中国典型超高硫煤有机相中分子氯存在的实验证据

EXPERIMENTAL EVIDENCE FOR NATURALLY OCCURRING MOLECULAR CHLORINE (Cl_2) IN ORGANIC PHASE OF CHINESE SUPER HIGH SULFUR COAL

运用高性能静态二次离子质谱从中国贵州六枝超高硫无烟煤有机相中观测到分子氯 (Cl2 )的团簇负离子 ,从而首次获得分子氯在原煤中存在的实验证据。结合不久前从相同原煤有机相观测到元素硫 (S8)的研究结果 ,表明易挥发性元素能够以其化学单质状态在原煤有机相中稳定存在 ;

A series of negative ions corresponding to chlorine clusters with formula of Cl 1 4 (see Figure 1) and 69 GaCl 1 4 (see Figure 2) have been first detected from organic phase of Chinese super high organic sulfur coal (S org =7 23% and S total =8 39%), with high performance time of fight secondary ion mass spectrometry (TOF SIMS) By comparing a species of sulfur cluster ions of S 1 12 (see ref 4) and 69 GaS 1 4 that has been derived from the same phase of the same coal under TOF SIMS and determined as indicators of elemental sulfur (S 8 and S 12 ) by GC/MS and MS/MS combined with chemical extractions (see ref ), the chlorine cluster ions can only be described as tracers of molecular chlorine (Cl 2) A rechecking program with sodium chloride (NaCl) in both fine powders and crystal block as test specimens has performed with TOF SIMS, but no chlorine cluster ions could be found, except for simple chlorine ion (Cl -) The program provides further suggestion of the chlorine cluster ions indicating molecular chlorine (Cl 2) that most probably exist as one of chemical states naturally in the coal, particularly in its organic phase As behaviors and principles of chlorine chemical reaction are concerned, naturally occurring molecular chlorine (Cl 2) in coal's organic phase is more reliable, while the so called 'hydrogen chlorine (HCl)' or 'organic chlorines (Cl org )' once suggested in the past, see ref [1,2,3,15,16] for instances, is relatively questionable As discussion, the author suggests that in geochemistry the formation and preservation of molecular chlorine (Cl 2) as well as elemental sulfur (S 8) in sulfur rich coal are probably due to three aspects: a) gaseous substances emitted from the deeper Earth (see ref 17 and 18) are probably contributed to the upper coal seam in nature; b) nano pores appearing in organic phase of coal (see ref 19) might encapsulate the substances and c) chemically reductive circumstance of natural coal might provides a good condition of retaining them in history of coal formation