WO2018010358A1 - Method for preparing styrene from side-chain alkylation of methylbenzene and synthesis gas - Google Patents

Method for preparing styrene from side-chain alkylation of methylbenzene and synthesis gas Download PDF

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WO2018010358A1
WO2018010358A1 PCT/CN2016/106948 CN2016106948W WO2018010358A1 WO 2018010358 A1 WO2018010358 A1 WO 2018010358A1 CN 2016106948 W CN2016106948 W CN 2016106948W WO 2018010358 A1 WO2018010358 A1 WO 2018010358A1
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molecular sieve
toluene
oxide
styrene
metal oxide
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Chinese (zh)
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许磊
李沛东
徐力
袁扬扬
张晓敏
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中国科学院大连化学物理研究所
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
    • B01J29/70—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
    • 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
    • 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
    • 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
    • B01J29/64—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • 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
    • 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
    • C07C2529/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L
    • C07C2529/64—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L 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 new process for producing styrene from toluene and syngas, and belongs to the field of chemical industry.
  • Styrene is the most abundant chemical product in benzene derivatives. It is also the most basic aromatic hydrocarbon chemical. It can be used in the manufacture of polystyrene (PS), acrylonitrile-butadiene-styrene resin (ABS), and hair. A variety of downstream chemical products such as bubble polystyrene (EPS) and styrene-butadiene rubber (SBR). At present, industrial styrene is mainly prepared by ethylbenzene dehydrogenation. The process consists of two steps of alkylation of benzene and ethylene to ethylbenzene and ethylbenzene dehydrogenation to styrene.
  • PS polystyrene
  • ABS acrylonitrile-butadiene-styrene resin
  • SBR styrene-butadiene rubber
  • the hydrogen transfer reaction of methanol and styrene in the product and the decomposition of methanol are related to the alkali strength of the catalyst.
  • the strong alkali strength of the catalyst is the key to the activation of the side chain of toluene, thus increasing the conversion of toluene and improving the product.
  • the selectivity of styrene and the inhibition of methanol decomposition have irreconcilable contradictions.
  • the object of the present invention is to provide a method for producing styrene from toluene and syngas, which can not only reduce the cost of raw materials, but also eliminate the dehydrogenation step in the preparation of traditional styrene by replacing the methanol with syngas for the side chain alkylation reaction of toluene. , reduce energy consumption, and avoid the toluene methanol side chain
  • the hydrogen transfer reaction of styrene and methanol in the basic reaction improves the styrene/ethylbenzene ratio of the product, and has the characteristics of high conversion of toluene and high selectivity of styrene in the product.
  • the method for alkylating a toluene with a side chain of a synthesis gas to produce styrene characterized in that a raw material gas containing toluene and a synthesis gas is introduced into a reactor and contacted with a hydrogen-reduced bifunctional catalyst, and is subjected to side chain alkylation. Reaction to prepare styrene;
  • the molar ratio of H 2 and CO in the synthesis gas is 0.5 to 3:1, and the molar ratio of toluene to CO in the synthesis gas is 0.5 to 10:1;
  • the bifunctional catalyst comprises a basic molecular sieve and a metal oxide
  • the reaction temperature of the side chain alkylation reaction is 300 to 550 ° C
  • the mass space velocity of toluene is WHSV of 0.2 to 6 h -1
  • the reaction pressure is 0.1 to 30 MPa.
  • the molar ratio of H 2 and CO in the synthesis gas is 0.5 to 1.5.
  • the molar ratio of toluene to CO in the synthesis gas is from 0.5 to 6:1. Further preferably, the molar ratio of toluene to CO in the synthesis gas in the feed gas is from 2 to 6:1.
  • the reaction temperature of the side chain alkylation reaction is from 350 to 500 °C.
  • the reaction pressure of the side chain alkylation reaction is from 0.5 to 10 MPa.
  • the method for alkylating a toluene with a side chain of a syngas to produce styrene comprises at least the following steps:
  • the raw material 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 10 MPa.
  • the gas is contacted with a hydrogen-reduced bifunctional catalyst to produce styrene via a side chain alkylation reaction.
  • the hydrogen reduction time in step a) is from 1 to 5 h.
  • the mass ratio of the basic molecular sieve to the metal oxide is 0.1 to 10:1. Further preferably, in the bifunctional catalyst, the mass ratio of the basic molecular sieve to the metal oxide is 0.2 to 2:1.
  • 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 sieve can be purchased commercially or through a non-alkali metal molecular sieve (such as ammonium type). Or H-type) is obtained by exchange with an alkali metal ion solution.
  • the basic molecular sieve is a basic molecular sieve that undergoes toluene conversion to promote element modification
  • the toluene conversion promoting element is at least selected from the group consisting of Na, K, Rb, Cs, Ti, B, N, P, Ce, La, W, Zn, Ag, Cs, Mg, Ca, Sr, Ba, Cu, Co.
  • the toluene conversion promoting element is selected from at least one of Rb, Cs, B, and P.
  • the metal oxide contains an oxide of zinc, an oxide of chromium, an oxide of aluminum, and an oxide of metal M;
  • the metal M is at least one selected from the group consisting of Ti, Zr, V, Cu, Ag, Nb, Mo, Mn, W, and Ta.
  • the metal oxide is composed of an oxide of zinc, an oxide of chromium, an oxide of aluminum, and an oxide of metal M; the molar ratio of each metal element in the metal oxide is:
  • Zn: Cr: Al: M: 10 to 40: 20 to 70: 10 to 50: 1 to 5.
  • the metal oxide is composed of an oxide of zinc, an oxide of chromium, an oxide of aluminum, and an oxide of metal M; 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 preferably a nitrate or acetate, and the precipitating agent is selected from the group consisting of sodium carbonate, ammonium carbonate, potassium carbonate or aqueous ammonia.
  • the preparation steps of the metal oxide include:
  • the bifunctional molecular sieve is prepared by the following steps:
  • the toluene conversion promoting element is at least selected from the group consisting of Na, K, Rb, Cs, Ti, B, N, P, Ce, La, W, Zn, Ag, Mg, Ca, Sr, Ba, Cu, Co, and V.
  • 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 After mixing the basic molecular sieve and the metal oxide, the catalyst is formed by ball milling for 1 to 40 hours by grinding or ball milling.
  • 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 method for producing styrene provided by the present invention has the characteristics of high toluene conversion rate and high selectivity of styrene in the product.
  • the method for producing styrene provided by the present invention has good stability of the bifunctional catalyst, and no obvious deactivation phenomenon is observed in the fixed bed reactor for 500 hours.
  • the method for producing styrene provided by the invention is simple in operation and meets industrial application requirements. Convenient for large-scale industrial production.
  • 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, detected by FID detector, separated by CO, CO 2 and H 2 on Porapark Q4m ⁇ 1/8′′ packed column, and detected by TCD detector.
  • conversion of toluene X toluene carbon monoxide conversion rate X CO , styrene selective S styrene and ethylbenzene selective S ethylbenzene are calculated as follows:
  • the alkali metal type molecular sieves used in the examples were all commercially available.
  • the basic molecular sieve is modified by an ion exchange and/or an equal volume impregnation method using a compound containing a toluene conversion promoting element; the specific steps are:
  • Ion exchange method 15 g of molecular sieve was placed in 100 mL of ion exchange liquid containing toluene conversion promoting element compound, exchanged at 80 ° C for 2 h, exchanged 4 times in the same step, and then washed with deionized water to filter until the filtrate reached neutrality. It is dried overnight at 120 ° C, calcined in air at 500 ° C for 5 h, and the sample is compressed, crushed and sieved to 20 to 40 mesh for use.
  • Equal volume impregnation firstly, the carrier to be impregnated is 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 immersing 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.
  • Samples of Z-1 # to Z-4 # and samples CAT-1 # to CAT-10 # 1g each of 20 to 40 mesh were packed in a small fixed-bed reactor, and the quartz sand was filled at both ends, first at 10 mL/ The flow rate of min is reduced at 350 ° C for 4 h under hydrogen atmosphere, and then the synthesis gas is introduced into the synthesis gas.
  • the pressure of the system is raised to a predetermined reaction pressure of 2 MPa through a back pressure valve. After the pressure is stabilized, the raw material is fed with a high-pressure micro feed pump.

Abstract

The present invention relates to a method for preparing styrene with high selectivity from methylbenzene and synthesis gas, comprising: leading raw gas containing methylbenzene and synthesis gas into a reactor, enabling the raw gas to be in contact with a dual-function catalyst that is subjected to hydrogen reduction, and performing a side-chain alkylation reaction to prepare styrene. The dual-function catalyst comprises alkaline molecular sieves and a metallic oxide. According to the method, the synthesis gas is used for replacing methanol to conduct the side-chain alkylation reaction of methylbenzene, so that the cost of raw materials can be reduced, a dehydrogenation step in a conventional styrene preparation process is omitted, the energy consumption is reduced, a hydrogen transfer reaction of styrene and methanol in the side-chain alkylation reaction of methylbenzene and methanol is avoided, and the styrene/ethylbenzene ratio of products is increased. The method has the characteristics of high methylbenzene conversion rate and high selectivity of styrene in the products.

Description

一种甲苯与合成气侧链烷基化制苯乙烯的方法Method for alkylating toluene and syngas side chain to produce styrene 技术领域Technical field
本发明涉及一种甲苯与合成气制苯乙烯的新工艺，属于化工领域。The invention relates to a new process for producing styrene from toluene and syngas, and belongs to the field of chemical industry.
背景技术Background technique
苯乙烯(ST)是苯的衍生物中用量最大的化工产品，也是最基本的芳烃化学品，可用于制造聚苯乙烯(PS)、丙烯腈-丁二烯-苯乙烯树脂(ABS)、发泡级聚苯乙烯(EPS)、苯乙烯-丁二烯橡胶(SBR)等多种下游化工产品。目前，工业上苯乙烯主要通过乙苯脱氢法制备。该工艺由苯和乙烯烷基化生成乙苯和乙苯脱氢制苯乙烯两步组成，不但工艺流程长，而且存在副反应多、能耗大、过度依赖石油资源等问题。基于乙苯脱氢法存在的问题，新的苯乙烯生产工艺的开发是化工领域的一个研究热点。在众多新工艺中，甲苯甲醇侧链烷基化制苯乙烯技术被认为有着很好的工业应用前景，该反应由Sidorenko等(Dokl.Akad.NaukSSSR,1967,173(1):132-134)于上世纪60年代首先报道，经过几十年的发展，一般认为深度改性的CsX分子筛有着较好的甲苯甲醇侧链烷基化活性，此类催化剂已被多次公开报道，如US4140726、US8697539、CN103917504A和Catalysis Today 2014,226:117-123等。由于该过程甲醇分解量大，产物中苯乙烯易与甲醇发生氢转移反应生成乙苯等问题，该工艺至今未能成功实现工业化。Styrene (ST) is the most abundant chemical product in benzene derivatives. It is also the most basic aromatic hydrocarbon chemical. It can be used in the manufacture of polystyrene (PS), acrylonitrile-butadiene-styrene resin (ABS), and hair. A variety of downstream chemical products such as bubble polystyrene (EPS) and styrene-butadiene rubber (SBR). At present, industrial styrene is mainly prepared by ethylbenzene dehydrogenation. The process consists of two steps of alkylation of benzene and ethylene to ethylbenzene and ethylbenzene dehydrogenation to styrene. The process is long, and there are many side reactions, high energy consumption, and excessive dependence on petroleum resources. Based on the problems of ethylbenzene dehydrogenation, the development of new styrene production process is a research hotspot in the chemical industry. In many new processes, the side-chain alkylation of toluene methanol to styrene technology is considered to have good industrial application prospects, which is determined by Sidorenko et al. (Dokl. Akad. NaukSSSR, 1967, 173(1): 132-134). It was first reported in the 1960s that after decades of development, it is generally believed that deeply modified CsX molecular sieves have better side chain alkylation activity of toluene methanol. Such catalysts have been reported many times, such as US4140726, US8697539. , CN103917504A and Catalysis Today 2014, 226: 117-123, etc. Due to the large amount of methanol decomposition in the process, the styrene in the product is liable to undergo hydrogen transfer reaction with methanol to form ethylbenzene, and the process has not been successfully industrialized.
甲醇和产物中的苯乙烯发生氢转移反应以及甲醇的分解都与催化剂的碱强度有关，而催化剂具有较强的碱强度又是甲苯侧链活化的关键，因此提高甲苯的转化率和提高产物中苯乙烯的选择性以及抑制甲醇的分解有着不可调和的矛盾。The hydrogen transfer reaction of methanol and styrene in the product and the decomposition of methanol are related to the alkali strength of the catalyst. The strong alkali strength of the catalyst is the key to the activation of the side chain of toluene, thus increasing the conversion of toluene and improving the product. The selectivity of styrene and the inhibition of methanol decomposition have irreconcilable contradictions.
发明内容Summary of the invention
本发明的目的在于提供一种甲苯与合成气制苯乙烯的方法，通过以合成气替代甲醇进行甲苯侧链烷基化反应，不仅可以降低原料成本，省略传统苯乙烯制备过程中的脱氢步骤，降低能耗，而且避免了甲苯甲醇侧链烷 基化反应中苯乙烯和甲醇的氢转移反应，提高了产物的苯乙烯/乙苯比，具有甲苯转化率高，产物中苯乙烯选择性高等特点。The object of the present invention is to provide a method for producing styrene from toluene and syngas, which can not only reduce the cost of raw materials, but also eliminate the dehydrogenation step in the preparation of traditional styrene by replacing the methanol with syngas for the side chain alkylation reaction of toluene. , reduce energy consumption, and avoid the toluene methanol side chain The hydrogen transfer reaction of styrene and methanol in the basic reaction improves the styrene/ethylbenzene ratio of the product, and has the characteristics of high conversion of toluene and high selectivity of styrene in the product.
所述甲苯与合成气侧链烷基化制苯乙烯的方法，其特征在于，将含有甲苯和合成气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，经侧链烷基化反应制备苯乙烯；The method for alkylating a toluene with a side chain of a synthesis gas to produce styrene, characterized in that a raw material gas containing toluene and a synthesis gas is introduced into a reactor and contacted with a hydrogen-reduced bifunctional catalyst, and is subjected to side chain alkylation. Reaction to prepare styrene;
所述原料气中，合成气中H2和CO的摩尔比例为0.5～3:1，甲苯与合成气中CO的摩尔比例为0.5～10:1；The molar ratio of H 2 and CO in the synthesis gas is 0.5 to 3:1, and the molar ratio of toluene to CO in the synthesis gas is 0.5 to 10:1;
所述双功能催化剂包含碱性分子筛和金属氧化物；The bifunctional catalyst comprises a basic molecular sieve and a metal oxide;
所述侧链烷基化反应的反应温度为300～550℃，甲苯的质量空速WHSV为0.2～6h-1，反应压力为0.1～30MPa。The reaction temperature of the side chain alkylation reaction is 300 to 550 ° C, the mass space velocity of toluene is WHSV of 0.2 to 6 h -1 , and the reaction pressure is 0.1 to 30 MPa.
优选地，所述原料气中，合成气中H2和CO的摩尔比例为0.5～1.5。Preferably, in the raw material gas, the molar ratio of H 2 and CO in the synthesis gas is 0.5 to 1.5.
优选地，所述原料气中，甲苯与合成气中CO的摩尔比例为0.5～6:1。进一步优选地，所述原料气中，甲苯与合成气中CO的摩尔比例为2～6:1。Preferably, in the raw material gas, the molar ratio of toluene to CO in the synthesis gas is from 0.5 to 6:1. Further preferably, the molar ratio of toluene to CO in the synthesis gas in the feed gas is from 2 to 6:1.
优选地，所述侧链烷基化反应的反应温度为350～500℃。Preferably, the reaction temperature of the side chain alkylation reaction is from 350 to 500 °C.
优选地，所述侧链烷基化反应的反应压力为0.5～10Mpa。Preferably, the reaction pressure of the side chain alkylation reaction is from 0.5 to 10 MPa.
作为一种实施方式，所述甲苯与合成气侧链烷基化制苯乙烯的方法，至少包含以下步骤：As an embodiment, the method for alkylating a toluene with a side chain of a syngas to produce styrene comprises at least the following steps:
a)向载有双功能催化剂的反应器中通入氢气，300℃～550℃下还原0.5h～10h，得到经过氢气还原的双功能催化剂；a) introducing hydrogen into the reactor carrying the bifunctional catalyst, and reducing it at 300 ° C to 550 ° C for 0.5 h to 10 h to obtain a bifunctional catalyst which is reduced by hydrogen;
b)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0.5～10Mpa的条件下，原料气与经过氢气还原的双功能催化剂接触，经侧链烷基化反应制备苯乙烯。b) After the completion of the step a), the raw material 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 10 MPa. The gas is contacted with a hydrogen-reduced bifunctional catalyst to produce styrene via a side chain alkylation reaction.
优选地，步骤a)中氢气还原的时间为1～5h。Preferably, the hydrogen reduction time in step a) is from 1 to 5 h.
优选地，所述双功能催化剂中，碱性分子筛与金属氧化物的质量比为0.1～10:1。进一步优选地，所述双功能催化剂中，碱性分子筛与金属氧化物的质量比为0.2～2:1。Preferably, in the bifunctional catalyst, the mass ratio of the basic molecular sieve to the metal oxide is 0.1 to 10:1. Further preferably, in the bifunctional catalyst, the mass ratio of the basic molecular sieve to the metal oxide is 0.2 to 2:1.
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所得，也可以通过非碱金属型分子筛(如铵型 或H-型)与碱金属离子溶液交换得到。Preferably, the basic molecule is selected from at least one of an L-type molecular sieve, a β-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 sieve can be purchased commercially or through a non-alkali metal molecular sieve (such as ammonium type). Or H-type) is obtained by exchange with an alkali metal ion solution.
优选地，所述碱性分子筛为经过甲苯转化促进元素改性的碱性分子筛；Preferably, the basic molecular sieve is a basic molecular sieve that undergoes toluene conversion to promote element modification;
所述甲苯转化促进元素选自Na、K、Rb、Cs、Ti、B、N、P、Ce、La、W、Zn、Ag、Cs、Mg、Ca、Sr、Ba、Cu、Co中的至少一种。优选地，所述甲苯转化促进元素选自Rb、Cs、B、P中的至少一种。The toluene conversion promoting element is at least selected from the group consisting of Na, K, Rb, Cs, Ti, B, N, P, Ce, La, W, Zn, Ag, Cs, Mg, Ca, Sr, Ba, Cu, Co. One. Preferably, the toluene conversion promoting element is selected from at least one of Rb, Cs, B, and P.
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。Preferably, the molar ratio of silicon to aluminum in the basic molecular sieve is Si/Al = 1 to 10:1. Further preferably, the molar ratio of silicon to aluminum in the basic molecular sieve is Si/Al = 1 to 5:1. Still more preferably, the molar ratio of silicon to aluminum in the basic molecular sieve is Si/Al = 1 to 4:1.
优选地，所述金属氧化物含有锌的氧化物、铬的氧化物、铝的氧化物和金属M的氧化物；Preferably, the metal oxide contains an oxide of zinc, an oxide of chromium, an oxide of aluminum, and an oxide of metal M;
其中，所述金属M选自Ti、Zr、V，Cu、Ag、Nb、Mo、Mn、W、Ta中的至少一种。The metal M is at least one selected from the group consisting of Ti, Zr, V, Cu, Ag, Nb, Mo, Mn, W, and Ta.
优选地，所述金属氧化物由锌的氧化物、铬的氧化物、铝的氧化物和金属M的氧化物组成；所述金属氧化物中各金属元素的摩尔比为：Preferably, the metal oxide is composed of an oxide of zinc, an oxide of chromium, an oxide of aluminum, and an oxide of metal M; the molar ratio of each metal element in the metal oxide is:
Zn：Cr：Al：M：＝10～40：20～70：10～50：1～5。Zn: Cr: Al: M: = 10 to 40: 20 to 70: 10 to 50: 1 to 5.
进一步优选地，所述金属氧化物由锌的氧化物、铬的氧化物、铝的氧化物和金属M的氧化物组成；所述金属氧化物中各金属元素的摩尔比为：Further preferably, the metal oxide is composed of an oxide of zinc, an oxide of chromium, an oxide of aluminum, and an oxide of metal M; the molar ratio of each metal element in the metal oxide is:
Zn：Cr：Al：M：＝3.9～12.2：3.9～17.2：5.8～14.4：1。Zn:Cr:Al:M:=3.9 to 12.2: 3.9 to 17.2: 5.8 to 14.4:1.
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。所述可溶性盐优选硝酸盐或醋酸盐，所述沉淀剂选自碳酸钠、碳酸铵、碳酸钾或氨水。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 preferably a nitrate or acetate, and the precipitating agent is selected from the group consisting of sodium carbonate, ammonium carbonate, potassium carbonate or aqueous ammonia.
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：As a preferred embodiment, the preparation steps of the metal oxide include:
i)将锌的可溶性盐、铬的可溶性盐、铝的可溶性盐和金属M的可溶性盐按照比例混合，得到混合溶液I；i) a soluble salt of zinc, a soluble salt of chromium, a soluble salt of aluminum and a soluble salt of metal M are mixed in proportion to obtain a mixed solution I;
ii)搅拌加热混合溶液I至50～90℃(优选65～75℃)，加入沉淀剂，调节体系pH至7～8；Ii) stirring and heating the mixed solution I to 50 ~ 90 ° C (preferably 65 ~ 75 ° C), adding a precipitant, adjusting the system pH to 7 ~ 8;
iii)60～80℃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。Iii) After aging at 60 to 80 ° C for at least 3 hours, a solid is isolated, dried at 110 to 130 ° C, and calcined at 450 to 600 ° C for 1 to 6 hours to obtain the metal oxide.
作为一种优选的实施方式，所述双功能分子筛通过以下步骤制备得到：As a preferred embodiment, the bifunctional molecular sieve is prepared by the following steps:
(I)采用离子交换和/或等体积浸渍法，用含有甲苯转化促进元素的化 合物对碱性分子筛进行改性；(I) using ion exchange and/or equal volume impregnation, with the conversion of toluene-containing promoting elements The compound is modified with a basic molecular sieve;
所述甲苯转化促进元素选自Na、K、Rb、Cs、Ti、B、N、P、Ce、La、W、Zn、Ag、Mg、Ca、Sr、Ba、Cu、Co、V中的至少一种；The toluene conversion promoting element is at least selected from the group consisting of Na, K, Rb, Cs, Ti, B, N, P, Ce, La, W, Zn, Ag, Mg, Ca, Sr, Ba, Cu, Co, and V. One type;
(II)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M元素的溶液中加入沉淀剂，至体系pH值至7～8后，于60～80℃下老化4h，所得固体经干燥、450℃～600℃煅烧1～6h，即得所述金属氧化物；(II) Preparation of metal oxide by coprecipitation method: adding a precipitant to a solution containing Zn element, Cr element, Al element and M element under stirring at 50 to 90 ° C until the pH of the system reaches 7-8. After aging at 60-80 ° C for 4 h, the obtained solid is dried, calcined at 450 ° C ~ 600 ° C for 1 ~ 6h, the metal oxide is obtained;
(III)将步骤(I)改性得到的碱性分子筛和步骤(II)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：(III) The basic molecular sieve obtained by modifying the step (I) and the metal oxide prepared in the step (II) are prepared in at least one of the following three ways to obtain a bifunctional catalyst:
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；Mode (1): After the basic molecular sieve and the metal oxide are separately formed, they are uniformly mixed by mechanical means;
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；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;
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1～40h后再进行催化剂成型。Mode (3) After mixing the basic molecular sieve and the metal oxide, the catalyst is formed by ball milling for 1 to 40 hours by grinding or ball milling.
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。As an embodiment, 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.
作为一种实施方式，所述反应器的数目大于1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。As an embodiment, 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.
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)本发明所提供的制苯乙烯的方法，具有甲苯转化率高，产物中苯乙烯选择性高等特点。(1) The method for producing styrene provided by the present invention has the characteristics of high toluene conversion rate and high selectivity of styrene in the product.
(2)本发明所提供的制苯乙烯的方法，利用合成气作为甲苯的侧链烷基化试剂制备苯乙烯，避免了甲苯甲醇侧链烷基化反应中苯乙烯和甲醇的氢转移反应，提高了产物的苯乙烯/乙苯比，不仅有效的抑制了产物中乙苯的生成，也降低了甲苯侧链烷基化反应的原料成本。(2) The method for producing styrene provided by the invention, wherein syngas is prepared by synthesizing gas as a side chain alkylating agent of toluene, thereby avoiding hydrogen transfer reaction of styrene and methanol in the side chain alkylation reaction of toluene methanol. Increasing the styrene/ethylbenzene ratio of the product not only effectively inhibits the formation of ethylbenzene in the product, but also reduces the raw material cost of the side chain alkylation reaction of toluene.
(3)本发明所提供的制苯乙烯的方法，所采用的双功能催化剂稳定性好，在固定床反应器上，连续运行500h的未见有明显的失活现象。(3) The method for producing styrene provided by the present invention has good stability of the bifunctional catalyst, and no obvious deactivation phenomenon is observed in the fixed bed reactor for 500 hours.
(4)本发明所提供的制苯乙烯的方法，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 producing styrene provided by the invention is simple in operation and meets industrial application requirements. 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。实施例中，甲苯的转化率X甲苯、一氧化碳转化率XCO、苯乙烯选择性S苯乙烯和乙苯选择性S乙苯的计算方法如下：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, separated by CO, CO 2 and H 2 on Porapark Q4m×1/8′′ packed column, and detected by TCD detector. , conversion of toluene X toluene , carbon monoxide conversion rate X CO , styrene selective S styrene and ethylbenzene selective S ethylbenzene are calculated as follows:
Figure PCTCN2016106948-appb-000001
Figure PCTCN2016106948-appb-000001
Figure PCTCN2016106948-appb-000002
Figure PCTCN2016106948-appb-000002
Figure PCTCN2016106948-appb-000003
Figure PCTCN2016106948-appb-000003
Figure PCTCN2016106948-appb-000004
Figure PCTCN2016106948-appb-000004
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。采用离子交换和/或等体积浸渍法，用含有甲苯转化促进元素的化合物对碱性分子筛进行改性；具体步骤为：The alkali metal type molecular sieves used in the examples were all commercially available. The basic molecular sieve is modified by an ion exchange and/or an equal volume impregnation method using a compound containing a toluene conversion promoting element; the specific steps are:
离子交换法：取15g分子筛置于100mL含有甲苯转化促进元素化合物的离子交换液中，80℃下交换2h，按相同步骤交换4次后用去离子水抽滤洗涤至滤出液达到中性为止，120℃烘干过夜，500℃空气中焙烧5h，样品经压片、破碎并筛分为20～40目备用。 Ion exchange method : 15 g of molecular sieve was placed in 100 mL of ion exchange liquid containing toluene conversion promoting element compound, exchanged at 80 ° C for 2 h, exchanged 4 times in the same step, and then washed with deionized water to filter until the filtrate reached neutrality. It is dried overnight at 120 ° C, calcined in air at 500 ° C for 5 h, and the sample is compressed, crushed and sieved to 20 to 40 mesh for use.
等体积浸渍：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。 Equal volume impregnation : firstly, the carrier to be impregnated is 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 immersing 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.
所得样品编号与具体实验方法和条件的关系如表1所示。The relationship between the obtained sample number and specific experimental methods and conditions is shown in Table 1.
表1Table 1
Figure PCTCN2016106948-appb-000005
Figure PCTCN2016106948-appb-000005
实施例2金属氧化物样品的制备Example 2 Preparation of Metal Oxide Samples
OX-1#的制备：Preparation of OX-1 # :
取8.2g Zn(NO3)2·6H2O，6.3g Cr(NO3)3·9H2O，7.5g Al(NO3)3·9H2O、0.9g Cu(NO3)·3H2O的金属盐溶于100mL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，洗涤，120℃烘干过夜，520℃焙烧2h，样品经压片、破碎并筛分为20～40目备用，所得样品记为OX-1#。Take 8.2 g of Zn(NO 3 ) 2 ·6H 2 O, 6.3 g of Cr(NO 3 ) 3 ·9H 2 O, 7.5 g of Al(NO 3 ) 3 ·9H 2 O, 0.9 g of Cu(NO 3 )·3H 2 The metal salt of O is dissolved in 100 mL of deionized water, and stirred at 70 ° C under high speed. The pH is adjusted to 7 by adding 1 mol/L Na 2 CO 3 solution, and the temperature is aged at 80 ° C for 5 h, filtered, washed, and dried at 120 ° C overnight. After calcination at 520 ° C for 2 h, the sample was compressed, crushed and sieved to 20-40 mesh for use, and the obtained sample was recorded as OX-1 # .
OX-2#～OX-5#的制备：Preparation of OX-2 # ～OX-5 # :
具体实验步骤同OX-1#的制备，金属盐的种类、用量以及沉淀剂溶液与样品编号的关系如表2所示。The specific experimental procedure is the same as the preparation of OX-1 # , the type and amount of the metal salt, and the relationship between the precipitant solution and the sample number are shown in Table 2.
表2Table 2
Figure PCTCN2016106948-appb-000006
Figure PCTCN2016106948-appb-000006
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Example 3 Elemental Composition Analysis of Basic Molecular Sieve Samples and Metal Oxide Samples
采用XRF对样品Z-1#～Z-6#以及样品OX-1#～OX-5#的元素组成进行分析，结果如表3和表4所示：The elemental compositions of samples Z-1 # to Z-6 # and samples OX-1 # to OX-5 # were analyzed by XRF. The results are shown in Tables 3 and 4:
表3table 3
Figure PCTCN2016106948-appb-000007
Figure PCTCN2016106948-appb-000007
表4Table 4
样品sample 金属元素摩尔比例Metal element molar ratio
OX-1# OX-1 # Zn：Cr：Al：Cu(M)：＝7.5：4.6：7.1：1Zn:Cr:Al:Cu(M):=7.5:4.6:7.1:1
OX-2# OX-2 # Zn：Cr：Al：Cu(M)：＝7.1：9.6：9.9：1Zn:Cr:Al:Cu(M):=7.1:9.6:9.9:1
OX-3# OX-3 # Zn：Cr：Al：Ag(M)：＝7.5：3.9：5.8：1Zn:Cr:Al:Ag(M):=7.5:3.9:5.8:1
OX-4# OX-4 # Zn：Cr：Al：Zr(M)：＝12.2：17.2：14.4：1Zn:Cr:Al:Zr(M):=12.2:17.2:14.4:1
OX-5# OX-5 # Zn：Cr：Al：Mn(M)：＝3.9：10.2：8.2：1Zn:Cr:Al:Mn(M):=3.9:10.2:8.2:1
实施例4双功能催化剂样品的制备Example 4 Preparation of a Bifunctional Catalyst Sample
将实施例1制备得到的碱性分子筛样品Z-1#～Z-6#中的至少一种和金属氧化物样品OX-1#～OX-5#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。At least one of the basic molecular sieve samples Z-1 # to Z-6 # prepared in Example 1 and at least one of the metal oxide samples OX-1 # to OX-5 # in the QM-3SP2 type ball mill After the ball was milled for 20 hours, the sample was compressed, crushed and sieved to 20 to 40 mesh for use.
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。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 5.
表5table 5
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 # OX-1#：Z-1#＝2:1OX-1 # :Z-1 # =2:1
CAT-2# CAT-2 # OX-1#：Z-1#＝1:1OX-1 # :Z-1 # =1:1
CAT-3# CAT-3 # OX-1#：Z-1#＝1:2OX-1 # :Z-1 # =1:2
CAT-4# CAT-4 # OX-1#：Z-1#＝1:5OX-1 # :Z-1 # =1:5
CAT-5# CAT-5 # OX-1#：Z-3#＝1:2OX-1 # :Z-3 # =1:2
CAT-6# CAT-6 # OX-1#：Z-4#＝1:2OX-1 # :Z-4 # =1:2
CAT-7# CAT-7 # OX-1#：Z-2#＝1:2OX-1 # :Z-2 # =1:2
CAT-8# CAT-8 # OX-3#：Z-5#＝1:2OX-3 # :Z-5 # =1:2
CAT-9# CAT-9 # OX-4#：Z-6#＝1:2OX-4 # :Z-6 # =1:2
CAT-10# CAT-10 # OX-5#：Z-4#＝1:2OX-5 # :Z-4 # =1:2
实施例5催化剂评价(不同催化剂)Example 5 Catalyst Evaluation (Different Catalysts)
分别取20～40目的样品Z-1#～Z-4#、样品CAT-1#～CAT-10#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10mL/min流速的氢气气氛下350℃还原4h，然后通入合成气，通过背压阀，使体系压力升至预定反应压力2MPa，压力稳定后，以高压微量进料泵通入原料甲苯，进料量按甲苯计算，重时空速WHSV＝2h-1，合成气组成为H2/CO(摩尔比)为2:1，进料中甲苯/CO(摩尔比)为2:1，反应在440℃条件下进行操作。反应两小时样品Z-1#～Z-4#、样品CAT-1#～CAT-10#的结果列于表6。Samples of Z-1 # to Z-4 # and samples CAT-1 # to CAT-10 # 1g each of 20 to 40 mesh were packed in a small fixed-bed reactor, and the quartz sand was filled at both ends, first at 10 mL/ The flow rate of min is reduced at 350 ° C for 4 h under hydrogen atmosphere, and then the synthesis gas is introduced into the synthesis gas. The pressure of the system is raised to a predetermined reaction pressure of 2 MPa through a back pressure valve. After the pressure is stabilized, the raw material is fed with a high-pressure micro feed pump. Calculated by toluene, the weight hourly space velocity WHSV=2h -1 , the composition of syngas is H 2 /CO (molar ratio) is 2:1, the toluene/CO (molar ratio) is 2:1 in the feed, and the reaction is at 440 °C. Under the operation. The results of the two-hour reaction samples Z-1 # to Z-4 # and the samples CAT-1 # to CAT-10 # are shown in Table 6.
表6Table 6
Figure PCTCN2016106948-appb-000008
Figure PCTCN2016106948-appb-000008
*芳烃产物中除苯乙烯乙苯外，主要是异丙苯；一氧化碳转化的产物中还有部分二氧化碳，以上两项表中未列出；Z-1#～Z-4#作为催化剂时的产物中几乎没有发现乙苯和苯乙烯的存在。* In addition to styrene ethylbenzene, the aromatic hydrocarbon product is mainly cumene; some carbon dioxide is also contained in the carbon monoxide conversion product, which is not listed in the above two tables; the product of Z-1 # ～Z-4 # as a catalyst Almost no evidence of the presence of ethylbenzene and styrene was observed.
实施例6催化剂评价(不同进料比例)Example 6 Catalyst Evaluation (Different Feed Ratios)
取1g20～40目的催化剂样品CAT-3#装填在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10mL/min流速的氢气气氛下350℃还原4h，然后通入合成气，通过背压阀，使体系压力升至预定反应压力2MPa，压力稳定后，以高压微量进料泵通入原料甲苯，进料量按甲苯计算，重时空速WHSV＝2h-1，合成气组成为H2/CO(摩尔比)为2:1，反应在440℃条 件下进行操作，进料中甲苯/CO(摩尔比)分别取1:2、3:1、6:1，反应两小时的结果列于表7。1g 20~40 mesh catalyst sample CAT-3 # was packed in a small fixed-bed reactor. The catalyst was packed with quartz sand at both ends. The catalyst was first reduced at 350 °C for 4 h under a hydrogen atmosphere of 10 mL/min flow rate, and then passed into syngas. Back pressure valve, the system pressure is raised to the predetermined reaction pressure 2MPa, after the pressure is stabilized, the raw material toluene is introduced into the high-pressure micro feed pump, the feed amount is calculated according to toluene, the weight hourly space velocity WHSV=2h -1 , and the synthesis gas composition is H 2 / CO (molar ratio) is 2:1, the reaction is operated at 440 ° C, the toluene / CO (molar ratio) in the feed is taken 1:2, 3:1, 6:1, the reaction is two hours Listed in Table 7.
表7Table 7
Figure PCTCN2016106948-appb-000009
Figure PCTCN2016106948-appb-000009
实施例7催化剂评价(不同反应温度)Example 7 Catalyst Evaluation (Different Reaction Temperatures)
取1g 20～40目的催化剂样品CAT-3#装填在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10mL/min流速的氢气气氛下350℃还原4h，然后通入合成气，通过背压阀使体系压力升至预定反应压力2MPa，压力稳定后，以高压微量进料泵通入原料甲苯，进料量按甲苯计算，重时空速WHSV＝2h-1，合成气组成为H2/CO(摩尔比)2:1，进料中甲苯/CO(摩尔比)2:1，反应温度分别取380℃和470℃，反应两小时的结果列于表8。1 g of catalyst sample CAT-3 # 20-40 was packed in a small fixed bed reactor. The catalyst was packed with quartz sand at both ends. The catalyst was first reduced at 350 ° C for 4 h under a hydrogen atmosphere at a flow rate of 10 mL/min, and then introduced into syngas. The pressure of the system is raised to a predetermined reaction pressure of 2 MPa through a back pressure valve. After the pressure is stabilized, the raw material toluene is introduced into the high-pressure micro feed pump. The feed amount is calculated as toluene, the weight hourly space velocity WHSV=2h -1 , and the composition of the synthesis gas is H. 2 / CO (molar ratio) 2:1, toluene / CO (molar ratio) 2:1 in the feed, the reaction temperature was 380 ° C and 470 ° C, respectively, and the results of the reaction for two hours are shown in Table 8.
表8Table 8
Figure PCTCN2016106948-appb-000010
Figure PCTCN2016106948-appb-000010
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 present invention. The present invention is disclosed by the preferred embodiments, but is not intended to limit the present invention. It is within the scope of the technical solution of the present invention to make a slight change or modification with the technical content disclosed above, which is equivalent to the equivalent embodiment, without departing from the scope of the present invention.

Claims (10)

  1. 一种甲苯与合成气制苯乙烯的方法，其特征在于将含有甲苯和合成气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，经侧链烷基化反应制备苯乙烯；A method for producing styrene from toluene and syngas, characterized in that a raw material gas containing toluene and synthesis gas is introduced into a reactor and contacted with a hydrogen-reduced bifunctional catalyst, and styrene is prepared by a side chain alkylation reaction;
    所述原料气中，合成气中H2和CO的摩尔比例为0.5～3:1，甲苯与合成气中CO的摩尔比例为0.5～10:1；优选地，合成气中H2和CO的摩尔比例为0.5～1.5:1；甲苯与合成气中CO的摩尔比例为2～6:1；In the raw material gas, the molar ratio of H 2 and CO in the synthesis gas is 0.5 to 3:1, and the molar ratio of toluene to CO in the synthesis gas is 0.5 to 10:1; preferably, H 2 and CO in the synthesis gas The molar ratio is 0.5 to 1.5:1; the molar ratio of toluene to CO in the synthesis gas is 2 to 6:1;
    所述双功能催化剂包含碱性分子筛和金属氧化物；The bifunctional catalyst comprises a basic molecular sieve and a metal oxide;
    所述侧链烷基化反应的反应温度为300～550℃，甲苯的质量空速WHSV为0.2～6h-1，反应压力为0.1MPa～30MPa；优选地，所述侧链烷基化反应的反应温度为350～500℃；反应压力为0.5～10Mpa。The side chain alkylation reaction has a reaction temperature of 300 to 550 ° C, the toluene mass space velocity WHSV is 0.2 to 6 h -1 , and the reaction pressure is 0.1 MPa to 30 MPa; preferably, the side chain alkylation reaction The reaction temperature is 350 to 500 ° C; and the reaction pressure is 0.5 to 10 MPa.
  2. 根据权利要求1所述的方法，其特征在于，至少包含以下步骤：The method of claim 1 including at least the following steps:
    a)向载有双功能催化剂的反应器中通入氢气，300～550℃下还原0.5h～10h，得到经过氢气还原的双功能催化剂；a) introducing hydrogen into the reactor carrying the bifunctional catalyst, and reducing it at 300-550 ° C for 0.5 h to 10 h to obtain a bifunctional catalyst which is reduced by hydrogen;
    b)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0.5～10Mpa的条件下，原料气与经过氢气还原的双功能催化剂接触，经侧链烷基化反应制备苯乙烯。b) After the completion of the step a), the raw material 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 10 MPa. The gas is contacted with a hydrogen-reduced bifunctional catalyst to produce styrene via a side chain alkylation reaction.
  3. 根据权利要求1所述的方法，其特征在于，所述双功能催化剂中，碱性分子筛与金属氧化物的质量比为0.1～10:1。The method according to claim 1, wherein in the bifunctional catalyst, the mass ratio of the basic molecular sieve to the metal oxide is from 0.1 to 10:1.
  4. 根据权利要求1所述的方法，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。The method according to claim 1, wherein the basic molecule is selected from at least one of an L-type molecular sieve, a β-type molecular sieve, a mordenite molecular sieve, an X-type molecular sieve, and a Y-type molecular sieve.
  5. 根据权利要求1所述的方法，其特征在于，所述碱性分子筛为经过甲苯转化促进元素改性的碱性分子筛；The method according to claim 1, wherein the basic molecular sieve is a basic molecular sieve that undergoes toluene conversion to promote element modification;
    所述甲苯转化促进元素选自Na、K、Rb、Cs、Ti、B、N、P、Ce、La、W、Zn、Ag、Cs、Mg、Ca、Sr、Ba、Cu、Co中的至少一种。The toluene conversion promoting element is at least selected from the group consisting of Na, K, Rb, Cs, Ti, B, N, P, Ce, La, W, Zn, Ag, Cs, Mg, Ca, Sr, Ba, Cu, Co. One.
  6. 根据权利要求1所述的方法，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；优选地，所述碱性分子筛中的硅铝摩尔比为Si/Al＝1～5:1。The method of claim 1 wherein the silicon in the basic molecular sieve The molar ratio of aluminum is Si/Al = 1 to 10:1; preferably, the molar ratio of silicon to aluminum in the basic molecular sieve is Si/Al = 1 to 5:1.
  7. 根据权利要求1所述的方法，其特征在于，所述金属氧化物含有锌的氧化物、铬的氧化物、铝的氧化物和金属M的氧化物；The method according to claim 1, wherein said metal oxide contains an oxide of zinc, an oxide of chromium, an oxide of aluminum, and an oxide of metal M;
    其中，所述金属M选自Ti、Zr、V，Cu、Ag、Nb、Mo、Mn、W、Ta的至少一种。The metal M is at least one selected from the group consisting of Ti, Zr, V, Cu, Ag, Nb, Mo, Mn, W, and Ta.
  8. 根据权利要求7所述的方法，其特征在于，所述金属氧化物由锌的氧化物、铬的氧化物、铝的氧化物和金属M的氧化物组成；所述金属氧化物中各金属元素的摩尔比为：The method according to claim 7, wherein said metal oxide is composed of an oxide of zinc, an oxide of chromium, an oxide of aluminum, and an oxide of metal M; each metal element in said metal oxide The molar ratio is:
    Zn：Cr：Al：M：＝10～40：20～70：10～50：1～5。Zn: Cr: Al: M: = 10 to 40: 20 to 70: 10 to 50: 1 to 5.
  9. 根据权利要求3-8任一项所述的方法，其特征在于，所述双功能催化剂通过以下步骤制备得到：The method according to any one of claims 3-8, wherein the bifunctional catalyst is prepared by the following steps:
    (I)采用离子交换和/或等体积浸渍法，用含有甲苯转化促进元素的化合物对碱性分子筛进行改性；(I) modifying the basic molecular sieve with a compound containing a toluene conversion promoting element by ion exchange and/or an equal volume impregnation method;
    所述甲苯转化促进元素选自Na、K、Rb、Cs、Ti、B、N、P、Ce、La、W、Zn、Ag、Cs、Mg、Ca、Sr、Ba、Cu、Co中的至少一种；The toluene conversion promoting element is at least selected from the group consisting of Na, K, Rb, Cs, Ti, B, N, P, Ce, La, W, Zn, Ag, Cs, Mg, Ca, Sr, Ba, Cu, Co. One type;
    (II)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M元素的溶液中加入沉淀剂，至体系pH值至7～8后，于60～80℃下老化至少3h，所得固体经干燥、450℃～600℃煅烧1～6h，即得所述金属氧化物；(II) Preparation of metal oxide by coprecipitation method: adding a precipitant to a solution containing Zn element, Cr element, Al element and M element under stirring at 50 to 90 ° C until the pH of the system reaches 7-8. After aging at 60-80 ° C for at least 3 h, the obtained solid is dried, calcined at 450 ° C ~ 600 ° C for 1 ~ 6h, the metal oxide is obtained;
    (III)将步骤(I)改性得到的碱性分子筛和步骤(II)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：(III) The basic molecular sieve obtained by modifying the step (I) and the metal oxide prepared in the step (II) are prepared in at least one of the following three ways to obtain a bifunctional catalyst:
    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；Mode (1): After the basic molecular sieve and the metal oxide are separately formed, they are uniformly mixed by mechanical means;
    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；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;
    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后再进行催化剂成型。Mode (3) After mixing the basic molecular sieve and the metal oxide, the catalyst is formed by ball milling after grinding or ball milling.
  10. 根据权利要求1所述的方法，其特征在于，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。 The method of claim 1 wherein the reactor is selected from at least one of a fixed bed reactor, a fluidized bed reactor, or a moving bed reactor.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111054429A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst for preparing ethylbenzene and styrene by toluene side chain alkylation and application thereof
CN111054428A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst for synthesizing ethylbenzene and styrene by toluene side chain alkylation and application thereof
CN112934254A (en) * 2019-12-11 2021-06-11 中国科学院大连化学物理研究所 Bifunctional catalyst for catalyzing n-heptane conversion and preparation method thereof
CN114433220A (en) * 2020-10-30 2022-05-06 中国石油化工股份有限公司 Preparation method of benzene and synthesis gas alkylation catalyst
CN114456034A (en) * 2020-10-21 2022-05-10 中国石油化工股份有限公司 Method for preparing ethylbenzene and xylene from oxygen-containing compound

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109748774B (en) * 2017-11-01 2022-02-01 中国石油化工股份有限公司 Method for preparing ethylbenzene styrene from synthesis gas
CN109847789B (en) * 2017-11-30 2021-03-02 中国科学院大连化学物理研究所 Bifunctional catalyst and preparation method thereof, and method for preparing styrene from toluene and methanol
CN111215126B (en) * 2018-11-26 2021-11-02 中国科学院大连化学物理研究所 Preparation method and application of catalyst
CN109529910B (en) * 2018-11-29 2020-08-07 中国科学院大连化学物理研究所 Catalyst for toluene methanol side-chain alkylation reaction and styrene preparation method
CN111686789B (en) * 2019-03-13 2021-07-16 中国科学院大连化学物理研究所 Na atom modified MOR-based catalyst and method for preparing liquid fuel by directly converting synthesis gas
CN112844448B (en) * 2019-11-28 2023-07-04 中国科学院大连化学物理研究所 Catalyst for preparing ethylbenzene by directly converting catalytic synthesis gas and toluene and application thereof
CN111437822A (en) * 2020-05-19 2020-07-24 南京师范大学 Method for preparing cumene hydroperoxide by adopting ternary composite metal catalytic oxidation
CN113731482A (en) * 2021-09-24 2021-12-03 陕西延长石油（集团）有限责任公司 Preparation method and application of catalyst for preparing toluene and xylene from synthesis gas and benzene

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102123975A (en) * 2008-08-18 2011-07-13 弗纳技术股份有限公司 Method for production of styrene from toluene and syngas
CN103664485A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Method for producing ethylbenzene and styrene through side chain alkylation of toluene and methanol

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103772134B (en) * 2012-10-25 2015-09-09 中国石油化工股份有限公司 For the method for methylbenzene methanol side chain alkylation preparation of styrene
CN104557374B (en) * 2013-10-28 2017-04-19 中国石油化工股份有限公司 Toluene/methanol side chain alkylation method
CN104926580B (en) * 2014-03-17 2017-04-19 中国石油化工股份有限公司 Method for preparing ethylbenzene and styrene through toluene and methanol side chain alkylation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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