WO2018076910A1 - 一种制备芳烃的方法 - Google Patents

一种制备芳烃的方法 Download PDF

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WO2018076910A1
WO2018076910A1 PCT/CN2017/098510 CN2017098510W WO2018076910A1 WO 2018076910 A1 WO2018076910 A1 WO 2018076910A1 CN 2017098510 W CN2017098510 W CN 2017098510W WO 2018076910 A1 WO2018076910 A1 WO 2018076910A1
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reaction
methanol
molecular sieve
catalyst
carbon monoxide
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French (fr)
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倪友明
朱文良
刘中民
陈之旸
刘勇
刘红超
马现刚
刘世平
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to RU2019109439A priority Critical patent/RU2715244C1/ru
Priority to US16/344,375 priority patent/US10927051B2/en
Priority to GB1905146.5A priority patent/GB2570416B8/en
Publication of WO2018076910A1 publication Critical patent/WO2018076910A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • 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
    • 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
    • C07C15/04—Benzene
    • 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
    • C07C15/06—Toluene
    • 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
    • C07C15/08—Xylenes
    • 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
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a process for the preparation of aromatic hydrocarbons, in particular to the preparation of said aromatic hydrocarbons by means of a catalyst carrying an acidic ZSM-5 molecular sieve containing no metal promoters using methanol and carbon monoxide.
  • Aromatic hydrocarbons especially Benzene, Toluene and Xylene, collectively known as BTX, are important organic chemical raw materials with a yield and scale second only to ethylene and propylene. Their derivatives are widely used in fuels, petrochemicals, Chemical products and fine chemicals such as chemical fiber, plastic and rubber.
  • aromatics are mainly produced from petroleum.
  • 70% of BTX aromatics in the world come from the catalytic reforming process unit of the refinery.
  • the catalytic reforming technology is a process type in which naphtha is used as a raw material, and semi-regeneration and continuous regeneration reforming are employed.
  • Catalytic reforming generally employs a platinum-containing catalyst. Typical processes for catalytic reforming are represented by UOP's CCR platformer process and IFP's Aromizer process.
  • the aromatics production process of the petroleum route includes gasoline hydrogenation technology, aromatics extraction technology, heavy aromatics lightening technology, and light hydrocarbon aromatization technology.
  • the invention provides a method for preparing aromatic hydrocarbons by using methanol, which is advantageous for improving aromatic hydrocarbon selectivity and catalyst life, and having no significant decrease in performance after catalyst regeneration; It is achieved by carbon monoxide and an acidic ZSM-molecular sieve containing no metal promoter as a catalyst.
  • the method for producing an aromatic hydrocarbon comprises preparing a hydrocarbon by reacting methanol and carbon monoxide through a reactor carrying a catalyst containing an acidic ZSM-molecular sieve containing no metal promoter.
  • the molar ratio of methanol to carbon monoxide is less than or equal to 1:1.
  • the molar ratio of methanol to carbon monoxide is less than or equal to 1:20 and greater than or equal to 1:100.
  • the acidic ZSM-5 molecular sieve is a hydrogen type ZSM-5 molecular sieve.
  • the acidic ZSM-5 molecular sieve is a hydrogen-type ZSM-5 molecular sieve that is not impregnated with a metal adjuvant, is not ion exchanged, and is not physically mixed.
  • the acidic ZSM-5 molecular sieve has at least one of a micron structure, a nanostructure, a microporous structure, and a mesoporous-microporous structure.
  • reaction conditions are specifically as follows: reaction temperature of 350 deg.] C to 550 deg.] C, a reaction pressure of 0.5MPa to 10.0MPa, the methanol WHSV 0.01h -1 to 20h -1.
  • the reaction temperature is from 390 ° C to 480 ° C
  • the reaction pressure is from 3 MPa to 7 MPa
  • the mass flow rate of methanol is from 0.3 h -1 to 3.0 h -1 .
  • the reactor is a fixed bed reactor, a moving bed reactor or a fluidized bed reactor that effects a continuous reaction.
  • the reactor is a fixed bed reactor.
  • the reactor is one or more fixed bed reactors. It can take the form of a continuous reaction.
  • the fixed bed reactor may be one or plural. When multiple fixed bed reactors are employed, the reactors may be in series, in parallel, or in a combination of series and parallel.
  • the method provided by the present invention is added to the methanol aromatization reaction as compared with the prior art.
  • Carbon monoxide can increase and stabilize aromatics, especially BTX selectivity, while also extending the single-pass life of the catalyst.
  • the catalyst provided by the present invention has no significant decrease in performance after repeated regeneration of the catalyst in which the aromatization of methanol is deactivated under a carbon monoxide atmosphere.
  • the method provided by the present invention omits the step of adding a metal auxiliary agent, and simplifies the process.
  • the method provided by the invention does not require the addition of a metal auxiliary agent, which greatly saves cost and is environmentally friendly.
  • Automated analysis was performed using an Agilent 7890 gas chromatograph with a gas autosampler, a TCD detector connected to a TDX-1 packed column, and an FID detector connected to a FFAP capillary column.
  • both conversion and selectivity are calculated based on the number of moles of carbon:
  • Methanol conversion [(methanol carbon moles in feed) - (mole carbon moles in discharge)] ⁇ (moles of methanol in feed) x 100%
  • Liquid hydrocarbons hydrocarbons containing 5 carbons and above
  • selectivity (carbon moles of liquid hydrocarbons in the discharge) ⁇ (carbon moles of all products in the discharge) ⁇ 100%
  • Aromatic selectivity (carbon moles of aromatics in the discharge) ⁇ (carbon moles of all products in the discharge) ⁇ 100%
  • BTX selectivity (carbon moles of BTX in the discharge) ⁇ (carbon moles of all products in the discharge) ⁇ 100%
  • HZSM-5 200 (atomic ratio) hydrogen type ZSM-5 molecular sieve purchased by Nankai University Catalyst Factory, referred to as HZSM-5 (200), is divided into 20-40 mesh particles after tableting, and filled into an inner diameter of 16mm.
  • reaction temperature (T) 550 ° C
  • reaction pressure (P) 10 MPa
  • methanol mass space velocity (WHSV) 20 h -1
  • Carbon monoxide: methanol (CO: MeOH) 100:1.
  • Example 9 The catalyst deactivated in Example 9 was treated with a mixture of a volume fraction of 2% oxygen and 98% nitrogen at 550 ° C for 10 h to regenerate the catalyst for one round under the conditions of Example 9. reaction. Five rounds were regenerated in the same manner, and the catalytic activity data after 20 hours of each reaction was selected for comparison. The results are shown in Table 2.
  • Example 9 The HZSM-5 (30) in Example 9 was impregnated with a zinc nitrate solution by an equal volume method, dried and calcined at 550 ° C to obtain an acidic ZSM-5 molecular sieve having a zinc content of 2%, abbreviated as Zn/HZSM-5 (30).
  • the reaction was carried out under the conditions of Example 9, and regeneration was carried out under the conditions of Example 10, so that the catalyst was regenerated for one round and reacted under the conditions of Example 9. Five rounds were regenerated in the same manner, and the catalytic activity data after 20 hours of each reaction was selected for comparison. The results are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

本发明公开了一种制备芳烃的方法，特别涉及使用甲醇和一氧化碳通过载有不含金属助剂的酸性ZSM-5分子筛的催化剂的反应器，在反应条件下制备得到所述芳烃。本发明所提供的方法与现有技术相比，在甲醇芳构化反应中加入一氧化碳，能提高并稳定芳烃尤其是BTX选择性，同时也延长了催化剂单程寿命；失活的催化剂经过多次重生后性能无明显下降；并且催化剂制备工艺省略了添加金属助剂这一步，不但简化了工艺，而且大大节约了成本，并且有利于环境保护。

Description

一种制备芳烃的方法 技术领域
本发明涉及一种制备芳烃的方法，特别涉及使用甲醇和一氧化碳通过载有不含金属助剂的酸性ZSM-5分子筛的催化剂制备所述芳烃。
背景技术
芳烃尤其是苯(Benzene)，甲苯(Toluene)和二甲苯(Xylene)，统称为BTX，是产量和规模仅次于乙稀和丙烯的重要有机化工原料，其衍生物广泛用于燃料、石化、化纤、塑料和橡胶等化工产品和精细化工品。
目前芳烃主要以石油为原料进行生产，其中世界范围内70％的BTX芳烃来自炼油厂的催化重整工艺单元。催化重整技术是以石脑油为原料，采用半再生和连续再生重整的工艺类型，催化重整一般采用含铂催化剂。催化重整的典型工艺代表为UOP公司的CCR platformer工艺和IFP公司的Aromizer工艺。另外，石油路线的芳烃生产工艺还有汽油加氢技术、芳烃抽提技术、重芳烃轻质化技术以及轻烃芳构化技术。
随着社会的不断发展，世界上对芳烃的需求量不断增长，然而石油资源日益紧张造成芳烃尤其是BTX的价格居高不下。鉴于中国“富煤贫油”的能源结构现状，大力发展煤化工路线制芳烃具有非常重要的意义。在煤化工制芳烃技术中，以煤化工平台产品甲醇为原料制取芳烃的技术(MTA)研究最为广泛甲醇制芳烃技术一般采用锌、镓、银等金属助剂改性的酸性ZSM-5分子筛催化剂，然而高温条件下金属容易升华或聚集，芳烃选择性下降快，催化剂寿命短，BTX选择性不高，催化剂重生后性能下降明显等因素制约了甲醇制芳烃技术的大规模工业化应用。
因此，需要开发出一种有利于提高芳烃选择性和催化剂寿命，以及催化剂重生后性能无明显下降的利用甲醇制备芳烃的方法。
发明内容
本发明提供了一种有利于提高芳烃选择性和催化剂寿命，以及催化剂重生后性能无明显下降的利用甲醇制备芳烃的方法；该方法产生的效果主 要通过一氧化碳和作为催化剂的不含金属助剂的酸性ZSM-分子筛来实现。
具体来讲，本发明提供的制备芳烃的方法包括将甲醇和一氧化碳通过载有不含金属助剂的酸性ZSM-分子筛的催化剂的反应器，在反应条件下制备得到所述芳烃。
在一个具体实施方式中，所述甲醇和所述一氧化碳的摩尔比小于或等于1:1。
在一个具体实施方式中，所述甲醇和所述一氧化碳的摩尔比小于或等于1:20，且大于或等于1:100。
在一个具体实施方式中，所述酸性ZSM-5分子筛为氢型ZSM-5分子筛。
在一个具体实施方式中，所述酸性ZSM-5分子筛中的硅和铝的原子比为Si/Al＝3-200。
在一个具体实施方式中，所述酸性ZSM-5分子筛中的硅和铝的原子比为Si/Al＝10-40。
在一个具体实施方式中，所述酸性ZSM-5分子筛是不经过金属助剂浸渍、不经过离子交换以及不经过物理混合的氢型ZSM-5分子筛。
在一个具体实施方式中，所述酸性ZSM-5分子筛具有微米结构、纳米结构、微孔结构、介孔-微孔结构中的至少一种。
在一个具体实施方式中，所述反应条件具体为：反应温度350℃至550℃，反应压力0.5MPa至10.0MPa，甲醇质量空速0.01h-1至20h-1。
在一个具体实施方式中，反应温度390℃至480℃，反应压力3MPa至7MPa，甲醇质量空速0.3h-1至3.0h-1。
在一个具体实施方式中，所述反应器为实现连续反应的固定床反应器、移动床反应器或流化床反应器。
在一个具体实施方式中，所述反应器为固定床反应器。
所述反应器为一个或多个固定床反应器。可以采用连续反应的形式。固定床反应器可以为一个，也可以为多个。当采用多个固定床反应器时，反应器之间可以是串联、并联、或者串联与并联相结合的形式。
本发明能产生的有益效果包括：
1)本发明所提供的方法与现有技术相比，在甲醇芳构化反应中加入 一氧化碳，能提高并稳定芳烃尤其是BTX选择性，同时也延长了催化剂单程寿命。
2)本发明所提供的方法与现有技术相比，在一氧化碳气氛下甲醇芳构化失活的催化剂经过多次重生后性能无明显下降。
3)本发明所提供的方法与现有技术相比，催化剂制备工艺省略了添加金属助剂这一步，简化了工艺。
4)本发明所提供的方法与现有技术相比，催化剂不需要添加金属助剂，大大节约了成本，并且有利于环境保护。
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，本发明的实施例中的原料可通过商业途径购买。
实施例中分析方法以及转化率、选择性计算如下：
利用带有气体自动进样器、连接TDX-1填充柱的TCD检测器以及连接FFAP毛细管柱的FID检测器的Agilent7890气相色谱仪进行自动分析。
在本发明的一些实施例中，转化率和选择性都基于碳摩尔数进行计算：
甲醇转化率＝[(进料中甲醇碳摩尔数)－(出料中甲醇碳摩尔数)]÷(进料中甲醇碳摩尔数)×100％
液烃(含5个碳及以上的烃类)选择性＝(出料中液烃的碳摩尔数)÷(出料中所有产物的碳摩尔数)×100％
芳烃选择性＝(出料中芳烃的碳摩尔数)÷(出料中所有产物的碳摩尔数)×100％
BTX选择性＝(出料中BTX的碳摩尔数)÷(出料中所有产物的碳摩尔数)×100％
实施例1
将南开大学催化剂厂购买的10g Si/Al＝19(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(19)，压片后筛分成20～40目的颗粒，装入内径为16mm的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝350℃，反应压力(P)＝0.5MPa，甲醇质 量空速(WHSV)＝0.01h-1，一氧化碳：甲醇(CO:MeOH)＝1:1。反应稳定后，用气相色谱分析产物，反应结果见表1。
实施例2
将南开大学催化剂厂购买的10g Si/Al＝200(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(200)，压片后筛分成20～40目的颗粒，装入内径为16mm的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝550℃，反应压力(P)＝10MPa，甲醇质量空速(WHSV)＝20h-1，一氧化碳：甲醇(CO:MeOH)＝100:1。反应稳定后，用气相色谱分析产物，反应结果见表1。
实施例3
将上海卓悦公司购买的10g Si/Al＝4(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(4)，压片后筛分成20～40目的颗粒，装入内径为16mm的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝450℃，反应压力(P)＝5MPa，甲醇质量空速(WHSV)＝2h-1，一氧化碳：甲醇(CO:MeOH)＝40:1。反应稳定后，用气相色谱分析产物，反应结果见表1。
实施例4
将上海卓悦公司购买的10g Si/Al＝70(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(70)，压片后筛分成20～40目的颗粒，装入内径为16mm的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝400℃，反应压力(P)＝3MPa，甲醇质量空速(WHSV)＝1h-1，一氧化碳：甲醇(CO:MeOH)＝20:1。反应稳定后，用气相色谱分析产物，反应结果见表1。
实施例5
将上海卓悦公司购买的10g Si/Al＝40(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(40)，压片后筛分成20～40目的颗粒，装入内径为16mm 的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝400℃，反应压力(P)＝3MPa，甲醇质量空速(WHSV)＝1h-1，一氧化碳：甲醇(CO:MeOH)＝20:1。反应稳定后，用气相色谱分析产物，反应结果见表1。
实施例6
将奥科公司购买的10g Si/Al＝25(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(25)，压片后筛分成20～40目的颗粒，装入内径为16mm的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝400℃，反应压力(P)＝3MPa，甲醇质量空速(WHSV)＝1h-1，一氧化碳：甲醇(CO:MeOH)＝20:1。反应稳定后，用气相色谱分析产物，反应结果见表1。
实施例7
将奥科公司购买的10g Si/Al＝25(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(25)，压片后筛分成20～40目的颗粒，装入内径为16mm的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝390℃，反应压力(P)＝3MPa，甲醇质量空速(WHSV)＝0.3h-1，一氧化碳：甲醇(CO:MeOH)＝20:1。反应稳定后，用气相色谱分析产物，反应结果见表1。
实施例8
将奥科公司购买的10g Si/Al＝25(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(25)，压片后筛分成20～40目的颗粒，装入内径为16mm的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝480℃，反应压力(P)＝7MPa，甲醇质量空速(WHSV)＝3h-1，一氧化碳：甲醇(CO:MeOH)＝100:1。反应稳定后，用气相色谱分析产物，反应结果见表1。
实施例9
将南开大学催化剂厂购买的10g Si/Al＝30(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(30)，压片后筛分成20～40目的颗粒，装入内径为16mm的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝400℃，反应压力(P)＝3MPa，甲醇质量空速(WHSV)＝1h-1，一氧化碳：甲醇(CO:MeOH)＝20:1。反应稳定后，用气相色谱分析产物，反应结果见表1。
对比例1
将南开大学催化剂厂购买的10g Si/Al＝30(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(30)，压片后筛分成20～40目的颗粒，装入内径为16mm的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝400℃，反应压力(P)＝3MPa，甲醇质量空速(WHSV)＝1h-1，氮气：甲醇(N2:MeOH)＝20:1。反应稳定后，用气相色谱分析产物，反应结果见表1。
对比例2
将南开大学催化剂厂购买的10g Si/Al＝30(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(30)，压片后筛分成20～40目的颗粒，装入内径为16mm的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝400℃，反应压力(P)＝0.1MPa，甲醇质量空速(WHSV)＝1h-1，氮气：甲醇(N2:MeOH)＝20:1。反应稳定后，用气相色谱分析产物，反应结果见表1。
对比例3
将南开大学催化剂厂购买的10g Si/Al＝30(原子比)的氢型ZSM-5分子筛，简称为HZSM-5(30)，压片后筛分成20～40目的颗粒，装入内径为16mm的不锈钢反应管内，用100ml/min氮气在550℃下活化4h，以下条件下反应：反应温度(T)＝400℃，反应压力(P)＝3MPa，甲醇质量空速(WHSV)＝1h-1，没有其它载气。反应稳定后，用气相色谱分析 产物，反应结果见表1。
表1实施例1-7和对比例1-3中的催化反应结果
Figure PCTCN2017098510-appb-000001
催化剂重生性能测试
实施例10
将实施例9中失活后的催化剂利用体积分数为2％氧气和98％氮气的混合气，在550℃处理10h，使得催化剂重生一轮，在实施例9的条件下 反应。按照同样的方式重生五轮，选取每轮反应20h后的催化活性数据进行比较，结果见表2。
对比例4
将实施例9中HZSM-5(30)用等体积法浸渍硝酸锌溶液，干燥后在550℃下煅烧得到锌含量为2％的酸性ZSM-5分子筛，简称为Zn/HZSM-5(30)，在实施例9的条件下反应，利用实施例10的条件进行重生，使得催化剂重生一轮，在实施例9的条件下反应。按照同样的方式重生五轮，选取每轮反应20h后的催化活性数据进行比较，结果见表2。
表2实施例10和对比例4中的催化反应结果
Figure PCTCN2017098510-appb-000002
从表2可知，不含金属助剂的酸性ZSM-5分子筛在重生之后，其芳烃选择性、BTX选择性和催化剂寿命都有明显的提高。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，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，均属于技术方案 范围内。

Claims (10)

  1. 一种制备芳烃的方法，其特征在于，包括将甲醇和一氧化碳通过载有不含金属助剂的酸性ZSM-分子筛的催化剂的反应器，在反应条件下制备得到所述芳烃。
  2. 根据权利要求1所述的方法，其特征在于，所述甲醇和所述一氧化碳的摩尔比小于或等于1:1。
  3. 根据权利要求2所述的方法，其特征在于，所述甲醇和所述一氧化碳的摩尔比小于或等于1:20，且大于或等于1:100。
  4. 根据权利要求1所述的方法，其特征在于，所述酸性ZSM-5分子筛为氢型ZSM-5分子筛。
  5. 根据权利要求1所述的方法，其特征在于，所述酸性ZSM-5分子筛中的硅和铝的原子比为Si/Al＝3-200。
  6. 根据权利要求5所述的方法，其特征在于，所述酸性ZSM-5分子筛中的硅和铝的原子比为Si/Al＝10-40。
  7. 根据权利要求1所述的方法，其特征在于，所述反应条件具体为：反应温度350℃至550℃，反应压力0.5MPa至10.0MPa，甲醇质量空速0.01h-1至20h-1。
  8. 根据权利要求7所述的方法，其特征在于，反应温度390℃至480℃，反应压力3MPa至7MPa，甲醇质量空速0.3h-1至3.0h-1。
  9. 根据权利要求1所述的方法，其特征在于，所述反应器为实现连续反应的固定床反应器、移动床反应器或流化床反应器。
  10. 根据权利要求9所述的方法，其特征在于，所述反应器为固定床反应器。
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CN112920006A (zh) * 2019-12-05 2021-06-08 中国科学院大连化学物理研究所 一种乙醇制取芳烃化合物的方法
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