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A kind of hydrogen type zsm-5/eu-1 eutectic zeolite, aromatic hydrocarbon isomerization catalyst and preparation method and application
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A technology of ZSM-5 and aromatics isomerization, which is applied in the direction of physical/chemical process catalysts, molecular sieve catalysts, chemical instruments and methods, etc., can solve the problem of liquid yield drop, unsuitable treatment of C8 aromatics isomerization process, reduction of benzene purity, etc. question
Active Publication Date: 2022-06-03
PETROCHINA CO LTD
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Problems solved by technology
This technology is not suitable for the isomerization process of C8 aromatics, otherwise it will cause a large amount of cracking of C8 aromatics raw materials, resulting in a decrease in liquid yield and no economic benefits
Using ZSM-5, EU-1 zeolite as the acid component, the C8 arene isomerization catalyst with Group VIII noble metal as the metal component has been applied industrially, showing good catalytic performance, but there are still acidic active centers and metal activity. center mismatch problem
In the ethylbenzene dealkylation type C8 aromatics isomerization catalyst, even if the Group VIII noble metal content is controlled below 0.05%, there will be a problem of high non-aromatic hydrocarbon content that azeotropes with benzene, reducing the azeotropic concentration of benzene at a low boiling point. Purity in Boilers Affects Yield and Energy Consumption in Aromatics Complexes
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Embodiment 1
[0068] The EU-1 zeolite is added to the NaOH solution, and after stirring uniformly, tetraethylammonium hydroxide, silica sol, silica and water are added, and the stirring is uniform. The solution was transferred to a stainless steel kettle, crystallized at 200°C for 30 hours, taken out, cooled to room temperature, washed with water until neutral, and dried at 100°C after suction filtration to obtain different SiO 2 / Al 2 O 3 The ZSM-5 / EU-1 eutectic zeolite.
Embodiment 2
[0070] The EU-1 zeolite was added to the NaOH solution, and after stirring uniformly, tetraethylammonium bromide, tetrapropylammonium bromide, silica sol and water were added, and the mixture was uniformly stirred. The solution was transferred to a stainless steel kettle, crystallized at 160°C for 36 hours, taken out, cooled to room temperature, washed with water until neutral, and dried at 100°C after suction filtration to obtain different SiO 2 / Al 2 O 3 The ZSM-5 / EU-1 eutectic zeolite.
[0071] Preparation of catalyst
Embodiment 3
[0073] Contains 70.0w% ZSM-5 / EU-1 eutectic zeolite (SiO 2 / Al 2 O 3 =100), 3.0w% Re, 27.0w% alumina, catalyst C3.
[0074] The SiO synthesized in Example 1 was 2 / Al 2 O 3 ZSM-5 / EU-1 eutectic zeolite of 100, fully mix with pseudo-boehmite powder, add 3.0w% nitric acid solution and mix well, use cylindrical orifice plate to extrude strip; cylindrical strip at room temperature After standing for 4 hours, it was dried at 120 °C for 2 hours, and calcined at 500 °C in air for 4 hours to prepare a catalyst carrier; -1 The obtained ammonium chloride solution was exchanged at 60-90 °C for 2 hours, washed with deionized water, and filtered; the obtained post-exchange support was immersed in a solution containing ammonium perrhenate at room temperature for 12 hours, and then dried at 120 °C 2 hours, calcination at 500°C for 4 hours, and reduction in hydrogen at 500°C for 4 hours to obtain catalyst C3.
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Abstract
The present invention relates to a hydrogen-type ZSM-5 / EU-1 eutectic zeolite, and an aromatic hydrocarbon isomerization catalyst containing the eutectic zeolite, a preparation method and application thereof. The ZSM-5 / EU-1 eutectic zeolite adopts the following method Preparation: Step 1): Add a certain amount of EU‑1 zeolite into the NaOH solution, stir evenly, add template agent, silicon source and water, and stir evenly; Step 2): Transfer the solution to a stainless steel kettle, in 100-300 After crystallization at ℃ for 12-36 hours, take it out, cool to room temperature, wash with water until neutral, filter with suction and dry to obtain ZSM-5 / EU-1 eutectic zeolite. The arene isomerization catalyst comprises, by weight: 10.0-80.0w% hydrogen ZSM-5 / EU-1 eutectic zeolite, 15.0-90.0w% binder, 0.1-5.0w% element VIIB of the periodic table group metal rhenium. The catalyst can be applied to the catalytic reaction process of ethylbenzene dealkylation type C8 aromatic hydrocarbon isomerization, and can effectively reduce the hydrogenation side reaction after ethylbenzene dealkylation.
Description
technical field [0001] The invention relates to a hydrogen-type ZSM-5 / EU-1 eutectic zeolite and an aromatic hydrocarbon isomerization catalyst containing the eutectic zeolite. The aromatics isomerization catalyst can be applied to the xylene isomerization unit of the aromatics complex, and isomerizes the raffinate oil after separating the target product p-xylene (or o-xylene) into a product that is close to thermodynamic equilibrium of xylene, At the same time, part of the ethylbenzene in the raw material is converted into benzene, which belongs to the technical field of catalysts. Background technique [0002] Since the boiling point of ethylbenzene is only 2.2°C lower than that of PX, it is very difficult and uneconomical to separate ethylbenzene from xylene by means of rectification, so ethylbenzene must be converted in the process of xylene isomerization. According to the different ways of ethylbenzene conversion, the industrial C8 aromatic isomerization technology can ...
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