CN110560086A - High-dispersion palladium-sulfur-doped active carbon catalyst and preparation and application thereof - Google Patents
High-dispersion palladium-sulfur-doped active carbon catalyst and preparation and application thereof Download PDFInfo
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
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- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
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Abstract
The invention provides a high-dispersion palladium-sulfur-doped activated carbon catalyst, a preparation method and application thereof, the preparation method adopts a method of firstly carrying out hydrothermal and then roasting to carry out sulfur doping, and the method can ensure that the doped sulfur exists on the surface of a carbon material more stably; the method for loading noble metal by the dipping method is simple and convenient and has low cost; in the high-dispersion palladium-sulfur-doped activated carbon catalyst, the doped sulfur on the surface of the carrier plays a role in anchoring, so that the high dispersion and size regulation of palladium nanoparticles can be realized, and the atom utilization rate of noble metal is effectively improved; the strong interaction between sulfur and metal ensures the high stability of the catalyst, so that the metal nano particles are not easy to agglomerate and run off in the acetylene hydrogenation reaction process, and the service life of the catalyst is prolonged; the catalyst has high selectivity to ethylene in the acetylene hydrogenation reaction, can completely convert acetylene, and has the advantages of mild use condition, good stability, small catalyst consumption and long service life.
Description
(I) technical field
The invention relates to a high-dispersion palladium-sulfur-doped active carbon catalyst, a preparation method thereof and application thereof in reaction for preparing ethylene by selective hydrogenation of acetylene.
(II) background of the invention
Ethylene is an important industrial organic synthetic raw material, and is mainly used for producing polyethylene, polyvinyl chloride, ethylene oxide, ethanol, acetaldehyde and the like on a large scale. Because of its wide use, ethylene has a great production demand in industry. Ethylene is mainly derived from the cracking of naphtha, and a byproduct acetylene is inevitably generated in the process, and low polymers formed by the polymerization of the acetylene have serious poisoning effect on a downstream ethylene polymerization catalyst. Commercial ethylene feed gas often contains 1% acetylene. Thus, the selective removal of small amounts of residual acetylene from ethylene streams is one of the important processes in the chemical industry, which requires that the feed gas be removed to below 5 ppm. Pd is widely applied to acetylene hydrogenation selective hydrogenation reaction as a high-activity noble metal, but has the problems of low ethylene selectivity, easy excessive hydrogenation and the like. Therefore, finding an effective means for modifying the Pd catalyst and improving the selectivity of ethylene has great significance for industrial production.
disclosure of the invention
The invention relates to a high-dispersion palladium-sulfur-doped active carbon catalyst, a preparation method thereof and application thereof in reaction for preparing ethylene by selective hydrogenation of acetylene. The method disclosed by the invention is simple to operate, generates less pollution, effectively enables the Pd metal to be highly dispersed on the surface of the carrier, improves the atom utilization rate of the noble metal, and is beneficial to industrial application.
The catalyst prepared by the invention can efficiently selectively convert a small amount of acetylene in ethylene airflow into ethylene, and has the advantages of high catalyst activity, good selectivity and stability, repeated recycling and the like.
The technical scheme of the invention is as follows:
a high-dispersion palladium-sulfur-doped active carbon catalyst is prepared by the following method:
(1) Preparing sulfur-doped activated carbon: dissolving a sulfur-containing precursor in deionized water, adding activated carbon, stirring and mixing uniformly at 40-80 ℃ at the speed of 300-1000 r/min, heating to 180-300 ℃ for hydrothermal for 10-40 h, cooling to room temperature (20-30 ℃), filtering, vacuum drying a filter cake at 40-80 ℃ for 8-15 h, heating the dried solid to 400-800 ℃ in an inert gas atmosphere, and roasting for 2-8 h to obtain sulfur-doped activated carbon;
The mass ratio of the sulfur-containing precursor to the activated carbon in terms of sulfur element is 0.01-0.1: 1, preferably 0.03 to 0.08: 1;
the sulfur-containing precursor is Na2S、K2one or a mixture of more than two of S, NaHS and KHS in any proportion;
the particle size of the activated carbon is 100-1000 meshes, preferably 200-800 meshes, and the specific surface area is 600-2000 m2A concentration of 1000 to 1800m is preferred2The pore volume is 0.3-0.8 mL/g, preferably 0.4-0.7 mL/g;
The inert gas is N2he or Ar;
(2) Loading of noble metal: uniformly mixing the obtained sulfur-doped active carbon and a noble metal compound solution by adopting an isometric impregnation method, standing for 6-12H, drying in vacuum at 40-80 ℃ for 12-20H, and then carrying out H2Reducing for 1-3 h at 50-200 ℃ in the atmosphere to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst;
The noble metal compound solution is prepared by dissolving a noble metal compound in a solvent; the invention has no special requirements on the concentration of the noble metal compound solution, and the technical personnel in the field can carry out conventional preparation according to the actual needs; the noble metal compound is chloropalladic acid, sodium chloropalladate or palladium acetate, preferably chloropalladic acid; the solvent can be deionized water, ethanol, 10-36 wt% HCl aqueous solution and the like, and the invention has no special requirement on the solvent; meanwhile, by adopting an isometric impregnation method, the noble metal can be considered to be fully loaded;
In the obtained catalyst, the noble metal (Pd) is supported in an amount of 0.01 to 0.15 wt%, preferably 0.05 to 0.1 wt%, based on the mass of the carrier.
The high-dispersion palladium-sulfur-doped active carbon catalyst prepared by the invention can be applied to the selective hydrogenation reaction of a small amount of acetylene in ethylene.
Before reaction evaluation, the catalyst is firstly put in H2reducing for 1-4 h at 50-200 ℃ in the atmosphere; the reaction conditions are as follows: the temperature is 60-180 ℃ (preferably 80-120 ℃), the pressure is 0.1-1 MPa, and the airspeed is 1000-15000 h-1(preferably 4000 to 8000 h)-1) The initial gas composition of the reaction is (volume fraction): 0.33% C2H2、0.66％H2、33.3％C2H4The balance N2。
Compared with the prior art, the invention has the following advantages:
(1) According to the preparation method of the high-dispersion palladium-sulfur-doped active carbon catalyst, sulfur is doped by a method of firstly carrying out hydrothermal treatment and then carrying out roasting, and the method can enable the doped sulfur to exist on the surface of a carbon material more stably; the method for loading noble metal by the dipping method is simple and convenient and has low cost;
(2) In the high-dispersion palladium-sulfur-doped activated carbon catalyst, the doped sulfur on the surface of the carrier plays a role in anchoring, so that the high dispersion and size regulation of palladium nanoparticles can be realized, and the atom utilization rate of noble metal is effectively improved; the strong interaction between sulfur and metal ensures the high stability of the catalyst, so that the metal nano particles are not easy to agglomerate and run off in the acetylene hydrogenation reaction process, and the service life of the catalyst is prolonged;
(3) The catalyst has high selectivity to ethylene in the acetylene hydrogenation reaction, and the acetylene can be completely converted;
(4) The catalyst of the invention has mild use condition, good stability, less catalyst consumption and long service life.
(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.
The first embodiment is as follows:
weighing Na2S·9H2o3.8218 g is dissolved in 50mL deionized water, mixed with 5g activated carbon uniformly, and magnetically stirred in a water bath at 40 ℃ for 60min at a stirring speed of 1000 r/min. Then transferring the mixture to a high-pressure hydrothermal reaction kettle for hydrothermal treatment for 40h at 180 ℃; cooling to room temperature, filtering, vacuum-filtering to obtain filter cake, vacuum-drying at 80 deg.C for 8 hr, and transferring to quartz boat. Placing the quartz boat in a tube furnace in N2raising the temperature to 800 ℃ at a heating rate of 3 ℃/min in the atmosphere, and maintaining the temperature for 2 hours. And taking out the carbon after cooling to room temperature to obtain the sulfur-doped activated carbon. And spreading 1g of the sulfur-doped activated carbon in a watch glass, dropwise adding a chloropalladate solution according to the loading amount of 0.1 wt% until the carrier is just wetted, and slightly stirring. Standing the catalyst uniformly wetted by the chloropalladate solution for 12h, and then drying the catalyst in vacuum at 80 ℃ for 12h to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst.
Example two:
Weighing Na2S·9H2O3.0580 g is dissolved in 50mL deionized water, mixed with 5g activated carbon uniformly, and magnetically stirred in a water bath at 60 ℃ for 40min at a stirring speed of 600 r/min. Then transferring the mixture to a high-pressure hydrothermal reaction kettle for hydrothermal treatment for 30 hours at the temperature of 250 ℃; cooling to room temperature, filtering, vacuum-filtering to obtain filter cake, vacuum-drying at 60 deg.C for 10 hr, and transferring to quartz boat. The quartz boat is placed in a tube type heating furnace, and is heated to 700 ℃ at the heating rate of 3 ℃/min under the He atmosphere, and is maintained for 3 h. And taking out the carbon after cooling to room temperature to obtain the sulfur-doped activated carbon. And spreading 1g of the sulfur-doped activated carbon in a watch glass, dropwise adding a palladium acetate solution according to the loading amount of 0.08 wt% until the carrier is just wetted, and slightly stirring. The catalyst uniformly wetted by the chloropalladate solution is allowed to standafter standing for 10h, drying for 15h under vacuum at 60 ℃ to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst.
Example three:
weighing Na2S·9H2O1.9123 g is dissolved in 50mL deionized water, mixed with 5g activated carbon uniformly, and magnetically stirred in a water bath at 80 ℃ for 50min at a stirring speed of 300 r/min. Then transferring the mixture to a high-pressure hydrothermal reaction kettle for hydrothermal treatment at 200 ℃ for 24 hours; cooling to room temperature, filtering, vacuum-filtering to obtain filter cake, vacuum-drying at 50 deg.C for 12 hr, and transferring to quartz boat. The quartz boat is placed in a tube type heating furnace, and is heated to 600 ℃ at the heating rate of 3 ℃/min under the Ar atmosphere, and the temperature is maintained for 4 h. And taking out the carbon after cooling to room temperature to obtain the sulfur-doped activated carbon. And spreading 1g of the sulfur-doped activated carbon in a watch glass, dropwise adding a chloropalladate solution according to the loading amount of 0.05 wt% until the carrier is just wetted, and slightly stirring. Standing the catalyst uniformly wetted by the chloropalladate solution for 8h, and then drying the catalyst in vacuum at 40 ℃ for 20h to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst.
Example four:
weighing Na2S·9H2o1.1469 g is dissolved in 50mL deionized water, mixed with 5g activated carbon uniformly, and magnetically stirred in a water bath at 60 ℃ for 30min at a stirring speed of 800 r/min. Then transferring the mixture to a high-pressure hydrothermal reaction kettle for hydrothermal treatment at 300 ℃ for 20 hours; cooling to room temperature, filtering, vacuum-filtering to obtain filter cake, vacuum-drying at 40 deg.C for 15 hr, and transferring to quartz boat. Placing the quartz boat in a tube furnace in N2Raising the temperature to 500 ℃ at a heating rate of 3 ℃/min in the atmosphere, and maintaining the temperature for 6 hours. And taking out the carbon after cooling to room temperature to obtain the sulfur-doped activated carbon. Then, 1g of the sulfur-doped activated carbon was spread in a petri dish, and a palladium nitrate solution was added dropwise to the petri dish at a loading amount of 0.03 wt% until just wet, followed by slight stirring. Standing the catalyst uniformly wetted by the chloropalladate solution for 6h, and then drying the catalyst in vacuum at 80 ℃ for 12h to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst.
Example five:
weighing Na2S·9H2dissolving O0.3827 g in 50mL deionized water, mixing with 5g activated carbon uniformly at 50 deg.CThe mixture was magnetically stirred in a water bath at a stirring rate of 600r/min for 60 min. Then transferring the mixture to a high-pressure hydrothermal reaction kettle for hydrothermal treatment for 22 hours at 220 ℃; cooling to room temperature, filtering, vacuum-filtering to obtain filter cake, vacuum-drying at 80 deg.C for 8 hr, and transferring to quartz boat. The quartz boat is placed in a tube type heating furnace, and is heated to 400 ℃ at the heating rate of 3 ℃/min under the Ar atmosphere, and the temperature is maintained for 8 hours. And taking out the carbon after cooling to room temperature to obtain the sulfur-doped activated carbon. Then, 1g of the sulfur-doped activated carbon was spread in a petri dish, and a chloropalladate solution was added dropwise to a capacity of 0.01 wt% until just wet, with slight stirring. Standing the catalyst uniformly wetted by the chloropalladate solution for 12h, and then drying the catalyst in vacuum at 70 ℃ for 14h to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst.
example six:
weighing K2s1.7688 g is dissolved in 50mL deionized water, and is mixed with 5g of active carbon uniformly, and is magnetically stirred for 50min in a water bath at the temperature of 80 ℃ at the stirring speed of 300 r/min. Then transferring the mixture to a high-pressure hydrothermal reaction kettle for hydrothermal treatment at 200 ℃ for 24 hours; cooling to room temperature, filtering, vacuum-filtering to obtain filter cake, vacuum-drying at 50 deg.C for 12 hr, and transferring to quartz boat. The quartz boat is placed in a tube type heating furnace, and is heated to 600 ℃ at the heating rate of 3 ℃/min under the Ar atmosphere, and the temperature is maintained for 4 h. And taking out the carbon after cooling to room temperature to obtain the sulfur-doped activated carbon. And spreading 1g of the sulfur-doped activated carbon in a watch glass, dropwise adding a chloropalladate solution according to the loading amount of 0.05 wt% until the carrier is just wetted, and slightly stirring. Standing the catalyst uniformly wetted by the chloropalladate solution for 8h, and then drying the catalyst in vacuum at 40 ℃ for 20h to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst.
Example seven:
0.8924g of NaHS is weighed and dissolved in 50mL of deionized water, and the solution is uniformly mixed with 5g of activated carbon and magnetically stirred for 60min in a water bath at the temperature of 40 ℃ at the stirring speed of 1000 r/min. Then transferring the mixture to a high-pressure hydrothermal reaction kettle for hydrothermal treatment for 40h at 180 ℃; cooling to room temperature, filtering, vacuum-filtering to obtain filter cake, vacuum-drying at 80 deg.C for 8 hr, and transferring to quartz boat. The quartz boat is placed in a tube type heating furnace, and is heated to 800 ℃ at the heating rate of 3 ℃/min under the atmosphere of N2, and the temperature is maintained for 2 h. And taking out the carbon after cooling to room temperature to obtain the sulfur-doped activated carbon. Then, 1g of the sulfur-doped activated carbon was spread on a petri dish, and a chloropalladate solution (Pd content not 0.01g/mL) was added dropwise in an amount of 0.1 wt%, followed by slight stirring. Standing the catalyst uniformly wetted by the chloropalladate solution for 12h, and then drying the catalyst in vacuum at 80 ℃ for 12h to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst.
Example eight:
1.1499g of KHS is weighed and dissolved in 50mL of deionized water, and is mixed with 5g of activated carbon uniformly, and is magnetically stirred for 60min in a water bath at 40 ℃ at the stirring speed of 1000 r/min. Then transferring the mixture to a high-pressure hydrothermal reaction kettle for hydrothermal treatment for 40h at 180 ℃; cooling to room temperature, filtering, vacuum-filtering to obtain filter cake, vacuum-drying at 80 deg.C for 8 hr, and transferring to quartz boat. The quartz boat is placed in a tube type heating furnace, and is heated to 800 ℃ at the heating rate of 3 ℃/min under the atmosphere of N2, and the temperature is maintained for 2 h. And taking out the carbon after cooling to room temperature to obtain the sulfur-doped activated carbon. Then, 1g of the sulfur-doped activated carbon was spread on a petri dish, and a chloropalladate solution (Pd content not 0.01g/mL) was added dropwise in an amount of 0.1 wt%, followed by slight stirring. Standing the catalyst uniformly wetted by the chloropalladate solution for 12h, and then drying the catalyst in vacuum at 80 ℃ for 12h to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst.
Example nine:
referring to example eight, the loading of palladium was varied to 0.15 wt%, and other conditions were unchanged.
Example ten:
Referring to example eight, the loading of palladium was varied to 0.12 wt%, and other conditions were unchanged.
example eleven:
referring to example eight, the loading of palladium was varied to 0.08 wt%, and other conditions were unchanged.
example twelve:
Referring to example eight, the loading of palladium was varied to 0.06 wt%, and other conditions were unchanged.
Example thirteen:
referring to example eight, the loading of palladium was varied to 0.04 wt%, and other conditions were unchanged.
Example fourteen:
Referring to example eight, the loading of palladium was varied to 0.02 wt%, and other conditions were unchanged.
Examples fifteen to nineteen:
Fifteen to nineteenth examples examine the influence of highly dispersed palladium-sulfur-doped activated carbon catalysts prepared with different sulfur doping amounts on the acetylene hydrogenation performance, and the evaluation data of the catalysts are shown in table 1.
The activity of the catalyst for acetylene selective hydrogenation reaction is evaluated according to the following method:
0.3g of catalyst is placed in a small quartz tube reactor, the quartz tube is placed in a heating jacket with controllable temperature, and the catalyst is in pure H before 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 completion of the reduction, the reaction was carried out at the temperature shown in Table 1. The reaction gas composition (volume fraction): 0.33 percent of acetylene, 0.66 percent of hydrogen, 33.3 percent of ethylene and the balance of nitrogen, the flow rate of reaction gas is 50mL/min, the reaction pressure is normal pressure, and the outlet of the reaction gas is connected with a gas chromatography for on-line detection.
TABLE 1 acetylene hydrogenation Performance of highly dispersed Palladium-Sulfur doped activated carbon with different Sulfur doping levels
| Examples | Catalyst and process for preparing same | Reaction temperature (. degree.C.) | conversion (%) | Selectivity (%) |
| 15 | Example one | 100 | 89.9 | 94.6 |
| 16 | Example two | 100 | 96.9 | 88.2 |
| 17 | EXAMPLE III | 100 | 99.3 | 83.5 |
| 18 | example four | 100 | 99.8 | 80.9 |
| 19 | EXAMPLE five | 100 | 98.9 | 78.4 |
Examples twenty to twenty-three:
the performance of the high-dispersion palladium-sulfur-doped activated carbon catalyst prepared by doping different sulfur precursors in the selective hydrogenation reaction of acetylene is examined in the twenty-third to twenty-third examples, and the evaluation method is the same as that in the fifteen third example.
TABLE 2 Performance of highly dispersed Pd-S-doped activated carbon catalysts prepared by doping different S precursors in the selective hydrogenation of acetylene
| Examples | catalyst and process for preparing same | Conversion (%) | selectivity (%) |
| 20 | EXAMPLE III | 99.8 | 83.5 |
| 21 | EXAMPLE six | 99.2 | 82.1 |
| 22 | EXAMPLE seven | 99.4 | 81.4 |
| 23 | example eight | 98.7 | 83.8 |
examples twenty-four to thirty:
Twenty-four to thirty examples examine the performance of highly dispersed palladium-sulfur-doped activated carbon catalysts with different palladium loading amounts in the selective hydrogenation reaction of acetylene, and the evaluation method is the same as that of the fifteen example.
TABLE 3 catalytic Performance of highly dispersed Palladium-Sulfur doped activated carbon catalysts of different Palladium loadings in acetylene Selective hydrogenation reaction
examples thirty-one to thirty-eight:
Examples thirty-one to thirty-eight examine the selective hydrogenation performance of highly dispersed palladium-sulfur-doped activated carbon catalysts for acetylene at different temperatures. The catalyst activity and selectivity were evaluated as above, only by changing the reaction temperature, and the catalyst evaluation results are shown in Table 4 below.
TABLE 4 Selective hydrogenation performance of palladium supported on in-situ sulfur-doped carbon material for acetylene at different temperatures
| Examples | Catalyst and process for preparing same | Reaction temperature (. degree.C.) | Conversion (%) | selectivity (%) |
| 31 | EXAMPLE seven | 50 | 60.9 | 93.3 |
| 32 | EXAMPLE seven | 60 | 79.4 | 92.0 |
| 33 | EXAMPLE seven | 80 | 92.8 | 85.1 |
| 34 | EXAMPLE seven | 100 | 99.2 | 80.7 |
| 35 | EXAMPLE seven | 120 | 98.9 | 81.9 |
| 36 | EXAMPLE seven | 140 | 99.9 | 79.8 |
| 37 | EXAMPLE seven | 160 | 99.3 | 78.3 |
| 38 | EXAMPLE seven | 180 | 99.7 | 70.3 |
Comparative example one:
The preparation method of the sulfur-free activated carbon supported palladium catalyst comprises the following steps:
then, 1g of the activated carbon was spread in a petri dish, and a chloropalladate solution was added dropwise at a loading of 0.05 wt% until the activated carbon was just wet, with slight stirring. And standing the catalyst uniformly wetted by the chloropalladate solution for 12h, and then drying the catalyst in vacuum at 80 ℃ for 12h to obtain the high-dispersion palladium-activated carbon catalyst.
The obtained catalyst has the same acetylene hydrogenation evaluation method, and acetylene is completely converted into ethane in the reaction.
Comparative example two:
Weighing Na2S·9H2O1.9106 g is dissolved in 50mL deionized water, mixed with 5g activated carbon uniformly, and magnetically stirred in a water bath at 40 ℃ for 60min at a stirring speed of 1000 r/min. Then transferring the mixture to a high-pressure hydrothermal reaction kettle for hydrothermal treatment for 40h at 180 ℃; cooling to room temperature, filtering, performing suction filtration to obtain a filter cake, and performing vacuum drying at 80 ℃ for 8h to obtain the sulfur-doped activated carbon. And spreading 1g of the sulfur-doped activated carbon in a watch glass, dropwise adding a chloropalladate solution according to the loading amount of 0.05 wt% until the carrier is just wetted, and slightly stirring. Standing the catalyst uniformly wetted by the chloropalladate solution for 12h, and then drying the catalyst in vacuum at 80 ℃ for 12h to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst.
The acetylene hydrogenation evaluation method of the obtained catalyst is the same as that of the catalyst, the reaction temperature is 80 ℃, the acetylene conversion rate is 99.9 percent, and the ethylene selectivity is 30.7 percent.
Comparative example three:
KHS 1.1499g was weighed out and mixed with 5g of activated carbon uniformly and transferred to a quartz boat. Placing the quartz boat in a tube furnace in N2in the atmosphere, the temperature is increased to 6 ℃ at the heating rate of 3 ℃/minMaintaining the temperature at 00 ℃ for 3 h. And taking out the carbon after cooling to room temperature to obtain the sulfur-doped activated carbon. Then, 1g of the sulfur-doped activated carbon was spread on a petri dish, and a chloropalladate solution (Pd content not 0.01g/mL) was added dropwise in an amount of 0.05 wt%, followed by slight stirring. Standing the catalyst uniformly wetted by the chloropalladate solution for 12h, and then drying the catalyst in vacuum at 80 ℃ for 12h to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst.
The acetylene hydrogenation evaluation method of the obtained catalyst is the same as that of the catalyst, the reaction temperature is 80 ℃, the acetylene conversion rate is 99.9 percent, and the ethylene selectivity is 41.2 percent.
Claims (5)
1. A high-dispersion palladium-sulfur-doped active carbon catalyst is characterized by being prepared by the following method:
(1) Preparing sulfur-doped activated carbon: dissolving a sulfur-containing precursor in deionized water, adding activated carbon, stirring and mixing uniformly at 40-80 ℃ at the speed of 300-1000 r/min, heating to 180-300 ℃ for hydrothermal for 10-40 h, cooling to room temperature, filtering, drying a filter cake at 40-80 ℃ for 8-15 h in vacuum, heating the dried solid to 400-800 ℃ in an inert gas atmosphere, and roasting for 2-8 h to obtain sulfur-doped activated carbon;
The mass ratio of the sulfur-containing precursor to the activated carbon in terms of sulfur element is 0.01-0.1: 1;
The sulfur-containing precursor is Na2S、K2One or a mixture of more than two of S, NaHS and KHS in any proportion;
(2) Loading of noble metal: uniformly mixing the obtained sulfur-doped active carbon and a noble metal compound solution by adopting an isometric impregnation method, standing for 6-12H, drying in vacuum at 40-80 ℃ for 12-20H, and then carrying out H2Reducing for 1-3 h at 50-200 ℃ in the atmosphere to obtain the high-dispersion palladium-sulfur-doped active carbon catalyst;
The noble metal compound solution is prepared by dissolving a noble metal compound in a solvent; the noble metal compound is chloropalladate, sodium chloropalladate or palladium acetate.
2. The highly dispersed palladium-sulfur-doped activated carbon catalyst according to claim 1, wherein in the step (1), the mass ratio of the sulfur-containing precursor to the activated carbon is 0.03-0.08 in terms of elemental sulfur: 1.
3. The highly dispersed palladium-sulfur doped activated carbon catalyst of claim 1 wherein the resulting catalyst has a noble metal Pd loading of 0.01 to 0.15 wt% based on the mass of the support.
4. Use of the highly dispersed palladium-sulfur-doped activated carbon catalyst of claim 1 in the selective hydrogenation of acetylene.
5. The application of claim 4, wherein the method of applying is:
before reaction, the catalyst is firstly added in H2Reducing for 1-4 h at 50-200 ℃ in the atmosphere; the reaction conditions are as follows: the temperature is 60-180 ℃, the pressure is 0.1-1 MPa, and the airspeed is 1000-15000 h-1the initial gas composition of the reaction is (volume fraction): 0.33% C2H2、0.66％H2、33.3％C2H4The balance N2。
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| CN115445636A (en) * | 2021-06-08 | 2022-12-09 | 中国科学院大连化学物理研究所 | Monoatomic dispersed palladium-based catalyst, and preparation method and application thereof |
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| CN115445636A (en) * | 2021-06-08 | 2022-12-09 | 中国科学院大连化学物理研究所 | Monoatomic dispersed palladium-based catalyst, and preparation method and application thereof |
| WO2022257025A1 (en) * | 2021-06-08 | 2022-12-15 | 中国科学院大连化学物理研究所 | Monatomically dispersed palladium-based catalyst, preparation method therefor and application thereof |
| CN115445636B (en) * | 2021-06-08 | 2023-12-12 | 中国科学院大连化学物理研究所 | Monoatomic dispersed palladium-based catalyst and preparation method and application thereof |
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Application publication date: 20191213 |