CN111230141B - Preparation method of PtRuCoS alloy nanocrystalline with floccule morphology - Google Patents
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Abstract
The invention relates to a preparation method of a PtRuCoS alloy nanocrystalline with a floccule morphology. The PtRuCoS alloy nano particles with the floccule morphology are prepared by a two-step reduction method by taking chloroplatinic acid, cobalt chloride, sodium sulfite and ruthenium chloride as raw materials and PVP and ethylene glycol as reducing agents as morphology regulating agents. The PtRuCoS alloy nanoparticles with the floc morphology, which are obtained by compounding the ternary metal alloy and S through a two-step reduction method, not only show good butadiene selective hydrogenation performance, but also can avoid passivation treatment before use, and have wide application prospects.
Description
Technical Field
The invention belongs to the field of functional nano-alloy. Specifically, the invention discloses a PtRuCoS alloy nanocrystalline with a floccule morphology prepared by a secondary hydrothermal reduction method.
Background
The noble metal catalyst has the advantages of high activity, large treatment capacity, good catalyst stability, long service life, simple and convenient operation and the like, so the noble metal catalyst is more suitable for selective hydrogenation reaction than other catalysts. However, the catalyst is expensive, and the catalyst activity is too high in the initial stage of the reaction, so that the problems of carbon deposition and temperature runaway of the catalyst are caused. Therefore, the noble metal catalyst needs to be passivated with organic sulfides during the start-up of the hydrogenation process. But usually H is used after loading the catalyst 2 S or organic sulfur is subjected to high-temperature purging, on one hand, gas leakage is easily caused and harms the life safety of human bodies and the environmental pollution, on the other hand, the requirement on start-up operation is higher, the production potential safety hazard is easily caused, and the consumption of energy consumption and human resources is increased, so that the preparation of the nano catalyst with the precious metal Pt and the non-precious metal S alloy has important significance on catalytic hydrogenation reaction.
How to further improve the catalytic activity, stability and catalytic selectivity of the Pt active center of the catalyst has been a major scientific and key technical problem concerned by scientists in the related field. In order to improve the catalytic activity of Pt, previous studies have mainly utilized the synergistic or electronic structure effect of two or more components by forming an alloy; and regulating the appearance of the nanocrystalline to change the atomic arrangement on the surface of the catalyst, and improving the catalytic selectivity of Pt on different reaction systems by utilizing the surface structure effect of catalytic reaction. At present, a solvothermal method is a common synthesis method in the synthesis process of precious metal alloys, and has the advantages of low cost, environmental friendliness, surface cleanness and the like, but because of the great difference between the reduction potentials of different metal salts, a problem for constructing a catalyst with a multi-metal alloy and a non-metal composite alloy is faced by scientists.
The cracking carbon four is mainly used for producing 1, 3-butadiene in industry, and is a byproduct of ethylene production by cracking refinery gas and petroleum hydrocarbons generated in the petroleum refining process. The 1-butene is an important chemical raw material and can be used for producing chemical products with high added values, such as sec-butyl alcohol, methyl ethyl ketone and the like; can also produce C eight and C twelve alpha olefins, and has wide application in the fields of petrochemical industry, fine chemical industry, medicine, pesticide and the like. In the prior art, 1-butene is generally lost in the selective hydrogenation of 1, 3-butadiene to 1-butene, mainly due to the formation of butane and the isomerization of 1-butene to 2-butene, so it is important to develop a catalyst which can hydrogenate 1, 3-butadiene to 1-butene and can prevent the formation of butane by excessive hydrogenation and the isomerization reaction. Most hydrogenation catalysts are noble metal catalysts, and in actual production, people often adopt the mode of inhibiting the generation of green oil by increasing the temperature. However, the consequence of increasing the calcination temperature is not only a decrease in the specific surface of the support, but more importantly a carbonisation of the noble metal catalyst and a severe decrease in the selectivity of the hydrogenation to 1-butene. Therefore, the development of the noble metal and sulfur composite alloy catalyst with high 1-butene selectivity has very important significance.
Disclosure of Invention
Aiming at the technical problems, the invention solves the technical problems that the yield of 1-butene in the traditional catalyst product in the 1, 3-butadiene hydrogenation reaction is low, the existing Pt nano-structured catalyst has poor catalytic selectivity, needs to be vulcanized in the initial application, has high preparation cost and the like, and provides the catalyst capable of improving the yield and the selectivity of the generated 1-butene.
In order to realize the purpose, the invention is realized by the following technical scheme:
the experimental steps of the preparation method of the flocculent PtRuCoS alloy nano catalyst are as follows:
1. mixing 100 μ L of H 2 PtCl 6 (0.1M)、100μL CoCl 2 (0.1M) and 240. Mu.L NaOH (0.2M), 3mL Na 2 SO 3 (0.02M) was added to 4.56mL of deionized water to prepare a growth solution, which was left to age overnight.
2. To the growth solution, 800. Mu.L of deionized water, 1mL of PVP (5 wt%), 200. Mu.L of HCOOH were added under magnetic stirring and stirred for 10min.
3. The solution obtained in step 2) was transferred to a 20mL reaction kettle and placed in an oven at 200 ℃ for 8h.
4. Centrifuging the solution after the reaction in the step 3), and then adding deionized water: ethanol =1, washing 3 times, yielding PtCoS nanowires.
5. Drying the PtCoS obtained in the step 4) in an oven at 80 ℃, and weighing the mass of the obtained PtCoS nanowire.
6.1 mg of the dried PtCoS was dispersed in 6mL of ethylene glycol and subjected to ultrasonic treatment at 40KHZ for 20min, and the PtCoS-EG mixed solution was preheated under magnetic stirring at 55 ℃ for 30min. Then 0.4mL of RuCl was injected with a syringe 3 (5 mM) was slowly added to the PtCoS-EG mixture solution and the water bath was maintained at 55 ℃ for an additional 10h.
(i.e., 1mgPtCoS for 6mL ethylene glycol for 0.4mL RuCl 3 (5 mM) introduction of Ru)
7. Centrifuging the solution after the reaction in the step 6), and reacting with ethanol: acetone =2, 1 washing 2 times, and water washing 2 times, to obtain the PtRuCoS alloy with the floc morphology.
It should be noted that, the invention adopts a two-step method to synthesize the ternary metal alloy and the S composite material, previous research shows that it is relatively difficult to synthesize the ternary metal alloy by a solvothermal method, because the difference of reduction potentials between different metals is large, in the synthesis system of the invention, if a Ru precursor is added into the solution system of the step 1 to synthesize by a one-step method, only PtCoS alloy can be obtained but no flocculent PtRuCoS nano-particles can be obtained, therefore, it is necessary to use PtCoS as a seed crystal to synthesize the ternary alloy of PtRuCo by the secondary reduction of PEG under relatively mild conditions, and it is surprisingly found that with the extension of reaction time, the crystal morphology tends to a pellet morphology, i.e. the distribution of surface elements of the alloy is rearranged, which shows that the gibbs free energy of the alloy surface is reduced as a whole with the extension of reaction time, while for the butadiene hydrogenation reaction, the presence of Ru element makes the catalyst have extremely high selectivity for the hydrogenation of butadiene to form 1-butene, and has important significance for the research on the catalytic hydrogenation mechanism of butadiene.
The invention has the beneficial effects that: the PtRuCoS alloy nano particles with the floccule morphology are prepared by a two-step reduction method by taking chloroplatinic acid, cobalt chloride, sodium sulfite and ruthenium chloride as raw materials and PVP and ethylene glycol as reducing agents as morphology regulating agents. The PtRuCoS alloy nano particles with the floc morphology not only show good butadiene selective hydrogenation performance, but also can avoid passivation treatment before use, and have wide application prospect.
Drawings
FIG. 1 is a TEM spectrum of PtRuCoS alloy nanoparticles prepared in example 1;
FIG. 2 is an XRD pattern of alloy nanoparticles prepared in example 1;
FIG. 3 is a miniature fixed bed apparatus for the selective hydrogenation of 1, 3-butadiene according to the present application;
reference numerals: 1 high-purity nitrogen, 2 butadiene/nitrogen, 3 high-purity hydrogen, 4 two-way ball valves, 5 pressure gauges, 6 stop valves, 7 mass flow meters, 8 three-way valves, 9 mixers, 10 heating furnaces, 11 quartz reaction tubes, 12 temperature controllers with thermocouples, 13 oxidation reaction devices and 14SP6890 gas chromatographs.
Detailed Description
The following examples are intended to illustrate the practice and advantageous effects of the present invention, but are not to be construed as limiting the scope of the present invention.
Example 1
The experimental steps of the preparation method of the PtRuCoS alloy nano catalyst with the floc morphology are as follows:
1) mu.L of H 2 PtCl 6 (0.1M)、100μL CoCl 2 (0.1M) and 240. Mu.L NaOH (0.2M), 3mL Na 2 SO 3 (0.02M) was added to 4.56mL of deionized water to prepare a growth solution, which was left to age overnight.
2) Under magnetic stirring, 800. Mu.L of deionized water, 1mL of PVP (5 wt%), 200. Mu.L of HCOOH were added to the growth solution and stirred for 10min.
3) The solution obtained in step 2) was transferred to a 20mL reaction kettle and placed in an oven at 200 ℃ for 8h.
4) Centrifuging the solution after the reaction in the step 3), and then adding deionized water: ethanol =1, washing 3 times, yielding PtCoS nanowires.
5) Drying the PtCoS obtained in the step 4) in an oven at 80 ℃, and weighing the mass of the obtained PtCoS nanowire.
6) 1mg of the dried PtCoS is dispersed in 6mL of ethylene glycol and subjected to ultrasonic treatment at 40KHZ for 20min, and the PtCoS-EG mixed solution is preheated for 30min at 55 ℃ under magnetic stirring. Then 0.4mL of RuCl was injected with a syringe 3 (5 mM) was slowly added to the PtCoS-EG mixture solution and the water bath was maintained at 55 ℃ for an additional 10h.
(i.e., 1mgPtCoS for 6mL ethylene glycol for 0.4mL RuCl 3 (5 mM) introduction of Ru)
7) Centrifuging the solution after the reaction in the step 6), and reacting with ethanol: acetone =2 washes 1 and 2 washes with water to give a PtRuCoS alloy of floc morphology, as shown in fig. 2 and 3.
The evaluation of the selective hydrogenation of 1, 3-butadiene was carried out on a mini fixed bed continuous flow reactor, a quartz glass tube (inner diameter: 6 mm) was used as a reactor, and a microreaction device was shown in FIG. 3.
Taking 1mg of catalyst>Diluting 100-mesh quartz sand to 460mg, mixing, filling the mixture into the middle part of a quartz glass tube reactor (the height of a catalyst bed layer is about 1 cm), and observing the change of a reaction system pressure gauge and the indicated value of a mass flowmeter by closing a reaction tail gas outlet stop valve to check the tightness of the device. Before reaction, the catalyst is flowed at a certain temperature by N 2 Medium pretreatment for 0.5h at a flow rate of 19.3mlmin -1 . After the pretreatment of the catalyst is finished, resetting the temperature program through the temperature controller, and stopping introducing N 2 The feed gas was changed to 1, 3-butadiene (1.02% by weight)/N 2 ，H 2 ) 1.02% of 1, 3-butadiene/N 2 And H 2 The flow rates were 7.8ml min, respectively -1 And 5.7ml min -1 。
Samples after the reaction were collected and tested on-line by gas chromatography (SP 6890, FID detector, packed column 3 mm. Times.4m, GDX-501 adsorbent). Nitrogen is used as carrier gas, the temperature of the column chamber is 80 ℃, the temperature of the detection chamber is 160 ℃, and the temperature of the gasification chamber is 180 ℃. The hydrogenation of 1, 3-butadiene produced a mixed product of 1-butene, 2-butene, and n-butane, 1-butene produced 1, 3-butadiene by 1, 2-addition, butene produced 1, 4-addition, and both 1-butene and 2-butene further hydrogenated to n-butane, and the analytical data of the product are shown in Table 1.
According to the data in table 1, the catalyst PtRuCoS with floc morphology was catalytically reacted at 25 ℃, the butadiene conversion was only 5.1%, the selectivity to 1-butene in the product was 45.6%, the selectivity to 2-butene was 54.4%, when the reaction temperature was increased to 40 ℃, the butadiene conversion was 30%, the selectivity to 1-butene in the product was 52.1%, the selectivity to 2-butene was 39.6%, and a portion of the product was n-butane; the reaction temperature was further increased to 60 c to achieve 87.4% butadiene conversion with 73.7% selectivity to 1-butene, 12.5% selectivity to 2-butene and 13.8% selectivity to butane in the product, whereas at 70 c the butadiene hydroconversion was 100% with no 2-butene in the product and the majority of the product was butane. It can be seen that the hydrogenation is continuously advanced with the increase of the reaction temperature.
TABLE 1 hydrogenation of 1, 3-butadiene with catalyst PtRuCoS of floc morphology
Comparative example 2
On the basis of example 1, the PtCoS ternary alloy with nanowire morphology obtained in step 4 is subjected to the same experimental conditions as in example 1, and the prepared catalyst has the conversion rate of 1, 3-butadiene and the selectivity of hydrogenation products as shown in table 2:
according to the data in Table 2, the nano wire catalyst PtCoS was catalytically reacted at 25 ℃ with a butadiene conversion of only 4.9%, a 1-butene selectivity of 23.7% and a 2-butene selectivity of 76.3% in the product, a butadiene conversion of 31.1% when the reaction temperature was increased to 40 ℃, a 1-butene selectivity of 28.6% and a 2-butene selectivity of 56.1% in the product, and a portion of the product was n-butane; the reaction temperature was further increased to 60 ℃ to achieve 80.9% butadiene conversion with an increase in selectivity to 1-butene of 39.8%, 2-butene of 38.5% and butane of 21.7% in the product, whereas at a reaction temperature of 70 ℃ the butadiene hydroconversion was 100% and the majority of the product was butane.
TABLE 2 butadiene hydrogenation of PtCoS catalysts in nanowire form
Comparative example 3
On the basis of example 1, no precursor Na was added 2 SO 3 And the obtained nanocrystal is PtRuCo ternary alloy. The PtRuCo ternary alloy catalyst obtained was subjected to the same experimental conditions as in example 1 and the catalysts prepared were shown in table 3 for butadiene conversion and hydrogenation product selectivity:
TABLE 3 CAL hydrogenation of PtCo catalyst
According to the data in Table 3, the catalyst PtRuCo hydrogenated at 25 ℃ to achieve 78.6% butadiene conversion but with a 1-butene selectivity of 12.4% and a 2-butene selectivity of only 1.9%, with almost complete conversion of butadiene to n-butane as the reaction temperature was increased to 40 ℃.
The three catalysts are found in the comparison examination of the performance of the 1, 3-butadiene selective hydrogenation, and due to the existence of S in the alloy, the expected hydrogenation intermediate product can be obtained without carrying out sulfidation treatment when the noble metal reacts on the hydrogenation. In contrast, the addition of the element Ru has high selectivity to 1-butene.
Claims (2)
1. A preparation method of a PtRuCoS alloy nanocrystalline with a floccule morphology is characterized in that the experimental steps of the preparation method of the PtRuCoS alloy nanocrystalline with the floccule morphology are as follows:
1) mu.L of H 2 PtCl 6 (0.1M)、100μL CoCl 2 (0.1M) and 240. Mu.L NaOH (0.2M), 3mL Na 2 SO 3 (0.02M) was added to 4.56mL of deionized water to prepare a growth solution, which was left to stand and aged overnight;
2) Under magnetic stirring, 800 μ L of deionized water, 1mL of PVP (5 wt%), 200 μ L of HCOOH were added to the growth solution, and stirred for 10min;
3) Transferring the solution obtained in the step 2) into a 20mL reaction kettle, and placing the reaction kettle in an oven to keep the temperature at 200 ℃ for 8 hours;
4) Centrifuging the solution after the reaction in the step 3), and then adding deionized water: washing 3 times with ethanol =1 to obtain PtCoS nanowires;
5) Drying the PtCoS obtained in the step 4) in an oven at 80 ℃, and weighing the mass of the obtained PtCoS nanowire;
6) Taking 1mg to obtain PtCoS after drying, dispersing in 6mL of glycol, performing ultrasonic treatment at 40KHZ for 20min, and preheating the PtCoS-glycol mixed solution at 55 ℃ for 30min under magnetic stirring; then 0.4mL of RuCl was injected with a syringe 3 (5 mM) slowly adding the PtCoS-glycol mixed solution, and continuously keeping the temperature of the water bath at 55 ℃ for 10 hours;
7) Centrifuging the solution after the reaction in the step 6), and reacting with ethanol: acetone =2 washes 1 and 2 washes with water to obtain a flocculus morphology PtRuCoS alloy.
2. PtRuCoS alloy nanocrystalline with a floccule morphology obtained according to the preparation method of claim 1.
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| CN110380068A (en) * | 2019-05-15 | 2019-10-25 | 济南大学 | A kind of implementation method improving methanol fuel cell electrooxidation activity and stability using PtCuNi alloy |
| CN110534756A (en) * | 2019-09-09 | 2019-12-03 | 济南大学 | A kind of preparation method optimizing porous complicated and confused shape Pt-Ru-Ni alloy nanoparticle performance |
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| JP2012157863A (en) * | 2004-10-29 | 2012-08-23 | Umicore Ag & Co Kg | Method for manufacturing of noble metal alloy catalyst and catalyst prepared therewith |
| CN102553581A (en) * | 2012-01-13 | 2012-07-11 | 北京化工大学 | Active component morphology controllable loaded noble metal catalyst and preparation method thereof |
| CN107845816A (en) * | 2017-10-23 | 2018-03-27 | 济南大学 | A kind of coarse shape of octahedron PtCoFe alloy particles and preparation method thereof |
| CN107845817A (en) * | 2017-10-23 | 2018-03-27 | 济南大学 | A kind of method using coarse shape of octahedron PtCoFe nanocatalysts catalysis oxidation formic acid electrochemistry |
| CN108767282A (en) * | 2018-06-27 | 2018-11-06 | 济南大学 | A kind of preparation method of the Pt-Ni-Cu alloy nanoparticles of porous multiple-limb |
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| CN110534756A (en) * | 2019-09-09 | 2019-12-03 | 济南大学 | A kind of preparation method optimizing porous complicated and confused shape Pt-Ru-Ni alloy nanoparticle performance |
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