Method for circularly and rapidly pre-vulcanizing sulfur tolerant shift catalyst and carrying out segmental pre-vulcanizing by utilizing sulfur tolerant shift catalyst

A technology of catalyst circulation and sulfur-resistant conversion, which is applied in the direction of catalyst activation/preparation, chemical instruments and methods, and physical/chemical process catalysts. Prolongation and other issues, to achieve the effect of reducing the time required for vulcanization and temperature rise, significant economic and social benefits, and less venting

Active Publication Date: 2014-03-26
CHINA PETROLEUM & CHEM CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This vulcanization method not only greatly prolongs the time required, but also the activity of the catalyst after vulcanization is far below the expected requirements, and the activity declines quickly, so that the due economic benefits cannot be achieved. Therefore, the natural vulcanization method is not advisable.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] A 450 ktNH 3 / a's unit A, after the renovation of the unit in 2011, after replacing the sulfur-tolerant shift catalyst, all of them are cobalt-molybdenum-based sulfur-tolerant shift catalysts with a loading capacity of 188m 3 . Carry out circulation fast presulfurization according to the method of the present invention, according to the volume ratio of hydrogen: nitrogen = 1:6, hydrogen is added in the nitrogen and enters vulcanization furnace together with nitrogen to heat, when the conversion catalyst bed temperature reaches 210~215, constant temperature 4h After that, the catalyst sulfidation work is carried out. The circulation capacity of the vulcanization system is 36,000 m 3 / h, the air velocity of the circulating air is kept at 570~630h -1 , the system pressure is 1.0MPa, the vulcanizing agent is slowly added in a small amount and several times, and the hydrogen sulfide concentration at the entrance of the vulcanization furnace is maintained at 25~30g / m 3 Be...

Embodiment 2

[0048] A certain 300 ktNH 3 Unit B of / a, after replacing the sulfur-tolerant shift catalyst in 2011, was fully filled with cobalt-molybdenum-based sulfur-tolerant shift catalyst, with a total loading capacity of 93m 3 . According to the method of the present invention, carry out circulation fast pre-sulfurization, according to the volume ratio of hydrogen: nitrogen = 1:19, hydrogen is added into the nitrogen and enters the vulcanization furnace together with the nitrogen for heating. After 2h, the catalyst vulcanization work is carried out. The circulation volume of the system is 36,000 m 3 / h, the air velocity of the circulating air is kept at 400~500h -1 , the system pressure is 1.2MPa, the vulcanizing agent is slowly added in a small amount and many times, and the hydrogen sulfide concentration at the entrance of the vulcanizing furnace is maintained at 30~40g / m 3 Between, the temperature rises to 280~300℃, and the heating rate is 80~100℃ / h.

[0049] When the hydrogen...

Embodiment 3

[0051] A certain 450ktNH 3 / a unit C, after replacing the sulfur-tolerant shift catalyst at the beginning of 2012, it was fully filled with cobalt-molybdenum-based sulfur-tolerant shift catalyst, with a total loading capacity of 165m 3 . Carry out vulcanization according to the inventive method, according to the volume ratio of hydrogen: nitrogen=1:9, hydrogen is added in the nitrogen and enters vulcanization furnace together with nitrogen and is heated, when conversion catalyst bed temperature reaches 200~205 ℃, after constant temperature 6h, Perform catalyst sulfidation work. The circulation volume of the system is 50,000 m 3 / h, the air velocity of the circulating air is kept at 1300~1500h -1 , the system pressure is 0.2MPa, the vulcanizing agent is slowly added in a small amount and several times, and the hydrogen sulfide concentration at the entrance of the vulcanization furnace is maintained at 20~30g / m 3 Between, the temperature rises to 220~230℃, and the heating ra...

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PUM

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Abstract

The invention relates to a segmental pre-vulcanizing method of a sulfur tolerant shift catalyst in a multi-segment conversion process, particularly relates to a method for rapidly pre-vulcanizing cobalt-molybdenum-series sulfur tolerant shift catalysts and belongs to the technical field of pretreatment of the sulfur tolerant shift catalyst. According to the method, aiming at the situations of the temperature raising and the slow vulcanizing speed caused due to insufficient vulcanizing conditions, a segmental vulcanizing method is utilized, namely the rapid pre-vulcanizing of a first-segment furnace is reinforced to raise the temperature of a subsequent second-segment furnace; first-segment vulcanizing conditions are reinforced to guarantee the vulcanization of the catalyst so as to realize the rapid, efficient and complete vulcanization, meanwhile, the temperature of a subsequent second-segment bed is raised by high-temperature vulcanized gas in a rapid vulcanizing process, and the subsequent working segments are similarly processed, so that the vulcanizing and temperature raising time is greatly shortened, and the vulcanizing cost is lowered; by utilizing a circular vulcanizing manner, the emptying quantity is few, the overtemperature is avoided, the vulcanizing process is convenient and safe, the pollution is light, and the method has remarkable economic and social benefits.

Description

technical field [0001] The invention relates to a cycle rapid presulfurization of a sulfur-tolerant shift catalyst and a method for segmented presulfurization thereof, which belongs to the technical field of sulfur-tolerant shift catalyst pretreatment, and specifically relates to a method for rapid presulfurization of a cobalt-molybdenum-based sulfur-tolerant shift catalyst. Background technique [0002] Most of the sulfur-tolerant shift catalysts use Co-Mo metal elements as active components, which are dispersed in Al in an oxidized state. 2 o 3 、Al 2 o 3 +Re 2 o 3 (Re stands for rare earth elements) and other porous carriers, it has the characteristics of wide temperature range, high conversion activity, and no sulfur poisoning problem. However, the new catalyst must be vulcanized into a vulcanized state before it is used to be active. The quality of the vulcanization process directly affects the conversion activity and stability of the catalyst, and directly affects ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J37/20
Inventor 白志敏余汉涛齐焕东赵庆鲁王敏田兆明陈依屏王昊姜建波郭建学李文柱郭杰
Owner CHINA PETROLEUM & CHEM CORP
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