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WO2018010359A1 - 一种双功能催化剂的制备方法及应用 - Google Patents

一种双功能催化剂的制备方法及应用 Download PDF

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WO2018010359A1
WO2018010359A1 PCT/CN2016/106951 CN2016106951W WO2018010359A1 WO 2018010359 A1 WO2018010359 A1 WO 2018010359A1 CN 2016106951 W CN2016106951 W CN 2016106951W WO 2018010359 A1 WO2018010359 A1 WO 2018010359A1
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molecular sieve
bifunctional catalyst
metal oxide
basic molecular
toluene
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许磊
李沛东
徐力
张晓敏
袁扬扬
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/163—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
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-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
    • B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • 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
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • 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
    • C07C2529/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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 invention relates to a preparation method of a bifunctional catalyst and an application thereof in preparing styrene and ethylbenzene, and belongs to the field of chemical industry.
  • Molecular sieve is a crystalline aluminosilicate whose skeleton consists of [AlO 4 - ] tetrahedron and [SiO 4 ] tetrahedron connected by oxygen bridge. Due to the presence of aluminum, the skeleton of the molecular sieve is negatively charged, requiring additional cations. It exists as a charge balancing ion. When the counter ion is an alkali metal ion, the negatively charged oxygen atom in the molecular sieve skeleton exhibits alkalinity, and the basicity of the molecular sieve increases as the atomic number of the alkali metal ion increases.
  • Different types of alkali metal molecular sieves can be prepared by ion exchange. For example, CsX can be prepared by ion exchange of NaX with a CsOH solution.
  • Alkali metal ion exchanged molecular sieves can be used for the alkylation of toluene methanol side chains to styrene, which was first reported by Sidorenko et al. (Dokl. Akad. NaukSSSR, 1967, 173(1): 132-134) in 1967.
  • the process of alkylation of toluene methanol side chain to styrene is considered to be a styrene production route with potential industrial application value.
  • the alkali metal ion exchanged molecular sieve has a good toluene methanol side chain.
  • a bifunctional catalyst comprising a metal oxide catalyst for carbon monoxide activation and a basic molecular sieve catalyst for toluene side chain activation.
  • the catalyst is used for the reaction of toluene methanol to styrene co-production of ethylbenzene, has good stability, not only realizes the reuse of carbon monoxide generated by methanol decomposition, but also greatly increases the conversion rate of the raw material toluene and improves the styrene in the product. And ethylbenzene selectivity.
  • the bifunctional catalyst is characterized by comprising a basic molecular sieve and a metal oxide; and the mass ratio of the basic molecular sieve to the metal oxide is from 0.1 to 10:1.
  • the mass ratio of the basic molecular sieve to the metal oxide is from 0.5 to 4:1. As another preferred embodiment, the mass ratio of the basic molecular sieve to the metal oxide is from 1 to 5:1 to 3.
  • the basic molecule is selected from at least one of an L-type molecular sieve, a ⁇ -type molecular sieve, a mordenite molecular sieve, an X-type molecular sieve, and a Y-type molecular sieve.
  • the basic molecular sieve is an alkali metal type molecular sieve; the alkali metal is selected from at least one of Na, K, Rb, and Cs.
  • the alkali metal type molecular sieves are commercially available or can be obtained by exchanging a solution of a non-alkali metal type molecular sieve (e.g., ammonium type or H-type) with a solution containing a soluble alkali metal salt.
  • the soluble alkali metal salt is selected from at least one of an alkali metal carbonate, a hydrogencarbonate, an acetate, an oxalate, a nitrate, a sulfate, a chloride, and a hydroxide.
  • the basic molecular sieve is a basic molecular sieve modified with an alkali metal element and/or an auxiliary element; the auxiliary element is boron and/or phosphorus.
  • the auxiliary element has a mass percentage of 0.01% to 5% in the basic molecular sieve; and the alkali metal element has a mass percentage of 1 to 40% in the basic molecular sieve.
  • the metal oxide is composed of an oxide of zinc, an oxide of chromium, an oxide of aluminum, and an oxide of copper; the molar ratio of each metal element in the metal oxide is:
  • the metal oxide is composed of an oxide of zinc, an oxide of chromium, an oxide of aluminum, and an oxide of copper; the molar ratio of each metal element in the metal oxide is:
  • the metal oxide is prepared by a coprecipitation method in which a soluble salt of a corresponding metal is mixed with a precipitating agent.
  • the soluble salt is selected from at least one of a nitrate, a sulfate, an acetate, and an oxalate.
  • the soluble salt is a nitrate and/or acetate.
  • the precipitating agent is selected from at least one of sodium carbonate, ammonium carbonate, and potassium carbonate.
  • the preparation steps of the metal oxide include:
  • the preparation method of any of the above bifunctional catalysts comprises the following steps:
  • Mode (2) grinding the basic molecular sieve and the metal oxide separately or ball milling by a ball mill, and after uniformly mixing, performing catalyst molding;
  • the catalyst is molded by grinding or ball milling.
  • the aging is aging at 50 to 90 ° C for at least 3 h.
  • a method for preparing styrene-co-produced ethylbenzene characterized in that a raw material gas containing toluene and methanol is introduced into a reactor and contacted with a hydrogen-reduced bifunctional catalyst to prepare styrene. And ethylbenzene;
  • the bifunctional catalyst is selected from one of any of the above bifunctional catalysts;
  • the molar ratio of toluene to methanol is 0.5 to 10:1; the mass space velocity WHSV of toluene is 0.2 to 6 h -1 ; the reaction pressure is 0.1 to 20 MPa; and the reaction temperature is 300 to 550 °C.
  • the reaction pressure is from 0.1 to 6 MPa.
  • the products of methanol decomposition are mainly H 2 and CO, which are the main components of synthesis gas, and the synthesis gas is the main raw material for industrial preparation of methanol.
  • the catalyst for the reaction is generally a metal oxide catalyst, such as a typical low pressure methanol catalyst: Cu /ZnO/Al 2 O 3 ; High-pressure methanol catalyst: ZnO/Cr 2 O 3 , etc., such metal oxides have the function of activating CO in the synthesis gas.
  • the bifunctional catalyst of the invention combines the metal oxide catalyst with the basic molecular sieve catalyst, on the one hand, the synthesis gas produced by the decomposition of methanol can be regenerated into methanol to reduce the methanol consumption; on the other hand, the synthesis gas is
  • the active species produced by activation on the metal oxide can be directly alkylated with the activated toluene on the basic molecular sieve to form styrene to achieve the purpose of increasing the conversion of toluene.
  • the method for preparing styrene co-producing ethylbenzene comprises at least the following steps:
  • Step I) After the reduction is completed, the feed gas is introduced into the reactor at a reaction temperature of 350 to 500 ° C, a mass airspeed of toluene of WHSV of 1 to 6 h -1 , and a reaction pressure of 0.5 to 5 MPa. The gas is contacted with a hydrogen-reduced bifunctional catalyst to prepare styrene and ethylbenzene.
  • the number of the reactors is at least one, and the reactor is selected from at least one of a fixed bed reactor, a fluidized bed reactor, or a moving bed reactor.
  • the number of reactors is greater than one, each reactor comprising at least one bifunctional catalyst bed, each reactor being connected directly in series and/or in parallel.
  • the bifunctional catalyst provided by the present invention greatly increases the conversion of toluene and the yield of ethylbenzene and styrene in the product by reusing the synthesis gas produced by methanol decomposition.
  • the bifunctional catalyst provided by the invention has good stability, and in the reaction of toluene and methanol, no obvious deactivation phenomenon is observed in the fixed bed reactor for 400 hours.
  • the method for preparing styrene and co-producing ethylbenzene provided by the invention is simple in operation, meets the requirements of industrial application, and has a good application prospect.
  • Figure 1 is a variation of toluene conversion and product selectivity of ethylbenzene and styrene with the reaction time of the catalyst CAT-6 #.
  • the elemental composition of the catalyst was measured using an Axios 2.4KW X-ray fluorescence analyzer (XRF) from PANAbalytical.
  • XRF X-ray fluorescence analyzer
  • the products were analyzed online using an Agilent 7890A chromatography.
  • the hydrocarbon components were separated by Agilent CP-WAX 25m ⁇ 32 ⁇ m ⁇ 1.2 ⁇ m capillary column and detected by FID detector; CO, CO 2 and H 2 were separated by Porapark Q 4m ⁇ 1/8′′ packed column and detected by TCD detector.
  • the conversion of toluene X toluene , methanol conversion rate X methanol , methanol decomposition rate D methanol , styrene selective S styrene , ethylbenzene selective S ethylbenzene , the calculation method is as follows:
  • 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. Calculate the mass of the desired impregnation precursor according to the amount of the load, dissolve the precursor of the corresponding mass in the deionized water of the mass required for the saturated adsorption of the carrier, stir evenly, and prepare the impregnation liquid to be placed in the immersion liquid. After immersion in an equal volume at 20 ° C for 24 hours, it was dried at 120 ° C, and calcined in air at 550 ° C for 4 hours.
  • Samples of Z-1 # , Z-2 # , Z-3 # 1g each of 20-40 mesh were taken in a small fixed-bed reactor, and the quartz sand was filled at both ends, first under a reducing atmosphere at a flow rate of 20 mL/min.
  • the mixture was reduced at 350 ° C for 4 h, and the composition of the reducing gas was H 2 /N 2 by volume 1/4.
  • N 2 is introduced , and the pressure of the system is raised to a predetermined reaction pressure of 3 Mpa through a back pressure valve.
  • the reaction process is accompanied by 10 mL/min of nitrogen gas.
  • the raw material is introduced into the raw material toluene and methanol, toluene.
  • the results of Z-1 # , Z-4 # , and Z-5 # 3 hours of reaction are shown in Table 8.

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Abstract

一种双功能催化剂及其制备方法及应用，双功能催化剂含有金属氧化物和碱性分子筛；碱性分子筛与金属氧化物的质量比为0.1-10:1。催化剂可用于甲苯甲醇制苯乙烯并联产乙苯的反应中，并提高了原料的转化率和产物的收率。

Description

一种双功能催化剂的制备方法及应用 技术领域
本发明涉及一种双功能催化剂的制备方法及其在制备苯乙烯和乙苯中的应用，属于化工领域。
背景技术
分子筛是一种晶体硅铝酸盐，其骨架由通过氧桥连接的[AlO4 -]四面体和[SiO4]四面体组成，由于铝的存在，分子筛的骨架带负电荷，需要额外的阳离子作为电荷平衡离子存在。当平衡离子是碱金属离子时，分子筛骨架中带负电的氧原子表现碱性，且分子筛的碱性随碱金属离子的原子序数增加而增加。不同类型的碱金属分子筛可通过离子交换制得，如CsX可以用CsOH溶液对NaX进行离子交换制备。
碱金属离子交换的分子筛可用于甲苯甲醇侧链烷基化制苯乙烯的反应，该反应由Sidorenko等(Dokl.Akad.NaukSSSR,1967,173(1):132-134)于1967年首先报道。甲苯甲醇侧链烷基化制苯乙烯工艺被认为是一条有着潜在工业应用价值的苯乙烯生产路线，经过近五十年的发展，一般认为碱金属离子交换的分子筛有着较好的甲苯甲醇侧链烷基化活性，文献(Journal of Catalysis 1972,(26):303-312)详细报道了不同类型的碱金属离子交换的分子筛上甲苯甲醇侧链烷基化反应特性，结果表明甲苯的转化率随碱金属离子交换的分子筛中碱金属的原子序数增加而增加，说明分子筛的碱性越强，甲苯的转化率越高。目前，深度改性的CsX分子筛有着较好的甲苯甲醇侧链烷基化活性，是目前研究的重点。此类催化剂已被多次公开报道，如CN103917504A、US4140726、US8697539和Applied Catalysis A:General,2012,443:214–220等。
目前的研究表明，当分子筛碱性较强时，虽然有利于提高甲苯的转化率，但甲醇的分解也很严重，因此提高甲苯的转化率和提高甲醇的利用率有着不可调和的矛盾。甲苯转化率低，甲醇分解严重、利用率低是限制该工艺路线实现工业化的主要因素。
发明内容
根据本发明的一个方面，提供了一种双功能催化剂，包括用于一氧化碳活化的金属氧化物催化剂和用于甲苯侧链活化的碱性分子筛催化剂两部分。该催化剂用于甲苯甲醇制苯乙烯联产乙苯的反应中，稳定性好，不仅对甲醇分解产生的一氧化碳实现了再利用，同时大幅提高了原料甲苯的转化率，并提高了产物中苯乙烯和乙苯选择性。
所述双功能催化剂，其特征在于，含有碱性分子筛和金属氧化物；碱性分子筛与金属氧化物的质量比为0.1～10:1。
作为一个优选的实施方式，碱性分子筛与金属氧化物的质量比为0.5～4:1。作为另一个优选的实施方式，碱性分子筛与金属氧化物的质量比为1～5:1～3。
优选地，所述碱性分子筛选自L型分子筛、β型分子筛、丝光沸石分子筛、X型分子筛、Y型分子筛中的至少一种。所述碱性分子筛为碱金属型分子筛；所述碱金属选自Na、K、Rb、Cs中的至少一种。所述碱金属型分子筛可以通过商业途径购买得到，也可以通过非碱金属型分子筛(如铵型或H-型)与含有可溶性碱金属盐的溶液交换得到。所述可溶性碱金属盐选自碱金属的碳酸盐、碳酸氢盐、醋酸盐、草酸盐、硝酸盐、硫酸盐、氯化物和氢氧化物中的至少一种。
优选地，所述碱性分子筛是经过碱金属元素和/或助剂元素改性的碱性分子筛；所述助剂元素是硼和/或磷。
进一步优选地，所述助剂元素在碱性分子筛中的质量百分含量为0.01％～5％；所述碱金属元素在碱性分子筛中的质量百分含量为1～40％。
优选地，所述碱性分子筛中的硅铝摩尔比为Si/Al＝1～10：1。进一步优选地，所述碱性分子筛中的硅铝摩尔比为Si/Al＝1～5：1。更进一步优选地，所述碱性分子筛中的硅铝摩尔比为Si/Al＝1～4：1。
优选地，所述金属氧化物由锌的氧化物、铬的氧化物、铝的氧化物和铜的氧化物组成；所述金属氧化物中各金属元素的摩尔比为：
Cu：Zn：Al：Cr＝30～65：15～40：10～30：1～10。
进一步优选地，所述金属氧化物由锌的氧化物、铬的氧化物、铝的氧化物和铜的氧化物组成；所述金属氧化物中各金属元素的摩尔比为：
Cu：Zn：Al：Cr：＝10.4～14.8：3.8～7.9：2.7～4.4：1。
所述金属氧化物通过将相应金属的可溶性盐与沉淀剂混合共沉淀法制得。所述可溶性盐选自硝酸盐、硫酸盐、醋酸盐、草酸盐中的至少一种。优选地，所述可溶性盐为硝酸盐和/或醋酸盐。所述沉淀剂选自碳酸钠、碳酸铵、碳酸钾中的至少一种。
作为一种优选的实施方式，所述金属氧化物的制备步骤包括：
i)将锌的可溶性盐、铬的的可溶性盐、铝的可溶性盐和铜的的可溶性盐按照比例混合，得到混合溶液I；
ii)搅拌加热混合溶液I至50～90℃(优选65～75℃)，加入浓度为0.1～2mol/L的沉淀剂，调节体系pH至7～8；
iii)50～90℃下老化至少3h后，分离得到固体，经110～130℃烘干、450～600℃焙烧1～6h即得到所述金属氧化物。
优选地，上述任一双功能催化剂的制备方法包含以下步骤：
(a)碱性分子筛的制备：用含有碱金属离子的浸渍液对分子筛进行等体积浸渍改性；和/或用含有硼和/或磷元素的浸渍液对分子筛进行等体积浸渍改性；
(b)采用共沉淀方法制备金属氧化物：50～90℃搅拌条件下，向含有Zn元素、Cr元素、Al元素和Cu元素的溶液中加入沉淀剂，至体系pH值至7～8后老化，所得固体经干燥焙烧后，即得所述金属氧化物；
(c)将步骤(a)得到的碱性分子筛和步骤(b)制备得到的金属氧化物按照下述3种方式中的至少一种，制备得到双功能催化剂：
方式(1)：碱性分子筛和金属氧化物分别成型后，经机械混合均匀；
方式(2)：将碱性分子筛和金属氧化物分别研磨或球磨机球磨，经混合均匀后，再进行催化剂成型；
方式(3)将改性碱性分子筛和金属氧化物混合后，经研磨或球磨机球磨再进行催化剂成型。
优选地，所述老化为在50～90℃下老化至少3h。
根据本发明的又一方面，提供一种制备苯乙烯联产乙苯的方法，其特征在于，将含有甲苯和甲醇的原料气通入反应器与经过氢气还原的双功能催化剂接触，制备苯乙烯和乙苯；
所述双功能催化剂选自上述任意双功能催化剂中的一种；
所述原料气中，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300～550℃。优选地，所述反应压力为0.1～6MPa。
甲醇分解的产物主要是H2和CO，也就是合成气的主要成分，而合成气是工业上制备甲醇的主要原料，该反应的催化剂一般为金属氧化物催化剂，如典型低压制甲醇催化剂：Cu/ZnO/Al2O3；高压制甲醇催化剂：ZnO/Cr2O3等，此类金属氧化物具备活化合成气中CO的功能。本发明所述的双功能催化剂，通过将金属氧化物催化剂与碱性分子筛催化剂复合，一方面可以使甲醇分解产生的合成气重新生成甲醇，达到降低甲醇消耗的目的；另一方面，合成气在金属氧化物上活化产生的活性物种可以直接与碱性分子筛上活化的甲苯发生侧链烷基化反应生成苯乙烯达到提高甲苯转化率的目的。
优选地，所述制备苯乙烯联产乙苯的方法至少包含以下步骤：
I)向载有双功能催化剂的反应器中通入含有氢气和氮气的还原气，300～550℃下还原3～12h，得到经过氢气还原的双功能催化剂；所述还原气中，H2/N2体积比为0.1～4：1；
II)步骤I)还原结束后，向反应器中通入原料气，在反应温度350～500℃、甲苯的质量空速WHSV为1～6h-1、反应压力为0.5～5MPa的条件下，原料气与经过氢气还原的双功能催化剂接触，制备苯乙烯和乙苯。
作为一种实施方式，所述反应器的数目为至少一个，所述反应器选自固定床反应器、流化床反应器或移动床反应器中的至少一种。
作为一种实施方式，所述反应器的数目大于一个，每个反应器中包含至少一个双功能催化剂床层，每个反应器直接通过串联和/或并联的方式连接。
本发明的有益效果包含但不限于：
(1)本发明所提供的双功能催化剂，通过对甲醇分解产生的合成气进行再利用，大幅度提高甲苯的转化率和产物中乙苯和苯乙烯的收率。
(2)本发明所提供的双功能催化剂的制备方法简单，有利于大规模工 业化生产。
(3)本发明所提供的双功能催化剂稳定性好，用于甲苯和甲醇的反应中，在固定床反应器上，运行400h未见有明显的失活现象。
(4)本发明所提供的制备苯乙烯联产乙苯的方法，操作简便，满足工业应用要求，具有很好的应用前景。
附图说明
图1为CAT-6#催化剂上甲苯转化率及产物中苯乙烯和乙苯选择性随反应时间的变化规律。
具体实施方式
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。
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。
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。
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；CO、CO2和H2采用Porapark Q 4m×1/8″填充柱分离，TCD检测器检测。
实施例中，甲苯的转化率X甲苯、甲醇转化率X甲醇、甲醇分解率D甲醇、苯乙烯选择性S苯乙烯、、乙苯选择性S乙苯、计算方法如下：
Figure PCTCN2016106951-appb-000001
Figure PCTCN2016106951-appb-000002
Figure PCTCN2016106951-appb-000003
Figure PCTCN2016106951-appb-000004
Figure PCTCN2016106951-appb-000005
实施例1碱性分子筛样品的制备
碱性分子筛样品Z-1#的制备
分别取NaX(Si/Al＝1.17)、NaY(Si/Al＝2.51)、Naβ(Si/Al＝3.93)各20g，以0.5mol/L CsCl溶液125ml，在80℃下交换4次，用去离子水洗涤抽滤至滤出液加入硝酸银溶液无沉淀生成为止，120℃烘干过夜，500℃空气中焙烧5h，磨碎后经压片、破碎并筛分为20-40目备用，所得样品记为Z-1#～Z-3#。
等体积浸渍碱性分子筛样品Z-4#～Z-8#的制备
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，制成浸渍液取待浸渍样品置于浸渍液中，在20℃下等体积浸渍24小时后，经120℃烘干，550℃空气中焙烧4h备用。
所得样品编号与具体实验方法和条件的关系如表1所示。
表1
Figure PCTCN2016106951-appb-000006
实施例2金属氧化物样品的制备
金属氧化物OX-1#的制备：
取7.9g Cu(NO3)·3H2O、7.1g Zn(NO3)2·6H2O、5.6g Al(NO3)3·9H2O、1.3g Cr(NO3)3·9H2O溶于125ml去离子水中，70℃下高速搅拌下，加入1mol/L的Na2CO3溶液调节pH至7，80℃下恒温老化5h过滤，120℃过夜烘干，520℃焙烧2h，磨碎后经压片、破碎并筛分为20-40目备用，所得样品记为OX-1#。
OX-2#～OX-3#的制备：
具体实验步骤同OX-1#的制备，金属盐的种类和用量与样品编号的关系如表2所示。
表2
Figure PCTCN2016106951-appb-000007
实施例3碱性分子筛样品和金属氧化物样品的元素组成分析
采用XRF对样品Z-1#～Z-8#以及样品OX-1#～OX～3#的元素组成进行分析，结果如表3和表4所示：
表3
Figure PCTCN2016106951-appb-000008
表4
样品 金属元素摩尔比例
OX-1# Cu：Zn：Al：Cr：＝10.4：7.9：4.4：1
OX-2# Cu：Zn：Al：Cr：＝9.7：5.5：4.1：1
OX-3# Cu：Zn：Al：Cr：＝14.8：3.8：2.7：1
实施例4双功能催化剂样品的制备
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OX-1#～OX～3#中的至少一种在QM-3SP2型球磨机上球磨20h后，样品经压片、破碎并筛分为20～40目备用。
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5所示。
表5
Figure PCTCN2016106951-appb-000009
实施例5催化剂评价(不同催化剂)
分别取20～40目的样品CAT-1#～CAT-11#各1g，装填在小型固定床反应器中，两端装填石英砂后，首先在20mL/min流速的还原气氛下350℃还原4h，还原气组成为H2/N2体积比1/4。还原结束后通入N2，通过背压阀，使体系压力升至预定反应压力3Mpa，反应过程中伴10mL/min氮气，压力稳定后，以高压微量进料泵通入原料甲苯和甲醇，甲苯甲醇摩尔进料比为3:1，进料量按甲苯计算，重时空速WHSV＝2h-1，反应在425℃条件下进行。CAT-1#～CAT-11#反应3小时的结果列于表6。其中，CAT-6#催化剂上运行400h的连续实验结果如图1所示。
表6
Figure PCTCN2016106951-appb-000010
*芳烃产物中除苯乙烯乙苯外，还有少量碳9以上芳烃生成，表中未列出。
实施例6催化剂评价(不同反应压力)
取1g 20～40目的催化剂样品CAT-6#装填在小型固定床反应器中，催化剂两端装填石英砂，除反应压力外，其他预处理条件与反应条件如实施例5，压力分别取0.1MPa、1MPa、6MPa，反应3小时结果列于表7。
表7
Figure PCTCN2016106951-appb-000011
*芳烃产物中除苯乙烯乙苯外，还有少量碳9以上芳烃生成，表中未列出。
对比例
分别取20～40目的样品Z-1#、Z-2#、Z-3#各1g，装填在小型固定床反应器中，两端装填石英砂后，首先在20mL/min流速的还原气氛下350℃还原4h，还原气组成为H2/N2体积比1/4。还原结束后通入N2，通过背压阀，使体系压力升至预定反应压力3Mpa，反应过程中伴10mL/min氮气，压力稳定后，以高压微量进料泵通入原料甲苯和甲醇，甲苯甲醇摩尔进料比为3:1，进料量按甲苯计算，重时空速WHSV＝2h-1，反应在425℃条件下进行。Z-1#、Z-4#、Z-5#反应3小时的结果列于表8。
表8
Figure PCTCN2016106951-appb-000012
*芳烃产物中除苯乙烯乙苯外，还有少量碳9以上芳烃生成，表中未列出。
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。

Claims (10)

  1. 一种双功能催化剂，其特征在于，所述双功能催化剂含有金属氧化物和碱性分子筛；碱性分子筛与金属氧化物的质量比为0.1～10:1。
  2. 根据权利要求1所述的双功能催化剂，其特征在于，所述碱性分子筛选自L型分子筛、β型分子筛、丝光沸石分子筛、X型分子筛、Y型分子筛中的至少一种。
  3. 根据权利要求1所述的双功能催化剂，其特征在于，所述碱性分子筛是经过碱金属元素和/或助剂元素改性的碱性分子筛；所述助剂元素是硼和/或磷。
  4. 根据权利要求3所述的双功能催化剂，其特征在于，所述助剂元素在碱性分子筛中的质量百分含量为0.01％～5％；所述碱金属元素在碱性分子筛中的质量百分含量为1～40％。
  5. 根据权利要求1所述的双功能催化剂，其特征在于，所述碱性分子筛中的硅铝摩尔比为Si/Al＝1～10：1。
  6. 根据权利要求1所述的双功能催化剂，其特征在于，所述金属氧化物由锌的氧化物、铬的氧化物、铝的氧化物和铜的氧化物组成；所述金属氧化物中各金属元素的摩尔比为：
    Cu：Zn：Al：Cr＝30～65：15～40：10～30：1～10。
  7. 根据权利要求1至6任一项所述双功能催化剂，其特征在于，制备方法包含以下步骤：
    (a)碱性分子筛的制备：用含有碱金属离子的浸渍液对分子筛进行等体积浸渍改性；用含有硼和/或磷元素的浸渍液对碱金属改性的分子筛进行等体积浸渍改性；
    (b)采用共沉淀方法制备金属氧化物：50～90℃搅拌条件下，向含有Zn元素、Cr元素、Al元素和Cu元素的溶液中加入沉淀剂，至体系pH值至7～8后老化，所得固体经干燥焙烧后，即得所述金属氧化物；
    (c)将步骤(a)得到的碱性分子筛和步骤(b)制备得到的金属氧化 物按照下述3种方式中的至少一种，制备得到双功能催化剂：
    方式(1)：碱性分子筛和金属氧化物分别成型后，经机械混合均匀；
    方式(2)：将碱性分子筛和金属氧化物分别研磨或球磨机球磨，经混合均匀后，再进行催化剂成型；
    方式(3)将碱性分子筛和金属氧化物混合后，经研磨或球磨机球磨再进行催化剂成型。
  8. 根据权利要求7所述的双功能催化剂，其特征在于，所述老化为在50～90℃下老化至少3h。
  9. 一种制备苯乙烯并联产乙苯的方法，其特征在于，将含有甲苯和甲醇的原料气通入反应器与经过氢气还原的双功能催化剂接触，制备苯乙烯和乙苯；
    所述双功能催化剂选自权利要求1至8任一项所述的双功能催化剂中的一种；
    所述原料气中，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300～550℃。
  10. 根据权利要求9所述的方法，其特征在于，至少包含以下步骤：
    i)向装有双功能催化剂的反应器中通入含有氢气和氮气的还原气，300～550℃下还原3～12h，得到经过氢气还原的双功能催化剂；所述还原气中，H2/N2体积比为0.1～4：1；
    ii)步骤a)还原结束后，向反应器中通入原料气，在反应温度350～500℃、甲苯的质量空速WHSV为1～6h-1、反应压力为0.5～5MPa的条件下，原料气与经过氢气还原的双功能催化剂接触，制备苯乙烯和乙苯。
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CN113941362A (zh) * 2021-10-19 2022-01-18 浙江大学 一种用于碳碳偶联反应的酸碱双位点催化剂及其应用
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