WO2018010360A1 - Preparation and application of high-performance toluene side-chain alkylation catalyst - Google Patents

Preparation and application of high-performance toluene side-chain alkylation catalyst Download PDF

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WO2018010360A1
WO2018010360A1 PCT/CN2016/106953 CN2016106953W WO2018010360A1 WO 2018010360 A1 WO2018010360 A1 WO 2018010360A1 CN 2016106953 W CN2016106953 W CN 2016106953W WO 2018010360 A1 WO2018010360 A1 WO 2018010360A1
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alkali metal
molecular sieve
metal oxide
supported
catalyst
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许磊
李沛东
徐力
张晓敏
袁扬扬
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中国科学院大连化学物理研究所
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/082—X-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/073—Ethylbenzene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
    • C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
    • C07C15/46—Styrene; Ring-alkylated styrenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/88—Growth and elimination reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y

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  • the catalyst provided by the invention has good stability and is continuously operated on a fixed bed reactor. There was no obvious inactivation at 500h.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

A dual-function catalyst and a preparation method therefor. The catalyst comprises a basic molecular sieve and a supported alkali metal oxide, wherein the basic molecular sieve is an alkali metal molecular sieve having an FAU structure; the supported alkali metal oxide comprises a carrier and an alkali metal oxide supported on the carrier. The catalyst can greatly improve the conversion rate of toluene while keeping the high selectivity of styrene in products in a toluene-methanol side-chain alkylation reaction system.

Description

一种高性能甲苯侧链烷基化催化剂的制备及其应用Preparation and application of a high performance toluene side chain alkylation catalyst 技术领域Technical field
本发明涉及一种双功能催化剂、其制备方法以及在甲苯甲醇制苯乙烯联产乙苯反应中的应用。The invention relates to a bifunctional catalyst, a preparation method thereof and the use of the reaction of toluene methanol to styrene co-production of ethylbenzene.
背景技术Background technique
苯乙烯可用于生产SBR橡胶、ABS塑料、SBN树脂等，是合成橡胶和塑料工业的重要原料。目前主流的苯乙烯生产路线是乙苯脱氢法，该工艺存在设备投资大，副反应多，能耗高等问题，因此人们对新的苯乙烯生产工艺的开发有着浓厚的兴趣。Styrene can be used in the production of SBR rubber, ABS plastic, SBN resin, etc. It is an important raw material for the synthetic rubber and plastics industries. At present, the mainstream styrene production route is ethylbenzene dehydrogenation. This process has great problems such as large equipment investment, many side reactions, and high energy consumption. Therefore, people have a strong interest in the development of new styrene production processes.
1967年首先报道了一种由甲苯甲醇侧链烷基化制苯乙烯的工艺，该工艺被认为有着重要的工业应用价值。该反应既需要催化剂提供酸性，也需要催化剂提供碱性，在众多种类的催化剂中，碱金属离子交换的分子筛被认为有着较好的活性，其中深度改性的CsX分子筛是目前研究的重点。尽管CsX分子筛在同类催化剂中有着最好的催化活性，但甲苯的转化率仍然偏低，是限制甲苯甲醇侧链烷基化工艺工业应用的主要因素。In 1967, a process for the alkylation of toluene methanol side chains to styrene was first reported, which is considered to have important industrial application value. The reaction requires both the acidity of the catalyst and the basicity of the catalyst. Among many kinds of catalysts, the alkali metal ion exchanged molecular sieve is considered to have good activity, and the deeply modified CsX molecular sieve is the focus of current research. Although CsX molecular sieves have the best catalytic activity among similar catalysts, the conversion of toluene is still low, which is the main factor limiting the industrial application of toluene methanol side chain alkylation process.
发明内容Summary of the invention
本发明的目的在于提供一种催化剂，该催化剂在甲苯甲醇侧链烷基化体系中，可大幅度提高甲苯转化率，同时，可以保持产物中苯乙烯具有较高的选择性。SUMMARY OF THE INVENTION It is an object of the present invention to provide a catalyst which greatly increases the conversion of toluene in the side chain alkylation system of toluene methanol while maintaining a high selectivity for styrene in the product.
所述催化剂，其特征在于，包括碱性分子筛和负载型碱金属氧化物；The catalyst characterized by comprising a basic molecular sieve and a supported alkali metal oxide;
其中，所述碱性分子筛为具有FAU结构的碱金属型分子筛；Wherein the basic molecular sieve is an alkali metal type molecular sieve having a FAU structure;
所述负载型碱金属氧化物包括载体及负载在载体上的碱金属氧化物。The supported alkali metal oxide includes a support and an alkali metal oxide supported on the support.
优选地，所述碱性分子筛为碱金属型的X分子筛和/或碱金属型的Y分子筛。进一步优选地，所述碱性分子筛中的碱金属元素选自Na、K、Rb、Cs中的至少一种。Preferably, the basic molecular sieve is an alkali metal type X molecular sieve and/or an alkali metal type Y molecular sieve. Further preferably, the alkali metal element in the basic molecular sieve is at least one selected from the group consisting of Na, K, Rb, and Cs.
优选地，所述碱性分子筛中的硅铝摩尔比为Si/Al＝1～10。进一步优选地，所述碱性分子筛中的硅铝摩尔比为Si/Al＝1～3。 Preferably, the molar ratio of silicon to aluminum in the basic molecular sieve is Si/Al = 1 to 10. Further preferably, the molar ratio of silicon to aluminum in the basic molecular sieve is Si/Al = 1 to 3.
优选地，所述载体选自SiO2、α-Al2O3、活性炭、SiC、ZrO2、TiO2中的至少一种。Preferably, the support is at least one selected from the group consisting of SiO 2 , α-Al 2 O 3 , activated carbon, SiC, ZrO 2 , and TiO 2 .
优选地，负载在载体上的碱金属氧化物选自钠的氧化物、钾的氧化物、铷的氧化物、铯的氧化物中的至少一种。Preferably, the alkali metal oxide supported on the carrier is at least one selected from the group consisting of an oxide of sodium, an oxide of potassium, an oxide of cerium, and an oxide of cerium.
优选地，负载型碱金属氧化物中，碱金属氧化物质量负载量为5～25％。Preferably, in the supported alkali metal oxide, the alkali metal oxide has a mass loading of 5 to 25%.
优选地，所述碱性分子筛与负载型碱金属氧化物的质量比为0.5～10:1。Preferably, the mass ratio of the basic molecular sieve to the supported alkali metal oxide is from 0.5 to 10:1.
优选地，上述任意催化剂的制备方法包含以下步骤：Preferably, the preparation method of any of the above catalysts comprises the following steps:
(a)碱性分子筛：(a) Basic molecular sieves:
负载型碱金属氧化物的制备：用含有碱金属离子的浸渍液对载体进行等体积浸渍后，经干燥、焙烧得到负载型碱金属氧化物；Preparation of supported alkali metal oxide: impregnation of the support in an equal volume with an impregnation liquid containing an alkali metal ion, followed by drying and calcination to obtain a supported alkali metal oxide;
(b)将步骤(a)得到的负载型碱金属氧化物与碱性分子筛按照下述3种方式中的至少一种，制备得到催化剂：(b) preparing the catalyst by the supported alkali metal oxide obtained in the step (a) and the basic molecular sieve in at least one of the following three ways:
方式(1)：负载型碱金属氧化物和碱性分子筛分别成型后，经机械混合均匀；Mode (1): After the supported alkali metal oxide and the basic molecular sieve are separately formed, they are mechanically mixed uniformly;
方式(2)：将负载型碱金属氧化物和碱性分子筛分别研磨或球磨机球磨，经混合均匀后，再进行催化剂成型；Mode (2): grinding the supported alkali metal oxide and the basic molecular sieve separately or ball milling by a ball mill, and after uniformly mixing, performing catalyst molding;
方式(3)将负载型碱金属氧化物和碱性分子筛混合后，经研磨或球磨机球磨再进行催化剂成型。Mode (3) After mixing the supported alkali metal oxide and the basic molecular sieve, the catalyst is molded by grinding or ball milling.
优选地，所述碱金属离子选自钾离子、铷离子、铯离子中的至少一种。Preferably, the alkali metal ion is at least one selected from the group consisting of potassium ions, strontium ions, and strontium ions.
本发明的又一目的在于提供了一种所述催化剂的应用，其特征在于，所述催化剂用于甲苯甲醇制苯乙烯联产乙苯的反应。It is still another object of the present invention to provide an application of the catalyst, characterized in that the catalyst is used for the reaction of toluene methanol to styrene to co-produce ethylbenzene.
优选地，甲苯甲醇制苯乙烯联产乙苯的反应原料气中，甲苯与甲醇摩尔比为0.5～10：1；甲苯的质量空速WHSV为0.2～6h-1；反应压力为0.1～20MPa；反应温度370～500℃。Preferably, the reaction raw material gas of toluene methanol to styrene co-produced ethylbenzene, the molar ratio of toluene to methanol is 0.5-10:1; the mass space velocity of toluene WHSV is 0.2-6h -1 ; the reaction pressure is 0.1-2020 MPa; The reaction temperature is 370 to 500 °C.
本发明的有益效果包括但不限于：Advantages of the invention include, but are not limited to:
(1)本发明所提供的催化剂，用于甲苯甲醇制苯乙烯并联产乙苯的反应中，具有甲苯转化率高，产物中苯乙烯选择性高等特点。(1) The catalyst provided by the invention is used for the reaction of producing toluene in parallel with toluene methanol to produce ethylbenzene, and has the characteristics of high toluene conversion rate and high selectivity of styrene in the product.
(2)本发明所提供的催化剂稳定性好，在固定床反应器上，连续运行 500h的未见有明显的失活现象。(2) The catalyst provided by the invention has good stability and is continuously operated on a fixed bed reactor. There was no obvious inactivation at 500h.
(3)本发明所提供的甲苯甲醇制苯乙烯联产乙苯的方法，在高甲苯转化率条件下，有效抑制了产物中苯乙烯向乙苯转化，从而保持了较高的苯乙烯选择性。(3) The method for co-producing ethylbenzene from toluene methanol to styrene provided by the invention can effectively inhibit the conversion of styrene to ethylbenzene in the product under the condition of high toluene conversion rate, thereby maintaining high styrene selectivity. .
(4)本发明所提供的甲苯甲醇制苯乙烯联产乙苯的方法，操作简便，满足工业应用要求，便于进行大规模工业化生产。(4) The method for co-producing ethylbenzene from toluene methanol to styrene provided by the invention is simple in operation, meets industrial application requirements, and is convenient for large-scale industrial production.
具体实施方式detailed description
下面结合实施例详述本发明，但本发明并不局限于这些实施例。同时实施例只是给出实现制备苯乙烯的部分条件，但并不意味着必须满足这些条件才可以达到此目的。The invention will be described in detail below with reference to examples, but the invention is not limited to the examples. While the examples are merely given to the partial conditions for the preparation of styrene, it is not meant that these conditions must be met in order to achieve this.
如无特别说明，实施例中所采用原料均来自商业购买，仪器设备采用厂家推荐的参数设置。Unless otherwise stated, the materials used in the examples were all purchased commercially, and the equipment was set by the manufacturer's recommended parameters.
实施例中，催化剂的元素组成采用PANAbalytical公司的Axios 2.4KW型X射线荧光分析仪(XRF)测定。In the examples, the elemental composition of the catalyst was measured using an Axios 2.4KW X-ray fluorescence analyzer (XRF) from PANAbalytical.
实施例中，产物采用安捷伦7890A色谱在线分析。烃类组分采用Agilent CP-WAX 25m×32μm×1.2μm毛细管柱分离，FID检测器检测，Porapark Q4m×1/8″填充柱分离CO、CO2和H2，TCD检测器检测。In the examples, the products were analyzed online using an Agilent 7890A chromatography. The hydrocarbon components were separated by Agilent CP-WAX 25m×32μm×1.2μm capillary column, detected by FID detector, and separated by CO, CO 2 and H 2 on Porapark Q4m×1/8′′ packed column, detected by TCD detector.
实施例中，甲苯转化率X甲苯、苯乙烯选择性S苯乙烯、乙苯选择性S乙苯定义如下：In the examples, toluene conversion X toluene , styrene selective S styrene , ethylbenzene selective S ethylbenzene are defined as follows:
Figure PCTCN2016106953-appb-000001
Figure PCTCN2016106953-appb-000001
Figure PCTCN2016106953-appb-000002
Figure PCTCN2016106953-appb-000002
Figure PCTCN2016106953-appb-000003
Figure PCTCN2016106953-appb-000003
实施例1碱性分子筛样品的制备Example 1 Preparation of a Basic Molecular Sieve Sample
实施例中所采用的碱金属型分子筛均来自商业购买。The alkali metal type molecular sieves used in the examples were all commercially available.
碱金属X型分子筛：Alkali metal X type molecular sieve:
取80g硅铝比(Si/Al)为1.17的NaX分子筛，按质量平均分成四份，分别以0.5mol/L CsOH溶液100ml，在80℃下交换1～4次，用去离子水洗涤抽滤至滤出液呈中性为止，120℃烘干过夜，550℃空气中焙烧4h，交换1～4次的样品分别记为Z-1#、Z-2#、Z-3#、Z-4#。Take 80g of NaX molecular sieve with a ratio of silicon to aluminum (Si/Al) of 1.17, divide it into four parts by mass, and respectively exchange 100ml of 0.5mol/L CsOH solution, exchange 1-4 times at 80 °C, wash and filter with deionized water. Until the filtrate is neutral, dry at 120 ° C overnight, 550 ° C air roasting for 4 h, exchange 1 ~ 4 times of the sample are recorded as Z-1 # , Z-2 # , Z-3 # , Z-4 # 。.
碱金属Y型分子筛：Alkali metal Y type molecular sieve:
取硅铝比(Si/Al)为2.13的NaY分子筛20g，以0.5mol/L CsOH溶液100ml，在80℃条件下交换3次，120℃烘干过夜，550℃焙烧4h，样品记为Z-5#。Take 20 g of NaY molecular sieve with a ratio of silicon to aluminum (Si/Al) of 2.13, exchange 100 ml of 0.5 mol/L CsOH solution, exchange 3 times at 80 ° C, dry at 120 ° C overnight, and calcine at 550 ° C for 4 h. The sample is recorded as Z- 5 # .
取硅铝比(Si/Al)为2.89的NaY分子筛各20g，分别以0.5mol/L CsOH溶液100ml、0.5mol/L KOH溶液100ml、0.5mol/L RbOH溶液100ml，在80℃条件下交换3次，120℃烘干过夜，550℃焙烧4h，样品分别记为Z-6#、Z-7#、Z-8#。Take 20g of NaY molecular sieve with a ratio of silicon to aluminum (Si/Al) of 2.89, respectively, 100ml of 0.5mol/L CsOH solution, 100ml of 0.5mol/L KOH solution, 100ml of 0.5mol/L RbOH solution, and exchange at 80°C. times, 120 ℃ drying overnight, 550 ℃ calcined 4h, samples were referred to as Z-6 #, Z-7 #, Z-8 #.
所得样品编号、离子交换液种类和浓度以及离子交换度如表1所示。采用XRF元素分析对所得样品进行元素分析，离子交换度根据交换前后样品中的钠含量进行计算。The obtained sample number, ion exchange liquid type and concentration, and ion exchange degree are shown in Table 1. The obtained sample was subjected to elemental analysis by XRF elemental analysis, and the degree of ion exchange was calculated based on the sodium content in the sample before and after the exchange.
表1Table 1
Figure PCTCN2016106953-appb-000004
Figure PCTCN2016106953-appb-000004
实施例2金属氧化物样品的制备Example 2 Preparation of Metal Oxide Samples
等体积浸渍法：Equal volume impregnation method:
首先将待浸渍载体抽真空，然后用去离子水测定载体对去离子水的饱和吸附量。按负载量计算出所需浸渍前驱物的质量，将相应质量的前驱物溶于载体饱和吸附所需质量的去离子水中，搅拌均匀，制成浸渍液。在室温下等体积浸渍24小时后，经120℃烘干，550℃空气中焙烧4h备用。负载氧化物和负载前驱物的种类及负载量如表2所示。The carrier to be impregnated is first evacuated, and then the saturated adsorption amount of the carrier to deionized water is determined by deionized water. The mass of the desired impregnation precursor is calculated according to the amount of the load, and the precursor of the corresponding mass is dissolved in the deionized water of the mass required for the saturated adsorption of the carrier, and stirred uniformly to prepare an impregnation liquid. After immersion in an equal volume for 24 hours at room temperature, it was dried at 120 ° C, and calcined in air at 550 ° C for 4 hours. The types and loadings of the load oxide and the load precursor are shown in Table 2.
表2Table 2
样品sample 载体*Carrier* 浸渍前驱体Impregnated precursor 负载氧化物Load oxide 负载量(质量)Load (mass)
AC-1# AC-1 # B型SiO2 B type SiO 2 醋酸钠Sodium acetate 氧化钠Sodium oxide 10％10%
AC-2# AC-2 # B型SiO2 B type SiO 2 醋酸钾Potassium acetate 氧化钾Potassium oxide 10％10%
AC-3# AC-3 # B型SiO2 B type SiO 2 醋酸铯Barium acetate 氧化铯Yttrium oxide 5％5%
AC-4# AC-4 # B型SiO2 B type SiO 2 醋酸铯Barium acetate 氧化铯Yttrium oxide 10％10%
AC-5# AC-5 # B型SiO2 B type SiO 2 醋酸铯Barium acetate 氧化铯Yttrium oxide 25％25%
AC-6# AC-6 # α-Al2O3 α-Al 2 O 3 醋酸铯Barium acetate 氧化铯Yttrium oxide 10％10%
AC-7# AC-7 # 活性炭Activated carbon 醋酸铯Barium acetate 氧化铯Yttrium oxide 10％10%
AC-8# AC-8 # SiCSiC 醋酸铯Barium acetate 氧化铯Yttrium oxide 10％10%
AC-9# AC-9 # ZrO2 ZrO 2 醋酸铯Barium acetate 氧化铯Yttrium oxide 10％10%
AC-10# AC-10 # TiO2 TiO 2 醋酸铯Barium acetate 氧化铯Yttrium oxide 10％10%
*：载体中的B型SiO2是指B型硅胶。*: Type B SiO 2 in the carrier means B type silica gel.
实施例3催化剂样品的制备Example 3 Preparation of Catalyst Samples
将实施例1制备得到的碱性分子筛样品Z-1#～Z-8#中的至少一种和金属氧化物样品AC-1#～AC-10#中的至少一种混合，取20～40目，得到的催化剂记为CAT-1#～CAT-13#。其中CAT-1#～CAT-14#在QM-3SP2型球磨机上球磨20h；CAT-15#通过机械混合均匀；CAT-16#分别研磨，经混合均匀后，再进行催化剂成型。Mixing at least one of the basic molecular sieve samples Z-1 # to Z-8 # prepared in Example 1 and at least one of the metal oxide samples AC-1 # to AC-10 # , taking 20 to 40 The catalyst obtained was recorded as CAT-1 # to CAT-13 # . Among them, CAT-1 # ～CAT-14 # ball milled on QM-3SP2 ball mill for 20h; CAT-15 # was mechanically mixed uniformly; CAT-16 # was separately ground, and after mixing, catalyst molding was carried out.
所得双功能催化剂样品的编号与其所含碱性分子筛样品和金属氧化物样品种类和质量比例的关系如表3所示。 The relationship between the number of the obtained bifunctional catalyst sample and the type and mass ratio of the basic molecular sieve sample and the metal oxide sample contained therein is shown in Table 3.
表3table 3
样品sample 碱性分子筛样品和金属氧化物样品的种类及质量比Type and mass ratio of basic molecular sieve samples and metal oxide samples
CAT-1# CAT-1 # Z-1#：AC-4#：＝4:1Z-1 # :AC-4 # :=4:1
CAT-2# CAT-2 # Z-2#：AC-4#：＝4:1Z-2 # :AC-4 # :=4:1
CAT-3# CAT-3 # Z-3#：AC-4#：＝4:1Z-3 # :AC-4 # :=4:1
CAT-4# CAT-4 # Z-4#：AC-4#：＝4:1Z-4 # :AC-4 # :=4:1
CAT-5# CAT-5 # Z-5#：AC-6#：＝4:1Z-5 # :AC-6 # :=4:1
CAT-6# CAT-6 # Z-6#：AC-7#：＝4:1Z-6 # :AC-7 # :=4:1
CAT-7# CAT-7 # Z-7#：AC-8#：＝4:1Z-7 # :AC-8 # :=4:1
CAT-8# CAT-8 # Z-8#：AC-9#：＝4:1Z-8 # :AC-9 # :=4:1
CAT-9# CAT-9 # Z-3#：AC-10#：＝4:1 Z-3 #: AC-10 #: = 4: 1
CAT-10# CAT-10 # Z-3#：AC-1#：＝4:1Z-3 # :AC-1 # :=4:1
CAT-11# CAT-11 # Z-3#：AC-2#：＝4:1Z-3 # :AC-2 # :=4:1
CAT-12# CAT-12 # Z-3#：AC-3#：＝4:1Z-3 # :AC-3 # :=4:1
CAT-13# CAT-13 # Z-3#：AC-5#：#＝4:1Z-3 # :AC-5 # : # =4:1
CAT-14# CAT-14 # Z-3#：AC-4#：＝1:2Z-3 # :AC-4 # :=1:2
CAT-15# CAT-15 # Z-3#：AC-4#：＝2:1Z-3 # :AC-4 # :=2:1
CAT-16# CAT-16 # Z-3#：AC-4#：＝10:1Z-3 # :AC-4 # :=10:1
对比例1催化剂制备Comparative Example 1 Catalyst Preparation
由实施例1得到的Z-3#和Z-4#分子筛直接作为催化剂，记为CAT-D1#和CAT-D2#。Z-3 #, and Z-4 # zeolite obtained in Example 1 directly as the catalyst, referred to as CAT-D1 # and CAT-D2 #.
对比例2催化剂制备Comparative Example 2 Catalyst Preparation
由实施例1得到的Z-3#和Z-4#分子筛直接作为载体负载，通过等体积浸渍法，负载氧化铯，氧化铯的质量负载量为2％，得到的催化剂记为CAT-D3#和CAT-D4#。The Z-3 # and Z-4 # molecular sieves obtained in Example 1 were directly supported as a carrier, and the mass loading amount of cerium oxide was 2% by an equal volume impregnation method, and the obtained catalyst was recorded as CAT-D3 # And CAT-D4 # .
实施例4催化剂评价Example 4 Catalyst Evaluation
分别将表3中的催化剂和对比例1、对比例2得到的催化剂压片、破碎并筛分为20-40目，各取1g装入小型固定床反应器中，催化剂两端装填石 英砂，催化剂首先在40ml/min流速的氦气气氛下550℃活化1h，然后降温至反应温度，用微量进料泵通入原料甲苯甲醇，甲苯甲醇摩尔进料比、空速、反应压力、反应温度见表4。产物通过安捷伦7890A气相色谱仪进行检测，反应结果列于表4。The catalysts in Table 3 and the catalysts obtained in Comparative Example 1 and Comparative Example 2 were respectively tableted, crushed and sieved into 20-40 mesh, and 1 g each was charged into a small fixed bed reactor, and the catalyst was loaded at both ends of the catalyst. In the sand, the catalyst was first activated at 550 ° C for 1 h in a helium atmosphere at a flow rate of 40 ml/min, then cooled to the reaction temperature, and the feed toluene methanol, toluene methanol molar feed ratio, space velocity, reaction pressure, The reaction temperature is shown in Table 4. The product was tested by an Agilent 7890A gas chromatograph and the results are shown in Table 4.
表4Table 4
Figure PCTCN2016106953-appb-000005
Figure PCTCN2016106953-appb-000005
以上所述，仅是本发明的几个实施例，并非对本发明做任何形式的限 制，虽然本发明以较佳实施例揭示如上，然而并非用以限制本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于本发明技术方案范围内。 The above is only a few embodiments of the present invention, and is not intended to limit the scope of the present invention. The present invention is disclosed in the above preferred embodiments, but is not intended to limit the present invention. Any person skilled in the art can make a slight use of the technical contents disclosed above without departing from the technical scope of the present invention. Variations or modifications are equivalent to equivalent embodiments, and are within the scope of the technical solution of the present invention.

Claims (10)

  1. 一种催化剂，其特征在于，包括碱性分子筛和负载型碱金属氧化物；a catalyst comprising a basic molecular sieve and a supported alkali metal oxide;
    其中，所述碱性分子筛为具有FAU结构的碱金属型分子筛；Wherein the basic molecular sieve is an alkali metal type molecular sieve having a FAU structure;
    所述负载型碱金属氧化物包括载体及负载在载体上的碱金属氧化物。The supported alkali metal oxide includes a support and an alkali metal oxide supported on the support.
  2. 根据权利要求1所述的催化剂，其特征在于，所述碱性分子筛为碱金属型的X分子筛和/或碱金属型的Y分子筛。The catalyst according to claim 1, wherein the basic molecular sieve is an alkali metal type X molecular sieve and/or an alkali metal type Y molecular sieve.
  3. 根据权利要求1所述的催化剂，其特征在于，所述载体选自SiO2、α-Al2O3、活性炭、SiC、ZrO2、TiO2中的至少一种。The catalyst according to claim 1, wherein the support is at least one selected from the group consisting of SiO 2 , α-Al 2 O 3 , activated carbon, SiC, ZrO 2 , and TiO 2 .
  4. 根据权利要求1所述的催化剂，其特征在于，负载在载体上的碱金属氧化物选自钠的氧化物、钾的氧化物、铷的氧化物、铯的氧化物中的至少一种。The catalyst according to claim 1, wherein the alkali metal oxide supported on the carrier is at least one selected from the group consisting of an oxide of sodium, an oxide of potassium, an oxide of cerium, and an oxide of cerium.
  5. 根据权利要求1所述的催化剂，其特征在于，负载型碱金属氧化物中，碱金属氧化物的质量负载量为5％～25％。The catalyst according to claim 1, wherein the supported alkali metal oxide has a mass loading of the alkali metal oxide of 5% to 25%.
  6. 根据权利要求1所述的催化剂，其特征在于，所述碱性分子筛与负载型碱金属氧化物的质量比为0.5～10:1。The catalyst according to claim 1, wherein the mass ratio of the basic molecular sieve to the supported alkali metal oxide is from 0.5 to 10:1.
  7. 根据权利要求1至6任一项所述催化剂，其特征在于，制备方法包含以下步骤：The catalyst according to any one of claims 1 to 6, wherein the preparation method comprises the steps of:
    (a)负载型碱金属氧化物的制备：用含有碱金属离子的浸渍液对载体进行等体积浸渍后，经干燥、焙烧得到负载型碱金属氧化物；(a) preparation of supported alkali metal oxide: impregnation of the support in an equal volume with an impregnation liquid containing an alkali metal ion, followed by drying and calcination to obtain a supported alkali metal oxide;
    (b)将步骤(a)得到的负载型碱金属氧化物与碱性分子筛按照下述3种方式中的至少一种，制备得到催化剂：(b) preparing the catalyst by the supported alkali metal oxide obtained in the step (a) and the basic molecular sieve in at least one of the following three ways:
    方式(1)：负载型碱金属氧化物和碱性分子筛分别成型后，经机械混合均匀；Mode (1): After the supported alkali metal oxide and the basic molecular sieve are separately formed, they are mechanically mixed uniformly;
    方式(2)：将负载型碱金属氧化物和碱性分子筛分别研磨或球磨机球磨，经混合均匀后，再进行催化剂成型；Mode (2): grinding the supported alkali metal oxide and the basic molecular sieve separately or ball milling by a ball mill, and after uniformly mixing, performing catalyst molding;
    方式(3)将负载型碱金属氧化物和碱性分子筛混合后，经研磨或球磨机球磨再进行催化剂成型。Mode (3) After mixing the supported alkali metal oxide and the basic molecular sieve, the catalyst is molded by grinding or ball milling.
  8. 根据权利要求7所述的催化剂，其特征在于，所述碱性分子筛在与 负载型碱金属氧化物混合前，先与含有碱金属离子的溶液进行离子交换；所述碱金属离子选自钾离子、铷离子、铯离子中的至少一种。The catalyst according to claim 7 wherein said basic molecular sieve is in Before the supported alkali metal oxide is mixed, ion exchange is performed with a solution containing an alkali metal ion; the alkali metal ion is selected from at least one of potassium ion, strontium ion, and strontium ion.
  9. 权利要求1至8任一项所述的催化剂在甲苯甲醇制苯乙烯联产乙苯反应中的应用。Use of the catalyst according to any one of claims 1 to 8 for the reaction of co-production of ethylbenzene with toluene methanol to styrene.
  10. 根据权利要求9所述的应用，其特征在于，所述原料甲苯与甲醇摩尔比为0.5～10：1；甲苯的质量空速WHSV为0.2～6h-1；反应压力为0.1～20MPa；反应温度350～500℃。 The application according to claim 9, wherein the raw material has a molar ratio of toluene to methanol of 0.5 to 10:1; the mass space velocity of toluene is 0.5 to 6 h -1 ; the reaction pressure is 0.1 to 20 MPa; and the reaction temperature is 350 ~ 500 ° C.
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