Petrophysics

Chapter 2

Instructor: Xiuyu Wang

School of Petroleum Engineering

China University of Petroleum-Beijing
 Chapter 2: Physical properties of
natural gas under high pressure

 2.1 The Apparent Molecular Weight and Density of

Natural Gas

 2.2 The Equation of State（状态方程） for Natural

Gas and the Law of Corresponding State（对比状态
原理）

 2.3 The Physical Properties of Natural Gas at High

Pressure

 2.4 Water Vapor Content of Natural Gas and the

Gas Hydrate（天然气水合物）
2.1 The Apparent Molecular
Weight and Density of
Natural Gas
气体的分子量和密度
 Composition of natural gas

（1）mole fraction （2）volume fraction

ni
yi  N （2－1） i 
Vi

n
N （2－2）
i V i
i 1 i 1

ni——mole number of ith Vi——volume of ith component

N
——total volume of gas
component  i
V
i 1
N

 n ——total mole number of gas

i 1
i

N——number of components
 Composition of natural gas

（3）mass fraction
wi
Gi  N

w
i 1
i
（2－3）

Wi——mass of ith component

N

w
i 1
i ——total mass of gas

Convert the mass fraction to mole fraction, using:

Gi / M i
yi  N （2－4）
G /M
i 1
i i

Example 2-1, pg.26

 Molecular weight of natural gas

 Since natural gas is a mixture, the concept

of apparent molecular(视分子量) weight is
introduced：

N
M   ( yi M i ) （2－5）
i 1

yi——mole fraction of the ith component

Mi ——molecular weight of the ith component

Example 2-2, pg.27

Density and relative density of natural gas

 Density of natural gas is the ratio of its mass

to its volume. Unit: g／cm3 , kg／m3
g  m / v （2－5）

PM
 According to EOS：  g  ZRT

 Relative density：  g   g / a

 g  M / 29
2.2 The Equation of State（状态方程） for
Natural Gas and the Law of Corresponding
State（对比状态原理）
 EOS(状态方程) for ideal gas

 What is ideal gas?

(1)The volume occupied by the molecules is
insignificant
(2)There are no attractive or repulsive forces
between the molecules
(3)There is no loss of internal energy upon collision
P ——absolute pressure of gas，MPa；
V ——volume occupied by gas，m3；

PV  nRT T—— absolute temperature, K;

n——mole numbers of gas，kmol；
R——universal gas constant；
R = 0.008314 MPa·m3/（kmol·K）
 EOS(状态方程) for real gas

PV  ZnRT
Z is known as the compressibility factor (压缩因子).

It is the ration of the volume actually occupied by a gas at

given pressure and temperature to the volume of an ideal
gas.

Vreal gas
Z
Videal gas
 At 10.5MPa，
and 60℃ ，
what’s the z-
factor for
ethane？

This chart is for pure substance. How to

know the compressibility of natural gas，
which is a mixture?

1
1
 Principle of corresponding state(对比态定律)

 Under the same conditions of reduced pressure

(对比压力)and reduced temperature(对比温度),
pure-hydrocarbon gases have the same
compressibility factors.
reduced pressure (对比压力)and reduced
temperature(对比温度) are for pure-hydrocarbons
P T
Pr  Tr  （2—12）
Pc Tc

Pr 、Tr——reduced pressure (temperature)，dimensionless；

P 、 T——absolute pressure（MPa）and temperature（K）；
Pc 、 Tc——critical(临界) pressure（MPa）and temperature（K）
 表 2—3 一些烃类气体的物性常数表
组分名称 分子式 分子量 沸点,℃ 临界压力 临界温度 液体密度（标准 偏心因子
3
（0.1MPa 下） Pc，MPa Tc，K 条件下）g/cm ω
甲烷 CH4 16.043 -161.50 4.6408 190.67 0.3 0.0115
乙烷 C2H6 30.070 -88.61 4.8835 303.50 0.3564 0.0908
丙烷 C3H 8 44.097 -42.06 4.2568 370.00 0.5077 0.1454
异丁烷 i? C4H10 58.124 -11.72 3.6480 408.11 0.5631 0.1756
正丁烷 n? C4H10 58.124 -0.50 3.7928 425.39 0.5844 0.1928
异戊烷 i? C5H12 72.151 27.83 3.3336 460.89 0.6247 0.2273
正戊烷 n? C5H12 72.151 36.06 3.3770 470.11 0.6310 0.2510
正己烷 n? C6H14 86.178 68.72 3.0344 507.89 0.6640 0.2957
正庚烷 n? C7H16 100.205 98.44 2.7296 540.22 0.6882 0.3506
正辛烷 n? C8H18 114.232 125.67 2.4973 569.39 0.7068 0.3978
正壬烷 n? C9H20 128.259 150.78 2.3028 596.11 0.72l 7 0.4437
正癸烷 n? C10H22 142.286 174.11 2.1511 619.44 0.7342 0.0.4502
注：偏心因子ω的意义及应用见第三章

2—4 一些非烃类气体的物性常数
名 称 分子式 分子量 沸点,℃ 临界压力 临界温度 液体密度（标准 偏心因子
3
（0.1MPa 下） Pc，MPa Tc，K 条件下）g/cm ω
空气 N2，O2 28.964 -194.28 3.7714 132.78 0.856
二氧化碳 CO2 44.010 -186.43 7.3787 304.17 0.827 0.2250
氦 He 4.003 -372.52 0.2289 5.278 /
氢气 H2 2.016 -459.73 1.3031 33.22 0.07 -0.2234
硫化氢 H2S 34.076 -315.74 9.0080 373.56 0.79 0.0949
氮气 N2 28.013 -371.19 3.3936 126.11 0.808 0.0355
氧气 O2 31.999 -389.22 5.0807 154.78 1.14 0.0196
水 H2O 18.015 100 22.1286 647.33 1.0 0.3210
 How to get compressibility of natural gas?

Since natural gas is mixture,

pseudo critical(拟临界) and
pseudo reduced(拟对比)
properties are introduced
Ppc   yi Pci
T pc   yi Tci
Ppc,Tpc——pseudo critical P & T；
yi——mole fraction of ith component；
Pci，Tci——critical P & T of ith component

With the pseudo critical parameters, we

can get pseudo reduced parameters
P P
Ppr  
Ppc  y i Pci
T T
T pr  
T pc  y i Tci
How to get compressibility of natural gas?

If specific gravity of natural gas is known, the

pseudo critical parameters can be obtained
by Fig.2-4, and then refer to Fig.2-3.

Example 2-3, 2-4

 Effect of non-hydrocarbon components

Above methods can only be used when the

non-hydrocarbon content is less than 5% by
volume (N2＜2%, CO2＜1%, CH4>50% ),
otherwise, the methods undergo the
correction.

(1)Method of chart correction

(2)Method of empirical formula

Page37, Example 2-5, 2-6
 2.3 The Physical Properties of
Natural Gas under High Pressure
 Gas formation volume factor(体积系数)

Why we need formation volume factor (FVF) of

natural gas?

In reservoir engineering calculations, it’s need

to convert the gas volume in reservoir
conditions (due to high T & P) to standard
gas volume (surface volume)
Gas at Surface
GasVolume in Place
Bg 
GasVolume at Surface

Gas in reservoir
Gas formation volume factor(体积系数)
Formation volume factor, is defined :

V (reservoir condition)
Bg  （2－44）
Vsc ( surface standard condition, 0.1MPa & 20℃)
Bg——volume factor of natural gas，m3/(标)m3；
Vsc——volume under surface standard condition，(标)m3；
V——volume under reservoir condition，m3

nRTsc
Vsc  （2－45）
Psc

Under surface standard conditions, the natural gas is

approximately regarded as ideal gas, so Z=1
Under reservoir temperature and pressure:
ZnRT
V （2－46）
P

Substitute (2-45) & (2-46) into (2-44): Bg is related to P & T.

V ZTPsc 273  t Psc Z

Bg    （2—47）
Vsc Tsc P 293 P

Along with the development of reservoir, the gases are continuously

depleted out and reservoir P decreases. However, reservoir T is stable.
Therefore, it’s reasonable to regard Bg as a function only of reservoir P.

273  t Psc Z CZ
Bg  =
293 P P
标准状态（Standard Condition)：20ºC，1atm
表2—9不同国家或不同场合对标准状态的规定

1mol 理想气体
国家或机构 规定温度、压力
在该状态下的体积
物理学标准状态 0℃,760mmHg(0.101325MPa) 22.4L
中国 石油工业 20℃(293K)，0.101325MPa 24.04L
前苏联 石油工业 20℃(293K)，0.101325MPa 24.04L
美国 石油工业 20.0℃(68℉), 0.101325MPa 24.04L
美国 高压气体协会 20.0℃(68℉),1atm 24.04L
美国 气体协会 60℉(15.6℃)，30in Hg（760mmHg） 23.68L
英国 60℉(15.6℃)，30in Hg（760mmHg） 23.68L
 0.06
0.05 120℃
Bg，m 3 /标m 3

0.04
0.03
0.02
0.01
0.00
0 20 40 60 80 100
P，MPa
图2—6 某天然气气样 P-Bg 关系

Bg << 1,so the swelling coefficient is introduced.

The definition of swelling coefficient is the ratio of the 1

Eg 
surface gas volume to the underground gas volume. Bg
Isothermal compressibility(等温压缩率)
Isothermal compressibility is the volumetric
change rate of gas along with the change of
pressure: 1 V
Cg   ( )T （2—48）
V P
ZnRT
To calculate C g of natural gas V
P
1 1 Z 1 1 Z 1 1 1 Z
Cg     = (  )
P Z P Ppc  Ppr ZPpc Ppr Ppc Ppr Z Ppr （2—56）

Pseudo-reduced compressibility factor of natural gas:

C pr  C g  Ppc
What’s the unit of Cg and Cpr???
How to get Cg of natural gas?
天然气视对比压缩系数Cpr可由已知的视对比参数（Ppr，Tpr）由图2—8查出。

Two methods:
(1)Using Fig.2-3, get Z factor and its gradient
(2)Using Fig.2-8, get Cpr

Fig. 2-8 Pseudo-reduced compressibility Cpr versus Tpr and Ppr

 Viscosity of natural gas

The viscosity of natural gas depends on its

composition, T, and P

The changing
regularities are different 1.6
at high/low pressure 1.4
1.2 High pressure region
高压区（稠气体）
condition.
Pr 1
0.8
0.6
The partition between 0.4
Low低压区（稀气体）
pressure region
high and low pressure 0.2
can be seen in Fig.2-9 0
0 2 4 6 8 10
Tr
图2—9 计算气体粘度时高压区与低压区的划分
 At low pressure

Molecular dynamics of gas:

1
    （2—59）
3

 ——density of gas；
 ——average velocity of gas molecular；

 ——average free-travel length of gas molecular

(1) There is no relationship between velocity and P

(2) Density is proportional to P
(3) Free-travel length is inversely proportional to P

Its viscosity almost has nothing to do with P (it is

feasible only for low pressure conditions that are
nearby the atmospheric pressure)
 Effect of T (at low pressure)

As T increases:
(1)Molecules movement increases
(2)More collisions between each other
(3)Kinetic energy of molecules increase
(4)The internal friction of the fluid is raised

Higher temperature results in greater viscosity

 At low pressure

(1)For hydrocarbons, the

viscosity decreases
with the increase in
molecular weight

(2)The viscosity of non-

hydrocarbon is
relatively higher than
that of hydrocarbon
 Summary (at low P)

 Its viscosity almost has nothing to do with P

 Higher temperature results in greater

viscosity

 For hydrocarbons, the viscosity decreases

with the increase in molecular weight

 The viscosity of non-hydrocarbon is

relatively higher than that of hydrocarbon
 At high P

Under high pressure, the gases possess

characteristics that typically belong to
liquid fluids, since the interaction between
gas molecular is dominant.

 Higher pressure, higher viscosity

 Higher temperature, lower viscosity
 Bigger molecular weight, higher viscosity
Determination viscosity of natural gas
(1)Carr viscosity chart

I. get viscosity by specific

gravity (or Mg) and temperature

II. Add the adjustment factor

due to non-hydrocarbon gases

Example 2-11

Only used under atmospheric

pressure
 For higher P

Get viscosity under

atmospheric pressure, the same
as above (by specific gravity or
apparent molecular weight)  g1

Calculate the pseudo critical P

&T, and pseudo reduced P&T

Refer to Fig.2-12 to get the

viscosity ratio  g
 g1
g
  g   g1  ( )
 g1
(2)Based on natural gas composition

g 
 i gi i
y  M 0.5

 gi i
 M 0.5

 gi is determined by Fig. 2-10

Example 2-12

Only used under atmospheric pressure

2.4 Water Vapor Content of
Natural Gas and the Gas
Hydrate（天然气水合物）
 Water content in natural gas

Part of reservoir water tends to be volatilized into the

gas, due to long time connection, and the water
exists as water vapor.
The water vapor content (water content for
short)depends on the following factors:
 P&T: water content decreases with the increase in P,
and increases with the increase in T
 Reservoir water salinity: it decreases with the
increase in salinity
 Specific gravity: the greater specific gravity, the
less water content
 Absolute humidity (绝对湿度)

The absolute humidity refer to the mass of the

water vapor contained in 1m3 natural gas

W P
X   vw （2—66）
V RwT

X——absolute humidity，kg/m3；
W——mass of water vapor，kg；
V——volume of water vapor，m3；
Pvw——partial pressure of water vapor，Pa；
T——absolute temperature of natural gas，K；
Rw——gas constant of water vapor Rw  461.53kg m3 / (kg K )
 Relative humidity (相对湿度)

The relative humidity is defined as the ratio of

the absolute humidity to the saturation
absolute humidity(饱和绝对湿度)

X Pvw ( partial pressure)

  （2-68）
X s Psw ( saturationvapor pressure)

For absolute dry gas, partial pressure is 0, and  is 0

When natural gas reaches state of saturation,  is 1

For normal natural gas, 0    1

 Determination of water content

Dew-point (露点) diagram

X=Xo×Cs×Cβ

X——the water-vapor content of the natural

gases with a special gravity of rg, g/m3;
Xo——the water-vapor content of the
natural gases with a special gravity of 0.6 g/m3;
Cβ——the adjustment coefficient for
special gravity, equals X/Xo;
CS——the adjustment coefficient for salt
content, equals the ratio of the water-vapor
content when the gas is in contact with salty
water to the water-vapor content when the gas
is in contact with pure water.

The dashed line indicates the

hydrates(水合物) begin to form
 Hydrate （水合物）

At specific conditions of P & T, hydrocarbon

gas and liquid water combine to form
crystal solids. The solids are called ‘natural
gas hydrates' or ‘hydrates’ for short
M+nH2O=M(H2O)n
In petroleum engineering, the significance of research
on hydrates are:

 It’s a kind of important resources and has large

reserves

 During gas production, hydrates may occur in

wellbores and at the surface chokes which makes
difficulty for gas production

 On the surface, the gas may change to hydrates,

which improves the efficiency of storage and
transportation
The
tendency
should be
known
 Prevention during production

During gas production, the T&P are reduced

(especially by passing choke). This creates
conditions to form hydrates.

 The fundamental approach is to remove the

water from the gases
 Raise the T of gases before/after the chokes
 Inject inhibiting agent into the gas flow
ahead of chokes
 Transportation

When pipeline is not convenient, it’s needed to

resort to high P vessel transportation. This
implied low efficiency and insecurity.

If the natural gases are transformed to

hydrates ,high efficiency and security can
be warranted.
 天然气水合物（可燃冰）

1. Large resource
据测算，中国南海天然气水合物的资源量为
700亿吨油当量，约相当中国陆上石油、天
然气资源量总数的二分之一。

2. Less pollution, large energy

每1立方米的可燃冰可转化为164立方米的天
然气和0.8立方米的水。预测分布范围约为
4000万km2，储量够人类使用1000年。

3. Assumed Production methods：

①热解法。②降压法。③二氧化碳置换
法。

4. Potential danger of production

水合物的存在能保持沉积层机械的稳定性。
假设分解掉了，就可能造成海底滑坡。