RELIEF OF CHEMICAL REACTORS

UNDER RUNAWAY CONDITIONS - Introduction

DR JASBIR SINGH
jsingh@helgroup.com
www helgroup com
www.helgroup.com
Harry Yang, HEL Beijing

(Harry.Yang@helchina.com)
TEL : 010 8210 1033

HEL Ltd
London, UK

HEL Inc
New Jersey, USA

HEL India
India

HEL China
Chna

HEL AG
Germany

REACTOR PROTECTION
TECHNIQUES
1. Reduce the potential for an incident

Choice of chemistry, operating conditions

Choice of solvent
Inventory etc
etc. etc
etc.

2. Provide automated controls/alarms

High temperature and pressure shut offs

Intelligent controls

3. Design to cope with the residual hazard

Final back-stop is Venting (relief) of reactor

REACTOR VENTING

Pressure Relief Valve

or

Bursting disk
or

or

If ppressure
essu e too high,
g , va
valve
ve oor ve
ventt opens
ope s ..
relieves the pressure and protects reactor

VENTING SIZING CRITERIA

Vapour/gas removal rate vapour/gas generation rate

If this is not satisfied .. Pressure increases in reactor ..
Explosion results!

Phenolic Resin runaway .. Vent not large enough

better chemistry - faster

TWO DECISIONS THAT DETERMINE VENT SIZE

Maximum Rate of Gas/Vapor generation

What is the fluid entering the vent .. only gas/vapour or liquid too?

Venting Common liquids ... subjected to fire

Before
P

During
P

After
P

Time

PRESSURE RELIEF OF PROCESS

EQUIPMENT

Maximum allowable pressure, Pm

Overpressure

PRESSU
URE

V t opens att relief

Vent
li f sett pressure, Ps

Normal
Operation

Fault
condition
develops

Vent opens

TIME
8

BASIC CALCULATION
OF RELIEF SIZING

Problem specification
Identifyy the source term of vapour/gas
p
g ((e.g.
g external heat input
p from a
fire) .. Worst Credible Maloperation (WCM)

Calculation
Size the vent to pass the maximum required vapour/gas rate (ie at WCM)

WHAT IS THE WORST CREDIBLE

MALOPERATION (WCM)
MALOPERATION
loss of cooling?
external fire?
recipe errors?
raw material impurities?
blockages?
g
loss of,, or resumed,, agitation?
temperature too high?
temperature too low?
leaks?
Not easy to decide which will need largest Vent

10

PROCESS CONDITIONS
DURING RELIEF
Relief Pressure
Ps = Maximum Allowable Working Pressure (MAWP)
Pm = 110% of Ps (in barg) (BS 5500),
up to 121% of Ps for fire relief ( ASME codes)
Information/data needed
From any value of pressure obtain the corresponding temperature (by
experiment
i
t or estimation
ti ti methods)
th d )
Find physical property data at any temperature

11

TYPICAL APPROACH
TO RELIEF SIZING : Fire Case

For a Fire :
Vapour generation rate =

Heat from fire

latent heat of vapourisation

Vapour/gas removal rate vapour/gas generation rate

Use compressible gas flow equations to calculate that this
vapour rate can be removed
At the relief conditions

12

TYPICAL APPROACH
TO RELIEF SIZING: Reaction Hazard
For a chemical reaction:
Vapour generation rate = (reaction rate reaction enthalpy)
latent heat of vapourisation
Vapour/gas removal rate vapour/gas generation rate

Use compressible gas flow equations to calculate that this

vapour rate can be removed

BUT .. Is this correct?

How is data obtained?
13

DATA .. Vent Sizing for runaway reactions

Is the rate of reaction known?
Incorrect temperature?
Incorrect
I
recipe?
i ?
Wrong order of addition?
Contamination, etc. ?

Is the reaction enthalpy known?

New reactions may be promoted in the runaway
Is the pressure-temperature relationship known?
Composition dependence during the reaction
Non-condensable gas generation in addition to vapour?

Is vapor still vented?

What happens if liquid is entrained?

VENTING REACTIONS: Data Needed

Is the rate of reaction known?
R l
Rarely

Is the reaction enthalpy known?

U lik l for
Unlikely
f all
ll scenarios
i
Is the pressure-temperature relationship known?
U lik l for
Unlikely
f reall mixtures
i
in
i vent
Is vapor still vented?
Unlikely
Hence ... conventional vent sizing approach NOT CORRECT

What next?

15

DIERS RESEARCH
Design inst for emergency Relief Systems

The DIERS research programme in the United States. 29 companies

formed DIERS in 1976 in collaboration with AIChE.
AIChE $ 1.6
1 6 million
(1979 money) programme: still continuing.
Methodology
M h d l
Equipment (VSP, Phi-tec II)
Software (Safire, Superchems for DIERS)
Workbooks for chemical reactor relief system sizing. More digestible restatement (with some updating) of the material presented in the DIERS
manual. Willday and Etchells, ISBN 0 7176 1389 5, HSE Books

KEY STEPS TO VENT SIZING

Based on DIERS methodology (I)
Establish main source of pressure rise during runaway
- is pressure rise due to vapour pressure increase, or
- is it p
primarily
y due to ggas ggeneration ((typical
yp
decompositions)
p
)
How? using low-phi-adiabatic calorimeter

Establish vapor/liquid ratio entering vent

- Is it all gas (or vapour)
- homogeneous two-phase mixture
- somewhere in between.

How? using
g low-phi
p adiabatic calorimeter

KEY STEPS TO VENT SIZING

Based on DIERS methodology (II)
To size Vent needed to p
protect reactor
- Determine the maximum gas or vapour generation rate.
Perform Tests to determine worst case ((WCM )
- Select the equation for gas or appropriate two-phase flow and size
p with maximum rate of ggas/vapour
p
the vent to cope
- Obtain physical property data (mostly direct from tests)

How?
Well established DIERS methodology.
Requires extensive training.

KEY FINDING OF DIERS methodology (III)

- Traditionally,
y, assumed that vapor/gas
p g will separate
p
from liquid
q
and enter the vent.
- However, most chemicals especially mixtures under pressure will
not vent as gas/vapor
- Instead, mixture of liquid with gas/vapour will enter the vent

This has profound implications ...

most vents are UNDERSIZED ..

by factor of 10 !

VENTING REACTIVE LIQUIDS .. Under runaway reaction

Time

20

IMPORTANCE OF LIQUID ENTRAINMENT

Pressure rises when vapour is generated by liquid
heating.
g
Venting of Vapour ... reduces pressure.
Venting of same mass of liquid .. makes hardly any
difference to pressure
So liquid
q
essentially
y blocks the vent .. stopping
pp g vapour
p
escape
As a result, a ten-fold increase in vent
area may be needed

21

FLOW REGIME ON PRESSURE RELIEF

Many reacting systems generate a two-phase flow on pressure relief.
This is accentuated by high reactor fill levels, high relief set pressures,
high superficial velocities, naturally foamy systems, etc.
Possible flow regimes are:
All gas/vapour flow
Churn turbulent flow (bubbles coalesce, increase in size and
rise fast)
Bubbly flow (small discrete bubbles rising relatively slowly)
Homogeneous two-phase flow (naturally foamy)

22

FLOW REGIME ON PRESSURE RELIEF

For high velocity venting, characteristic final void fractions are:
P

Homogeneous
or foamy

Bubbly

Churn
turbulent

All gas or
vapour

f ~ = 1

f ~ = 0.8

f ~ = 0.65

f ~ = start

I
Increasing
i size
i off vent for
f the
h same d
depressurisation
i i duty
d
23

THE COMPLETE DISPOSAL SYSTEM

Atmosphere,
p
,
scrubber, flare
incinerator,etc

Cooling

Reactor

Catchpot,
dump tank,
quench tank

Vapour condensation
24

VENTING RUNWAY REACTIONS .. DATA...

Modelling runway reactions very time consuming and
requires
i
much
h input
i
t data
d t
In most cases, input data is not available
Anyway, experimental verification is needed
Hence, widely accepted solution is direct testing using

low-phi,
p , adiabatic calorimeter.

25

PHI- Factor

Phi-factor = 1 +

(Mass X specific heat) test cell

((Mass X specific
p
heat)) reactants

Testing in Standard ARC 2 + <

Data for relief sizing:

better chemistry - faster

< 1.1

Data from ARC devices ...

cannot be used for vent sizing

HEL Phi-Tec I (ARC)

DIERS developed concept of low-phi

using pressure compensation

low phi-factor with PHI-TEC II

Pressure Compensation allows low phi-factor test cells

better chemistry - faster

PHI-TEC Pressure Vessel

better chemistry - faster

PHI TEC II ADIABATIC CALORIMETER

Effect of PHI-Factor Decomposition of TBP

(20%) in Toluene

Higher phi-factor leads to artificially slower rise in temperature and a reduced

maximum temperature, low phi-factor resembles response of real plant

better chemistry - faster

Pressure-Time data for NMTS (20%) in Dioxane

Typical data in different test cells

better chemistry - faster

better chemistry - faster

dt
d

dT
d

( = 1.56
6)

Rate data NMTS (20%) in Dioxane

CONCLUSIONS
Most existing vents in industry are too small!
Vent
V sizing
i i for
f runaway chemical
h i l reactions
i
is
i complex!
l !
Training courses lasting 2-3 days are normally needed
Requires
q
a combination of chemical engineering
g
g with
calorimetry data