13C NMR Spectroscopy: A key contributor for development of the molecular structure of coal and other kerogens

This presentation goes over: A brief history of kerogen formation, coal macerals, development of molecular structures and modeling, oil shales, and the role played by combustion science.

13C NMR Spectroscopy: A Key Contributor for Development of the Molecular Structure of Coal and Other Kerogens Recipients of the ACS Storch Award in Fuel Chemistry Recipients with whom I either collaborated or was a joint author of a paper • $ • • # " " " • • $ $ " # " & & # # # ( ( # # ) $ % # " & & # # # ( ( # # ) $ % # $ ) " & # ' & & " ! & # # ' # & ! "# ! ! & ! # ! ' & ' # ( #' # & ' ! & # & # " ' " # & & & #& #& ' " $ " " )' ()' & $ " " " (%* " % $ $ % $ $ ! ! $ % Rock Eval Pyrolysis One of the most commonly used techniques is called Rock Eval Pyrolysis, which helps us identify the type and maturity of kerogen. # # ' • # • # • , # # • ! " # # # ( " ( # # $ # # ! 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( " - / * +.* ' $ 363* 8:,:8* 2:95+ Catenation Models 1° Catenation C4n+2H 20+4 ' xb 1 3 = 2 - c ():)::) CXX)) 0 .8 0.7 ocoo9 c9Y Circular Catenation C6n2H6n . ,J6 , D --------- -....... ---~ '#: ,.: I ,' ~oo 'O 0 ,' @©@ 0.2 D oo 0 000 I~ 0. 1 0.0 0 10 20 30 40 Carbons per Cluster M=4.15, C0=19.57 C - Co b = _ _2__....m"""-- x., 0.4 I o@ z 0.5 0.3 xb =1- -JC I - tanh • , " i 0 .6 x ' b 1 + tanh C - Co + __2_m_ xb" 50 80 THE ARGONNE PREMIUM COALS (LVB) Pocahontas Upper Freeport (MVB) Stockton (HVB) Pittsburgh #8 (HVB) Illinois #6 (HVB) Blind Canyon (HVB) (SB) Wyodak (L) Zap II 320 I I I I I I I I II 220 I I I I I I I I I' 120 I I I I I I I I PPM from TMS II 20 I I I I I I I I II -80 I I I I I a: w 60 z m t- 50 ocn - ..J ::> 40 Ic(o :!: - 30 I- u. "" "" - - c ... ... ,, - ... c ID ns ns 0 N > c .!!! 0 ' > .i::: ns 0 ns :i: () c .i::: GI :J en ,, .¥. c en Q) c 0 ... 0 z 12 m a: 10 .... 0 .... Ill Ill .¥. Q. GI GI :J 0 u.. .Cl Ill en en u .-:: 40 0. Cll ns c 0 .i::: c ns 20 0 0~ 0 Aromatic C :J 0 ns :::E 0 0. Bridg ehead Arom ati c-Alkyl AROMATIC STRUCTURES .¥. u :J en z m a: < 30 0 8 0 6 < I- 20 ..J 4 0 1- 2 u. o IL 0 A romatic C-H u Q. Q. =! 0 60 0 Q. ..J c( 0 < a: 10 c( 80 I- m 0 Beulah-Zap Wyodak Blind Canvon Illinois #6 Pittsburah #8 Stockton Upper Freeport Pocahontas Buck Mountain ..J c( 0 20 0 a: < ocn a:Z < 0 100 0 Ca,r bonyl C Aromatic C-0 Aliphatic C-0 OXYGEN STRUCTURES (fl. 10 o-+--~~ Aliph CH2, CH,C Aliph Methyl ALIPHATIC STRUCTURES Selected Average Cluster Paramaters 8 • 7 Coordination No. 12] Bridges and Loops ~ Cluster MW x 1/ 100 6 5 4 3 2 1 0 Q. ca N 0 > == - - 0 m .c ca CD co c 0 ±: 0. :::::> ..:.: () 0 (J) Coal t: 0 Q. Cl) Cl) ... LL :::::> (") () 0 0. .; :I Jtt () ~ m 60 - .c Cl Qi 50 • 3: • •• .& .& '- ca :l u a> 40 • 0 ==c ca (.) a> • • 20 "' 10 60 .& • • 30 .c :E .& Argonne SNL ACE RC AFR 65 70 75 80 • 85 % Carbon (daf) In parent coal 90 95 1or Sample Lattice Calculation b. 20% of bridge• broken, finite a. 90% of bridges broken, multl- f ragmenta outlined cluster finite fragments are outlined Monomers 30 Dimers 8 Trimers 4 Tetramers 0 Pentamers 1 Hexamers 1 Heptamers 3 • • -Z• I ••• ·::ir • • •• I .. • • • • • • - • • •• c. 45% of bridges broken, showing only finite fragments d. 45% of bridges broken, showing only Infinite matrix __ 1 , \ 0.8 • Typical pattern for mass release (tar, gas)and char formation in a coal pyrolysis experiment. u CD u: (I) Cl) \ ~' o.e ·; : 0 ~ •••••••••• Cher Ter G11 ~\ c 0 o -- ~-..Q__ ---v--...Q_ 0.4 CD 0 ~ 0 0 A- ·········n··-········-C·· .0. ---~---·· •••• 0.2 ~ ,.... .. 0 • Effect of coordination number on fraction of intact bridges (p) and the release of volatile matter (tar). 10 0 20 30 40 &O Time (ms) 1.a TarYi1ld n . P far various coardinatian a.a numbn a.& F(p) "' a.i a.2 a a a.z a.1 p a.& a.a 1.a Zap o --- \ 0 .8 • Modeling of mass release data in a lignite coal. 0 0 .6 -0--~" -----0-.._ __ CD ..... LL Cl) Cl) CD 0.4 ::? • Note the changes in dynamic variables as labile bridges break,char bonds form, and gas1 and gas2 evolve. Cher Ter A ············· Gu "°- c ·.;:. (.) o Ii.········· ....a ............ . ··~· ··· · 0.2 A·········· .··""····· oJ:-.:::-~-~---~..-.-.....,......................~-.-r-i~-r-r-r-r-r....-.-..-....,...,...~ 0.8 - - - - -- - - -- - - - - - . . , - - Bridget ·••••••••· Cher ................... Side Ch1ln1 - - 6111 - ............. ... ·- Gn2 ------- ,,.-·- ·-,..:;::;==""-·- ·- ·- ·- ·- · ..-/'' . 0. 0 ...J_..,_~_,.......o!~r-r-r~'T'""T-i,...,....,....,....,.--,.....,.....,._,.,...........r-r"""T"""T....,...........,-,--, 0 10 20 30 40 Time (ms) 60 60 70 CROSS LINKING IN CHARS (1250K) 5.0 ,....._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ___ 4.5. 4.0. en ~ 2.0~ r -ccc CD 1.5 1.0. ' • • @t • ILLINOIS NO. 6 1111 ZAP • 111 ••n•• POCOHONTAS o.s0.0 ~--------...---....----...-----f 0 100 200 300 RESIDENCE TIME (ms) COMPARISON CF NMR AND SWELLING DATA ZAP • The coordination number is a key factor in determining a number of properties such as swelling of coals during thermal processes. 1.2 1.2 ~ NVSR (1·X) ....0 ... NMR INDEX 1.0 -a:>< I U) z> ~ \ 0.8 0.6 HMR INDEX = M. - Mr M..-Mo ! b! c 0.6 a: ~ 0.4 ~ 0.0 200 0.2 400 600 100 1000 0.0 1200 TEMPERATURE (K) PITISBURGH NO. 8 1.4 - -- 1.2 ... D.,.,Q ..... .. •'•' '•' "· ~ ••••O•• NVSR (1·X) NMR INDEX 1.4 1.2 1.0 >< w 0.8 0.8 ~ 0.6 0.6 ~ 0.4 D.4 D.2 D.2 >< 1.0 a: > z c I • Pittsburgh #8 swells as bridges break and structural mobility increases. ~ z •• • 0.4 >< w 0.8 • 0.2 • The lignite, Zap, does not swell but undergoes further x-linking due to loss of carbonyl functional groups that promote additional x-linking. 1.0 £C U) D.O 200 z 400 100 100 1000 TEMPERATURE (K) D.D 1200 # # " # ! Green River Oil Shale Green River oil shale interbedded with gray layers of volcanic tuff from the Mahogany Zone in the Piceance Basin, Colorado. This speicmen in on display at the museum of the Geological Survey of Japan. Source: Geology and Resources of Some World Oil-Shale Deposits, U.S. Department of the Interior, U.S. Geological Survey, Scientific Investigations Report 2005-5294 (Green River) Greenriver Kerogen N-15 200 MHz Char Fresh 300 200 100 0 -100 -200 PPM -300 -400 -500 -600 $ $ ")(! %) &#' &$$ Kerogen Samples C-13 CPJ\11..AS 200 After HF Wash 100 0 PPM - 1 00 % $%' ! ! % " & ! %' " ! ' " " + • !#"%" % ) / 0 • ! !"! - . " - ' " ! ! " ) & " " % 4 !! ! / (). , ! # , %!# 1 0 . " &) - ! , ! !, , 1 ! " ) /" , , !! !! "0 . & % !" ! " ! ") & !" % "% . & % !" ! !" % "% ! ! " ! 4335 • ( ! ( "! ! ") " # . " # ! • %" ' !" 34 % !" # " ! " 3 " ! 374 ' &" - ) + !" ' - ' ! 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