CHFEN 5503

Memorandum
To: Dr. Terry Ring
From: Mr. Stan Holbrook
Date: October 13, 2005
Sb!ect: "naly#i# o$ %atral &a# an' an (nkno)n (#ing &a# *+romatogra,+y
On Se,t. 22 - 2., 2005, a #erie# o$ analy#e# )ere ,er$orme' on t+e H/ 5010 Serie# 22
&a# *+romatogra,+. T+e re#lting 'ata )a# #e' in an attem,t to 'etermine t+e
concentration# o$ +y'rocarbon# in natral ga# an' nkno)n 31. T+e#e )ere $on' to
#ome le4el o$ accracy, t+og+ t+ere are rea#on# to belie4e t+at t+e calclation met+o'#
#e' )ere $la)e'.
Theory
*+romatogra,+y i# a ,roce're in )+ic+ attraction# bet)een a mobile ,+a#e an' a
#tationary ,+a#e are e5,loite' to ,er$orm a #e,aration an' can be #e' $or large #cale
#e,aration# or #mall #cale analy#i#. 6ac+ com,on' i# retaine' $or a 'i$$erent amont o$
time accor'ing to it# attraction to t+e #tationary ,+a#e. T+ere$ore, a ,olar com,on'
interacting )it+ a non7,olar #tationary ,+a#e )ill +a4e a #+ort retention time )+ile a non7
,olar com,on' )ill +a4e a larger retention time.
&a# c+romatogra,+y i# a ga# ,+a#e #e,aration #ing t+e ,rinci,le# o$ c+romatogra,+y.
T+e #tationary ,+a#e i# #ally #ome ty,e o$ ,oly#ilo5ane )it+ 'i$$erent #b#titent
gro,# a''e' to ac+ie4e t+e 'e#ire' ,olarity. S,ecie# are #e,arate' accor'ing to t+eir
#i8e an' t+eir a'#or,tion on t+e #tationary ,+a#e. T+ere$ore, )+en a mi5tre o$ #traig+t7
c+aine' +y'rocarbon# i# analy8e' by ga# c+romatogra,+y t+e #,ecie# )it+ le## carbon#
elte $ir#t.
T+e 'etector #e' $or t+e#e e5,eriment# )a# a T+ermal *on'cti4ity Detector 9T*D:.
T+i# 'etector $nction# by mea#ring t+e t+ermal con'cti4ity o$ t+e elting ga#
com,are' to t+at o$ a ,re #am,le o$ carrier ga# 9He:. "# t+e con'cti4ity c+ange#, a
,eak i# gi4en a# a rea'ot.
Results
&* rea'ot# )ere obtaine' $or natral ga#, met+ane, et+ane, ,ro,ane, btane an' an
nkno)n #ing t+e H/ 5010 Serie# 22 &a# *+romatogra,+, ( o$ ( 2n4entory 31003;0.
De to a ,roblematic #e,tm, t+ere i# an air im,rity in eac+ o$ t+e mea#rement#,
#+o)ing , bet)een 0.20 an' 0.30 on t+e c+romatogra,+#. 2n natral ga# 9Figre# 57;:,
it #+o)# , a# a little +m, ,iggybacke' on t+e met+ane ,eak. On t+e ot+er
c+romatogra,+# 9Figre# 17<,.:, it #+o)# , a# t+e $ir#t ,eak. 2n a''ition to error
a##ociate' )it+ air entering t+e #y#tem, #ome o$ t+e c+romatogra,+# #+o) a 4ale )+ere
no #,ecie# elte'. T+i# i# $rom 'ri$t, an' t+o#e occrrence# are marke' accor'ingly.
Since t+e retention time o$ a #,ecie# i# t+e #ame regar'le## o$ t+e ot+er #,ecie# in t+e
mi5tre, t+e ,eak# on t+e natral ga# c+romatogra,+# a# )ell a# t+at o$ t+e nkno)n can
be i'enti$ie'. Figre# 17< are t+e c+romatogra,+# o$ ,re +y'rocarbon# )+o#e retention
time# )ere #e' to label t+e ,eak# on t+e natral ga# 9Figre# 57;: an' t+e nkno)n
9Figre .:.
Figre 1. &a# c+romatogra,+ $or a ,re #am,le o$ met+ane
Figre 2. &a# c+romatogra,+ $or a ,re #am,le o$ et+ane
Met+ane
"ir
6t+ane
"ir
Figre 3. &a# c+romatogra,+ $or a ,re #am,le o$ ,ro,ane
Figre <. &a# c+romatogra,+ $or a ,re #am,le o$ btane
Figre 5. &a# c+romatogra,+ o$ a #am,le o$ natral ga#
/ro,ane
"ir
=tane
"ir Dri$t
Met+ane
6t+ane /ro,ane
=tane He5ane
/entane
"ir im,rity an'
*O2
Dri$t
Figre ;. &a# c+romatogra,+ o$ a #econ' #am,le o$ natral ga#
Figre .. &a# c+romatogra,+ o$ a #am,le o$ nkno)n 31
=y t+i# met+o', t+e #,ecie# in t+e nkno)n are 'etermine'. T+e concentration# o$ t+e
#,ecie# are #ome)+at more com,licate' to 'etermine. T+ere are t)o #im,le )ay# t+at
)ol' bot+ #eem to be able to 'etermine t+e concentration#: com,aring t+e area# n'er
t+e ,eak# 9taking t+e total area n'er t+e ,eak# to be 100>:, an' com,aring t+e 4ale#
$or t+e area n'er t+e ,eak o$ kno)n #am,le# to t+o#e o$ t+e nkno)n.
"ccor'ing to t+e latter met+o', t+e 4olme ,ercent o$ met+ane an' et+ane in natral ga#
are 110> an' ;.;5>, re#,ecti4ely, )+ile t+e combine' ,ercent# o$ t+e t+ree com,onent#
o$ t+e nkno)n e?al 130>. T+ere$ore, t+i# met+o' #eem# to ca#e ,+y#ically
im,o##ible re#lt#. T+i# col' be 'e to a nmber o$ rea#on#, one o$ )+ic+ )ill be
treate' +ere.
@+en t+e #am,le )a# taken, t+e #yringe )a# $ille' $rom a ,re##ri8e' 4e##el at room
tem,eratre. Since t+e ,lnger 'i' not ,#+ in or ot, it i# a##me' t+at t+e ga# )a# at
atmo#,+eric ,re##re. (,on in!ection, t+e ga# )a# $orce' into a +eate' c+amber t+ereby
/ro,ane
"ir
Dri$t
6t+ane =tane
Met+ane
6t+ane
/ro,ane
/entane
He5ane
"ir im,rity an'
*O2
Dri$t
increa#ing t+e ,re##re in t+at c+amber bot+ by a''ition o$ material a# )ell a# t+e +eating
an' e5,an#ion o$ t+e entering ga#. "# t+e ga# entere' t+e colmn an' elte' ot, t+e
,re##re in t+e #y#tem #lo)ly 'ecrea#e'. T+ere$ore, t+e ,artial ,re##re o$ t+e $ir#t
eltent i# +ig+er t+an t+at o$ t+e #econ' 9a##ming #imilar amont#:. "# t+e ,re##re in
t+e colmn 'ecrea#e#, t+e concentration o$ any gi4en com,on' #eem# to 'ecrea#e. "l#o,
t+e ,re##re in t+e colmn at any gi4en time in eac+ analy#i# )ill 4ary.
"# $or t+e $ormer ca#e, t+e 4olme ,ercent# $or t+e com,on'# in natral ga# are $airly
accrate 9Table 1:. *om,aring t+e 4ale# to t+o#e ,ro4i'e' by Ae#tar &a#, t+e error in
met+aneB%2B*O2 concentration i# only ;..>, mc+ clo#er to reality t+an t+e re#lt# $rom
t+e latter met+o'.
Table 1 Natural Gas Composition Data from Questar Gas and Experimental Data.
Component Vol%, Questar
Vol%, GC,
Method 1 % error
Vol%, GC,
Method 2 % error
Methane/N2/CO2 !.2 11" 1#.$ %%." #.#$"
Ethane !.&$# #.#' '2." $.% $%.2!'
(ropane "."2 2.$' 2"' 2.2 1!!
)utane ".&1$ "."& ".' ".' '$.$
*ea+ier *Cs ".11' 1.' 12"!
"ccor'ing to t+e more accrate met+o', t+e nkno)n )a# $on' to +a4e t+e $ollo)ing
concentration#:
Table 2. ,elati+e Con-entrations of .pe-ies in /n0no1n 1
Species Vol%
Ethane 22."
(ropane $!.#
)utane &&.!
T+e 'etector 9T*D: #e' $or t+e colmn, +o)e4er, may ca#e ,roblem# )it+ t+i# #econ'
met+o'. T+e t+ermal con'cti4ity 4arie# accor'ing to t+e com,on'. Since a T*D only
mea#re# t+ermal con'cti4ity, it 'oe# not actally calclate t+e amont o$ #b#tance
,a##ing t+rog+, only t+e c+ange in t+ermal con'cti4ity. "# t+e lengt+ o$ t+e c+ain
increa#e#, t+e t+ermal con'cti4ity 'ecrea#e# 9Table ".1:. T+at )ol' mean t+at t+e
concentration o$ et+ane i# +ig+er t+an t+at calclate' #ince t+e 'e4iation in con'cti4ity
i# #malle#t $or et+ane, gi4ing a #maller ,eak t+an an e?i4alent amont o$ btane )ol'.
One $alt in bot+ t+e#e met+o'# i# in inert im,ritie#. =eca#e t+e #e,tm leake',
nkno)n ?antitie# o$ air )ere allo)e' to enter t+e #y#tem a# ,re4io#ly mentione'.
"ny inert #,ecie# 9*O2, %2, He, etc: in t+e natral ga# an' t+e nkno)n )ol' +a4e
been inter,rete' a# entering air an' neglecte' in t+e#e mea#rement#. T+ere$ore, t+e
4olme ,ercent# #+o)n in Table 2 are gi4en a# i$ t+ere )ere no inert #,ecie# in t+e
mi5tre, an' t+eir e$$ect# on t+e ,ercent# m#t be taken into accont by #ome ot+er
met+o' 9i.e. FT2R:.
&a# c+romatogra,+y ,ro4e' to be a 4ery e$$icient met+o' o$ #e,aration, t+og+ le##
e$$ecti4e a# a ?ick analy#i# tool. 2t i# a##me' t+at a #tan'ar' met+o' col' be ,ro'ce'
in or'er to analy8e t+e com,o#ition o$ mi5tre#, bt $or ?ick analy#i# #c+ a# t+i#,
re#lt# are inconcl#i4e.
",,en'i5 ". Table an' &* Ot,t Data
Table 2.1 Thermal Condu-ti+it3 of Gases
1
Species k (mW/m*!
Ethane 1%."
(ropane 1'.2
)utane 1&.#
*elium 1!2.#
&* Ot,t Data:
Sample Name = Methane 1
2n#trment C 5010 22 "c?i#ition /ort C D/3
Hea'ing 1 C
Hea'ing 2 C
Ra) File %ame C *:D*/DataD&* St'ent DataD501022 T*D DataD&ro, Tito 1722705
=.0035.R"@ Date Taken 9en': C 1B22B2005 3:<2:<1 /M
Met+o' File %ame C *:D*/S,iritD%atral &a# Met+o' .705D%at&a#=.met Met+o'
Eer#ion C 2
*alibration File %ame C *alibration Eer#ion C 0
/eak 3 Ret. Time %ame "mont "mt >"rea "rea > Ty,e @i't+
1 0.3; 0.00 %B" <53;11 100.000 == 0.05
Total "rea C <53;10.1 Total Heig+t C 125325.1 Total "mont C 0
Sample Name = Ethane 1
2n#trment C 5010 22 "c?i#ition /ort C D/3
Hea'ing 1 C
Hea'ing 2 C
Ra) File %ame C *:D*/DataD&* St'ent DataD501022 T*D DataD&ro, Tito 1722705
=.003;.R"@ Date Taken 9en': C 1B22B2005 3:<1:01 /M
Met+o' File %ame C *:D*/S,iritD%atral &a# Met+o' .705D%at&a#=.met Met+o'
Eer#ion C 2
*alibration File %ame C *alibration Eer#ion C 0
/eak 3 Ret. Time %ame "mont "mt >"rea "rea > Ty,e @i't+
1 0.20 0.00 %B" 00;;0 11..0; == 0.05
2 1..1 0.00 %B" ;;351. 00.21< == 0.10
Total "rea C .5225..< Total Heig+t C .5;25.02 Total "mont C 0
Sample Name = Propane 1
1
+tt,:BB))).airli?i'e.comBenBb#ine##B,ro'ct#Bga#e#Bga#'ataBin'e5.a#,
2n#trment C 5010 22 "c?i#ition /ort C D/3
Hea'ing 1 C
Hea'ing 2 C
Ra) File %ame C *:D*/DataD&* St'ent DataD501022 T*D DataD&ro, Tito 1722705
=.003..R"@ Date Taken 9en': C 1B22B2005 3:51:3. /M
Met+o' File %ame C *:D*/S,iritD%atral &a# Met+o' .705D%at&a#=.met Met+o'
Eer#ion C 2
*alibration File %ame C *alibration Eer#ion C 0
/eak 3 Ret. Time %ame "mont "mt >"rea "rea > Ty,e @i't+
1 0.2. 0.00 %B" 21;10< 31.50. == 0.05
2 5.10 0.00 %B" <5<;25 ;0.<13 == 0.20
Total "rea C .51520.5 Total Heig+t C 11;2<1.5 Total "mont C 0
Sample Name = Butane 1
2n#trment C 5010 22 "c?i#ition /ort C D/3
Hea'ing 1 C
Hea'ing 2 C
Ra) File %ame C *:D*/DataD&* St'ent DataD501022 T*D DataD&ro, Tito 1722705
=.0031.R"@ Date Taken 9en': C 1B22B2005 <:2;:15 /M
Met+o' File %ame C *:D*/S,iritD%atral &a# Met+o' .705D%at&a#=.met Met+o'
Eer#ion C 2
Met+o' De#cri,tion C %atral ga# e5am,le 7 c+annel = Met+o' Date C
.B20B2005 .:<3:0; /M
*alibration File %ame C *alibration Eer#ion C 0
2nternalB65ternal C F%o 'ataG *alibration Date C F%o 'ataG
Rn Time C 11.3.125 Data Sam,ling Rate C 5.00325.
"mont 2n!ecte' C 0.05 Diltion Factor C 1
Sam,le @eig+t C 1 2nt St' "mont C 1
/eak @i't+ C 0.2 /eak T+re#+ol' C 0
O,erator C Manal 2ntegration C not manally integrate'
/eak 3 Ret. Time %ame "mont "mt >"rea "rea > Ty,e @i't+
1 0.2; 0.00 %B" 122<2 0.103 =E 0.0;
2 2.02 0.00 %B" 21.51< 21.15. E= 5.0<
3 1... 0.00 %B" 10<5510 ...1<0 == 0.<.
Total "rea C 13553<; Total Heig+t C 30;<;.0< Total "mont C 0
Sample Name = Nat !as 1
2n#trment C 5010 22 "c?i#ition /ort C D/3
Hea'ing 1 C
Hea'ing 2 C
Ra) File %ame C *:D*/DataD&* St'ent DataD501022 T*D DataD&ro, Tito 1722705
=.003<.R"@ Date Taken 9en': C 1B22B2005 3:3<:10 /M
Met+o' File %ame C *:D*/S,iritD%atral &a# Met+o' .705D%at&a#=.met Met+o'
Eer#ion C 2
*alibration File %ame C *alibration Eer#ion C 0
/eak 3 Ret. Time %ame "mont "mt >"rea "rea > Ty,e @i't+
1 0.3; 0.00 %B" <11250 ;;.000 S== 0.05
2 1.03 0.00 %B" <<12. 5.112 T=E 0.10
3 2.35 0.00 %B" 1.101; 23.11< TEE 2.;1
< ;.30 0.00 %B" 1250. 1.;.; TE= 0.21
5 1.0; 0.00 %B" 2001 0.30. == 0.30
; 10.01 0.00 %B" 2.00 0.3.2 == 0.31
. 11.31 0.00 %B" 5.5. 0...1 == 0.55
Total "rea C .<;<13.0 Total Heig+t C 122211.1 Total "mont C 0
Sample Name = Nat !as "
2n#trment C 5010 22 "c?i#ition /ort C D/3
Hea'ing 1 C
Hea'ing 2 C
Ra) File %ame C *:D*/DataD&* St'ent DataD501022 T*D DataD&ro, Tito 1722705
=.00<0.R"@ Date Taken 9en': C 1B22B2005 <:<1:02 /M
Met+o' File %ame C *:D*/S,iritD%atral &a# Met+o' .705D%at&a#=.met Met+o'
Eer#ion C 2
*alibration File %ame C *alibration Eer#ion C 0
/eak 3 Ret. Time %ame "mont "mt >"rea "rea > Ty,e @i't+
1 0.3; 0.00 %B" <.1510 ;1.<0< S== 0.05
2 1.01 0.00 %B" 3;125 5.23< T=E 0.10
3 2.03 0.00 %B" 13001. 20.112 TEE 3.10
< ;.3. 0.00 %B" 3003< <.351 TE= 0.22
5 10..0 0.00 %B" 15.5 0.220 == 0.2.
; 11.21 0.00 %B" <0.0 0.511 == 0.51
Total "rea C ;1022..1 Total Heig+t C 120113.1 Total "mont C 0
Sample Name = #n$no%n 1
2n#trment C 5010 22 "c?i#ition /ort C D/3
Hea'ing 1 C
Hea'ing 2 C
Ra) File %ame C *:D*/DataD&* St'ent DataD501022 T*D DataD&ro, Tito 172.7
05.00;..R"@ Date Taken 9en': C 1B2.B2005 3:21:01 /M
Met+o' File %ame C *:D*/S,iritD%atral &a# Met+o' .705D%at&a#=.met Met+o'
Eer#ion C 2
*alibration File %ame C *alibration Eer#ion C 0
/eak 3 Ret. Time %ame "mont "mt >"rea "rea > Ty,e @i't+
1 0.2< 0.00 %B" 2<330; 10.0<; == 0.0<
2 1..3 0.00 %B" 1<;0.1 10.031 =E 0.11
3 5.31 0.00 %B" 3313;5 25.1;2 EE 0.1.
< 0.0. 0.00 %B" 2.0110 20.033 EE 1.3;
5 0.00 0.00 %B" 3<1.02 25.120 E= 0.23
Total "rea C 13<0.21 Total Heig+t C 1533.;.. Total "mont C 0