典型高硫煤热解过程中硫、氮的变迁及其交互作用机制
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摘要
基于我国的基本国情,煤炭在可预见的未来仍将是中国的主体能源,但其大幅度开采和利用已引起优质煤资源的急剧下降,导致能源安全和环境保护的矛盾日益突出。高硫煤等非优质煤种的储量相对较高,但自身禀赋的高硫含量的特点在一定程度上限制了其开发和利用的范围。为了有效控制高硫煤利用过程中污染物的排放,并为高硫煤利用过程中硫、氮污染物的协同调控提供理论依据,本论文在前期相关研究的基础上,针对高硫煤热解过程中硫、氮的变迁及其交互作用机制进行了研究。主要包括下列几个方面的内容：
(1)选择煤阶、硫含量及硫赋存形态不同的四种高硫煤(Coal A、Coal B、Coal C和Coal D)为研究对象,采用传统的程序升温热解法结合S-XANES现代分析技术对高硫煤热解过程中硫的变迁规律进行了研究。结果表明富含有机硫的不同变质程度Coal A和Coal D中硫的存在形态完全不同,其中Coal A所含活泼二硫化物和硫化物的比例较高,在低于500℃的热解温度下容易分解从而导致煤中硫主要分布在气相中；Coal D中主要以复杂噻吩结构存在,在1000℃下仍难分解,使得煤中的硫主要滞留于半焦中。煤中氮在热解过程中主要残留于半焦中,生成的HCN和NH3所占比例较小。Coal A和Coal C中的氮分配到焦油中的比例要高于其它两种煤样,这与两种煤中弱有机结构所占的比例以及含氮官能团所处的化学环境有关。
煤中硫铁矿的分解对硫的变迁行为有着非常重要的影响。在煤热解过程中硫铁矿分解反应分两步进行：首先,随着温度的升高,硫铁矿开始分解产生FeS和活性硫；600℃之后,产生的FeS再次发生反应。煤中形态硫除部分分解、释放外,也存在着相互转化。在低于600℃下,煤中一些活泼的有机硫化物和硫铁矿硫发生分解并以气相硫的形式释放。在高于600℃下,煤焦中的形态硫主要以内部转化为主。HCN和NH3的最大释放温区较高,大约在650℃左右。其中HCN的生成主要来源于吡啶氮和吡咯氮的开环反应,而NH3的生成除了来源于季氮的分解外,还存在HCN的二次反应。
(2)使用目前典型的脱硫技术对高硫煤进行前处理,考察了不同预处理方法对煤热解过程中硫、氮释放的影响。由于煤中硫铁矿赋存状态的差异,导致了其在Coal B浮选过程中的脱除要易于Coal C。浮选所得精煤在热解过程中含硫气体的累积释放率都高于原煤,但在600℃出现的H2S和COS的释放峰几乎消失。热解过程中HCN和NH3释放规律的变化分别与吡咯氮和季氮的变化相关。HCl/HF处理消除煤中矿物质固硫作用的同时,也改善了煤样的孔结构,从而促进了含硫气体的释放。矿物质的脱除消弱了HCN向NH3(或N2等)的催化转化,使得HCN的释放量增加,NH3的释放量减小。HNO3处理后,煤中硫铁矿几乎被全部脱除,使得在600℃处H2S和COS的释放峰消失。但由于硝酸根的残留,使得HCN和NH3在整个实验温区内的释放量都有所增加。
超声溶剂萃取脱除了Coal A和Coal D中部分形态硫,其中有机硫的脱除占总硫脱除的80%左右。超声溶剂萃取主要脱除了煤中小分子相,从而改善了超分子体系的孔结构,促进了Coal D中硫铁矿分解产生的活性硫释放；但对Coal A热解过程中H2S释放的影响不大。煤中季氮结构的稳定性相对较弱,溶剂萃取过程可以脱除部分季氮,使得热解过程中NH3的释放量有所下降。经浮选、HCl/HF酸洗、HNO3酸洗和超声溶剂萃取逐级处理的Coal C中的硫有了较大程度的脱除,其总硫含量从5.0%下降到1.88%。经过逐级处理,煤的表面积、化学结构以及表面硫和氮的存在形态都发生了部分改变,有利于Coal C在热解过程中含硫气体的释放。对于含氮气体,HCN和NH3的释放量在HN03处理之前变化不大,HN03处理之后,其释放量明显增加。
(3)通过不同前处理脱硫对高硫煤热解过程中H2S和NH3释放的影响分析,同时借助于含硫、含氮模型化合物的热解实验及其机理探讨,验证了煤中硫、氮在变迁过程中存在竞争氢的相互作用,其中H2S和NH3的同时生成是竞争作用发生的前提。模型化合物快速热解实验中H2S和NH3生成竞争活性氢的结果显示,三种不同形态的含硫模型化合物对咔唑热解生成NH3的影响不同,这与含硫模型化合物在热解过程中供氢能力的大小有关。苯甲基硫醚和2-萘硫酚在热解过程中可以提供活性氢使其进攻咔唑,从而促进咔唑分解并生成NH3,相应地降低了H2S的释放。相反,二苯并噻吩的热解活性低于咔唑,在热解过程中咔唑分解产生的活性氢可以促进二苯并噻吩发生开环反应,使得H2S的释放量增加,NH3的释放量减少。
Based on the energy consumption situation of China, coal is still the main energy resource in the foreseeable future. But it has been mined and utilized in a large-scale, resulting in the shortage of high-quality coal. Most importantly, the subsequent issues of energy security and environment protection have become increasingly prominent. Low-quality coal, such high-sulfur coal, occupies a relatively high proportion in coal reserve, but the feature of high sulfur content restrains its utilization range. In order to effectively control the emission of pollutants during utilizing the high-sulfur coal, and provide the fundamental theory for the synergistic regulation of sulfur and nitrogen-containing pollutants during further utilization of high-sulfur coals, the transformation of sulfur and nitrogen and the competition for active hydrogen in the pyrolysis of high-sulfur coals have been focused. The study mainly includes the several parts as following.
(1) Four high sulfur coals (Coal A, Coal B, Coal C and Coal D) with different coal rank, sulfur content and sulfur forms were selected as the experimental samples. The essential transformation behaviors of sulfur in high sulfur coal were studied by the traditional temperature-programmed pyrolysis combining with S-XANES of modern analytical technology. The results show that there are different existing forms of sulfur in different rank Coal A and Coal D with high organic sulfur content. There are more active disulfide and sulfide in Coal A with lower coal rank, which can be decomposed and released into the gas products at below pyrolysis temperature of500℃; more complex thiophenic structure exists in the higher rank Coal D, which are difficultly decomposed even at1000℃, leading to more sulfur retain in char. During coal pyrolysis, most of nitrogen in coal retains in char, only small proportion of nitrogen transforms into HCN and NH3. The proportion of nitrogen in tar from Coal A and Coal C are higher than that of others coals, which is related to the proportion of unstable organic structure in coal matrix and the chemical surrounding of N-containing functional groups in coal.
Decomposition of pyrite in coal plays an important role in the transformation of sulfur during pyrolysis of high-sulfur coal. Two step reactions were included in the process of decomposition of pyrite. Firstly, pyrite begins to decompose into FeS and active sulfur with the increase of temperature, and then FeS also transforms into active sulfur above600℃. For the transformation behavior of sulfur, except for the decomposition and release of some sulfur forms, there exists inter-conversion among the different sulfur forms. Below600℃, some unstable organic sulfur and pyrite can decompose and release into gases products. Above600℃, inter-conversions of different sulfur forms play a dominant role on the transformation behavior of sulfur. Furthermore, the maximum release temperature region of HCN and NH3locate in the higher temperature range, around650℃. The ring cleavage reaction of pyridine and pyrrole is the main pathway for the formation of HCN during coal pyrolysis, while the formation of NH3are resulting from the decomposition of quaternary-N and the secondary reactions of HCN.
(2) The traditional pre-desulfurization processes were used to pretreat four high-sulfur coals and the effect of these processes on the release of sulfur and nitrogen during pyrolysis of high-sulfur coal were investigated. The removal degree of pyrite for Coal B is higher than that of Coal C by flotation because of the difference of existing forms of pyrite in these two coals. The accumulative yields of S-containing gaseous products from clean coals are higher than that of raw coals, but the release peaks of H2S and COS almost disappear above600℃for the clean coals.
The change in nitrogen forms on the coal's surface before and after flotation should be the main factor influencing the various release trends of HCN and NH3during coal pyrolysis. The formations of HCN and NH3are related to the proportion of pyrrolic-N and quaternary-N in coal, respectively. The fixing sulfur capacity of minerals is eliminated through HCl/HF pre-treated process, whilst the pore structure of coal is improved, which can promote the release of S-containing gases products. The removal of these minerals weakens the catalytic role on the secondary reaction of HCN transform into NH3(or N2), resulting in the increase of the release amount of HCN, and the decrease of NH3. The HNO3treatment can nearly remove all the pyrite in coal, resulting in the disappearance of the release peak of H2S and COS at600℃. Moreover, the residual of nitrate increases the release amount of HCN and NH3at the whole experimental temperature range.
Part of sulfur was removed for Coal A and Coal D by the ultrasonic solvent extraction, and the removal of organic sulfur occupies80%of the entire removed sulfur. The solvent extraction can remove some small molecular phases in the coal and improves the pore structure of coal matrix, leading to the increase of the release of active sulfur formed by the decomposition of pyrite in Coal D. However, ultrasonic solvent extraction has a little effect on the release of H2S from Coal A. The stability of quaternary-N structure is weak and it can be partly removed by this process, resulting in the decreasing the release of NH3during pyrolysis of pre-treated coals. Step-by-step pre-treatment (flotation, HCl/HF acid-washing, HNO3acid-washing and solvent extraction) can remove most of sulfur in Coal C (total sulfur content to1.88%from5.0%), whilst the surface area, chemical structure and the sulfur and nitrogen forms on the surface of Coal C are changed. This process improves the release of S-containing gases during pyrolysis of Coal C. The release of HCN and NH3are almost unchanged, but the release amount of HCN and NH3are obvious increased after HNO3treatment.
(3) By means of the release behaviors of H2S and NH3during pyrolysis of raw coal and different pretreated samples and combining with the pyrolysis results of S-and N-containing model compounds, it is convinced that there exists the competition of active hydrogen during thermal transformation of sulfur and nitrogen in coal. And the simultaneous formation of H2S and NH3in the similar temperature range is the precondition of the competition occurring during pyrolysis. The results of competing active hydrogen for H2S and NH3from rapid pyrolysis of model compounds show that the effects of three S-containing model compounds on the formation of NH3from the carbazole pyrolysis are different, which depends on the capacity of donating hydrogen from the S-containing model compounds during pyrolysis. The decomposition of benzyl-thioether and2-naphthalenethiol can provide the active hydrogen to promote the ring cleavage reaction of carbazole and increases the release of NH3, whilst decreases the release of H2S. The thermal activity of dibenzothiophene is lower than that of carbazole, so the ring cleavage reaction of dibenzothiophene can be promoted by the active hydrogen from the decomposition of carbazole during pyrolysis, resulting in the increase of the release amount of H2S and the decrease of NH3release amount.
(1)选择煤阶、硫含量及硫赋存形态不同的四种高硫煤(Coal A、Coal B、Coal C和Coal D)为研究对象,采用传统的程序升温热解法结合S-XANES现代分析技术对高硫煤热解过程中硫的变迁规律进行了研究。结果表明富含有机硫的不同变质程度Coal A和Coal D中硫的存在形态完全不同,其中Coal A所含活泼二硫化物和硫化物的比例较高,在低于500℃的热解温度下容易分解从而导致煤中硫主要分布在气相中；Coal D中主要以复杂噻吩结构存在,在1000℃下仍难分解,使得煤中的硫主要滞留于半焦中。煤中氮在热解过程中主要残留于半焦中,生成的HCN和NH3所占比例较小。Coal A和Coal C中的氮分配到焦油中的比例要高于其它两种煤样,这与两种煤中弱有机结构所占的比例以及含氮官能团所处的化学环境有关。
煤中硫铁矿的分解对硫的变迁行为有着非常重要的影响。在煤热解过程中硫铁矿分解反应分两步进行：首先,随着温度的升高,硫铁矿开始分解产生FeS和活性硫；600℃之后,产生的FeS再次发生反应。煤中形态硫除部分分解、释放外,也存在着相互转化。在低于600℃下,煤中一些活泼的有机硫化物和硫铁矿硫发生分解并以气相硫的形式释放。在高于600℃下,煤焦中的形态硫主要以内部转化为主。HCN和NH3的最大释放温区较高,大约在650℃左右。其中HCN的生成主要来源于吡啶氮和吡咯氮的开环反应,而NH3的生成除了来源于季氮的分解外,还存在HCN的二次反应。
(2)使用目前典型的脱硫技术对高硫煤进行前处理,考察了不同预处理方法对煤热解过程中硫、氮释放的影响。由于煤中硫铁矿赋存状态的差异,导致了其在Coal B浮选过程中的脱除要易于Coal C。浮选所得精煤在热解过程中含硫气体的累积释放率都高于原煤,但在600℃出现的H2S和COS的释放峰几乎消失。热解过程中HCN和NH3释放规律的变化分别与吡咯氮和季氮的变化相关。HCl/HF处理消除煤中矿物质固硫作用的同时,也改善了煤样的孔结构,从而促进了含硫气体的释放。矿物质的脱除消弱了HCN向NH3(或N2等)的催化转化,使得HCN的释放量增加,NH3的释放量减小。HNO3处理后,煤中硫铁矿几乎被全部脱除,使得在600℃处H2S和COS的释放峰消失。但由于硝酸根的残留,使得HCN和NH3在整个实验温区内的释放量都有所增加。
超声溶剂萃取脱除了Coal A和Coal D中部分形态硫,其中有机硫的脱除占总硫脱除的80%左右。超声溶剂萃取主要脱除了煤中小分子相,从而改善了超分子体系的孔结构,促进了Coal D中硫铁矿分解产生的活性硫释放；但对Coal A热解过程中H2S释放的影响不大。煤中季氮结构的稳定性相对较弱,溶剂萃取过程可以脱除部分季氮,使得热解过程中NH3的释放量有所下降。经浮选、HCl/HF酸洗、HNO3酸洗和超声溶剂萃取逐级处理的Coal C中的硫有了较大程度的脱除,其总硫含量从5.0%下降到1.88%。经过逐级处理,煤的表面积、化学结构以及表面硫和氮的存在形态都发生了部分改变,有利于Coal C在热解过程中含硫气体的释放。对于含氮气体,HCN和NH3的释放量在HN03处理之前变化不大,HN03处理之后,其释放量明显增加。
(3)通过不同前处理脱硫对高硫煤热解过程中H2S和NH3释放的影响分析,同时借助于含硫、含氮模型化合物的热解实验及其机理探讨,验证了煤中硫、氮在变迁过程中存在竞争氢的相互作用,其中H2S和NH3的同时生成是竞争作用发生的前提。模型化合物快速热解实验中H2S和NH3生成竞争活性氢的结果显示,三种不同形态的含硫模型化合物对咔唑热解生成NH3的影响不同,这与含硫模型化合物在热解过程中供氢能力的大小有关。苯甲基硫醚和2-萘硫酚在热解过程中可以提供活性氢使其进攻咔唑,从而促进咔唑分解并生成NH3,相应地降低了H2S的释放。相反,二苯并噻吩的热解活性低于咔唑,在热解过程中咔唑分解产生的活性氢可以促进二苯并噻吩发生开环反应,使得H2S的释放量增加,NH3的释放量减少。
Based on the energy consumption situation of China, coal is still the main energy resource in the foreseeable future. But it has been mined and utilized in a large-scale, resulting in the shortage of high-quality coal. Most importantly, the subsequent issues of energy security and environment protection have become increasingly prominent. Low-quality coal, such high-sulfur coal, occupies a relatively high proportion in coal reserve, but the feature of high sulfur content restrains its utilization range. In order to effectively control the emission of pollutants during utilizing the high-sulfur coal, and provide the fundamental theory for the synergistic regulation of sulfur and nitrogen-containing pollutants during further utilization of high-sulfur coals, the transformation of sulfur and nitrogen and the competition for active hydrogen in the pyrolysis of high-sulfur coals have been focused. The study mainly includes the several parts as following.
(1) Four high sulfur coals (Coal A, Coal B, Coal C and Coal D) with different coal rank, sulfur content and sulfur forms were selected as the experimental samples. The essential transformation behaviors of sulfur in high sulfur coal were studied by the traditional temperature-programmed pyrolysis combining with S-XANES of modern analytical technology. The results show that there are different existing forms of sulfur in different rank Coal A and Coal D with high organic sulfur content. There are more active disulfide and sulfide in Coal A with lower coal rank, which can be decomposed and released into the gas products at below pyrolysis temperature of500℃; more complex thiophenic structure exists in the higher rank Coal D, which are difficultly decomposed even at1000℃, leading to more sulfur retain in char. During coal pyrolysis, most of nitrogen in coal retains in char, only small proportion of nitrogen transforms into HCN and NH3. The proportion of nitrogen in tar from Coal A and Coal C are higher than that of others coals, which is related to the proportion of unstable organic structure in coal matrix and the chemical surrounding of N-containing functional groups in coal.
Decomposition of pyrite in coal plays an important role in the transformation of sulfur during pyrolysis of high-sulfur coal. Two step reactions were included in the process of decomposition of pyrite. Firstly, pyrite begins to decompose into FeS and active sulfur with the increase of temperature, and then FeS also transforms into active sulfur above600℃. For the transformation behavior of sulfur, except for the decomposition and release of some sulfur forms, there exists inter-conversion among the different sulfur forms. Below600℃, some unstable organic sulfur and pyrite can decompose and release into gases products. Above600℃, inter-conversions of different sulfur forms play a dominant role on the transformation behavior of sulfur. Furthermore, the maximum release temperature region of HCN and NH3locate in the higher temperature range, around650℃. The ring cleavage reaction of pyridine and pyrrole is the main pathway for the formation of HCN during coal pyrolysis, while the formation of NH3are resulting from the decomposition of quaternary-N and the secondary reactions of HCN.
(2) The traditional pre-desulfurization processes were used to pretreat four high-sulfur coals and the effect of these processes on the release of sulfur and nitrogen during pyrolysis of high-sulfur coal were investigated. The removal degree of pyrite for Coal B is higher than that of Coal C by flotation because of the difference of existing forms of pyrite in these two coals. The accumulative yields of S-containing gaseous products from clean coals are higher than that of raw coals, but the release peaks of H2S and COS almost disappear above600℃for the clean coals.
The change in nitrogen forms on the coal's surface before and after flotation should be the main factor influencing the various release trends of HCN and NH3during coal pyrolysis. The formations of HCN and NH3are related to the proportion of pyrrolic-N and quaternary-N in coal, respectively. The fixing sulfur capacity of minerals is eliminated through HCl/HF pre-treated process, whilst the pore structure of coal is improved, which can promote the release of S-containing gases products. The removal of these minerals weakens the catalytic role on the secondary reaction of HCN transform into NH3(or N2), resulting in the increase of the release amount of HCN, and the decrease of NH3. The HNO3treatment can nearly remove all the pyrite in coal, resulting in the disappearance of the release peak of H2S and COS at600℃. Moreover, the residual of nitrate increases the release amount of HCN and NH3at the whole experimental temperature range.
Part of sulfur was removed for Coal A and Coal D by the ultrasonic solvent extraction, and the removal of organic sulfur occupies80%of the entire removed sulfur. The solvent extraction can remove some small molecular phases in the coal and improves the pore structure of coal matrix, leading to the increase of the release of active sulfur formed by the decomposition of pyrite in Coal D. However, ultrasonic solvent extraction has a little effect on the release of H2S from Coal A. The stability of quaternary-N structure is weak and it can be partly removed by this process, resulting in the decreasing the release of NH3during pyrolysis of pre-treated coals. Step-by-step pre-treatment (flotation, HCl/HF acid-washing, HNO3acid-washing and solvent extraction) can remove most of sulfur in Coal C (total sulfur content to1.88%from5.0%), whilst the surface area, chemical structure and the sulfur and nitrogen forms on the surface of Coal C are changed. This process improves the release of S-containing gases during pyrolysis of Coal C. The release of HCN and NH3are almost unchanged, but the release amount of HCN and NH3are obvious increased after HNO3treatment.
(3) By means of the release behaviors of H2S and NH3during pyrolysis of raw coal and different pretreated samples and combining with the pyrolysis results of S-and N-containing model compounds, it is convinced that there exists the competition of active hydrogen during thermal transformation of sulfur and nitrogen in coal. And the simultaneous formation of H2S and NH3in the similar temperature range is the precondition of the competition occurring during pyrolysis. The results of competing active hydrogen for H2S and NH3from rapid pyrolysis of model compounds show that the effects of three S-containing model compounds on the formation of NH3from the carbazole pyrolysis are different, which depends on the capacity of donating hydrogen from the S-containing model compounds during pyrolysis. The decomposition of benzyl-thioether and2-naphthalenethiol can provide the active hydrogen to promote the ring cleavage reaction of carbazole and increases the release of NH3, whilst decreases the release of H2S. The thermal activity of dibenzothiophene is lower than that of carbazole, so the ring cleavage reaction of dibenzothiophene can be promoted by the active hydrogen from the decomposition of carbazole during pyrolysis, resulting in the increase of the release amount of H2S and the decrease of NH3release amount.
引文
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