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You cannot consider sensible heat in the equation of relief load calculation for
fire case; then just the latent heat should be considered. As per API 521 you can
use a minimum value of 115 kj/kg for the latent heat if no accurate latent heat
value is available.. The American Petroleum Institute (API) recommendation of the minimum value
of latent heat of vaporization of hydrocarbon mixtures is too large to accept for safe fire relief system
design when no accurate latent-heat value is available near the critical point. Note: recommendation by
API for minimum approximate heat of vaporization of multicomponent hydrocarbon mixtures in the
absence of latent-heat data at the critical point is 50Btu/lb (116kJ/kg) see Section 3.15.3.1 of API
Recommended Practice 521: Guide for Pressure-Relieving and Depressuring Systems, 1997).3.The need
of accurate thermodynamic property data of fluid mixtures necessary to validate the thermodynamic
model at relief system operating conditions. Currently, these types of data are scarce in the open
literature because data measurements have been difficult at the temperatures and pressure of interest
Thermodynamic methods for pressure relief system design parameters. Available from:
https://www.researchgate.net/publication/244342877_Thermodynamic_methods_for_pressure_relief_s
ystem_design_parameters [accessed Aug 18, 2017].

METHOD TO CALCULATE THE LATENT HEAT OF VAPORISATION

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Home > News > Engineering Articles > Calculating Safety Valve Fire Relief Loads For Multicomponent Systems | Carmagen
Engineering

Calculating Safety Valve Fire Relief Loads for Multicomponent


Systems
By Roberto L. Machado, P.E.
According to the ASME Code, pressure vessels must be protected against overpressure caused by
exposure to external fires. When a vessel containing liquid is exposed to an external fire, the
contained liquid will vaporize and, potentially, cause the vessel pressure to exceed its maximum
allowable working pressure unless the resulting vapor is relieved at a flow rate equal to the vapor
generation rate.
The first step in determining the required safety valve relief area to prevent overpressure due to fire
exposure is to calculate the rate of vapor generation associated with the fire. For single component
liquids such as water, this is straightforward. The rate of vapor generation is calculated by dividing the
rate of heat input into the vessel, Q, by the latent heat of vaporization of the liquid, .
API Standard 521 / ISO 23251 provide the following equation to determine the rate of heat input into
a vessel exposed to fire:

Where:
Q = rate of heat input, Btu/h
C = 21,000 for areas having good drainage (typically paved)
C = 34,500 for areas having poor drainage (typically unpaved)
F = environmental factor = 1.0 for uninsulated vessel
F = environmental factor = 0.075 for insulated vessels
AW = wetted surface of the vessel

Once the rate of heat input has been determined using the above equation, the rate of vapor
generation can be obtained by:

Where:
= latent heat of vaporization at relieving conditions, Btu/lb
The required relief rate for a given vapor generation rate is lower than the rate of vapor generation
because part of the vapor generated accumulates in the additional vapor space created in the vessel
as the liquid inventory is depleted. To account for this phenomenon, the required relief rate is
multiplied by a correction factor that depends on the relative densities of the vapor and liquid in the
vessel, as follows:

Where:
Wr = mass relief rate, lb/h
rL = liquid density, lb/ft3
rV = vapor density, lb/ft3
In many cases, especially for systems that operate away from the thermodynamic critical
temperature, the correction factor is close to unity and is often disregarded.
The latent heat of vaporization for pure component liquids at relieving conditions can be readily
obtained from the literature. The relieving conditions are the accumulated relieving pressure and the
corresponding saturation temperature (boiling point) of the liquid at the relieving pressure. For
overpressure protection of a vessel during a fire, the ASME Code allows an accumulated relieving
pressure of up to 121% of the vessels maximum allowable working pressure.
When the liquid contained in a vessel is a multicomponent liquid, the calculation of the vapor
generation rate is not straightforward. The reason is that, for a multicomponent liquid, the
composition, temperature, and heat of vaporization do not remain constant during a fire exposure. At
the onset of a fire, the lighter components of the liquid vaporize first and change the composition of
the residual liquid. This causes an increase in the boiling temperature of the residual liquid which
absorbs part of the heat input into the vessel. Furthermore, as the liquid inventory in the vessel is
depleted, the wetted surface also decreases, which results in a reduction in the heat input to the
vessel. Thus, when the vessel contains a multicomponent liquid, the rate of vapor generation is not
constant and, depending on conditions, may increase or decrease during the fire.
The determination of the limiting relief load caused by fire exposure of a vessel containing a multi-
component liquid typically requires a time-dependent analysis that considers all of the above
variables. This analysis involves performing a sequential vaporization of the liquid contents to
determine the amount of vapor generated during each step and the increment of time over which the
vaporization occurs. The analysis must also consider the progressive decrease in wetted surface area
as the liquid inventory is depleted. In many cases, the limiting relief load will occur at the onset of
vaporization because, at that point, the wetted surface is at a maximum. However, this is not always
the case because, at the onset of vaporization, when the vessel is still relatively full of liquid, most of
the heat absorbed may go into raising the temperature of the residual liquid (sensible heat) rather
than into vaporizing the lighter components (latent heat). One approach for the time dependent
analysis is as follows:

1. Start with the composition of the liquid contained in the vessel.


2. Using a computerized flow-sheeting model, perform a flash calculation at the relieving
pressure and the corresponding saturation (bubble point) temperature to establish the initial
condition at the onset of vaporization. The composition of the feed to this flash is that of liquid
inventory present in the vessel at the onset of the fire. For computational convenience, the
flow rate may be set at a rate numerically equal to the liquid inventory in the vessel at the
onset of the fire or some convenient number such as 1000 lb/h.

3. Perform a flash calculation at a small increase of fraction vaporized (or a small increase of
temperature) at constant pressure.

4. Divide the heat input from the preceding flash by the mass flow rate of vapor generated by
the flash. This quantity represents the amount of heat absorbed per unit mass vaporized and
is the value of to be used in Equation 2.

5. Determine the total rate of heat input into the vessel using Equation 1 and the wetted surface
at the onset of vaporization. This is the value of Q to be used in Equation 2.

6. Calculate the required relief rate using Equation 3.

7. Using the residual liquid inventory and physical properties from Step 3, recalculate the wetted
surface, Aw, for use in the next iteration.

8. Using the residual liquid from the flash in Step 3, perform a flash calculation at a small
increase in fraction vaporized (or a small increase in temperature) at constant pressure.

9. Repeat steps 4, 5, 6, 7, and 8 until 90% of the original liquid inventory has been vaporized or
until the thermodynamic critical temperature is reached, whichever occurs first. Once the
critical temperature is reached, vaporization can no longer take place and the relief rate is
calculated using the rate of thermal expansion of the supercritical gas remaining in the vessel.

10. For each of the iterations above, calculate the required relief area using the standard sizing
equations from API RP 520. The limiting relief load is the one requiring the largest relief area.

2010-2014 Carmagen Engineering, Inc.


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HomeForumsChemical EngineersActivitiesSafety Relief Valve engineering (PSV) Forum

Latent Heat in HYSYS for multicomponent mixture 4

thread1203-340882

Forum Search FAQs Links MVPs

ErimusOilnGas (Petroleum)(OP)13 Mar 13 11:41

Hi I am trying to get a value for latent heat of a mixture. I require the latent heat to use in W=Q/L to give
me a required relief rate.

I have a few questions which noone can really seem to answer :

1 - If i copy my stream and set vap fract to 0.01, the mass heat of vap displayed in the properties tab for
that stream. Is this the latent heat for the mixture or just the lightest component?

2 - In thinking method 1 was not correct I copied the stream set it to operating conditions and then put it
through a heat exchanger (as is the case for vapour expansion and relief)I set my outlet to the relieving
pressure . Is this the correct methos ... it give a latent heat for the outlet stream which is in the right ball
park but im not sure as when i manually change the vap frac of the outlet this doesnt effect the latent
heat which i would expect it to do as it is changing the temperature and as such the points at which my
mixture will vaporize off.

Please ask if i have not included enough information.

Help much appreciated.

Cheers

Jonny

Replies continue below

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apetri (Chemical)13 Mar 13 13:13

I am not an expert with your software however almost all simulators allow to calculate latent heat as
difference between enthalpy of gas and enthalpy of liquid,

for example with Prode and Excel to calculate latent heat I write in a cell
=StrGH(1)-StrGL(1)

which returns the desired value,

since your simulator exports methods in Excel probably you have a similar option

MortenA (Petroleum)14 Mar 13 07:30

apetri - carefull now

For calculating the latent heat e.g. for a safety valve calculation you DONT want to "evaporate" all of the
liquid - because this will give you a much higher latent heat than the INITIAL latent heat (the heavier
components have a higher latent heat - and if water is a part of the stream it will shoot thhrough the
roof).

In HYSYS take a copy of your stream. Set the pressure to your relief pressure (+21% if the is an API 520
sizing) and set the vapour fration to zero - this will calculate the boiling temperature.

Now and a heater unit operation and add "enough" heat to vaporize a small fraction. This should not be .
00000001 because thats too harsh, but maybe something like 0.001-0.01.

Then do the math:

Q_lat (KJ/KG)=Q (added heat)/mass evaporated (or use mol if you are looking fo molar latent heat).

apetri (Chemical)14 Mar 13 10:31

MortenA, carefull now :-)

given a gas and liquid composition at specified T,P, (supposing we are in two phase area)

if you subtract the enthalpy of liquid phase from that of vapor phase you **DO NOT** "evaporate" all of
the liquid,

but only the vapor phase with the composition calculated by your simulator (at specified T,P),
from that point of view the two procedures are equivalent.

ErimusOilnGas (Petroleum)(OP)15 Mar 13 07:54

Should the latent heat value (mass heat of vap) not change as I alter the vap fraction ? Surely the latent
heat value should change as the vap fract increase(temp therefore increases) heavier end start to
vapourize off?

Is the latent heat for the mixture or simply for the light ends? at bubble point 0.01 vap frac?

Cheers

Jonny

apetri (Chemical)15 Mar 13 14:00

for a multicomponent mixture you can define a latent heat for the vapor or (incipient vapor) fraction,

to calculate the latent heat for the mixture SUM(Wi*Hvi) where Wi is the (weight fraction) composition
of gas fraction and Hvi the latent heat of each component,

according the above if the composition changes (when vaporizing) (most probably) also latent heat will
change,

I do not know your software, the procedure described by MorternA seems (to me) quite complex but
that is a personal comment being familiar with another software (Prode) which allows to calculate these
properties directly in Excel

MortenA (Petroleum)19 Mar 13 06:29

I still dont agree with apetri.

At the operating P&T assuming that we have a two phase (or 3 phase) mix in a vessel then at a fire what
happens is:

1) Pressure start to increase due to the bubble point P increaese


2) Pressure meeets SP of your valve, this is not so important because you only want to size for your max
rfelief case (for API 520 sizing at SP+21%)

3) So now the temperature has increased so much that you have a vapour pressure= SP+21%

4) You are NOT interested in what the "average" latent heat of evaporating all the light components have
been so far - what you want to know is: What is the laten heat required to evaporate the "next" fraction.

5) Therefore you do as i earlier stated: add a "little" heat and see how much this evaporates (mol og
mass) and then calculate the equivalent laten heat mass or mol.

This can then be used for sizing the PSV in accordance with api

Again i think that apetri "oversimplifies" it when he writes "to calculate the latent heat for the mixture
SUM(Wi*Hvi) where Wi is the (weight fraction) composition of gas fraction and Hvi the latent heat of
each component" bacause Hvi will be pressure/temperature dependant AND its not what the
concentration of the current vapour phase is - its what the composition of the next fraction that
evaporates off is.

I have worked with HYSYS for +15 years and has found that the methode that describe is fast and gives
accurate results (OK i have rarely had the chance to benchmark these results (truth: never))

Best regards

Morten

apetri (Chemical)20 Mar 13 05:17

Morten,

I believe that for a incipient vapor fraction (see my previous post) the correct solution is

Hv = SUM(Wi*Hvi)

where Wi is the (weight fraction) composition of gas fraction and Hvi the latent heat of each component

Hvi = Hvgi-Hvli (Hvgi enthalpy of vapor, Hvli enthalpy of liquid)


this is a rigorous result, not an estimate as you suggested, see all the literature including the Properties
of Gases and Liquids by

Prausnitz, Poling, Reid.

As you correctly noted the main problem when estimating latent heat for a wide boling mixture with the
purpose to size a PSV is the

definition of some average or maximum value,

Your procedure has several limits, you calculate a "istantaneous" value (equivalent to Hv = SUM(Wi*Hvi)
discussed above) and you assume

vapor-liquid equilibria when discharging, which could not be true.

There are different alternatives, for example one could estimate the initial condition (when PSV opens)
and from that calculate some average latent heat (or some other values required to size the PSV) .

Consider a simple case, a HP vapor-liquid separator with operating conditions 50Bara 15C

the separator is protected by a PSV with set point (opens at) 100 Bara

composition (mol)

C1 0.7

C2 0.04

c3 0.07

c4 0.12

cO2 0.05

H2O 0.02
with model Peng Robinson, standard correlation and BIPs from database the phase envelope is that
included (blue line on the right being

the water dew point line)

at operating conditions of 50Bara 15C the calculated compositions (vapor-liquid-liquid) have been
included

To estimate the conditions when PSV opens one can solve a Volume-Pressure flash operation,

we know the volume at operating conditions (50Bara 15C) which is about 0.0133 m3/kg, the initial
pressure (50 Bara) and the pressure

(100 Bara) when the PSV opens, We assume that volume of vessel (and fluid) is constant.

Solving the V-P flah operation returns a temperature (@100Bara) of 168C (much higher than Bubble
point temperature) with the fluid all in

vapor state.

Knowing the conditions at 100 Bara one can calculate the difference of enthalpy (@100Bara 168C -
@50Bara 50C) and from that estimate the

values required to size the PSV

Working with Excel and Prode Properties I can solve quickly these calc's with a very limited effort (just
two macros in Excel cells)

and compare results from different procedures (for example that which you suggested),

this is in my opinion a important advantage.

http://files.engineering.com/getfile.aspx?folder=f90c436c-d9e8-4b9d-855e-2e

http://files.engineering.com/getfile.aspx?folder=d3ae3780-2e0d-44e3-8b1b-d6
http://files.engineering.com/getfile.aspx?folder=31f65220-d268-40b4-8b26-11

MikeClay (Chemical)20 Mar 13 13:12

Apetri:

The method that you describe will end up treating the wide boiling mixture as a single component with a
heat of vaporization in the range of 50-150 BTU/lb. However, in order to boil off any vapor, the
temperature must rise. In wide boiling mixtures, the sensible heat can account for 80-90% of the total
heat input. Morton's method takes this effect into account. I've seen instantaneous heats of vaporization
as high as 2000 BTU/lb. If a dynamic model is run, the required relief area will be similar to Morton's
analysis. It should also be noted that the maximum relief area is seldom the initial relief area. In all of the
dynamic models that I have run with crude oil, the dynamic model gives a smaller relief valve size than
just using the Hysys/Unisim mass heat of vaporization.

--Mike--

delittle (Petroleum)20 Mar 13 14:03

Mike,

the method described by apetri Hv = SUM(Wi*Hvi) where Wi is the incipient vapor fraction (see above
posts) should returns the same values as that described by Morten, they both return "istantaneous"
values (as mentioned by apetri),

You seem to be inferring your conclusion from the description of the procedure for estimating t,p,w
conditions where PSV opens, that has a different scope.

MikeClay (Chemical)20 Mar 13 16:30

The two methods will create latent heat of vaporization (HoV) that differ by a factor of 5 to 10. The
individual HoV will be in the range of 50 to 150 BTU/lb (see the chart in API 521). If you sum the weight
fractions times the individual HoV, the number will still be in the range of 50 to 150 BTU/lb. The Method
that Morton describes will typically give a heat of vaporization of 300 to 1000 BTU/lb. I know these
values seem high, but for a wide boiling crude, a lot of the heat is absorbed as sensible heat.

--Mike--

delittle (Petroleum)21 Mar 13 04:46

Mike,
the original post did ask a method for calculating the latent heat of a mixture

>I am trying to get a value for latent heat of a mixture.

and Hv = SUM(Wi*Hvi) where Wi is the incipient vapor fraction is a correct answer

in my opinion the method proposed by Morten

>Set the pressure to your relief pressure (+21% if the is an API 520 sizing) and set the vapour fration to
zero - this will calculate the >boiling temperature.

>Now and a heater unit operation and add "enough" heat to vaporize a small fraction. This should not be
.00000001 because thats too >harsh, but maybe something like 0.001-0.01.

>Then do the math:

>Q_lat (KJ/KG)=Q (added heat)/mass evaporated (or use mol if you are looking fo molar latent heat).

does consider a initial value (with sensible + latent) which for wide boiling mixtures may be very different
from some average or minimum value (for latent heat) and as result you can undersize the PSV,

also the method may be not applicable in many cases (see the example provided by apetri where the
mixture is all in vapor phase when the PSV opens),

considering these limits it would be preferable a method to estimate the initial conditions (as that
proposed by apetri) or run a dynamic simulation (which should produce equivalent results).

With a fire case one should evaluate the whole process to evidence high temperatures and possible
failures of vessel (keep in mind that we are discharging at constant pressure not depressuring),

that is a very important point to consider.

don1980 (Chemical)22 Mar 13 18:33

It's important to recognize that no matter how you size the PSV, it's a short term and very imperfect layer
of protection from fire exposure. Whenever you have a mixture, especially one with a wide boiling range,
there's just no single sizing basis that's objectively correct.
In a lot of cases the PSV isn't going to adequately protect the vessel regardless of the PSV size. I'm
referring to cases such as:

vapor filled vessels

vessels containing supercritical fluid

vessels containing a high boiling liquid

vessels with a lot of unwetted surface area

vessels which will quickly become empty of liquid

For those vessels we ought to be focused on other layers of protection because the PSV (no matter the
size) isn't going to provide meaningful protection. In such cases consider one or any combination of the
following: (1) fire resistant insulation, (2) water spray, (3) auto depressurization.

Most hydrocarbons have a Hvap in the range of 100-180 btu/lb. Once the PSV opens the mixture
composition will inevitable change with time. Personally, I don't see much value in spending a lot of time
selecting the Hvap, as long as I've selected an Hvap that's reasonable for that particular mixture.

To strongly argue for one value over another you have to know how long the fire will last, but of course
we don't know how long it will last, and if it last too long then the vessel fails regardless of which
number we choose.

MortenA (Petroleum)23 Mar 13 10:37

Im on the "client side" but has also been on the consultant side. If a consultant came to me I would not
accept the methodology suggested by aperitif unless it did not cause me to choose a large than required
psv such as I think there is a risk off.

apetri (Chemical)25 Mar 13 04:55

I agree with Delittle

"considering these limits it would be preferable a method to estimate the initial conditions (as that
proposed by apetri) or run a dynamic simulation (which should produce equivalent results)."
and don1980

"Most hydrocarbons have a Hvap in the range of 100-180 btu/lb. Once the PSV opens the mixture
composition will inevitable change with time. Personally, I don't see much value in spending a lot of time
selecting the Hvap, as long as I've selected an Hvap that's reasonable for that particular mixture."

Morten,

you do not share a numerical case and I am unable to compare the values, however there is this post
from MikeClay

"The two methods will create latent heat of vaporization (HoV) that differ by a factor of 5 to 10. The
individual HoV will be in the range of 50 to 150 BTU/lb (see the chart in API 521). If you sum the weight
fractions times the individual HoV, the number will still be in the range of 50 to 150 BTU/lb. The Method
that Morton describes will typically give a heat of vaporization of 300 to 1000 BTU/lb. I know these
values seem high, but for a wide boiling crude, a lot of the heat is absorbed as sensible heat"

according that your procedure calculates a higher latent heat and (consequently) a lower mass flux and
lower discharging area, which may be not acceptable,

in my opinion if you do not wish to utilize a procedure for estimating initial conditions and from those
some average / maximum value for latent heat as I do in my example then you may run a dynamic
simulation and see what happens,

but do not forget these comments from delittle

"With a fire case one should evaluate the whole process to evidence high temperatures and possible
failures of vessel (keep in mind that we are discharging at constant pressure not depressuring), that is a
very important point to consider."

and don1980
"To strongly argue for one value over another you have to know how long the fire will last, but of course
we don't know how long it will last, and if it last too long then the vessel fails regardless of which
number we choose"

ErimusOilnGas (Petroleum)(OP)25 Mar 13 12:39

Guys, firstly thank you all for your input into this thread.

TO give you abit more background, I work for the client and am currectly reviewing PSV calcs which have
been completed by an outside consultant, namely looking at those which have highlighted anomalies
where a suggestion that a valve is undersized has been made. Myjob is essentially to sense check there
assumptions.

In this case the consulting party has stated the boiling range for the mixture and stated they will use the
lowest latent heat as this will be the worst case relief from W = Q/L. This worst case however is
something which we see in industry too many times and where it can be a more accurate case should be
provided otherwise the valve ends up being oversized and PSV chatter occuring.

They had also assumed a component mixture where I am now taking average smaple reading to try and
give the best case relief.

The 'Dynamic Modelling' suggstion is probably the best option however we do not have that at our
disposal. Therefore it becomes difficult to really choose a vap frac at which to take the latent heat .. as
previously stated this will indeed change as the temperature increases.

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