CN111250117B - Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in catalyzing acetylene hydrochlorination reaction - Google Patents
Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in catalyzing acetylene hydrochlorination reaction Download PDFInfo
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- CN111250117B CN111250117B CN202010082748.6A CN202010082748A CN111250117B CN 111250117 B CN111250117 B CN 111250117B CN 202010082748 A CN202010082748 A CN 202010082748A CN 111250117 B CN111250117 B CN 111250117B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- C—CHEMISTRY; METALLURGY
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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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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Abstract
The invention provides a supported mercury-free catalyst, a preparation method thereof and application thereof in catalyzing acetylene hydrochlorination, and relates to the technical field of catalysts. The invention provides a supported mercury-free catalyst which comprises a carrier and an active component loaded on the carrier; the carrier is a halloysite nanotube; the active component is noble metal halide and/or noble metal complex, and the loading amount of noble metal elements in the active component on the carrier is 0.05-1 wt%. The catalyst provided by the invention is a mercury-free catalyst, is green and environment-friendly, can efficiently catalyze the hydrochlorination of acetylene, and has high catalytic activity. The results of the examples show that the catalyst provided by the invention catalyzes the hydrochlorination reaction of acetylene, the conversion rate of acetylene is more than 91%, and the selectivity of vinyl chloride is more than 97%. The invention also provides a preparation method of the supported mercury-free catalyst for acetylene hydrochlorination, which is simple in process and easy to operate.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a supported mercury-free catalyst, a preparation method thereof and application thereof in catalyzing acetylene hydrochlorination.
Background
Vinyl chloride is an important monomer for synthesizing polyvinyl chloride, and the industrial production thereof mainly comprises an acetylene method (acetylene hydrochlorination method), an ethylene method, an ethane method and a combination method. According to the resource characteristics of 'lean oil and rich coal' in China, an acetylene hydrochlorination method taking coal as a raw material is a mainstream process for producing vinyl chloride in China. However, the mercuric chloride/activated carbon catalyst used in the process is toxic, harmful to the environment and ecology and is not favorable for the sustainable development of the chlor-alkali industry.
Disclosure of Invention
In view of the above, the present invention aims to provide a supported mercury-free catalyst, a preparation method thereof, and an application thereof in catalyzing acetylene hydrochlorination. The catalyst provided by the invention is mercury-free, green and environment-friendly, and can efficiently catalyze the hydrochlorination reaction of acetylene.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a supported mercury-free catalyst, which comprises a carrier and an active component supported on the carrier;
the carrier is a halloysite nanotube;
the active component is noble metal halide and/or noble metal complex, and the loading amount of noble metal elements in the active component on the carrier is 0.05-1 wt%.
Preferably, the noble metal halide is a noble metal chloride; the noble metal complex is a noble metal chloride complex; the noble metal element in the noble metal halide and the noble metal complex is one or more of gold, platinum, palladium, ruthenium, rhodium and silver.
Preferably, the loading amount of the noble metal element in the active component on the carrier is 0.1-0.8 wt%.
The invention provides a preparation method of the supported mercury-free catalyst in the scheme, which comprises the following steps:
(1) Modifying the halloysite nanotube by a pretreatment reagent to obtain a modified halloysite nanotube; the pretreatment reagent is a nitrogen-containing reagent;
(2) Dipping the active component on the modified halloysite nanotube by an ultrasonic dipping or microwave dipping method to obtain the supported mercury-free catalyst; the loading amount of the noble metal element in the active component on the halloysite nanotube is 0.05-1 wt%.
Preferably, the method for modifying in step (1) is: mixing the aqueous solution of the pretreatment reagent with the halloysite nanotube, and sequentially refluxing, filtering, washing a solid phase and drying to obtain a modified halloysite nanotube; the pretreatment reagent comprises one or more of ammonium chloride, ammonium fluoride, urea, ethylenediamine, aniline, polyaniline and polypyrrole.
Preferably, the mass concentration of the aqueous solution of the pretreatment reagent is 1-20%; the reflux temperature is 40-100 ℃ and the reflux time is 0.5-24 h.
Preferably, the ultrasonic impregnation or microwave impregnation method in the step (2) is specifically as follows:
and (2) preparing the active component into an impregnating solution, dropwise adding the impregnating solution onto the modified halloysite nanotube, then carrying out ultrasonic impregnation or microwave impregnation, and drying to obtain the supported mercury-free catalyst.
Preferably, the temperature of the ultrasonic impregnation or the microwave impregnation is 20-45 ℃ and the time is 10-60 min.
Preferably, the drying temperature is independently 80-140 ℃, and the drying time is independently 4-24 h.
The invention also provides an application of the supported mercury-free catalyst in the scheme or the supported mercury-free catalyst prepared by the preparation method in the scheme in catalyzing acetylene hydrochlorination.
The invention provides a supported mercury-free catalyst, which comprises a carrier and an active component supported on the carrier; the carrier is a halloysite nanotube; the active component is noble metal halide and/or noble metal complex, and the loading amount of noble metal elements in the active component on the carrier is 0.05-1 wt%. In the invention, the halloysite nanotube has a hollow tubular structure, good water dispersibility, different properties of the inner wall and the outer wall, high adsorbability, biocompatibility and environmental friendliness, not only has the characteristics of good crystallization and complete form, but also can adsorb or graft functional molecules on the inner wall and the outer wall of the halloysite nanotube by utilizing the high length-diameter ratio and the high adsorbability of the halloysite nanotube. The catalyst provided by the invention is a mercury-free catalyst, is green and environment-friendly, can efficiently catalyze the hydrochlorination reaction of acetylene, and has high catalytic activity. The results of the examples show that the catalyst provided by the invention catalyzes the hydrochlorination of acetylene, the acetylene conversion rate is more than 91%, and the vinyl chloride selectivity is more than 97%.
The invention also provides a preparation method of the supported mercury-free catalyst, which is simple in process and easy to operate.
Detailed Description
The invention provides a supported mercury-free catalyst, which comprises a carrier and an active component supported on the carrier;
the carrier is a halloysite nanotube;
the active component is noble metal halide and/or noble metal complex, and the loading amount of noble metal elements in the active component on the carrier is 0.05-1 wt%.
The source of the halloysite nanotubes is not particularly required in the present invention, and halloysite nanotubes from sources well known to those skilled in the art can be used. The halloysite nanotube material is a novel nano material which has a hollow tubular structure, good water dispersibility, different properties of inner and outer walls, high adsorbability, biocompatibility and environmental friendliness, has good crystallization and complete form, overcomes the defect that the nano material is easy to agglomerate, and also has high length-diameter ratio and high adsorbability, and functional molecules can be adsorbed or grafted on the inner and outer walls of the tube.
In the present invention, the noble metal halide is preferably a noble metal chloride; the noble metal complex is preferably a noble metal chloro complex; the noble metal element in the noble metal halide and the noble metal complex is preferably one or more of gold, platinum, palladium, ruthenium, rhodium and silver. The source of the noble metal halide or noble metal complex is not particularly critical in the present invention, and any corresponding halide or complex known to those skilled in the art may be used.
In the present invention, the loading amount of the noble metal element in the active component on the support is preferably 0.1 to 0.8wt%, more preferably 0.5wt%. The invention takes the halide and/or complex of noble metal as active component to load on halloysite nanotube, the binding force between the active component and the carrier is strong, and the catalytic activity and stability of the catalyst can be improved.
The catalyst provided by the invention is a mercury-free catalyst, is green and environment-friendly, can efficiently catalyze the hydrochlorination of acetylene, and has high catalytic activity.
The invention provides a preparation method of the supported mercury-free catalyst in the scheme, which comprises the following steps:
(1) Modifying the halloysite nanotube by a pretreatment reagent to obtain a modified halloysite nanotube; the pretreatment reagent is a nitrogen-containing reagent;
(2) Dipping the active component on the modified halloysite nanotube by an ultrasonic dipping or microwave dipping method to obtain the supported mercury-free catalyst; the loading amount of the noble metal element in the active component on the halloysite nanotube is 0.05-1 wt%.
The halloysite nanotube is modified by a pretreatment reagent to obtain the modified halloysite nanotube. In the present invention, the pretreatment reagent is a nitrogen-containing reagent; the pretreatment reagent preferably comprises one or more of ammonium chloride, ammonium fluoride, urea, ethylenediamine, aniline, polyaniline and polypyrrole. In the invention, the modification method comprises the following steps: and mixing the aqueous solution of the pretreatment reagent with the halloysite nanotube, and sequentially refluxing, filtering, washing and drying to obtain the modified halloysite nanotube.
In the present invention, the aqueous solution of the pretreatment reagent preferably has a mass concentration of 1 to 20%, more preferably 9 to 15%; the mass ratio of the halloysite nanotubes to the pretreatment reagent is preferably 1. In the present invention, the method of mixing the aqueous solution of the pretreatment reagent with the halloysite nanotubes is preferably: pouring the halloysite nanotube into the aqueous solution of the pretreatment reagent for a few times, and then stirring for 4-10 h. The present invention preferably first dries the halloysite nanotubes at 100 ℃ for 4 hours prior to mixing with the aqueous solution of the pretreatment reagent. In the present invention, the temperature of the reflux is preferably 40 to 100 ℃, more preferably 50 to 70 ℃; the time is preferably from 0.5 to 24 hours, more preferably from 10 to 15 hours. The present invention does not require any particular manipulation of the reflux, and may be performed by methods well known in the art. In the present invention, the method of filtration is preferably suction filtration. After filtration, the resulting solid was washed and dried in this order. In the present invention, the washing detergent is preferably distilled water, and the number of times of washing is not particularly limited, and the obtained solid can be washed to neutrality. In the present invention, the drying temperature is preferably 80 to 140 ℃, more preferably 90 to 110 ℃; the time is preferably 4 to 24 hours, and more preferably 8 to 15 hours; the present invention does not require any particular embodiment of the drying process, and the drying process may be performed in a manner known in the art. And drying to obtain the modified halloysite nanotube.
According to the invention, the halloysite nanotube is modified by the pretreatment reagent, so that functional groups on the surface of the halloysite nanotube can be increased, the hydrophilicity of the halloysite nanotube can be increased, the morphology of the halloysite nanotube can be changed, and the dispersion degree of active components can be improved.
After the modified halloysite nanotube is obtained, the active component is impregnated on the modified halloysite nanotube by an ultrasonic impregnation or microwave impregnation method to obtain the supported mercury-free catalyst; the loading amount of the noble metal element in the active component on the halloysite nanotube is 0.05-1 wt%. In the present invention, the method of ultrasonic impregnation or microwave impregnation is specifically preferably: and (3) preparing the active component into an impregnation liquid, dropwise adding the impregnation liquid onto the modified halloysite nanotube, then carrying out ultrasonic impregnation or microwave impregnation, and drying to obtain the supported mercury-free catalyst.
In the present invention, the active ingredient is preferably prepared into an impregnation solution according to the principle of an equal-volume impregnation method, specifically: testing the saturated water absorption (volume) of the modified halloysite nanotube, wherein the obtained saturated water absorption is the volume of the prepared impregnation liquid; and calculating the mass of the active component in the impregnation liquid according to the loading amount of the noble metal element in the active component, thereby obtaining the concentration of the impregnation liquid. According to the invention, the impregnation liquid is dropwise added onto the modified halloysite nanotube, so that the effect of the catalyst is improved.
In the present invention, the ultrasonic impregnation or microwave impregnation is: and carrying out ultrasonic or microwave treatment on the modified halloysite nanotube dropwise added with the impregnation liquid. The specific apparatus for ultrasonic or microwave impregnation is not particularly required in the present invention, and corresponding apparatus well known in the art may be employed. In the invention, the temperature of the ultrasonic or microwave impregnation is preferably 20-45 ℃, and more preferably 30 ℃; the time is preferably 10 to 60min, more preferably 20 to 40min. The frequency of the ultrasonic or microwave impregnation is not particularly critical to the present invention and may be any frequency known to those skilled in the art.
After ultrasonic or microwave impregnation, normal-temperature impregnation is preferably performed again, and the time for normal-temperature impregnation is preferably 10h. In the present invention, the drying temperature is preferably 80 to 140 ℃, more preferably 100 to 120 ℃; the drying time is preferably 4 to 24 hours, more preferably 5 to 15 hours. And drying to obtain the supported mercury-free catalyst.
The preparation method of the supported mercury-free catalyst provided by the invention is simple in process and easy to operate.
The invention also provides application of the supported mercury-free catalyst in the scheme or the supported mercury-free catalyst prepared by the preparation method in the scheme in catalyzing acetylene hydrochlorination. The conditions for the hydrochlorination of acetylene are not particularly critical to the present invention and may be any conditions known to those skilled in the art. In the specific embodiment of the invention, a fixed bed reactor is adopted for carrying out acetylene hydrochlorination catalytic reaction, and the reaction conditions are as follows: normal pressure, raw gas space velocity of 30-300 h -1 The raw material gas ratio is V (HCl): v (C) 2 H 2 ) 1, and the reaction temperature is 100-220 ℃. The catalyst provided by the invention is used for catalyzing acetylene hydrochlorination, the acetylene conversion rate is more than 91%, and the vinyl chloride selectivity is more than 97%.
The supported mercury-free catalyst provided by the present invention, the preparation method thereof and the application thereof in catalyzing acetylene hydrochlorination are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 5g of powdery halloysite nanotubes, and drying at 100 ℃ for 4h. Pouring the mixture into 100mL of urea solution (the mass fraction of urea is 9 wt%), and magnetically stirring the mixture for 4 hours at normal temperature and at the rotating speed of 800r/min. And then refluxing for 4h at 70 ℃, carrying out suction filtration and washing with distilled water on the halloysite nanotube after urea treatment to be neutral, and drying for 8h at 90 ℃ to obtain the urea modified halloysite nanotube.
Weighing a certain amount of palladium chloride, and preparing into H with a certain concentration at room temperature 2 PdCl 4 And (3) dipping the catalyst in a dipping solution to ensure that the loading amount of metal palladium in the catalyst is 0.5wt%, dipping the dipping solution on the dried modified halloysite nanotube carrier drop by drop, ultrasonically dipping for 1h at 30 ℃, dipping for 10h at normal temperature, and drying for 5h at 100 ℃ to obtain the halloysite palladium-based catalyst.
3g of the catalyst thus obtained was charged into a fixed bed reactor (made of quartz glass). Under the reaction conditions: normal pressure, feed gas space velocity of 135h -1 The raw material gas proportion is V (HCl): v (C) 2 H 2 ) 1.15, the catalyst was subjected to acetylene hydrochlorination activity evaluation under the condition of a reaction temperature of 160 ℃, and the evaluation results were: the acetylene conversion was 91.15% and the vinyl chloride selectivity was 97.64%.
Example 2
Weighing 5g of powdery halloysite nanotubes, and drying at 100 ℃ for 4h. Pouring the mixture into 100mL of ammonium fluoride solution (the mass fraction is 7 wt%), and magnetically stirring the mixture for 5 hours at normal temperature at the rotating speed of 800r/min. And then refluxing for 4h at 60 ℃, carrying out suction filtration and washing with distilled water on the halloysite nanotube treated by ammonium fluoride until the halloysite nanotube is neutral, and drying for 8h at 90 ℃ to obtain the ammonium fluoride modified halloysite nanotube.
Weighing a certain amount of palladium chloride, and preparing H with a certain concentration at room temperature 2 PdCl 4 And (3) dipping the catalyst in a dipping solution to ensure that the loading amount of metal palladium in the catalyst is 0.5wt%, dipping the dipping solution on the dried modified halloysite nanotube carrier drop by drop, carrying out ultrasonic dipping at 25 ℃ for 1h, dipping at normal temperature for 10h, and drying at 100 ℃ for 5h to obtain the halloysite palladium-based catalyst.
3g of the catalyst thus obtained was charged into a fixed bed reactor (made of quartz glass). Under the reaction conditions: normal pressure, raw gas space velocity of 135h -1 The raw material gas proportion is V (HCl): v (C) 2 H 2 ) 1.15, the catalyst was subjected to acetylene hydrochlorination activity evaluation under the condition of a reaction temperature of 160 ℃, and the evaluation results were: the acetylene conversion rate is 92.01 percent, and the highest selectivity of the chloroethylene can reach 97.21 percent.
Comparative example
Weighing 5g of powdery halloysite nanotubes, and drying at 100 ℃ for 4h.
Weighing a certain amount of palladium chloride, and preparing into H with a certain concentration at room temperature 2 PdCl 4 And (3) dipping the catalyst in a dipping solution to ensure that the loading amount of metal palladium in the catalyst is 0.5wt%, dipping the dipping solution on the dried halloysite nanotube carrier drop by drop, carrying out ultrasonic dipping at 30 ℃ for 1h, dipping at normal temperature for 10h, and drying at 100 ℃ for 5h to obtain the halloysite palladium-based catalyst.
3g of the catalyst prepared above was charged into a fixed bed reactor (quartz glass material) under the reaction conditions: normal pressure, raw gas space velocity of 135h -1 The raw material gas proportion is V (HCl): v (C) 2 H 2 ) 1.15, the catalyst was subjected to acetylene hydrochlorination activity evaluation under the condition of a reaction temperature of 160 ℃, and the evaluation results were: the acetylene conversion was 66.59% and the vinyl chloride selectivity was 97.65%.
The embodiments show that the catalyst provided by the invention is a mercury-free catalyst, is green and environment-friendly, can efficiently catalyze the hydrochlorination of acetylene, and has high activity, the acetylene conversion rate is more than 91 percent, and the vinyl chloride selectivity is more than 97 percent; and the preparation method is simple.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A preparation method of a supported mercury-free catalyst comprises the following steps:
weighing 5g of powdery halloysite nanotubes, drying at 100 ℃ for 4h, pouring the powdery halloysite nanotubes into 100mL of urea solution, wherein the mass fraction of urea is 9wt%, and magnetically stirring at normal temperature for 4h at the rotating speed of 800r/min; then refluxing for 4h at 70 ℃, carrying out suction filtration and washing with distilled water on the halloysite nanotube after urea treatment to be neutral, and drying for 8h at 90 ℃ to obtain a urea modified halloysite nanotube;
weighing a certain amount of palladium chloride, and preparing H with a certain concentration at room temperature 2 PdCl 4 Dipping liquid, ensuring that the loading capacity of metal palladium in the catalyst is 0.5wt%, then dipping the dipping liquid on the dried modified halloysite nanotube carrier drop by drop, carrying out ultrasonic dipping for 1h at 30 ℃, dipping for 10h at normal temperature, and drying for 5h at 100 ℃ to obtain the supported mercury-free catalyst;
the supported mercury-free catalyst is applied to catalyzing acetylene hydrochlorination.
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| CN102380380A (en) * | 2011-09-02 | 2012-03-21 | 新疆大学 | Mercury-free catalyst system for acetylene hydrochlorination and use thereof |
| CN102357366B (en) * | 2011-09-02 | 2016-05-18 | 新疆大学 | For the non-mercury catalyst of acetylene hydrochlorination reaction |
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| "Non-mercury catalytic acetylene hydrochlorination over the NH4F Urea-modified Pd/HY catalyst for vinyl chloride monomer production";Lu Wang et al.;《J. Name.》;20160205;第1-5页 * |
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