 ℃ for 12h, washing a solid product with methanol and deionized water, drying at 110 ℃ for 8-12 h, finally placing in a muffle furnace, and roasting at 350-700 ℃ for 2-6h to obtain Co (OH)2A carrier;
the weight ratio of the cobalt chloride hexahydrate, the precipitator and the propylene oxide is 1: (1-5): (1-10);
the precipitant is sodium dodecyl sulfate, hexamethylenetetramine, ammonium nitrate, ammonium fluoride or ammonium chloride;
(3) high dispersion Pd/Co (OH)2Preparation of the catalyst: mixing Co (OH)2Immersing the carrier in a palladium impregnation solution, uniformly dispersing, impregnating for 9-12h at room temperature, placing the system in a microwave reactor, carrying out microwave for 20-80min at the temperature of 110-2A catalyst;
in the catalyst, the supported amount of the palladium compound in terms of palladium is 0.01 to 0.5wt% based on the mass of the carrier.
2. The use according to claim 1, wherein in step (1) of the method for preparing a catalyst, the palladium compound in the palladium impregnation solution is present in a concentration of 0.001 to 0.01g/mL, calculated as palladium.
3. The use according to claim 1, wherein in step (2) of the preparation method of the catalyst, the ratio of the amounts of the cobalt chloride hexahydrate, the precipitant and the propylene oxide is 1: 2: 10.
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| CN113231077A (en) * | 2021-05-12 | 2021-08-10 | 昆明理工大学 | Preparation method and application of defect-rich carrier interface reduction anchoring precious metal catalyst |
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| US7592402B2 (en) * | 2004-04-30 | 2009-09-22 | Sumitomo Chemical Company, Limited | Process for producing modified particle; carrier; catalyst component for addition polymerization; process for producing catalyst for addition polymerization; and process for producing addition polymer |
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