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A molecular sieve and modification technology, which is applied in the direction of molecular sieve catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of large crystallinity drop and achieve high crystallinity and good practicability
Inactive Publication Date: 2014-10-15
PETROCHINA CO LTD
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Problems solved by technology
HCl, HNO 3 and H 2 SO 4 Dealumination is simply relying on H + Dealumination, so the crystallinity drops greatly, and the acid concentration and modification time must be strictly controlled
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Embodiment 1
[0022] This example investigates the influence of citric acid concentration on the effect of industrial USY modification.
[0023] (1) Prepare citric acid solutions with different concentrations (0.10mol / L, 0.15mol / L, 0.20mol / L and 0.25mol / L);
[0024] (2) Weigh 4 parts of industrial USY, 12g each, and put them into 250ml three-necked flasks respectively;
[0025] (3) Add 60ml of citric acid solution with different concentrations in turn, stir, and heat up to 70°C;
[0026] (4) When the temperature rises to 70°C, continuously add 60ml of 0.10mol / L ammonium fluorosilicate solution at a rate of 1ml / min;
[0027] (5) After the feeding is completed, continue to react for 3 hours;
[0028] (6) The obtained product was washed with deionized water until neutral, and dried at a constant temperature of 110°C for 16 hours to obtain modified samples, which were labeled as F-2, F-3, F-1, and F-4.
Embodiment 2
[0030] This example investigates the effect of ammonium fluorosilicate feeding rate on the modification of industrial USY molecular sieves. The modification method is the same as in Example 1, except that the fixed citric acid concentration is 0.15mol / L, and the feed rate of ammonium fluorosilicate is changed to 0.75ml / min, 1ml / min, 1.25ml / min and 1.5ml / min respectively, The obtained modified samples are marked as F-8, F-3, F-9, and F-10.
Embodiment 3
[0032] This example investigates the effect of reaction time on the modification effect of industrial USY molecular sieves. The modification method is the same as in Example 2, except that the feeding rate of ammonium fluorosilicate is fixed at 1ml / min, and the reaction time is changed to 2h, 3h, 4h and 5h respectively, and the modified samples obtained are marked as F-11, F- 3, F-12 and F-13.
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Abstract
The invention relates to a USY molecular sieve modification method. The USY molecular sieve modification method comprises the following steps of adding a citric acid solution having a concentration of 0.10-0.35mol/L into a USY molecular sieve according to a solid-liquid quality ratio of 1: 5 for modification with stirring at a reaction temperature of 500-1200 DEG C, after a temperature is increased to a preset temperature of 600-900 DEG C, adding an ammonium fluosilicate solution having a concentration of 0.05-0.20mol/L into the reaction product at a rate of 0.1-3.5ml/min according to a volume ratio of citric acid to the ammonium fluosilicate solution of 0.5-3.0, after material addition, carrying out a reaction process at a temperature of 50-120 DEG C for 1-6h, carrying out washing by deionized water until a pH value is 7, and carrying out constant-temperature drying at a temperature of 110 DEG C. The USY molecular sieve obtained by the USY molecular sieve modification method has substantially improved specific surface, secondary pore volume and moderate strong acid level and can be used for a hydrocracking catalyst for maximizing middle distillates as desired products.
Description
technical field [0001] The present invention relates to a kind of USY molecular sieve modification method used as hydrocracking catalyst, Background technique [0002] Hydrocracking technology is one of the important secondary processing methods for heavy oil lightening. Due to its wide range of processing raw materials, many types of products with good quality, high production flexibility and high yield of liquid products, it is widely used in refineries and play an important role in the production of clean fuels. At the same time, the worldwide demand for middle distillate oil continues to grow, and the requirements for oil product quality also continue to increase. The pressure on refineries to produce high-quality middle distillate oil products is increasing. Therefore, the medium-oil hydrocracking process capable of producing high-quality clean fuels has been more and more widely used, and the medium-oil hydrocracking catalyst is the core and key of this technology. ...
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