CN-121975554-A - Method for adding sulfur into low-sulfur coal for transforming catalyst vulcanization

Abstract

The invention relates to the technical field of catalyst vulcanization in the coal gasification process, and particularly discloses a method for changing catalyst vulcanization by adding sulfur into low-sulfur coal, which comprises the steps of fully mixing byproduct sulfur and boiler slag by adopting a banburying process to prepare a slag sulfur mixture; the method comprises the steps of fully and uniformly mixing the slag-sulfur mixture with low-sulfur coal, feeding the mixture into a coal mill for pulverizing to obtain coal dust, carrying out on-line vulcanization of a shift catalyst in a coal gasifier by utilizing the coal dust, setting slag sampling once every half hour after adding the slag-sulfur mixture, and carrying out real-time monitoring on H 2 S concentration, grey water pH value and sulfate radical concentration in synthetic gas. The invention adopts the byproduct sulfur and boiler slag to carry out banburying and compounding to prepare the slag sulfur mixture, and uniformly mixes the slag sulfur mixture and low sulfur coal in proportion to prepare powder, and realizes the stable combustion of coal dust and the on-line vulcanization of the shift catalyst by controlling the outlet temperature, the circulating air quantity and the pressurized conveying temperature of the coal mill.

Inventors

• LI LIN
• ZHENG XIRUI
• REN XIANGWEI
• NIU TIAN
• BI LIJUN
• YIN XING
• GUO YONG
• ZHANG YU

Assignees

• 中化学(内蒙古)新材料有限责任公司

Dates

Publication Date

20260505

Application Date

20251226

Claims (9)

1. 1. A method of adding sulfur to low sulfur coal for shift catalyst sulfiding comprising the steps of: step 1, fully mixing byproduct sulfur and boiler slag by adopting a banburying process to prepare a slag sulfur mixture; Step 2, fully and uniformly mixing the slag-sulfur mixture and low-sulfur coal, and then feeding the mixture into a coal mill for pulverizing to obtain coal dust; And 3, performing online vulcanization of a shift catalyst in the coal gasifier by utilizing coal dust, setting slag sampling once every half hour after adding a slag-sulfur mixture, and monitoring the H 2 S concentration, the grey water pH value and the sulfate radical concentration in the synthetic gas in real time.
2. 2. The method for adding sulfur to low-sulfur coal for shift catalyst sulfiding according to claim 1, wherein the mass ratio of byproduct sulfur to boiler slag in step 1 is 1:1.5-3.
3. 3. The method for adding sulfur to low sulfur coal for shift catalyst sulfiding according to claim 1, wherein the particle size of the slag sulfur mixture in step 1 is 5-10mm.
4. 4. The method for adding sulfur to low-sulfur coal for shift catalyst sulfiding according to claim 1, wherein the raw materials for preparing the slag sulfur mixture in step 1 further comprise carrier auxiliary agents, wherein the mass of the carrier auxiliary agents is 5-8% of the total mass of byproduct sulfur and boiler slag.
5. 5. The method for adding sulfur to low sulfur coal for shift catalyst sulfiding according to claim 4, wherein the carrier auxiliary agent is fly ash and solid sodium silicate in a mass ratio of 1-3:1.
6. 6. The method for adding sulfur to low sulfur coal for shift catalyst sulfiding according to claim 5, wherein said fly ash is a secondary fly ash and said solid sodium silicate has a modulus of 3.10-3.40.
7. 7. The method for adding sulfur to low sulfur coal for shift catalyst sulfiding according to claim 1, wherein the mass ratio of slag sulfur mixture to low sulfur coal in step 2 is 1:70-90.
8. 8. The method for adding sulfur to low-sulfur coal for shift catalyst sulfiding according to claim 1, wherein in said step 2, the outlet temperature of the coal mill is 90-95 ℃, the circulating air volume is 85000-90000Nm3/h, the pulverized coal bin temperature is 98-102 ℃, and the pressurized delivery temperature of high-pressure carbon dioxide is 100-108 ℃.
9. 9. The method for adding sulfur to low-sulfur coal for shift catalyst sulfidation according to claim 1, wherein the real-time monitoring of the H 2 S concentration, the grey water pH value and the sulfate radical concentration in the synthesis gas in the step 3 specifically means that the continuous online H 2 S gas and grey water electrochemical sensor is adopted, the sampling period is set to be 2H once, and the real-time monitoring of the H 2 S concentration, the grey water pH value and the sulfate radical concentration in the synthesis gas is carried out.

Description

Method for adding sulfur into low-sulfur coal for transforming catalyst vulcanization Technical Field The invention relates to the technical field of catalyst vulcanization in a coal gasification process, in particular to a method for adding sulfur into low-sulfur coal for changing catalyst vulcanization. Background The main components of coal gasification are synthesis gas of CO and H 2, the component CO content of which is usually high and unsuitable for downstream process requirements. To increase the effective hydrogen production of the synthesis gas, it is often necessary to convert a portion of the CO to H 2 by a shift reaction. The cobalt-molybdenum catalyst is the main body of the catalyst of the current low-temperature transformation process, and the catalyst needs to be vulcanized before use and after reverse vulcanization, and has catalytic activity after oxides such as CoO, moO 3 and the like are converted into sulfides. The traditional catalyst is usually vulcanized by adopting high-sulfur coal or adding vulcanizing agents such as CS 2 and the like or by preprocessing the vulcanized catalyst, but the problems are that 1, the high-sulfur coal influences the stability of coal quality, changes the working condition of a gasification furnace and has operation risks, 2, the vulcanizing agents such as CS 2 and the like are toxic and have complex operation, and 3, the preprocessing of the vulcanized catalyst takes long time or is difficult to continuously operate on line. Therefore, on the premise of keeping stable supply of low-sulfur coal, on-line sulfuration of the catalyst is realized, high catalytic activity and safety and economy are ensured, and the method is a technical problem which is urgently needed to be solved at present. Based on the above statements, the present invention proposes a method for adding sulfur to low sulfur coal for shift catalyst sulfiding. Disclosure of Invention In order to solve the problems of unstable coal quality, large volatilization loss of vulcanizing agent, high safety risk, unmatched process parameters and the like in the aspect of low-sulfur coal catalyst vulcanization in the prior art, the invention provides a method for changing the catalyst vulcanization by adding sulfur into low-sulfur coal. The method overcomes the technical defects of the traditional vulcanization method, ensures that the activity and the service life of the catalyst are obviously improved, and has excellent practical value and market application potential. The invention provides a method for adding sulfur into low-sulfur coal for transforming catalyst vulcanization, which adopts the following technical scheme: a method of adding sulfur to low sulfur coal for shift catalyst sulfiding comprising the steps of: step 1, fully mixing byproduct sulfur and boiler slag by adopting a banburying process to prepare a slag sulfur mixture; Step 2, fully and uniformly mixing the slag-sulfur mixture and low-sulfur coal, and then feeding the mixture into a coal mill for pulverizing to obtain coal dust; And 3, performing online vulcanization of a shift catalyst in the coal gasifier by utilizing coal dust, setting slag sampling once every half hour after adding a slag-sulfur mixture, and monitoring the H 2 S concentration, the grey water pH value and the sulfate radical concentration in the synthetic gas in real time. Preferably, the mass ratio of the byproduct sulfur to the boiler slag in the step 1 is 1:1.5-3. Preferably, the particle size of the slag-sulfur mixture in the step1 is 5-10mm. The invention ensures even distribution, improves the dispersity of sulfur, reduces volatilization, ensures the uniformity of sulfur content and further ensures good stability and reactivity by controlling the mass ratio of byproduct sulfur and boiler slag and the refined grain diameter of slag sulfur mixture. Preferably, the preparation raw materials of the slag-sulfur mixture in the step 1 further comprise a carrier auxiliary agent, wherein the mass of the carrier auxiliary agent is 5-8% of the total mass of byproduct sulfur and boiler slag. Preferably, the carrier auxiliary agent is fly ash and solid sodium silicate with the mass ratio of 1-3:1. Preferably, the fly ash is secondary fly ash, and the modulus of the solid sodium silicate is 3.10-3.40. Preferably, the mass ratio of the slag-sulfur mixture to the low-sulfur coal in the step 2 is 1:70-90. Preferably, the outlet temperature of the coal mill in the step 2 is 90-95 ℃, the circulating air quantity is 85000-90000Nm3/h, the pulverized coal bin temperature is 98-102 ℃, and the pressurized conveying high-pressure carbon dioxide temperature is 100-108 ℃. The invention can ensure the release of the effective sulfur components and maintain the stability of coal quality, and maintain the fluidity and gasification performance of coal dust, thereby rapidly realizing the vulcanization of the catalyst. The control of the outlet temperature of the coal mill is favorable