WO2018192559A1 - 负载型高选择性核壳结构双金属催化剂及其制备方法和应用 - Google Patents

负载型高选择性核壳结构双金属催化剂及其制备方法和应用 Download PDF

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WO2018192559A1
WO2018192559A1 PCT/CN2018/083832 CN2018083832W WO2018192559A1 WO 2018192559 A1 WO2018192559 A1 WO 2018192559A1 CN 2018083832 W CN2018083832 W CN 2018083832W WO 2018192559 A1 WO2018192559 A1 WO 2018192559A1
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metal
core
catalyst
shell
platinum
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French (fr)
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巩金龙
蔡伟亭
慕仁涛
曾亮
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Tianjin University
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J37/06—Washing
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    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a preparation method and application of a highly selective propane dehydrogenation propylene catalyst, in particular to a PtFe@Pt core-shell catalyst supported on a SBA-15 carrier, a preparation method thereof and a propane The effect of dehydrogenation to propylene on propylene selectivity.
  • Bimetallics exhibit excellent catalytic performance over many catalytic reactions compared to single metal catalysts. By adjusting the structure, composition and morphology of the bimetallic catalyst, the stability, activity and selectivity of the catalyst can be greatly improved. Designing and synthesizing bimetallic catalysts with special structures and compositions is one of the effective ways to improve the catalytic performance.
  • Metal Pt has a wide range of applications in many catalytic reactions due to its excellent catalytic properties. However, due to the expensive price of Pt metal, the reduction of Pt has become an urgent problem to be solved. Therefore, by adding other metals, the metal Pt is modified on the one hand, and the Pt reduction can be achieved on the other hand.
  • the synthetic sub-surface layer has a special sandwich structure of Ni, which can improve the catalytic oxidation reaction activity of carbon monoxide.
  • propylene can be used to synthesize chemical products such as acrylonitrile, polypropylene and propylene oxide. Due to the high energy consumption, low selectivity, and shortage of petroleum resources in the production process of traditional propylene, it is an effective way to solve the problem to find a more economical and efficient production method of propylene. Therefore, propane dehydrogenation (PDH) propylene production has received increasing attention, with approximately five million tons of propylene produced per year by a propane dehydrogenation process. In the process of dehydrogenation of propane, Pt catalyst has been widely used in industry for its excellent reactivity.
  • PDH propane dehydrogenation
  • the object of the present invention is to overcome the deficiencies of the prior art, and to solve the problem of low selectivity of propylene for pure Pt catalyst, a Pt3d@ with high selectivity of propylene is prepared by the steps of impregnation, high temperature hydrogen reduction and acid washing.
  • Catalyst for Pt/SBA-15 core-shell structure It is applied to the process of propane dehydrogenation. By adding 3d transition metal, the d-band center of Pt atoms on the surface is reduced, the carbon deposition problem of pure Pt in the high-temperature reaction process is weakened, and the selectivity and improvement of propylene are improved.
  • the catalytic performance of Pt is to overcome the deficiencies of the prior art, and to solve the problem of low selectivity of propylene for pure Pt catalyst, a Pt3d@ with high selectivity of propylene is prepared by the steps of impregnation, high temperature hydrogen reduction and acid washing.
  • Catalyst for Pt/SBA-15 core-shell structure It is
  • the core composed of metal platinum and 3d metal is formed in the catalyst, and the distribution content of metal platinum gradually decreases from the surface to the inner core, and the distribution content of the 3d metal (iron, cobalt, ruthenium) gradually increases.
  • the carrier is commercially available SBA-15; the 3d metal is Fe, Co or Ni.
  • the preparation method of the supported high-selective core-shell bimetallic catalyst is carried out according to the following steps:
  • Step 1 The carrier is placed in an impregnation system for stirring and impregnation until the solvent is completely evaporated in the impregnation system to load the metal platinum and the 3d metal into the support in the impregnation system.
  • step 1 the carrier is commercially available SBA-15.
  • the 3d metal is Fe, Co or Ni.
  • the temperature is room temperature 20-25 degrees Celsius
  • the time is 20-24 hours
  • mechanical stirring or ultrasonic stirring is selected
  • the stirring speed is 200-300 rpm.
  • the impregnation system consists of deionized water, ethanol and a metal precursor aqueous solution, and the volume ratio of deionized water to ethanol is (1-2): (1-3), preferably an equal volume ratio; in the metal precursor In the aqueous solution, the molar ratio of the metal platinum to the 3d metal is (3-5): (1-1.5), preferably 3: (1-1.5) or (3-5): 1; the carrier mass is 100% by weight, the metal platinum The mass percentage is from 0.5% to 1%, preferably from 0.75% to 0.8%.
  • Step 2 after the carrier responsible for the metal platinum and the 3d metal is dried, calcined in an air atmosphere to form a metal oxide, and is heated at a rate of 2-5 ° C/min from room temperature 20-25 degrees Celsius to 300-350 ° C. 4h;
  • step 2 it is selected to dry in an oven at 50-70 ° C for 10-12 h, after which it is taken out and ground to a powder.
  • Step 3 the carrier treated in step 2 is subjected to high temperature reduction under a hydrogen-argon atmosphere, and is heated at a temperature increase rate of 2-5%/min from room temperature of 20-25 degrees Celsius to 400-450 ° C to maintain the temperature for 4-6 hours.
  • the volume percentage of hydrogen is 5 to 10%.
  • metal platinum having a small free energy tends to be concentrated on the surface of the material, 3d metal (iron, cobalt, rhodium). On the contrary, it tends to be enriched inside the material, so that from the surface of the material to the inner core, the metal platinum and the 3d metal (iron, cobalt, ruthenium) exhibit the opposite distribution trend, and the distribution content of the metal platinum gradually decreases.
  • the distribution of 3d metal (iron, cobalt, bismuth) is gradually increasing.
  • step 4 the catalyst of the high temperature reduction in step 3 is subjected to an acid treatment to remove the residual 3d metal on the surface to form a shell layer composed of metal platinum, and an inner core composed of metal platinum and 3d metal.
  • the acid to be acid-treated is selected to dissolve the 3d metal without reacting with the metal platinum, for example, a 5*10 -4 mol/l dilute aqueous solution of nitric acid, and pickled at room temperature 20-25 degrees Celsius for 1-20 minutes.
  • the metal platinum for example, a 5*10 -4 mol/l dilute aqueous solution of nitric acid
  • pickled at room temperature 20-25 degrees Celsius for 1-20 minutes Preferably, 10-20 min; 0.3 g of the reduced catalyst is placed in 15 ml of 5*10 -4 mol/l dilute aqueous nitric acid solution, shaken for 30 s, left to stand, centrifuged by a centrifuge, and washed with deionized water 3-5
  • the washed catalyst for removing the supernatant was dried in an oven at 60-80 ° C for 10-12 h.
  • the catalyst When used, the catalyst is subjected to a tableting treatment to obtain a 20-40 mesh particulate catalyst for use.
  • the catalyst When in use, the catalyst is charged into the reactor, a nitrogen-hydrogen mixture gas is introduced, and the temperature rise rate at 3-5 ° C / min is raised from room temperature 20-25 ° C to 600-620 ° C and the catalyst is reduced by heat preservation, and the reduction time is at least 0.5 hours, preferably 1-2h, the volume percentage of hydrogen in the nitrogen-hydrogen mixture is 10-15%; after the reduction is completed, the temperature of the reactor is controlled to be 550-650 ° C, and the mass velocity of propane is 3-10 h -1
  • the reaction gas was subjected to a reaction in which a molar ratio of propane to hydrogen was 1:1, a balance gas was nitrogen, and a volume ratio of propane, hydrogen and nitrogen was 7:7:11.
  • the catalyst of the invention adopts SBA-15 as a carrier, Pt as an active component, 3d transition metal as an auxiliary agent to modify and improve the catalytic reaction performance of surface Pt.
  • the 3d transition metal is used to form a bimetallic catalyst with a special core-shell structure with Pt.
  • the addition of 3d metal in the core reduces the center of the d-band of the surface Pt atom, weakens the adsorption of propylene, and makes the propylene easier to take off. Attached, thereby improving the selectivity to propylene, on the other hand, the addition of 3d transition metal, to reduce the amount of Pt, to achieve the reduction of Pt, making the use of Pt more efficient.
  • the catalyst of the invention is suitable for use in a hydrogen atmosphere, and has good effects on dehydrogenation of propane to propylene.
  • the dehydrogenation activity is high under high temperature conditions, and the overall selectivity of propylene is up to 85%, achieving high propylene. Selective purpose.
  • Figure 1 is a schematic illustration of the technical solution of the present invention in which a light colored sphere represents metal platinum and a dark colored sphere represents a 3d metal.
  • curve 1 is the catalyst PtFe@Pt/SBA-15 of the present invention
  • curve 2 is the catalyst Pt/SBA-15.
  • Figure 3 is an XRD line diagram (2) of the catalyst of the present invention, wherein curve 1 is the catalyst PtFe@Pt/SBA-15 of the present invention, and curve 2 is the catalyst Pt/SBA-15.
  • Fig. 4 is a schematic view showing the XPS peak of Fe 2p before and after pickling of the catalyst in the present invention.
  • Figure 5 is a temperature-programmed propylene desorption curve (C3H6-TPD) of the catalyst of the present invention, wherein curve 1 is the catalyst PtFe@Pt/SBA-15 of the present invention, and curve 2 is the catalyst Pt/SBA-15.
  • C3H6-TPD temperature-programmed propylene desorption curve
  • Figure 6 is a graph showing the carbon monoxide diffuse reflection absorption vibration spectrum (CO-FTIR) of the catalyst of the present invention, wherein curve 1 is the catalyst PtFe@Pt/SBA-15 of the present invention, and curve 2 is the catalyst Pt/SBA-15.
  • CO-FTIR carbon monoxide diffuse reflection absorption vibration spectrum
  • Fig. 7 is a graph showing the activity test (propane conversion) of PtFe@Pt/SBA-15, Pt/SBA-15 corresponding catalysts of different pickling times, respectively pickled for 5 min/10 min/20 min.
  • Fig. 8 is a graph showing the activity test (propylene selectivity) of PtFe@Pt/SBA-15, Pt/SBA-15 corresponding catalysts of different pickling times, respectively pickled for 5 min/10 min/20 min.
  • Figure 10 is a graph showing the percentage of the catalyst 3d metal (such as iron) washed off according to the pickling time of the present invention, the abscissa is time min, and the ordinate is the molar ratio of the washed 3d metal to the initial 3d metal (ie, The mole percentage that was washed off).
  • the catalyst 3d metal such as iron
  • Figure 11 is a graph of EDS line before and after pickling of the catalyst in the present invention, curve 1 is metal Pt, and curve 2 is metal Fe.
  • Figure 12 is an X-ray boundary absorption line diagram of the catalyst before and after pickling in the present invention, wherein curve 1 is PtFe/SBA-15 before pickling, curve 2 is PtFe@Pt/SBA-15 after pickling, curve 3 is Fe foil, curve 4 is ferric oxide nanoparticles.
  • the invention is further described in detail below by way of specific examples.
  • the calcined catalyst was placed in a high temperature resistant quartz boat and placed in a tube furnace, passed through a 5% H 2 /Ar, and reduced at 400 ° C for 4 h (heating rate 2 ° C / min).
  • the powder catalyst which is pickled for 10 min PtFe@Pt/SBA-15--10 is a 20-40 mesh granular catalyst
  • the catalyst after pickling PtFe@Pt/SBA-15 for 10 min was charged into a fixed bed reactor, and a nitrogen-hydrogen mixed gas was introduced, and the catalyst was pre-reduced at 600 ° C for 1 h, and nitrogen-hydrogen was mixed.
  • the volume ratio of hydrogen in the gas is 10%.
  • the reactor bed temperature is controlled to 600 ° C, and the reaction gas is introduced at a propane mass space velocity of 10 h -1 , wherein the molar ratio of propane to hydrogen is 1:1, the equilibrium gas is nitrogen, propane, hydrogen and The volume ratio of nitrogen was 7:7:11.
  • Propane conversion, propylene selectivity, and propylene yield are calculated in the following formulas:
  • the reaction product was analyzed on-line by gas chromatography.
  • the initial selectivity to propylene before and after iron addition was as follows:
  • the catalyst Pt/SBA-15 was prepared by the preparation process of the invention without adding 3d metal element, and the catalyst PtFe@Pt/SBA-15 was the catalyst of the invention. It can be seen from the table that after adding iron, the surface Pt The overall selectivity of the atom for propylene has indeed improved. This indicates that the addition of iron reduces the center of the d-band of the surface Pt atom by the electronic effect and the lattice effect, and weakens its adsorption to propylene, thereby effectively improving the selection of propylene on the surface Pt atom compared with pure Pt. Properties, that is, a catalyst which achieves high selectivity to propylene and the amount of Pt used.
  • Fig. 4 is an XPS bond energy peak of the 2p orbital of Fe element before and after pickling. It can be seen from the figure that after pickling, the peak energy of the 2p orbital of Fe is 707.9 ev, and the peak of the 2p orbital of Fe after pickling is 709.9 ev. It can be seen that the peak of 2p of Fe shifts to a higher energy before pickling than after pickling, which indicates that the Fe element exhibits an oxidation state at this time.
  • the Fe Before the pickling, the Fe is easily oxidized in the air due to the presence of post-Fe on the surface of the particles, thus exhibiting an oxidation state. After pickling, since Fe is present in the inner core, it can be protected by the surface Pt so that it is not oxidized, thereby presenting a metallic state. Therefore, from the XPS diagram, we can get the final synthesized catalyst which is the surface-enriched structure of Pt.
  • the instrument used in the ICP test was an ICP-MS (7700x, Agilent) instrument manufactured by Agilent. Using carbon monoxide diffuse reflection absorption vibration spectroscopy (CO-FTIR) and temperature programmed propylene desorption (C3H6-TPD, rising from 100 degrees Celsius to 10 degrees Celsius per minute to 800 degrees Celsius), it was found that the wave number increased after adding 3d metal. The position of the peak changes, indicating that the center of the d-band of the surface metal platinum decreases, resulting in a decrease in adsorption capacity.
  • the catalyst of the present invention was subjected to pickling. As shown in the figure, as the pickling time increased, the amount of Fe element washed out showed a tendency to increase substantially first.
  • the X-ray boundary absorption spectrum was tested on the catalyst before and after pickling (PtFe/SBA-15 before pickling, PtFe@Pt/SBA-15 after pickling), as shown in Figure 12, catalyst samples before and after pickling.
  • Fe K-edge XANES spectral results.
  • the spectrum of Fe 2 O 3 nanoparticles and standard metal iron foil is also used as a reference. It is generally believed that the peaks of the adsorption energies of 7115eV and 7132Ev in the Fe K-edge XANES spectrum correspond to the electronic transitions from the 1s to 3d orbitals in the Fe atoms, and the Fe electron transitions from 1s to 4p, respectively.
  • the Fe K-line absorption edge structure in the PtFe/SBA-15 catalyst sample is similar to that of Fe 2 O 3 before pickling, and the peak intensity of the absorption edge white line is relatively high, which is due to Fe- O caused by interaction.
  • the white line intensity of the Fe K absorption edge in the PtFe@Pt catalyst obtained is lowered, and the position of the absorption edge is shifted to a lower energy, and the spectral line structure is similar to that of the metal Fe foil. Therefore, in response to the XPS results, the catalyst before the pickling is exposed to the air, and the surface Fe is oxidized by the oxygen in the air to change from the metallic state to the oxidized state.
  • the signal of Pt appears earlier than the signal of Fe, indicating the formation of the Pt skin structure.
  • the thickness of the Pt skin is about -1.3 nm, with an average thickness of about 3-5 layers of Pt atoms.
  • the reaction was carried out by the method of Example 1, except that the standing time after the step (5) of the catalyst shaking vibration in the nitric acid solution was 5 min, and the obtained catalyst was pickled for 5 min of PtFe@Pt/SBA-15--- 5 min catalyst.
  • the reaction was carried out by the method of Example 1, except that the standing time of the step (5) after the catalyst shaking in the nitric acid solution was 20 min, and the obtained catalyst was pickled for 20 min of PtFe@Pt/SBA-15--- 20 min catalyst.
  • the reaction was carried out by the method of Example 1, except that the standing time after the step (5) of the catalyst shaking vibration in the nitric acid solution was 60 min, and the obtained catalyst was pickled for 60 min of PtFe@Pt/SBA-15--- 60 min catalyst.
  • the reaction was carried out by the method of Example 1, except that the step (5) was placed in the nitric acid solution without pickling, and the obtained catalyst was an unacid washed PtFe@Pt/SBA-15---0 min catalyst.
  • the standing time after the oscillating ultrasonication was 5 min, and the obtained catalyst was a PtCo@Pt/SBA-15--5 min catalyst which was pickled for 5 min.
  • the reaction was carried out by the method of Example 6, except that the standing time after the step (5) of the catalyst shaking vibration in the nitric acid solution was 10 min, and the obtained catalyst was pickled for 10 min of PtCo@Pt/SBA-15--- 10 min catalyst.
  • the reaction was carried out by the method of Example 6, except that the standing time after the step (5) of the catalyst shaking vibration in the nitric acid solution was 20 min, and the obtained catalyst was pickled for 20 min of PtCo@Pt/SBA-15--- 20 min catalyst.
  • the reaction was carried out by the method of Example 6, except that the standing time after the step (5) of the catalyst shaking vibration in the nitric acid solution was 60 min, and the obtained catalyst was pickled for 60 min of PtCo@Pt/SBA-15--- 60 min catalyst.
  • the standing time after the oscillating ultrasonication was 5 min, and the obtained catalyst was a PtCo@Pt/SBA-15--5 min catalyst which was pickled for 5 min.
  • the reaction was carried out by the method of Example 10 except that the standing time of the step (5) after the catalyst shaking ultrasonic in the nitric acid solution was 10 min, and the obtained catalyst was pickled for 10 min of PtCo@Pt/SBA-15--- 10 min catalyst.
  • the reaction was carried out by the method of Example 10 except that the standing time after the step (5) of the catalyst shaking vibration in the nitric acid solution was 20 min, and the obtained catalyst was pickled for 20 min of PtCo@Pt/SBA-15--- 20 min catalyst.
  • the reaction was carried out by the method of Example 10 except that the standing time after the step (5) of the catalyst shaking vibration in the nitric acid solution was 60 min, and the obtained catalyst was pickled for 60 min of PtCo@Pt/SBA-15--- 60 min catalyst.
  • the PtCo/SBA-15 and PtNi/SBA-15 core-shell catalysts have a particularly low selectivity for propylene when acid pickled for 5 min, because Co and Ni have a carbon-carbon bond bond, and this The core-shell structure has not yet formed, thereby reducing the selectivity to propylene.
  • the catalyst of the present invention can be prepared by parameter adjustment in accordance with the raw material formulation and preparation process of the present invention, and exhibits substantially the same performance as the examples.
  • the present invention has been described in detail above, and it should be understood that any simple modifications, alterations, or other equivalents of those skilled in the art without The scope of protection of the invention.

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Abstract

一种负载型高选择性核壳结构双金属催化剂及其制备方法和应用，以SBA-15为载体，以Pt为活性组分，3d过渡金属为助剂，采用3d过渡金属并与Pt形成具有核壳结构的双金属催化剂，一方面，核内3d金属的加入，降低了表面Pt原子的d带中心，减弱了对于丙烯的吸附，从而提高了对于丙烯的选择性，另一方面，3d过渡金属的加入，可以达到减少Pt的用量的目的，实现Pt的减量化，使得Pt的利用更高效。该催化剂适用于临氢气氛下，对丙烷脱氢制丙烯具有良好的效果，在高温条件下脱氢活性高，丙烯的总体选择性可以达到85％，实现了高的丙烯选择性。

Description

负载型高选择性核壳结构双金属催化剂及其制备方法和应用 技术领域
本发明涉及一种高选择性丙烷脱氢制丙烯催化剂的制备方法和应用，具体的说，是涉及一种负载于SBA-15载体上的PtFe@Pt核壳结构催化剂及其制备方法和在丙烷脱氢制丙烯中对于丙烯选择性的影响。
背景技术
相比于单金属催化剂而言，双金属在许多催化反应过程中都表现优异的催化反应性能。通过调变双金属催化剂的结构，组成及形貌，可以大大提高催化剂的稳定性，活性和选择性。设计合成特殊结构和组成的双金属催化剂，是提高催化反应性能的有效途径之一。而金属Pt以其优良的催化性能使之在许多催化反应中都有广泛的应用。但由于Pt金属昂贵的价格，实现Pt的减量化成为亟待解决的问题。因此，通过加入其他金属，一方面对金属Pt改性，另一方面可以实现Pt的减量化。在多想催化反应过程中，对于金属纳米颗粒而言，起到催化反应作用的只有表面原子。通过在次表层加入其他过渡金属，利用表面自由能的差异，形成表面富集Pt的核壳结构，利用过渡金属和Pt之间的电子效应和结构效应，可以降低表面Pt原子的d带中心，改善表面Pt原子的催化反应性能，同时，加入过渡金属也达到了实现Pt的减量化的目的。例如，合成次表层有Ni的特殊的三明治结构，可以很好的提高一氧化碳的催化氧化反应活性，其中次表层Ni的存在降低了表面Pt的d带中心，进而减弱对于一氧化碳的吸附。在ORR反应过程中，合成PtCualloy@Pt的核壳结构，通过Cu的电子和结构效应，提高了表面Pt的ORR反应性能，同时也实现了Pt的减量化。
丙烯作为十分重要的化工产品和原料之一，可以用来合成丙烯腈，聚丙烯，环氧丙烷等化工产品。由于传统丙烯的生产工艺的高耗能，低选择性，以及石油资源的短缺，寻找一种更经济高效的制丙烯的生产方式成为解决问题的有效办法。因此，丙烷脱氢(PDH)制丙烯工艺受到越来越多的关注，每年约五百万吨的丙烯是通过丙烷脱氢工艺 生产的。而在丙烷脱氢反应过程中，Pt催化剂以其优良的反应活性，在工业上已经有了很广泛的应用。然而，一方面，由于金属Pt的价格昂贵，地球储量很小，实现Pt的高效利用就成为近年来研究的热点之一。而另一方面，丙烷脱氢制丙烯的反应式为：
Figure PCTCN2018083832-appb-000001
Figure PCTCN2018083832-appb-000002
ΔH 298K＝124.3KJ/g.mol，显然，这是一个强吸热反应，受热力学平衡的限制，高温，低压有利于反应的进行。然而，过高的反应温度会导致积碳的产生，降低对于丙烯的选择性。因此，设计合成特殊有效的催化剂，使之减弱对于丙烯中间体的吸附，提高对于丙烯的选择性，也是一个需要亟待解决的问题。
发明内容
本发明的目的在于克服现有技术的不足，要解决的是对于纯Pt催化剂丙烯选择性低的问题，通过浸渍，高温氢气还原和酸洗等步骤制备了一种具有丙烯高选择性的Pt3d@Pt/SBA-15核壳结构的催化剂。将其应用于丙烷脱氢反应过程中，通过加入3d过渡金属，降低了表面Pt原子的d带中心，减弱了纯Pt在高温反应过程中的积碳问题，进而提高了丙烯的选择性，改善了Pt的催化性能。
本发明的技术目的通过下述技术方案予以实现：
负载型高选择性核壳结构双金属催化剂，在载体上负载金属铂和3d金属，以载体质量为100wt％，金属铂的质量百分数为0.5％-1％，优选0.75％-0.8％(即金属铂质量/载体质量)；金属铂和3d金属的摩尔比为(3-5)∶(0.75-1)，优选3∶(0.75-0.85)；在催化剂表面形成一层由金属铂组成的壳层，在催化剂中形成由金属铂和3d金属组成的内核，且自表面到内核，金属铂的分布含量逐渐减少，3d金属(铁、钴、镊)的分布含量逐渐增多。
载体为市售SBA-15；3d金属为Fe、Co或者Ni。
负载型高选择性核壳结构双金属催化剂的制备方法，按照下述步骤进行：
步骤1，将载体置于浸渍体系中进行搅拌浸渍，直至浸渍体系中溶剂全部蒸发，以使浸渍体系中金属铂和3d金属负载到载体上
在步骤1中，载体为市售SBA-15。
在步骤1中，3d金属为Fe、Co或者Ni。
在步骤1中，在进行搅拌浸渍时，温度为室温20-25摄氏度，时间为20-24小时，选择机械搅拌或者超声搅拌，搅拌速度为200-300转/min。
在步骤1中，浸渍体系由去离子水、乙醇和金属前驱体水溶液组成，去离子水和乙醇的体积比为(1-2)∶(1-3)，优选等体积比；在金属前驱体水溶液中，金属铂和3d金属的摩尔比为(3-5)∶(1-1.5)，优选3∶(1-1.5)或者(3-5)∶1；以载体质量为100wt％，金属铂的质量百分数为0.5％-1％，优选0.75％-0.8％。
步骤2，将负责金属铂和3d金属的载体干燥后，在空气气氛中进行焙烧形成金属氧化物，以2-5℃/min的速度自室温20-25摄氏度升至300-350℃焙烧2-4h；
在步骤2中，选择在50-70℃的烘箱中干燥10-12h，之后取出研磨至粉末。
步骤3，在氢气-氩气气氛下对经步骤2处理的载体进行高温还原，以2-5％/min的升温速率自室温20-25摄氏度升至400-450℃保持温度还原4-6h，在氢气和氩气组成的混合气体中，氢气的体积百分数为5-10％。
在步骤3的高温还原过程中，鉴于金属铂和3d金属的热动力学不同和表面自由能不同，自由能小的金属铂倾向于富集到材料的表面，3d金属(铁、钴、镊)则相反，倾向于富集到材料内部，这样一来，自材料的表面到内核，金属铂和3d金属(铁、钴、镊)呈现出恰恰相反的分布趋势，金属铂的分布含量逐渐减少，3d金属(铁、钴、镊)的分布含量逐渐增多。
步骤4，将步骤3高温还原的催化剂进行酸处理，以去除表面残留的3d金属，形成一层由金属铂组成的壳层，以及由金属铂和3d金属组成的内核。
在步骤4中，选择进行酸处理的酸，能够溶解3d金属且不予金属铂发生反应，例如5*10 -4mol/l的稀硝酸水溶液，室温20-25摄氏度下酸洗1-20min，优选10-20min；取还原后的催化剂0.3g放在15ml5*10 -4mol/l的稀硝酸水溶液中，震荡超声30s，静置后用离心机进行离心分离，并用去离子水洗涤3-5次，将洗完的除去上清液的催化剂置于60-80℃的烘箱中干燥10-12h。
负载型高选择性核壳结构双金属催化剂在丙烷脱氢中的应用。
在进行使用时，催化剂进行压片处理，以得到20-40目的颗粒状催化剂进行使用。
在进行使用时，催化剂装入反应器，通入氮氢混合气，在3-5℃/min的升温速率自 室温20-25摄氏度升至600-620℃并保温对催化剂进行还原，还原时间至少0.5小时，优选1-2h，氮氢混合气中氢气体积百分数为10-15％；待还原完成后，控制反应器温度为550-650℃，以丙烷质量空速为3-10h -1通入反应气进行反应，其中丙烷和氢气摩尔比为1∶1，平衡气为氮气，丙烷、氢气和氮气的体积比7∶7∶11。
与现有技术相比，本发明的技术方案具有如下有益效果：
(1)本发明的催化剂以SBA-15为载体，以Pt为活性组分，3d过渡金属为助剂修饰和改良表面Pt的催化反应性能。采用3d过渡金属并与Pt形成具有特殊核壳结构的双金属催化剂，一方面，核内3d金属的加入，降低了表面Pt原子的d带中心，减弱了对于丙烯的吸附，使得丙烯更容易脱附，从而提高了对于丙烯的选择性，另一方面，3d过渡金属的加入，达到减少Pt的用量的目的，实现Pt的减量化，使得Pt的利用更高效。
(2)本发明的催化剂适用于临氢气氛下，对丙烷脱氢制丙烯具有良好效果，在高温条件下脱氢活性很高，丙烯的总体选择性可达85％，实现了很高的丙烯选择性目的。
附图说明
图1是本发明技术方案的示意图，其中浅色小球代表金属铂，深色小球代表3d金属。
图2是本发明中催化剂的XRD谱线图(1)，其中曲线1为本发明催化剂PtFe@Pt/SBA-15，曲线2为催化剂Pt/SBA-15。
图3是本发明中催化剂的XRD谱线图(2)，其中曲线1为本发明催化剂PtFe@Pt/SBA-15，曲线2为催化剂Pt/SBA-15。
图4是本发明中催化剂酸洗前后Fe 2p的XPS峰示意图。
图5是本发明中催化剂的程序升温丙烯脱吸附曲线(C3H6-TPD)，其中曲线1为本发明催化剂PtFe@Pt/SBA-15，曲线2为催化剂Pt/SBA-15。
图6是本发明中催化剂的一氧化碳漫反射吸收振动光谱曲线(CO-FTIR)，其中曲线1为本发明催化剂PtFe@Pt/SBA-15，曲线2为催化剂Pt/SBA-15。
图7是PtFe@Pt/SBA-15，Pt/SBA-15对应的不同酸洗时间的催化剂的活性测试图(丙烷转化率)，分别酸洗5min/10min/20min。
图8是PtFe@Pt/SBA-15，Pt/SBA-15对应的不同酸洗时间的催化剂的活性测试图(丙烯 选择性)，分别酸洗5min/10min/20min。
图9是Pt3d@Pt/SBA-15(3d＝Fe，Co，Ni)在不同酸洗时间，不同3d过渡金属时对于丙烯选择性高出对应酸洗时间下的Pt/SBA-15的丙烯选择性的差值示意图(采出活性)。
图10是本发明催化剂3d金属(如铁)被洗掉的百分比随酸洗时间的变化曲线图，横坐标为时间min，纵坐标为被洗掉的3d金属与初始3d金属的摩尔比(即被洗掉的摩尔百分数)。
图11是本发明中催化剂酸洗前后的EDS线扫图，曲线1为金属Pt，曲线2为金属Fe。
图12是本发明中催化剂酸洗前后的X射线境边吸收谱线图，其中曲线1为酸洗前PtFe/SBA-15，曲线2为酸洗后PtFe@Pt/SBA-15，曲线3为Fe箔，曲线4为三氧化二铁纳米颗粒。
具体实施方式
下面通过具体的实施例对本发明作进一步的详细描述。将负载于负载在SBA-15上的Pt和3d过渡金属的核壳结构的双金属催化剂，命名为Pt3d@Pt/SBA-15(3d＝Fe，Co，Ni)催化剂。
实施例1
(1)取5ml去离子水，6ml乙醇置于100ml的烧杯中搅拌至混合均匀，加入提前配制好的0.010g/ml的氯铂酸溶液0.75ml，以及提前配制好的过渡金属Fe的硝酸盐溶液，使得Pt∶Fe＝3∶1(摩尔比)，继续搅拌。此时在搅拌的溶液中加入称量好的1g的SBA-15。
(2)搅拌24h后，待溶液成凝胶状，将烧杯放在80℃的烘箱中干燥12h。
(3)将干燥完成的固体研磨至粉末，放在坩埚内并于马弗炉中在300℃下焙烧2h(以2℃/min升温速率)。
(4)将焙烧完成的催化剂放在耐高温的石英舟中，并置于管式炉中，通入5％的H 2/Ar，在400℃下还原4h(升温速率2℃/min)。
(5)取还原后的催化剂0.3g放在0.0005mol/l的稀硝酸溶液中，震荡超声30s，静置10min，后用离心机进行离心分离，并用去离子水洗涤3次，将洗完的除去上清液 的催化剂置于60℃的烘箱中干燥12h。得到负载于负载在SBA-15上的Pt和3d过渡金属的核壳结构的双金属催化剂，其分子式为酸洗10minPtFe@Pt/SBA-15---10催化剂
(6)将酸洗10minPtFe@Pt/SBA-15---10的粉末催化剂压片为20-40目的颗粒状催化剂；
(7)将压片后的PtFe@Pt/SBA-15酸洗10min的催化剂装入固定床反应器，通入氮氢混合气，在600℃温度下对所述催化剂预还原1h，氮氢混合气中氢气体积比为10％。
(8)还原完成后控制反应器床层温度为600℃，以丙烷质量空速为10h -1通入反应气，其中丙烷和氢气摩尔比为1∶1，平衡气为氮气，丙烷、氢气和氮气的体积比7∶7∶11。
丙烷转化率、丙烯选择性以及丙烯收率以下列各式进行计算：
转化率：
Figure PCTCN2018083832-appb-000003
选择性：
Figure PCTCN2018083832-appb-000004
收率：
Figure PCTCN2018083832-appb-000005
反应产物采用气象色谱仪在线分析，对于在酸洗10min时，内核加铁前后对于丙烯的初始选择性如下表：
表1、次表层加Fe(即内层加入3d金属)对于丙烷脱氢反应过程中丙烯选择性的影响
催化剂种类 Pt/SBA-15 PtFe@Pt/SBA-15
丙烯初始选择性(％) 84 69
催化剂Pt/SBA-15采用本发明的制备工艺在不添加3d金属元素的条件下进行制备，催化剂PtFe@Pt/SBA-15为本发明催化剂，从表中可以看出，加入铁之后，表面Pt原子对于丙烯的总体选择性确实有所提高。这说明铁的加入，通过电子效应和晶格效应，降低了表面Pt原子的d带中心，减弱了其对于丙烯的吸附，从而和纯Pt相比，有效的提高了表面Pt原子对于丙烯的选择性，即获得达到丙烯高选择性并Pt的使用量的催化剂。 从XRD表征来看，加入铁之后，催化剂整体晶型没有发生显著变化，出现针对铁元素的峰位置变换。图4是酸洗前后Fe元素的2p轨道的XPS键能峰。从图中可以看出，酸洗之后，Fe的2p轨道的峰能量在707.9ev，而酸洗之后Fe的2p轨道的峰在709.9ev。可以看到，酸洗之前相比于酸洗之后，Fe的2p的峰向更高能量偏移，这也就说明了Fe元素此时呈现氧化态。在没有酸洗之前，由于颗粒表面仍然后Fe的存在，导致在空气中Fe很容易被氧化，故而呈现一个氧化态。而在酸洗之后，由于Fe都存在于内核里，它可以被表面的Pt保护，使之不被氧化，从而呈现一个金属态。因此从XPS图中我们可以得到最后合成的催化剂是Pt在表面富集的结构。XPS所用表征仪器为PE公司生产的PHI 1600ESCA仪器，其X射线源采用Al靶(hν＝1486.6eV)。
ICP测试所用仪器为安捷伦公司生产的ICP-MS(7700x，Agilent)仪器。采用一氧化碳漫反射吸收振动光谱(CO-FTIR)和程序升温丙烯脱吸附(C3H6-TPD，自100摄氏度以每分钟10摄氏度的速度升温至800摄氏度)进行测试，发现在加入3d金属后，波数上升，峰位置发生变化，说明表面金属铂的d带中心下降，导致吸附能力下降。将本发明催化剂进行酸洗，如图所示，随着酸洗时间的增加，Fe元素被洗掉的量呈现一个先增加后基本不变的趋势。在开始的10分钟内，随着酸洗时间的增加，Fe元素被洗掉的量逐渐增加，10分钟时，Fe大概被洗掉了24.7％左右(催化剂中保留初始投料中75％的铁)，之后再继续增加酸洗时间，Fe被洗掉的量不再增加。这也就说明，最后得到的催化剂中仍然还有Fe原子，Fe原子并没有完全被洗掉。
对酸洗前后的催化剂(酸洗前PtFe/SBA-15，酸洗后PtFe@Pt/SBA-15)进行了X射线境边吸收谱的测试，如附图12所示，酸洗前后催化剂样品的Fe K-edge XANES光谱结果。同时，为了更好的说明问题，以Fe 2O 3纳米颗粒和标准金属铁箔的光谱也作为参比。一般认为，Fe K-edge XANES光谱中7115eV和7132Ev吸附能的峰分别对应表示Fe原子中从1s到3d轨道的电子跃迁，以及从1s到4p的Fe电子跃迁。由附图12结果可以发现，酸洗前，PtFe/SBA-15催化剂样品中的Fe K线吸收边结构与Fe 2O 3相似，并且吸收边白线的峰强度比较高，这是由于Fe-O相互作用引起的。而经过酸洗处理后，即得到的PtFe@Pt催化剂中Fe K吸收边的白线强度降低，并且吸收边的位置向较低能量偏移，其谱线结构与金属Fe箔相似。所以，和XPS结果相呼应，酸洗前催化剂暴露于空 气中，表面的Fe会被空气中的氧氧化而使得其由金属态变为氧化态。反之，酸洗后，则保护Fe不会被空气中的氧氧化。XANES的研究结果进一步支持了次表层修饰的Fe和表面富集Pt的结构形成，这与ICP和XPS的结果是一致的-最后经过高温还原加之酸洗的数据，得到的是一种Pt在表面富集的一种核壳结构，也就是所说的PtFe@Pt的核壳结构的催化剂。为了直接证明次表层3d过渡金属修饰，表面富集Pt结构的形成，我们给出酸洗后即最终得到的PtFe@Pt催化剂EDS谱线，如附图11所示，在纳米粒子的两侧，Pt的信号出现早于Fe的信号，说明Pt skin结构的形成。同时，可以看到Pt skin的厚度大约为～1.3nm，平均约为3-5层Pt原子的厚度。
实施例2：
采用实施例1方法进行反应，其区别仅在于步骤(5)放在硝酸溶液中的催化剂震荡超声之后的静置时间为5min，所得催化剂为酸洗5min的PtFe@Pt/SBA-15---5min催化剂。
实施例3：
采用实施例1方法进行反应，其区别仅在于步骤(5)放在硝酸溶液中的催化剂震荡超声之后的静置时间为20min，所得催化剂为酸洗20min的PtFe@Pt/SBA-15---20min催化剂。
实施例4：
采用实施例1方法进行反应，其区别仅在于步骤(5)放在硝酸溶液中的催化剂震荡超声之后的静置时间为60min，所得催化剂为酸洗60min的PtFe@Pt/SBA-15---60min催化剂。
实施例5：
采用实施例1方法进行反应，其区别仅在于步骤(5)放在不放在硝酸溶液中酸洗，所得催化剂为未酸洗的PtFe@Pt/SBA-15---0min催化剂。
实施例6：
采用实施例1方法进行反应，其区别仅在于步骤(1)中加入过渡金属Co的硝酸盐，使得Pt∶Co＝3∶1(质量比)，同时步骤(5)放在硝酸溶液中的催化剂震荡超声之后的静置时间为5min，所得催化剂为酸洗5min的PtCo@Pt/SBA-15---5min催化剂。
实施例7：
采用实施例6方法进行反应，其区别仅在于步骤(5)放在硝酸溶液中的催化剂震荡超声 之后的静置时间为10min，所得催化剂为酸洗10min的PtCo@Pt/SBA-15---10min催化剂。
实施例8：
采用实施例6方法进行反应，其区别仅在于步骤(5)放在硝酸溶液中的催化剂震荡超声之后的静置时间为20min，所得催化剂为酸洗20min的PtCo@Pt/SBA-15---20min催化剂。
实施例9：
采用实施例6方法进行反应，其区别仅在于步骤(5)放在硝酸溶液中的催化剂震荡超声之后的静置时间为60min，所得催化剂为酸洗60min的PtCo@Pt/SBA-15---60min催化剂。
实施例10：
采用实施例1方法进行反应，其区别仅在于步骤(1)中加入过渡金属Ni的硝酸盐，使得Pt∶Ni＝3∶1(摩尔比)，同时步骤(5)放在硝酸溶液中的催化剂震荡超声之后的静置时间为5min，所得催化剂为酸洗5min的PtCo@Pt/SBA-15---5min催化剂。
实施例11：
采用实施例10方法进行反应，其区别仅在于步骤(5)放在硝酸溶液中的催化剂震荡超声之后的静置时间为10min，所得催化剂为酸洗10min的PtCo@Pt/SBA-15---10min催化剂。
实施例12：
采用实施例10方法进行反应，其区别仅在于步骤(5)放在硝酸溶液中的催化剂震荡超声之后的静置时间为20min，所得催化剂为酸洗20min的PtCo@Pt/SBA-15---20min催化剂。
实施例13：
采用实施例10方法进行反应，其区别仅在于步骤(5)放在硝酸溶液中的催化剂震荡超声之后的静置时间为60min，所得催化剂为酸洗60min的PtCo@Pt/SBA-15---60min催化剂。
关于上述实施例结果和数据，对于这种负载在SBA-15的具有核壳结构Pt3d@Pt/SBA-15(3d＝Fe，Co，Ni)催化剂而言，对比不同3d过渡金属和酸洗时间的催化剂，对于丙烷脱氢反应过程中丙烯选择性的影响。
(一)不同酸洗时间对于丙烷脱氢反应过程中丙烯选择性的影响，参见表2。
表2、不同酸洗时间及不同3d过渡金属加入次表层对于丙烷脱氢反应过程中和Pt/SBA-15的丙烯选择性的差值的影响
酸洗时间(min) PtFe@Pt/SBA-15 PtCo@Pt/SBA-15 PtNi@Pt/SBA-15
5 4％ -20％ -35％
10 16％ 10％ 1％
20 14％ 9％ 0.3％
60 13％ 6％ -0.7％
首先，从表中横向方向来看，可以看出，随着酸洗时间的增加，对于负载在SBA-15上的核壳结构催化剂Pt3d@Pt/SBA-15(3d＝Fe，Co，Ni)对于丙烯的选择性和Pt/SBA-15相比，呈现一个先增加后基本不变的趋势。并且均在酸洗时间为10min时达到了一个最大值。这说明，3d过渡金属的加入降低了表面Pt的d带中心，从而提高了对于丙烯的选择性。
其次，从纵向方向来看，加入不同3d过渡金属，和纯Pt相比，对于丙烯选择性的提高有所区别。由表中可以看到，对于丙烯的选择性提高的幅度，PtFe/SBA-15＞PtCo/SBA-15＞PtNi/SBA-15。这说明，当不同3d过渡金属加入时，对于表面Pt的电子影响和结构影响是不同的，因此对于降低Pt原子的d带中心的程度也不同，因此对于丙烯选择性的提高也有所不同。同时，可以看到，在酸洗5min时，PtCo/SBA-15和PtNi/SBA-15核壳结构催化剂对于丙烯选择性特别低，这是因为Co和Ni有断碳碳键的作用，而此时核壳结构还没有形成，从而降低了对于丙烯的选择性。
依照本发明内容的原料配方和制备工艺进行参数调整，均可制备本发明的催化剂，且表现出与实施例基本一致的性能。以上对本发明做了示例性的描述，应该说明的是，在不脱离本发明的核心的情况下，任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。

Claims (15)

  1. 负载型高选择性核壳结构双金属催化剂，其特征在于，在载体上负载金属铂和3d金属，以载体质量为100wt％，金属铂的质量百分数为0.5％-1％；金属铂和3d金属的摩尔比为(3-5)∶(1-1.5)；在催化剂表面形成一层由金属铂组成的壳层，在催化剂中形成由金属铂和3d金属组成的内核，且自表面到内核，金属铂的分布含量逐渐减少，3d金属的分布含量逐渐增多；3d金属为Fe、Co或者Ni。
  2. 根据权利要求1所述的负载型高选择性核壳结构双金属催化剂，其特征在于，金属铂的质量百分数为0.75％-0.8％，金属铂和3d金属的摩尔比为3∶(0.75-0.85)。
  3. 根据权利要求1或者2所述的负载型高选择性核壳结构双金属催化剂，其特征在于，载体为市售SBA-15。
  4. 负载型高选择性核壳结构双金属催化剂的制备方法，其特征在于，按照下述步骤进行：
    步骤1，将载体置于浸渍体系中进行搅拌浸渍，直至浸渍体系中溶剂全部蒸发，以使浸渍体系中金属铂和3d金属负载到载体上；3d金属为Fe、Co或者Ni；浸渍体系由去离子水、乙醇和金属前驱体水溶液组成，去离子水和乙醇的体积比为(1-2)∶(1-3)；在金属前驱体水溶液中，金属铂和3d金属的摩尔比为(3-5)∶(1-1.5)；以载体质量为100wt％，金属铂的质量百分数为0.5％-1％；
    步骤2，将负责金属铂和3d金属的载体干燥后，在空气气氛中进行焙烧形成金属氧化物，以2-5℃/min的速度自室温20-25摄氏度升至300-350℃焙烧2-4h；
    步骤3，在氢气-氩气气氛下对经步骤2处理的载体进行高温还原，以2-5％/min的升温速率自室温20-25摄氏度升至400-450℃保持温度还原4-6h，在氢气和氩气组成的混合气体中，氢气的体积百分数为5-10％；金属铂倾向于富集到材料的表面，3d金属倾向于富集到材料内部，自材料的表面到内核，金属铂和3d金属呈现出恰恰相反的分布趋势，金属铂的分布含量逐渐减少，3d金属的分布含量逐渐增多；
    步骤4，将步骤3高温还原的催化剂进行酸处理，以去除表面残留的3d金属，形成一层由金属铂组成的壳层，以及由金属铂和3d金属组成的内核。
  5. 根据权利要求4所述的负载型高选择性核壳结构双金属催化剂的制备方法，其特征在于，在步骤1中，载体为市售SBA-15；在进行搅拌浸渍时，温度为室温20-25摄氏度，时间为20-24小时，选择机械搅拌或者超声搅拌，搅拌速度为200-300转/min。
  6. 根据权利要求4所述的负载型高选择性核壳结构双金属催化剂的制备方法，其特征在于，在步骤1中，去离子水和乙醇的体积比为等体积比；在金属前驱体水溶液中，金属铂和3d金属的摩尔比为3∶(1-1.5)或者(3-5)∶1；以载体质量为100wt％，金属铂的质量百分数为0.75％-0.8％。
  7. 根据权利要求4所述的负载型高选择性核壳结构双金属催化剂的制备方法，其特征在于，在步骤4中，选择进行酸处理的酸，能够溶解3d金属且不予金属铂发生反应。
  8. 根据权利要求4所述的负载型高选择性核壳结构双金属催化剂的制备方法，其特征在于，在步骤4中，室温20-25摄氏度下酸洗1-20min，优选10-20min。
  9. 根据权利要求7所述的负载型高选择性核壳结构双金属催化剂的制备方法，其特征在于，在步骤4中，选择进行酸处理的酸为5*10 -4mol/l的稀硝酸水溶液。
  10. 根据权利要求8所述的负载型高选择性核壳结构双金属催化剂的制备方法，其特征在于，在步骤4中，室温20-25摄氏度下酸洗10-20min。
  11. 如权利要求1所述的负载型高选择性核壳结构双金属催化剂在丙烷脱氢中的应用。
  12. 根据权利要求11所述的负载型高选择性核壳结构双金属催化剂在丙烷脱氢中的应用，其特征在于，在进行使用时，催化剂进行压片处理，以得到20-40目的颗粒状催化剂进行使用。
  13. 根据权利要求11所述的负载型高选择性核壳结构双金属催化剂在丙烷脱氢中的应用，其特征在于，在进行使用时，催化剂装入反应器，通入氮氢混合气，在3-5℃/min的升温速率自室温20-25摄氏度升至600-620℃并保温对催化剂进行还原，待还原完成后，控制反应器温度为550-650℃，以丙烷质量空速为3-10h -1通入反应气进行反应，其中丙烷和氢气摩尔比为1∶1，平衡气为氮气，丙烷、氢气和氮气的体积比7∶7∶11。
  14. 根据权利要求13所述的负载型高选择性核壳结构双金属催化剂在丙烷脱氢中的应用，其特征在于，在进行使用时，还原时间至少0.5小时，氮氢混合气中氢气体积百 分数为10-15％。
  15. 根据权利要求13所述的负载型高选择性核壳结构双金属催化剂在丙烷脱氢中的应用，其特征在于，在进行使用时，还原时间为1-2h。
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