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A start-up method of a catalyst containing molecular sieves for heavy-duty sulfides with low boiling points

A sulfide and catalyst technology, which is applied in the field of heavy catalyst containing molecular sieve low boiling point sulfide, can solve the problems of difficulty in ensuring the stability of catalyst activity and inability to use passivation, so as to avoid the loss of catalyst activity and improve stability , the effect of stable start

Active Publication Date: 2018-10-16
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] The passivation process in CN201110321354.2 and CN201210432673.5 is a reversible process, it is difficult to ensure the activity stability of the catalyst, and both use heavy oil products with an initial boiling point greater than 200 ° C as the passivation oil, so they cannot be used for final Passivation of lower gasoline fractions

Method used

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  • A start-up method of a catalyst containing molecular sieves for heavy-duty sulfides with low boiling points
  • A start-up method of a catalyst containing molecular sieves for heavy-duty sulfides with low boiling points
  • A start-up method of a catalyst containing molecular sieves for heavy-duty sulfides with low boiling points

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] The composite molecular sieve of 5kg aluminum oxide powder, 0.84kg ZSM-5 and SAPO-11 (the weight percentage of ZSM-5 in the composite molecular sieve is 45%) and 0.3kg of turnip powder were kneaded for 5min, and 0.2kg of phosphoric acid was dissolved in 4L water, added to the mixed powder, kneaded and extruded into rods, dried in the air at 100°C, and calcined at 600°C for 5 hours to obtain an Al2O3 carrier containing molecular sieves.

[0026] Dissolve 5.23kg of ammonium molybdate and 18.66kg of nickel acetate in 32L of ammonia water, stir until completely dissolved to form an impregnating solution, impregnate it on the carrier, dry it in the air at 120°C, bake at 420°C for 5 hours, and use 55% sulfur Catalyst A was obtained by impregnating the thioether compound for 4h.

[0027] Fill 500ml of the above catalyst A into a 500ml adiabatic bed hydrogenation reactor, contact with hydrogen and naphtha for 40 hours for activation treatment, the activation reaction temperatur...

Embodiment 2

[0034] Knead 270g of alumina powder, 15g of ZSM-5, 15g of β and 15g of turnip powder for 5 minutes, dissolve 15g of glacial acetic acid in 250ml of water, add it to the mixed powder, knead and extrude into strips, and dry in air at 120°C. Calcined at 540°C for 4 hours to obtain an Al2O3 carrier containing molecular sieves.

[0035] Dissolve 19.62g of ammonium molybdate and 79.96g of nickel acetate in 140ml of ammonia water, stir until completely dissolved to form an impregnating solution, impregnate it on the carrier, dry it in the air at 120°C, and bake it at 450°C for 4 hours, using 55% sulfur The thioether compound was impregnated for 4h to obtain catalyst B.

[0036] Fill 100ml of the above-mentioned catalyst B in a 100ml adiabatic bed hydrogenation reactor, contact with hydrogen and naphtha for 35 hours for activation treatment, the activation reaction temperature is 240°C, the reaction pressure is 2.4MPa, the volume space velocity is 2.0h-1, hydrogen oil The volume rati...

Embodiment 3

[0043] Knead the compound molecular sieve of 22.4kg aluminum oxide powder, 1.6kg ZSM-5 and SAPO-11 (the weight percentage of ZSM-5 in the compound molecular sieve is 60%) and 1.2kg kale powder for 5min, and dissolve 1.12kg glacial acetic acid In 16.8L of water, added to the mixed powder, kneaded and extruded into rods, dried in the air at 110°C, and calcined at 490°C for 6 hours to obtain an Al2O3 carrier containing molecular sieves.

[0044] Add 1.52kg ammonium molybdate and 0.36kg ammonium metatungstate to 1.44L ammonia water and stir until completely dissolved, then add 4.42kg basic nickel carbonate, stir until completely dissolved, then add 0.64kg cobalt nitrate, stir to completely dissolve Prepare impregnating liquid, impregnate on carrier, dry in air at 110°C, bake at 440°C for 6 hours, impregnate with sulfide compound containing 55% sulfur for 4h, and obtain catalyst C.

[0045] Fill 500ml of the above-mentioned catalyst C into a 500ml adiabatic bed hydrogenation reacto...

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Abstract

The invention relates to a starting method of a heavy catalyst containing molecular sieve low-boiling point sulfide. The starting method comprises the following steps of firstly, activating the loaded sulfided heavy catalyst containing low-boiling point sulfide in a reactor, and then passivating; lowering the inlet temperature of the reactor, using a mixture of low olefin light oil and catalytic cracking gasoline raw material as a passivator, and increasing temperature in an oscillating gradient way, so as to match the ratio of catalytic cracking gasoline in the passivated oil with the passivating temperature, and complete the passivating starting project. The starting method has the advantages that the catalytic cracking gasoline raw material which is diluted by the low olefin light oil is used as the passivator, the permanent passivating and reversible passivating are also realized in the passivating process, and the purposes of stable starting, and improving of activity and stability of catalyst are realized; the ratio of catalytic cracking gasoline raw material is gradually increased in the passivating process; when the passivating process is finished, the pitching-in of raw material oil is finished at the same time, so as to save a process of introducing raw material after the passivating is finished.

Description

technical field [0001] The invention relates to a start-up method of a heavy catalyst containing molecular sieve low boiling point sulfide, which mainly uses raw material oil with low olefin content as a passivator to passivate the sulfided catalyst after activation treatment by raising the temperature in a swinging step It is suitable for the start-up process of low-boiling sulfide heavy catalysts containing molecular sieves, especially for selective hydrogenation of catalytic cracked gasoline to remove diolefins, mercaptan thioetherification, Start-up process of thiophene alkylation catalyst. Background technique [0002] According to the distribution characteristics of sulfur, mercaptans and olefins in FCC gasoline, it can be divided into three components: (1) light fraction LCN with low sulfur and high olefin content; (2) middle fraction MCN with moderate sulfur and olefin content; 3) Heavy fraction HCN with high sulfur and low olefin content. According to the raw mate...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G45/12C10G45/38B01J29/85B01J29/80B01J33/00
Inventor 张忠东姚文君蔡进军王玲玲王廷海向永生高源李自夏
Owner PETROCHINA CO LTD
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