Chemical Industry and Engineering Progress ›› 2024, Vol. 43 ›› Issue (7): 3620-3636.DOI: 10.16085/j.issn.1000-6613.2024-0753
• Column: Thermochemical Reaction Engineering Technology • Previous Articles
CAO Jingpei(), YAO Naiyu, PANG Xinbo, ZHAO Xiaoyan, ZHAO Jingping, CAI Shijie, XU Min, FENG Xiaobo, YI Fengjiao
Received:
2024-05-07
Revised:
2024-06-19
Online:
2024-08-14
Published:
2024-07-10
Contact:
CAO Jingpei
曹景沛(), 姚乃瑜, 庞新博, 赵小燕, 赵静平, 蔡士杰, 徐敏, 冯晓博, 伊凤娇
通讯作者:
曹景沛
作者简介:
曹景沛(1983—),男,教授,研究方向为煤与生物质定向热转化。E-mail:caojingpei@cumt.edu.cn。
基金资助:
CLC Number:
CAO Jingpei, YAO Naiyu, PANG Xinbo, ZHAO Xiaoyan, ZHAO Jingping, CAI Shijie, XU Min, FENG Xiaobo, YI Fengjiao. Research progress and development history of coal pyrolysis[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3620-3636.
曹景沛, 姚乃瑜, 庞新博, 赵小燕, 赵静平, 蔡士杰, 徐敏, 冯晓博, 伊凤娇. 煤热解研究进展及其发展历程[J]. 化工进展, 2024, 43(7): 3620-3636.
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URL: https://hgjz.cip.com.cn/EN/10.16085/j.issn.1000-6613.2024-0753
化学键 | 键能/kJ·mol-1 | 化学键 | 键能/kJ·mol-1 |
---|---|---|---|
Car—Car | 2057 | 284 | |
Car—H | 425 | ||
Cal—H | 392 | 251 | |
Car—Cal | 332 | ||
Cal—O | 314 | 339 | |
Cal—Cal | 297 | ||
301 | 284 |
化学键 | 键能/kJ·mol-1 | 化学键 | 键能/kJ·mol-1 |
---|---|---|---|
Car—Car | 2057 | 284 | |
Car—H | 425 | ||
Cal—H | 392 | 251 | |
Car—Cal | 332 | ||
Cal—O | 314 | 339 | |
Cal—Cal | 297 | ||
301 | 284 |
煤化程度 | 产物 | ||
---|---|---|---|
半焦/焦炭 | 焦油/热解水 | 热解气 | |
褐煤 | 59.5 | 31.5 | 9.0 |
长焰煤 | 64.7 | 29.0 | 6.3 |
气煤 | 64.4 | 29.2 | 6.4 |
焦煤 | 73.3 | 21.7 | 5.0 |
无烟煤 | 95.2 | 2.1 | 2.7 |
煤化程度 | 产物 | ||
---|---|---|---|
半焦/焦炭 | 焦油/热解水 | 热解气 | |
褐煤 | 59.5 | 31.5 | 9.0 |
长焰煤 | 64.7 | 29.0 | 6.3 |
气煤 | 64.4 | 29.2 | 6.4 |
焦煤 | 73.3 | 21.7 | 5.0 |
无烟煤 | 95.2 | 2.1 | 2.7 |
煤化程度 | 焦油 | |||||||||
---|---|---|---|---|---|---|---|---|---|---|
芳香族 | 脂肪族 | 酚类 | 酮类 | 醇类 | 醛类 | 酸类/酯类 | 含氮化合物 | 含硫化合物 | 其他含氧化合物 | |
褐煤 | 28.8 | 17.1 | 32.2 | 3.1 | 7.4 | 0.3 | 1.5 | 2.9 | 1.2 | — |
长焰煤 | 26.5 | 27.1 | 35.1 | 1.8 | 4.8 | 0.3 | 0.9 | 1.2 | 0.08 | 1.9 |
气煤 | 19.5 | 31.8 | 31.1 | 2.5 | 2.3 | 0.4 | 1.3 | 6.1 | 2.9 | 2.1 |
焦煤 | 65.0 | 7.6 | 6.6 | 1.0 | 3.8 | 0.4 | 0.8 | 4.3 | 7.3 | 3.3 |
无烟煤 | 44.8 | 1.5 | 0 | — | 28.4 | — | 3.8 | 11.7 | — | 4.4 |
煤化程度 | 焦油 | |||||||||
---|---|---|---|---|---|---|---|---|---|---|
芳香族 | 脂肪族 | 酚类 | 酮类 | 醇类 | 醛类 | 酸类/酯类 | 含氮化合物 | 含硫化合物 | 其他含氧化合物 | |
褐煤 | 28.8 | 17.1 | 32.2 | 3.1 | 7.4 | 0.3 | 1.5 | 2.9 | 1.2 | — |
长焰煤 | 26.5 | 27.1 | 35.1 | 1.8 | 4.8 | 0.3 | 0.9 | 1.2 | 0.08 | 1.9 |
气煤 | 19.5 | 31.8 | 31.1 | 2.5 | 2.3 | 0.4 | 1.3 | 6.1 | 2.9 | 2.1 |
焦煤 | 65.0 | 7.6 | 6.6 | 1.0 | 3.8 | 0.4 | 0.8 | 4.3 | 7.3 | 3.3 |
无烟煤 | 44.8 | 1.5 | 0 | — | 28.4 | — | 3.8 | 11.7 | — | 4.4 |
煤种 | H2 | CO | CO2 | CH4 | C2H6 | C2H4 | C3H8 | C3H6 |
---|---|---|---|---|---|---|---|---|
褐煤 | 4.17 | 3.00 | 4.99 | 2.33 | 0.22 | 0.25 | 0.05 | 0.14 |
长焰煤 | 4.70 | 2.67 | 2.69 | 3.36 | 0.34 | 0.18 | 0.07 | 0.08 |
气煤 | 6.01 | 1.22 | 3.40 | 4.40 | 0.44 | 0.23 | 0.10 | 0.13 |
焦煤 | 21.24 | 0.41 | 0.28 | 9.17 | 0.95 | 0.25 | 0.17 | 0.12 |
无烟煤 | 18.77 | 0.78 | 1.45 | 9.89 | 0.19 | 0.05 | 0.02 | 0.02 |
煤种 | H2 | CO | CO2 | CH4 | C2H6 | C2H4 | C3H8 | C3H6 |
---|---|---|---|---|---|---|---|---|
褐煤 | 4.17 | 3.00 | 4.99 | 2.33 | 0.22 | 0.25 | 0.05 | 0.14 |
长焰煤 | 4.70 | 2.67 | 2.69 | 3.36 | 0.34 | 0.18 | 0.07 | 0.08 |
气煤 | 6.01 | 1.22 | 3.40 | 4.40 | 0.44 | 0.23 | 0.10 | 0.13 |
焦煤 | 21.24 | 0.41 | 0.28 | 9.17 | 0.95 | 0.25 | 0.17 | 0.12 |
无烟煤 | 18.77 | 0.78 | 1.45 | 9.89 | 0.19 | 0.05 | 0.02 | 0.02 |
组成 | 神府原煤 | 镜质组 | 惰质组 |
---|---|---|---|
酚类 | 38.7 | 41.6 | 21.1 |
苯类 | 16.6 | 11.1 | 23.8 |
萘类 | 18.9 | 24.9 | 14.4 |
长链烃类 | 6.0 | 17.8 | 3.8 |
含氧化合物 | 10.7 | 2.8 | 24.8 |
其他 | 9.2 | 1.8 | 12.2 |
组成 | 神府原煤 | 镜质组 | 惰质组 |
---|---|---|---|
酚类 | 38.7 | 41.6 | 21.1 |
苯类 | 16.6 | 11.1 | 23.8 |
萘类 | 18.9 | 24.9 | 14.4 |
长链烃类 | 6.0 | 17.8 | 3.8 |
含氧化合物 | 10.7 | 2.8 | 24.8 |
其他 | 9.2 | 1.8 | 12.2 |
压力 | 煤种 | 反应条件 | CH4/% | H2/% | CO/% | 焦油(daf)/% | 水(daf)/% |
---|---|---|---|---|---|---|---|
1MPa | 唐山烟煤 | 600℃,N2气氛 | 1.1 | 1.2 | 0.25 | 9.0 | 4.7 |
2MPa | 1.4 | 1.0 | 0.23 | 12.5 | 4.6 | ||
3MPa | 1.0 | 0.8 | 0.75 | 11.0 | 4.9 | ||
压力 | 煤种 | 反应条件 | CH4(daf)/L·g-1 | H2(daf)/L·g-1 | CO(daf)/L·g-1 | 焦油(daf)/% | 气体(daf)/% |
0.1MPa | 西部烟煤 | 700℃,N2气氛 | 0.038 | 0.072 | 0.054 | 3.20 | 10.5 |
0.5MPa | 0.039 | 0.065 | 0.048 | 4.05 | 9.2 | ||
1.0MPa | 0.042 | 0.055 | 0.043 | 4.45 | 8.2 | ||
1.5MPa | 0.045 | 0.054 | 0.042 | 4.40 | 8.0 |
压力 | 煤种 | 反应条件 | CH4/% | H2/% | CO/% | 焦油(daf)/% | 水(daf)/% |
---|---|---|---|---|---|---|---|
1MPa | 唐山烟煤 | 600℃,N2气氛 | 1.1 | 1.2 | 0.25 | 9.0 | 4.7 |
2MPa | 1.4 | 1.0 | 0.23 | 12.5 | 4.6 | ||
3MPa | 1.0 | 0.8 | 0.75 | 11.0 | 4.9 | ||
压力 | 煤种 | 反应条件 | CH4(daf)/L·g-1 | H2(daf)/L·g-1 | CO(daf)/L·g-1 | 焦油(daf)/% | 气体(daf)/% |
0.1MPa | 西部烟煤 | 700℃,N2气氛 | 0.038 | 0.072 | 0.054 | 3.20 | 10.5 |
0.5MPa | 0.039 | 0.065 | 0.048 | 4.05 | 9.2 | ||
1.0MPa | 0.042 | 0.055 | 0.043 | 4.45 | 8.2 | ||
1.5MPa | 0.045 | 0.054 | 0.042 | 4.40 | 8.0 |
反应气氛 | 煤种 | 反应条件 | CO2/mmol·g-1 | CO/mmol·g-1 | CH4/mmol·g-1 | H2/mmol·g-1 | 焦油/% | 气体/% |
---|---|---|---|---|---|---|---|---|
N2 | 神府原煤 | 650℃,无催化剂,气体流速50mL/min | 0.65 | 0.05 | 0.83 | 0.43 | 4.10 | 27.24 |
H2 | 0.86 | 0.02 | 3.61 | — | 7.39 | 19.99 | ||
CH4 | 0.11 | 0.20 | — | 7.68 | 9.37 | 13.45 | ||
H2/CO | 3.50 | — | 2.23 | — | 7.44 | 19.89 | ||
反应气氛 | 煤种 | 反应条件 | CO2/% | CO/% | CH4/% | H2/% | C n H m /% | 焦油/% |
N2 | 平朔煤 | 600℃,气体流速800mL/min | 5.2 | 8.5 | 29.3 | 23.2 | 3.0 | 9.5 |
H2 | 4.8 | 10.3 | 39.64 | 41.1 | 2.5 | 11.5 | ||
CH4/CO2 | 10.8 | 12.8 | 43.2 | 28.2 | 4.3 | 12.0 |
反应气氛 | 煤种 | 反应条件 | CO2/mmol·g-1 | CO/mmol·g-1 | CH4/mmol·g-1 | H2/mmol·g-1 | 焦油/% | 气体/% |
---|---|---|---|---|---|---|---|---|
N2 | 神府原煤 | 650℃,无催化剂,气体流速50mL/min | 0.65 | 0.05 | 0.83 | 0.43 | 4.10 | 27.24 |
H2 | 0.86 | 0.02 | 3.61 | — | 7.39 | 19.99 | ||
CH4 | 0.11 | 0.20 | — | 7.68 | 9.37 | 13.45 | ||
H2/CO | 3.50 | — | 2.23 | — | 7.44 | 19.89 | ||
反应气氛 | 煤种 | 反应条件 | CO2/% | CO/% | CH4/% | H2/% | C n H m /% | 焦油/% |
N2 | 平朔煤 | 600℃,气体流速800mL/min | 5.2 | 8.5 | 29.3 | 23.2 | 3.0 | 9.5 |
H2 | 4.8 | 10.3 | 39.64 | 41.1 | 2.5 | 11.5 | ||
CH4/CO2 | 10.8 | 12.8 | 43.2 | 28.2 | 4.3 | 12.0 |
催化剂 | 原料 | 催化剂 | 载气 | 结果 | 催化类型 | 参考文献 |
---|---|---|---|---|---|---|
金属类 | 霍林河褐煤 | 金属氯化物 (CaCl2、KCl、NiCl2、CoCl2和ZnCl2) | N2 | 促进有机物更多的转化为轻质物质 | 直接催化热解 | [ |
低阶煤 | 熔融碳酸盐 (Li2CO3、Na2CO3和K2CO3) | Ar | 增加烃类含量从而增加油的质量 | 直接催化热解 | [ | |
褐煤、亚烟煤和烟煤 | 碱金属及碱土金属 | He | 对酚类化合物和缩合芳烃分解为轻质芳烃具有良好的催化活性 | 直接催化热解 | [ | |
内蒙古和新疆褐煤 | 钼基和铁基催化剂 | N2 | 有利于煤的解聚反应,焦油产率提高 | 直接催化热解 | [ | |
褐煤 | 铁矿石 (褐铁矿、赤铁矿、菱铁矿和磁铁矿) | N2 | 褐铁矿在轻质芳烃生产方面有最好的性能 | 热解挥发分催化热解 | [ | |
半焦类 | 神东长焰煤 | 半焦催化剂 | N2 | 可为焦油的分解提供活性表面和催化无机组分,有利于焦油的提质升级 | 直接催化热解 | [ |
山西烟煤 | 半焦和金属浸渍半焦催化剂 (Co-char、Ni-char、Cu-char和Zn-char) | N2 | 提高焦油中轻质焦油比例,降低N、S含量,提高焦油H/C比例 | 热解挥发分催化热解 | [ | |
呼伦贝尔褐煤 | 生物质半焦 | N2 | 可为裂解重馏分煤焦油提供催化活性位点,热解产生的轻质焦油比例提高 | 热解挥发分催化热解 | [ | |
神木亚烟煤 | 半焦催化剂和商用椰壳活性炭 | N2 | 提高煤焦油的质量,增加轻焦油的含量和气体产率 | 热解挥发分催化热解 | [ | |
山西烟煤 | 金属改性半焦催化剂 (Ni-char、Fe-Ni-char、Mg-Ni-char、Ce-Ni-char和Zr-Ni-char) | N2 | 焦油中轻质焦油产率提高,S和N的含量降低 | 热解挥发分催化热解 | [ | |
分子筛类 | 宁夏烟煤 | Y型 | He | BTEXN的产率提高,焦油质量提高 | 热解挥发分催化热解 | [ |
汾西烟煤 | USY | He | 苯的含量增加了500%,甲苯、乙苯、二甲苯和萘等化合物的含量也有不同程度的增加 | 热解挥发分催化热解 | [ | |
宁夏烟煤 | 多级孔Y型 | — | BTEXN等轻芳烃的总量从5600ng/mg(原煤热解)增加到18800ng/mg | 热解挥发分催化热解 | [ | |
胜利褐煤 | HZSM-5 | Ar | 高铝含量的ZSM-5(SiO2/Al2O3=50)产生BTEXN效果更好 | 热解挥发分催化热解 | [ | |
胜利褐煤 | 金属改性ZSM-5 (Co、Mo、Ni改性) | Ar | 金属的引入使焦油中芳烃含量增加,有机氧含量明显降低 | 热解挥发分催化热解 | [ | |
神东煤 | 多级孔HZSM-5 | Ar | 多级孔ZSM-5可以促进脂肪烃的裂解环化和酚池的解离,提高了焦油中轻质芳烃的收率 | 直接催化热解 | [ | |
金属负载 ZSM-22 (Co、Mo) | 榆林煤 | H2/N2 | 选择性地提高了脂肪族、芳烃和酚类的相对含量,而抑制了醇类和含氮化合物的相对含量 | 热解挥发分催化热解 | [ |
催化剂 | 原料 | 催化剂 | 载气 | 结果 | 催化类型 | 参考文献 |
---|---|---|---|---|---|---|
金属类 | 霍林河褐煤 | 金属氯化物 (CaCl2、KCl、NiCl2、CoCl2和ZnCl2) | N2 | 促进有机物更多的转化为轻质物质 | 直接催化热解 | [ |
低阶煤 | 熔融碳酸盐 (Li2CO3、Na2CO3和K2CO3) | Ar | 增加烃类含量从而增加油的质量 | 直接催化热解 | [ | |
褐煤、亚烟煤和烟煤 | 碱金属及碱土金属 | He | 对酚类化合物和缩合芳烃分解为轻质芳烃具有良好的催化活性 | 直接催化热解 | [ | |
内蒙古和新疆褐煤 | 钼基和铁基催化剂 | N2 | 有利于煤的解聚反应,焦油产率提高 | 直接催化热解 | [ | |
褐煤 | 铁矿石 (褐铁矿、赤铁矿、菱铁矿和磁铁矿) | N2 | 褐铁矿在轻质芳烃生产方面有最好的性能 | 热解挥发分催化热解 | [ | |
半焦类 | 神东长焰煤 | 半焦催化剂 | N2 | 可为焦油的分解提供活性表面和催化无机组分,有利于焦油的提质升级 | 直接催化热解 | [ |
山西烟煤 | 半焦和金属浸渍半焦催化剂 (Co-char、Ni-char、Cu-char和Zn-char) | N2 | 提高焦油中轻质焦油比例,降低N、S含量,提高焦油H/C比例 | 热解挥发分催化热解 | [ | |
呼伦贝尔褐煤 | 生物质半焦 | N2 | 可为裂解重馏分煤焦油提供催化活性位点,热解产生的轻质焦油比例提高 | 热解挥发分催化热解 | [ | |
神木亚烟煤 | 半焦催化剂和商用椰壳活性炭 | N2 | 提高煤焦油的质量,增加轻焦油的含量和气体产率 | 热解挥发分催化热解 | [ | |
山西烟煤 | 金属改性半焦催化剂 (Ni-char、Fe-Ni-char、Mg-Ni-char、Ce-Ni-char和Zr-Ni-char) | N2 | 焦油中轻质焦油产率提高,S和N的含量降低 | 热解挥发分催化热解 | [ | |
分子筛类 | 宁夏烟煤 | Y型 | He | BTEXN的产率提高,焦油质量提高 | 热解挥发分催化热解 | [ |
汾西烟煤 | USY | He | 苯的含量增加了500%,甲苯、乙苯、二甲苯和萘等化合物的含量也有不同程度的增加 | 热解挥发分催化热解 | [ | |
宁夏烟煤 | 多级孔Y型 | — | BTEXN等轻芳烃的总量从5600ng/mg(原煤热解)增加到18800ng/mg | 热解挥发分催化热解 | [ | |
胜利褐煤 | HZSM-5 | Ar | 高铝含量的ZSM-5(SiO2/Al2O3=50)产生BTEXN效果更好 | 热解挥发分催化热解 | [ | |
胜利褐煤 | 金属改性ZSM-5 (Co、Mo、Ni改性) | Ar | 金属的引入使焦油中芳烃含量增加,有机氧含量明显降低 | 热解挥发分催化热解 | [ | |
神东煤 | 多级孔HZSM-5 | Ar | 多级孔ZSM-5可以促进脂肪烃的裂解环化和酚池的解离,提高了焦油中轻质芳烃的收率 | 直接催化热解 | [ | |
金属负载 ZSM-22 (Co、Mo) | 榆林煤 | H2/N2 | 选择性地提高了脂肪族、芳烃和酚类的相对含量,而抑制了醇类和含氮化合物的相对含量 | 热解挥发分催化热解 | [ |
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