陈帅, 刘明君, 周伟, 赵广播, 曹庆喜, 高继慧. 准东次烟煤在H2O2水溶液中的氧化解聚[J]. 煤炭学报, 2020, 45(2). DOI: 10.13225/j.cnki.jccs.2019.0058
引用本文: 陈帅, 刘明君, 周伟, 赵广播, 曹庆喜, 高继慧. 准东次烟煤在H2O2水溶液中的氧化解聚[J]. 煤炭学报, 2020, 45(2). DOI: 10.13225/j.cnki.jccs.2019.0058
CHEN Shuai, LIU Mingjun, ZHOU Wei, ZHAO Guangbo, CAO Qingxi, GAO Jihui. Oxidative depolymerization of Zhundong subbituminous coal in H2O2 solution[J]. Journal of China Coal Society, 2020, 45(2). DOI: 10.13225/j.cnki.jccs.2019.0058
Citation: CHEN Shuai, LIU Mingjun, ZHOU Wei, ZHAO Guangbo, CAO Qingxi, GAO Jihui. Oxidative depolymerization of Zhundong subbituminous coal in H2O2 solution[J]. Journal of China Coal Society, 2020, 45(2). DOI: 10.13225/j.cnki.jccs.2019.0058

准东次烟煤在H2O2水溶液中的氧化解聚

Oxidative depolymerization of Zhundong subbituminous coal in H2O2 solution

  • 摘要: H2O2氧化不仅可以用来研究煤的结构,也可将煤转化为高值化学品,是一种有前景的低阶煤利用方法。中国目前储量丰富的低阶煤资源是准东次烟煤,特对H2O2氧化准东次烟煤进行研究,为其利用提供基础数据。利用H2O2氧化解聚准东次烟煤,采用N2吸附仪和FTIR分析其物理化学特性,采用热重分析仪(TG)分析其燃烧特性,并采用GC/MS对氧化产物的组成进行分析。结果表明,随着温度的升高,转化率增大。当温度为80 ℃时,转化率达到45.67%。通过H2O2与准东次烟煤的反应,可破坏煤中的孔隙结构,降低比表面积和总孔容,引起煤颗粒收缩,使煤结构变得致密;可断裂煤中的桥键和C—O醚键,并促使芳香结构开环。氧化残煤中的灰分含量降低,N和S含量降低,挥发分含量增加,H/C和O/C原子比增加。和原煤相比,氧化残煤中脂肪侧链变长,脂肪支链减少,C=O含量增加,C—O含量和脂肪族氢含量减少。同时,氧化残煤较好地保持了原煤的燃烧特性。GC/MS检测到氧化产物中含有14种物质,包括2种链烷酸、2种苯羧酸、5种烃类、4种含氮或含硫物质和1种酯类。在所检测的物质中,(Z)-二十二碳-13-烯酰胺、二(6-甲基庚基)邻苯二甲酸酯和棕榈酸的含量最高。检测的含氮或含硫物质揭示准东煤中有机氮和有机硫的存在形式包括酰胺、磺酸和磺酰。

     

    Abstract: Coal oxidation by H2 O2 can serve as a method to study the coal structure,while it is also capable to convert coal to value-added chemicals,being a promising way to utilize low-rank coal resources. The Zhundong subbituminous coal is China’s current reserves of low-rank coal resources. The H2 O2 oxidation of Zhundong subbituminous coal was investigated to provide some necessary basic data for its utilization. The Zhundong subbituminous coal was oxidized with H2 O2 ,and its physicochemical properties were analyzed by N2 adsorption and FTIR. The combustion characteris- tics and the composition of the oxidation products were also analyzed by thermogravimetric analyzer ( TG) and GC /MS,respectively. Results show that as the temperature increases,the conversion rate increases,and the conversion rate reaches 45. 67% when the temperature is 80 ℃ . The pore structure in coal is destroyed,the specific surface area and total pore volume reduce that cause coal particles to shrink and make coal structure dense,the bridge bond and C—O ether bond in coal are ruptured,and the ring opening of aromatic structure is enhanced during the reaction of H2 O2 with Zhundong subbituminous coal. The ash content reduces,the N and S contents reduce,the volatile content increa- ses,and H / C and O / C atomic ratios increase in the oxidized residual coal. Compared with raw coal,the fatty side chains become longer,the fatty branch chains decrease,the content of C O increases,and the content of C—O and aliphatic hydrogen decrease in the oxidized residual coal. Meanwhile,the oxidized residual coal maintains the combus- tion characteristics of the raw coal better. 14 compounds are detected with GC / MS in the oxidation product,including 2 alkanoic acids,2 benzenecarboxylic acids,5 hydrocarbons,4 nitrogen-containing or sulfur-containing species and 1 kind of ester. Among the compounds detected,in (Z)-docosa-13-enamide,bis(6-methylheptyl) phthalate and palmitic acid are the highest. The detected nitrogen or sulfur-containing compounds reveal that the presence of organic nitrogen and organic sulfur in the Zhundong coal includes amides,sulfonic acids and sulfonyl groups.

     

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