Molecular sieve based catalyst and preparation and application thereof
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A molecular sieve and catalyst technology, which is applied in the field of aromatics preparation, can solve the problems of large investment in fluidized beds, catalyst wear, and increased product cost, and achieve the effects of prolonging life, improving stability, and increasing activity.
Inactive Publication Date: 2013-10-30
SHANGHAI ADVANCED RES INST CHINESE ACADEMY OF SCI
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Problems solved by technology
Adopt fluidized bed reactor and modified HZSM-5 molecular sieve catalyst (Chinese invention patent application, publication number CN 101244969, open date on March 25th, 2008), although can improve the selectivity of aromatics and the space-time yield, but fluidization Large bed investment and serious catalyst wear will increase product cost
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Embodiment 1
[0026] 1. Preparation of HZn-ZSM-5 molecular sieve catalyst
[0027] 1) Using zinc nitrate as raw material, Zn-ZSM-5 molecular sieve was prepared by in situ synthesis method to control SiO 2 / Al 2 o 3 (Molar ratio) = 100, SiO 2 / Zn (molar ratio) = 200.
[0028] 2) with silica sol (SiO 2 ·nH 2 O) is a binder, and its content is controlled to account for 10% of the mass of the catalyst, and the Zn-ZSM-5 molecular sieve is extruded and roasted to obtain a strip-shaped Zn-ZSM-5 molecular sieve.
[0029] 3) Treat the strip Zn-ZSM-5 molecular sieve with 0.1M NaOH solution, that is, stir for 1 hour at 80°C and the mass ratio of NaOH solution to Zn-ZSM-5 molecular sieve is 30, and then dry it at 120°C .
[0030] 4) Using 0.5 mol / L ammonium chloride solution, at 90° C., under the condition that the mass ratio of the solution to the molecular sieve solid is 10:1, ion-exchange the Zn-ZSM-5 molecular sieve three times, each time for 2 hours.
[0031] 5) Washing, drying, and then cal...
Embodiment 2～4
[0035] SiO 2 / ZnO (molar ratio) is controlled to be 150,100,50 respectively, all the other steps are with embodiment 1. The prepared HZn-ZSM-5 molecular sieve catalyst was used as an MTA catalyst, and the MTA reaction was carried out under the same conditions as in Example 1. The product distribution is shown in Table 1.
Embodiment 5
[0037] 1. Preparation of HAg-ZSM-5 molecular sieve catalyst
[0038] Using silver nitrate as raw material, Ag-ZSM-5 molecular sieves were prepared by in situ synthesis to control SiO 2 / Al 2 o 3 (molar ratio)=100 and SiO2 / Ag (molar ratio)=200. All the other steps are the same as in Example 1.
[0039] 2. MTA reaction
[0040] The prepared HAg-ZSM-5 molecular sieve catalyst was used as the MTA catalyst, and the MTA reaction was carried out under the same conditions as in Example 1. The product distribution is shown in Table 1.
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Abstract
The invention discloses a molecular sieve based catalyst, which mainly comprises a Zn, Ag, Ga and La modified HZSM-5 molecular sieve and a binder, wherein the binder accounts for 5-50% of the total mass of the catalyst; the molar ratio of SiO2 to Al2O3 in the molecular sieve is 10-1000, and the molar ratio of SiO2 to metals is over 20. The invention also discloses preparation methods of the catalyst and the application of the catalyst in MTA (methanol to aromatics) reactions. The preparation method 1 comprises the following steps of: firstly carrying out extrusion moulding on the skeleton metal containing ZSM-5 molecular sieve; then treating by using alkali liquor; and finally carrying out ion exchange and high-temperature roasting to obtain the target product. The preparation method 2 comprises the following steps of: firstly carrying out extrusion moulding on the ZSM-5 molecular sieve; then, treating by using alkali liquor; and finally carrying out ion exchange, auxiliary soaking and high-temperature roasting to obtain the target product. According to the invention, through controlling the conditions such as the silica-alumina ratio of the molecular sieve and alkali treatment, the service life of the ZSM-5 molecular sieve on a fixed bed reactor is prolonged, and the activity of the catalyst and the selectivity of MTA reaction are improved.
Description
technical field [0001] The invention relates to the preparation of aromatic hydrocarbons, in particular to a modified HZSM-5 molecular sieve catalyst and the application of the molecular sieve catalyst in the reaction of preparing aromatic hydrocarbons from methanol. Background technique [0002] Aromatics are an important class of organic chemical raw materials, and their derivatives are widely used in the production of chemical products and fine chemicals such as chemical fibers, plastics and rubber. With the continuous development of petrochemical and textile industries, the demand for light aromatics is increasing all over the world. At present, the raw material for the production of aromatics is mainly petroleum. With the depletion of petroleum resources, it is imminent to find alternative routes. Among them, the preparation of aromatics from coal through methanol is a current research hotspot. my country has abundant coal reserves, and its downstream product, methanol...
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