Catalyst, preparation method thereof and application of catalyst in catalytic acetylene hydrogenation
By loading a catalyst with highly dispersed palladium onto fullerenes, the problem of low dispersion of active components in existing catalysts was solved, achieving efficient acetylene hydrogenation and ethylene selectivity, and extending the catalyst's lifespan.
Patent Information
- Application Number
- CN202410649179.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-23
- Publication Date
- 2025-11-25
AI Technical Summary
Existing selective hydrogenation catalysts for acetylene suffer from problems such as low dispersion of active components and insufficient selectivity and stability for ethylene, resulting in low ethylene production efficiency.
Fullerene is used as a support, and highly dispersed palladium is loaded as the active component. The palladium valence state is stabilized by electron transfer, which improves the activity and selectivity of the catalyst. The preparation method includes mixing, aging, drying, calcination and reduction treatment.
It improves the feed conversion rate and ethylene selectivity of the acetylene hydrogenation reaction, extends the catalyst life, and is environmentally friendly.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the field of catalysts, and particularly relates to a catalyst, and further relates to a method for preparing the catalyst and application of the catalyst in catalyzing hydrogenation of acetylene. BACKGROUND
[0002] Ethylene industry, as an important component of chemical industry, has a very significant influence on economic development. In industry, the dominant process for producing ethylene is steam catalytic cracking of naphtha, and the C2 fraction obtained therefrom usually contains a small amount of acetylene (0.5-3.0%), which can cause irreversible deactivation of Ziegler-Natta catalyst in the process of olefin polymerization. The industrial production of high-purity ethylene often requires removal of a small amount of acetylene from the post-cracking feed. The methods for removing acetylene in industry include rectification extraction, acetylene copper precipitation, acetone absorption, ammoniation, complexation and selective hydrogenation, etc. The selective hydrogenation method has the characteristics of high acetylene removal efficiency, simple process flow and high atomic utilization rate, etc.
[0003] The catalyst for selective hydrogenation of acetylene is generally a solid supported catalyst, which is composed of an active component and a carrier. Common carriers include alumina, silica, molecular sieve, activated carbon, magnesium oxide and titanium oxide, and the active component is usually a group VIII element such as Pd, Pt and Ni.
[0004] Fullerene is usually added to the catalyst as an additive. SUMMARY
[0005] One of the purposes of the present application is to provide a catalyst, which has a high dispersion degree of active component, a high proportion of zero-valent palladium in the active component and a small Dv50 particle size; the catalyst has a high raw material conversion rate, a high ethylene selectivity, a good stability and a long service life in catalyzing hydrogenation of acetylene. On this basis, another purpose of the present application is to provide a method for preparing the catalyst and application of the catalyst in catalyzing hydrogenation of acetylene.
[0006] To achieve the above-mentioned purposes, the first aspect of the present application relates to a catalyst, which comprises a fullerene carrier and an active component supported on the fullerene carrier, the active component being selected from one or more of palladium and its salts; the dispersion degree of the active component is 30%-40%, for example, 32%, 34%, 35%, 37%, 38% or 40%.
[0007] The inventors of the present application attempt to develop a catalyst suitable for selective hydrogenation of acetylene by using fullerene as a carrier. In the present application, the active component is supported on fullerene, and electron transfer occurs between fullerene and the active component, which stabilizes the valence state of palladium at a suitable state, significantly improves the conversion rate of raw material acetylene and the selectivity of ethylene, and the stability of the catalyst is good.
[0008] In any embodiment of the first aspect of the present application, the active component comprises Pd 0 ; optionally, the Pd 0 is present in the active component in a molar percentage of 75-85%, such as 76%, 78%, 79%, 80%, 81%, 82%, 84%, 85%.
[0009] In any embodiment of the first aspect of the present application, the Pd 0 is present in the active component in a molar percentage, wherein the molar amount of the active component is calculated based on the total molar amount of Pd in all valence states.
[0010] In this way, the valence state of palladium is reduced, and its higher electron density repels the carbon-carbon double bond of ethylene, weakening the binding force between ethylene and palladium, and further improving the selectivity of ethylene.
[0011] In any embodiment of the first aspect of the present application, the Dv50 particle size of the catalyst is 1-3 nm, such as 1 nm, 1.2 nm, 1.4 nm, 1.6 nm, 2.0 nm, 2.2 nm, 2.3 nm, 2.4 nm, 2.6 nm, 2.7 nm, 2.8 nm, 3 nm.
[0012] In any embodiment of the first aspect of the present application, the mass percentage of the active component in the catalyst is 0.1%-10% based on the mass of palladium element, such as 0.1%, 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 7%, 8%, 10%.
[0013] In any embodiment of the first aspect of the present application, the fullerene is selected from one or more of hollow fullerene, endohedral fullerene, heterocyclic fullerene; optionally, the fullerene is selected from one or more of C 60 , C 70 , La@C 82 , SiC2@C 60 , C 59 N. Among them, C 60 , C 70 , La@C 82 , SiC2@C 60 , C 59 N is directly purchased from the market or prepared according to the conventional method in the art.
[0014] The second aspect of the present application relates to a method for preparing a catalyst, comprising the following steps:
[0015] mixing the fullerene dispersion liquid with an alkali solution to obtain a mixture;
[0016] mixing the raw material containing the active component source with the mixture, reacting and aging at 60-120°C (preferably 80-120°C, for example 90°C, 100°C, 110°C, 120°C), solid-liquid separation, collecting the solid phase;
[0017] drying and calcining the solid phase to obtain the catalyst.
[0018] In any embodiment of the second aspect of the present application, the step of preparing the solid phase comprises one or more of the following:
[0019] The reaction time is 2-6 hours, for example 2, 3, 4, 5, 6 hours;
[0020] The reaction is carried out under stirring;
[0021] The reaction is carried out under stirring at a rotation speed of 400-600 r / min (for example 500 r / min);
[0022] The aging time is 1-2 hours, for example 1, 1.5, 2 hours;
[0023] The aging is not carried out under stirring.
[0024] In any embodiment of the second aspect of the present application, the aging is carried out under static condition.
[0025] In any embodiment of the second aspect of the present application, the method further comprises: after calcining, the catalyst is subjected to reduction treatment.
[0026] In any embodiment of the second aspect of the present application, the reduction treatment comprises one or more of the following:
[0027] The reduction treatment is carried out at 150-300°C (preferably 150-250°C, for example 150°C, 200°C, 240°C);
[0028] The reduction treatment time is 2-6 hours, for example 2, 3, 4, 5, 6 hours;
[0029] The reduction treatment is carried out in a hydrogen atmosphere.
[0030] In any embodiment of the second aspect of the present application, the alkali solution is slowly added to the fullerene dispersion liquid for mixing.
[0031] In any embodiment of the second aspect of the present application, the pH value of the mixture is 9-10.
[0032] In any embodiment of the second aspect of the present application, the mass ratio of the palladium element in the active component source-containing raw material to the fullerene in the fullerene dispersion liquid is 0.001-0.11, for example, 0.001, 0.002, 0.003, 0.004, 0.005, 0.007, 0.009, 0.01, 0.03, 0.05, 0.07, 0.09, 0.1, 0.11.
[0033] In any embodiment of the second aspect of the present application, the drying temperature is 60-120°C (for example, 80°C, 90°C, 100°C, 110°C, 120°C), and the drying time is 10-14 hours (for example, 10, 11, 12, 13, 14 hours).
[0034] In any embodiment of the second aspect of the present application, the calcination temperature is 150-300°C (for example, 160°C, 170°C, 180°C, 200°C, 220°C, 230°C, 250°C, 270°C, 280°C, 300°C), and the calcination time is 2-6 hours (for example, 2, 3, 4, 5, 6 hours).
[0035] In any embodiment of the second aspect of the present application, the calcination is performed in an air atmosphere.
[0036] In any embodiment of the second aspect of the present application, the calcination rate is 1-5°C / min, for example, 1°C / min, 2°C / min, 3°C / min, 4°C / min, 5°C / min.
[0037] In any embodiment of the second aspect of the present application, the solid phase is washed with water before drying.
[0038] In any embodiment of the second aspect of the present application, the dried product is crushed into powder before calcination.
[0039] In any embodiment of the second aspect of the present application, the fullerene dispersion liquid is obtained by mixing fullerene with water under ultrasonic and stirring conditions.
[0040] In any embodiment of the second aspect of the present application, the content of fullerene in the fullerene dispersion liquid is 1-5 mg / mL, for example, 1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL, 5 mg / mL.
[0041] In any embodiment of the second aspect of the present application, the alkali solution is selected from one or more of aqueous ammonia, urea solution, sodium carbonate solution, potassium carbonate solution, sodium hydroxide solution, and potassium hydroxide solution.
[0042] In any embodiment of the second aspect of the present application, the molar concentration of the alkali solution is 0.5-1 mol / L, for example 0.5 mol / L, 0.75 mol / L, 1 mol / L.
[0043] In any embodiment of the second aspect of the present application, the raw material containing the active component source is added to the mixture.
[0044] In any embodiment of the second aspect of the present application, the mass concentration of the palladium dispersion or palladium salt solution is 0.1-1.2 mg / mL, for example 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.7 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.2 mg / mL.
[0045] In any embodiment of the second aspect of the present application, the solid-liquid separation is performed by suction filtration.
[0046] The third aspect of the present application relates to a method for preparing a catalyst, comprising the following steps:
[0047] The fullerene dispersion is mixed with a solution of an active component source to obtain a catalyst precursor; wherein the active component source is selected from one or more of palladium salts and organic complexes of palladium;
[0048] The catalyst precursor is dried and calcined to obtain a catalyst.
[0049] In any embodiment of the third aspect of the present application, the method further comprises: after calcination, the catalyst is subjected to reduction treatment.
[0050] In any embodiment of the third aspect of the present application, the reduction treatment comprises one or more of the following:
[0051] The reduction treatment is performed at 150-300°C (preferably 150-250°C, for example 150°C, 200°C, 240°C);
[0052] The time for the reduction treatment is 2-6 hours, for example 2, 3, 4, 5, 6 hours;
[0053] The reduction treatment is performed in a hydrogen atmosphere.
[0054] In any embodiment of the third aspect of the present application, the active component source is selected from one or more of palladium nitrate, palladium acetate, sodium chloropalladate, palladium acetylacetonate, palladium dibenzylideneacetone, palladium tetraphenylphosphine.
[0055] In any embodiment of the third aspect of the present application, the concentration is performed at 30-80°C (for example 40°C, 50°C, 60°C, 70°C, 75°C, 80°C).
[0056] In any embodiment of the third aspect of the application, the concentration is performed under stirring.
[0057] In any embodiment of the third aspect of the application, the mass ratio of palladium element in the solution of the active component source to fullerene in the fullerene dispersion is 0.001-0.11, for example 0.001, 0.002, 0.003, 0.004, 0.005, 0.007, 0.009, 0.01, 0.03, 0.05, 0.07, 0.09, 0.1, 0.11.
[0058] In any embodiment of the third aspect of the application, the drying temperature is 60-120°C (for example 80°C, 90°C, 100°C, 110°C, 120°C), and the drying time is 10-14 hours (for example 10, 11, 12, 13, 14 hours).
[0059] In any embodiment of the third aspect of the application, the calcination temperature is 150-300°C (for example 160°C, 170°C, 180°C, 200°C, 220°C, 230°C, 250°C, 270°C, 280°C, 300°C), and the calcination time is 2-6 hours (for example 2, 3, 4, 5, 6 hours).
[0060] In any embodiment of the third aspect of the application, the calcination is performed in an air atmosphere.
[0061] In any embodiment of the third aspect of the application, the heating rate of the calcination is 1-5°C / min, for example 1°C / min, 2°C / min, 3°C / min, 4°C / min, 5°C / min.
[0062] In any embodiment of the third aspect of the application, the dried product is crushed into a powder before calcination.
[0063] In any embodiment of the third aspect of the application, the fullerene dispersion is obtained by mixing fullerene and anhydrous ethanol under ultrasonic and stirring conditions.
[0064] In any embodiment of the third aspect of the application, the content of fullerene in the fullerene dispersion is 1-5 mg / mL, for example 1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL, 5 mg / mL.
[0065] In any embodiment of the third aspect of the application, the mass concentration of the solution of the active component source is 0.1-1.2 mg / mL, for example 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.7 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.2 mg / mL.
[0066] The catalyst prepared by the method of the second or third aspect of the present application is the catalyst of the first aspect of the present application.
[0067] The fourth aspect of the present application relates to the use of the catalyst of the first aspect of the present application or the catalyst prepared by the method of the second or third aspect of the present application in catalyzing the hydrogenation of acetylene.
[0068] In any embodiment of the fourth aspect of the present application, the reaction temperature for the hydrogenation of acetylene is 100-140℃, preferably 120-130℃, for example 120℃ or 130℃.
[0069] In any embodiment of the fourth aspect of the present application, the reaction pressure for the hydrogenation of acetylene is normal pressure.
[0070] Normal pressure generally refers to standard atmospheric pressure, specifically, when the temperature is 0℃, the pressure generated by a mercury column of 760 mm in height at sea level with a latitude of 45° is the standard atmospheric pressure.
[0071] In any embodiment of the fourth aspect of the present application, the raw gas for the hydrogenation of acetylene comprises 0.5-2% acetylene (for example 1%) and 4-12% hydrogen (for example 5%, 6%, 8%, 10%, 11%), and the rest is argon.
[0072] In any embodiment of the fourth aspect of the present application, the space velocity for the hydrogenation of acetylene is 55000-65000 mL·g -1 ·h -1 , for example 60000 mL·g -1 ·h -1 .
[0073] The present application has the following beneficial effects:
[0074] The catalyst of the present application has high dispersion of the active component, high molar proportion of zero-valent palladium in the active component, and small Dv50 particle size.
[0075] The catalyst of the present application has an acetylene conversion rate of 99.5±0.5% in the reaction of catalyzing the hydrogenation of acetylene, and an ethylene selectivity as high as 91.0±1.0%.
[0076] The catalyst of the present application has good stability, long service life, is easy to recycle, and is environmentally friendly. BRIEF DESCRIPTION OF DRAWINGS
[0077] In order to make the content of the present application more easily understood, the present application will be further described in detail below according to specific embodiments of the present application and in conjunction with the drawings, in which:
[0078] Figure 1 XPS spectrum of the catalyst of Example 1 of the present application.
[0079] Figure 2 The acetylene conversion rate and ethylene selectivity of the catalyst of Example 1 of the present application in the catalytic hydrogenation of acetylene are plotted against time. DETAILED DESCRIPTION
[0080] The embodiments of the present application will be apparent from the following description of the embodiments, taken in conjunction with the accompanying drawings, which together refer to the following description: in the description, common features are denoted by common reference characters, and there can be only some specific embodiments described which clearly show the principles of the present application. The description of at least one exemplary embodiment is merely intended to illustrate the application in its application or use and by no means to limit the application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the scope of the present application.
[0081] Example 1
[0082] 0.2 g of fullerene C 60 was weighed and added into 100 mL of deionized water under ultrasonic and stirring conditions to obtain a dispersion of fullerene. A 0.5 mol / L sodium carbonate solution was slowly added to the dispersion of fullerene under stirring conditions until the pH value was 10 to obtain a mixture. The above operations were all carried out at room temperature, the power of ultrasonic was 30 W, the stirring speed of each step was 500 r / min, and the stirring time was 30 min.
[0083] The amount of 0.5 mg / mL palladium nitrate solution was calculated according to the 0.1 wt% loading of palladium element relative to the whole catalyst, and then the palladium nitrate solution was added to the mixture, reacted at 100°C in an oil bath and under stirring conditions at a speed of 500 r / min for 2 hours, and then aged at 100°C in an oil bath under static conditions for 1 hour. After ending and cooling to room temperature, the precipitate was obtained by suction filtration, washed with deionized water for 2-3 times, and then dried at 80°C for 12 h. The dried product was ground into powder and continuously transferred to a muffle furnace, heated to 250°C at a rate of 2°C / min in an air atmosphere and calcined for 3 h, and then reduced in a hydrogen gas flow of 50 mL / min at 200°C for 2 h to obtain the catalyst, marked as Pd / C 60 -DP-1.
[0084] Example 2
[0085] The reaction temperature and aging temperature were 120°C, and the rest were the same as in Example 1 to obtain the catalyst, marked as Pd / C 60 -DP-2.
[0086] Example 3
[0087] The reduction treatment is carried out at 240℃, and the rest is the same as in Example 1 to obtain the catalyst, marked as Pd / C 60 - DP-3.
[0088] Example 4
[0089] The amount of 0.5mg / mL palladium nitrate solution is calculated according to the 0.5wt% loading of palladium element relative to the whole catalyst, and then the palladium nitrate solution is added into the mixture, and the rest is the same as in Example 1 to obtain the catalyst, marked as Pd / C 60 - DP-4.
[0090] Example 5
[0091] 0.2g of fullerene C 60 is weighed and added into 100mL of anhydrous ethanol under ultrasonic and stirring conditions to obtain a dispersion solution of fullerene. The above operation is carried out at room temperature, the power of ultrasonic is 30W, the stirring speed is 500r / min, and the stirring time is 30min.
[0092] The amount of 0.5mg / mL palladium nitrate solution is calculated according to the 0.5wt% loading of palladium element relative to the whole catalyst, and then the palladium nitrate solution is added into the mixture, and the rest is the same as in Example 1 to obtain the catalyst, marked as Pd / C 60 - IM-5.
[0093] Example 6
[0094] The reduction treatment is carried out at 240℃, and the rest is the same as in Example 5 to obtain the catalyst, marked as Pd / C 60 - IM-6.
[0095] Comparative Example 1
[0096] The reaction temperature and aging temperature are 50℃, and the rest is the same as in Example 1 to obtain the catalyst, marked as Pd / C 60 - DP-I.
[0097] Comparative Example 2
[0098] The reaction temperature and aging temperature are 200°C, and the rest are the same as in Example 1 to obtain a catalyst, marked as Pd / C 60 -DP-II.
[0099] Comparative Example 3
[0100] The reduction treatment is carried out at 350°C, and the rest are the same as in Example 1 to obtain a catalyst, marked as Pd / C 60 -DP-III.
[0101] Comparative Example 4
[0102] The reduction treatment is carried out at 350°C, and the rest are the same as in Example 5 to obtain a catalyst, marked as Pd / C 60 -IM-IV.
[0103] Comparative Example 5
[0104] The fullerene is replaced by equal mass of α-Al2O3, and the rest are the same as in Example 1 to obtain a catalyst, marked as Pd / α-Al2O3-DP.
[0105] Test Example 1
[0106] 1. Test of Pd dispersion:
[0107] The Micromeritics AutoChem II 2920 instrument is used to determine the dispersion of the metal on the surface of the catalyst by CO pulse adsorption. After the catalyst sample is loaded into the U-shaped tube of the instrument and reduced at 200°C for 2 hours under a hydrogen atmosphere, CO gas is switched in, 1.0 mL is injected each time, and the process is repeated 20 times to obtain the adsorption amount of CO on the surface of Pd (N CO ), and the dispersion of Pd is calculated according to D = N CO *R Pd / CO / N Pd ; wherein N Pd represents the molar amount of Pd atoms in the catalyst, and R Pd / CO represents the stoichiometric ratio of chemical adsorption, which is 1 here.
[0108] 2. Test of the molar ratio of zero-valent Pd to active component:
[0109] The catalyst sample is pressed into a thin sheet, and the Nexsa-type energy spectrometer is used to perform XPS testing under the following conditions: Al K α (hv = 1486.6 eV) is used as the emission source, the ultra-high vacuum is 10-7 Pa, the test voltage is 12 kV, and the beam current is 6 mA. The XPS spectrum of the catalyst of Example 1 is shown in Figure 1The measured XPS spectrum needs to be corrected according to the binding energy (284.6 eV) of carbon C1s, and the analysis result is fitted using XPS Peak software, and the peak area (A) of Pd 3d 5 / 2 of different valence states in the region is calculated according to Pd 0 + Pd 0 + Pd δ+ ) = A(Pd 0 ) / [A(Pd 0 )+A(Pd δ+ )] to calculate the molar ratio of zero-valent palladium in the active component; wherein A(Pd 0 ) represents the peak area of the zero-valent palladium peak in the Pd 3d 5 / 2 region, and A(Pd δ+ ) represents the peak area of the remaining valence state palladium peak in the Pd 3d 5 / 2 region.
[0110] 3. Test of Dv50 particle size:
[0111] The catalyst sample is ultrasonically dispersed in ethanol, dropped into a copper grid with a carbon film, dried under infrared lamp irradiation, and placed in a TEM instrument with a model FEI Tecnai F30 to take pictures, and the obtained TEM image is analyzed for particle size distribution using Nano measure software to obtain the Dv50 particle size.
[0112] The above results are shown in Table 1.
[0113] Table 1 Parameter test results
[0114]
[0115] From the above table, it can be seen that: compared with Comparative Examples 1-3 and 5, the palladium dispersion of the catalyst of the present application Example 1-4 is higher, and the molar ratio of zero-valent palladium in the active component is higher. Compared with Comparative Examples 2-3 and 5, the volume average particle size Dv50 of the catalyst of the present application Example 1-4 is smaller. Compared with Comparative Example 4, the palladium dispersion of the catalyst of the present application Example 5-6 is higher, and the volume average particle size Dv50 is smaller. Compared with Comparative Example 4, the molar ratio of zero-valent palladium in the active component of the catalyst of the present application Example 5 is higher.
[0116] Test Example 2
[0117] The catalyst is added to a fixed bed reactor. The mixed raw material gas is introduced: 1% acetylene, 4-12% hydrogen, argon as balance gas, space velocity 60000 mL·g -1 ·h -1wherein the percentage content is volume percentage, acetylene is catalytically hydrogenated to generate ethylene, the reaction temperature is 120℃, the reaction time is 6h, and the reaction product is detected by gas chromatography analysis. The operation conditions of the gas chromatography are as follows: the chromatographic column is KB-Al2O3; the temperature of the chromatographic column is 200℃; the chromatographic detector is FID, and the temperature is 200℃; the temperature of the sample inlet is 180℃; and the carrier is N2.
[0118] According to the detection results of the reaction product, the acetylene conversion rate and the ethylene selectivity are calculated, and the results are shown in Table 2.
[0119] The catalyst is added into a fixed bed reactor. The mixed raw material gas is introduced, which is 1% acetylene, 4-12% hydrogen, and argon as the balance gas, and the space velocity is 60000 mL·g -1 ·h -1 wherein the percentage content is volume percentage, acetylene is catalytically hydrogenated to generate ethylene, the reaction temperature is 120℃, the reaction time is 100h, sampling is performed once per hour, and the reaction product is detected by gas chromatography analysis, and the operation conditions of the gas chromatography are the same as above. According to the detection results, the acetylene conversion rate and the ethylene selectivity are calculated, and the curve of the acetylene conversion rate and the ethylene selectivity of the catalyst of Example 1 catalyzing acetylene hydrogenation with time is shown in Figure 2 It can be known that the catalyst of the application still has high raw material conversion rate and ethylene selectivity after being used for 100 hours, has good stability, and has long service life.
[0120] Table 2
[0121]
[0122]
[0123] It can be known from the above table that: compared with Comparative Examples 1-2 and 5, the acetylene conversion rate and the ethylene selectivity of the catalyst of Example 1-4 of the application are higher. Compared with Comparative Example 3, the ethylene selectivity of the catalyst of Example 1-4 of the application is higher. Compared with Comparative Example 4, the acetylene conversion rate and the ethylene selectivity of the catalyst of Example 5-6 of the application are higher.
[0124] Obviously, the above examples are only examples for clearly illustrating, and are not limitation to the embodiments. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. All the embodiments do not need to be exhausted, and the obvious changes or variations derived therefrom are still within the protection scope of the application.
Claims
1. A catalyst comprising a fullerene support and an active component supported on the fullerene support, said active component being selected from one or more of palladium and its salts; said active component having a dispersion of 30%–40%.
2. The catalyst according to claim 1, wherein, The active component includes Pd 0 Optionally, the Pd 0 The molar percentage of the active component is 75%–85%.
3. The catalyst according to claim 1 or 2, wherein, The catalyst has a Dv50 particle size of 2–3 nm.
4. The catalyst according to any one of claims 1 to 3, wherein, The active component in the catalyst comprises 0.1%–10% by mass of palladium; and / or, The fullerene is selected from one or more of hollow fullerenes, endogenous fullerenes, and heterocyclic fullerenes; optionally, the fullerene is selected from C 60 C 70 、La@C 82 SiC2@C 60 C 59 One or more of N.
5. A method for preparing a catalyst, comprising the following steps: The fullerene dispersion was mixed with an alkaline solution to obtain a mixture; The raw material containing the active component source is mixed with the mixture, reacted and aged at 60℃–120℃, followed by solid-liquid separation, and the solid phase is collected; wherein, The raw material containing the active component source is selected from one or more of palladium dispersion and palladium salt solution; The solid was dried and calcined to obtain the catalyst.
6. The method according to claim 5, wherein the step of preparing the solid phase is characterized in that... One or more of the following: The reaction time is 2–6 hours; The reaction was carried out under stirring conditions; The reaction was carried out under stirring conditions at a speed of 400–600 r / min; The aging time is 1–2 hours; The aging process is not carried out under stirring conditions.
7. The method according to claim 5 or 6, further comprising: After calcination, the catalyst is subjected to reduction treatment; Optionally, it is characterized by one or more of the following: Reduction treatment was carried out at 150℃–300℃; The reduction process takes 2–6 hours; The reduction process is carried out in a hydrogen atmosphere.
8. The method according to any one of claims 5 to 7, characterized in that... One or more of the following: The alkaline solution was slowly added to the fullerene dispersion and mixed. The pH value of the mixture is 9–10; The mass ratio of palladium in the raw material containing the active component source to fullerene in the fullerene dispersion is 0.001–0.
11. The drying temperature is 60℃–120℃, and the drying time is 10–14 hours; The roasting temperature is 150℃–300℃, and the roasting time is 2–6 hours; Calcination in air atmosphere; The heating rate for the roasting is 1–5 °C / min; Before drying, the solid phase is washed with water; Before roasting, the dried product is crushed into powder; The fullerene dispersion was obtained by mixing fullerene with water under ultrasonic and stirring conditions. The fullerene content in the fullerene dispersion is 1–5 mg / mL; The alkaline solution is selected from one or more of ammonia water, urea solution, sodium carbonate solution, potassium carbonate solution, sodium hydroxide solution, and potassium hydroxide solution; The molar concentration of the alkaline solution is 0.5–1 mol / L; The raw material containing the active component source is added to the mixture and mixed. The mass concentration of the palladium dispersion or palladium salt solution is 0.1–1.2 mg / mL; Solid-liquid separation is achieved through vacuum filtration.
9. A method for preparing a catalyst, comprising the following steps: The fullerene dispersion was mixed with a solution of the active component source and concentrated to obtain the catalyst precursor; wherein... The active component source is selected from one or more palladium salts and organic complexes of palladium; The catalyst precursor was dried and calcined to obtain the catalyst.
10. The method of claim 9, further comprising: After calcination, the catalyst is subjected to reduction treatment; Optionally, it is characterized by one or more of the following: Reduction treatment was carried out at 150℃–300℃; The reduction process takes 2–6 hours; The reduction process is carried out in a hydrogen atmosphere.
11. The method according to claim 9 or 10, characterized in that... One or more of the following: The active component source is selected from one or more of palladium nitrate, palladium acetate, sodium chloropalladium, palladium acetylacetonate, palladium dibenzylidene acetylacetonate, and tetrakis(triphenylphosphine)palladium; Concentrate at 30℃–80℃; The concentration was carried out under stirring conditions; The mass ratio of palladium in the solution of the active component source to fullerene in the fullerene dispersion is 0.001–0.
11. The drying temperature is 60℃–120℃, and the drying time is 10–14 hours; The roasting temperature is 150℃–300℃, and the roasting time is 2–6 hours; Calcination in air atmosphere; The heating rate for the roasting is 1–5 °C / min; Before roasting, the dried product is crushed into powder; The fullerene dispersion was obtained by mixing fullerene with anhydrous ethanol under ultrasonic and stirring conditions. The fullerene content in the fullerene dispersion is 1–5 mg / mL; The mass concentration of the solution of the active component source is 0.1–1.2 mg / mL.
12. The use of the catalyst according to any one of claims 1 to 4 or the catalyst prepared by any one of claims 5 to 11 in the catalytic hydrogenation of acetylene.
13. The application according to claim 12, characterized in that... One or more of the following: The reaction temperature for the hydrogenation of acetylene is 100℃–140℃; The reaction pressure for the hydrogenation of acetylene is atmospheric pressure; The feed gas for acetylene hydrogenation consists of 0.5 vol%–2 vol% acetylene and 4 vol%–12 vol% hydrogen, with the remainder being argon. The space velocity for acetylene hydrogenation is 55,000–65,000 mL·g -1 ·h -1 .