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A kind of recycling method of spent CO sulfur-tolerant shift catalyst

A waste catalyst, sulfur-resistant shift technology, applied in chemical instruments and methods, physical/chemical process catalysts, inorganic chemistry, etc., can solve the problems of very sensitive poison, narrow active temperature range, insufficient purity, etc., to save molybdenum resources, No secondary pollution and the effect of improving sulfur resistance

Active Publication Date: 2016-08-24
湖北双雄催化剂有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

More than 70 years ago, Fe-Cr series high-temperature shift catalyst was first used, and then Cu-Zn series low-temperature shift catalyst was developed. The disadvantage of being very sensitive to poisonous substances
By-product Al(OH) 3 The purity is not enough, the use value is not big
The by-product potassium nitrate needs to be concentrated, crystallized, washed, and dried. The whole process is long, the amount of acid and alkali used is large, and the energy consumption is also large.
And during the roasting process of the spent catalyst, SO will be produced 2 , NO, NO 2 Exhaust gas, serious environmental pollution

Method used

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  • A kind of recycling method of spent CO sulfur-tolerant shift catalyst

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Experimental program
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Effect test

Embodiment 1

[0019] A kind of spent CO sulfur-resistant shift catalyst, through X-ray fluorescence analysis, its composition is mass fraction (%): Co (calculated as CoO): 3.8%, Mo (calculated as MoO 3 Total): 11.5%, K 2 O: 1.5%, S (as SO 2 Total): 14.1%, Al 2 o 3 : 69.1%. This spent catalyst is crushed to 100 orders, gets the waste catalyst after 18kg pulverizes, and 200kgFe(OH) 3 (with Fe 2 o 3 Mass fraction ≥ 70%), 18kgCr(OH) 3 (in Cr 2 o 3 mass fraction ≥ 61%), milled together for 1-2 hours, passed through an 8-mesh screen to make particles, roasted at a low temperature of 250 ° C to 300 ° C for 6-8 hours, and then mixed with graphite and pressed into tablets to form a CO high-temperature shift catalyst. . According to the national chemical industry standard HG / T 3546-2011, the activity (calculated by the conversion rate of carbon monoxide): 61%; the average particle radial crush resistance: 365N / cm; the particle fraction below 160N / cm: 5% ; Wear rate: 3.2%; Loss on ignition ...

Embodiment 2

[0021] A kind of spent CO sulfur-resistant shift catalyst, through X-ray fluorescence analysis, its composition is mass fraction (%): Co (calculated as CoO): 2.6%, Mo (calculated as MoO 3 Total): 9.8%, K 2 O: 2.0%, S (as SO 2 Total): 11.7%, Al 2 o 3 : 73.9%. This waste catalyst is pulverized to 120 order, gets the waste catalyst after 20kg pulverizes, and 200kgFe(OH) 3 (with Fe 2 o 3 Mass fraction ≥ 70%), 18kgCr(OH) 3 (in Cr 2 o 3 mass fraction ≥ 61%), milled together for 1-2 hours, passed through an 8-mesh screen to make particles, roasted at a low temperature of 250 ° C to 300 ° C for 6-8 hours, and then mixed with graphite and pressed into tablets to form a CO high-temperature shift catalyst. . According to the national chemical industry standard HG / T 3546-2011, the activity (calculated by the conversion rate of carbon monoxide): 62%; the average particle radial crush resistance: 352N / cm; the particle fraction below 160N / cm: 0% ; Wear rate: 3.0%; Loss on ignition...

Embodiment 3

[0023] A kind of spent CO sulfur-resistant shift catalyst, through X-ray fluorescence analysis, its composition is mass fraction (%): Co (calculated as CoO): 1.5%, Mo (calculated as MoO 3 Total): 8.6%, K 2 O: 4.8%, S (as SO 2 Total): 9.2%, Al 2 o 3 : 75.9%. This spent catalyst is crushed to 120 orders, gets spent catalyst after 22kg crushes, and 200kgFe(OH) 3 (with Fe 2 o 3 Mass fraction ≥ 70%), 18kgCr(OH) 3 (in Cr 2 o 3 mass fraction ≥ 61%), milled together for 1-2 hours, passed through an 8-mesh screen to make particles, roasted at a low temperature of 250 ° C to 300 ° C for 6-8 hours, and then mixed with graphite and pressed into tablets to form a CO high-temperature shift catalyst. . According to the national chemical industry standard HG / T 3546-2011, the activity (calculated by the conversion rate of carbon monoxide): 60%; the average particle radial crush resistance: 382N / cm; the particle fraction below 160N / cm: 0% ; Wear rate: 2.8%; Loss on ignition mass frac...

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Abstract

The invention relates to a recycling method of waste CO sulfur-tolerant shift catalyst. The recycling method is to crush the waste CO sulfur-tolerant shift catalyst and grind it with Fe(OH)3 and Cr(OH)3 for 1 to 2 hours and then pass through Particles are made from an 8-mesh screen, and are roasted at a low temperature of 250°C to 300°C for 6 to 8 hours. After cooling, they are then pressed into tablets to form CO high-temperature shift catalysts. Tested according to the national chemical industry standard HG / T 3546-2011, all performance indicators are much higher than the quality and technical requirements of the commercially available B116 CO high-temperature shift catalyst. This recycling method can achieve 100% resource utilization rate of used CO sulfur-tolerant shift catalysts. There is no need to remove sulfur from the used catalysts, and no SO2, NO, NO2 exhaust gases, waste liquids and waste residues are produced during the entire recycling process. produce. There is truly no secondary pollution and no new "three wastes" are produced. It not only saves molybdenum resources, but also is environmentally friendly.

Description

technical field [0001] The invention relates to a method for recycling a waste CO sulfur-tolerant shift catalyst, belonging to the technical field of catalysts. Background technique [0002] CO sulfur-tolerant shift catalyst is an important catalyst for hydrogen production in ammonia, methanol and other industries. More than 70 years ago, Fe-Cr series high-temperature shift catalyst was first used, and then Cu-Zn series low-temperature shift catalyst was developed. Such as the shortcomings of being very sensitive to poisons. In order to solve these problems, Co-Mo series wide-temperature sulfur-tolerant shift catalysts have been developed. [0003] When using heavy oil, residual oil or coal as raw material to produce synthetic ammonia raw material gas, the use of Co-Mo series wide temperature shift catalyst can directly transform the sulfur-containing gas, and then undergo desulfurization and decarbonization, simplifying the process and significantly reducing energy consum...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/049B01J35/02C01B3/16B01J35/00
CPCY02P20/52
Inventor 周志斌黄远军肖辉亚程瑞徐晓毅
Owner 湖北双雄催化剂有限公司