Al Delma PPT Oil &gas Day 4

fundamentals of Naturals Oil and Gas
Measurements (Quality and Quantity)
Course title – 0 days ATC_xxxx_PR_R 00.00

CO2 Process Analyzer•
Gas Quality Measurement

(Online Gas Analyzer)

CO2 Process Analyzer

An analyzer is an instrument or device which conducts chemical
analysis (or similar) on samples or sample streams
• Analyzers - auto-analyzers
• Allows a sample stream to flow from the process equipment
into, an analyzer; sometimes conditioning the sample stream in
between such as reducing pressure or changing the sample
temperature..

TYPES OF ANALYZERS
Scalar Network Analyzer
Only measures amplitude (i.e. scalar properties) of a device
 Vector Network Analyzer
1. Measure amplitude and phase (l.e. vector properties) of device under
test
2. AKA Gain-phase meter or automatic network analyzer
 Large Signal Network Analyzer
Highly Specialised for large Signal Analysis (2)

Structure and Operation
When a "detector"
The infrared light is
chamber absorbs some
emitted and passes
of the infrared The combination of
through the sample
radiation, it heats up out put voltages' from
Gas ,a reference gas
and expands. This the detector chambers
with a known mixture
causes rise from the sample gas
of the gases in
in pressure within the can then be compared
question and then
Sealed vessel that can to the output voltages
through the" detector"
be detected either with from the reference
chambers containing
A pressure transducer or chamber.
the pure forms of the
with a similar device.
gases in question.

CO2 Gas detector
The CO2 sensors can be easily integrated directly into the gas lines. It
is possible to measure the carbon dioxide concentration in waste
gasses from fermentations, independent of the gas flow.
Additional gas coolers, pumps and valves are not needed to make the
measurements. Fast and reliable measure data without a lot of
maintenance are the result. With the aid of standard interfaces, the
sensors can be connected to any process control system
Measuring range: 0 to 10 CO2 Vol.%, 0 to 25 CO2 Vol.%, 0 to 50
CO2 Vol.%, Measuring principle: infrared, dual beam
Accuracy: < ± 0,2 % FS ± 3% reading
Long-term stability: < ± 2% reading / year
https://www.youtube.com/watch?v=LBFKKQZo4kg

Detector Construction
small volume chamber

gas chromatograph column capillary
is directly plumbed to the bottom of
flame jet
column effluents are mixed with
hydrogen and air to be burned up
in the flame jet
An electronic igniter (electrically
heated filament) lights on the flame
Charge particles created during

combustor create a current b/w the
detector's electrodes

Structure and Operation
The infrared Ugh' is When a "detector"

emitted and passes chamber absorbs some The combination of
of the infrared
through the sample output voltages from
radiation, it heats up
gas, a reference gas and expands. This the detector chambers
with a known mixture causes a rise from the sample gas
of the gases in in pressure within the can then be compared
question and then sealed vessel that can to the output voltages
through the" detector" be detected either with from the reference
a
chambers containing chamber.
pressure transducer or
the pure forms of the with a similar device.
gases in question.

Principle
(Zirconia Oxygen Analyzers)
Determines oxygen concentration using the
conductivity of a zirconia ceramic cell. Zirconia
ceramic cells only allow oxygen ions to pass
through at high temperatures
. • Reference gas on one side and sample

gas on the other side
• Oxygen ions move from the side with
the highest concentration of oxygen to
that with the lowest concentration.
• The movement of ions generates an
EMF (Electro Motive Force) which can
be measured to determine the oxygen
content.
Analysis methods
During combustion with an excess of air A=1.1 it develops 11.5 m3 of
flue gases ( for each m3 of burned gas) as :
(C02) 1.0m3 + (02) 02m3 + (N2) a.3m3 + (H20) 2.0m3 = 11.5 m3
Analysis 00 Dry basis If you remove all water contents from flue gases,
condensating , the analyzer
will measure Oxygen as 02 ='0.2: 9.5 = 2.1%.
This is a measurement on ·dry basis" as we refer to Oxygen contents to
the volume of dry flu gases (9.5 m3) with excess of air A.~1.1
Analysis 00 Wet basis
If we don't remove all water contents the analyzer will
measure Oxygen as O2 = 0.2 : 11.5 = 1.7%
ℶ
This is a measurement on et basis" as we refer to Oxygen contents to
the volume of dry flu gases (11.5m) with excess of air ) =1.1
Flue gas analyzers use electrochemical sensors that need dry gas to
measure. For this reason all measurements are obtained on dry basis.

Destructive and Non-destructive
Analysis
( Destructive Analysis: sample stream is modified by the
analyzer
• e.g. reducing the pressure, changing the sample temperature,

addition of reagents.
• Sample stream can not be returned to the process
Non- destructive Analysis: sampled stream is not

substantially modified by the analyzer
relies upon use of electromagnetic radiation, sound, and

inherent properties of materials to examine samples sample
stream can be returned to the process

CO2 Gas detector continue
Housing: Aluminum, IP 65
Dimension / Weight: 100 x 100 x 130 mm W x D x H / 750 g
Connection material: Steel 1.4571 / Sapphire / Viton / PTFE
Connection: G 1 1/4 '', GL 45, Tricam etc.
Operating temperature: 5 to 30 °C, 15 to 40°C, 25 to 50°C
Pressure range: 800 to 2000 mbar
Pressure dependence: compensated, < ± 3 % reading (range)
Operating humidity: 0 to 100% RH
Power supply: 24 VDC, 1 A
Output: RS 232, 4 to 20 mA

Dual H2S and CO2 Gas Analyzer

Introduction:
Natural gas is color less and odorless in its most pure form. When
extracted, it can contain Sulphur compounds such as H2 S and Mercaptans
that when in the presence of moisture can produce Sulphur acid that can
degrade the pipeline. So for reasons of public safety as well as pipeline
integrity, there is a need to measure and control precisely the level of
odorant species in natural gas: - adjust the amount of Sulphur molecules in
the gas - control of odorant passivation - aids in detection of leaks based
on the gas chromatography principles, to measure H2 S, all mercaptans,
sulfides, Tetrahydrothiophene (THT) and total Sulphur in natural gas. Due
to the advantages of the “MEDOR” technology, a new guideline was
defined, ASTM D7493-08 (as the Standard Test Method for Online
Measurement of Sulphur Compounds in Natural Gas and Gaseous Fuels
by Gas Chromatograph and Electrochemical Detection).

Hydrogen sulfide (H2S) is always present in biogas, normally at
concentrations between 80 – 4,000 ppmv depending on the feedstock.
The primary mechanism for production of this compound is the
reduction of sulfur-containing proteins under anaerobic conditions by
sulphate-reduction microorganisms (Trogisch, 2004). Inorganic sulfur,
particularly sulfates, can also be biochemically converted producing
considerable H2S. Hydrogen sulfide is corrosive to most equipment
(pipelines, compressors, gas storage tanks, engines, etc.) and acts as
strong poison for fuel cells and reformer catalysts. Furthermore, H2S
combustion leads to sulfur dioxide emissions, which have harmful
environmental effects. Due to the potential problems that hydrogen
sulfide can cause, it is recommended to remove it early in the process
of biogas upgrading. The level at which gas quality specifications are
exceeded and sulfur abatement is required varies by application,
equipment and vendor. The following table outlines the typical
tolerance of H2S levels for different biogas utilization equipment.

In general, H2S removal methods can be classified in two big groups
according to their principle: the physical-chemicals, which are the
traditional ones and currently still dominate the market, and the
biotechnological. In the past two decades increasing attention has been
paid to biotechnological methods and they have experience a large
development as having the same or even higher efficiency than the
physical-chemical methods (> 99%) their operating costs are lower, they
avoid catalysts, and they do not generally produce secondary streams
that have to be specifically treated. Nevertheless, basic and applied
research for optimization of the biological systems is in general still
required. Methods that combined physical-chemicals and
biotechnological technologies have been also developed.

Adsorption
For H2S biogas removal the most employed methods are adsorption in
activated carbon and iron oxides and absorption with chelated iron salts.
For biogas upgrading to natural gas quality H2S is often combined with
CO2 removal in water or alkaline scrubbers or by absorption in non-water
physical solvents as the Selex process. The addition of iron chloride or
air/oxygen to the digester is widely used for a rough reduction of H2S
when using for example boilers or engines. Biofilters and bio trickling
filters are also commonly used in Denmark and other countries for H2S
removal before CHP engine units. But for those applications that required
very low levels of H2S (< 50 ppm) an additional method or a second
cleaning step after the biological method must be utilized. Moreover
biological system introduced normally oxygen for the biological process as
air, which reduces the quality of the biogas by increasing the N2
concentration. In some cases, lower levels of H2S can be reached with
biological systems. For example, Biogas Cleaner can supplied plants with a
performance guarantee of 10 ppm.
Hydrogen Sulphide and Overall Sulphur
Content
Natural gas contains, among other things, small amounts of hydrogen
sulphide (H2S - up to 5 mg/m3n of hydrogen sulphide as a daily
average, ). The hydrogen sulphide content is especially important for
determining whether the pipeline network will be subject to corrosion. For
this reason, the hydrogen sulphide content should be kept as low as
possible.
When the natural gas is delivered for distribution (to the customers), a
Sulphur us smelling substance is added - THT (Tetrahydrothiophene). The
smelling substance ensures that the otherwise odorless natural gas can be
detected in the event of a gas leak. The amount of the smelling substance
added is equal to a Sulphur content of 4-7 mg/m3n.
https://www.youtube.com/watch?v=bDMajyGpREY
HOW TO ANALYSE H2S
Equipment Specificities
The energy Med or is able to analyze H2 S, all mercaptans, Diethyl
sulfide (DES), Dimethyl sulfide (DMS), Dimethyl disulfide (DMDS),
THT and total Sulphur directly without convertor. In addition the
internal calibration stream (permeation tube installed into the instrument)
is analyzed at each cycle, at very low levels (ppb-ppm). Results are thus
automatically validated. No external calibration cylinders are required
for operation. The energy Medor can detect total Sulphur compounds
thanks to a Sulphur specific detector. Below examples of the analyses
sulphur compounds:
1.Hydrogensulphide (H2 S) 2. MethylMercaptan
3. Ethyl Mercaptan 4. N Propyl Mercaptan
5. Iso Propyl Mercaptan 6. Tertiary Butyl Mercaptan
7. Tetrahydrothiophene (THT) 8. Total Mercaptans (2+3+4+5+6 )

Emission Eliminator

Integrated Thinking
Drivers of environmental degradation are linked in complex ways
Single issue analysis leads to “silo” thinking
Systems analysis leads to integrated thinking
Integrated thinking inspires creative and inclusive solutions
Creative and inclusive solutions deliver environmental benefits aligned
with GEF focal area objectives
Examples: Water, Food & Energy Nexus; Urban Environments;
Integrated Approach Pilots.
https://www.youtube.com/watch?v=564Cp10aeu8

Availability of Cost of Power
& Fuel Cost of Water Human Health
Food
Biodiversity impacts Food prices

Natural Disasters
Water, Food, Energy Nexus

Availability, distribution, access and sustainability of
Water Food, energy and their resilience in the face of
climate change.
9. Managing the Human- Objective 1: Promote
4.Water/Food/ SFM 1: To LD 3: Integrated
interface: innovation &
Energy/Ecosystem maintain forest Landscapes
landscape/seascape technology transfer
Security Nexus resources
approach Course title – 0 days ATC_xxxx_PR_R 00.00
THE DALY RULES FOR SUSTANABILITY.
(1) Renewable resources such as fish,

soil, and groundwater must be used
no faster than the rate at which they
regenerate.
(2) Nonrenewable resources such as
minerals and fossil fuels must be
used
no faster than renewable substitutes
for them can be put into place.
(3) Pollution and wastes must be
emitted no faster than natural systems
can absorb them recycle them or
render them harmless.
Fundamentals of natrals oil and gas

measurments
Pollution and
Climate Waste &
Bio-diversity Buildings
Change Water
Transport Industry &

Jobs Land-Use Planning
Urban Environments
Urban environments are complex systems that touch
our lives and the environment across all focal areas.
Use integrated thinking for creative solutions.
Program 3:
6. Prevent the Loss 5. Mainstreaming Integrated low-
Climate resilient SLM in
and Degradation of urban systems carbon urban
Coastal Habitat Development
Course title – 0 days ATC_xxxx_PR_R 00.00 systems
Sustainable Development.
Sustainable development is understood as satisfying the needs of the
present generation without compromising the needs of future
generations.
Sustainability includes taking into account three aspects:
1. Economic: we need economic growth; to assure our material
welfare.
2. Environmental: we need to minimize environmental damage,
pollution, and exhaustion of resources.
3. Social: this is equity; the world's resources should be better shared
between the rich and the poor.

measurments
Natural gas plant with zero emissions
• https://www.youtube.com/watch?v=1zDZmIDbDO0

measurments
H2S Gas Analyzer

Methods of Analysis
Volumetric Procedure : (Simple Method)

Or sat Apparatus is used
O2 , CH4, H2, CO2, N2
Gas Chromatography :
Advantage : speed
CH4 ,CO2 , air (N2 + O2 )

Gas Chromatography
• Previously calibrated for each gas
• Suitable for routine work, frequent analysis
• TCD (Thermo Conductivity Detector) is used in GC for gas analysis

Volumetric Analysis
• Combustion of hydrogen and methane

Measure amount of CO2 produced during combustion
• If hydrogen and methane burned together
Possibility of explosion

Volumetric Analysis
(continue )
Separate oxidation of H2 and CH4
* Hydrogen oxidized by passing the gas through a heated unit

charged with cupric oxide

* Methane is oxidized by bringing it and O2 with a catalyst at a lower
temperature.


CO2
• Take 100 mL sample, contact with a solution of KOH

CO2 + 2KOH K2CO3 + H2O
Potassium Carbonate

CO2
( Continue)
CO2 disappears from the gaseous phase
Volume reduction = V CO2

Hydrogen Sulfide
H2S + 2KOH K2S + 2H2O

Volume of H2S is too small, can be ignored


Hydrogen Sulfide
HS 2 corrosive

• If gas will be used as a fuel,
should contain < 1.14 mg/L

H2S + I2 2HI + S

• Excess iodine is indicated with starch indicator.

Hydrocarbon VOC in Water Analyzer

VOCs are liquids or solids that contain organic carbon (carbon bonded to
carbon, hydrogen, nitrogen, or sulfur, but carbonate carbon as in CaCO 3
nor carbide carbon as in CaC2 or CO or CO2), which vaporize at significant
rates.
Some VOCs (e.g., benzene) are toxic and carcinogenic, and are regulated
individually as hazardous pollutants. Most VOCs are believed not very
toxic to humans.
Our principal concern with VOCs is that they participate in the “smog”
reaction and also in the formation of secondary particles in the atmosphere.
Some VOCs are powerful infrared absorbers and thus contribute to the
problem of global warming.

• Most VOC emissions are of refined petroleum products, use as
fuels or solvents.
1. Vapor Pressure, Equilibrium Vapor Content, Evaporation
• To understand which chemicals are volatile we must consider the
idea of vapor pressure.
• Fig. 10.1 (next slide) shows vapor pressures as a function of
temperature for a variety of compounds.

measurments
• From Fig.10.1, at 212oF, water’s normal boiling point, water has a
pressure of 14.696 psia (=760 torr = 1 atmosphere = 101.3 kPa ≈ 14.7
psia).
• At room temperature (68oF = 20oC) the vapor pressure of water is
0.339 psia = 17.5 torr = 0.023 atm.
Course title – 0 days ATC_xxxx_PR_R 00.00 52

• At this temperature water does not boil but it does evaporate if the
surrounding air is not saturated.
• The vaporization behavior of volatile liquids is summarized in
Table 10.2 (next slide).

• In a closed container a volatile liquid will come to phase equilibrium
with the vapor above it.
• If it is a pure liquid, then, the pressure in the container will be the vapor
pressure of the liquid.
• If the container also contains a gas like air, then at equilibrium that air
will be saturated with the vapor evaporated from the liquid.

• For the low pressures of interest for air pollution control, we make
only small errors if we assume that the vapor mix behaves as a perfect
gas, and that we can estimate the content of volatile liquid in the vapor
mix by Raoult’s law: p
yi  xi i
(1)
P
where yi = mol fraction of component in the
vapor
xi = mol fraction of component in the
liquid
pi = vapor pressure of pure component
P = total pressure

Example 1
• Estimate the water content of air that is in equilibrium with pure water
at 68oF = 20oC.
• Solution:
From Fig. 10.1, we find
pi 0.023 atm
yi  xi  1.00  0.023  2.3% #
P 1 atm

Example 2
• Repeat Example 1 for a liquid mixture of 50 mol% benzene and 50
mol% toluene in equilibrium with air in a closed container.
• Solution:
From Fig. 10.1, the vapor pressures of benzene and toluene at 68 oF
are about 1.5 and 0.4 psia, respectively.

• Using more extensive tables, we find that values are 1.45 and 0.42
psia.
• The applying Eq. (1),
pbenzene 1.45 psia

ybenzene  xbenzene  0.5  0.049
P 14.7 psia
ptoluene 0.42 psia
ytoluene  xtoluene  0.5  0.014
P 14.7 psia
yair  1  0.049  0.014  0.937 #

VOCs
• We may now state, as an approximate rule, that VOCs are those
organic liquids or solids whose room temperature vapor pressure are
greater than about 0.01 psia (= 0.0007 atm) and whose atmospheric
boiling points are up to about 500oF (=260oC).
• This means most organic compounds with less than about 12 carbon
atoms.

• Fig. 10.1 contains data for only a few of the millions of organic
chemicals in the VOC vapor pressure range.
• The Clean Air ACT Amendments of 1990 of the U.S. list 189
compounds that are considered to be health hazards and that are to be
regulated to prevent or minimize emissions; most are VOCs.

• The legal definition used for regulatory purposes does not set a lower
vapor pressure limitation and excludes a large variety of compounds
that have negligible photochemical reactivity, including methane,
ethane, and most halogenated compounds.
• The terms VOC and hydrocarbon (HC) are not identical, but often
are practically identical.

• Hydrocarbons are only slightly soluble in water.
• Polar VOCs, which almost all contain an oxygen or nitrogen atom in
addition to carbons and hydrogens (alcohols, ethers, aldehydes and
ketones, carboxylic acids, esters, amines, nitriles) are much more
soluble in water.

• This difference in solubilities makes the polar VOCs easier to remove
from a gas stream by scrubbing with water, but harder to remove
from water once they dissolve in it.
• Table 10.3 (next slide) shows some typical values of these
solubilities.
• Within each chemical family the solubility decreases with increasing
molecular weight.

Control by Prevention
• The ways of doing this for VOCs are substitution, process
modification, and leakage control.
3.1 Substitution
• Water-based paints are concentrated oil-based paints, emulsified in
water.
• After water evaporates, the small amount of organic solvent in the
remaining paint must also evaporate for the paint to harden.

• There are numerous other examples where a less volatile solvent can
be substituted for the more volatile one.
• This replacement normally reduces but does not eliminate the
emission of VOCs.
• Replacing gasoline as a motor fuel with compressed natural gas or
propane is also a form of substitution that reduces the emissions of
VOCs.

Process Modification
• Replacing gasoline-powered vehicles with electric-powered vehicles
is a form of process modification that reduces the emissions of
VOCs, as well as emission of carbon monoxide and nitrogen oxides,
in the place the vehicle is.
• On the other hand, it causes other emissions where the electricity is
generated.

Total Sulphur Analyzer

Total Sulfide in Natural Gas

measurments
Moisture Measurement Technologies
for Natural Gas
The measurement of moisture in natural gas is an important parameter for
the processing, storage and transportation of natural gas globally. Natural
gas is dehydrated prior to introduction into the pipeline and distribution
network. However, attempts to reduce dehydration result in a reduction in
“gas quality” and an increase in maintenance costs and transportation as
well as potential safety issues.. Consequently, to strike the right balance, it is
important that the water component of natural gas is measured precisely and
reliably. Moreover, in custody transfer of natural gas between existing and
future owners maximum allowable levels are set by tariff, normally
expressed in terms of absolute humidity (mg/m3 or lbs/mmscfh) or dew
point temperature. Several technologies exist for the online measurement
and for spot sampling of moisture content. This paper reviews the most
commonly used moisture measuring instruments and provides a comparison
of those technologies.
Prior to transportation, water is separated from raw natural gas.
However some water still remains present in the gaseous state as water
vapor. If the gas cools or comes in contact with any surface that is
colder that the prevailing dew point temperature of the gas, water will
condense in the form of liquid or ice. Under pressure, water also has
the unique property of being able to form a lattice structure around
hydrocarbons such as methane to form solid hydrates. Ice or solid
hydrates can cause blockage in pipelines. In addition, water combines
with gases such as Hydrogen Sulfide (H2S) and Carbon Dioxide (CO2)
to form corrosive acids. Water in natural gas also increases the cost of
transportation in pipelines by adding mass and as water vapor has no
calorific or heating value it also adds to the expense of compression
and transportation.When natural gas is sold, there are contractual
requirements to limit the concentration of water vapor
https://www.youtube.com/watch?v=AwlaK5t1gks


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fundamentals of Naturals Oil and Gas

Measurements (Quality and Quantity)

Course title – 0 days ATC_xxxx_PR_R 00.00

Gas Quality Measurement

Course title – 0 days ATC_xxxx_PR_R 00.00

CO2 Process Analyzer

Course title – 0 days ATC_xxxx_PR_R 00.00

Course title – 0 days ATC_xxxx_PR_R 00.00

Course title – 0 days ATC_xxxx_PR_R 00.00

Course title – 0 days ATC_xxxx_PR_R 00.00

Course title – 0 days ATC_xxxx_PR_R 00.00

small volume chamber

Charge particles created during

Course title – 0 days ATC_xxxx_PR_R 00.00

The infrared Ugh' is When a "detector"

Course title – 0 days ATC_xxxx_PR_R 00.00

. • Reference gas on one side and sample

Course title – 0 days ATC_xxxx_PR_R 00.00

• e.g. reducing the pressure, changing the sample temperature,

Non- destructive Analysis: sampled stream is not

relies upon use of electromagnetic radiation, sound, and

Course title – 0 days ATC_xxxx_PR_R 00.00

Course title – 0 days ATC_xxxx_PR_R 00.00

Dual H2S and CO2 Gas Analyzer

Course title – 0 days ATC_xxxx_PR_R 00.00

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Course title – 0 days ATC_xxxx_PR_R 00.00

Course title – 0 days ATC_xxxx_PR_R 00.00

Course title – 0 days ATC_xxxx_PR_R 00.00

Course title – 0 days ATC_xxxx_PR_R 00.00

Course title – 0 days ATC_xxxx_PR_R 00.00

Biodiversity impacts Food prices

Water, Food, Energy Nexus

(1) Renewable resources such as fish,

Fundamentals of natrals oil and gas

Transport Industry &

Fundamentals of natrals oil and gas

Fundamentals of natrals oil and gas

Course title – 0 days ATC_xxxx_PR_R 00.00

Volumetric Procedure : (Simple Method)

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• Combustion of hydrogen and methane

• If hydrogen and methane burned together

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* Hydrogen oxidized by passing the gas through a heated unit

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• Take 100 mL sample, contact with a solution of KOH

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CO2 disappears from the gaseous phase

Volume reduction = V CO2

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H2S + 2KOH K2S + 2H2O

Volume of H2S is too small, can be ignored

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Fundamentals of natrals oil and gas

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