Passivation method of low boiling point sulfide heavy catalyst

A technology of sulfide and low boiling point, which is applied in the direction of physical/chemical process catalysts, catalyst protection, molecular sieve catalysts, etc. It can solve the problems of unusable passivation and difficulty in ensuring the stability of catalyst activity, so as to improve stability and avoid catalyst activity. Loss, the effect of stable operation

Active Publication Date: 2018-09-04
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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  • Passivation method of low boiling point sulfide heavy catalyst
  • Passivation method of low boiling point sulfide heavy catalyst
  • Passivation method of low boiling point sulfide heavy catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] 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.

[0025] Dissolve 19.62g of ammonium molybdate and 79.96g of nickel acetate in 140ml of ammonia water, stir to dissolve completely to form an impregnation solution, impregnate it on the carrier, dry it in the air at 120°C, and roast it at 450°C for 4 hours to obtain catalyst A.

[0026] Fill 100ml of the above-mentioned catalyst A into a 100ml adiabatic bed hydrogenation reactor. After the catalyst is vulcanized, lower the inlet temperature of the reactor to 100°C. The feed rate of 131g / h introduces catalytically cracked gasoline and catalytic reformed oil into the reaction system at the same time; the inlet temperature of the reactor is increased at a heati...

Embodiment 2

[0032] The composite molecular sieve of 250g aluminum oxide powder, 42g ZSM-5 and SAPO-11 (the weight percentage composition of ZSM-5 is 45% in the composite molecular sieve) and 15g turnip powder are kneaded 5min, 10g phosphoric acid is dissolved in 200ml water, add Put it into the mixed powder, knead it, extrude it, dry it in the air at 100°C, and bake it at 600°C for 5 hours to obtain an Al2O3 carrier containing molecular sieves.

[0033] Dissolve 26.16g of ammonium molybdate and 93.30g of nickel acetate in 160ml of ammonia water, stir to dissolve completely to form an impregnating solution, impregnate it on the carrier, dry it in air at 120°C, and roast at 420°C for 5 hours to obtain catalyst B.

[0034] Fill 100ml of the above-mentioned catalyst B into a 100ml adiabatic bed hydrogenation reactor. After the sulfidation of the catalyst is completed, reduce the inlet temperature of the reactor to 120°C. At a feed rate of 130g / h, FCC gasoline and naphtha were introduced into ...

Embodiment 3

[0040] The composite molecular sieve of 2800g aluminum oxide powder, 200g ZSM-5 and SAPO-11 (the weight percentage composition of ZSM-5 is 60% in the composite molecular sieve) and 150g squash powder kneading 5min, 140g glacial acetic acid is dissolved in 2100ml water, Add it into the mixed powder, knead it, extrude it, dry it in the air at 110°C, and bake it at 490°C for 6 hours to obtain an Al2O3 carrier containing molecular sieves.

[0041] Add 190g of ammonium molybdate and 45g of ammonium metatungstate into 180ml of ammonia water and stir until completely dissolved, then add 552g of basic nickel carbonate, stir until completely dissolved, then add 80g of cobalt nitrate, stir to completely dissolve to form an impregnation solution, Impregnated on the carrier, dried in air at 110°C, and calcined at 440°C for 6 hours to obtain catalyst C.

[0042] Fill 500ml of the above-mentioned catalyst C into a 500ml adiabatic bed hydrogenation reactor. After the catalyst is vulcanized, ...

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Abstract

The invention relates to a passivation method of a low-boiling-point sulfide heavy catalyst. After an oxidation-state low-boiling-point sulfide heavy catalyst filled in a reactor is sulfidized, the inlet temperature of the reactor is reduced, a mixture of low-olefin light oil and a catalytic gasoline raw material is taken as a passivant, the proportion of catalytic gasoline in passivation oil is matched with the passivation temperature by oscillating type ladder warming, and the passivation starting up process is completed. According to the passivation method of the low-boiling-point sulfide heavy catalyst, the low-olefin light oil diluted catalytic gasoline raw material is taken as the passivant, the passivation process has both permanent passivation and reversible passivation, and the purposes of stabilizing starting up and improving catalyst activity stability are realized. At the same time, the proportion of the catalytic gasoline raw material is improved gradually in the passivation process, cut-in of raw oil is completed the moment the passivation process is ended, and the raw material introducing process after the passivation process is omitted.

Description

technical field [0001] The invention relates to a passivation method for a low-boiling-point sulfide heavy-duty catalyst, which mainly uses raw material oil with low olefin content as a passivator to passivate the catalyst by swinging stepwise temperature rise to achieve the purpose of avoiding overheating It is suitable for the passivation process of low boiling sulfide heavy catalysts containing molecular sieves, especially for the passivation process of catalytic cracking gasoline selective hydrogenation to remove diolefins, mercaptan thioetherification, and thiophene alkylation catalysts. 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 materia...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J33/00B01J29/46B01J29/85B01J35/10
Inventor 常晓昕蔡进军姚文君王玲玲王廷海向永生高源李自夏
Owner PETROCHINA CO LTD
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