煤矿乏风瓦斯变压吸附分离吸附剂的研究

发布时间：2018-03-20 13:13

本文选题：乏风瓦斯　切入点：变压吸附　出处：《北京工业大学》2013年博士论文　论文类型：学位论文

【摘要】：主要围绕乏风瓦斯富集和分离，进行了负载金属改性活性炭、KOH改性活性炭和活性炭纤维、高温焙烧改性活性炭等变压吸附分离吸附剂的研究工作，并进行了中试用吸附剂的工业化制备和中试实验。以吸附剂的分离系数α、吸附能力选择系数W、吸附选择参数S和吸附量V等为评价参数，以孔径、孔容、比表面积等为参考，进行改性碳材料吸附剂的筛选。活性炭中选择PA-1进行金属负载改性，10~20mesh椰壳炭进行高温焙烧和KOH活化改性，选择ZC1326作为ACF中最适合的改性材料。采用水热法负载金属改性活性炭PA-1进行了金属离子的选择，其中以Ti改性尤为突出。采用分离系数、吸附选择能力系数、吸附选择参数和在150kPa时的CH4吸附量来评价吸附剂的性能，并进行了常温常压穿透实验测试其吸附性能。分离系数α由PA-1的4.0变化为Ti-PA-1-160℃的4.3和Ti-PA-1-160℃-1100℃的3.9，吸附能力选择系数W也从PA-1和Ti-PA-1-160℃的2.8降至Ti-PA-1-160℃-1100℃的2.2，，相应的吸附选择参数S为：11.20、12.04和8.58，但其在150kPa时对甲烷的吸附量V却从22.7cm~3/g升至34.4cm~3/g，增加了51.5%。1100℃N_2保护焙烧的Ti改性活性炭CH4常压穿透曲线的穿出点为111s，比未改性的活性炭和160℃水热方法Ti改性活性炭滞后了41%和50%。浸渍负载Sr改性活性炭表现出对N_2极低的吸附性能。采用KOH和活性炭混合法改性椰壳炭及KOH溶液浸渍法改性活性炭纤维进行实验研究。当KOH：C=2：1、碳化温度和活化温度分别为500℃和800℃、碳化时间和活化时间分别为1h和2h时，改性后的活性炭吸附效果最佳，对甲烷的吸附量V高达51.6cm~3/g，分离系数α为4.2，吸附选择能力W系数为2.5，吸附选择参数S为10.50，分别比未改性前变化了+63.8%，-10.6%，+4.2%和-6.9%。当KOH浓度为13%、活化时间为40min、活化温度为800℃时，改性后的活性炭纤维吸附效果最佳，分离系数α为4.2，吸附选择能力系数W为2.4，吸附选择参数S为10.08，虽然三个参数比未改性前分别降低了4.5%、11.1%和15.2%，但其对甲烷的吸附量V却达到49.4cm~3/g，比未改性前增加了48.3%。采用高温焙烧对活性炭进行改性研究。考察了不同焙烧温度、不同焙烧时间、不同焙烧气氛对椰壳炭分离CH4/N_2性能和物理性能的影响，采用分离系数、吸附选择能力系数、吸附选择参数和在150kPa时的CH4吸附量来评价吸附剂的性能，并进行了常温常压穿透实验测试其吸附性能。在实验研究范围内发现N_2保护下600℃焙烧4h时，改性椰壳炭的物理性能没有明显改变的情况下，具有良好的吸附分离性能。此时改性后的活性炭分离系数α为4.8，比未改性前的4.7增大了2.1%；吸附选择能力系数W为2.2，比未改性前的2.4降低了8.3%，吸附选择参数S为10.56，比未改性前的11.28降低了6.4%，对甲烷的吸附量V为36.0cm~3/g，比未改性前的31.5cm~3/g增大了14.3%；常压穿透曲线穿出点为172s，比未改性前的55s滞后了212.7%。中试用吸附剂的工业化制备采用氮气保护650℃焙烧4h、1mol/LHCl溶液浸泡24h、洗涤和热风烘干工艺，制得烘干后的活性炭为3745kg，总的损失率为22.4%。搭建了一套原料气进气量为1000m~3/h的煤矿乏风瓦斯分离富集中试试验装置。利用乏风减量装置，通过旋流富集在出口中心部分最高可获取的甲烷浓度可达0.3%。在乏风瓦斯平均浓度约为0.2%的条件下，吸附分离富集系统出口的瓦斯浓度≥1%，回收率可达到50%左右。
[Abstract]:Mainly around the ventilation gas enrichment and separation of metal loaded activated carbon modified KOH, modified activated carbon and activated carbon fiber, research PSA adsorbent temperature roasting modified activated carbon, and the trial adsorbent for the industrial preparation and pilot experiment.
In order to separate the coefficient of adsorbent, selectivity coefficient W adsorption capacity, adsorption parameters S and V adsorption amount as evaluation parameters, the aperture, Kong Rong, the specific surface area for reference, modify the selection agent of carbon materials in the activated carbon adsorption. PA-1 modified 10~ 20mesh supported metal, coconut shell carbon calcination and activation of KOH modified, modified materials of ACF ZC1326 is selected as the most suitable.
Metal modified activated carbon PA-1 was the choice of metal ions loaded by hydrothermal method, which modified by Ti is particularly prominent. The separation factor, capacity factor of selective adsorption, adsorption parameters and the adsorption amount of CH4 in the 150kPa to evaluate performance of the adsorbent, and the atmospheric penetration test and its adsorption properties the separation coefficient by 4. The change of PA-1 Ti-PA-1-160 and Ti-PA-1-160 4.3 DEG -1100 DEG C 3.9, adsorption capacity selection coefficient W from the PA-1 and Ti-PA-1-160 C 2.8 to 2.2 DEG -1100 DEG Ti-PA-1-160, the corresponding adsorption parameter selection of the S were 11.20,12.04 and 8.58, but the adsorption capacity of V in 150kPa methane is increased from 22.7cm~3/g to 34.4cm~3/g, 51.5%.1100 C N_2 piercing point protection roasting Ti modified activated carbon CH4 atmospheric penetration curve was 111S, modified activated than unmodified activated carbon and 160 DEG C hydrothermal method Ti Carbon lagged by 41% and 50%. impregnated Sr modified activated carbon showed a very low adsorption performance to N_2.
Modified activated carbon fiber was studied with modified coconut shell charcoal and KOH solution dipping method using KOH and activated carbon hybrid method. When KOH:C=2:1, carbonization temperature and activation temperature were 500 degrees and 800 degrees, carbonization time and activation time were 1H and 2H, the modified activated carbon adsorption effect is the best the adsorption capacity of methane, V up to 51.6cm~3/g, separation coefficient is 4.2, W coefficient is 2.5 adsorption, adsorption parameters of S was 10.50, respectively, than the unmodified variation before +63.8%, -10.6%, +4.2% and -6.9%. when the KOH concentration is 13%, the activation time was 40min, activation temperature was 800 when the change of the adsorption effect of activated carbon fiber, separation coefficient is 4.2, the adsorption ability coefficient W is 2.4, the adsorption parameter selection of S was 10.08, while the three parameter than the unmodified before were reduced by 4.5%, 11.1% and 15.2%, but the methane adsorption capacity of V has reached 49.4cm~3/g, An increase of 48.3%. before the unmodified
High temperature roasting of activated carbon was modified. The effects of the calcination temperature, calcination time, calcination atmosphere on the effects of different coconut shell carbon separation CH4/N_2 and physical properties, the separation coefficient, capacity coefficient of selective adsorption, adsorption parameters and the adsorption amount of CH4 in the 150kPa to evaluate performance of the adsorbent. And the atmospheric penetration test. The adsorption performance of N_2 under the protection of 600 DEG 4H calcined in the range of experimental studies, no significant changes in physical properties of the modified coconut shell charcoal case has good adsorption separation performance. The modified activated carbon separation coefficient is 4.8, than unmodified before 4.7 increased 2.1%; adsorption ability coefficient W is 2.2, than the unmodified before 2.4 reduced 8.3%, adsorption parameter selection of S was 10.56, 11.28 of the former than the unmodified reduced 6.4%, adsorption capacity of methane is 36 V The cm~3/g, increased by 14.3% than that before the unmodified 31.5cm~3/g; the penetration point of the atmospheric pressure was 172s, and the 55s lagged behind the unmodified 212.7%..
In the trial of adsorbent prepared by industrial nitrogen protection 650 C roasting 4h, 1mol/LHCl solution 24h, washing and drying process, after drying the prepared activated carbon is 3745kg, the total loss rate of a set of raw gas into the gas of 1000m~3/h coal mine ventilation air methane separation and enrichment test device 22.4%.. Use of ventilation air reduction device, through the cyclone enriched in the central part of the highest export available methane concentration up to 0.3%. in the average concentration of VAM is about 0.2% under the condition that the gas concentration is more than 1% adsorption separation and preconcentration system for export, the recovery rate can reach about 50%.

【学位授予单位】：北京工业大学
【学位级别】：博士
【学位授予年份】：2013
【分类号】：TD712

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