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HYDRATE INHIBITION METHODS

Note: The source of the technical material in this volume is the Professional
Engineering Development Program (PEDP) of Engineering Services.
Warning: The material contained in this document was developed for Saudi
Aramco and is intended for the exclusive use of Saudi Aramcos employees.
Any material contained in this document which is not already in the public
domain may not be copied, reproduced, sold, given, or disclosed to third
parties, or otherwise used in whole, or in part, without the written permission
of the Vice President, Engineering Services, Saudi Aramco.

Chapter : Chemical
File Reference: CHE-206.02

For additional information on this subject, contact


PEDD Coordinator on 874-6556

Engineering Encyclopedia

Dehydration and Hydrate Inhibition


Hydrate Inhibition Methods

CONTENT

PAGE

INTRODUCTION...........................................................................................................................8
TEMPERATURE CONTROL METHODS AND EQUIPMENT
USED TO INHIBIT HYDRATE FORMATION IN A NATURAL GAS STREAM ......................9
Downhole Regulators.....................................................................................................10
Downhole Regulator Design.............................................................................10
Indirect Heaters ..............................................................................................................11
Indirect Heater Design.......................................................................................11
Indirect Heater Sizing.........................................................................................13
Advantages and Disadvantages of Temperature Control Methods .........................14
Downhole Regulators.........................................................................................14
Indirect Heaters ..................................................................................................15
Comparison of Temperature Control Methods ...............................................15
CALCULATING METHANOL INJECTION RATE REQUIRED
TO INHIBIT HYDRATE FORMATION IN A NATURAL GAS STREAM.................................17
Chemical Injection..........................................................................................................17
Equation for Calculating Required Depressions
of Hydrate-Formation Temperatures................................................................17
Hammerschmidt Equation.................................................................................18
Methanol..........................................................................................................................19
Methanol Applications .......................................................................................21
Methanol Injection System.................................................................................22
Hammerschmidt Equation Modified
for High Concentrations of Methanol................................................................25
Determining Methanol Injection Rates (General Applications)..................................26
Calculating Water Content of Gas Stream (W)...............................................27
Determining Hydrate-Formation Temperature (TH) .......................................27

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Calculating Methanol Concentration Required


to Depress Hydrate-Formation Temperature.................................................28
Calculating Methanol Injection Rates (q MeOH) .............................................28
Calculating Methanol Injection Rates (Cryogenic Applications)................................31
Determining Water Content ..............................................................................32
Determining Hydrate-Formation Temperature................................................32
Calculating Required Depression of Hydrate-Formation Temperature .......32
Determining Solubility of Methanol in Hydrocarbons......................................34
Calculating Methanol Injection Rates ...............................................................34
CALCULATING GLYCOL INJECTION RATE REQUIRED
TO INHIBIT HYDRATE FORMATION IN A NATURAL GAS STREAM.................................41
Glycol Concentration and Dilution ................................................................................43
Selecting Glycol Type ....................................................................................................45
Glycol Injection and Recovery System .........................................................................46
Glycol Injection and Recovery System Using Two Separators......................46
Glycol Injection and Recovery System
Using a Three-Phase Separator ......................................................................48
Glycol Injection and Recovery System Components ..................................................50
Separators ..........................................................................................................50
Reboiler...............................................................................................................50
Inhibitor Pump.....................................................................................................52
Glycol Losses .....................................................................................................52
Nozzle Selection and Placement......................................................................52
Calculating Glycol Injection Rates.................................................................................56
Water Content, Hydrate-Formation Temperature, and Safety Margin .........57
Concentration of Glycol......................................................................................57
Effects of Dilution Restrictions on Calculating Glycol Concentrations..........58
Calculating Glycol Injection Rates: Graphical Method...................................62

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SUMMARY..................................................................................................................................65
Temperature Control Methods......................................................................................65
Chemical Injection..........................................................................................................65
Methanol..............................................................................................................66
Glycol...................................................................................................................66
Calculating Inhibitor Injection Rates Summary............................................................68
WORK AID 1: PROCEDURES AND RESOURCES FOR CALCULATING
METHANOL INJECTION RATE REQUIRED TO INHIBIT
HYDRATE FORMATION IN A NATURAL GAS STREAM..........................69
Work Aid 1A: Procedures and Resources for Calculating
Methanol Injection Rates (General Applications).............................69
Required Depression of Hydrate-Formation Temperatures .........................69
Hammerschmidt Equation.................................................................................69
Hammerschmidt Equation (Eqn. 3)
Solved for the Weight Percent of Inhibitor .......................................................70
Free Water Condensed Out of Gas Stream ...................................................70
Methanol Injection Rate Required to Compensate for Vapor Losses..........71
Methanol Injection Rate Required
to Achieve Aqueous Methanol Concentration.................................................71
Total Methanol Injection Rate ............................................................................71
Work Aid 1B: Procedures and Resources for Calculating
Methanol Injection Rates (Cryogenic Applications) ..........................76
Depression Of Hydrate-Formation Temperatures......................................................76
Hammerschmidt Equation Modified
for High Concentrations of Methanol................................................................76
Flow Rate of Free Water ...................................................................................77
Depressed Hydrate-Formation Temperature (THdepressed) ......................78
Safety Margin......................................................................................................78
Methanol Injection Rate: Vapor Losses ...........................................................78

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Methanol Injection Rate: Solubility in Hydrocarbon Liquid .............................79


Methanol Injection Rate Required
to Achieve Aqueous Methanol Concentration.................................................79
Total Methanol Injection Rate (Cryogenic).......................................................79
Methanol Injection Rate Converted to gpm......................................................80
WORK AID 2: PROCEDURES AND RESOURCES FOR CALCULATING
GLYCOL INJECTION RATE REQUIRED TO INHIBIT
HYDRATE FORMATION IN A NATURAL GAS STREAM..........................89
Depression Of Hydrate-Formation Temperatures (Thermodynamic) ..........89
Hammerschmidt Equation.................................................................................90
Hammerschmidt Equation (Eqn. 3)
Solved for the Weight Percent of Inhibitor .......................................................90
Free Water Condensed Out of Gas Stream ...................................................90
Flow Rate of Free Water, q water (Glycol Injection Rate Calculations)........91
Rich Glycol Concentration Required
to Meet Dilution Restrictions (w richdilution)....................................................91
Inhibitor Injection Rate (Dilution Restricted).....................................................92
GLOSSARY............................................................................................................................. 100
ADDENDUM A: SYMBOLS FOR PHYSICAL QUANTITIES USED IN CHE 206.02..... 103
ADDENDUM B: ABBREVIATED LIST OF EQUATIONS USED IN CHE 206.02.......... 104
Depression of Hydrate-Formation Temperatures ................................................... 104
Depression of Hydrate-Formation Temperatures (Thermodynamic) .................... 104
Hammerschmidt Equations........................................................................................ 104
Derivations of Hammerschmidt Equations............................................................... 104
Hammerschmidt Equation (Eqn. 3)
Solved for the Weight Percent of Inhibitor .................................................... 104
Hammerschmidt Equation Modified
for High Concentrations of Inhibitor ............................................................... 104

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Hammerschmidt Equation Modified


for High Concentrations of Methanol............................................................. 105
Free Water Condensed Out of Gas Stream ............................................................ 105
Methanol Injection Rate (General Applications)....................................................... 105
Methanol Injection Rate Required to Compensate for Vapor Losses....... 105
Methanol Injection Rate Required
to Achieve Aqueous Methanol Concentration.............................................. 105
Total Methanol Injection Rate ......................................................................... 105
Flow Rate of Free Water (Cryogenic Applications) ................................................ 105
Depressed Hydrate-Formation Temperature (THdepressed) ............................... 106
Safety Margin............................................................................................................... 106
Methanol Injection Rate: Vapor Losses (Cryogenic Applications) ........................ 106
Methanol Injection Rate: Solubility in Hydrocarbon Liquid ...................................... 106
Methanol Injection Rate Required
to Achieve Aqueous Methanol Concentration.......................................................... 106
Total Methanol Injection Rate (Cryogenic)................................................................ 106
Methanol Injection Rate Converted to gpm............................................................... 106
Flow Rate of Free Water, q water (Glycol Injection Rate Calculations)................. 106
Rich Glycol Concentration Required
to Meet Dilution Restrictions (w richdilution)............................................................ 107
Inhibitor Injection Rate (Dilution Restricted).............................................................. 107
ADDENDUM C: INDIRECT HEATER SIZING CALCULATIONS ..................................... 108

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List of Figures
Figure 1: Typical Indirect Heater..............................................................................................12
Figure 2: Typical Wellhead Heater Installation.......................................................................12
Figure 3: Comparison Of Temperature Control Methods.....................................................16
Figure 4: Effect Of Methanol On Hydrate Formation In Propane .........................................20
Figure 5: Methanol Injection System .......................................................................................22
Figure 6: Methanol Injection And Recovery System ..............................................................24
Figure 7: Mass Balance Around Separator ...........................................................................33
Figure 8: Flow Of Gas Stream In Methanol Injection Sample Problem (Cryogenic)..........35
Figure 9: Mass Balance Around Separator In Methanol Injection Sample Problem
(Cryogenic) .........................................................................................................38
Figure 10: Comparison Of Chemical Injection Inhibitors ......................................................41
Figure 11: Freezing Points Of Aqueous Glycol Solutions.....................................................43
Figure 12: Allowable Glycol Dilutions......................................................................................44
Figure 13: Dow Chemical Glycol Recommendations ...........................................................45
Figure 14: Glycol Injection And Recovery System .................................................................47
Figure 15: Glycol Injection And Recovery System (Three-Phase) .......................................49
Figure 16: Boiling Point Of Meg ..............................................................................................51
Figure 17: Glycol Sprayed Onto The Tube Sheet Of A Heat Exchanger ............................54
Figure 18: Increase In Pressure Drop Because Of Hydrate Formation..............................55
Figure 19: Nozzle Placed At Three Locations: One Flow Rate...........................................55
Figure 20: Nozzle Placed At One Location: Three Flow Rates...........................................56
Figure 21: Comparison Of Hydrate Inhibition Methods.........................................................66
Figure 22: Comparison Of Chemical Inhibitors .....................................................................67
Figure 30: Summary Of Method For Calculating Methanol Injection Rates
(Steps 1 To 4).....................................................................................................72
Figure 31: Summary Of Method For Calculating Methanol Injection Rates
(Steps 5 To 9).....................................................................................................73
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Figure 32: Depression Of Hydrate-Formation Temperatures, ?T (Methanol) ..................74


Figure 33: Methanol Vapor-To-Liquid Composition Ratios .................................................75
Figure 34: Summary Of Calculating Methanol Injection Rate
For Cryogenic Applications (Steps 1 To 4).....................................................81
Figure 35: Summary Of Calculating Methanol Injection Rate
For Cryogenic Applications (Steps 5 To 8).....................................................82
Figure 36: Summary Of Calculating Methanol Injection Rate
For Cryogenic Applications (Steps 9 To 14) ..................................................83
Figure 37: Depression Of Hydrate-Formation Temperature By Methanol
(Modified Hammerschmidt Equation) .............................................................84
Figure 38: Solubility Of Methanol In Hydrocarbon Vapor (65F To -20F)..........................84
Figure 39: Solubility Of Methanol In Hydrocarbon Vapor (-20F To -120F)......................85
Figure 40: Solubility Of Methanol In Hydrocarbon Vapor (-125F To -175F)....................85
Figure 41: Solubility Of Methanol In Hydrocarbon Liquid......................................................86
Figure 42: Density Of Aqueous Methanol Solutions..............................................................87
Figure 43: Water Content (W) Of Natural Gas At Low Temperatures.................................88
Figure 44: Calculating Glycol Injection Rates (Steps 1 To 6) ...............................................93
Figure 45: Calculating Glycol Injection Rates (Steps 7 To 11).............................................94
Figure 46: Physical Properties Of Hydrate Inhibitors ............................................................95
Figure 47: Allowable Glycol Dilutions......................................................................................96
Figure 48: Freezing Points Of Aqueous Glycol Solutions.....................................................96
Figure 49: Density Of Meg Solutions ......................................................................................97
Figure 50: Depression Of Hydrate-Formation Temperature (MEG) ...................................98
Figure 51: MEG Injection Rate.................................................................................................99
Figure 52: Symbols Used In Che 206.02 ............................................................................ 103
Figure 53: Coil Size Selection.............................................................................................. 110
Figure 54: Heater-Coil Transfer Coefficients...................................................................... 110

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INTRODUCTION
The previous module, ChE 206.01, covered predicting hydrate
formation.
This module covers the following methods of
preventing, or inhibiting, the formation of hydrates.

Temperature control

Methanol injection

Glycol injection

This module first covers the inhibition hydrate formation by means


of indirect heaters and downhole regulators to control gas stream
temperatures. The module then discusses the calculation of
methanol injection rates that are required to inhibit hydrate
formation for both general and cryogenic applications. Finally, the
module discusses the calculation of injection rates, including the
use of graphical methods.

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TEMPERATURE CONTROL METHODS AND EQUIPMENT USED TO INHIBIT


HYDRATE FORMATION IN A NATURAL GAS STREAM
Heating a natural gas or depressurizing it (thus cooling it) while it
is under hot conditions can inhibit hydrate formation. In above
ground operations, the temperature drop caused by
depressurizing (expanding) a gas can result in the temperature of
the gas stream dropping below its hydrate-formation temperature.
Because of the high temperatures underground, a gas stream can
be expanded underground without the resulting temperature
dropping below its hydrate-formation temperature. Therefore,
expanding a gas stream in a well bore helps prevent hydrateformation in downstream processing.
The two main pieces of equipment used to control gas stream
temperature and inhibit hydrate formation are downhole regulators
and indirect heaters.
Downhole regulators inhibit hydrate
formation by expanding gas streams while they are in the wellbore.
Indirect heaters inhibit hydrate formation both at wellheads
(wellhead heaters) and along flowlines (flowline heaters). Indirect
heaters are often used to inhibit hydrate formation caused by
expansion or to replace heat lost by a flowline to the surrounding
air and ground.
Downhole regulators and indirect heaters are used around the
world. Saudi Aramco however, does not commonly use either
temperature control method. Saudi Aramcos only gas wells, Khuff
gas, operate at a high enough temperature that hydrates are not a
problem. Saudi Aramcos gas pipelines do not use indirect
heaters as the gas in these lines has already been processed to
some extent (such as dew-point conditioning) that hydrates are not
a problem.

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Downhole Regulators
The use of downhole regulators to inhibit hydrate formation by
controlling gas stream temperatures is generally feasible when the
gas well has the following conditions:

A high reservoir pressure that is not expected to decline


rapidly

Excess pressure

High capacity

The temperature and pressure of a gas stream as well as its


composition determine whether hydrates will form when gas is
expanded into the flowlines. Cooling occurs as gas is expanded
across the choke. Downhole regulators lower the pressure of the
gas stream from well pressure to near-salesline pressure in the
wellbore. Operating conditions resulting from the expansion of the
gas are outside the hydrate-formation range of the gas stream
because of the high temperatures in the well.

Downhole Regulator Design


Downhole regulators contain a spring-loaded valve and stem that
outside vendors set from the surface by using a wireline (wire
used to lower tools into the wellbore) run through the wellbore
tubing. The pressure drop across the regulator remains constant
and does not depend, within a broad range, on the flow rate of the
well.
The design of downhole regulators requires using complex
calculations that must account for the following:

Downhole pressures and temperatures

Well depth

Wellbore configuration

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The performance of these involved calculations is not necessary


because production equipment vendors provide detailed
information on the design of downhole regulators. However,
simpler calculations estimate the feasibility of installing downhole
regulators.

Indirect Heaters
Two types of indirect heaters are used to inhibit hydrate formation:
wellhead and flowline. The expansion of gas streams at or near
wellheads often results in the formation of hydrates. Wellhead
heaters keep the temperatures of these gas streams above their
hydrate-formation temperatures.
Flowlines in other parts of the world often lose enough heat to the
surrounding air and ground to lower the temperature of the gas
stream below its hydrate-formation temperature. Flowline heaters
inhibit hydrate formation by replacing this lost heat and keeping
the temperature of the gas stream above its hydrate-formation
temperature. Flowline heaters also inhibit hydrate formation by
heating gas streams expanded or choked downstream from the
wellhead.

Indirect Heater Design


Different heater designs accomplish the same purpose: to heat
the gas. Flowline heaters do not require the chokes and highpressure safety valves that wellhead heaters need.
Indirect heaters are vessels that contain a fire tube and a coil
immersed in a heat transfer fluid (usually water or a glycol and
water mixture) within a heater shell. The fire tube is usually fired by
gas. The coil contains the fluid (the gas stream) to be heated and
operates at full gas pressure. The heater shell operates at
atmospheric pressure. Figure 1 shows a typical indirect heater.

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FIGURE 1: TYPICAL INDIRECT HEATER

Wellhead heaters - Figure 2 shows a schematic of a typical


wellhead heater.

FIGURE 2: TYPICAL WELLHEAD HEATER INSTALLATION

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Flowline heaters heat gas streams above their


hydrate-forming temperatures. In many cases, properly designed
and placed wellhead heaters provide sufficient heat to eliminate
the need for flowline heaters.
Flowline Heaters -

Unlike wellhead heaters, flowline heaters do not require most of


the equipment shown in Figure 2. Flowline heaters require a
bypass valve so that a heater can be removed from service or to
allow the pipeline to be scrapped.

Indirect Heater Sizing


The determination of the size of a heater depends on the following
conditions:

Amounts of gas, water, oil, or condensate expected in the


heater

Inlet temperature and pressure

Outlet temperature and pressure (to avoid hydrate-forming


conditions)

The size of heater coils to use depends on the volume of fluid


flowing through the coil and the required heat-transfer load.
When heater coils are sized, it is important to consider operating
conditions in addition to normal, steady-state operating
conditions. Transient startup of a shut-in well may require extra
heating capacity. The temperature and pressure conditions of a
shut-in well and the extra liquids accumulated while the well was
shut in may increase the heating load. Often, heaters are
necessary only while wells are being started up. Installing preheat
coils ahead of chokes is generally practical for wells operated only
intermittently.
Heat requirements that at first appear large
can often be reduced or even eliminated by optimizing the
operation of a gas system. For instance, the combination of gas
streams from multiple wells can produce higher gas flow
temperatures. Furthermore, the reduction of gas pressures of the
lines at a central point is generally more efficient than separately
reducing the gas pressures of the lines.
System Optimization -

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However, the reduction of flowline pressures at a central point


requires extra-strength gathering lines that can withstand wellhead
shut-in pressures. The regulation of the pressure of gathering
lines by the installation of well shut-in valves eliminates the need
for extra-strength piping.
Indirect Heater Sizing Calculations - The

calculations required to size


indirect heaters are complex and are not covered in detail. The
procedure for sizing an indirect heater is described below and in
Addendum C.

The need for a heater preheat coil is determined.

The outlet temperature of the heater is determined.

The heat required to heat the gas is calculated.

The size and surface area of the heating coil is determined.

Advantages and Disadvantages of Temperature Control Methods


Downhole Regulators
Downhole regulators have the following advantages:

Low initial investment

Do not require routine service

Downhole regulators
disadvantages:

have

the

following

limitations

or

They may not inhibit hydrate formation during startup. It may be


necessary to inhibit hydrate formation by injecting either
methanol or glycol until the gas flow and temperature stabilize.

Generally, an outside vendor must change the pressure drop


on the regulator.

When well output falls below normal production levels,


processors must remove and replace downhole regulators with
another hydrate inhibition method.

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When work is performed inside a wellbore, the well may be


permanently damaged.

Indirect Heaters
The advantages of using indirect heaters to inhibit the formation of
hydrates include the following:

Minimal maintenance or attention required

Very low chemical requirements

The disadvantages of using indirect heaters to inhibit hydrates


include the following:

Difficulty of supplying clean and reliable fuel to remote


locations

Large operating (fuel) costs if cheap fuel is not available

Potentially large capital costs

Significant plot space required

Special safety equipment needed because of fire hazard

Comparison of Temperature Control Methods


Figure 3 compares the use of downhole regulators and wellhead
heaters to inhibit hydrate formation. The high capital costs of
heaters generally limit their use to large hydrate inhibition
installations. Downhole regulators work best in large reservoirs
with high gas pressures that are not expected to decline rapidly.

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DESIGN FACTORS

DOWNHOLE
REGULATORS

Investment

Very low

Very high

None

Very high

Fuel

Low

Low

Chemicals

None

Very low

Plot Area

None

Very high

Hazards

High

High

Downtime

Low

Low

Operating Maintenance

Source:

WELLHEAD HEATERS

Dehydration and Hydrate Inhibition. Exxon Production Research Company, Production


Operations Division. July 1986. With permission from Exxon Production Research
Company.
FIGURE 3: COMPARISON OF TEMPERATURE CONTROL METHODS

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CALCULATING METHANOL INJECTION RATE REQUIRED TO INHIBIT HYDRATE


FORMATION IN A NATURAL GAS STREAM
Chemical Injection
Currently, methanol (MeOH) and monoethylene glycol (MEG) are
the two chemicals most commonly injected into gas streams to
inhibit hydrate formation. Consider the use of chemical injection to
inhibit hydrate formation for the following:

Gas pipelines in which hydrates form at localized points

Gas streams operating a few degrees above their hydrate


formation temperature

Gas-gathering systems in pressure-declining fields

Situations where hydrate problems are of short duration

Hydrate inhibitors act similarly to antifreeze. Adding a known


quantity of an inhibitor to a known quantity of pure liquid reduces
the hydrate-formation temperature by a calculable amount.
Equation for Calculating Required Depressions of Hydrate-Formation
Temperatures
Hydrate inhibitors act similarly to antifreeze. Adding a known
quantity of an inhibitor to a known quantity of pure liquid reduces
the hydrate-formation temperature by a calculable amount.
Equation 1 calculates the required depression of hydrateformation temperatures as follows:
T = TH - Tminimum+ S

(Eqn. 1)

where:
T

= Depression of hydrate-formation temperature, F

TH

= Hydrate-formation temperature of gas stream, F

Tminimum = Minimum temperature of system, F


S

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= Safety factor to account for uncertainty in TH, F

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Hammerschmidt Equation
The flow rate of the chemical inhibitor required to depress the
hydrate-formation temperature of a gas stream can be calculated
by hand or with computer programs. Computer programs (PRO/II
and HYSIM) use thermodynamic equations (Eqn. 2) that describe
the freezing point depression of an ideal solution.
T =

n
RT02

In 1+ inhibitor
Hf

n solvent

(Eqn. 2)

where:
T

= Depression of hydrate-formation temperature, F

= Gas constant

T0

= Normal freezing point (absolute temperature


scale)

Hf

= Enthalpy of fusion per mole of solvent

ninhibitor = Moles of solute (inhibitor)


nsolvent = Moles of solvent
The simplification of Eqn. 2 for hand calculations results in the
Hammerschmidt equation (Eqn. 3). Theoretically, this equation
applies only to typical natural gases with solute concentrations
less than 0.20 mole fraction.
In practice, however, the
Hammerschmidt equation has been successfully used for glycol
systems with inhibitor concentrations up to 0.40 mole fraction (70
wt % MEG) and with temperatures as low as -40F to -50F. The
Hammerschmidt equation is as follows:

T =

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KHwI
100M - MwI

(Eqn. 3)

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Equation 4 is the Hammerschmidt equation (Eqn. 3) solved for the


weight percent of inhibitor.
wI =

(T)(M)

(100)

KH + (T)(M)

(Eqn. 4)

where:
wI

= Weight percent of the chemical inhibitor in the


solution

= Depression of hydrate-formation temperature, F

= Molecular weight of the chemical inhibitor


(methanol or glycol)

KH

= 2,335 for methanol and 4,000 for glycol

Methanol
Methanol works well as a hydrate inhibitor because of the following
reasons:

It can attack or dissolve hydrates already formed.

It does not react chemically with any natural gas constituents.

It is not corrosive.

It is reasonable in cost.

It is soluble in water at all concentrations.

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Methanol significantly depresses hydrate-formation temperatures.


Figure 4 shows the effect of methanol on the hydrate-formation
temperature of propane.

Source:

Katz, Donald L. and Robert L. Lee; Natural Gas Engineering: Production and Storage. McGraw-Hill.
1990. With permission from the Gas Processors Suppliers Association.

FIGURE 4: EFFECT OF METHANOL ON HYDRATE FORMATION IN PROPANE

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Methanol Applications
Because methanols material cost is so low and its vapor losses
so high, methanol is often not recovered. Not requiring a recovery
system significantly reduces capital costs. Therefore, methanol
injection is generally economical for temporary installations,
situations with low gas volumes, or situations with mild, infrequent,
or seasonal hydrate problems.
For instance, the Uthmaniyah Gas Plant uses methanol injection in
case its solid desiccant dehydration system fails. Because of its
high volatility, methanol is also injected to inhibit hydrate formation
in pipelines.

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Methanol Injection System


Figure 5 shows a simplified schematic of a typical methanol
injection system. This system inhibits hydrate formation at a
choke or pressure-reducing valve. A gas-driven pump injects the
methanol into the gas stream upstream of the choke or pressurereducing valve.
The temperature controller measures the
temperature in the gas stream and adjusts the power-gas control
valve. The power-gas control valve controls the flow of power gas,
which controls the methanol injection rate.

Source:

Dehydration and Hydrate Inhibition. Exxon Production Research Company, Production Operations
Division. July 1986. With permission from Exxon Production Research Company.

FIGURE 5: METHANOL INJECTION SYSTEM

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Figure 6 shows the cycle of a typical methanol injection and


recovery system for a cryogenic application. The free-water
knockout first removes free water and other entrained liquids.
Then the system injects methanol into a gas-gas exchanger before
the gas stream enters a chiller. The methanol-hydrocarbon
separator removes the methanol from the gas stream. The water
wash tower washes the methanol from liquid hydrocarbons
collected in the flash drum and the methanol-hydrocarbon
separator.
The reduction of the amount of free water in a gas stream before
the gas stream reaches the chemical injection point considerably
reduces the amount of chemical inhibitor required. A free-water
knockout installed at a wellhead removes free water, and thereby
reduces the amount of inhibitor needed.

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Washed
propane
To fractionation
HC
gas
Methanolhydrocarbon
separator

Gas-gas
exchanger

Water
wash
tower

Propane
product from
depropanizer
Vent gas

Chiller

Feed
gas

Spray
Nozzle
Dissolved
gas

Freewater
knockout

Flash
drum

Reflux
pump
Methanol
still

Water
surge
drum

Excess water
Methanol
injection pump

Source:

Methanol
storage

Nielsen, R. B. and R. W. Bucklin. "Use of Methanol for Hydrate Control in Expander Plants." Fluor
Engineers and Constructors, Inc. Presented at 1981 Gas Conditioning Conference. With permission
from Fluor engineers and Constructors, Inc.

FIGURE 6: METHANOL INJECTION AND RECOVERY SYSTEM

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For instance, the saturated water content of gas at reservoir


conditions of 2,500 psia and 200F is 315 lb H2O/MMSCF. The
saturated water content of this same gas at wellhead conditions of
2,000 psia and 120F is 65 lb H2O/MMSCF. Therefore, the gas
at wellhead conditions contains 250 lb H2O/MMSCF of free water.
If this extra free water is not removed, extra chemical inhibitors
have to be used. However, the use of extra chemical inhibitors
increases the cost of the operation.
of Injecting Methanol - The injection of methanol
considerably upstream of a hydrate-forming location allows the
methanol to distribute and vaporize completely. Because of
methanols high volatility, nozzle placement and design are not as
critical as they are for glycol injection. Methanol injection nozzles
should be located as follows:
Method

Upstream of front-end exchangers

At the inlets of turboexpanders

At any refrigerated condensers in downstream fractionation

To prevent the water-methanol solution from freezing in


turboexpander outlets operating below -102F, methanol injection
control must be very accurate.
Hammerschmidt Equation Modified for High Concentrations of Methanol
The modified Hammerschmidt equation (Eqn. 5) accurately
calculates hydrate-formation temperature depressions for inhibitor
concentrations higher than 0.20 mole fraction and for methanol
injection systems that are operating with temperatures as low as 160F.
2

T = -

RT0
Hf

ln xwater
(Eqn. 5)

where:
T

= Depression of hydrate-formation temperature, F

= Gas constant

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T0

= Normal freezing point (absolute temperature


scale)

Hf

= Enthalpy of fusion per mole of solvent

xwater

= Mole fraction of water in the aqueous-methanol


solution

The substitution of methanol-specific values results in the


following:
T = -129.6 In (1- xMeOH )

(Eqn. 6)

where:
xMeOH

= Mole fraction of MeOH in the aqueous-methanol


solution

Figure 37 (in Work Aid 1B) tabulates hydrate-formation


temperature depressions (?T) calculated by using the modified
Hammerschmidt equation (Eqn. 6).
Methanol depresses hydrate-formation temperatures a maximum
of 234F at a concentration of 90 wt % or 0.835 mole fraction. At
concentrations higher than
90 wt %, methanol forms a solid at low temperatures. Generally,
methanol is not used at concentrations above 30 wt %. However,
applications that require maximum depression of hydrateformation temperatures, such as in a turboexpander plant,
generally use methanol concentrations of 90 wt %.
Determining Methanol Injection Rates (General Applications)
This module covers two methods for calculating methanol injection
rates. The first method (general applications) does not use high
methanol concentrations (above 30 wt %) or compensate for
methanol solubility in hydrocarbon liquids. The second method
(cryogenic applications) considers both high methanol
concentrations and the solubility of methanol in hydrocarbon
liquids. It is covered in a later section.

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To determine methanol injection rates, the following conditions


need to be accounted for:

The amount of free water condensed from the natural gas after
chilling or expanding

The concentration of methanol required to depress the hydrateformation temperature

The flow rate of the gas stream

The solubility of methanol in the hydrocarbon vapor

Calculating Water Content of Gas Stream (W)


To determine the water content of the gas stream, use the
following methods, which were covered in ChE 206.01:

Gravity graphic

HYSIM

K-value

SimSci

To calculate the amount of water condensed out of the gas stream,


you need to determine the saturation temperature of the gas
stream. Although the condensation of hydrocarbons can be
significant in some cases, the methods used in this module to
calculate the amount of water condensed do not account for them.
The effect of hydrocarbon condensation can be accounted for by
developing overall mass balances and by applying the principles
of this module.

Determining Hydrate-Formation Temperature (T H)


For general applications, you can use the gravity graphic method
to determine hydrate-formation temperature. For cryogenic
applications (such as in a turboexpander plant), you should use a
more sophisticated method, preferably a computer program (such
as PRO/II or HYSIM).

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Calculating Methanol Concentration Required to Depress Hydrate-Formation


Temperature
For methanol concentrations up to 30 wt %, use the
Hammerschmidt equation (Eqn. 3). Figure 32 (in Work Aid 1A)
plots experimental data that correspond to the Hammerschmidt
equation.
For general applications that use methanol
concentrations below 30 wt %, a safety margin of 5F to 10F
must be applied to compensate for uncertainties in the
Hammerschmidt equation and in operating conditions. Because
the Hammerschmidt equation is conservative, 5F is generally
sufficient.
Safety Margin (S) -

Calculating Methanol Injection Rates (q MeOH)


The total methanol injection rate is calculated in two steps. First,
calculate the methanol injection rate required to achieve the
concentration of methanol in the aqueous solution which inhibits
hydrate formation (q MeOHaq). Then calculate the methanol
injection rate required to compensate for methanol vapor losses
(q MeOHvapor). The sum of the two injection rates is the total
methanol injection rate required to inhibit hydrate formation. The
equations developed in Work Aid 1 for the calculation of methanol
injection rates assume that pure methanol is injected.
Calculating the methanol injection rate to
compensate for vapor losses requires determining the methanol
vapor-to-liquid composition ratio. Figure 32 (in Work Aid 1A)
plots vapor-to-liquid composition ratios at various temperatures
and pressures.
Calculating Vapor Losses -

The following sample problem demonstrates how to calculate a


methanol injection rate by using Work Aid 1A. The nine steps of
this sample problem parallel the numbered steps of the procedure
summarized in Figure 30 and Figure 31 in Work Aid 1A.

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Sample Problem:
Calculating Methanol Injection Rates
(General Applications)
Calculate the methanol injection rate required to inhibit the
formation of hydrates in a saturated gas stream being cooled in a
chiller. Refer to Work Aid 1A.
Given:
Gas specific gravity = 0.67
Inlet temperature=70F
Chiller temperature = 40F
Operating pressure = 700 psia
Solution:
1.

The gas stream is saturated at the inlet temperature, 70F.

2.

The method covered in ChE 206.01 to determine the water


content of the gas at 70F and 40F is used to calculate that
the amount of free water condensed out of the gas stream in
the chiller is 12 lb H2O/MMSCF.
Winlet
Wchiller
W

=
=
=
=
=

23 lb H2O/MMSCF (at 70F and 700 psia)


11 lb H2O/MMSCF (at 40F and 700 psia)
Winlet - Wchiller
(Eqn. 7)
23 lb H2O/MMSCF - 11 lb H2O/MMSCF
12 lb H2O/MMSCF

3.

The gravity graphic method covered in ChE 206.01 is used


to determine the hydrate-formation temperature of the gas
stream is 58F.

4.

The hydrate-formation temperature of the gas stream must


be depressed by 23F.
?T

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=
=
=

TH - Tminimum + S
58F - 40F + 5F
23F

(Eqn. 1)

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A T of 23F and the Hammerschmidt equation (Eqn. 4) are


used to determine the gas stream requires a 24 wt %
concentration of methanol in the aqueous solution (w I).

5.

(T)(M)

wI

(100)

= KH + (T)(M)

(Eqn. 4)

(23F) 32.0

lb
mole
(100 )
lb

2,335 + (23F) 32.0

mole
=
= 24 wt % MeOH
6.

The injection rate required to compensate for methanol vapor


losses is
28.1 lb MeOH/MMSCF.
By refering to Figure 33, the vapor-to-liquid composition ratio
is determined to be 1.17 lb MeOH/MMSCF/wt % MeOH at
40F and 700 psia.

q MeOHvapor = (vapor-to-liquid composition ratio)(w MeOH)


1.17 lb MeOH
MMSCF 24 wt % MeOH
q MeOHvapor = wt % MeOH
= 28.1 lb MeOH/MMSCF
7.

(Eqn. 9)

The methanol injection rate required to obtain 24 wt % MeOH


in the aqueous solution (q MeOHaq) is 3.8 lb/MMSCF.

(W )(w MeOH )
w water
q MeOHaq =
12 lb H2O/MMSCF 24 wt % MeOH
76 wt % H2O
=
= 3.8 lb MeOH/MMSCF
8.

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(Eqn. 10)

The total methanol injection rate (qMeOH) required is 31.9 lb


MeOH/MMSCF.

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q MeOHtotal
= q MeOHvapor + q MeOHaq
= 28.1 lb MeOH/MMSCF + 3.8 lb MeOH/MMSCF
= 31.9 lb MeOH/MMSCF
9.

(Eqn. 11)

The density of methanol found in Figure 46 is used to convert


the total injection rate to gal MeOH/MMSCF as follows:

31.9 lb MeOH gal MeOH


=
MMSCF
6.55 lb MeOH
gal MeOH
4.9
=
MMSCF
Answer:

The methanol injection rate required for this system is


4.9 gal MeOH/MMSCF.

Calculating Methanol Injection Rates (Cryogenic Applications)


The calculation of methanol injection rates for cryogenic
applications follows the same general procedure just described
for general applications. Calculations for cryogenic applications
require the following:

A much larger safety factor (typically, at least 35F)

The calculation of an additional methanol injection rate to


compensate for methanol absorbed by a liquid hydrocarbon
component

Graphs with more complete data

More precise
temperatures

The use of very high methanol concentrations (90 wt %)

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Work Aid 1B groups the steps of this procedure into the following
sequential tasks:
1.

Calculating the water content and hydrate-formation


temperature of the gas stream (Figure 34)

2.

Calculating the required depression of the hydrate-formation


temperature, the safety margin, and determining the solubility
of methanol in hydrocarbons (Figure 35)

3.

Calculating the methanol injection rate (Figure 36)

Determining Water Content


As in the method for general applications, the amount of water that
is condensed out of the gas stream when the gas stream is cooled
or expanded in the chiller, separator, or other piece of equipment
must be calculated. Again, the saturation temperature of the gas
stream needs to be determined. Because graphs plotting data for
cryogenic conditions are in different units of measurement, the
flow rate of water needs to be converted to lb H2O/hr.

Determining Hydrate-Formation Temperature


To calculate the hydrate-formation temperature (TH) for the gas
stream, a method more sophisticated than the gravity graphic
method, such as the K-value method, or a computer program,
such as PRO/II, must be used.

Calculating Required Depression of Hydrate-Formation Temperature


For most situations, you should use a concentration of 90 wt %
methanol in the aqueous solution and calculate the depressed
hydrate-formation temperature. A methanol concentration of 90 wt
% depresses hydrate-formation temperatures by 234F. Figure
37 tabulates the results of the modified Hammerschmidt equation
(Eqn. 6).

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To adjust the flow rate of the injected inhibitor, a


concentration of methanol lower than 90 wt % may need to be
used. However, a proper safety margin (generally 35F) should be
maintained. The safety margin is the difference between the
hydrate-formation temperature and the depressed hydrateformation temperature (THdepressed). Safety margins should also
be calculated for downstream equipment.
Safety Margin -

The performance of a mass balance around the chiller, separator,


or other piece of equipment helps clarify the calculations. Figure 7
shows a mass balance around a separator.

Source:

Reproduced with permission from Hydrocarbon Processing, April 1983.

FIGURE 7: MASS BALANCE AROUND SEPARATOR

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Determining Solubility of Methanol in Hydrocarbons


Figures 38, 39, and 40 in Work Aid 1B plot the solubility of
methanol in hydrocarbon vapor (the vapor-to-liquid composition
ratio) for different temperature ranges. Figure 41 in Work Aid 1B
plots the solubility of methanol in hydrocarbon liquid.
Because the data extrapolated from plant data (dashed line) is
more conservative, you should (when possible) use it. Even
though this data is relatively conservative, you should still add a
safety margin of 20%.
In addition to these figures, computer programs such as PRO/II
and HYSIM also calculate methanol losses. Results generated by
computer programs, however, should be compared with results
from other sources.

Calculating Methanol Injection Rates


As in the general method, the total methanol injection rate is the
sum of partial injection rates required to do the following:

Achieve the required concentration of methanol in the aqueous


solution

Compensate for methanol vapor losses

Compensate for methanol lost when it dissolves into the


hydrocarbon liquid component

Because of the units of


measurement used in Figures 38, 39, and 40, the calculation of
the injection rate to account for vapor losses requires
multiplication of the vapor-to-liquid composition ratio by the flow
rate of the hydrocarbon vapor, instead of the gas stream feed rate.
The conversion of the injection rate to lb MeOH/hr requires the use
of the conversion factor of 379.5 SCF/lb-mole.
Injection Rate to Account for Vapor Losses -

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Because
of the units of measurement used in Figure 41, the calculation of
the injection rate to account for solubility hydrocarbon liquid
requires multiplication of the solubility of methanol by the flow rate
of the hydrocarbon liquid and the molecular weight of methanol (32
lb/mole).
Injection Rate to Account for Solubility Hydrocarbon Liquid -

The following sample problem demonstrates how to calculate a


methanol injection rate for a cryogenic application by using Work
Aid 1B. The fourteen steps of this sample problem parallel the
numbered steps of the procedure summarized in Figure 34,
Figure 35, and Figure 36 in Work Aid 1B.

Sample Problem:
Calculating Methanol Injection Rates
(Cryogenic Applications)
Referring to Work Aid 1B, calculate the methanol injection rate
required to inhibit hydrate formation in a separator. Figure 8
shows the flow of the gas stream. A gas-gas exchanger and a
chiller cool the gas stream before it is separated.
Given:

Source:

Nielsen, R. B. and R. W. Bucklin. "Use of Methanol for Hydrate Control in Expander Plants." Fluor
Engineers and Constructors, Inc. Presented at 1981 Gas Conditioning Conference. With permission
from Fluor Engineers and Constructors, Inc.

FIGURE 8: FLOW OF GAS STREAM IN METHANOL INJECTION SAMPLE PROBLEM (CRYOGENIC)

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Solution:
1. The water content of the inlet gas is given.
2. The methods described in the ChE 206.01 are used to
determine that the amount of free water condensed out of the
gas stream (W) is 2.24 lb H2O/MMSCF.
From ChE 206.01:
Woutlet
W

3.

= 0.012 lb H2O/MMSCF
= Winlet - Woutlet
(Eqn. 7)
= 2.25 lb H2O/MMSCF - 0.012 lb H2O/MMSCF
= 2.24 lb H2O/MMSCF

The flow rate of the condensed water is 168 lb H2O/hr.

qwater =

1 day
) 24 hr

(W)(q gas stream


(Eqn. 12)
2.24 lb H 2O
1,800 MMSCF 1 day

day
24 hr
= MMSCF
lb H 2O
168
=
hr

4.

The methods from ChE 206.01 are used to determine that


the hydrate-formation temperature (TH) of the gas stream is
45F.

5.

By using 90 wt % MeOH in the aqueous solution and


referring to Figure 37, the depressed hydrate-formation
temperature is determined to be -189F.
From Figure 38:
?T = 234F
THdepressed

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= TH - ? T
= 45F - 234F
= -189F

(Eqn. 13)

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6.

A methanol concentration of 90 wt % provides a safety


margin of 89F.
S = Tminimum - (TH - T)
= -100F - (45F - 234F)
= 89F

(Eqn.14)

7.

By referring to Figure 39, and using the values for the


temperature (-100F) and the pressure (600 psia) in the
separator, the solubility of methanol in hydrocarbon vapor is
determined to be 0.83 lb MeOH/MMSCF/mole fraction
MeOH in the aqueous solution.

8.

The plant data in Figure 41 is used to calculate the solubility


of methanol in hydrocarbon liquid at -100F. The addition of
a 20% safety margin results in the following:
0.2

From Figure 41: Solubility of MeOH in HC liquid=

mole MeOH
100 mole HC liquid

0.24
Adding a 20% safety margin:

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mole MeOH
100 mole HC liquid

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Figure 9 shows the mass balance around the separator.

Source:

Reproduced with permission from Hydrocarbon Processing, April 1983.

FIGURE 9: MASS BALANCE AROUND SEPARATOR IN METHANOL INJECTION SAMPLE PROBLEM


(CRYOGENIC)

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9.

The methanol injection rate required to account for methanol


vapor losses
(q MeOHvapor) is 45 lb MeOH/hr. From Figure 37, 90 wt %
methanol equals 0.835 mole fraction.

q MeOHvapor
=
(vapor-to-liquid composition ratio)(xMeOH)

SCF
379. 5

lb -mole

10 6

(qHCvapor)
(Eqn. 15)
0.83 lb MeOH
MMSCF
0.835 mole fraction MeOH
q MeOHvapor = mole fraction MeOH
173,000 mole HC vapor 379.5 SCF
lb-mole

6
hr
10
45 lb MeOH
hr
=
10. The methanol injection rate required to account for methanol
dissolved in hydrocarbon liquid is 1,940 lb MeOH/hr. From
Figure 46, the molecular weight of methanol (MMeOH) is 32
lb/mole.
q MeOHliquid =
=

(Solub ility of MeOH in HCliquid )(qHCliquid )(MMeOH )


0.24 mole MeOH
100 mole HC liquid

25,200 mole HC liquid


hr

(Eqn. 16)

32 lb MeOH
mole MeOH

= 1,940 lb MeOH/hr

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11. The methanol injection rate required to obtain a


concentration of 90 wt % MeOH in the aqueous solution is
1,510 lb MeOH/hr.

q MeOHaq =

w MeOHaq q water
w water aq

(Eqn. 17)
90 lb MeOH
168 lb H 2 O 100 lb aqueous solution

hr
10 lb H 2O
= 100 lb aqueous solution
= 1,510 lb MeOH/hr
12. The total methanol injection rate required for this system is
3,500 lb MeOH/hr.
q MeOHtotal

= q MeOHvapor + q MeOHliquid+ q MeOHaq(Eqn. 18)


= 45 lb MeOH/hr + 1,940 lb MeOH/hr + 1,510
lb MeOH/hr
= 3,495 lb MeOH/hr
3,500 lb MeOH/hr

13. From Figure 42, the density of methanol at 100F is 6.47


lb/gal. The conversion of the units of the methanol injection
rate results in the following:

1hr
q MeOH = (q MeOHtotal) densityMeOH
(Eqn. 19)
60 min
gal MeOH
hr
lbMeOH 6.47 lb MeOH 60 min
= 3,500

hr
= 9.0 gpm
Answer: The methanol injection rate required for this system is
9.0 gpm.

Source:

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Nielsen, R. B. and R. W. Bucklin. Use of Methanol for Hydrate Control in


Expander Plants. Fluor Engineers and Constructors, Inc. Presented at
1981 Gas Conditioning Conference. With permission from Fluor
Engineers and Constructors, Inc.

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CALCULATING GLYCOL INJECTION RATE REQUIRED TO INHIBIT HYDRATE


FORMATION IN A NATURAL GAS STREAM
Like methanol, glycol inhibits hydrate formation when injected into
gas streams.
Figure 10 compares the advantages and
disadvantages of glycol and methanol injection.

INHIBITOR
Glycol

ADVANTAGES
Usually lower operating cost than
methanol when both systems recover
injected chemical
Low vapor losses (low volatility)

DISADVANTAGES/ LIMITATIONS
High initial cost
Possibility of glycol contamination
Limited use (only noncryogenic
applications)
Cannot dissolve hydrates already
formed

Methanol

Relatively low initial cost

High operating cost

Simple system

Generally, use glycol injection if


methanol injection rate is over 30 gph

Does not generally need to be


recovered

Large vapor losses (high volatility)

Low viscosity
When injected, distributes well into gas
streams
Can dissolve hydrates already formed
FIGURE 10: COMPARISON OF CHEMICAL INJECTION INHIBITORS

Glycol does not evaporate as easily as methanol. In some


applications, glycol does not dissolve into liquid hydrocarbons as
easily as methanol. Glycol solubility in hydrocarbon liquid
increases with:

Glycol molecular weight

Temperature increase

Increase in glycol concentration in water-glycol mixture

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Glycol solubility also depends on hydrocarbon type. Glycols are


more soluble in aromatics and naphthenes than in paraffin
hydrocarbons. Glycol solubility in hydrocarbons at 60F and for
50-70 wt % of glycol concentrations, range from 10 to 50 ppm for
EG and 20 to 100 ppm for DEG. These losses are ~0.3 to 3 gal
glycol per 1000 barrels of condensate. Recovering glycol,
therefore, is generally more economical than recovering methanol.
Economical recovery of glycol often lowers its operating cost
below methanols operating cost because recovery compensates
for higher material cost. As a general rule, if the calculated
methanol injection rate for a natural gas stream exceeds 30 gph,
glycol injection should be chosen.

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Glycol Concentration and Dilution


In addition to inhibiting hydrate formation, you also need to choose
glycol concentrations that do not freeze. Figure 11 shows the
freezing points of various aqueous glycol solutions.

KEY:

Source:

MEG
DEG
TEG
TREG

=
=
=
=

Monoethylene glycol
Diethylene glycol
Triethylene glycol
Tetraethylene glycol (not generally used for hydrate inhibition)

Engineering Data Book, Vol. 2, 10th ed.


Processors Suppliers Association.

GPSA, Tulsa.

1987. With permission from the Gas

FIGURE 11: FREEZING POINTS OF AQUEOUS GLYCOL SOLUTIONS

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Note that solutions with glycol concentrations between about 60 wt


% and 80 wt % do not freeze. Because of this, glycol solutions are
generally kept between these concentrations, even if lower
concentrations are required to depress the hydrate-formation
temperature.
When glycol injection is performed below 20F, the glycol freezing
point must be considered. Glycols crystallize, but do not freeze
solid, which inhibits flow and proper separation. For this reason, it
is common practice to keep glycol concentrations between 60-80
wt %.
If unknowns exist, the inhibitor should not be diluted over 5-10% by
the pipeline stream being inhibited. For pipeline protection above
20F, a greater dilution may be tolerated but should not exceed
~20%. For spot injection, such as a heat exchanger, where
distribution is a problem, dilution may be limited to 5%.
To avoid the formation of emulsions, the water content of the
injected inhibitor (lean glycol) solution should be greater than 20 wt
%. Therefore, the injection rate of pure glycol required by the
system to inhibit hydrate formation is first calculated and then the
injection rate of the lean glycol solution is calculated.
To keep the concentration of the glycol between 60 wt % and 80
wt %, the extent to which the free water dilutes the injected glycol
must be determined. Figure 12 lists and summarizes dilution
restrictions.

SITUATION

Source:

ALLOWABLE OR
RECOMMENDED DILUTION OF
GLYCOL

Unknowns about the system


exist

Not over 5% to 10%

Spot injection (in a heat


exchanger, for example)

If distribution of glycol is a
problem, limit to about 5%

Pipelines operating above 20F

Up to about 20%

Francis S. Manning and Richard E. Thompson's Oilfield Processing of Petroleum, Volume One: Natural
Gas. Copyright PennWell Books, 1991.

FIGURE 12: ALLOWABLE GLYCOL DILUTIONS

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Selecting Glycol Type


The glycols normally used for hydrate inhibition are the following:

MEG

DEG

TEG

Selection of the appropriate type of glycol depends on the


composition of the gas stream and on information provided by the
glycol vendor.
For instance, Dow Chemical recommends that its glycols be used
at concentrations of 70 wt % to 75 wt % to avoid freezing
problems. Dow Chemical also makes the recommendations for
selecting glycols listed in Figure 13.

SITUATION/CONDITION

RECOMMENDATION

Natural gas transmission in


which recovery is not important

Use MEG because it depresses hydrateformation temperatures the most.

Injected glycol contacts


hydrocarbon liquids

Use MEG because it has the lowest


solubility of the glycols in high molecularweight hydrocarbons.

Severe vapor losses

Use DEG or TEG because both glycols


have lower vapor pressures than the other
glycols.

Severe vapor losses and


injected glycol contacts
hydrocarbon liquids

When both of these conditions are present,


DEG may be the best choice

Source: Dow Chemical reported by Exxon, p. 16.

FIGURE 13: DOW CHEMICAL GLYCOL RECOMMENDATIONS

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Glycol Injection and Recovery System


To help you understand the method for calculating glycol injection
rates, this section briefly describes two glycol injection and
recovery systems. The two systems differ in the method used to
remove the glycol from the hydrocarbons. The first system uses
two separators: one separator removes glycol from hydrocarbon
gas and the other separator removes glycol from hydrocarbon
liquid. The second system uses a three-phase single separator
that combines these two steps. This system also includes the
control system for varying the glycol injection rate.

Glycol Injection and Recovery System Using Two Separators


Figure 14 shows a typical glycol injection and recovery system that
uses a low temperature separator and a glycol-oil separator. In
this system, glycol injection inhibits the formation of hydrates while
a heat exchanger and a choke cool the gas stream.

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Source:

Francis S. Manning and Richard E. Thompson's Oilfield Processing of Petroleum, Volume One: Natural
Gas. Copyright PennWell Books, 1991.

FIGURE 14: GLYCOL INJECTION AND RECOVERY SYSTEM

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The glycol injection and recovery system shown in Figure 14 uses


the following:

A free-water knockout to remove free water from the gas


stream.

Glycol injection just before the heat exchanger and just before
the choke.

A low-temperature separator to remove gas from the gas,


glycol-water, and hydrocarbon mixture.

The separated cold, dry gas to pre-cool the gas stream in the
gas-gas heat exchanger.

A glycol-oil separator to remove rich glycol from the


hydrocarbon condensate.

The rich glycol to cool the regenerated glycol in the glycolglycol heat exchanger.

A glycol regenerator fired by fuel gas to regenerate the glycol


to the specified concentration for injection.

Glycol Injection and Recovery System Using a Three-Phase Separator


Figure 15 shows a typical glycol injection and recovery system
that uses a three-phase separator. The power-gas-driven pump,
the temperature controller, and the injection point shown in Figure
15 are similar to the methanol injection system shown in Figure 5.
A gas-driven pump injects the glycol into the gas stream upstream
from the choke or pressure-reducing valve. The temperature
controller measures the temperature in the gas stream and adjusts
the power-gas control valve. The power-gas control valve controls
the flow of power gas, which controls the injection rate.

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Source:

Dehydration and Hydrate Inhibition. Exxon Production Research Company, Production Operations
Division. July 1986. With permission from Exxon Production Research Company.

FIGURE 15: GLYCOL INJECTION AND RECOVERY SYSTEM (THREE-PHASE)

The recovery side of the system shown in Figure 15 includes a


reboiler and a three-phase separator. The glycol injection and
recovery cycle is as follows:

The injection nozzle injects the lean glycol into the gas stream.

The lean glycol absorbs the water and inhibits hydrate


formation in the choke or pressure-reducing valve.

The three-phase separator separates the water and rich glycol


from the hydrocarbon gas and liquid.

The separated components are piped to their respective


destinations.

The reboiler boils off excess water from the rich glycol, and
thereby prepares it to be injected again.

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Glycol Injection and Recovery System Components


Separators
The low-temperature separator shown in Figure 14 separates the
hydrocarbon gas from the hydrocarbon condensate-rich glycol
mixture. The glycol-oil separator in Figure 14 flashes the
remaining hydrocarbon condensate-rich glycol mixture to a low
pressure and then separates out the rich glycol. As shown in
Figure 15, three-phase separators combine the functions of the
low-temperature separator and the glycol-oil separator by
separating the inhibited gas stream into cold gas, hydrocarbon
condensate, and rich glycol in one vessel.
Separating the rich glycol from the hydrocarbon liquid is more
difficult than separating hydrocarbon liquid from vapor.
Performing both separations in one vessel sacrifices some
effectiveness and efficiency. Generally, three-phase separators
require longer residence times (20 to 40 minutes) and suffer
higher glycol losses.

Reboiler
The temperature in the reboiler depends on the type and
concentration of the glycol used. Reboilers in hydrate inhibition
systems do not regenerate glycols to the same high levels of purity
used in dehydration systems.
Figure 16 plots boiling temperatures of MEG. For example,
Figure 16 shows that the temperature of the reboiler should be set
at about 250F to achieve a lean MEG concentration of 75 wt % at
1 atm (absolute). It is important not to exceed the boiling point of
pure glycol because doing so causes thermal degradation.

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KEY:

B = Boiling curve
C = Condensing curve

Source:

Dehydration and Hydrate Inhibition. Exxon Production Research Company, Production Operations
Division. July 1986. With permission from Exxon Production Research Company.

FIGURE 16: BOILING POINT OF MEG

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Inhibitor Pump
A drum on top of a typical power-gas-driven pump contains the
inhibitor: methanol or glycol. The drum connects directly to the
pump (generally, a positive displacement pump). Methods for
monitoring the inhibitor injection rate include inserting a calibrated
dipstick through the top of the drum or pumping the inhibitor into a
measured vessel. Drums are replaced when empty.

Glycol Losses
Glycol injection systems that involve both hydrocarbon liquids and
gases generally lose glycol to the following:

Solubility (normally about 0.3 to 3 gallons of glycol per 1000


barrels of hydrocarbon liquid produced)

Leakage

Carryover with hydrocarbon liquid and in the reboiler

Vaporization in the reboiler and during injection

Nozzle Selection and Placement


Nozzle selection and placement indirectly affect glycol injection
calculations. Although calculated to inhibit hydrate formation,
injection rates may need to be adjusted to maintain a flow rate or
pressure recommended for a particular nozzle design or
placement.
Because of glycols low vapor pressure, nozzle design is more
critical for glycol than it is for methanol. To mix adequately with the
natural gas, glycol requires a fine, well-distributed mist. Also, to
inhibit hydrates fully, the nozzle must be placed to ensure full
coverage. Installing backup nozzles in parallel with the primary
nozzle allows nozzle removal, replacement, or inspection without
interrupting inhibitor service.

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Nozzle design is especially important in the


design of glycol injection systems for cold separation facilities.
The criteria for selecting a nozzle include the following:
Nozzle Selection -

Capacity

Spray angle

Sufficient pressure drop between the nozzle and the gas


stream over the expected range of operating conditions

Normally, a pressure differential of 100 psi to 150 psi sufficiently


atomizes glycol. Also, gas stream velocities above 12 ft/s help
ensure atomization.
Normally, nozzles are located just upstream of
the heat exchanger or chiller where hydrates form. The spray from
a properly located nozzle covers the entire tube sheet of a heat
exchanger.
Nozzle Placement -

Inadequate atomization causes the formation of glycol droplets


that settle and flood the bottom of the heat exchanger. As a result,
the glycol inhibits hydrate formation in the bottom, but not the top,
of the heat exchanger. Flooding of the bottom of the heat
exchanger also significantly decreases its effectiveness. Figure
17 shows injected glycol fully covering the tube sheet of a heat
exchanger.

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Source:

Rosen, Ward; Manual P-8: Hydrate Inhibition, 2nd ed. Petroleum Learning Programs, Ltd. Houston.
1991. With permission of Petroleum Learning Programs, Ltd.

FIGURE 17: GLYCOL SPRAYED ONTO THE TUBE SHEET OF A HEAT EXCHANGER

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Inadequate coverage can leave some tubes with a concentration


of glycol that is too low, which will result in the formation of
hydrates. As shown in Figure 18, hydrates plug the tubes, and
thereby increase the differential pressure across the heat
exchanger.

Source:

Rosen, Ward; Manual P-8: Hydrate Inhibition, 2nd ed. Petroleum Learning Programs, Ltd. Houston.
1991. With permission of Petroleum Learning Programs, Ltd.

FIGURE 18: INCREASE IN PRESSURE DROP BECAUSE OF HYDRATE FORMATION

Figure 19 shows three nozzle placements. Locating the nozzle too


close to the tube sheet reduces coverage. Locating the nozzle too
far from the tube sheet produces too wide a spray, which provides
too little glycol to the tube sheet.

Spray pattern with


proper nozzle
location
Source:

Spray pattern with


nozzle too close
to tube sheet

Spray pattern with


nozzle too far
from tube sheet

Rosen, Ward; Manual P-8: Hydrate Inhibition, 2nd ed. Petroleum Learning Programs, Ltd. Houston.
1991. With permission of Petroleum Learning Programs, Ltd.

FIGURE 19: NOZZLE PLACED AT THREE LOCATIONS: ONE FLOW RATE

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Figure 20 shows one nozzle location but three flow rates. Too low
a nozzle flow rate produces the same result as a nozzle located
too close to the tube sheet. Too high a nozzle flow rate produces
the same result as a nozzle located too far from the tube sheet.

Glycol

Glycol

Spray pattern at
proper glycol
flow rate
Source:

Spray pattern at
high glycol
flow rate

Glycol
Spray pattern at
low glycol
flow rate

Rosen, Ward; Manual P-8: Hydrate Inhibition, 2nd ed. Petroleum Learning Programs, Ltd. Houston.
1991. With permission of Petroleum Learning Programs, Ltd.

FIGURE 20: NOZZLE PLACED AT ONE LOCATION: THREE FLOW RATES

Calculating Glycol Injection Rates


Calculating glycol injection rates is similar to calculating methanol
injection rates, but it is more critical to maintain the glycol solution
between 60 wt % and 80 wt %. Also, glycol vapor losses are
insignificant: therefore, you do not need to account for them.
The method used to calculate methanol injection rates can be
used for glycol. However, because dilution is much more critical
for glycol, the method must be altered to account for glycol dilution
restrictions.
If you account for vapor and solubility losses, you can also use this
method for calculating methanol injection rates. With methanol,
however, the methanol concentration required to inhibit hydrates is
generally the minimum concentration allowed.

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The following sections briefly describe the method for calculating


glycol injection rates and how it differs from the method for
calculating methanol injection rates.
Water Content, Hydrate-Formation Temperature, and Safety Margin
As in the methanol calculations, the saturation temperature of the
gas stream needs to be determined. Whether the saturation
temperature of the gas stream is equal to or greater than the
temperature of the gas stream needs to be determined.
For most applications, the gravity graphic method is sufficient.
However, computer programs are best for design and critical
applications.
Equation 1 in Work Aid 1 uses a 5F safety margin (S) because it
is usually adequate to calculate the required depression of the
hydrate-formation temperature.

Concentration of Glycol
As with methanol, the Hammerschmidt equation (Eqn. 4) is used
to calculate the minimum glycol concentration that depresses the
hydrate-formation temperature of the gas stream.
wI =

where:

(T) (M)
KH + (T) (M)

(100)

(Eqn. 4)

w I = Weight percent of the chemical inhibitor


T = Depression of hydrate-formation temperature, F
M = Molecular weight of the chemical inhibitor
(methanol or glycol)
KH = 2,335 for methanol and 4,000 for glycol

Figure 50 in Work Aid 2 plots the results of the Hammerschmidt


equation solved for weight percent (Eqn. 4). These graphs greatly
simplify the calculation of inhibitor injection rates.

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Effects of Dilution Restrictions on Calculating Glycol Concentrations


Because of glycols dilution restrictions, you
need to determine the concentration of lean glycol (w lean). Vendor
specifications and/or reboiler temperatures usually dictate the
concentration of lean glycol (usually less than 80 wt % glycol).
Because pure glycol is not generally used, glycol injection rates
need to be increased to account for dilution.
Lean Glycol Solution -

Because dilution restrictions also apply to the


glycol concentration required to depress the hydrate-formation
temperature (w rich), the glycol concentration calculated by the
Hammerschmidt equation needs to be compared to the vendor
dilution recommendations.
Rich Glycol Solution -

If the glycol concentration required to depress the hydrateformation temperature is lower than the minimum glycol
concentration recommended by the vendor (usually greater than
60 wt % glycol), the glycol concentration recommended by the
vendor should generally be used.
In addition to the restrictions on the
concentrations of the lean and rich glycol solutions, the dilution of
the lean glycol may need to be limited. The concentration of the
rich glycol solution should be calculated by subtracting the allowed
amount of dilution recommended in Figure 12 or recommended by
a vendor from the concentration of the lean glycol.
Dilution of Rich Glycol Solution -

Once the
concentrations of the lean and rich glycol solutions have been
determined, an inhibitor injection rate that maintains both
concentrations should be calculated. Equation 22 calculates
inhibitor injection rates.
Equation

for

Calculating

W
q injection =
where: q injection
W

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Inhibitor

1
100 100

wrich w lean

Injection

Rate

qgas stream
(Eqn. 22)

= Inhibitor injection rate


= Water condensed from gas stream

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w rich

= Weight percent of glycol in the rich glycol

w lean

= Weight percent of glycol in lean glycol

q gas stream = Flow rate of gas stream


The following sample problem demonstrates how to calculate
glycol injection rates by using Work Aid 2. The eleven steps of this
sample problem parallel the numbered steps of the procedure
summarized in Figure 44 and Figure 45 in Work Aid 2.
Sample Problem: Calculating Glycol Injection Rates
Referring to Work Aid 2, calculate the glycol (MEG) injection rate
required to inhibit hydrates in the following gas stream cooled in a
buried pipeline.
Given:
Operating pressure
Minimum operating temperature
Saturation temperature of gas stream
Gas stream flow rate
Specific gravity

=
=
=
=
=

900 psia
45F
90F
10 MMSCFD
0.7

Solution:
1.

The water content at the saturation temperature is


substracted from the water content at the operating
temperature which results in a free water (q water) flow rate of
38.4 lb H2O/MMSCF.

From ChE 206.01:

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=
=
=

WTsaturation = 48 lb H2O/MMSCF
WTminimum = 9.6 lb H2O/MMSCF
WTsaturation - WTminimum
(Eqn. 8)
48 lb H2O/MMSCF - 9.6 lb H2O/MMSCF
38.4 lb H2O/MMSCF

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2.

The water content is multiplied by the gas stream flow rate,


which results in the following:
q water

=
=
=

W (q gas stream)
(Eqn. 20)
lb H 2 O
38.4
10 MMSCF
MMSCF
day
lb H 2 O
384
day

3.

By the gravity graphic method (covered in ChE 206.01), the


hydrate-formation temperature is 64F.

4.

The minimum operating temperature is subtracted from the


hydrate-formation temperature, and a safety factor is added,
which results in the required depression of the hydrateformation temperature of 24F.
T =
=
=

5.

TH - Tminimum + S
64F - 45F + 5F
24F

(Eqn. 1)

The Hammerschmidt equation solved for the weight percent


of inhibitor
(Eqn. 4) is used to determine that the system requires a 27
wt % concentration of glycol.
(T)(M)

(100)
K
+
(T)(M)
wI = H
(Eqn. 4)
(24)(62.10)
(100)
(4,000) + (24)(62.10)
=
= 27 wt % MEG

6.

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Let us suppose that the vendor recommends a lean glycol


concentration of 75 wt % MEG.

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7.

If there is an allowable dilution of 10%, the concentration of


the rich glycol is 65 wt % MEG.
w rich = w lean - (allowable dilution) (Eqn. 21)
= 75 wt % MEG - 10%
= 65 wt % MEG

8.

The rich glycol solution calculated in Step 7 is used because


it satisfies both hydrate inhibition and dilution restriction
conditions.

9.

From Figure 48, 65 wt % MEG and 75 wt % MEG do not


freeze.

10. Equation 22 is used to determine that the system requires


1,870 lb pure MEG/day.
W

1
100 100

wrich w lean

qgas stream

q injection =
38.4 lb H2 O
1

MMSCF
100 lb solution - 100 lb solution
=
65 lb MEG
75 lb MEG
lb
MEG
1,870
day
=

(Eqn. 22)

10 MMSCF
day

11. The value calculated in Step 9 and the density of MEG (from
Figure 49 assuming an injector solution temperature of 90F)
are used to determine that the system requires a lean glycol
injection rate of 276 gpd.
lb MEG 100lb lean glycol solution
galleanMEG
x
x
day
75lb MEG
9.07 lblean MEG
275 galleanMEG solution
=
day

q injection = 1870

Answer:
This system requires a minimum injection rate of 276 gallons of 75
wt % MEG (at 90F) per day.

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Calculating Glycol Injection Rates: Graphical Method


You can also use graphs to calculate glycol injection rates. When
available, graphs combine several of the steps required to
calculate glycol injection rates. Figure 51 (in Work Aid 2) plots
lean and rich MEG solutions and inhibitor injection rates. After
determining the concentrations of the lean and rich MEG solutions,
you can quickly determine the MEG injection rate on the y-axis of
Figure 51.
The following sample problem demonstrates how to calculate
glycol injection rates by using the graphical method described in
Work Aid 2. The eleven steps of this sample problem parallel the
numbered steps of the procedure summarized in Figure 44 and
Figure 45.
Sample Problem: Calculating Glycol Injection Rates (Graphical
Method)
Referring to Work Aid 2, calculate the glycol (MEG) injection rate
required to inhibit hydrates in the following gas stream.
Given:
Operating temperature
Chiller (minimum) temperature
Gas stream rate
Gas pressure
Specific gravity

=
=
=
=
=

85F
-10F
10 MMSCFD
800 psig
0.75

Solution:
1.

The water content at the chiller temperature is subtracted


from the water content at the operating temperature
(because the saturation temperature is equal to the
operating temperature), and the resulting amount of water
condensed (?W) is 44.5 lb H2O/MMSCF.

From ChE 206.01:


WTchiller

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WToperating
=
46 lb H2O/MMSCF
= 1.5 lb H2O/MMSCF

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These values are used to calculate the amount of water


condensed as follows:
W = WToperating - WTchiller
(Eqn. 7)
= 46 lb H2O/MMSCF - 1.5 lb H2O/MMSCF
= 44.5 lb H2O/MMSCF
2.

The flow rate of free water (q water) is 445 lb H2O/day.


q water

=
=
=

W (q gas stream)
(Eqn. 20)
44.5 lb H2O/MMSCF (10 MMSCFD)
445 lb H2O/day

3.

The gravity graphic method (ChE 206.01) is used to


determine that the hydrate-formation temperature is 64F.

4.

The chiller temperature is subtracted from the hydrateformation temperature and a safety margin is added, with the
result that the required depression of the hydrate-formation
temperature is 79F.
T = TH - Tchiller + S
= 64F - (-10F) + 5F
= 79F

(Eqn. 1)

5.

From Figure 50, the system requires a rich glycol


concentration of
67 wt % MEG to inhibit hydrate formation.

6.

The vendor recommends 80 wt % MEG lean glycol solution.

7.

Let us suppose that the rich MEG concentration should


remain above the general recommendation of 60 wt % MEG.

8.

The rich glycol concentration calculated in Step 5 (67 wt %)


meets both dilution and hydrate inhibition restrictions.

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9.

From Figure 48, 67 wt % MEG does not freeze and 80 wt %


MEG freezes at 50F.

10. Using the injection rate from Figure 51 and multiplying by the
flow rate of the gas stream, the system requires 2,225 lb of
MEG per day.
From Figure 51:

q MEG = 5

lb MEG
lb H2O

Converting units of measure:

5lb MEG 445lb H2 O


x
lbH2 O
day
lb MEG
= 2,225
day
11. Converting the units of measurement of glycol injection rate is
not necessary.
q MEGtotal

Answer:

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This system requires a minimum MEG injection rate of


2,225 lb MEG per day.

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SUMMARY
Hydrates can be inhibited in gas streams by controlling the
temperature of the gas stream or by injecting a chemical inhibitor.

Temperature Control Methods


The temperature of natural gas streams changes when the steams
are expanded or heated. Frequently, the temperature drop
caused by the expansion of a gas lowers the operating conditions
of a gas stream into its hydrate-formation zone. Expanding a gas
stream within the wellbore often keeps the gas stream above its
hydrate-formation temperature.
The two main pieces of equipment used to control gas stream
temperatures are downhole regulators and indirect heaters.
Downhole regulators inhibit hydrate formation by expanding gas
streams while they are in the wellbore. Indirect heaters inhibit
hydrate formation both at wellheads and along flowlines. Wellhead
heaters are often used to inhibit hydrate formation caused by
choking or expansion. Flowline heaters replace the heat lost by a
flowline to the surrounding air and ground.
Chemical Injection
Methanol (MeOH) and monoethylene glycol (MEG) are the two
chemicals most commonly injected into gas streams to inhibit
hydrate formation. Chemical injection is used to inhibit hydrate
formation in the following:

Situations where hydrate problems are of short duration

Gas streams operating a few degrees above their hydrateformation temperature

Gas-gathering systems in pressure-declining fields

Gas pipelines in which hydrates form at localized points

Figure 21 compares the four methods of hydrate inhibition


discussed in this module.

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DESIGN
FACTORS

GLYCOL
INJECTION

METHANOL
INJECTION

DOWNHOLE
REGULATORS

WELLHEAD
HEATERS

Investment

High*
Medium*

Very low
None

Very low
None

Very high
Very high

Low

Low

Low

Low

High
Very high*
High*
Low

Very high
Very low
Medium
Low

None
None
High
Low

Very low
Very high
High
Low

Fuel
Operating
Maintenance
Chemicals
Plot Area
Hazards
Downtime
* If glycol is recovered.
Source:

Dehydration and Hydrate Inhibition. Exxon Production Research Company, Production Operations
Division. July 1986. With permission from Exxon Production Research Company.

FIGURE 21: COMPARISON OF HYDRATE INHIBITION METHODS

Methanol
Methanol works well as a hydrate inhibitor because its
characteristics are as follows:

It is not corrosive.

It does not react chemically with any natural gas constituents.

It is soluble in water at all concentrations.

It is reasonable in cost.

Can dissolve existing hydrates to some degree.

Glycol
Glycol does not evaporate as easily as methanol. In some
applications, glycol does not dissolve into liquid hydrocarbons as
easily as methanol. Recovering glycol, therefore, is generally
more economical than recovering methanol. Economical recovery
of glycol often compensates for its higher material cost, lowering
its operating cost below that of methanol.

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Figure 22 compares using methanol and glycol to inhibit hydrates.

INHIBITOR

Glycol

ADVANTAGES

Usually lower operating cost


than methanol when both
systems recover injected
chemical
Low vapor losses (low
volatility)

DISADVANTAGES/
LIMITATIONS

High initial cost (if glycol is


recovered)
Possibility of glycol
contamination
Limited use (only
noncryogenic applications)
Cannot dissolve
hydrates already formed

Relatively low initial cost

High operating cost

Simple system

Generally, use glycol


injection if methanol
injection rate is over
30 gal/hr

Methanol

Does not generally need to be


recovered
Low viscosity

Large vapor losses (high


volatility)

When injected, distributes well


into gas streams
Can dissolve hydrates
already formed
Source:

Dehydration and Hydrate Inhibition. Exxon Production Research Company, Production Operations
Division. July 1986. With permission from Exxon Production Research Company.

FIGURE 22: COMPARISON OF CHEMICAL INHIBITORS

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Calculating Inhibitor Injection Rates Summary


The approach to calculating injection rates for methanol or glycol is
similar. The procedure can be briefly summarized as follows:

The amount of free water at the injection point is calculated.

The depression of the hydrate-formation temperature required


by the system is calculated.

The concentration of inhibitor required in the aqueous solution


to achieve the required depression of the hydrate-formation
temperature is determined.

When glycol is used, glycol concentrations are adjusted to


meet dilution restrictions.

When methanol is used, the amount of methanol lost to vapor


losses and solubility in hydrocarbon liquids is calculated.

The total injection rate required by the system is calculated.


This rate is the sum of the following partial injection rates
required to do the following:
-

Achieve the required inhibitor concentration in the aqueous


solution

Compensate for inhibitor dissolved into hydrocarbon liquid


components

If methanol, compensate for vapor losses

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WORK AID 1: PROCEDURES AND RESOURCES FOR CALCULATING METHANOL


INJECTION RATE REQUIRED TO INHIBIT HYDRATE FORMATION IN
A NATURAL GAS STREAM
Work Aid 1A: Procedures and Resources for Calculating Methanol Injection Rates
(General Applications)
Note:

The equations developed for this Work Aid make the


implicit assumption that pure methanol is injected.
Otherwise, significant errors can result when these
equations are used for cryogenic applications. When in
doubt, perform overall mass balances.

Required Depression of Hydrate-Formation Temperatures


T =TH - Tminimum + S
where:

(Eqn. 1)

Depression of hydrate-formation temperature, F

TH

Hydrate-formation temperature of gas stream, F

Tminimum

Safety factor to account for uncertainty in TH, F

Miminum temperature of system, F

Hammerschmidt Equation

(W )(w MeOH )

(w water )

where:

(Eqn. 3)

T = Depression of hydrate-formation temperature, F


KH = 2,335 for methanol and 4,000 for glycol
wI

= Weight percent of the chemical inhibitor in the solution

= Molecular weight of the chemical inhibitor (methanol or glycol)

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Hammerschmidt Equation (Eqn. 3) Solved for the Weight Percent of Inhibitor


1 day
24 hr

where: w I =

(Eqn. 4)

Weight percent of the chemical inhibitor in the solution

T =

Depression of hydrate-formation temperature, F

Molecular weight of the chemical inhibitor (methanol or glycol)

KH =

2,335 for methanol and 4,000 for glycol

Free Water Condensed Out of Gas Stream


If the saturation temperature equals the operating temperature:
W = WToperating - WTminimum

(Eqn. 7)

where: W = Amount of free water condensed out of the gas


stream, lb/MMSCF
WToperating = Saturated water content of the gas stream at its
operating temperature, lb/MMSCF
WTminimum = Saturated water content of the gas stream at the
minimum temperature of the gas stream, lb/MMSCF
If the saturation temperature is higher than the operating
temperature:
W = WTsaturation - WTminimum

(Eqn. 8)

where: W = Amount of free water condensed out of the gas


stream, lb/MMSCF
WTsaturation

=Water content of a gas stream at its saturation temperature, lb/

WTminimum =

Saturated water content of the gas stream at the


minimum temperature of the gas stream,
lb/MMSCF

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Methanol Injection Rate Required to Compensate for Vapor Losses


q MeOHvapor = (vapor-to-liquid composition ratio)(w MeOH)
where: q MeOHvapor
w MeOH

(Eqn. 9)

= Methanol injection rate required to compensate for


vapor losses, lb MeOH/MMSCF/wt % MeOH

= Weight percent of methanol in the aqueous solution

Methanol Injection Rate Required to Achieve Aqueous Methanol Concentration

(W )(w MeOH )
q MeOHaq =
where: q MeOHaq

(w water )

(Eqn. 10)

= Methanol injection rate required to achieve the


concentration of methanol in the aqueous solution
that inhibits hydrate formation, lb/MMSCF

W = Amount of free water condensed out of the gas stream, lb/MMSCF


w MeOH = Weight percent of methanol in the aqueous
solution
w water = Weight percent of water in the aqueous solution
Total Methanol Injection Rate
q MeOHtotal=q MeOHvapor + q MeOHaq

(Eqn. 11)

where: q MeOHtotal = Total methanol injection rate required to inhibit


hydrate formation, lb/MMSCF
q MeOHvapor = Methanol injection rate required to compensate for
vapor losses, lb/MMSCF
q MeOHaq

Saudi Aramco DeskTop Standards

= Methanol injection rate required to achieve the


concentration of methanol in the aqueous solution
that inhibits hydrate formation, lb/MMSCF

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Figures 30 and 31 summarize the procedure for calculating MeOH


injection rates for general hydrate-inhibition applications.

Source:

Underground Storage of Fluids, 1968. With permission from Ulrich's Book Store.

FIGURE 30: SUMMARY OF METHOD FOR CALCULATING METHANOL INJECTION RATES


(STEPS 1 TO 4)

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STEP
5

QUANTITY
Concentration of MeOH in
aqueous solution (wt %
MeOH)

EQUATION, METHOD, OR RESOURCE


Use the Hammerschmidt equation (Eqn. 4):

1
100 100

wrich w lean

qgas stream
(Eqn. 4)

Or use Figure 32.


To determine M, use Figure 46.
6

MeOH injection rate to


account for MeOH vapor
losses, q MeOHvapor

To determine the vapor-to-liquid composition


ratio, use Figure 33.

MeOH injection rate to


obtain MeOH wt %
calculated in Step 3,
q MeOHaq

Qt
q MeOHaq = (U) (LMTD )

Total MeOH injection rate


(lb MeOH/MMSCF),
q MeOHtotal

To add the injection rates calculated in Steps 6


and 7, use Eqn. 11.

If necessary, convert
q MeOHtotal to appropriate
units

Divide q MeOHtotal (Step 7) by density of


MeOH.

q MeOHvapor = (vapor-to-liquid composition


ratio) x (w MeOH)
(Eqn. 9)

(Eqn. 10)

q MeOHtotal = q MeOHvapor + q MeOHaq

To determine the density of MeOH, assume it is


6.56 lb/gal or use Figure 42.
Source:

Katz, Donald L. and Robert L. Lee, Natural Gas Engineering: Production and Storage, McGraw-Hill,
1990, p. 220, Table 5.5.

FIGURE 31: SUMMARY OF METHOD FOR CALCULATING METHANOL INJECTION RATES


(STEPS 5 TO 9)

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Source:

Katz, Donald L. and Robert L. Lee. Natural Gas Engineering: Production and Storage. McGraw-Hill.
1990. With permission from McGraw-Hill.

FIGURE 32: DEPRESSION OF HYDRATE-FORMATION TEMPERATURES,


?T (METHANOL)

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Source:

Katz, Donald L. and Robert L. Lee. Natural Gas Engineering: Production and Storage. McGraw-Hill.
1990. With permission from McGraw-Hill.

FIGURE 33: METHANOL VAPOR-TO-LIQUID COMPOSITION RATIOS

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Work Aid 1B: Procedures and Resources for Calculating Methanol Injection Rates
(Cryogenic Applications)
The procedure outlined below is based on the
assumption that pure methanol is injected.

Note:

Depression Of Hydrate-Formation Temperatures


T = TH - Tminimum+ S

(Eqn. 1)

where: T

= Depression of hydrate-formation temperature,


F

TH

= Hydrate-formation temperature of gas stream,


F

Tminimum = Minimum temperature of system, F


S

= Safety factor to account for uncertainty in TH, F

Hammerschmidt Equation Modified for High Concentrations of Methanol


T = -129.6 ln 1-xMeOH

where:

(Eqn. 6)

T = Depression of hydrate-formation temperature, F

xMeOH = Mole fraction of MeOH in the aqueous-methanol


solution

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Free Water Condensed Out of Gas Stream


If the saturation temperature equals the operating temperature:
W = WToperating - WTminimum
where:

(Eqn. 7)

W = Amount of free water condensed out of the gas


stream, lb/MMSCF

WToperating

= Saturated water content of the gas stream at its


operating temperature, lb/MMSCF

WTminimum

= Saturated water content of the gas stream at the


minimum temperature of the gas stream,
lb/MMSCF

If the saturation temperature is higher than the operating


temperature:
W = WTsaturation - WTminimum

(Eqn. 8)

W =Amount of free water condensed out of the gas


stream, lb/MMSCF

where:
WTsaturation

= Water content of a gas stream at its saturation


temperature,
lb/MMSCF

WTminimum

= Saturated water content of the gas stream at the


minimum temperature of the gas stream,
lb/MMSCF

Flow Rate of Free Water

1 day
q water = (W) (q gas stream) 24 hr
where:

q water
W

(Eqn. 12)

=Flow rate of free water in a gas stream, lb/hr


= Amount of free water in a gas stream per unit
of gas, lb/MMSCF

q gas stream = Flow rate of gas stream, MMSCF/D

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Depressed Hydrate-Formation Temperature (T Hdepressed)


THdepressed = TH - T

(Eqn. 13)

where: THdepressed = Hydrate-formation temperature resulting


from injection of chemical inhibitor, F
TH

= Hydrate-formation temperature of gas


stream, F

= Depression of hydrate-formation
temperature, F

Safety Margin
S =Tminimum - (TH - T)
where:

(Eqn. 14)

= Safety margin, F

Tminimum = Minimum temperature of gas stream, F


TH

= Hydrate-formation temperature of gas


stream, F

= Depression of hydrate-formation
temperature, F

Methanol Injection Rate: Vapor Losses


q MeOHvapor = (vapor-to-liquid composition ratio)(x MeOH)

SCF
379. 5

lb -mole

10 6

(q HCvapor )
(Eqn. 15)
where: q MeOHvapor=

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Methanol injection rate required to


compensate for vapor losses, lb/hr

x MeOH

Mole fraction of methanol in the aqueous


solution

q HCvapor

Molar flow rate of hydrocarbon vapor, lbmole/hr

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Methanol Injection Rate: Solubility in Hydrocarbon Liquid


q MeOHliquid = (solubility of MeOH in HC liquid)(qHCliquid)(MMeOH )

(Eqn. 16)

where: q MeOHliquid = Methanol injection rate to compensate for


methanol absorbed by hydrocarbon liquid,
lb/hr
q HCliquid

= Molar flow rate of hydrocarbon liquid, lbmole/hr

MMeOH

= Molecular weight of methanol

Methanol Injection Rate Required to Achieve Aqueous Methanol Concentration


q MeOHaq =

wMeOH aq qwater
w water aq

(Eqn. 17)

where: q MeOHaq

= Methanol injection rate required to achieve


the concentration of methanol in the
aqueous solution that inhibits hydrate
formation, lb/hr

wMeOHaq

= Weight percent of methanol in the aqueous


solution

qwater
wwateraq

= Mass flow rate of free water, lb/hr


= Weight percent of water in the aqueous
solution

Total Methanol Injection Rate (Cryogenic)


q MeOHtotal = q MeOHvapor + q MeOHliquid + q MeOHaq
where:

(Eqn. 18)

q MeOHtotal = Total methanol injection rate required to


inhibit hydrate formation, lb/hr
q MeOHvapor = Methanol injection rate required to
compensate for vapor losses, lb/hr

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q MeOHliquid

= Methanol injection rate to compensate


for methanol absorbed by hydrocarbon
liquid, lb/hr

q MeOHaq = Methanol injection rate required to


achieve the concentration of methanol in
the aqueous solution that inhibits hydrate
formation, lb/hr
Methanol Injection Rate Converted to gpm

q MeOH = q MeOHtotal

1 hr
densityMeOH 60 min

where: q MeOH

(Eqn. 19)

= Methanol injection rate converted to gpm

q MeOHtotal = Total MeOH injection rate required to inhibit


hydrate formation, lb/hr
densityMeOH =

Density of methanol, lb/gal

Figures 34, 35, and 36 summarize the method for calculating


methanol injection rates to inhibit hydrate formation in cryogenic
applications. The steps of this procedure are grouped into the
following sequential tasks:
1. Calculating the water content and
temperature of the gas stream (Figure 34)

hydrate-formation

2. Calculating the required depression of the hydrate-formation


temperature, the safety margin, and determining the solubility
of methanol in hydrocarbons (Figure 35)
3. Calculating the methanol injection rate (Figure 36)

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STEP

QUANTITY

Saturation temperature of
gas stream, Tsaturation

EQUATION, METHOD, OR RESOURCE

Minimum temperature of
the system, Tminimum
2

If the saturation temperature equals the


Amount of water
condensed in gas stream, operating temperature:
W
W = WToperating - WTminimum
(Eqn. 7)
If the saturation temperature is higher than
the operating temperature:
W = WTsaturation - WTminimum

(Eqn. 8)

To determine WT, use the methods


described in ChE 206.01.
3

Flow rate of condensed


water, q water

Use Eqn 12:

Hydrate-formation
temperature, TH

To determine the hydrate-formation


temperature (TH), use the gravity graphic
method or a computer program
(ChE 206.01).

1 day
q water = (W) x (q gas stream) x 24 hr

FIGURE 34: SUMMARY OF CALCULATING METHANOL INJECTION RATE


FOR CRYOGENIC APPLICATIONS (STEPS 1 TO 4)

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STEP
5

QUANTITY

Depressed hydrateformation temperature,


THdepressed

METHOD OR RESOURCE TO USE

Use 90 wt % MeOH in the aqueous solution.


To calculate T, use Figure 37 or Eqn. 6:
T = -129.6 ln 1-xMeOH

(Eqn. 6)

For 90 wt % MeOH, T = 234F.


TH depressed = TH - T
6

Safety margin, S

(Eqn. 13)

Use Eqn. 14 (Eqn. 1 solved for S):


S = T - (TH - Tminimum)

(Eqn.14)

The safety margin (S) should be at least


35F.
7

Solubility of MeOH in
hydrocarbon vapor
(vapor-to-liquid
composition ratio)

Perform a mass balance around the chiller,


separator, or other piece of equipment.

Solubility of MeOH in
hydrocarbon liquid

Use solubility data extrapolated from plant


data in Figure 41.

Use Figure 38, 39, or 40.

Add a safety margin of 20%.

FIGURE 35: SUMMARY OF CALCULATING METHANOL INJECTION RATE


FOR CRYOGENIC APPLICATIONS (STEPS 5 TO 8)

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STEP
9

10

11

12

QUANTITY

EQUATION, METHOD, OR RESOURCE

MeOH injection rate to


compensate for MeOH
vapor losses,
q MeOHvapor

Use Eqn. 15:

MeOH injection rate to


compensate for MeOH
absorbed by HC liquid,
q MeOHliquid

Use Eqn. 16:

MeOH injection rate to


obtain 90 wt % MeOH in
the aqueous solution,
q MeOHaq

Use Eqn. 17:

Total MeOH injection


rate, q MeOHtotal

Use Eqn. 18:

q MeOHvapor =
(vapor-to-liquid composition ratio)(x MeOH)

SCF
379. 5

lb -mole
(qHCvapor)
(Eqn. 15)

10 6

q MeOHliquid = (solubility of MeOH in HC liquid)


(qHCliquid)(MMeOH )
(Eqn. 16)

q MeOHaq =

w MeOHaq q water
w water aq

(Eqn. 17)

q MeOHtotal = q MeOHvapor + q MeOHliquid


+ q MeOHaq
(Eqn. 18)
13

If necessary, convert
injection rate units

Use Eqn. 19:

1
1 hr
q MeOH = q MeOHtotal
60 min (Eqn.
density MeOH
19)
To determine the density of methanol, either use
Figure 42 or assume the density of methanol equals
6.56 lb/gal.

FIGURE 36: SUMMARY OF CALCULATING METHANOL INJECTION RATE


FOR CRYOGENIC APPLICATIONS (STEPS 9 TO 14)

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Source:

MEOH, MOLE
FRACTION

MeOH, WT %

T, F

0.0

0.0

0.0

0.1

16.5

13.7

0.2

30.8

28.9

0.3

43.2

46.2

0.4

54.2

66.2

0.5

64.0

89.8

0.7

80.6

156

0.8

87.7

209

0.835

90.0

234

Nielsen, R. B. and R. W. Bucklin. "Use of Methanol for Hydrate Control in Expander Plants. Fluor
Engineers and Constructors, Inc" Presented at 1981 Gas Conditioning Conference. With permission
from Fluor Engineers and Constructors, Inc.

FIGURE 37: DEPRESSION OF HYDRATE-FORMATION TEMPERATURE BY METHANOL


(MODIFIED HAMMERSCHMIDT EQUATION)

Source:

Reproduced with permission from Hydrocarbon Processing, April 1983.

FIGURE 38: SOLUBILITY OF METHANOL IN HYDROCARBON VAPOR (65F TO -20F)

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Source:

Reproduced with permission from Hydrocarbon Processing, April 1983.

FIGURE 39: SOLUBILITY OF METHANOL IN HYDROCARBON VAPOR (-20F TO -120F)

Source:
Reproduced with permission from Hydrocarbon Processing, April 1983.

FIGURE 40: SOLUBILITY OF METHANOL IN HYDROCARBON VAPOR (-125F TO -175F)

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Source:

Reproduced with permission from Hydrocarbon Processing, April 1983.

FIGURE 41: SOLUBILITY OF METHANOL IN HYDROCARBON LIQUID

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8.5
5%
10%
20%

8.0

30%
40%
50%

7.5

60%
70%
80%

7.0
90%
100%
wt % MeOH

6.5

6.0
-80

-60

-40

-20

20
40
60
Temperature, F

80

100

120

Lange's Handbook of Chemistry, 11th edition 1973


Calculated pt. based on excess volume data,
thermodynamics research lab. Washington University, 1973
Calculated freezing pt. at various temp. and wt% based on
Lange's graph and pure methanol and water density
Extended curve
Pure methanol
Given freezing pt. by Lange's graph

Source:

Nielsen, R. B. and R. W. Bucklin. "Use of Methanol for Hydrate Control in Expander Plants. Fluor
Engineers and Constructors, Inc." Presented at 1981 Gas Conditioning Conference. With permission
from Fluor Engineers and Constructors, Inc.

FIGURE 42: DENSITY OF AQUEOUS METHANOL SOLUTIONS

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Source:

Nielsen, R. B. and R. W. Bucklin. "Use of Methanol for Hydrate Control in Expander Plants. Fluor
Engineers and Constructors, Inc" Presented at 1981 Gas Conditioning Conference. With permission
from Fluor Engineers and Constructors, Inc.

FIGURE 43: WATER CONTENT (W) OF NATURAL GAS AT LOW TEMPERATURES

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WORK AID 2: PROCEDURES AND RESOURCES FOR CALCULATING GLYCOL


INJECTION RATE REQUIRED TO INHIBIT HYDRATE FORMATION IN
A NATURAL GAS STREAM

The procedure outlined below is based on the assumptions that


the condensation of hydrocarbons and the loss of glycol in the
hydrocarbon phase is insignificant (both assumptions directionally
underestimate the amount of glycol required).
T = TH - Tminimum+ S
where:

(Eqn. 1)

Depression of hydrate-formation
temperature, F

TH

Hydrate-formation temperature of gas


stream, F

Tminimum =

Minimum temperature of system, F

Safety factor to account for uncertainty in


TH, F

Depression Of Hydrate-Formation Temperatures (Thermodynamic)


T =

where:

n
RT02

In 1+ inhibitor
Hf

n solvent

(Eqn. 2)

= Depression of hydrate-formation
temperature, F

= Gas constant

T0

= Normal freezing point (absolute


temperature scale)

Hf

= Enthalpy of fusion per mole of solvent

ninhibitor = Moles of solute (inhibitor)


n solvent = Moles of solvent (water)

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Hammerschmidt Equation
T=

KHwI
100M - M wI

(Eqn. 3)

where: T = Depression of hydrate-formation temperature, F


KH = 2,335 for methanol and 4,000 for glycol
w I = Weight percent of the chemical inhibitor in the
solution
M = Molecular weight of the chemical inhibitor
(methanol or glycol)
Hammerschmidt Equation (Eqn. 3) Solved for the Weight Percent of Inhibitor
wI =
where:

(T)(M ) (100 )
KH + (T )(M)

(Eqn. 4)

wI

Weight percent of the chemical inhibitor in


the solution

Depression of hydrate-formation
temperature, F

Molecular weight of the chemical inhibitor


(methanol or glycol)

KH =

2,335 for methanol and 4,000 for glycol

Free Water Condensed Out of Gas Stream


If the saturation temperature equals the operating temperature:
W = WToperating - WTminimum
where:

(Eqn. 7)

= Amount of free water condensed out of


the gas stream, lb/MMSCF

WToperating = Saturated water content of the gas stream


at its operating temperature, lb/MMSCF

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WTminimum = Saturated water content of the gas stream


at the minimum temperature of the gas
stream, lb/MMSCF
If the saturation temperature is higher than the operating
temperature:
W = WTsaturation - WTminimum
where: W

(Eqn. 8)

= Amount of free water condensed out of


the gas stream, lb/MMSCF

WTsaturation = Water content of a gas stream at its


saturation temperature, lb/MMSCF
WTminimum = Saturated water content of the gas stream
at the minimum temperature of the gas
stream, lb/MMSCF
Flow Rate of Free Water, q water (Glycol Injection Rate Calculations)
q water = (W)(q gas stream)
where: q water
W

(Eqn. 20)

= Flow rate of free water in a gas stream,


lb/D
= Amount of free water in a gas stream per
unit of gas, lb/MMSCF

q gas stream = Flow rate of gas stream, MMSCF/D


Rich Glycol Concentration Required to Meet Dilution Restrictions (w richdilution)
w rich = w lean - (allowable dilution)
where:

(Eqn. 21)

w rich = Weight percent of glycol in the rich glycol


w lean = Weight percent of glycol in lean glycol

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Inhibitor Injection Rate (Dilution Restricted)

W
q injection =

1
qgas stream
100 - 100
wrich wlean

where: q injection

(Eqn. 22)

= Inhibitor injection rate, lb/D

= Content of water in gas stream,


lb/MMSCF

w rich

= Weight percent of glycol in the rich glycol

w lean

= Weight percent of glycol in lean glycol

q gas stream = Flow rate of gas stream, MMSCF/D

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Figures 44 and 45 summarize the procedure for calculating glycol


injection rates.
STEP
1

QUANTITY

EQUATION, METHOD, OR RESOURCE

If the saturation temperature equals the


Amount of water
condensed in gas stream, operating temperature:
W
W = WToperating - WTminimum
(Eqn. 7)
If the saturation temperature is higher than
the operating temperature:
W = WTsaturation - WTminimum

(Eqn. 8)

To determine WT, use the methods


described in ChE 206.01.
2

Flow rate of free water,


q water

Use Eqn. 20:


q water = (W) x (q gas stream)

(Eqn. 20)

Hydrate-formation
temperature, TH

To determine the hydrate-formation


temperature (TH), use the gravity graphic
method or a computer program
(ChE 206.01).

Required depression of
hydrate-formation
temperature, T

T = TH - Tminimum + S

Concentration of glycol in Use Hammerschmidt equation (Eqn. 4) or


aqueous solution required Figure 50.
to inhibit hydrateformation temperature, w w = (T)(M) (100)
(Eqn. 4)
I
richinhibit
KH + (T)(M)

(Eqn. 1)

To determine the molecular weight of the


inhibitor, use Figure 46.
6

Lean glycol concentration


required to meet dilution
restrictions

Use between 60 wt % and 80 wt % glycol or


specific vendor recommendations.

FIGURE 44: CALCULATING GLYCOL INJECTION RATES (STEPS 1 TO 6)

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STEP
7

QUANTITY

Rich glycol concentration


required to meet dilution
restrictions, w richdilution

METHOD OR RESOURCE TO USE

Use Eqn. 21:


w rich = w lean - (allowable dilution)
To determine allowable dilution (usually
between 5 wt % and 20 wt%), use
Figure 47 or recommendations of the glycol
vendor.
Or, use minimum glycol concentration
specifically recommended by vendor or within
general range of 60 wt % to 80 wt %.

Rich glycol concentration


used to calculate inhibitor
injection rate,
w rich

Ensure that both the hydrate inhibition


(Step 5) and dilution restriction conditions are
met (Step 7).
Use the greater of the values calculated in
Step 5 (w richinhibit) and Step 7 (w richdilution).

10

Freezing point of glycol


solutions

To determine the freezing point of a glycol


solution when glycol concentrations outside of
the 60 wt % to 80 wt % are used, use Figure
48.

Inhibitor injection rate,


q injection

Use Eqn. 22:


W
q injection =

1
qgas stream
100
100
(
)
wrich wlean

Or, use Figure 51 to calculate the inhibitor


injection rate in lb MEG/lb H2O and multiply
by the condensed water rate.
11

If necessary, convert
glycol injection rate to
appropriate units

To determine the density of glycol, use Figure


46 or Figure 49.

FIGURE 45: CALCULATING GLYCOL INJECTION RATES (STEPS 7 TO 11)

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PROPERTY

MeOH

MEG

DEG

TEG

TREG

Molecular Weight

32.04

62.10

106.10

150.20

194.23

Boiling Point at 760mm


Hg, F

148.10

387.10

427.60

532.90

597.2

Vapor Pressure at 77F,


mm Hg

94

0.12

<0.01

< 0.01

< 0.01

Specific Gravity at 77F

0.7868

1.110

1.113

1.119

1.120

Specific Gravity at 140F

--

1.085

1.088

1.092

1.092

Density at 77F, lb/gal

6.55

9.26

9.29

9.34

9.34

Freezing Point, F

-144

17

19

22

Pour Point, F

--

< -75

-65

-73

-42

Absolute Viscosity at 77F,


Centipoise (cP)

0.55

16.5

28.2

37.3

39.9

Absolute Viscosity at
140F, Centipoise (cP)

0.36

5.1

7.6

9.6

10.2

Surface Tension at 77F,


Dynes/cm

22

47

44

45

45

Specific Heat at 77F,


Btu/lb/F

0.27

0.58

0.55

0.53

0.52

Flash Point, F

--

240

280

320

365

Fire Point, F

--

245

290

330

375

Decomposition
Temperature, F

--

329

328

404

460

Heat of Vaporization at
14.7 psi, Btu/lb

473

364

232

179

--

Source:

Dehydration and Hydrate Inhibition. Exxon Production Research Company, Production Operations
Division. July 1986. With permission from Exxon Production Research Company.

FIGURE 46: PHYSICAL PROPERTIES OF HYDRATE INHIBITORS

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SITUATION

ALLOWABLE OR RECOMMENDED DILUTION


OF GLYCOL

Unknowns about the system exist

Not over 5% to 10%

Spot injection (in a heat exchanger,


for example)

If distribution of glycol is a problem, 5%

Pipelines operating above 20F

Up to about 20 %

Source:

Francis S. Manning and Richard E. Thompson's Oilfield Processing of Petroleum, Volume One: Natural
Gas. Copyright PennWell Books, 1991.

FIGURE 47: ALLOWABLE GLYCOL DILUTIONS

Source:

Engineering Data Book, Vol. 2, 10th ed. GPSA, Tulsa. 1987. With permission from the Gas
Processors Suppliers Association.

FIGURE 48: FREEZING POINTS OF AQUEOUS GLYCOL SOLUTIONS

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Source:

Francis S. Manning and Richard E. Thompson, Oilfield Processing of Petroleum, Volume One: Natural
Gas. Copyright PennWell Books, 1991.

FIGURE 49: DENSITY OF MEG SOLUTIONS

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Source: Sheilan, p. 111, Figure 3.

FIGURE 50: DEPRESSION OF HYDRATE-FORMATION TEMPERATURE (MEG)

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lb H 2O

Concentration of rich MEG =

Concentration of rich MEG =

Concentration of rich MEG =

12

Concentration of rich MEG =

14

Concentration of rich MEG =

Hydrate Inhibition Methods

10

0
100

80
60
40
Concentration of inject ed lean MEG , wt %

20

Source: Sheilan, p. 112, Figure 4.

FIGURE 51: MEG INJECTION RATE

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GLOSSARY
aqueous solution

A solution in which the solvent is water.

borehole

See wellbore.

dilution

When injected, the amount by which a chemical


inhibitor is diluted by the free water in a gas stream.
The difference between the concentration of a
chemical inhibitor in the injection solution and the
concentration of the chemical inhibitor in the
aqueous solution.

choke

A device that restricts and controls the flow rate of


well fluids.

DEG

Diethylene glycol.

downhole

A term describing tools, equipment, and instruments


used in the wellbore. Also describes conditions or
techniques applying to the wellbore.

emulsion

A stable dispersion of one liquid in a second


immiscible liquid, such as oil dispersed in water.

enthalpy

A thermodynamic property (H) of a system equal to


the sum of the system's internal energy (U) and the
product of pressure (p) and volume (V). The formula
is H = U + pV.

expansion loop

A loop of tubing in the flowline that adjusts when


temperature changes cause change in flowline
length.

fire tube

In a heater, the tubing in contact with the heater bath.

free-water knockout

A tank or separator vessel that separates free water


from a gas stream.

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heater bypass valve

A valve that bypasses gas around the heater after


wellhead pressure has been drawn down to nearsalesline pressure.

heater coil

A multiple-pass steel coil.

heater flame arrestor

A device that prevents the heater fire from flashing


back through the air intake.

high-pressure flowline

Tubing, normally at least 150 ft long, designed to


withstand full wellhead shut-in pressure.

immiscible

Pertaining to fluids that do not mix with each other.

lean glycol

A glycol solution with a relatively low water content.

log mean temperature


difference (LMTD)

The temperature difference of one side of a heat


exchanger minus the temperature difference of the
other side of the heat exchanger divided by the
natural logarithm of the ratio of these two
temperature differences.

long-nose heater choke A pressure-reducing valve.


MEG

Monoethylene glycol.

reboiler

A heater that reheats or reboils part of a process


stream drawn off a distilling column and then
reintroduced to the column as vapor.

reboiling

The process of reheating the bottoms product from


a distilling column to ensure more complete
fractionation.

relief valve

A valve that protects the low-pressure flowline from


over pressures.

residue gas

Gas that remains after processing in a separator.


Any gas from a processing unit treated as residue.

rich glycol

A glycol solution with a relatively high water content.

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safety-drilled

The drilling of small holes halfway into the return


bends of heater tubing. When these holes leak, the
tubing has worn halfway through and should be
replaced.

safety shut-in wing


valve

A pneumatically actuated valve that closes when it


senses low flowline pressure downstream
(indicating a rupture) or abnormally high or low
pressure upstream.

shut in

The closing of valves on a well to stop production.

still

A column in which the absorbed product is distilled


from the lean solution.

TEG

Triethylene glycol.

three-phase separator

A pressure vessel that separates fluids into a vapor


phase and two liquid phases.

TREG

Tetrathylene glycol.

tubing string

The entire length of tubing run into a wellhole.

wellbore

The hole in the earth made by the drill. The uncased


drill hole from the surface to the bottom of the well.
Also known as borehole.

wellhead

The top of the casing and the attached control and


flow valves. The wellhead is where control valves,
testing equipment, and take-off piping are located.

wireline

A small-diameter metal line used in wireline


operations.

wireline operations

The lowering of mechanical tools (such as valves or


recovery tools) into a well.

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ADDENDUM A: SYMBOLS FOR PHYSICAL QUANTITIES USED IN CHE 206.02


SYMBOL

DEFINITION

Hf

Enthalpy of fusion per mole of solvent

Depression of hydrate-formation temperature, F

KH

Constant used in Hammerschmidt equation; 2,335


for methanol and 4,000 for glycol

Molecular weight, lb/mole

Number of moles of a substance

Flow rate

Gas constant

Safety factor to account for uncertainty in TH

T0

Normal freezing point


(absolute temperature scale)

T
TH

Operating temperature, F
Hydrate-formation temperature of gas stream, F

Mole fraction of a substance in a solution

Water content

Weight percent of a substance in a solution

FIGURE 52: SYMBOLS USED IN ChE 206.02

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ADDENDUM B: ABBREVIATED LIST OF EQUATIONS USED IN CHE 206.02


For those equations below that are based on the
implicit assumption that the concentration of injected
methanol is 100%, it should be recognized that the
equations give the correct answer only when the
concentration is 100%. Significant errors can result
when the injected methanol is less than 100% as, for
example, in the case of cryogenic applications.

NOTE:

Depression of Hydrate-Formation Temperatures


T = TH Tmin imum + S

(Eqn. 1)

Depression of Hydrate-Formation Temperatures (Thermodynamic)


T =

n
RT02

In 1+ inhibitor
Hf

n solvent

(Eqn. 2)

KHw I
100M Mw I

(Eqn. 3)

Hammerschmidt Equations

T =

Derivations of Hammerschmidt Equations


Hammerschmidt Equation (Eqn. 3) Solved for the Weight Percent of Inhibitor
wI =

(T)(M)

(100)

KH + (T)(M)

(Eqn. 4)

Hammerschmidt Equation Modified for High Concentrations of Inhibitor


2

T = -

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RT0
Hf

ln xwater
(Eqn. 5)

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Hammerschmidt Equation Modified for High Concentrations of Methanol


T = 129.6 In (1- xMeOH )

(Eqn. 6)

Free Water Condensed Out of Gas Stream


If the saturation temperature equals the operating temperature:
W = WToperating - WTminimum

(Eqn. 7)

If the saturation temperature is higher than the operating


temperature:
W = WTsaturation - WTminimum

(Eqn. 8)

Methanol Injection Rate (General Applications)


Methanol Injection Rate Required to Compensate for Vapor Losses
q MeOHvapor = (vapor-to-liquid composition ratio)(w MeOH)

(Eqn. 9)

Methanol Injection Rate Required to Achieve Aqueous Methanol Concentration


q MeOHaq =

(W )(w MeOH )

(w water )

(Eqn. 10)

Total Methanol Injection Rate


q MeOHtotal = q MeOHvapor + q MeOHaq

(Eqn. 11)

Flow Rate of Free Water (Cryogenic Applications)


q water = (W)(q gas stream)

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(Eqn. 12)

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Depressed Hydrate-Formation Temperature (T Hdepressed)


TH depressed = TH - T

(Eqn. 13)

S = Tminimum - (TH - T)

(Eqn. 14)

Safety Margin

Methanol Injection Rate: Vapor Losses (Cryogenic Applications)


q MeOHvapor = (vapor-to-liquid composition ratio)(x MeOH)

SCF
379. 5
lb -mole (Eqn. 15)
(qHCvapor)

10 6

Methanol Injection Rate: Solubility in Hydrocarbon Liquid


q MeOHliquid = (solubility of MeOH in HC liquid)(qHCliquid)(MMeOH )

(Eqn. 16)

Methanol Injection Rate Required to Achieve Aqueous Methanol Concentration


q MeOHaq =

w MeOHaq q water
w water aq

(Eqn. 17)

Total Methanol Injection Rate (Cryogenic)


q MeOHtotal = q MeOHvapor + q MeOHliquid + q MeOHaq

(Eqn. 18)

Methanol Injection Rate Converted to gpm

1 hr
q MeOH = q MeOHadjusted x densityMeOH x 60 min

(Eqn. 19)

Flow Rate of Free Water, q water (Glycol Injection Rate Calculations)


q water = (W) x (q gas stream)

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(Eqn. 20)

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Rich Glycol Concentration Required to Meet Dilution Restrictions


(w richdilution)
w rich = w lean - (allowable dilution)

(Eqn. 21)

Inhibitor Injection Rate (Dilution Restricted)


q injection = W

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wrich w lean

qgas stream

(Eqn. 22)

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ADDENDUM C: INDIRECT HEATER SIZING CALCULATIONS


The procedure for sizing an indirect heater is described in the
following steps:
1.

2.

3.

Determine if the heater requires a preheat coil.

Determine the maximum pressure and the lowest


temperature that can be expected at the inlet of the
heater.

Calculate the hydrate-formation temperature (Th) of the


inlet gas.

If Ti is not at least 10F higher than Th, then the heater


may require a preheat coil.

Determine the outlet temperature of the heater.

Calculate the hydrate-formation temperature of the


outlet gas. Use the pressure downstream of the choke.

The heaters required outlet temperature is determined


such that as the gas flows through the pipeline, losing
heat to the surroundings, the gas will arrive at its
destination at a suitable margin (i.e., 15F) over the
hydrate-formation temperature.

Calculate the heat required to heat the gas.

Determine the heater load (Qg) of the gas for the above
inlet and outlet conditions.

Calculate the amount of heat required to heat any


condensate or oil produced with the gas (Qo).

Calculate the amount of heat required to heat any water


produced with the gas (Qw).

Estimate the amount of heat lost to the atmosphere


(Qa). A 10% allowance for heat loss is commonly used.
Qa = 0.10 (Qw + Qo + Qg)

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Calculate the total heat input required.


Qt = Qg + Qo + Qw + Qa
where:

4.

Determine the size and surface area of the heating coil.

Select coil size from Figure 53.

Estimate an overall heat transfer coefficient (U) from


Figure 54.

Calculate the log mean temperature difference (LMTD).

Calculate the area (A) of the heating coil required:


A=

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Qt = Total heat input

Qt
(U) (LMTD )

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FIGURE 53: COIL SIZE SELECTION

FIGURE 54: HEATER-COIL TRANSFER COEFFICIENTS

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