WO2020143338A1 - 一种负载型PtZn金属间合金催化剂及其制备方法和应用 - Google Patents

一种负载型PtZn金属间合金催化剂及其制备方法和应用 Download PDF

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WO2020143338A1
WO2020143338A1 PCT/CN2019/119858 CN2019119858W WO2020143338A1 WO 2020143338 A1 WO2020143338 A1 WO 2020143338A1 CN 2019119858 W CN2019119858 W CN 2019119858W WO 2020143338 A1 WO2020143338 A1 WO 2020143338A1
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ptzn
supported
intermetallic alloy
catalyst
propane
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巩金龙
陈赛
曾亮
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Tianjin University
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01J23/56—Platinum group metals
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/0201—Impregnation
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    • B01J37/08—Heat treatment
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    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/60—Platinum group metals with zinc, cadmium or mercury
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • 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 present invention relates to a supported catalyst, in particular, to a SiO 2 supported PtZn intermetallic alloy catalyst and its preparation method and application of the catalyst in the dehydrogenation of low-carbon alkanes to olefins (using propane dehydrogenation to propylene as an example) example).
  • Low-chain olefins are the basic raw materials of chemical industry, especially propylene, and the demand has become more and more vigorous in recent years.
  • Propylene is the basic raw material of the three major synthetic materials, mainly used in the production of acrylonitrile, acetone, propylene oxide and other products.
  • the supply of propylene mainly comes from the by-products of the cracking of naphtha to ethylene and the catalytic cracking of petroleum.
  • ethane has become cheaper and more readily available.
  • the ethylene production process has also begun to shift from naphtha cracking to ethane steam cracking.
  • the Catofin process uses a Cr-based catalyst, uses a fixed-bed reactor, and regenerates the catalyst once in an average of 12 minutes, with a single-pass conversion rate of 55%-60% and a selectivity of 90%.
  • the Oleflex process uses Pt catalysts, using a moving bed reactor, fully continuous operation, single-pass conversion rate of about 35%-40%, selectivity 84%. Both of the two catalysts are seriously deactivated due to carbon deposition, and the catalyst needs to be regenerated, and cadmium is highly toxic and unfavorable to the environment, while platinum is expensive, which severely limits the development of the propane dehydrogenation process. Therefore, it is of great practical significance to find an inexpensive PDH catalyst with low toxicity and high activity and stability, and to reduce the amount of Pt.
  • the dehydrogenation of lower alkanes is a structure-insensitive reaction, which means that single atom Pt can catalyze the dehydrogenation reaction.
  • these side reactions are structurally sensitive reactions. The larger the Pt particle size, the more favorable these side reactions occur [Molecular understandings on the activation of light hydrocarbons over heterogeneous catalysts. Chemical Science 2015, 6(8), 4403-4425]. Therefore, using unit point Pt as the active site for the dehydrogenation of lower alkanes is expected to achieve the production of lower olefins with high selectivity.
  • the intermetallic alloy is a bimetallic alloy in which the catalytically active metals are separated by inert metal atoms in the form of single atoms. They are mostly used in low-temperature electrocatalytic reactions, but their applications in high-temperature low-carbon alkane dehydrogenation reactions are rarely reported. .
  • the purpose of the present invention is to overcome the shortcomings of the prior art, to solve the technical problems of the existing Pt-based catalysts, such as easy carbon deactivation and large amount of precious metals, to provide a supported PtZn intermetallic alloy catalyst and its preparation Method and application in propane dehydrogenation, the catalyst has high activity, high stability, ultra-low precious metal content, catalytic dehydrogenation deactivation rate is slow, can improve propylene yield.
  • the mass percentage content of Pt is not more than 1% (metal Pt mass/carrier mass ⁇ 100wt%), and the mass percentage content of Zn is not more than 1.7% (metal Zn mass/carrier mass ⁇ 100wt%).
  • the carrier is silica, molecular sieve, zeolite or alumina.
  • the mass percentage content of Pt is 0.025%-1%, preferably 0.1%-0.5%.
  • the mass percentage content of Zn is 0.025%-1.5%, preferably 0.17%-0.85%.
  • Pt and Zn atoms are arranged in an orderly interval and form an atomically ordered intermetallic alloy.
  • the preparation method of the above catalyst is carried out according to the following steps:
  • Step 1 Place the support in a solution containing metal platinum and metal zinc for impregnation, so that the metal platinum and metal zinc are supported on the support;
  • the soluble zinc salt and chloroplatinic acid are selected to provide metallic zinc and metallic platinum, respectively, and are evenly dispersed in deionized water;
  • the soluble zinc salt is zinc nitrate, zinc chloride, or zinc sulfate.
  • the support is silica, molecular sieve, zeolite or alumina.
  • step 1 the amount of carrier is 1 part by mass, the amount of metal platinum is 0.0025-0.01 parts by mass, the amount of metal zinc is 0.0025-0.017 parts by mass, each part is 1g, and equal volume impregnation can be selected.
  • step 1 ultrasonic is used to disperse during the impregnation.
  • the ultrasonic time is 0.5h-1h. After impregnation, it is naturally dried at room temperature 20-25°C for 10-12h, and then completely dried at 80-120°C.
  • step 2 the support carrying metal platinum and metal zinc in step 1 is placed in a hydrogen atmosphere for reduction, and the reduction (heat preservation) temperature is 400-700 degrees Celsius to obtain a supported PtZn intermetallic alloy catalyst.
  • step 2 the reduction temperature is 500-600 degrees Celsius.
  • step 2 the reduction time is 0.5-3 hours, preferably 0.5-1 hour.
  • step 2 the temperature is raised from room temperature 20-25 degrees Celsius at a rate of 5-10 degrees Celsius per minute to the reduction temperature for heat preservation, and then naturally cooled to room temperature 20-25 degrees Celsius.
  • the carrier carrying metal platinum and metal zinc is always in the whole process In a hydrogen atmosphere, remove the hydrogen after cooling to room temperature.
  • the supported PtZn intermetallic alloy catalyst is compressed into a granular catalyst, and the mesh size is selected to be 20-40 mesh, and then the obtained granular catalyst is loaded into a fixed bed reactor, nitrogen is introduced, and the temperature is raised to a pretreatment temperature of 500-700 °C; pre-heating with hydrogen, maintained at the pre-treatment temperature of 0.5h-1h, cooling down to the reaction temperature of 500-650 °C; through the reaction gas, the molar ratio of hydrogen and propane is (0-2): 1 Nitrogen is the equilibrium gas, keeping the total gas number unchanged, and the reaction space velocity based on propane is 1-5h -1 .
  • the temperature for the pretreatment with hydrogen is 600-700 degrees Celsius; the reaction temperature is 600-650 degrees Celsius; the molar ratio of hydrogen to propane is 1:1, and the reaction space velocity based on propane is 3-4h -1 .
  • the PtZn intermetallic alloy supported by the catalyst of the present invention has a high specific surface area and mesoporous pores, which is conducive to the uniform distribution of active components and the diffusion of gas molecules; with a small amount of Pt as the active component (0.025%-1%, industrial Pt catalysts have a Pt content of more than 0.5%), which reduces the Pt content in the catalyst and reduces the cost of the catalyst; Pt and Zn form an atomically ordered intermetallic alloy, and the ordered separation of Pt and Zn atoms greatly improves on the one hand
  • the atomic utilization rate of Pt on the other hand, promotes the desorption of the product propylene, and suppresses the side reactions such as CC bond breakage and deep dehydrogenation, thus improving the activity, selectivity and stability of the catalyst.
  • the catalyst of the invention is prepared by a co-impregnation method, the raw materials are easily available, the process is simple, the repeatability is high, and it has certain industrial significance.
  • the catalyst of the present invention is suitable for use in the presence of hydrogen, and has good effects on propane dehydrogenation to produce propylene. Under high temperature conditions, the dehydrogenation activity is high, the propylene selectivity can reach more than 90%, and has good stability.
  • FIG. 1 is an AC-HAADF-TEM photograph of a SiO 2 supported PtZn intermetallic alloy catalyst prepared in Example 1 of the present invention.
  • Example 2 is an XRD test spectrum diagram of the SiO 2 supported PtZn intermetallic alloy catalyst prepared in Example 1 of the present invention.
  • FIG. 3 is an activity test chart of PtZn intermetallic alloy catalysts supported on SiO 2 and Al 2 O 3 respectively in Example 1 of the present invention.
  • the curve above the chemical formula in the figure corresponds to propylene selectivity, and the lower curve corresponds to the conversion of propane.
  • FIG. 4 is a test curve diagram of the effect of different Zn mass percentages on catalytic activity in the embodiment of the present invention.
  • the upper curve in the figure corresponds to propylene selectivity, and the lower curve corresponds to propane conversion.
  • FIG. 5 is a test curve diagram of the effect of different Pt content on catalytic activity in the embodiment of the present invention.
  • the upper curve in the figure corresponds to propylene selectivity, and the lower curve corresponds to propane conversion.
  • FIG. 6 is a test curve diagram of the effect of different pre-reduction temperatures on catalytic activity in the embodiment of the present invention.
  • the upper curve in the figure corresponds to propylene selectivity, and the lower curve corresponds to propane conversion.
  • FIG. 7 is a test curve diagram of the effect of different reaction temperatures on catalytic activity in the embodiment of the present invention.
  • the upper curve in the figure corresponds to propylene selectivity, and the lower curve corresponds to propane conversion.
  • FIG. 8 is a test curve diagram of the influence of different propane space velocity on catalytic activity in the embodiment of the present invention.
  • the upper curve in the figure corresponds to propylene selectivity, and the lower curve corresponds to propane conversion.
  • FIG. 9 is a test curve diagram of the influence of different propane/hydrogen ratios on catalytic activity in the embodiment of the present invention.
  • the upper curve in the figure corresponds to propylene selectivity, and the lower curve corresponds to the propane conversion rate.
  • the catalyst activity is expressed in terms of propane conversion rate and propylene selectivity and deactivation rate.
  • the propylene selectivity and deactivation rate are calculated by the following formula:
  • Fig. 1 is an AC-HAADF-TEM image of the PtZn/SiO 2 catalyst prepared in Example 1. From the figure, it can be seen that Pt and Zn atoms are arranged in an orderly manner, while PtZn monoatomic alloy is attached to SiO 2 On the surface of the carrier. 2 is an XRD pattern of the PtZn/SiO 2 catalyst prepared in Example 1, which is the crystal phase structure of the PtZn intermetallic alloy.
  • the reaction products were analyzed online using a gas chromatograph.
  • the relationship between propane conversion and propylene selectivity and time is shown in Figure 3. It can be seen that the catalyst using silica as the carrier has an initial propane conversion rate of 48.1%, 47.8% after 10 hours, and a deactivation rate of only 0.0028, while the propylene selectivity has been maintained at a high level (>94%); using three
  • the catalyst with aluminum oxide as the carrier has inferior propane conversion and propylene selection.
  • Example 1 The method of Example 1 was used for preparation and reaction, the only difference was that the mass of zinc nitrate (Zn(NO 3 ) 2 ⁇ 6H 2 O) in step (1) was 0.026g; the obtained catalyst was based on the mass of the carrier and the mass of Zn The percentage content is 0.06%.
  • Example 1 The method of Example 1 was used for preparation and reaction, the only difference was that the mass of zinc nitrate (Zn(NO 3 ) 2 ⁇ 6H 2 O) in step (1) was 0.234g; the obtained catalyst was based on the mass of the carrier and the mass of Zn The percentage content is 0.5%.
  • Example 2 The preparation and reaction were carried out by the method of Example 1, except that the mass of H 2 PtCl 6 in step (1) was 0.0011 g, the obtained catalyst was based on the mass of the carrier, and the mass percentage of Pt was 0.05%.
  • Example 2 The preparation and reaction were carried out by the method of Example 1, except that the mass of H 2 PtCl 6 in step (1) was 0.007 g, the obtained catalyst was based on the mass of the carrier, and the mass percentage of Pt was 0.3%.
  • Example 1 using silica as a carrier
  • the adjustment of the process parameters can achieve the preparation of the catalyst of the present invention, and after testing, the performance is basically consistent with the examples.
  • the above describes the present invention by way of example. It should be noted that, without departing from the core of the present invention, any simple modification, modification, or other equivalent replacements that can be made by those skilled in the art without costly creative work fall into this book. The scope of protection of the invention.

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Abstract

本发明公开了一种负载型PtZn金属间合金催化剂及其制备方法和应用，该催化剂以SiO 2为载体，以Zn为助剂，负载少量活性组分Pt；其中Pt的质量百分含量为0.025％-1％，Zn的质量百分含量为0.025％-1.7％；制备时采用共浸渍方法，将SiO 2载体浸渍于氯铂酸和硝酸锌的水溶液中，经过干燥、高温还原后得到PtZn/SiO 2催化剂，该催化剂具有高活性和高稳定性，且价格低廉，毒性小。本发明的催化剂适用于低链烷烃脱氢制烯烃反应，特别是临氢气氛下的丙烷脱氢制丙烯，在高温条件下脱氢活性很高，丙烯选择性可达到90％以上，稳定性良好，并且Pt用量少，利用率高，相比工业Pt系催化剂更为廉价。

Description

一种负载型PtZn金属间合金催化剂及其制备方法和应用 技术领域
本发明涉及负载型催化剂，具体来说，是涉及一种SiO 2负载的PtZn金属间合金催化剂及其制备方法和该催化剂在低碳烷烃脱氢制烯烃中的应用(以丙烷脱氢制丙烯为例)。
技术背景
低链烯烃(诸如乙烯，丙烯，丁烯，丁二烯等)是化工的基础原料，尤其是丙烯，近年来需求越来越旺盛。丙烯是三大合成材料的基本原料，主要用于生产丙烯腈、丙酮、环氧丙烷等产品。目前，丙烯供应主要来自石脑油裂解制乙烯和石油催化裂化过程的副产品。但是，随着页岩气技术的发展，乙烷变得越来越廉价易得，乙烯生产工艺也开始从石脑油裂解转向乙烷蒸汽裂解，因而丙烯的供应受到限制，价格也随之上升。加上传统工艺的高耗能、低选择性以及石油资源的短缺，促使人们寻找更经济更高效的丙烯等低链烯烃生产方式。由于丙烷与丙烯之间存在较大的价格差，丙烷脱氢(PDH)工艺近年来受到越来越多的关注。2013年10月，天津渤化年产能60万吨的丙烷脱氢装置的投产，丙烷脱氢大幕在中国正式拉开。2014-2016年间，丙烷脱氢(含混烷)产能已每年至少投产三套装置的速度增长。截止2017年底，中国丙烷脱氢(含混烷)总产能达513.5万吨，在总产能中占比达15％。
丙烷脱氢的反应式为:
Figure PCTCN2019119858-appb-000001
△H 298K＝124.3kJ/g.mol。由于丙烷催化脱氢反应是强吸热反应，受热力学平衡控制，高温、低压条件有利于反应的进行。目前，丙烷脱氢主要有五大工艺，包括Catofin(Lummus)、Oleflex(UOP)、STAR(UHDE)、FBD(Snamprogetti and Yarsintez)和Linde-BASF PDH，所有这些技术都采用Pt系和Cr系催化剂，其中Catofin(Lummus)和Oleflex(UOP)是应用最广泛的两套工艺。Catofin工艺采用Cr系催化剂，使用固定床反应器，平均12分钟对催化剂再生一次，单程转化率在55％-60％，选择性90％。而Oleflex工艺选用Pt系催化剂，使用移动床反应器，完全连续化操作，单程转化率在35％-40％左右，选择性84％。两大催化剂都由于积碳而失活严重，需要对催化剂进行再生，并且镉有剧毒，对环境不利，而铂价格昂贵，严重限制了丙烷脱氢工艺的发展。由此寻找一种廉价低毒且具有较高活性和稳定性的PDH催化剂，降低Pt 的用量，具有十分巨大的实际意义。
低碳烷烃脱氢反应是结构不敏感反应，这意味着单原子Pt能够催化脱氢反应。而对于低碳烷烃脱氢过程中伴随的副反应如氢解、异构化和积碳等，这些副反应是结构敏感反应，Pt颗粒粒径越大越有利于这些副反应的发生[Molecular understandings on the activation of light hydrocarbons over heterogeneous catalysts.Chemical Science 2015,6(8),4403-4425]。因此，用单位点Pt作低碳烷烃脱氢的活性位有望实现高选择性生产低碳烯烃。金属间合金是一种双金属合金，其中具有催化活性的金属以单原子的形式被惰性金属原子间隔，多应用于低温电催化反应，但是其在高温低碳烷烃脱氢反应中的应用罕有报道。
发明内容
本发明的目的在于克服现有技术的不足，要解决的是现有Pt系催化剂的容易积碳失活、贵金属用量较大的技术问题，提供了一种负载型PtZn金属间合金催化剂及其制备方法和在丙烷脱氢中的应用，该催化剂具有高活性、高稳定性、超低贵金属含量，催化脱氢失活速率慢，能够提高丙烯收率。
本发明的技术方案通过下述技术方案予以实现。
一种负载型PtZn金属间合金催化剂，以Pt为活性组分，Zn为助剂负载到载体上，Pt与Zn形成原子有序的金属间合金，以催化剂中载体质量为基准(100wt％)，Pt的质量百分含量不大于1％(金属Pt质量/载体质量×100wt％)，Zn的质量百分含量不大于1.7％(金属Zn质量/载体质量×100wt％)。
所述载体为二氧化硅、分子筛、沸石或者氧化铝。
Pt的质量百分含量为0.025％-1％，优选0.1％—0.5％。
Zn的质量百分含量为0.025％-1.5％，优选0.17％—0.85％。
Pt与Zn原子有序间隔排列并形成原子有序的金属间合金。
上述催化剂的制备方法，按照下述步骤进行：
步骤1，将载体置于含有金属铂和金属锌的溶液中进行浸渍，以使金属铂和金属锌负载到载体上；
在步骤1中，选择可溶性锌盐和氯铂酸分别提供金属锌和金属铂，并均匀分散在去离 子水中；可溶性锌盐为硝酸锌、氯化锌或者硫酸锌。
在步骤1中，载体为二氧化硅、分子筛、沸石或者氧化铝。
在步骤1中，载体用量为1质量份，金属铂用量为0.0025-0.01质量份，金属锌用量为0.0025-0.017质量份，每一质量份为1g，可选择等体积浸渍。
在步骤1中，进行浸渍时选择超声进行分散，超声时间为0.5h-1h，浸渍后在室温20—25摄氏度下自然干燥10—12h，然后在80-120℃下完全干燥
步骤2，将步骤1中负载金属铂和金属锌的载体置于氢气气氛中进行还原，还原(保温)温度为400—700摄氏度，得到负载型PtZn金属间合金催化剂。
在步骤2中，还原温度为500—600摄氏度。
在步骤2中，还原时间为0.5—3小时，优选0.5—1小时。
在步骤2中，由室温20—25摄氏度以每分钟5—10摄氏度的速度升温至还原温度进行保温，再自然冷却至室温20—25摄氏度，整个过程中负载金属铂和金属锌的载体始终处于氢气气氛之中，待冷却至室温后再抽走氢气。
本发明的负载型PtZn金属间合金催化剂在低链烷烃脱氢制备低链烯烃中的应用，特别是丙烷脱氢制丙烯。在进行使用时，按照下述步骤进行：
将负载型PtZn金属间合金催化剂压片为颗粒状催化剂，选用目数大小为20-40目，再将所得颗粒状催化剂装入固定床反应器，通入氮气，升温至预处理温度500-700℃；通入氢气进行预处理，维持在预处理温度0.5h-1h，降温至反应温度500-650℃；通入反应气进行反应，其中氢气和丙烷的摩尔比为(0-2):1，氮气为平衡气，保持总气数不变，基于丙烷的反应空速为1-5h -1。
使用氢气进行预处理的温度为600—700摄氏度；反应温度为600—650摄氏度；氢气和丙烷的摩尔比为1:1，基于丙烷的反应空速为3-4h -1。
本发明的催化剂在载体上负载的PtZn金属间合金，具有高比表面积和介孔孔道，有利于活性组分均匀分布和气体分子扩散；以少量Pt为活性组分(0.025％-1％，工业Pt系催化剂Pt含量在0.5％以上)，减少了催化剂中Pt含量，降低了催化剂的成本；Pt与Zn形成原子有序的金属间合金，Pt和Zn原子有序间隔，一方面极大地提高了Pt的原子利用率；另一方面促进了产物丙烯的脱附，抑制了C-C键断裂和深度脱氢等副反应，因而很好 地提升了催化剂的活性、选择性和稳定性。本发明的催化剂采用共浸渍法制备，原料易得，过程简单，重复性高，具有一定的工业意义。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的效果，在高温条件下脱氢活性很高，丙烯选择性可达到90％以上，并具有良好的稳定性。
附图说明
图1是本发明实施例1所制得的SiO 2负载PtZn金属间合金催化剂的AC-HAADF-TEM照片。
图2是本发明实施例1所制得的SiO 2负载的PtZn金属间合金催化剂的XRD测试谱线图。
图3是本发明实施例1中分别使用SiO 2和Al 2O 3负载的PtZn金属间合金催化剂的活性测试图，图中位于化学式上方的曲线对应丙烯选择性，下方的曲线对应丙烷转化率。
图4是本发明实施例中不同Zn的质量百分含量对催化活性的影响测试曲线图，图中上方曲线对应丙烯选择性，下方的曲线对应丙烷转化率。
图5是本发明实施例中不同Pt含量对催化活性的影响测试曲线图，图中上方曲线对应丙烯选择性，下方的曲线对应丙烷转化率。
图6是本发明实施例中不同预还原温度对催化活性的影响测试曲线图，图中上方曲线对应丙烯选择性，下方的曲线对应丙烷转化率。
图7是本发明实施例中不同反应温度对催化活性的影响测试曲线图，图中上方曲线对应丙烯选择性，下方的曲线对应丙烷转化率。
图8是本发明实施例中不同丙烷空速对催化活性的影响测试曲线图，图中上方曲线对应丙烯选择性，下方的曲线对应丙烷转化率。
图9是本发明实施例中不同丙烷/氢气比对催化活性的影响测试曲线图，图中上方曲线对应丙烯选择性，下方的曲线对应丙烷转化率。
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，以下实施例可以使本专业技术人员更全面的理解本发明，但不以任何方式限制本发明。
实施例1：
(1)将0.0021g质量份的H 2PtCl 6和0.078g质量份的Zn(NO 3) 2·6H 2O溶于4mL去离子水中；
(2)将1.0000gSiO 2(或Al 2O 3)浸渍于上述溶液，超声0.5h，室温干燥12h，100℃完全干燥；
(3)将(2)得到的固体在600℃下还原1h，得到PtZn/SiO 2(或PtZn/Al 2O 3)催化剂，该催化剂以其中载体质量为基准，Pt的质量百分含量为0.1％，Zn的质量百分含量为0.17％；
(4)将制备好的SiO 2(或Al 2O 3)负载的PtZn金属间催化剂压片为20-40目的颗粒状催化剂；
(5)将压片后的SiO 2(或Al 2O 3)负载的PtZn金属间颗粒状催化剂装入固定床反应器，通入氮气，升温至预处理温度600℃；通入氢气进行预处理，在600℃下维持1h；反应温度为600℃，一丙烷质量空速为4h -1，反应气中氢气和丙烷的摩尔比为1:1，平衡气为氮气。
催化剂活性以丙烷转化率和丙烯选择性及失活速率进行表示，丙烯选择性及失活速率以下式进行计算：
选择性：
Figure PCTCN2019119858-appb-000002
转化率：
Figure PCTCN2019119858-appb-000003
失活速率：
Figure PCTCN2019119858-appb-000004
其中，
Figure PCTCN2019119858-appb-000005
代表反应器入口处丙烷的体积流速，
Figure PCTCN2019119858-appb-000006
分别代表反应器出口处丙烷、丙烯的气体体积流速，X initial和X final分别代表反应初始及10h后的丙烷转化 率。
图1是实施例1所制得PtZn/SiO 2催化剂的AC-HAADF-TEM图，从图中可以看出Pt和Zn原子以原子有序的方式间隔排列，而PtZn单原子合金附着在SiO 2载体表面上。图2是实施例1所制得PtZn/SiO 2催化剂的XRD图，为PtZn金属间合金的晶相结构。
反应产物采用气相色谱仪在线分析，丙烷转化率和丙烯选择性与时间的关系如图3所示。可以看出使用二氧化硅为载体的催化剂，初始丙烷转化率达48.1％，10h后为47.8％，失活速率仅为0.0028，而丙烯选择性一直保持在高水平(>94％)；使用三氧化二铝为载体的催化剂，丙烷转化率和丙烯选择均不及前者。
实施例2：
用实施例1方法进行制备和反应，其区别仅在于步骤(1)中硝酸锌(Zn(NO 3) 2·6H 2O)的质量为0.026g；所得催化剂以载体质量为基准，Zn的质量百分含量为0.06％。
实施例3：
用实施例1方法进行制备和反应，其区别仅在于步骤(1)中硝酸锌(Zn(NO 3) 2·6H 2O)的质量为0.234g；所得催化剂以载体质量为基准，Zn的质量百分含量为0.5％。
实施例4：
用实施例1方法进行制备和反应，其区别仅在于步骤(1)中H 2PtCl 6的质量为0.0011g，所得催化剂以载体质量为基准，Pt的质量百分含量为0.05％。
实施例5：
用实施例1方法进行制备和反应，其区别仅在于步骤(1)中H 2PtCl 6的质量为0.007g，所得催化剂以载体质量为基准，Pt的质量百分含量为0.3％。
实施例6：
用实施例1方法进行制备和反应，其区别仅在于步骤(3)中的还原温度为300℃。
实施例7：
用实施例1方法进行制备和反应，其区别仅在于步骤(5)中的反应温度为520℃。
实施例8：
用实施例1方法进行制备和反应，其区别仅在于步骤(5)中的反应温度为550℃。
实施例9：
用实施例1方法进行制备和反应，其区别仅在于步骤(5)中的反应温度为620℃。
实施例10：
用实施例1方法进行制备和反应，其区别仅在于步骤(5)中的丙烷质量空速为9.5h -1。
实施例11：
用实施例1方法进行制备和反应，其区别仅在于步骤(5)中的氢气：丙烷＝0。
实施例12：
用实施例1方法进行制备和反应，其区别仅在于步骤(5)中的氢气：丙烷＝0.5。
实施例13：
用实施例1方法进行制备和反应，其区别仅在于步骤(5)中的氢气：丙烷＝2。
对于上述实施例结果，均采用反应初始和10h时的活性数据做对比，测试条件和方法与实施例1相同(采用二氧化硅为载体)，以考察不同参数对催化剂反应性能的影响。
(一)Zn的质量百分含量(以催化剂中载体质量为基准)对PtZn/SiO 2催化剂反应活性的影响，参见图4。反应条件同实施例1、2、3。从图中可以看出，当Zn的质量分数为0.06-0.5％时，催化剂同时实现高的稳定性和活性，初始所得丙烷转化率约为48％，选择性达约96％，同时失活速率为0.0028h -1左右。反应条件同实施例1、4、5。
(二)Pt的质量百分含量(以催化剂中载体质量为基准)对PtZn/SiO 2催化剂反应活性的影响，参见图5。反应条件同实施例1、4、5。从图中可以看出，当Pt的质量分数为0.05％时，虽然活性很好但稳定性不佳。当Pt的质量分数适中时(0.1％)，催化剂能同时实现很好的活性和稳定性，初始所得丙烷转化率为48％，选择性达95％，同时失活速率仅为0.014h -1。
(三)预还原温度对PtZn/SiO 2催化剂反应活性的影响，参见图6。反应条件同实施例1、6。从图中可以看出，预还原温度对反应活性和选择性有着重要的影响，高温还原是形成金属间合金的必要条件，较佳的还原温度为600℃。
(四)反应温度对PtZn/SiO 2催化剂催化活性的影响，参见图7。反应条件同实施例1、7、8、9。从图中可以看出，随着反应温度的增加，丙烷转化率逐渐增加，但是丙烯选择性有所降低，在600度时有最好的转化率和选择性。
(五)丙烷空速比对丙烷脱氢活性的影响，参见图8。反应条件同实施例1、10。从 图8可以看出，随着丙烷空速的增加，丙烷的转化率有所降低，所以最佳空速是4h -1。
(六)丙烷：氢气对丙烷脱氢活性的影响，参见图9。反应条件同实施例1、11、12、13。从图中可以看出，随着H 2：C 3H 8的增加，丙烷的转化率有所降低，但是丙烯的选择性显著增加，说明了H 2分压对丙烷脱氢反应有显著影响，其中最佳的比例为丙烷：氢气＝1。
根据本发明内容进行工艺参数的调整，均可实现本发明催化剂的制备，经测试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 (10)

  1. 一种负载型PtZn金属间合金催化剂，其特征在于，以Pt为活性组分，Zn为助剂负载到载体上，Pt与Zn形成原子有序的金属间合金，以催化剂中载体质量为基准，Pt的质量百分含量不大于1％，Zn的质量百分含量不大于1.7％。
  2. 根据权利要求1所述的一种负载型PtZn金属间合金催化剂，其特征在于，Pt的质量百分含量为0.025％-1％，优选0.1％—0.5％。
  3. 根据权利要求1所述的一种负载型PtZn金属间合金催化剂，其特征在于，Zn的质量百分含量为0.025％-1.5％，优选0.17％—0.85％。
  4. 根据权利要求1或者2或者3所述的一种负载型PtZn金属间合金催化剂，其特征在于，所述载体为二氧化硅、分子筛、沸石或者氧化铝。
  5. 一种负载型PtZn金属间合金催化剂的制备方法，其特征在于，按照下述步骤进行：
    步骤1，将载体置于含有金属铂和金属锌的溶液中进行浸渍，以使金属铂和金属锌负载到载体上；
    步骤2，将步骤1中负载金属铂和金属锌的载体置于氢气气氛中进行还原，还原温度为400—700摄氏度，得到负载型PtZn金属间合金催化剂。
  6. 根据权利要求5所述的一种负载型PtZn金属间合金催化剂的制备方法，其特征在于，在步骤1中，选择可溶性锌盐和氯铂酸分别提供金属锌和金属铂，并均匀分散在去离子水中；可溶性锌盐为硝酸锌、氯化锌或者硫酸锌；载体为二氧化硅、分子筛、沸石或者氧化铝；载体用量为1质量份，金属铂用量为0.0025-0.01质量份，金属锌用量为0.0025-0.017质量份。
  7. 根据权利要求5所述的一种负载型PtZn金属间合金催化剂的制备方法，其特征在于，在步骤2中，还原温度为500—600摄氏度；还原时间为0.5—3小时，优选0.5—1小时。
  8. 根据权利要求5所述的一种负载型PtZn金属间合金催化剂的制备方法，其特征在于，在步骤2中，由室温20—25摄氏度以每分钟5—10摄氏度的速度升温至还原温度进行保温，再自然冷却至室温20—25摄氏度，整个过程中负载金属铂和金属锌的载体始终处于氢气气氛之中，待冷却至室温后再抽走氢气。
  9. 如权利要求1—4之一所述的一种负载型PtZn金属间合金催化剂在低链烷烃脱氢制备低链烯烃中的应用。
  10. 根据权利要求9所述的应用，其特征在于，负载型PtZn金属间合金催化剂在丙烷脱氢制丙烯中的应用，按照下述步骤进行：将负载型PtZn金属间合金催化剂压片为颗粒状催化剂，选用目数大小为20-40目，再将所得颗粒状催化剂装入固定床反应器，通入氮气，升温至预处理温度500-700℃；通入氢气进行预处理，维持在预处理温度0.5h-1h，降温至反应温度500-650℃；通入反应气进行反应，其中氢气和丙烷的摩尔比为(0-2):1，氮气为平衡气，保持总气数不变，基于丙烷的反应空速为1-5h -1；优选的，使用氢气进行预处理的温度为600—700摄氏度；反应温度为600—650摄氏度；氢气和丙烷的摩尔比为1:1，基于丙烷的反应空速为3-4h -1。
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