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Regularities of chlorine concentration and form location in Russion coals
Coal Science J . A . Pajares and J . M . D . T a s c 6 n (Editors) 1995 E l s e v i e r Science B . V .
R e g u l a r i t i e s of c h l o r i n e c o n c e n t r a t i o n Russion coals Iu.N. Zharov
1705
and form location in
Fossil Fuels Institute, 29 Leninsky prospekt Moscow, GSP-1, 117910, Russia Chlorine has been studed mainly in Russian coals from Pechersky, Kuznetsky, Lensky, Sachalinsky and some other basins and fields of the North-East and Primorje. Chlorine is investigated in coals by prospecting works together with other elements in saueple dublicates from pores and mining opening, In quality specifications of solid fuel supplied to consumers, the obligatory determination of element content is not get prided. The attention of specialists to chlorine is stimulated because of unpleosand properties of galoid and its compounds, what takes place by widly coal use, Burning and technological t r e a t m e n t of solid fuel is accompanied by i n s t r u m e n t s corrosion, o u t p u t decrease and products composition change and increase of toxic component emission. Chemical analyse of chlorine in coals and brown coals (GOST 9326-77) is the basic valuation method of its content, corresponding to the international standard JSO 587-1974, Supersensitive (up to 0.001%) neutron-activation method of chlorine determination is not widely used today by mass determination. in spite of biogene accumulation ability, the high modility of chlorine doesnt allow it to accumulate selectively at different stages of peat-coal forming process. In the rank peat - brow coal - coal chlorine is even dishibuted, isnt concentrating noticeable in organic of mineral matters. Geological age and m a t t e r s composition of coal controls chlorine accumulation weakly. J t s average content at objects, here special determinations have been conducted, is 0.05-0.1%, what corresponds to element clark in brow coals and coals. The minimal content of chlorine is 9 more often to meet zn highly transformed coals and anthracites (Table.l). The high chlorine contens, exceeding 0.4-0.6% are founded in salty coals, refined szmul~aneously " '* " of water soluble n a t r i u m and potassium. However in Russia fields of salty coals has not been discovered. Today relate high 1 ~-" accumu,a~ions are found in coals of Kansko-Achinsk, Sachalinsky, Arkagalinsky and Bikinsky basius {1,2). Investigated coals relate in accordance with geochemical value of saltness K / N a - 0.3-0.6 to weakly salty category.
1706 Maximal salt accumulation takes place at local areas of some mine seams and deep coal horizones, refined of highly mineralized waters (>10 g/l). Table 1 Chlorine content in coals f r o m Russion basins and fields (% for dry coal basis) Basin, Field Pechorsky Kuznetsky Kansko-Achinsky Lensky Partizansky Razdolnensky Ugiovsky Pav!ovskoe Arkagaiinsky Sachalinsky Anadirsky
Coal Age P C.3-P_ J]-2 J.3-K1 K K P P K2 N P2
Characteristic Mark Ash, % ~-3I~ 8-30 ~-T 20-25 B 9-12 B-~ 10-13 3K-T 26-39 ~ 30-34 B 18-38 B 10-25 )i 10-25 B-~ 15-20 B 15-20
Chlorine content Min Max Average 0.031 0.07 0.04 0.005 0.079 0.038 0.04 0.07 0.05 0.03 0.1 0.045 0.028 0.094 0.068 0.05 0.081 0.065 0.044 0.082 0.056 0.043 0.06 0.05 0.02 0.57 0.21 0.019 0.717 0.045 0.11 0.33 0.18
Early it was d e m o n s t r a t e d , Heat in coals of different saltness jhe content of n a t r i u m and potassium s u b m i t a normal low of distibution (3). The statistic analyse of experimental date shows t h a t chlorine distribution with all so connected from saltness degree of coal, but corresponds to lognormal distribution. In opinion of L . A . J a n o c h k i n a {1966) and Gr.Eskenazy (1969) the l o g a r y t h m i c typ of d i s t r i b u t i o n function d e m o n s t r a t e s a s u f u r r o r i t y of one m i g r a t i o n method and final fixation form of chemical element in n a t u r e . The !ognormal chlorine distribution in coals in this case cau be explained t h r o u g h its m i g r a t i o n in composition of w a t e r soluble haloid compounds with r e s u l t i n g deposition of NaC1 and partial KC1, MgC12, CaC12 or t h r o u g h chlorine moving in forms binding with organic and mineral maffer. Chlorine moving in peat and coal fields as a w a t e r soluble haloid f o r m resulted its binding with alkali elements. Its stated, t h a t function of correction of C1-Na content in coals corresponds to !ineai. In weakly salty and not salty coals chlorine q u a n t i t y doesut correlate with gross content of n a t r i u m and potassium. Chlorine, n a t r i u m and potassium concentrations, specialy in not salty coals, are independent values and its accumulation occured on d i f f e r t wags. The last s t a t m e u t corresponds to resalts of chlorine valuation in coals of U k r a i n a (4). In tab. 2 the results of chlorine, n a t r i u m and p o t a s s i u m are e x t r a c t i o n f r o m weakly salty and not salty brow coals of A r k a g a l i n s k y basin up to 8% of clorine, 52-59% of n a t r i u m and 8-33% of potassium are t r a n s f o r m a t e d into w a t e r extract, So it can be supposed, t h a t in the investigated coals chlorine is mainly in following forms: 1) as mineral form in cmposition of w a t e r soluble galit and silvin, 2) as mineral and (or) organic
1707 form in composition of not water soiube chlorine oxides and organic complex. In severae coals chlorine content forms are different (6,7). It seems t h a t coals with chlorine as a gaiit form. predominate. Table 2 Chlorine, n a t r i u m and potassium extraction from coals Denomination Content in dry coal, % Chlorine Natrium Potassium General W a t e r General W a t e r General W a t e r soluble soluble soluble 1Not salty brown 0.05 0.05 0.07 0.05 0.07 0.02 coal of "Buchta 0.02 0.02 0.15 0.09 0.07 0.02 Ugoinaja" field 0.02 0.02 0.08 0.0i 0.0i 0.0i 2Not salty and 0.37 0.37 0.37 0.36 0.02 0.02 weakly salty coal 0.40 0.40 0.29 0.29 0.02 0.02 of Anadirsky field 0.05 0.05 0.10 0.10 0.02 0.02 3Vc'eakiy salty coal 0.13 0.03 0.51 0.30 0.06 u.oz of Arkaga!insky 0.14 0.00 0.52 0.29 0.! 7 0.02 basin 0.04 0.00 0.59 0.31 0.37 0.03 REFERENCES 1. V.R.Kler, E.P.Dik, Iu.N.Zharov. Studing of salty coals. Prospecting and protection of depth, N2, 1987, p.30-34 M.Mmg~leeva, T.M.Thcherbakova, V K.Prjanishnikov. To question about saltness of ash of Berezovsky seam coal. Coal, N7, 1984, p.53-55 3. V.R.Kler, h . N . Z h a r o v , J.J.Slivinskaja. About potassium and n a t r i u m distribution in coals. Reports of Academy of science of the SU, v.298, N4, p.936-939 4. A.V.Ivanova, L.B.Zaitceva. Genesis problem of salty coals of the West Donbass. Geological Institute of Ukraina. P r e p r i n t 82-17, 1982, p.53 5. V.R.K!er, E.P.Dik. Studing of mineral components of power su!! coals. Prospecting and protection of depths, N4, 1981, p.32-35 6. Ja.E.Yudovitch, M.P.Ketric, A.V.Merz. A d m i x t h e r e elements in fossil coals "Science" Leningrad, 1985, p . 1 3 4 - i 4 0 7. L.Ya.Kizilshtein, Yu.A.Fedorov, A.G.Lutochin, V.V.Galtchikov. N a t r i u m in Donbass coals. Prospecting and protection of depths, N2, 1984, p.33-36
R e g u l a r i t i e s of c h l o r i n e c o n c e n t r a t i o n Russion coals Iu.N. Zharov
1705
and form location in
Fossil Fuels Institute, 29 Leninsky prospekt Moscow, GSP-1, 117910, Russia Chlorine has been studed mainly in Russian coals from Pechersky, Kuznetsky, Lensky, Sachalinsky and some other basins and fields of the North-East and Primorje. Chlorine is investigated in coals by prospecting works together with other elements in saueple dublicates from pores and mining opening, In quality specifications of solid fuel supplied to consumers, the obligatory determination of element content is not get prided. The attention of specialists to chlorine is stimulated because of unpleosand properties of galoid and its compounds, what takes place by widly coal use, Burning and technological t r e a t m e n t of solid fuel is accompanied by i n s t r u m e n t s corrosion, o u t p u t decrease and products composition change and increase of toxic component emission. Chemical analyse of chlorine in coals and brown coals (GOST 9326-77) is the basic valuation method of its content, corresponding to the international standard JSO 587-1974, Supersensitive (up to 0.001%) neutron-activation method of chlorine determination is not widely used today by mass determination. in spite of biogene accumulation ability, the high modility of chlorine doesnt allow it to accumulate selectively at different stages of peat-coal forming process. In the rank peat - brow coal - coal chlorine is even dishibuted, isnt concentrating noticeable in organic of mineral matters. Geological age and m a t t e r s composition of coal controls chlorine accumulation weakly. J t s average content at objects, here special determinations have been conducted, is 0.05-0.1%, what corresponds to element clark in brow coals and coals. The minimal content of chlorine is 9 more often to meet zn highly transformed coals and anthracites (Table.l). The high chlorine contens, exceeding 0.4-0.6% are founded in salty coals, refined szmul~aneously " '* " of water soluble n a t r i u m and potassium. However in Russia fields of salty coals has not been discovered. Today relate high 1 ~-" accumu,a~ions are found in coals of Kansko-Achinsk, Sachalinsky, Arkagalinsky and Bikinsky basius {1,2). Investigated coals relate in accordance with geochemical value of saltness K / N a - 0.3-0.6 to weakly salty category.
1706 Maximal salt accumulation takes place at local areas of some mine seams and deep coal horizones, refined of highly mineralized waters (>10 g/l). Table 1 Chlorine content in coals f r o m Russion basins and fields (% for dry coal basis) Basin, Field Pechorsky Kuznetsky Kansko-Achinsky Lensky Partizansky Razdolnensky Ugiovsky Pav!ovskoe Arkagaiinsky Sachalinsky Anadirsky
Coal Age P C.3-P_ J]-2 J.3-K1 K K P P K2 N P2
Characteristic Mark Ash, % ~-3I~ 8-30 ~-T 20-25 B 9-12 B-~ 10-13 3K-T 26-39 ~ 30-34 B 18-38 B 10-25 )i 10-25 B-~ 15-20 B 15-20
Chlorine content Min Max Average 0.031 0.07 0.04 0.005 0.079 0.038 0.04 0.07 0.05 0.03 0.1 0.045 0.028 0.094 0.068 0.05 0.081 0.065 0.044 0.082 0.056 0.043 0.06 0.05 0.02 0.57 0.21 0.019 0.717 0.045 0.11 0.33 0.18
Early it was d e m o n s t r a t e d , Heat in coals of different saltness jhe content of n a t r i u m and potassium s u b m i t a normal low of distibution (3). The statistic analyse of experimental date shows t h a t chlorine distribution with all so connected from saltness degree of coal, but corresponds to lognormal distribution. In opinion of L . A . J a n o c h k i n a {1966) and Gr.Eskenazy (1969) the l o g a r y t h m i c typ of d i s t r i b u t i o n function d e m o n s t r a t e s a s u f u r r o r i t y of one m i g r a t i o n method and final fixation form of chemical element in n a t u r e . The !ognormal chlorine distribution in coals in this case cau be explained t h r o u g h its m i g r a t i o n in composition of w a t e r soluble haloid compounds with r e s u l t i n g deposition of NaC1 and partial KC1, MgC12, CaC12 or t h r o u g h chlorine moving in forms binding with organic and mineral maffer. Chlorine moving in peat and coal fields as a w a t e r soluble haloid f o r m resulted its binding with alkali elements. Its stated, t h a t function of correction of C1-Na content in coals corresponds to !ineai. In weakly salty and not salty coals chlorine q u a n t i t y doesut correlate with gross content of n a t r i u m and potassium. Chlorine, n a t r i u m and potassium concentrations, specialy in not salty coals, are independent values and its accumulation occured on d i f f e r t wags. The last s t a t m e u t corresponds to resalts of chlorine valuation in coals of U k r a i n a (4). In tab. 2 the results of chlorine, n a t r i u m and p o t a s s i u m are e x t r a c t i o n f r o m weakly salty and not salty brow coals of A r k a g a l i n s k y basin up to 8% of clorine, 52-59% of n a t r i u m and 8-33% of potassium are t r a n s f o r m a t e d into w a t e r extract, So it can be supposed, t h a t in the investigated coals chlorine is mainly in following forms: 1) as mineral form in cmposition of w a t e r soluble galit and silvin, 2) as mineral and (or) organic
1707 form in composition of not water soiube chlorine oxides and organic complex. In severae coals chlorine content forms are different (6,7). It seems t h a t coals with chlorine as a gaiit form. predominate. Table 2 Chlorine, n a t r i u m and potassium extraction from coals Denomination Content in dry coal, % Chlorine Natrium Potassium General W a t e r General W a t e r General W a t e r soluble soluble soluble 1Not salty brown 0.05 0.05 0.07 0.05 0.07 0.02 coal of "Buchta 0.02 0.02 0.15 0.09 0.07 0.02 Ugoinaja" field 0.02 0.02 0.08 0.0i 0.0i 0.0i 2Not salty and 0.37 0.37 0.37 0.36 0.02 0.02 weakly salty coal 0.40 0.40 0.29 0.29 0.02 0.02 of Anadirsky field 0.05 0.05 0.10 0.10 0.02 0.02 3Vc'eakiy salty coal 0.13 0.03 0.51 0.30 0.06 u.oz of Arkaga!insky 0.14 0.00 0.52 0.29 0.! 7 0.02 basin 0.04 0.00 0.59 0.31 0.37 0.03 REFERENCES 1. V.R.Kler, E.P.Dik, Iu.N.Zharov. Studing of salty coals. Prospecting and protection of depth, N2, 1987, p.30-34 M.Mmg~leeva, T.M.Thcherbakova, V K.Prjanishnikov. To question about saltness of ash of Berezovsky seam coal. Coal, N7, 1984, p.53-55 3. V.R.Kler, h . N . Z h a r o v , J.J.Slivinskaja. About potassium and n a t r i u m distribution in coals. Reports of Academy of science of the SU, v.298, N4, p.936-939 4. A.V.Ivanova, L.B.Zaitceva. Genesis problem of salty coals of the West Donbass. Geological Institute of Ukraina. P r e p r i n t 82-17, 1982, p.53 5. V.R.K!er, E.P.Dik. Studing of mineral components of power su!! coals. Prospecting and protection of depths, N4, 1981, p.32-35 6. Ja.E.Yudovitch, M.P.Ketric, A.V.Merz. A d m i x t h e r e elements in fossil coals "Science" Leningrad, 1985, p . 1 3 4 - i 4 0 7. L.Ya.Kizilshtein, Yu.A.Fedorov, A.G.Lutochin, V.V.Galtchikov. N a t r i u m in Donbass coals. Prospecting and protection of depths, N2, 1984, p.33-36