Transcript Title goes here

The Genesis of
Hydrocarbons
& the Origins of
Petroleum
J. F. Kenney
Russian Academy of Sciences Joint Institute of Physics of the Earth
Gas Resources Corporation
The Evolution of Multicomponent Systems at
High Pressures: VI. The Thermodynamic
Stability of the Hydrogen-Carbon System: The
Genesis of Hydrocarbons and the Origin of
Petroleum.
J. F. Kenney, ([email protected])
Vladimir A. Kutcherov
Nikolai A. Bendeliani, Vladimir A. Alekseev
Proc. Natl. Acad. Sci. U.S.A. 99(17):1097610981.
http://www.GasResources.net
Dedication:
In the first instance, this article is
dedicated to the memory of Nikolai
Alexandrovich Kudryavtsev, who first
enunciated, in 1951(1), what has
become the modern Russian-Ukrainian
theory of abyssal, abiotic petroleum
origins. After Kudryavtsev, all the rest
followed.
This article is dedicated generally
to the many geologists, geochemists,
geophysicists, and petroleum engineers
of the former U.S.S.R. who, during the
past half century, developed modern
petroleum science. By doing so, they
raised their country from being, in
1946, a relatively petroleum-poor one,
to the greatest petroleum producing
and exporting nation in the world.
This article is dedicated specifically to the late
Academician Emmanuil Bogdanovich Chekaliuk, the
greatest statistical thermodynamicist ever to have
turned his formidable intellect to the problem of
petroleum genesis. In the Summer of 1976, during
the depths of the cold war and at immeasurable
hazard, Academician Chekaliuk chose to respond,
across a gulf of political hostility, to an unsolicited
letter from an unknown American chief executive
officer of a petroleum company headquartered in
Houston, Texas. Thenafter and for almost fifteen
years, Academician Chekaliuk was my teacher, my
collaborator, and my friend. [JFK]
0. Overview:
1. No more amnesia,connected with the
constraints of thermodynamics and “fossil”
fuels.
2. No more reticence,when confronting
same, (refer to article).
I. The constraints of
nd
the 2 law:
dQ  A  d  0
c , r ,
A
    i, 
i ,  ,

i,
dQ  A  d  0
c , r ,
A
    i, 
i ,  ,

i,
dSi

dt
dSi 
dX k
F

0
k k dt
F
J
 k k
k
 0
II. The thermodynamic
energy spectrum of
the H-C system, and
the H-C-O system.
kcal/mole
potentials of the
elemental components of the H-C
system, at STP:
Carbon - graphite &
diamond
Hydrogen - gas, H2.
1.0
Chemical potential, i ,
The chemical
0.5
Chemical potentials
of elemental carbon
Diamond
 = 0.685 kcal
0.0
Graphite
 = 0.00 kcal
-0.5
-1.0
graphite
diamond
1
Carbon number
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
Dodecane
(kcal/mole)
Chemical potentials
of n-Alkanes @ STP
30
Chemical potential, i,
The chemical
potentials of
the n-alkane
series of the
H-C system
at STP, from
CH4,
methane,
through
C20H42,
dodecane.
20
10
Diamond
0
n-alkanes
diamond
graphite
Graphite
-10
0
2
4
6
8 10 12 14 16 18 20
Carbon number
chemical potential,
, Kcal / mole
The chemical
potentials of all
the straight-chain
hydrocarbon
components of
the H-C system at
STP: n-alkanes,
n-alkenes, and
n-alkynes.
60
40
20
0
Methane -CH4
Ethane -C2H6 Ethene- C2H4
Ethyne - C2H2
Propane
Propene
Propyne
Butane
Butene
Butyne
Pentane
Pentene
Pentyne
Hexane
Hexene
Hexyne
Heptane
Heptene
Heptyne
Octane
Octene
Octyne
Nonane
Nonene
Nonyne
Decane
Decene
Decyne
C11H24
C11H21
C11H20
C12H26
C12H23
C12H22
C13H28
C13H25
C13H24
C14H30
C14H27
C14H26
C15H32
C15H29
C15H28
C16H34
C16H
C16H30
C17H36
C17H33
C17H32
C18H38
C18H35
C18H34
C19H40
C19H37
C19H36
Dodecane Dodecene
Dodecyne
80
Straight-chain
Hydrocarbons
alkynes
alkenes
alkanes
0
2
4
6
8 10 12 14 16 18 20
Carbon number
Straight-chain & cyclic
Hydrocarbons
, (Kcal / mole)
80
chemical potential,
The chemical
potentials of the
straight-chain
and cyclic hydrocarbons:
n-alkanes, n-alkenes, n-alkynes, cyclohexanes, cyclopentanes, and
alkylbenzenes,
at STP.
n-Alkynes
60
alkylbenzines
40
n-Alkenes
cyclopentanes
20
alkynes
alkylbenzenes
alkenes
cyclopentanes
cyclohexanes
alkanes
cycloHexanes
0
n-Alkanes
0
2
4
6
8
10
12
14
Carbon number
16
18
20
Naturally occurring
straight-chain & cyclic
hydrocarbons
, (Kcal / mole)
60
chemical potential,
The chemical
potentials of the
naturally occurring components of the HC system at
STP: n-alkanes,
n-alkenes,
cyclohexanes,
cyclopentanes,
and alkylbenzenes.
alkylbenzines
40
n-Alkenes
cyclopentanes
20
alkylbenzenes
alkenes
cyclopentanes
cyclohexanes
alkanes
cycloHexanes
0
n-Alkanes
0
2
4
6
8
10
12
14
Carbon number
16
18
20
Carbon number
, (Kcal / mole)
0
chemical potential,
Chemical
potentials of the
H-C system, at
STP, together
with representative compounds involving single and
multiple states
of oxidation,
(OH): alcohols
and carbohydrates.
2
4
6
8
alkylbenzines
10 12 14 16 18 20
50
0
-50
-100
cycloHexanes
n-Alkenes cycloPentanes
n-Alkanes
n-Alcohols
alkylbenzenes
n-alkenes
cyclopentanes
cyclohexanes
n-alkanes
alcohols
carbohydrates
-150
-200
-250
-300
Carbohydrates
-350
-400
Straight-chain & cyclic
hydrocarbons, alcohols
& carbohydrates
(1.)
The H-C system which constitutes natural
petroleum is a metastable one. At low pressures, all
heavier hydrocarbon molecules are unstable with respect to
methane and the stoichiometric quantity of hydrogen. All
heavier hydrocarbon molecules are only kinetically stable
against decomposition into methane and hydrogen, - similarly
as is diamond into graphite.
(2.)
Methane, or natural gas, does not polymerize into
heavy hydrocarbon molecules at low pressures, at any
temperature. Contrarily, increasing temperature at low
pressures must increase the rate of decomposition of heavier
hydrocarbons.
(3.)
Because the chemical potentials of all biotic
molecules lie far below that of methane, no hydrocarbon
molecule heavier than methane will evolve
spontaneously from any biotic molecule, or combination
of such.
An additional complication:
No benefit is gained from the
predictions of the Le Chatelier Braun rules:
1
5
CH 4  C6 H14  H 2
6
6
Increasing pressure does not drive methane to
transform into n-hexane and hydrogen.
Increasing temperature, at low pressures, will increase
the decomposition of hexane into methane and carbon.
A further complication:
The relative covolumes
inhibit hydrocarbon genesis:
V

 CH 4 
5 
1
V  C6 H14  H 2 
6 
6

 17.292 cm
SPHCT
3
SPHCT
 20.790 cm
Both the pressure and Gibbs potential depend
upon a third-order singularity in the reduced
density: ~ 1/(1-V*/V)3.
3
III. Determination of
the chemical
potentials.

i
F
F I
G J
Hn K o t

i

V ,T , n j i
The theoretical formalism:
ref
vdW
Q=Q Q
The formalism uses a factored partition function
with a reference system.
The reference system used is Scaled Particle
Theory [SPT] for mixtures of arbitrary convex, hardbody fluids fluids, which represents an exact
statistical mechanical solution.
The mean-field formalism developed for the
Simplified Perturbed Hard Chain Theory [SPHCT]
formalism is used to account for the attractive, van
der Waals component of the inter-particle potential.
Application of the formalism
of the factored partition
function:

p

p
i

  
F

IG
IG
i
F
ref
p
hc ref
hc
i
F
vdW
p
vdW
i
vdW



Statistical mechanical
analysis:
The exact SPT equation
of state for a mixture of
hard-body particles of
Boublík is used for the
reference system :
p
ref
1 



rs

   
 
2


    1     1   


2
2 

qs 1  2   5r s 


  

3
2

3  1   
 
 
p  p
IG

hc Boublik
in which
r    xi Ri , q    xi Ri2 ,
i
   xiVi ,
i
i
s    xi Si ,
    xiVi  
i
i





 2
1    ui ui 
Ri 
ri  

 d d


4      
0
0
 2

  ri  ri 
Si    u i  

 d d
   

0
0
 2
1     ri  ri 
Vi    ri  

 d d
3      
0
0













The following compositional
variables are defined:




  xi Ri   xi Si 
i
i






3   xiVi 
 i

and


2
  xi Ri 

  i
2


  xi Ri 
 i















The pressure and Gibbs free
enthalpy of the reference system:
p
ref
 c   c 2  c 3 
2
3
  1  1

3
1   


and


  ni i3  
 I  J  K 2 
ref
  
 G  N   xi ln 
  c3 ln 1    
3
 1   

 V 
 i







in which
c1  3  1,
c2  3   1  2,
I
 2c1  c3
J
 
K 
1
 3c1  3c2  5c3 
2
1
 3c1  3c2  3c3 
6
c3  1    6  5 
   6  1  1
 

1
  21  7   4 

2
1
  3  1  1
2









The van der Waals components
of pressure and chemical potential, from SPHCT:
vdW
vdW
p ,
p
vdW

vdW
U
|
b
g
c
h
|V
F
I
1
|
  k TcZ G
lnb
1  Y /  g

J
c1   / bY ghK |W
H
N k BT
cZm
 
V
1   / Y
B
m
CH4 
thane and the H-C system are robustly stable
against genesis of
alkane compounds.
At 10kbar, methane is
most stable against the
genesis of heavier H-C
compounds.
At approximately
40kbar, the stability of
the system inverts, and
methane becomes
unstable relative to
alkanes and hydrogen.
G(1/6C6H14 + 5/6H2)
Gibbs free enthalpy, kJ
1/nCnH2n+1 + (n-1)/nH2
At low pressures, me-
G(1/10C10H22 + 9/10H2)
200
G(1/4C4H10 + 3/4H2)
G(1/2C2H6 + 1/2H2)
100
G(CH4)
0
-100
-200
1
10
100
1000 10000 100000
pressure,
bar
Gibbs free enthalpy, kJ
Gibbs free
enthalpy of
methane &
n-alkane +
hydrogen
at transition
of genesis.
75
70
65
60
55
50
45
40
G(1/10C10H22 + 9/10H2)
35
G(1/4C4H10 + 3/4H2)
G(1/6C6H14 + 5/6H2)
G(1/2C2H6 + 1/2H2)
30
25
25000
G(CH4)
30000
35000
pressure,
bar
40000
IV. Experimental
investigations:
The spontaneous highpressure genesis of hydrocarbons. Reagents:
FeO, CaCO3, H2O.
The reagents were placed into
a high-pressure cell, brought to
pressures up to 50 kbar, and
2000K. Pressure was maintained
while temperature was reduced
rapidly to ambient.
The volatile products present
in the cell were analysed by gas
chromatograph.
Cumulative n-alkane abundance
Experimental
observation
of highpressure
genesis of
hydrocarbons:
1.0x10
4
CH4
C2 H6
C3 H8
C4H10
8.0x10
3
6.0x10
3
4.0x10
2.0x10
1.2x10
5
1.0x10
5
8.0x10
4
6.0x10
4
4.0x10
4
2.0x10
4
C5H12
C6H14
p = 40 kbar
3
3
0.0
0.0
600
800
1000
1200
Temperature, C
IV. Significance of the
theoretical &
experimental
results:
The pressures required for
the spontaneous genesis of
hydrocarbons determines
the depth for such.
250
temperature
200
2000
150
1500
100
1000
pressure
50
500
0
0
0
100 200 300 400 500 600 700
depth,
km
kbar
Temperature, K
2500
pressure,
Average
lapse rates
of pressure
and
temperature
with depth
of the
Earth.
3000
“Every ten or fifteen years since the
late 1800’s, ‘experts’ have predicted that oil reserves would last only
ten more years. These experts have
predicted nine out of the last zero
oil-reserve exhaustions.”
C. Maurice and C. Smithson, Doomsday
Mythology: 10,000 Years of Economic Crisis,
Hoover Institution Press, Stanford, 1984.
“Five generations of
imbecility are enough.”
(  ) Justice Oliver Wendell
Holmes
Jr.,Buck vs. Bell, (1927), 274 U.S., 200, 47 S.
CT. 584. (writing for the majority).
“No more B.S.”
J. F. Kenney