WO2018076909A1 - 一种用于合成芳烃的催化剂和其制备方法 - Google Patents

一种用于合成芳烃的催化剂和其制备方法 Download PDF

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WO2018076909A1
WO2018076909A1 PCT/CN2017/098509 CN2017098509W WO2018076909A1 WO 2018076909 A1 WO2018076909 A1 WO 2018076909A1 CN 2017098509 W CN2017098509 W CN 2017098509W WO 2018076909 A1 WO2018076909 A1 WO 2018076909A1
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Prior art keywords
molecular sieve
zinc
particles
acidic
composite oxide
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PCT/CN2017/098509
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English (en)
French (fr)
Inventor
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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中国科学院大连化学物理研究所
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Priority to GB1905139.0A priority Critical patent/GB2570592B/en
Priority to US16/343,870 priority patent/US11014076B2/en
Priority to RU2019109457A priority patent/RU2732247C1/ru
Publication of WO2018076909A1 publication Critical patent/WO2018076909A1/zh

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Definitions

  • the present invention relates to a catalyst for synthesizing an aromatic hydrocarbon and a process for the preparation thereof, and to a process for synthesizing an aromatic hydrocarbon using the catalyst.
  • 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 present invention has developed a catalyst having high selectivity and stable performance of aromatic hydrocarbons. Moreover, the catalyst of the present invention is particularly suitable for the one-step synthesis of aromatic hydrocarbons, thereby reducing the problem of a large amount of energy consumption due to the stepwise synthesis.
  • one of the present invention provides a catalyst comprising acidic molecular sieve particles and zinc aluminum composite oxide particles.
  • the zinc aluminum composite oxide particles may be added with other metal elements by impregnation or without impregnation modification.
  • the zinc-aluminum composite oxide particles further include other metal elements.
  • the other metal element is another metal element that removes zinc, aluminum, and radioactive elements.
  • the other metal element includes at least one of zirconium, copper, platinum, palladium, and chromium.
  • the mass ratio of the acidic molecular sieve particles to the zinc-aluminum composite oxide particles is from 1:19 to 19:1.
  • the mass ratio of the acidic molecular sieve particles to the zinc aluminum composite oxide particles is from 4:1 to 1:4.
  • the mass ratio of the acidic molecular sieve particles to the zinc aluminum composite oxide particles is from 2:1 to 1:2.
  • the particle diameters of the acidic molecular sieve particles and the zinc-aluminum composite oxide are each independently less than or equal to 5 mm.
  • the particle diameters of the acidic molecular sieve particles and the zinc-aluminum composite oxide are each independently less than or equal to 5 mm and greater than or equal to 0.1 mm.
  • the particle size of the acidic molecular sieve particles and the zinc-aluminum composite oxide particles are each independently less than or equal to 1 mm and greater than or equal to 0.1 mm.
  • the particle size of the particles is less than or equal to 0.5 mm and greater than or equal to 0.1 mm.
  • the particles have a particle size less than or equal to 0.5 mm and greater than or equal to 0.25 mm.
  • the acidic molecular sieve is an acidic molecular sieve having a pore structure having a dimension greater than or equal to a ten-membered ring.
  • the acidic molecular sieve comprises an acidic molecular sieve having at least one of MFI, BEA, FAU, EMT, MOR, FER, and MWW.
  • the acidic molecular sieve is an acidic molecular sieve having an MFI structure.
  • the acidic molecular sieve is an acidic ZSM-5 molecular sieve.
  • the acidic molecular sieve is an acidic ZSM-5 molecular sieve that has not been modified with a metal element.
  • the acidic ZSM-5 molecular sieve may be treated with or without desiliconization and/or dealuminated.
  • the post-silicone treatment is an alkaline solution treatment.
  • alkali solutions are aqueous solutions of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, and sodium hydrogencarbonate.
  • the post-aluminizing treatment is an acid solution treatment or a steam treatment.
  • acid solutions are aqueous solutions of hydrochloric acid, nitric acid, oxalic acid, citric acid, and acetic acid.
  • Conventional steam treatment temperatures range from 400 °C to 700 °C.
  • the acidic ZSM-5 molecular sieve has one or more of a micron structure, a nanostructure, a microporous structure, and a mesoporous-microporous structure.
  • the acidic ZSM-5 molecular sieve may not contain or contain one or more of metal elements such as zinc, gallium, silver, copper, iron, molybdenum, niobium, tantalum and the like.
  • the acidic ZSM-5 molecular sieve contains a metal mass fraction of 0-10%.
  • the position of the metal in the acidic molecular sieve is an ion exchange position of the molecular sieve, or a pore or surface of the acidic molecular sieve, or One or more of the skeleton of the acidic molecular sieve.
  • the manner in which the metal is introduced into the acidic molecular sieve is one or more of in situ synthesis, impregnation, or ion exchange.
  • the particle shape of the catalyst may be spherical, strip-shaped or clover-shaped, and may also be an irregular shape obtained by crushing and sieving large particles.
  • the particles may be zinc-aluminum composite oxide and powdery particles naturally formed without further molding during the preparation of the acidic molecular sieve.
  • the particle size of the powdery particles is less than or equal to 5 mm; preferably, the particle size of the powdery particles is less than or equal to 5 mm and greater than or equal to 0.1 mm; more preferably, the particles of the powdery particles The diameter is less than or equal to 0.5 mm and greater than or equal to 0.1 mm; most preferably, the powder particles have a particle size of less than or equal to 0.5 mm and greater than or equal to 0.25 mm.
  • the second aspect of the present invention provides a method of preparing the catalyst of one of the present invention, comprising the steps of:
  • a salt containing a zinc element and an aluminum element is formulated into an aqueous solution, and then the metal ion in the salt of the zinc-containing element and the aluminum element is coprecipitated by an aqueous solution of a precipitating agent, aged, and the precipitate is washed, dried, and calcined. Producing the zinc aluminum composite oxide particles;
  • the precipitating agent comprises at least one of sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, aqueous ammonia, sodium hydroxide, and potassium hydroxide.
  • the mixing mode is typically achieved by mechanical agitation.
  • the conditions of the coprecipitation are: a temperature of 60 ° C to 80 ° C, and a pH of 6.0 to 8.0.
  • step 1) calcination is carried out at 400 ° C to 600 ° C for 1 h to 4 h.
  • the concentration of the zinc element in the aqueous solution is from 0.1 mol/L to 2.0 mol/L; and the concentration of the aluminum element in the aqueous solution is from 0.1 mol/L to 2.0 mol/L. .
  • step 2) further comprising, after step 1), step 1-2) prior to step 2), placing the zinc-aluminum composite oxide particles in the removal of zinc, aluminum, and radioactive elements. It is modified in the salt solution of other metal elements.
  • the other metal elements include at least one of zirconium, copper, platinum, palladium, and chromium.
  • the concentration of the single metal element of the other metal element in the aqueous solution is from 0.1 mol/L to 2.0 mol/L.
  • the concentration of the zirconium element in the aqueous solution is from 0.1 mol/L to 2.0 mol/L; and the concentration of the copper element in the aqueous solution is from 0.1 mol/L to 2.0 mol. /L; the concentration of platinum in aqueous solution is 0.1mol / L to 2.0mol / L; the concentration of palladium in aqueous solution is 0.1mol / L to 2.0mol / L; the concentration of chromium in aqueous solution is 0.1mol / L to 2.0 mol/L.
  • a third aspect of the present invention provides a process for producing an aromatic hydrocarbon, which comprises preparing a raw material of a synthesis gas by passing it through a catalyst-carrying reactor under reaction conditions, wherein the catalyst is one of the inventions catalyst.
  • the syngas comprises hydrogen and carbon monoxide.
  • the molar ratio of hydrogen to carbon monoxide in the syngas is from 1:9 to 9:1.
  • the molar ratio of hydrogen to carbon monoxide in the syngas is from 1:3 to 3:1.
  • reaction conditions were: reaction temperature of 300 deg.] C to 450 °C, a reaction pressure of 0.5MPa to 10.0MPa, the synthesis gas hourly space velocity of 2000h -1 standard conditions to 20000h -1.
  • the reaction conditions are: a reaction temperature of 380 ° C to 420 ° C, a reaction pressure of 3 MPa to 5 MPa, and a volumetric space velocity of 4000 h -1 to 8000 h -1 in a standard state of synthesis gas.
  • the aromatic hydrocarbon means a hydrocarbon having a benzene ring structure in its molecule.
  • the aromatic hydrocarbon is at least one selected from the group consisting of benzene, toluene, ethylbenzene, methyl ethylbenzene, xylene, trimethylbenzene, and styrene.
  • the aromatic hydrocarbon is selected from one of benzene, toluene, and xylene.
  • the reactor is one or more fixed beds reactor. 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.
  • normal temperature means a temperature range of 20 ° C to 30 ° C.
  • the catalyst of the present invention has high selectivity to aromatic hydrocarbons, especially BTX, stable performance, and long single life.
  • the catalyst of the present invention is particularly suitable for the one-step synthesis of aromatic hydrocarbons, thereby reducing the problem of a large amount of energy consumption by stepwise synthesis.
  • the method provided by the present invention has no significant degradation in performance after repeated regeneration of the deactivated catalyst.
  • 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:
  • Carbon monoxide conversion [( moles of carbon monoxide carbon in the feed) - (molar carbon monoxide carbon in the discharge)] ⁇ (moles of carbon monoxide in the feed) ⁇ 100%
  • Aromatic selectivity (moles of aromatic hydrocarbons in the discharge) ⁇ (carbon moles of all hydrocarbon products in the discharge) ⁇ 100%
  • BTX selectivity (number of moles of BTX carbon in the discharge) ⁇ (molar moles of all hydrocarbon products in the discharge) ⁇ 100%
  • a sodium type ZSM-5 (Nankai University Catalyst Factory) having Si/Al 19 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-5 molecular sieve, and 550 in an air atmosphere. Calcined at °C for 4h, tableted, crushed and sieved to obtain acidic ZSM-5 molecular sieve particles of 0.25mm-0.50mm scale.
  • a sodium type ZSM-5 (Nankai University Catalyst Factory) having Si/Al 19 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-5 molecular sieve, and 550 in an air atmosphere. Calcined at °C for 4h, tableted, crushed and sieved to obtain acidic ZSM-5 molecular sieve particles of 0.25mm-0.50mm scale.
  • the zinc-aluminum composite oxide powder was impregnated with a Cr(NO 3 ) 3 solution having a Cr 2+ concentration of 0.25 mol/L at room temperature for 24 hours, dried, and calcined at 500 ° C for 2 hours to obtain a 5% chromium-modified zinc-aluminum composite oxide ( 5% Cr-ZnAlO x ) powder.
  • the 5% Cr-ZnAlO x powder was tableted, crushed and sieved to obtain 0.25 mm to 0.50 mm scale particles.
  • a sodium type ZSM-5 (Nankai University Catalyst Factory) having Si/Al 19 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-5 molecular sieve, and 550 in an air atmosphere. Calcined at °C for 4h, tableted, crushed and sieved to obtain acidic ZSM-5 molecular sieve particles of 0.25mm-0.50mm scale.
  • the zinc-aluminum composite oxide powder was impregnated with a Cu 2+ concentration of 0.4 mol/L Cu(NO 3 ) 2 solution at room temperature for 24 hours, dried, and calcined at 500 ° C for 2 h to obtain a zinc-aluminum composite oxide containing 7% copper modified (7).
  • %Cu-ZnAlO x The 7% Cu-ZnAlO x powder was tableted, crushed and sieved to obtain 0.25 mm to 0.50 mm scale particles.
  • a sodium type ZSM-5 (Nankai University Catalyst Factory) having Si/Al 19 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-5 molecular sieve, and 550 in an air atmosphere. Calcined at °C for 4h, tableted, crushed and sieved to obtain acidic ZSM-5 molecular sieve particles of 0.25mm-0.50mm scale.
  • a sodium type ZSM-5 (Nankai University Catalyst Factory) having Si/Al 19 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-5 molecular sieve, and 550 in an air atmosphere. Calcined at °C for 4h, tableted, crushed and sieved to obtain acidic ZSM-5 molecular sieve particles of 0.25mm-0.50mm scale.
  • the zinc-aluminum composite oxide powder was impregnated at room temperature for 24 h with Pd(NO 3 ) 3 having a Pd 2+ concentration of 0.1 mol/L and a Zr(NO 3 ) 4 mixed solution having a Zr 4+ concentration of 0.2 mol/L, and dried, 500 Calcination at ° C for 2 h gave a zinc-aluminum composite oxide (3% Pd-4% Zr-ZnAlO x ) powder containing 3% palladium and 4% zirconium. The 3% Pd-4% Zr-ZnAlO x powder was tableted, crushed and sieved to obtain 0.25 mm to 0.50 mm scale particles.
  • a sodium type ZSM-5 (Nankai University Catalyst Factory) having Si/Al 19 (atomic ratio) was exchanged three times with a 0.8 mol/L aqueous solution of ammonium nitrate at 80 ° C to obtain an ammonium type ZSM-5 molecular sieve, and 550 in an air atmosphere. Calcination at °C for 4 h gave an acidic ZSM-5 molecular sieve powder having a powder size of less than 0.1 mm.
  • the particle diameter of the acidic ZSM-5 molecular sieve particles in Example 1 was 4.5 mm to 5 mm, and the particle diameter of the ZnAlO x particles in Example 1 was 4.5 mm to 5 mm. Others are the same as in the first embodiment. Prepared as catalyst K.
  • the particle diameter of the acidic ZSM-5 molecular sieve particles in Example 1 was set to 0.8 mm to 1 mm, and the particle diameter of the ZnAlO x particles in Example 1 was set to 0.8 mm to 1 mm. Others are the same as in the first embodiment. Prepared as catalyst L.
  • the particle diameter of the acidic ZSM-5 molecular sieve particles in Example 1 was 0.1 mm to 0.2 mm, and the particle diameter of the ZnAlO x particles in Example 1 was 0.1 mm to 0.2 mm. Others are the same as in the first embodiment. Prepared as catalyst M.
  • reaction temperature (T) 400 ° C
  • reaction pressure (P) 4.0 MPa
  • the volumetric space velocity (GHSV) 5000 h -1 under standard conditions
  • V(H 2 )% 50%.
  • Example 14 The catalyst after deactivation in Example 14 was treated with a mixture of volume fraction of 2% oxygen and 98% nitrogen at 550 ° C for 10 h to regenerate the catalyst for one round, in the examples.
  • the reaction was carried out under conditions of 14. Five rounds were regenerated in the same manner, and the catalytic activity data after 500 hours of each reaction was selected for comparison. The results are shown in Table 2.

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Abstract

一种用于合成芳烃的催化剂及其制备方法，以及使用该催化剂合成芳烃的方法。催化剂包括酸性分子筛颗粒和锌铝复合氧化物颗粒。催化剂对芳烃，尤其是 BTX 选择性较高，性能稳定，且单程寿命长。

Description

一种用于合成芳烃的催化剂和其制备方法 技术领域
本发明涉及一种用于合成芳烃的催化剂及其制备方法，还涉及一种使用该催化剂合成芳烃的方法。
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金属锌、镓、银等金属改性的酸性ZSM-5分子筛催化剂，然而芳烃选择性下降快，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。众所周知，工业甲醇一般以合成气为原料进行生产，如果利用合成气直接制取芳烃可以缩短反应路径、节约能耗、减少污水排放以及降低固定投资。合成气直接制取芳烃研究较少，芳烃选择性低，催化剂稳定性差以及失活催化剂不能够重生等原因制约了该技术研究的进一步发展。
因此亟需一种芳烃选择性较高，性能稳定的催化剂。
发明内容
根据现有技术中存在的技术问题，本发明开发出了一种芳烃选择性较高，性能稳定的催化剂。而且本发明的催化剂特别适用于芳烃的一步合成，从而降低了分步合成带来的大量的能耗的问题。
具体来讲，本发明之一提供了一种催化剂，所述催化剂包括酸性分子筛颗粒和锌铝复合氧化物颗粒。
在一个具体实施方式中，所述锌铝复合氧化物颗粒可以通过浸渍或不通过浸渍改性加入其他金属元素。
但是作为优选的具体实施方式，所述锌铝复合氧化物颗粒中还包括其他金属元素。
作为一个更优选的具体实施方式，所述其他金属元素为除去锌、铝和放射性元素的其他金属元素。
作为一个进一步优选的具体实施方式，所述其他金属元素包括锆、铜、铂、钯和铬中的至少一种。
在一个具体实施方式中，所述酸性分子筛颗粒与所述锌铝复合氧化物颗粒的质量比为1:19至19:1。
在一个优选的具体实施方式中，所述酸性分子筛颗粒与所述锌铝复合氧化物颗粒的质量比为4:1至1:4。
在一个最优选的具体实施方式中，所述酸性分子筛颗粒与所述锌铝复合氧化物颗粒的质量比为2:1至1:2。
在一个具体实施方式中，所述酸性分子筛颗粒和锌铝复合氧化物的粒径各自独立地小于或等于5mm。
在一个具体实施方式中，所述酸性分子筛颗粒和锌铝复合氧化物的粒径各自独立地小于或等于5mm，且大于或等于0.1mm。
在一个优选的具体实施方式中，所述酸性分子筛颗粒和锌铝复合氧化物颗粒的粒径各自独立地小于或等于1mm，且大于或等于0.1mm。
在一个更优选的具体实施方式中，所述颗粒的粒径小于或等于 0.5mm，且大于或等于0.1mm。
在一个最优选的具体实施方式中，所述颗粒的粒径小于或等于0.5mm，且大于或等于0.25mm。
在一个具体实施方式中，所述酸性分子筛为具有尺度大于或等于十元环的孔道结构的酸性分子筛。
在一个具体实施方式中，所述酸性分子筛包括具有MFI、BEA、FAU、EMT、MOR、FER和MWW中的至少一种结构的酸性分子筛。
在一个优选的具体实施方式中，所述酸性分子筛为具有MFI结构的酸性分子筛。
在一个更优选的具体实施方式中，所述酸性分子筛为酸性ZSM-5分子筛。
在一个最优选的具体实施方式中，所述酸性分子筛为未经过金属元素改性的酸性ZSM-5分子筛。
在一个具体实施方式中，所述酸性ZSM-5分子筛中硅和铝的原子比为Si/Al＝3-200，优选Si/Al＝10-40。
在一个具体实施方式中，所述酸性ZSM-5分子筛可经过或不经过脱硅后处理和/或脱铝后处理。
在一个具体实施方式中，所述脱硅后处理是碱溶液处理。常用碱溶液有氢氧化钠、氢氧化钾、氢氧化铵、碳酸钠、碳酸氢钠的水溶液。
在一个具体实施方式中，所述脱铝后处理是酸溶液处理或水蒸气处理。常用酸溶液有盐酸、硝酸、草酸、柠檬酸、醋酸的水溶液。常规的水蒸气处理的温度为400℃至700℃。
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-微孔结构中的一种或几种。
在一个具体实施方式中，所述酸性ZSM-5分子筛中可以不含或含有锌、镓、银、铜、铁、钼、镧、铈等金属元素中的一种或者多种。
在一个具体实施方式中，所述酸性ZSM-5分子筛中含有的金属质量分数为0-10％。
在一个具体实施方式中，所述金属在所述酸性分子筛中的位置是分子筛的离子交换位置，或所述酸性分子筛的孔道或表面上，或所述 酸性分子筛的骨架上的一种或者多种。
在一个具体实施方式中，所述金属引入所述酸性分子筛的方式是原位合成、浸渍或者离子交换中的一种或者多种。
在一个具体实施方式中，所述催化剂的颗粒形状可以为球形、条形或三叶草形，还可以为大颗粒破碎并筛分后得到的不规则形状。
在一个具体实施方式中，所述颗粒可以为锌铝复合氧化物和酸性分子筛制备过程中未经过进一步成型而自然形成的粉状颗粒。进一步地，所述粉状颗粒的粒径小于或等于5mm；优选地，所述粉状颗粒的粒径小于或等于5mm，且大于或等于0.1mm；更优选地，所述粉状颗粒的粒径小于或等于0.5mm，且大于或等于0.1mm；最优选地，所述粉状颗粒的粒径小于或等于0.5mm，且大于或等于0.25mm。
本发明之二提供了一种制备本发明之一所述的催化剂的方法，包括如下步骤：
1)将含锌元素和铝元素的盐配成水溶液，然后利用沉淀剂的水溶液将所述含锌元素和铝元素的盐中的金属离子共沉淀，老化，再将沉淀物洗涤、干燥后煅烧制得所述锌铝复合氧化物颗粒；
2)将所述锌铝复合氧化物颗粒与所述酸性分子筛颗粒混合均匀。
在一个具体实施方式中，所述沉淀剂包括碳酸钠、碳酸钾、碳酸铵、碳酸氢钠、碳酸氢钾、碳酸氢铵、氨水、氢氧化钠和氢氧化钾中的至少一种。
在一个具体实施方式中，所述混合方式一般通过机械搅拌实现。
在一个具体实施方式中，在所述步骤1)中，共沉淀的条件为：温度为60℃至80℃，pH为6.0至8.0。
在一个具体实施方式中，在所述步骤1)中，在400℃至600℃煅烧1h至4h。
在一个具体实施方式中，在所述步骤1)中，锌元素在水溶液中的浓度为0.1mol/L至2.0mol/L；铝元素在水溶液中的浓度为0.1mol/L至2.0mol/L。
在一个具体实施方式中，还包括在步骤1)之后，步骤2)之前的步骤1-2)将所述锌铝复合氧化物颗粒置于除去锌、铝和放射性元 素的其他金属元素的盐溶液中改性。
在一个具体实施方式中，在所述步骤1-2)中，其他金属元素包括锆、铜、铂、钯和铬中的至少一种。
在一个具体实施方式中，在所述步骤1-2)中，所述其他金属元素的单种金属元素在水溶液中的浓度为0.1mol/L至2.0mol/L。
在一个具体实施方式中，在所述步骤1-2)中，锆元素在水溶液中的浓度为0.1mol/L至2.0mol/L；铜元素在水溶液中的浓度为0.1mol/L至2.0mol/L；铂元素在水溶液中的浓度为0.1mol/L至2.0mol/L；钯元素在水溶液中的浓度为0.1mol/L至2.0mol/L；铬元素在水溶液中的浓度为0.1mol/L至2.0mol/L。
本发明之三提供了一种制备芳烃的方法，将含有合成气的原料通过载有催化剂的反应器，在反应条件下制备所述芳烃，其中，所述催化剂为本发明之一中所述的催化剂。
在一个具体实施方式中，所述合成气包括氢气和一氧化碳。
在一个优选的具体实施方式中，在所述合成气中，氢气与一氧化碳的摩尔比为1:9至9:1。
在一个更优选的具体实施方式中，在所述合成气中，氢气与一氧化碳的摩尔比为1:3至3:1。
在一个具体实施方式中，所述反应条件为：反应温度300℃至450℃，反应压力0.5MPa至10.0MPa，合成气标准状态下体积空速2000h-1至20000h-1。
在一个优选的具体实施方式中，所述反应条件为：反应温度380℃至420℃，反应压力3MPa至5MPa，合成气标准状态下体积空速4000h-1至8000h-1。
本发明中，芳烃是指分子中含有苯环结构的碳氢化合物。
优选地，本发明中，芳烃选自苯、甲苯、乙苯、甲乙苯、二甲苯、三甲苯、苯乙烯中的至少一种。
在一个具体实施方式中，所述芳烃选自苯、甲苯、二甲苯中的一种。
在一个优选的具体实施方式中，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。
在本发明中，“粉末”、“颗粒”和“粉状颗粒”的概念可以互换。
在本发明中，常温是指20℃至30℃的温度范围。
本发明能产生的有益效果包括：
1)本发明的催化剂对芳烃，尤其是BTX选择性较高，性能稳定，且单程寿命长。
2)本发明的催化剂特别适用于芳烃的一步合成，从而降低了分步合成带来的大量的能耗的问题。
3)本发明所提供的方法与现有技术相比，失活的催化剂经过多次重生后性能无明显下降。
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均通过商业途径购买。
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，转化率和选择性均基于碳摩尔数进行计算：
一氧化碳转化率＝[(进料中的一氧化碳碳摩尔数)－(出料中的一氧化碳碳摩尔数)]÷(进料中的一氧化碳碳摩尔数)×100％
芳烃选择性＝(出料中的芳烃碳摩尔数)÷(出料中的所有烃类产物的碳摩尔数)×100％
BTX选择性＝(出料中的BTX碳摩尔数)÷(出料中的所有烃类产物碳摩尔数)×100％
下面通过实施例详述本发明，但本发明并不局限于这些实施例。
催化剂制备
实施例1
将Si/Al＝19(原子比)的钠型ZSM-5(南开大学催化剂厂)用0.8mol/L的硝酸铵水溶液在80℃交换3次得到铵型ZSM-5分子筛，在空气气氛下550℃煅烧4h，压片、破碎后筛分得到0.25mm-0.50mm尺度的酸性ZSM-5分子筛颗粒。
配制含0.25mol/L Zn2+与0.50mol/L Al3+混合硝酸盐水溶液1L，将0.5mol/L的碳酸钠溶液缓慢加入其中，控制共沉淀反应温度为70℃，pH值约为7.0，使金属离子共沉淀，并在此温度下老化2h，过滤、洗涤后干燥，500℃煅烧2h，压片、破碎后筛分得到0.25mm-0.50mm尺度的锌铝复合氧化物(ZnAlOx)颗粒。
取上述酸性ZSM-5分子筛颗粒4g与上述ZnAlOx颗粒1g均匀混合，制备成催化剂A。
实施例2
将Si/Al＝19(原子比)的钠型ZSM-5(南开大学催化剂厂)用0.8mol/L的硝酸铵水溶液在80℃交换3次得到铵型ZSM-5分子筛，在空气气氛下550℃煅烧4h，压片、破碎后筛分得到0.25mm-0.50mm尺度的酸性ZSM-5分子筛颗粒。
配制含0.25mol/L Zn2+和0.50mol/L Al3+混合硝酸盐水溶液1L，将0.5mol/L的碳酸铵溶液缓慢加入其中，控制共沉淀反应温度为70℃，pH值约为7.0，使金属离子共沉淀，并在此温度下老化2h，过滤、洗涤后干燥，500℃煅烧2h，得到锌铝复合氧化物粉末。利用Cr2+浓度为0.25mol/L的Cr(NO3)3溶液常温浸渍此锌铝复合氧化物粉末24h，干燥，500℃煅烧2h，得到含5％铬改性的锌铝复合氧化物(5％Cr-ZnAlOx)粉末。将5％Cr-ZnAlOx粉末压片、破碎后筛分得到0.25mm-0.50mm尺度颗粒。
取上述酸性ZSM-5分子筛颗粒4g与上述5％Cr-ZnAlOx颗粒1g均匀混合，制备成催化剂B。
实施例3
将Si/Al＝19(原子比)的钠型ZSM-5(南开大学催化剂厂)用0.8mol/L的硝酸铵水溶液在80℃交换3次得到铵型ZSM-5分子筛，在空气气氛下550℃煅烧4h，压片、破碎后筛分得到0.25mm-0.50mm尺度的酸性ZSM-5分子筛颗粒。
配制含0.1mol/L Zn2+和2.0mol/L Al3+混合硝酸盐水溶液1L，将0.5mol/L的碳酸钠溶液缓慢加入其中，控制共沉淀反应温度为70℃，pH值约为7.0，使金属离子共沉淀，并在此温度下老化2h，过滤、洗涤后干燥，500℃煅烧2h，得到锌铝复合氧化物粉末。利用Cu2+浓度为0.4mol/L Cu(NO3)2溶液常温浸渍此锌铝复合氧化物粉末24h，干燥，500℃煅烧2h，得到含7％铜改性的锌铝复合氧化物(7％Cu-ZnAlOx)粉末。将7％Cu-ZnAlOx粉末压片、破碎后筛分得到0.25mm-0.50mm尺度颗粒。
取上述酸性ZSM-5分子筛颗粒4g与上述7％Cu-ZnAlOx颗粒1g均匀混合，制备成催化剂C。
实施例4
将Si/Al＝19(原子比)的钠型ZSM-5(南开大学催化剂厂)用0.8mol/L的硝酸铵水溶液在80℃交换3次得到铵型ZSM-5分子筛，在空气气氛下550℃煅烧4h，压片、破碎后筛分得到0.25mm-0.50mm尺度的酸性ZSM-5分子筛颗粒。
配制含2.0mol/L Zn2+和0.1mol/L Al3+混合硝酸盐水溶液1L，将0.5mol/L的碳酸钠溶液缓慢加入其中，控制共沉淀反应温度为70℃，pH值约为7.0，使金属离子共沉淀，并在此温度下老化2h，过滤、洗涤后干燥，500℃煅烧2h，得到锌铝复合氧化物粉末。利用Cr2+浓度为0.1mol/L的Cr(NO3)3与Zr4+浓度为0.2mol/L的Zr(NO3)4混合溶液常温浸渍此锌铝复合氧化物粉末24h，干燥，500℃煅烧2h，得到含2％铬和4％锆改性的锌铝复合氧化物(2％Cr-4％Zr-ZnAlOx)粉末。将2％Cr-4％Zr-ZnAlOx粉末压片、破碎后筛分得到0.25mm-0.50mm尺度颗粒。
取上述酸性ZSM-5分子筛颗粒4g与上述3％Cr-4％Zr-ZnAlOx颗粒1g均匀混合，制备成催化剂D。
实施例5
将Si/Al＝19(原子比)的钠型ZSM-5(南开大学催化剂厂)用0.8mol/L的硝酸铵水溶液在80℃交换3次得到铵型ZSM-5分子筛，在空气气氛下550℃煅烧4h，压片、破碎后筛分得到0.25mm-0.50mm尺度的酸性ZSM-5分子筛颗粒。
配制含0.1mol/L Zn2+和0.50mol/L Al3+混合硝酸盐水溶液1L，将0.5mol/L的碳酸钠溶液缓慢加入其中，控制共沉淀反应温度为70℃，pH值约为7.0，使金属离子共沉淀，并在此温度下老化2h，过滤、洗涤后干燥，500℃煅烧2h，得到锌铝复合氧化物粉末。利用Pd2+浓度为0.1mol/L的Pd(NO3)3与Zr4+浓度为0.2mol/L的Zr(NO3)4混合溶液常温浸渍此锌铝复合氧化物粉末24h，干燥，500℃煅烧2h，得到含3％钯和4％锆改性的锌铝复合氧化物(3％Pd-4％Zr-ZnAlOx)粉末。将3％Pd-4％Zr-ZnAlOx粉末压片、破碎后筛分得到0.25mm-0.50mm尺度颗粒。
取上述酸性ZSM-5分子筛颗粒4g与上述3％Pd-4％Zr-ZnAlOx颗粒1g均匀混合，制备成催化剂E。
实施例6
将Si/Al＝19(原子比)的钠型ZSM-5(南开大学催化剂厂)用0.8mol/L的硝酸铵水溶液在80℃交换3次得到铵型ZSM-5分子筛，在空气气氛下550℃煅烧4h，得到酸性ZSM-5分子筛粉末，粉末尺寸小于0.1mm。
配制含0.25mol/L Zn2+与0.50mol/L Al3+混合硝酸盐水溶液1L，将0.5mol/L的碳酸钠溶液缓慢加入其中，控制共沉淀反应温度为70℃，pH值约为7.0，使金属离子共沉淀，并在此温度下老化2h，过滤、洗涤后干燥，500℃煅烧2h，得到锌铝复合氧化物(ZnAlOx)粉末，粉末尺寸小于0.1mm。
取上述酸性ZSM-5分子筛煅烧后的粉末1g与上述ZnAlOx粉末4g均匀混合，压片、破碎后筛分得到0.25～0.50mm尺度催化剂F。
实施例7
将Si/Al＝35(原子比)的钠型ZSM-5(奥科公司)用0.8mol/L的硝酸铵水溶液在80℃交换3次得到铵型ZSM-5分子筛，在空气气氛下550℃煅烧4h，压片、破碎后筛分得到0.25～0.50mm尺度的酸性ZSM-5分子筛颗粒。
配制含0.25mol/L Zn2+与0.50mol/L Al3+混合硝酸盐水溶液1L，将0.5mol/L的碳酸钠溶液缓慢加入其中，控制共沉淀反应温度为70℃，pH值约为7.0，使金属离子共沉淀，并在此温度下老化2h，过滤、洗涤后干燥，500℃煅烧2h，压片、破碎后筛分得到0.25mm-0.50mm尺度的锌铝复合氧化物(ZnAlOx)颗粒。
取上述酸性ZSM-5分子筛颗粒2.5g与上述ZnAlOx颗粒2.5g均匀混合，制备成催化剂G。
实施例8
将Si/Al＝40(原子比)的钠型ZSM-5(复旭公司)用0.8mol/L的硝酸铵水溶液在80℃交换3次得到铵型ZSM-5分子筛，在空气气氛下550℃煅烧4h，压片、破碎后筛分得到0.25～0.50mm尺度的酸性ZSM-5分子筛颗粒。
配制含0.25mol/L Zn2+与0.50mol/L Al3+混合硝酸盐水溶液1L，将0.5mol/L的碳酸钠溶液缓慢加入其中，控制共沉淀反应温度为70℃，pH值约为7.0，使金属离子共沉淀，并在此温度下老化2h，过滤、洗涤后干燥，500℃煅烧2h，压片、破碎后筛分得到0.25mm-0.50mm尺度的锌铝复合氧化物(ZnAlOx)颗粒。
取上述酸性ZSM-5分子筛颗粒4g与上述ZnAlOx颗粒1g均匀混合，制备成催化剂H。
实施例9
取实施例1中制备的酸性ZSM-5分子筛颗粒1g与实施例1中制备的ZnAlOx颗粒19g均匀混合，制备成催化剂I。
实施例10
取实施例1中制备的酸性ZSM-5分子筛颗粒19g与实施例1中制备的ZnAlOx颗粒1g均匀混合，制备成催化剂J。
实施例11
将实施例1中的酸性ZSM-5分子筛颗粒的粒径制为4.5mm-5mm，将实施例1中的ZnAlOx颗粒的粒径制为4.5mm-5mm。其他同实施例1。制备成催化剂K。
实施例12
将实施例1中的酸性ZSM-5分子筛颗粒的粒径制为0.8mm-1mm，将实施例1中的ZnAlOx颗粒的粒径制为0.8mm-1mm。其他同实施例1。制备成催化剂L。
实施例13
将实施例1中的酸性ZSM-5分子筛颗粒的粒径制为0.1mm-0.2mm，将实施例1中的ZnAlOx颗粒的粒径制为0.1mm-0.2mm。其他同实施例1。制备成催化剂M。
催化剂性能测试
实施例14
将催化剂A 5g装入内径为8mm的不锈钢反应管内，用50ml/min氢气在300在℃下活化4h，以下条件下反应：反应温度(T)＝400℃，反应压力(P)＝4.0MPa，标准状况下体积空速(GHSV)＝5000h-1，合成气(CO与H2混合气)中氢气的体积分数V(H2)％＝50％。反应500h后，用气相色谱分析产物，反应结果见表1。
实施例15-26
反应条件和反应结果见表1。其他操作同实施例14。
表1实施例14-26中的催化反应结果
Figure PCTCN2017098509-appb-000001
催化剂重生性能测试
实施例27
将实施例14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 14的条件下反应。按照同样的方式重生五轮，选取每轮反应500h后的催化活性数据进行比较，结果见表2。
表2实施例27中的催化反应结果
Figure PCTCN2017098509-appb-000002
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，均属于技术方案范围内。

Claims (10)

  1. 一种催化剂，其特征在于，所述催化剂包括酸性分子筛颗粒和锌铝复合氧化物颗粒。
  2. 根据权利要求1所述的催化剂，其特征在于，所述锌铝复合氧化物颗粒中还包括其他金属元素；
    优选所述其他金属元素为除去锌、铝和放射性元素的其他金属元素；
    更优选所述其他金属元素包括锆、铜、铂、钯和铬中的至少一种。
  3. 根据权利要求1或2所述的催化剂，其特征在于，所述酸性分子筛颗粒与所述锌铝复合氧化物颗粒的质量比为1:19至19:1；
    优选所述酸性分子筛颗粒与所述锌铝复合氧化物颗粒的质量比为4:1至1:4；
    最优选所述酸性分子筛颗粒与所述锌铝复合氧化物颗粒的质量比为2:1至1:2。
  4. 根据权利要求1至3中任意一项所述的催化剂，其特征在于，所述酸性分子筛颗粒和锌铝复合氧化物颗粒的粒径各自独立地小于或等于5mm；
    优选所述酸性分子筛颗粒和锌铝复合氧化物颗粒的粒径各自独立地小于或等于1mm，且大于或等于0.1mm。
  5. 根据权利要求1至4中任意一项所述的催化剂，其特征在于，所述酸性分子筛为具有尺度大于或等于十元环的孔道结构的酸性分子筛。
  6. 根据权利要求1至5中任意一项所述的催化剂，其特征在于，所述酸性分子筛包括具有MFI、BEA、FAU、EMT、MOR、FER和MWW中的至少一种结构的酸性分子筛；
    优选所述酸性分子筛为具有MFI结构的酸性分子筛；
    更优选所述酸性分子筛为酸性ZSM-5分子筛；
    最优选所述酸性分子筛为未经过金属元素改性的酸性ZSM-5分子筛。
  7. 一种制备根据权利要求1至6中任意一项所述的催化剂的方法，其特征在于，包括如下步骤：
    1)将含锌元素和铝元素的盐配成水溶液，然后利用沉淀剂的水溶液将所述含锌元素和铝元素的盐中的金属离子共沉淀，老化，再将沉淀物洗涤、干燥后煅烧制得所述锌铝复合氧化物颗粒；
    2)将所述锌铝复合氧化物颗粒与所述酸性分子筛颗粒混合均匀；
    优选所述沉淀剂包括碳酸钠、碳酸钾、碳酸铵、碳酸氢钠、碳酸氢钾、碳酸氢铵、氨水、氢氧化钠和氢氧化钾中的至少一种。
  8. 一种制备芳烃的方法，其特征在于，将含有合成气的原料通过载有根据权利要求1至6中任意一项所述的催化剂的反应器，在反应条件下制备所述芳烃。
  9. 根据权利要求8所述的方法，其特征在于，
    所述合成气包括氢气和一氧化碳；
    优选在所述合成气中，氢气与一氧化碳的摩尔比为1:9至9:1；
    更优选在所述合成气中，氢气与一氧化碳的摩尔比为1:3至3:1；
    所述反应条件为：反应温度300℃至450℃，反应压力0.5MPa至10.0MPa，合成气标准状态下体积空速2000h-1至20000h-1；
    优选所述反应条件为：反应温度380℃至420℃，反应压力3MPa至5MPa，合成气标准状态下体积空速4000h-1至8000h-1。
  10. 根据权利要求7或8所述的方法，其特征在于，所述芳烃选自苯、甲苯、乙苯、甲乙苯、二甲苯、三甲苯、苯乙烯中的至少一种；优选所述芳烃选自苯、甲苯、二甲苯中的至少一种。
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