煤层气中甲烷/氮气分离用椰壳活性炭的制备

Preparation of carbonaceous adsorbent used for separation of methane / nitrogen in coal bed methane

  • 摘要: 为解决变压吸附法提纯煤层气中甲烷遇到的吸附剂难题,以我国海南产椰壳炭化料为原料,采用二次炭化-水蒸气物理活化工艺制备生物质基活性炭,采用高压电子天平测量了298 K、0~1.0 MPa下CH4/N2在制备得椰壳活性炭上的吸附等温线,利用比表面积和孔径吸附仪测量了活性炭的孔径结构,详细研究了活化工艺参数对CH4/N2吸附分离性能及孔隙结构的影响。通过变压吸附装置检验了最佳工艺参数条件下制备椰壳活性炭的CH4提浓效果。研究结果表明,随着活化温度的提高,平衡分离系数逐步减小,吸附容量逐步增加,最佳活化温度为850 ℃;平衡分离系数和饱和吸附容量均随水蒸气流量的增加呈先增加后减小的趋势,最佳水蒸气流量为2.0 kg/h;平衡分离系数随活化时间延长先增加后减小,甲烷饱和吸附容量逐渐递增,最佳活化时间为40 min。升高活化温度对孔结构的发育影响显著,比表面积、微孔孔容和总孔容均呈递增趋势,表明升高温度有利于微孔的发育,可制备出微孔发达的活性炭。变压吸附评价结果表明在水蒸汽活化工艺最优条件下制备得椰壳活性炭可将20%CH4-80%N2模拟煤层气中的CH4体积浓度提高到48.3%,提浓幅度大于25%,回收率为80.58%,产能达到108.82 m3/(t·h);同时,该吸附剂对中高浓度煤层气也具有较好的分离效果,体现出较好的分离性能。

     

    Abstract: In order to solve the adsorbent problem encountered in the purification of methane from coal bed gas by pressure swing adsorption method,the biomass based activated carbon were prepared by the secondary car-bonization- steam physical activation process using coconut shell carbonized material as raw material. The ad-sorption isotherms of CH4 / N2 on coconut shell activated carbon prepared at 298 K and 0-1. 0 MPa were measured by high pressure electronic balance. The pore size structure of activated carbon was measured by specific surface area and pore size adsor- bent instrument. The influence of water vapor activation process parameters to CH4 / N2 adsorption separation perform- ance and pore structure were studied. The CH4 concentration effect of coconut shell activated carbon prepared under the optimum technological parameters was tested by pressure swing adsorption device. The results showed that the equilibrium separation coefficient decreases gradually with the increase of activation temperature,however,the adsorp- tion capacity increases gradually. The best activation temperature is 850 ℃ . The equilibrium separation coefficient and saturated adsorption capacity increase firstly and then decrease with the increase of the vapor flow rate. The best water vapor flow rate is 2. 0 kg / h. With the extension of activation time,the equilibrium separation coefficient decreases after increasing first,methane saturation adsorption capacity increases gradually, and the activation time is also best for 40 min. The activation temperature has significant impact on the development of pore structure. The specific surface area,micropore volume and total pore volume show an increasing trend,indicating that increasing temperature is con- ducive to the development of micropore,and activated carbon with developed micropore can be prepared. The evalua- tion results of pressure swing adsorption show that the volume concentration of CH4 in 20% CH4 -80% N2 simulated coalbed methane increases to 48. 3% with coconut shell activated carbon prepared under the optimum conditions of steam activation process,the enrichment range is more than 25 percentage points,the recovery rate is 80. 58% ,and the productivity is 108. 82 m3 / (t·h). At the same time,the adsorbent also has a good separation effect for medium and high concentration coalbed methane.

     

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