Mar.2006J.China Univof Mining &Tech(English Edition)Vol 16 No. 1GC/MS Analysis of fractional Extraction ofFusain from Tongting Bituminous Coal in CS2QiN Zhi-hong, JIANG Chun, SUN Hao, ZONG Zhi-minJIANG Bing, WEI Xian-yongSchool of chemical Engineering and Technology, China University of Mining Technology, Xuzhou, JiangSu 221008, ChinaAbstract: Fusain from Tongting(Huaibei, Anhui Province) bituminous(FTTB) coal was fractionally extracted usingSoxhlet extractor with CS2. Then the extracts were analyzed with GC/MS Comparison of experimental data betweenFTTB coal and clarain from Tongting bituminous(CTTB)coal was carried out. The results show that the kinds of smallmolecule components detected by GC/MS of FTTB are less than those of CTTB. Long-chain alkanes exist mostly in theextracts of fusain. Macromolecular networksredominant in the FTTB coal mainly composed of inertinite in thecoal petrography. The size of micropores in the FTTB coal is relatively small, and the development of micropores isrelatively low. Thus the content of aromatic compounds with affinity for micropores is relative low in FTTB, while thecontent of long-chain alkanes with affinity for macromolecule networks is relatively high. Sub-components in exinitedetermine the distribution of long-chain alkanes extracted in the last stage. Odd-numbered carbon distribution appearsaromatic molecules are firstly packed in micropores, and exist in a free state after micropores are saturaleutinite Smallwhen resin is most in exinite, while high carbon alkane distribution appears when exinite is dominant inKey words: coal; fusain; extraction; fractional sample: CS2; GC/MSCLC number: TQ 530 TQ 531.51 Introductionhavior of CS2-soluble components and coal petroraphyRelease of extracts from coal has a close relationship with extraction time which is called the sequence of extraction The sequence was futher in2 Experimentalvestigated using Soxhlet extractor with CS,. TheFtiR analysis of Fttb CTtB and the gC/MSFTTB coal was pulverized to pass through aanalysis of cttB were reported in references [1 and200-mesh screen (particle size 74 u m)and driedin a vacuum at 80c for 12 h before use. Table 1[2]. This paper discussed the GC/MS analysis of the shows the proximate and ultimate analyses of the coalextraction procedure of FTTB to reveal the relationship of constituent, existing state, solubilization bsample. Coal petrography of it is given in Table 2Table 1 Proximate and ultimate analyses of FttBwt(%)fLatHaaf67.883.3912.0Table 2 distributionrals andI matters of fttBV(%)Telinite Collinite Vitrodetrinite Resinite andMacrinite and Selerotinite arnd cutinite and seinertodetrinitenertodetrinite5.005.46Received 01 October 2005: accepted 25 December 2005中國煤化工Project 50474066 supported by National Natural Science Foundation of China: Project B200405Corresponding author. Tel: +86-516-83883 139, E-mail adnghon@pub.xzjinfo.netCNMHG&e Technologyin Zhi-hong et alGC/MS Analysis of Fractional Extraction of Fusain from Tongting Bituminous Coal in C人從減人M人人是從人人人 ara LhLw人人L減人N人M人人46810121416182022Time(min)Time(min)Fig 1 Total ion chromatograms of extracts with GC/MS analysisThe coal sample (2 g) was extracted using Sox-2-dimethylbenzo [2, 1-b] furan, bhT, 9-fluorenolhlet extractor with CS] for about 1000 hours and frac-(Z)-9-octadeca-carbene-amide etctionally sampled at timed intervals respectively. EachTable 3 shows the number distribution ofextraction solution was filtrated through a 0.8 u m GC/MS-detectable compounds in each fractionalmembrane filter and then sampled for GC/Ms analy- sample. The detectable compounds in FTTB total aresis. Organic compounds in the sampled solution were 117, which are less than those in CTTB having 189analyzed with GC/MS(Hewlett Packard 6890/5973) species. Detectable compounds of each sample fromand identified by comparison with authentic libraryFttB are less than those from cttb also. Thesephenomena closely relate to the coal petrography. The3 Results and discussionmajority of macerals in FTTB is inertinite(52%)andvitrinite(41%), while the content of vitrinite in CttBThe samples of extracts were taken 13 timesis 93%. The hydrogen content in inertinite is theduring the extraction period. Figure I shows the totallowest. and the carbon content in it is the highestion chromatograms of each sample held for 4-40minMacromolecular networks in inertinite are the biggestIt can be seen that the number of detectable comand most abundant. The size and the extent of parallelrientation of aromatic layers are close to or evenunds existing in FTTB are less than those in CTtBmoreover, both have a similar composition. Onlexceed those of anthracite The size of microporesaromatics with 1 to 6 rings are identified. Aromatics in inertinite is the smallest These reasons jointlywith one ring are tetramethylbenzene, 1-methyl-2 result in the decrease of variety and number of solu(1-methylethyl)-benzene, 1-ethyl-2, 3-dimethyl benble compounds from FTTBzene. Aromatics with two rings are mainly biphenyl, Table3 The number of GC/MS-detectable compounds innaphthalene and its alkyl substitutes, such as methyleach fractional sampleethyl, and isopropyl substituents and so on. Aromatics with 3 rings are abundant in phenanthrene, anthracene and their 1 to 3 methylated derivatives and asmall amount of fluorene and methyl fluorene. arcmatics with 4 rings are methyl pyrene, benzanthracene and 3-methyl benzo[j]-aceanthrenementheneAromatics with 5 rings are only benzpyrene, and 54712Aromatics with 6 rings only contain benzo [ghi]perylene. Aromatics with 5 or 6 rings have no substituents. Corresponding with CTTB, long-chain alNC: the number of compoundkanes continuously distribute from C13 to C33 alkanes,and long-chain alkenes only are checked out in the 13From thesampling points. Heteroatom-containing compounds pounds the foldetected include 2-hydroxyfluorene, 1, 2-dimethyl- variety of smalYH中國煤化工 ectable comCNMHGtained. Thew oute form is theJ. China Univ of Mining Tech(English Edition)Vol 16 No. 1most abundant of all. The time interval between the noticeably in the whole course of extraction, com-I and 2 sampling is so long that the release fault pared to CTTB, but they are not uniformly distributedcan not be observed. The distribution of small moleIn eacsample Long-chain alkanes from thecules in the form of micropore- inbuilt state presents pling and 10 sampling points are the most abundantwave character as a whole. The variety of detectable of all, but low carbon alkanes in the former and highcompounds from the 7 sampling is the least, which carbon alkanes in the latter. Alkanes from the 13could be contributed to the complexity and variety of sampling points show wave distribution as a wholemicropores. Small molecules in the form of net- and wave crests are at the 1 sampling, 5 samplingwork-inbuilt state are not explosively released, which and 10 sampling points. Long-chain alkenes barelycould be caused by the characteristics of inertinite appear at the 13 sampling point, and the content ofdescribed abovelong-chain alkenes of FTTB is far less than that ofIn general, pressure to cohesion that occurred in CTTB. Naphthalene and its methylated derivativesmicropores is lower than that in macropores, which barely appear at the 1 sampling, 12 sampling andpresents wetting and cohesion in micropores initially 13 sampling explosively. The more methyl subin the course of hot-evolution of coal. In addition, the stituents exist, the more continuous naphthalenes aregravitational fields of surface molecular of organic released. Anthracene, phenanthrene and their derivamatter in the wall of pores overlap each other. These tives appear at the it to 5 samplings, 8 and 9'could explain why micropores have a greater acting samplings. Others are distributed well except forforce on hydrocarbons than macropoanthracene and phenanthrene substituted withsmall hydrocarbon molecules first pack in micropores. 1-methyl in theWith the continuous formation of hydrocarbons, they anthracene, phenanthrene and their methyl derivativesare adsorbed in macropores. Small molecules in the content are very low in the 7,11 and 13free state form related above are the small molecules samplings. These distribution characteristics indicateadsorbed in the macropores or on the surface of coal, that long-chain alkanes are predominant in smallhile small molecules in the form of micro- molecules that can be extracted with cs, and thepore- inbuilt state usually make micropores saturated. content of aromatics and constituents containingThus, the quantities of small molecules in the form of aromatics are relatively low. It is likely thatmicropore-inbuilt state can reflect the degree of de- macromolecular networks are predominant in FTTBvelopment of micropores in coal. This could well The size of micropores in the coal sample is smallcontribute to the relationship of the number of and the development extent of micropores is lowGCMS-detectable compounds given in Table 3 and Therefore, the content of aromatics and constituentsreference [2] and the development of micropores in containing aromatics with affinity for micropores isvitrinite and inertiniterather low, while the content of long-chain alkanesFigure 2 to 4 indicate the ionic mass chroma- with affinity for macro- molecular network is muchtograms of long-chain alkagalkenes have a much strongeand anthracene and phenanthrene series in the ex- interaction with macromolecular or crosslinkingtracts. They show that long-chain alkanes exist more network structures than long-chain alkanes, so theydifficult to dissolvLABL人LLM⊥LAAA⊥A山15Time(min)中國煤化工Fig 2 Ionic mass chromatograms of long-chain alkanes(a) and naphCNMHGin Zhi-hong et alGC/MS Analysis of Fractional Extraction of Fusain from Tongting Bituminous Coal in Ca great number of high-carbon and long-chainpeed of transmission to the host of solventkanes appear at the 10 sampling, which is in accordwith the characteristic of cttB. The difference between them is that long-chain alkanes dissolved atMthat moment present typical odd-numbered carbondistribution for CTTB, but for FTTB, it presentshigh-carbon distribution, which is caused by thencomposition of exinite in them. The exinite of CttBcontains resinite and bituminite, but no sporinite andcutinite, while the exinite of FTTB contains sporiniteand cutinite, but no resinite and bituminite. Resiniteis the primary factor of odd carbon distribution, yetcutinite is the precursor of paraffin( C27-C33)of highmolecular weight generated from sub-bituminouscoal to bituminous coal 6-7 High carbon alkanesUpredominance(main peaks at C27 and C31) in 10 sam-plings of FTTB may be the reason that in thehot-evolution of cutinite, homologous products imbed17181920212223242526in the macromolecular networks or crosslinking netTime(min)works. The release of long-chain alkenes of fttb isFig 3 Ionic mass chromatograms of anthracene andslower than that of CTTB. It is likely that the lowphenanthrene series in extractscontent of long-chain alkenes in Fttb affects the-12人人A減Fig 4 Ionic mass chromatograms of long-chain alkenes in extractsNaphthalene and its derivates released explo- pounds are not present in the other samplings, inely in the 12 and 13 samplings seemingly indi- cluding the I sampling, which indicates that therecate that they have a strong affinity for macromo- are no benzene series in the free state form in the coallecular network, but the truth is just impossible to sample. It further proof that small alkanes pack in thedetermine. The diameter of micropores in inertinite is holes of micropores firstly, then in the free state formthe smallest and the effect of molecular sieve restricts just after saturationthe diameter of molecules adsorbed in the microporeIt was reported that the diameter of molecules adsorbed in the micropores was 1/2.5 of the diameter of 4 Conclusionsmicropores 8. Therefore only molecules with a smalldiameter are more easily adsorbed in these small di1)The variety of small molecule componentsameter micropores. Thus benzene and naphthalendetected by GC/Ms of FTTB is less than that ofseries are easily absorbed in the micropores. In addiCTTB for the inertinite abundant in fttB. The inertion, the smaller the diameter of micropores the tonite is low hydrogen, high carbon, ample macromostronger the acting force between small moleculeslecular networks and small diameter micropores etcinside and the wall of micropores, and the more dif-etc. which result in a decrease of the variety andficult it is to dissolve these small molecules 51number of extractible compoundsThereby benzene and naphthalene series are dissolved2) Macromolecular networks are predominant inin the last stages. It can be presumed that benzene the FTTB mainly composed of inertinite. The size ofseries still exist in the 12th and 13plings. The micropores in the coal is relatively smmall. and theionic mass spectra of m/z 77 are shown in figure 4. gree of development of micropores is relatively lowe can see that total ionic peaks obtained are di- Therefore, the content of aromatics and constituentsmethylethyl benzene, methylisopropyl benzene containing aror中國煤化工 mIcropores Istetramethyl benzene and penta-methyl benzene etcrelative low inCNMHG long-chainwhich proves the above deductions. These comalkanes with af101 maululliuicuuies is relativelyJ. China Univ of Mining Tech(English Edition)Vol 16 No. 1high. So FTTB and CTTB show different characteris- pores are saturated3 Sub-components in exinite determine the disAcknowledgementtribution of long-chain alkanes extracted in the laststage. In resinite, it shows mainly odd carbon numberScience Foundation of China Grant Nos. 90410018 anddistribution; while in cutinite, it mainly shows50474066), the Research Funds for the Doctoral Program ofhigh-carbon alkanes distributionHigher Education (No. 20020290007), the Key Project of4)Small aromatic molecules first fill the micro- Chinese Ministry of Education( Grant No. 104031)pores, and then exist in a free state after the microReferences[1] Qin Z H, Wei X Y, Jiang C, et al. FTiR analysis of extracts from two bituminous coals with CS2 using extraction in batchesournal of China University of Mining Technology, 2005, 34(5): 580-583 (In Chinese)[2] Qin Z H. Study on the Solubilization Behavior of Organic Matter in Coals [Ph D dessertation]. Xuzhou: China University ofMining Technology, 2004. (In Chines[3] Xie K C. Coal Structure and Its Reactivity. Beijing: Science Press, 2002: 16-17.(In Chinese[4] Harris L A, Yust C S. Transmission electron microscope observations of porosity in coal. Fuel, 1976, 55(3): 233[5] Zhao C Y. International Symposium on Coal-derived Hydrocarbon. Beijing: Petroleum Industry Press, 2000. 158-164.(In[6] Stach E, Mackowsky M-TH, TeicHu mller M, et al. Stach's Textbook of Coal Petrology. Beijing: China Coal Industry Publishing House, 1990: 190-191. (In ChineseBrooks J D. The use of coals as indicators of the occurrence of oil and gas Austral Petrol Explor Ass J, 1970(10): 35-50Yan J M, Zhang Q Y Adsorption and Coacervation-Surface and Pore of solids. BScience Press, 1986. ( In Chinese)(Continued from page 7References[I Yin B J, Zeng H, Yand ZY. Theory and Practice of A vO Technique. Beijing: Petroleum Indstry Press, 1995. (In Chinese)[2] Zhang T E, Wen C W, Lv S Z, et al. Background for Preventing Coal and Gas from Bursting. Beijing: Coal Industry Press1990.(In Chinese)[3] Xuerive R E, Jerdater L P. Prospecting Seismology. Beijing: Petroleum Indstry Press, 1999.(In Chinese)[4] Shuey RT. A simplification of the Zoeppritz equation. Geophyics, 1985, 50(4): 609-614[5] Widess M A. How thin is a Thin Bed Geophysics, 1973, 38(6): 1176-1180[6] Ye S L. Study on singular value decomposition of matrix and its application. Site Investigation Science and Technolog996(5):41-44.( In Chinese)[7] Ye S L, Zhu J J. Application of singular value decomposition and generalized rige estimation in surveying. The ChineseJournal of Nonferrous Metals, 1998, 8(1): 160-164.(In Chinese[8] Aimoghrabi H, Lang J Layers and bright spots. GeophyicS, 1986, 51(3): 699-709中國煤化工CNMHG