Distillation columns risk assessment: when the regular HAZOP evaluation is not enough

Dalva Janine RITA Carlos MARENCO Ivan MANTOVANI Fabiana. TEDESCHI Cludio TAKASE Rhodia Poliamida e Especialidades Ltda Paulnia, So Paulo, Brasil dalva.rita@br.rhodia.com; carlos.marenco@br.rhodia.com; ivan.montovani@br.rhodia.com; fabiana.tedeschi@br.rhodia.com; claudio.takase-External@@br.rhodia.com

SUMMARY The temperature increase is one of the process parameters deviations evaluated during HAZOP analyzes in a distillation system. One of the causes of this deviation can be the failure of the cooling system resulting in the reduction of condenser capacity which might cause the emission of volatile organic compounds to the atmosphere. In the presence of an ignition source, a fire with serious consequences on the health of the people might occur, and also important material losses. This risk can be reduced to an acceptable level by installing safety systems (such as steam valve closure). Nevertheless, in some distillation systems, the regular instrumental safety chain is not enough to guarantee a safe unit shut down. After the cooling system failure and the steam valve closure, the volatilization of the most volatile components due to the heat content that remains in the system might occur. This subsequent event might lead to a release of product to the atmosphere. The objective of this work is to alert about this possible scenario and propose an approach for the calculation of the amount of volatiles released to the atmosphere, using simplified heat balances.

1- INTRODUCTION
The HAZOP method (HAZard OPerability study) was developed by ICI in the early 70s. In the 1980s risk studies gradually came into use in petrochemicals, oil, chemicals, rail transport, automobiles and other industries. This methodology has been used to assess the safety of new projects or existing units and their modifications. The purpose of this risk analysis is to identify potential accident scenarios that can occur at a facility and to

reduce the corresponding risks to acceptable levels. The risk analysis is performed by a multi-disciplinary group. At Rhodia the HAZOP methodology principles were implemented in the beginning of 80s. The risk analysis is mandatory and performed at each 5 years for some facilities and at each 3 years to others1.

2. ASSESSING AND REDUCING THE RISK IN DISTILLATION COLUMNS

In the case of distillation systems, considering column and peripherals, different scenarios are evaluated during the HAZOP study. In steady state operation, normally, the HAZOP group analyses the deviations on temperature, pressure, level, flow rate, etc., and the possible consequences of those failures (such as human and environmental losses). A common cause of the temperature or pressure deviation is the total loss of cooling capacity. In this scenario, the loss of condensation capacity leads to the loss of reflux flow causing, by consequence, the variation of the temperature and pressure profiles of the distillation column. This scenario culminates in the unwanted event, a process accident: the emission of volatile products to the atmosphere via column vent system and its possible ignition. In addition, overpressure in the column above of the Maximum Allowed Working Pressure (MAWP) may occur, and by consequence causing the rupture of the column and/or its peripherals. Some recent studies presented the use of dynamic simulation for safety analysis in distillation systems 2, 3. The dynamic simulation was used to simulate the consequences of operational failures including reduction or total loss of cooling capacity and it is possible to observe the dynamic response (such as the pressure increase) and also to evaluate the safety systems installed. The reduction of the risk associated with the illustrated scenario is normally related to the installation of active safeguards, such as pressure relief devices (PSV) and instrumental safety chain. The Figure (1) shows a classic distillation system, with TISH safety chain type - (high temperature) installed in the column vent actuating by closing the on-off steam valve. The logic of the safety chain is such that an increase of the vent temperature above the stipulated value in steady state conditions, leads to the closure of the steam to the reboiler. Other safety chains might also act on other points of the facility preventing unwanted chain events. In HAZOP studies carried out at Rhodia 4, the reduction of the scenario risk is associated with the Instrumented Safety Systems reliability, expressed by the SIL (Safety Integrity Level).

VENT/ ATMOSPHERE

COOLING WATER

CONDENSER

PSV

REFLUX

LIGHTS

TISH

COLUMN

FEED

TIC

STEAM UV REBOILER

CONDENSATE

HEAVIES

Figure 1 Safety barriers in a distillation system

3. BEYOND REGULAR HAZOP ANALYSIS

In some distillation systems it is necessary to envisage beyond the horizon of conventional HAZOP analysis and the installed safety barriers. Let is consider the system showed in the Figure (1). After further analysis, one possible scenario has been identified for distillation systems where the difference of volatility of the compounds is high. In this case the safety barriers must take into account the intrinsic dynamic effect of the heat accumulation in the system. In this scenario, after losing cooling capacity and the safety barriers taking action (TISH, closing the steam to the column), the most volatile compound might be released to the atmosphere due to great difference of temperatures between the top and the bottom of the column. The necessary energy for the volatilization comes, basically, from the metal of the column, the metal of the reboiler and other possible peripherals, and amount of heat cumulated in the liquid at the bottom of the column. In this situation the inertia of the system is observed and this phenomenon might occur from 5 to 30 minutes after the safety barrier actuation. The amount of volatiles released to the atmosphere depends on the column and reboiler dimensions (amount of metal), difference of volatility of the

compounds, difference of temperature between the top and the bottom, the holdup of the column, the inertia of the steam valves and the capacity of the condensers.

4. METHODOLOGY APPROACH
The approach is based on the First Law of Thermodynamics and heat transfer equations and can easily be applied to the distillation columns operating in different conditions. Based on the results it is possible to evaluate the existing safety systems. The cumulated heat available for the evaporation of the most volatile component of the system takes into account different sources, as shown in the Equations (1) (4): 1) Heat content due to the steam in the reboiler

Q1 = mSTEAM 1 STEAM
2) Heat content due to the steam flow after the security system actuation (the inertia of the steam valves) Q2 = mSTEAM 2 STEAM 3) Heat content due to difference of temperature and composition between top and bottom of the column
Q3 = mbottom C pbottom T(bottom / Tf )

(1)

(2)

(3) 4) Heat content due to the metallic parts (column and reboiler tubes)

Q4 = mmetal C p metal T(metal / Tf )

(4) The equilibrium temperature or final temperature of the system (Tf) is the boiling temperature of the most volatile compound at the pressure of the vent system. Considering the Equations of (1) (4), the amount of product that can be evaporated will be given by: 4 Qi = 1

mcalc

(5)

mcalc is the maximum amount that can be evaporated in the system, but the amount effectively evaporated must take into account the holdup (of volatile product) of the column

If holdup + vol mcalc , so:

mevap = mcalc

(6)

If holdup +vol < mcalc , so:

mevap = holdup + vol

(7)

The amount of volatiles that effectively will be emitted by the vent system is calculated considering the remaining condensation capacity, as some water remains in the condenser. The reached temperature is Tf. The equation (8) represents the amount of heat removed due to presence of water and metal in the condenser, with temperature lower than Tf.

Qcond = mwater C pwater T(CW / Tf ) + mmetalcond C pmetal T( metal / Tf )

The amount of condensed volatiles will be given by:
mcond =

(8)

(Qcond )
p

(9)

Finally, the amount of volatiles released to the atmosphere will be:

memitted = mevap mcond

(10)

If the remaining condensation capacity is higher than the amount of evaporated product, there will not be emission of product to the atmosphere. Otherwise, it will be necessary the implementation of extra safety barriers to prevent the emission of product to the atmosphere via the vent system. The equations (1) to (10) represent a simple method to determine if a product emission will occur in distillation columns operating with very distinct temperatures between the top and the bottom. It is important to mention that if the system in question have many high volatility components it is necessary to increase the calculation accuracy of the equation (1) to (10) in order to consider these other volatiles present in the mixture, invalidating the simplification indicated in (7).

5. CONCLUSIONS AND FUTURE WORK

In HAZOP studies, the case of distillation columns is evaluated considering that the risk of any unwanted event is reduced by the installation of safety systems, and especially in the case of loss of cooling capacity, the usual safety barrier is the steam valve closure.

However, for some distillation systems, where the difference of volatility of the components is high, the simple safety chain suggested might not be enough to guarantee a safe unit shut down. The dynamic effect of cumulated heat in the system might provide energy enough causing the re-vaporization of the most volatile compound. In this case the risk of releasing volatiles to the atmosphere remains. By using simplified heat balances and construction and operation data of the column and peripherals, it is possible to evaluate the amount of volatile compounds that can be released to the atmosphere. This simplified approach can be used in different distillation systems and it is an alert to prevent organic emissions to the atmosphere. In addition, it is possible to assess, case by case, the risk level. In continuation to the study, a second approach will be carried out using dynamic simulation to quantify the rate of emission of volatiles to the atmosphere.

6. NOMENCLATURE
steam p T(i / j ) holdup+vol CW Cpi mwater mbottom mmetal mmetalcond mcalc mevap

memitted msteam1 msteam2 Q1 Q2 Q3 Q4 Qcond Tf

enthalpy of vaporization (steam) enthalpy of vaporization (most volatile compound) difference of temperature between i and j. holdup of the most volatile compound cooling water calorific capacity of the i amount of water in the condenser amount of product in the bottom of the column amount of metal (column and peripherals) amount of metal (condenser tubes) possible evaporated amount of volatile compound possible evaporated amount of volatile compound, considering the holdup of the most volatile compound amount of volatile compound released via vent system amount of steam in the reboiler amount of steam released from steam valves after the actuation of the safety system, due to the inertia of the valves heat transferred due to the steam in the reboiler heat transferred due to the steam flow after the security system actuation (the inertia of the steam valves) heat transferred due to the temperature and composition differences between top and bottom of the column heat transferred due to the metallic parts (column and reboiler tubes) amount of heat removed due to presence of water and metal in condenser equilibrium (final) temperature

6. REFERENCES
1. Rhodia Responsible Care Function, Procedure-Process Safety Risk Analysis; Rhodia S.A., 2007. 2. N.Ramzan, F. Compart, W.Witt, Application of Extended HAZOP and Event-Tree Analysis for investigating Operational Failures and Safety Optimization of Distillation Column Unit; Process Safety Progress vol. 26, (3), 2007. 3. S. Werner, W. Fred and Compart, Assessing Safety in Distillation Column Using Dynamic Simulation and Failure Mode and Effect Analysis (FMEA), Journal of Applied Sciences, vol. 7, (15), 2007. 4. Rhodia Responsible Care Function, Process Safety Guide-Assessing and Reducing Risks, Rhodia S.A, 2008.