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Recycling method for waste CO sulfur-tolerant shift catalysts

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

Active Publication Date: 2015-02-18
湖北双雄催化剂有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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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  • Recycling method for waste CO sulfur-tolerant shift catalysts

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Experimental program
Comparison scheme
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%) together for 1 to 2 hours, passed through an 8-mesh screen to make particles, roasted at a low temperature of 250°C to 300°C for 6 to 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 mass fr...

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%) together for 1 to 2 hours, passed through an 8-mesh screen to make particles, roasted at a low temperature of 250°C to 300°C for 6 to 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 mass f...

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-300°C for 6-8h, 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 fraction: 6.7%; T...

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Abstract

The invention relates to a recycling method for waste CO sulfur-tolerant shift catalysts. The recycling method comprises the following steps: crushing the waste CO sulfur-tolerant shift catalysts, milling the crushed waste CO sulfur-tolerant shift catalysts, Fe(OH)3 and Cr(OH)3 together for 1-2 hours to be made into particles through a 8-mesh screen cloth, roasting the particles for 6-8 hours at the low temperature of 250-300 DEG C, cooling the roasted particles, and then tabletting and shaping the cooled particles to obtain CO high-temperature shift catalysts. Through detection according to the national chemical industry standard HG / T 3546-2011, all the performance indexes are much higher than quality technology requirements of B116 type CO high-temperature shift catalysts which are sold in the market. Through the adoption of the recycling method, the resource utilization rate of the waste CO sulfur-tolerant shift catalysts reaches 100%, sulfur in waste catalysts does not need to be removed, SO2 waste gas, NO waste gas and NO2 waste gas are not generated in the whole recovery process, and waste liquid and waste residues are not generated, so that the purposes of zero secondary pollution and zero new 'three wastes' are really realized, and not only are molybdenum sources saved, but also the recycling method is environmental-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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IPC IPC(8): B01J27/049B01J35/02C01B3/16
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
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