Many nitrogen-containing aromatic compounds （NACs）, such as nitrobenzene （NB）, 4-nitrophenol （4-NP）, aniline （AN）, and 2,4-dinitrophenol （2,4-DNP）, are environmentally hazardous, and their removal from conta...Many nitrogen-containing aromatic compounds （NACs）, such as nitrobenzene （NB）, 4-nitrophenol （4-NP）, aniline （AN）, and 2,4-dinitrophenol （2,4-DNP）, are environmentally hazardous, and their removal from contaminated water is one of the main challenges facing wastewater treatment plants. In this study, synthetic wastewater containing NB, 4-NP, 2,4-DNP, and AN at concentrations ranging from 50 to 180 mg/L was fed into a sequencing batch reactor （SBR）. Analyses of the SBR system indicated that it simultaneously removed more than 99% of the NACs at loading rates of 0.36 kg NB/（m^3·d）, 0.3 kg 4-NP/（m^3·d）, 0.25 kg AN/（m^3·d）, and 0.1 kg 2,4-DNP/（m^3·d）. Bacterial groups of Bacteriodetes, Candidate division TM7, α-Proteobacteria, and β-Proteobacteria were dominant in the clone libraries of 16S rRNA genes retrieved from the microbial communities in the SBR system. ＂Cycle tests＂ designed to alter feeding and aeration parameters of the SBR system demonstrated that the resident microbial biome of the SBR system responded rapidly to changing conditions. Consumption of O2 was concomitant with the apparent mineralization of NACs. Aromatic ring-cleaving dioxygenase activities suggested that （1） AN and NB were degraded via catechol 2,3-dioxygenase; （2） 4-NP was degraded via 1,2,4-benzentriol 1,2-dioxygenase; and （3） 2,4-DNP was degraded via an unresolved pathway.展开更多
The contents of polycyclic aromatic sulfur compounds (PASCs) in the Kupferschiefer varied from sample to sample. Twenty PASCs were determined in the Kupferschiefer from Poland and Germany. Gold enrichment was only obs...The contents of polycyclic aromatic sulfur compounds (PASCs) in the Kupferschiefer varied from sample to sample. Twenty PASCs were determined in the Kupferschiefer from Poland and Germany. Gold enrichment was only observed in samples with higher PASC contents. At the same time, all the samples with gold enrichment originated from areas close to the redox boundary (the front section of Rote Fule) that was formed by oxidizing brines in contact with the reducing Kupferschiefer. It is proposed that the gold-bearing solutions encountered PASCs in the Kupferschiefer. PASCs could easily displace chloride ions from aurous chloride complexes to form stable gold S-chelates. Subsequent oxidation of these gold organic compounds could destroy the organic components and lead to the formation of metallic gold.展开更多
The density functional theory(DFT)with dispersion corrections was used to study the adsorption behavior of sulfur and nitrogen compounds on NiMoS phase.The calculations were performed based on a hexagonal cluster mode...The density functional theory(DFT)with dispersion corrections was used to study the adsorption behavior of sulfur and nitrogen compounds on NiMoS phase.The calculations were performed based on a hexagonal cluster model including the Mo-edge,the S-edge,and the rarely mentioned corner site.It was found that the adsorption of quinoline is stronger than that of benzothiophene at all the active sites.It indicated the origin of the inhibition effect of nitrogen compounds on HDS.And Ni atoms located around Mo-edge and corner site exhibit higher adsorption selectivity to sulfur compounds than the nitrogen ones.It means that the increase in Ni-promoting effect may weaken the inhibition effect of nitrogen compounds on HDS.展开更多
The RTS technology can produce ultra-low sulfur diesel at lower costs using available hydrogenation catalyst and device.However,with the increase of the mixing proportion of secondary processed diesel fuel in the feed...The RTS technology can produce ultra-low sulfur diesel at lower costs using available hydrogenation catalyst and device.However,with the increase of the mixing proportion of secondary processed diesel fuel in the feed,the content of nitrogen compounds and polycyclic aromatic hydrocarbons in the feed increased,leading to the acceleration of the deactivation rate of the primary catalyst and the shortening of the service cycle.In order to fully understand the reason of catalyst deactivation,the effect of mixing secondary processed diesel fuel oil on the operating stability of the catalyst in the first reactor was investigated in a medium-sized fixed-bed hydrogenation unit.The results showed that the nitrogen compounds mainly affected the initial activity of the catalyst,but had little effect on the stability of the catalyst.The PAHs had little effect on the initial activity of the catalyst,but could significantly accelerate the deactivation of the catalyst.Combined with the analysis of the reason of catalyst deactivation and the study of RTS technology,the direction of RTS technology process optimization was put forward,and the stability of catalyst was improved obviously after process optimization.展开更多
Supercritical water has been focused on as an environmentally attractive reaction media, in which organic materials can be decomposed into smaller molecules. The reaction behavior of pyrrole as a simple model compound...Supercritical water has been focused on as an environmentally attractive reaction media, in which organic materials can be decomposed into smaller molecules. The reaction behavior of pyrrole as a simple model compound of nonbasic nitrogen compounds found in petroleum residua was studied in supercritical water with a batch type reactor. The reaction was carried out at temperatures of 698-748 K and at various pressures under an argon atmosphere. The chemical species in the aqueous products were identified by GCMS （gas chromatography mass spectrometry） and quantified using GC-FID （gas chromatography flame ionization detector）. The effect of temperature and reaction time on the conversion process of pyrrole is presented. Under supercritical water conditions, pyrrole underwent successful decomposition in water into its derived compounds. The conversion of pyrrole could approach 81.12 wt% at 723 K and 40 MPa within 240 min of reaction time. The decomposition process was accelerated with the existence of water at the same temperature. Ultimate analysis of solid products was also conducted using a CHN analyzer. The process investigated in this study may form the basis for an efficient method of nitrogen compound decomposition in future.展开更多
Removal of air pollutants, such as nitrogen and sulphur containing compounds from a model oil (dodecane) was studied. An ionic liquid (1-ethyl-3-methylimidazolium chloride [C2mim] [Cl]) was used as an extractant. Liqu...Removal of air pollutants, such as nitrogen and sulphur containing compounds from a model oil (dodecane) was studied. An ionic liquid (1-ethyl-3-methylimidazolium chloride [C2mim] [Cl]) was used as an extractant. Liquid-liquid extraction by using 1-ethyl-3-methylimidazolium chloride [C2mim] [Cl] was found to be a very promising method for the removal of N- and S-compounds. This was evaluated by using a model oil (dodecane) with indole as a neutral nitrogen compound and pyridine as a basic nitrogen compound. Dibenzothiophene (DBT) was used as a sulphur compound. An extraction capacity of up to 90 wt% was achieved for the model oil containing pyridine, while only 76 wt% of indole in the oil was extracted. The extraction capacity of a model sulphur compound DBT was found to be up to 99 wt%. Regeneration of the spent ionic liquid was carried out with toluene back-extraction. A 1:1 toluene-to-IL wt ratio was performed at room temperature. It was observed that, for the spent ionic liquid containing DBT as a model compound more than 85 wt% (corresponding 3852 mg/kg) could be removed from the oil. After the second regeneration cycle, 86 wt% of the DBT was recovered from the ionic liquid to toluene. In the case of indole as the nitrogen containing species, more than 99 wt%, (corresponding to 2993 mg/kg) of the original indole was transferred from the model oil to the ionic liquid. After the first-regeneration cycle of the spent ionic liquid, 54 wt% of the indole–in-IL was transferred to toluene. Thus, both extractions of nitrogen and sulphur model compounds were successfully carried out from model oil and the back-extraction of these compounds from the ionic liquids to toluene demonstrated the proved the concept of the regeneration point of view.展开更多
基金Project supported by the Pilot Project of Knowledge Innovation Program of Chinese Academy of Sciences (No. KZCX2-YW-G-009)the National Natural Science Foundation of China (No. 20577067, 30230010).
文摘Many nitrogen-containing aromatic compounds （NACs）, such as nitrobenzene （NB）, 4-nitrophenol （4-NP）, aniline （AN）, and 2,4-dinitrophenol （2,4-DNP）, are environmentally hazardous, and their removal from contaminated water is one of the main challenges facing wastewater treatment plants. In this study, synthetic wastewater containing NB, 4-NP, 2,4-DNP, and AN at concentrations ranging from 50 to 180 mg/L was fed into a sequencing batch reactor （SBR）. Analyses of the SBR system indicated that it simultaneously removed more than 99% of the NACs at loading rates of 0.36 kg NB/（m^3·d）, 0.3 kg 4-NP/（m^3·d）, 0.25 kg AN/（m^3·d）, and 0.1 kg 2,4-DNP/（m^3·d）. Bacterial groups of Bacteriodetes, Candidate division TM7, α-Proteobacteria, and β-Proteobacteria were dominant in the clone libraries of 16S rRNA genes retrieved from the microbial communities in the SBR system. ＂Cycle tests＂ designed to alter feeding and aeration parameters of the SBR system demonstrated that the resident microbial biome of the SBR system responded rapidly to changing conditions. Consumption of O2 was concomitant with the apparent mineralization of NACs. Aromatic ring-cleaving dioxygenase activities suggested that （1） AN and NB were degraded via catechol 2,3-dioxygenase; （2） 4-NP was degraded via 1,2,4-benzentriol 1,2-dioxygenase; and （3） 2,4-DNP was degraded via an unresolved pathway.
文摘The contents of polycyclic aromatic sulfur compounds (PASCs) in the Kupferschiefer varied from sample to sample. Twenty PASCs were determined in the Kupferschiefer from Poland and Germany. Gold enrichment was only observed in samples with higher PASC contents. At the same time, all the samples with gold enrichment originated from areas close to the redox boundary (the front section of Rote Fule) that was formed by oxidizing brines in contact with the reducing Kupferschiefer. It is proposed that the gold-bearing solutions encountered PASCs in the Kupferschiefer. PASCs could easily displace chloride ions from aurous chloride complexes to form stable gold S-chelates. Subsequent oxidation of these gold organic compounds could destroy the organic components and lead to the formation of metallic gold.
基金We gratefully acknowledge the support from the National Key Research and Development Plan(Grant No.2017YFB0306603)China Petrochemical Corporation funding(Sinopec Group,No.117006)on this work.
文摘The density functional theory(DFT)with dispersion corrections was used to study the adsorption behavior of sulfur and nitrogen compounds on NiMoS phase.The calculations were performed based on a hexagonal cluster model including the Mo-edge,the S-edge,and the rarely mentioned corner site.It was found that the adsorption of quinoline is stronger than that of benzothiophene at all the active sites.It indicated the origin of the inhibition effect of nitrogen compounds on HDS.And Ni atoms located around Mo-edge and corner site exhibit higher adsorption selectivity to sulfur compounds than the nitrogen ones.It means that the increase in Ni-promoting effect may weaken the inhibition effect of nitrogen compounds on HDS.
基金This work was financially supported by the Technology Development Project of SINOPEC(121025)All of the staff in our laboratory had provided a lot of support in the analysis of oil samples and catalyst characterization.
文摘The RTS technology can produce ultra-low sulfur diesel at lower costs using available hydrogenation catalyst and device.However,with the increase of the mixing proportion of secondary processed diesel fuel in the feed,the content of nitrogen compounds and polycyclic aromatic hydrocarbons in the feed increased,leading to the acceleration of the deactivation rate of the primary catalyst and the shortening of the service cycle.In order to fully understand the reason of catalyst deactivation,the effect of mixing secondary processed diesel fuel oil on the operating stability of the catalyst in the first reactor was investigated in a medium-sized fixed-bed hydrogenation unit.The results showed that the nitrogen compounds mainly affected the initial activity of the catalyst,but had little effect on the stability of the catalyst.The PAHs had little effect on the initial activity of the catalyst,but could significantly accelerate the deactivation of the catalyst.Combined with the analysis of the reason of catalyst deactivation and the study of RTS technology,the direction of RTS technology process optimization was put forward,and the stability of catalyst was improved obviously after process optimization.
文摘Supercritical water has been focused on as an environmentally attractive reaction media, in which organic materials can be decomposed into smaller molecules. The reaction behavior of pyrrole as a simple model compound of nonbasic nitrogen compounds found in petroleum residua was studied in supercritical water with a batch type reactor. The reaction was carried out at temperatures of 698-748 K and at various pressures under an argon atmosphere. The chemical species in the aqueous products were identified by GCMS （gas chromatography mass spectrometry） and quantified using GC-FID （gas chromatography flame ionization detector）. The effect of temperature and reaction time on the conversion process of pyrrole is presented. Under supercritical water conditions, pyrrole underwent successful decomposition in water into its derived compounds. The conversion of pyrrole could approach 81.12 wt% at 723 K and 40 MPa within 240 min of reaction time. The decomposition process was accelerated with the existence of water at the same temperature. Ultimate analysis of solid products was also conducted using a CHN analyzer. The process investigated in this study may form the basis for an efficient method of nitrogen compound decomposition in future.
文摘Removal of air pollutants, such as nitrogen and sulphur containing compounds from a model oil (dodecane) was studied. An ionic liquid (1-ethyl-3-methylimidazolium chloride [C2mim] [Cl]) was used as an extractant. Liquid-liquid extraction by using 1-ethyl-3-methylimidazolium chloride [C2mim] [Cl] was found to be a very promising method for the removal of N- and S-compounds. This was evaluated by using a model oil (dodecane) with indole as a neutral nitrogen compound and pyridine as a basic nitrogen compound. Dibenzothiophene (DBT) was used as a sulphur compound. An extraction capacity of up to 90 wt% was achieved for the model oil containing pyridine, while only 76 wt% of indole in the oil was extracted. The extraction capacity of a model sulphur compound DBT was found to be up to 99 wt%. Regeneration of the spent ionic liquid was carried out with toluene back-extraction. A 1:1 toluene-to-IL wt ratio was performed at room temperature. It was observed that, for the spent ionic liquid containing DBT as a model compound more than 85 wt% (corresponding 3852 mg/kg) could be removed from the oil. After the second regeneration cycle, 86 wt% of the DBT was recovered from the ionic liquid to toluene. In the case of indole as the nitrogen containing species, more than 99 wt%, (corresponding to 2993 mg/kg) of the original indole was transferred from the model oil to the ionic liquid. After the first-regeneration cycle of the spent ionic liquid, 54 wt% of the indole–in-IL was transferred to toluene. Thus, both extractions of nitrogen and sulphur model compounds were successfully carried out from model oil and the back-extraction of these compounds from the ionic liquids to toluene demonstrated the proved the concept of the regeneration point of view.
