Comparative Risk Evaluation of Batch and Intensified Continuous Processes 13th International Symposium on Loss Prevention

S. Machefera, S. Bahrounb, N. Di Micelic, N. Gabasc, M. Cabassudc, C. Gourdonc, S.Lib, C. Valentinb, C. Jallutb, L. Falka, J. Jenckd, F. de Panthoue, J.-M. Franoisf
Laboratoire des Sciences du Gnie Chimique (LSGC)-CNRS, Nancy Universit, 1 rue Grandville, BP 20451, F-54001 Nancy, France b Universit de Lyon ; Universit Lyon 1 ; LAGEP, UMR CNRS 5007 ; ESCPE, 43 Bd du 11 novembre 1918, 69622 Villeurbanne Cedex, France c Universit de Toulouse; INPT, UPS; Laboratoire de Gnie Chimique CNRS UMR 5503; 5 rue Paulin Talabot, BP1301, F- 31106 Toulouse cedex 01, France d ENKI Innovation, 3 chemin des Balmes, 69110 Sainte-Foy-ls-Lyon, France e AET GROUP SAS, 6 monte du Coteau, 06800 Cagnes-sur-mer, France f Chilworth Sarl, 6 Htel dentreprises Pierre Blanche, Alle des Lilas, 01150 Saint Vulbas, France
a

1. Introduction Small (continuous) reactors are inherently safe. This is more or less the uniform tenor of those dealing with reactor intensification that leads to a significantly lower reactor hold-up. This safety benefit has especially established as characteristic of micro-reactors, which have shown a booming tendency since one decade with nowadays more than 250 new patents each year [1]. On micro scale, the term inherently safe may indeed be justified for some applications. Tubular reactors for gas phase reactions, as an example, can be designed explosion-resistant on a micro scale and potential explosions would have a significantly reduced blast [2]. However, on a production scale, the (parallelized) micro scale must normally be abandoned because of economical and practical reasons [3,4,5]. This results in reactor sizes on a millior centi scale in best case (some intermediates, consumer products and polymers). Reactors of several litres are more realistic for large scale productions (>100 t/a) or reactions that are limited by mass transfer and require longer residence times. Thus, inherent safety in terms of volume gets somewhat questionable for production scale. But there are first of all still other aspects to consider: Besides specific surface, other conditions are usually also intensified (high pressure, temperature, concentration) which can fortify other hazards or create new risks. Intensification also permits reaction routes which were infeasible in batch mode. This means that extremely hazardous reactions such as direct fluorinations [6] can be carried out, which implies major safety concerns already on a very small scale. Smaller reactors lead to certain control obstacles. Small holdups mostly leave less time for the operator and the control system to respond to disturbances [7]. Additional risk potential from up- or downstream operations and units may arise in continuous operation. Risk-scenarios such as no reaction or backflow can dislocate the risk for example to separation units or storage facilities. The corresponding vessel designs are normally less safe and their volume may not differ from batch processes (e.g. reagent storage) . Consequently a more differentiated discussion about safety of small intensified reactors is needed. We would like to contribute to this discussion by comparing an ortho-cresol hydrogenation process carried out in batch and intensified continuous mode. Process safety is assessed by means of a HAZOP study which has been carried out in a team of industrial

and academic contributors. Selected scenarios were investigated in detail by means of a dynamic process model. 2. Process Characteristics A catalyzed gas-liquid reaction is chosen as test case for the present study. Main reason for this choice is that these reactions are mostly limited by mass transfer. Consequently the safety study does not depend that much on the kinetics of the chosen system. Results obtained in the present study may be easily transferred to other gas-liquid reactions. 1.1 Continuous intensified minireactor Small size, intensified gas-liquid contactors which made it to production scale are rather rare. However, one such minireactor that permits considerable throughputs (ca. 100-1000 t/a) is the RAPTOR developed by the AETGroup [5]. This reactor has amongst others been used for the hydrogenation of o-cresol which is also taken as test case for this study. Figure 1 illustrates the continuous o-cresol hydrogenation process using this minireactor. Molten ocresol and suspended catalyst (Pd/C) are continuously fed to the minireactor after having been preheated to reaction temperature. Intensified mass transfer performance permits small residence times (a couple of minutes) which in turns permits a small reactor volume (<1 litre). Due to the intensified heat transfer characteristics the minireactor can be operated without solvent at elevated pressure and temperature conditions. The reactor characteristics are summarized in Table 1. The reaction product (o-methyl-cyclohexanol) is cooled and the surplus of hydrogen is degassed. The catalyst is removed by filtration before the reaction product is finally filled into drums.

Figure 1: Simplified flow sheet of the intensified continuous process for a hydrogenation reaction.

1.2 Virtual batch process The virtual o-cresol hydrogenation batch process has been defined according to industrial design standards. The initially inertised batch vessel is charged with granular o-cresol and solvent. After the reagent has been dissolved, catalyst is added and the mixture is heated to reaction temperature. Hydrogen is fed and dispersed into the slurry. The reaction is usually stopped after several hours at conversions of typically 95%. The mixture is cooled in the reactor and sent to a filtration unit before entering the second large vessel which serves for

solvent evaporation. The purified product is finally filled into drums. The flow sheet of the virtual batch process is illustrated in Figure 2. The reactor size has been determined based on the same productivity as for the continuous process described above. The batch process requires many preparative and changeover operations (see above). Moreover the exothermic reaction requires strong dilution (ethanol solvent) in order to be operated safely. Finally a reactor volume of 6m3 (2/3 filled) has shown to be necessary. The relevant process parameters are compared to those of the intensified continuous process in Table 1.

Figure 2: Simplified flow sheet of the batch process for a hydrogenation reaction. Table 1: Safety relevant process properties Intensified minireactor Reactor volume 0.0007 m3 Hydrogen pressure 200 bar Operation temperature 170 C Catalyst concentration 0.4% Solvent (ethanol) none Residence/operation time <3 min Adiabatic temperature rise 925C

Virtual batch process 6 m3 10 bar 100C 4% 75 vol.-% 4-5 h 100C

3. HAZOP study 3.1 Method The Hazard and Operability Study (HAZOP) is a procedure for the systematic, critical examination of the operability of a process. When applied to a process design or an operating plant, it indicates potential hazards that may arise from deviations from the intended design conditions [8]. These deviations are evaluated for each process unit and each process parameter by means of typical guide words such as more (quantitative increase), less (quantitative decrease), reverse (logical opposite of the design intent), before, after (relating to order or sequence) etc.. The hazards which are identified can be somewhat evaluated and quantified by using the following risk definition: Risk = Severity x Probability (3.1)

The hazards severity and its probability of occurrence were classified as shown in Table 2. After having identified a scenario with a potential risk, measures of loss prevention are discussed and the residual risk (safety measure considered) is re-evaluated. Herein different measures are by convention treated differently: Correctly designed rupture discs or safety valves reduce the probability of occurrence by three and two classes respectively. Safety measures which are implied by a central control system lead to a reduction by just one class. The HAZOP study requires a heterogeneous team of safety experts. For the present case a team of 13 chemical engineers and chemists was formed, there under specialists for process safety, process control and chemical reaction engineering. Members from academia as well as (process users) from industries participated. The study has been leaded and recorded by a safety expert (Chilworth Technology) using a computer assisted HAZOP software. Table 2: Definition of severity and probability classes for the HAZOP study
Severity of the scenario Classification Definition Minor injuries Minor environmental impact 1 Process unit marginally affected (moderate) Production not interrupted 2 (serious) Violation of emission standards Process unit seriously damaged Production interrupted Multiple severe injuries One possible dead Pollution remains on site Process unit not operable Considerable financial damage Multiple deaths on site Lethal effects off site Off site pollution Impact on brand image possible Process unit destroyed Multiple deaths on and off site Serious environmental damage Whole process closed Probablilty of occurrence Classification Definition (frequency) 1 1e-7 1e-6 1/y (quasi excluded) 2 1e-6 1e-5 1/y (improbable) 3 (very rare) 4 (rare) 5 (probable) 6 (occasional) 1e-5 1e-4 1/y

3 (fatal)

1e-4 1e-3 1/y 1e-3 1e-2 1/y 1e-2 1e-1 1/y

4 (major)

5 (disastrous)

7 (frequent)

1e-1 1e0

1/y

3.2 Results and Discussion For the batch process, 43 Scenarios have been identified and 17 were classified to be of relevant potential risk as illustrated in Figure 3. The continuous process, on the other hand, revealed 22 Scenarios of which 14 form a potential hazard. Considering also the residual risks we conclude from these quantitative results (Figure 3) of the HAZOP study that: The batch reactor constitutes a higher potential hazard (17 hazardous scenarios, 5 unacceptable risks) when compared to the continuous minireactor (14, 2) One scenario of the batch process remains of unacceptable residual risk. Apart from this the allocation of the residual risks shows no fundamental difference for the batch and intensified continuous process. It is worth mentioning, that most of the batch scenarios with a residual risk in the ALARP region (gray shaded) are associated to human failure (5 out of 6). Residual ALARP risks for the intensified continuous process have their origin predominantly in the principle of continuous operation (leakages, control failures etc.) rather than intensification (6 out of 7).

Hence these risks are unspecific with respect to the reactor and would as well be present in any other continuously operated process. Batch scenarios of unacceptable risk (black region) are rather characterized by a high severity whereas they are of high probability in the continuous minireactor. The last aspect is of special importance since it must not be forgotten, that each severity and probability class represents some kind of order of magnitude (Table 2). A closer look at the black scenarios is provided in Table 3. The impact of the solvent turns out to be the key difference between both processes. For the batch process the presence of a solvent leads to scenarios in which vessel rupture is expected because of the solvents vapour pressure or in which solvent vapours form an explosive mixture in the evaporation unit. In three out of five black scenarios the solvent is the activator of an incident. In the continuous minireactor, on the other side, the absence of solvent means a much higher adiabatic temperature rise, hence one scenario in which a thermal explosion would lead to an unacceptable potential risk. Another important difference is the role of scenarios based on operator failures which are obviously more frequent for the batch process and lead to an elevated number of corresponding scenarios of which two lead to severe hazards, e.g. forgotten inertisation.

Figure 3: Risk allocation of the HAZOP analysis for the hydrogenation of o-cresol Vessel size and respective quantities which are processed do not only have an impact on the severity of an incident: In contrast to the batch vessel, the minireactor could be installed in a blockhouse as ultimate safety measure. Another advantage of the minireactor is the possibility of instant drainage (low volume, high pressure). Loss prevention for the batch process is somewhat limited to process control and standard relief devices. The impact of working pressure is more difficult to evaluate. Within the HAZOP analysis this aspect has been considered indirectly by applying higher probabilities for corresponding scenarios. Main reason is the fact that the risk of leakage is elevated and radius of exposure may be larger. The latter is especially important to consider for the emitted hydrogen which can create flammable mixtures already at low volumetric fractions. However, a decomposition of the entire content of the minireactor would approximately correspond to an equivalent of 5g TNT, a pressure rise of 140mbar and broken windows in worst case.

Table 3: Description of those scenarios with high potential risk (s:severity, p:probability)
Batch reactor Scenario Reactor: Temperature (T) control failure Reactor : T-probe defect (Tmax not detected) Reactor: Hydrogen pressure reducer fails Reactor: No Inertisation after reaction (operator failure) Separator: solvent evaporation: No inertisation (operator failure) Consequences High vapour pressure (solvent) causes partial vessel rupture / Hydrogen jet emission and explosion (self ignition). Continuous hydrogen feed (normally stops at Tmax) / slow pressure increase / Hydrogen jet emission and explosion (see B1) Reactor design pressure is exceeded. Hydrogen jet emission and explosion (see B1) Hydrogen is not removed / contact with air in separator which is not designed for high pressures (e.g. condenser) / Explosion if ignition. Solvent vapours in contact with air / Explosion if ignition (e.g. electrostatic source) Continuous minireactor C1 Reactor jacket: No circulation of service liquid (pump failure) o-cresol reservoir (melt): Empty Adiabatic temperature rise, decomposition reaction, thermal explosion Aspiration of air, hydrogen moves upstream, mixture with air, explosion (3,7) Temperature control (stop agitation, stop hydrogen feed), rupture disc Flow rate control (3,3) pot. risk (s,p) (4,6) Safety measures Safety valve + rupture disc Safety valve + rupture disc + Pressure alarm Safety valve + rupture disc Safety valve + rupture disc Safety valve / rupture disc are normally NOT designed for this scenario res. risk (s,p) (4,2)

B1

B2

(4,6)

(4,1)

B3

(4,6)

(4,2)

B4

(3,7)

(3,4)

B5

(4,5)

(4,5)

C2

(3,7)

(3,6)

Process scenarios which are particularly difficult to evaluate are those which involve failure in the cooling system. Two factors complicate the evaluation of these scenarios which are particularly crucial for the undiluted minireactor with its adiabatic temperature rise of almost 1000K: Firstly the reaction (like most gas-liquid reactions) is believed to be limited by mass transfer. Hence standard procedures for thermal runaway calculations, assuming a kinetic regime, are not applicable [9]. Secondly the massive pressure-proof construction of the minireactor exerts certainly a pronounced effect on the dynamics of the reactor. A process model has therefore been developed which should give insight into the special dynamic behaviour of the intensified minireactor. 4. Dynamic simulation The intensified continuous minireactor has been modelled as reactor cascade. A kinetic and mass transfer model has been applied which includes adsorption of the reagents on the catalyst [10]. Possible decomposition reactions have not been implemented. Model details have been published elsewhere [11] Scenario B1, about which the HAZOP team felt most unsure, shall be taken as exemplary simulation. The simulation results as shown in Figure 4. After start up and maintenance of steady-state, the circulation of service liquid is stopped (hydrogen is fed further). After a

latent period of a few minutes, a critical wall (metal) temperature is exceeded which could possibly initiate consecutive decomposition reactions. However, thanks to the massive reactor construction the latent period provides enough time for countermeasures such as hydrogen feed cut, agitation stop and/or emergency drainage of the reactor. Hence the initial evaluation of Scenario B1 in the HAZOP analysis was confirmed by the reactor model. The strong impact of reactors metal mass on the latent period is illustrated in Figure 5. A construction where the metal mass is small when compared to process liquid mass would have allowed a significantly shorter time for countermeasures. Hence intensification in terms of pressure does not only constitute an additional hazard but indirectly contributes also to certain safety benefits.

Figure 4: Dynamic simulation of the HAZOP scenario B1 (intensified continuous minireactor)

Figure 5: Hypothetical impact of the intensified reactors metal mass on the latent period 5. Conclusions We compared a large scale batch reactor with an intensified continuous minireactor (RAPTOR) for a highly exothermic hydrogenation reaction in terms of safety. A model

assisted HAZOP analysis has been performed which highlighted critical operation scenarios. Against mainstream we cannot entirely confirm the statement that safety is inherent in smaller reactor designs. The qualitative difference of corresponding risks should rather be pointed out. In our example, the classical batch process is associated with potential risk scenarios of high severity. The intensified continuous minireactor reveals scenarios of similar risk which are of much lower severity, but significantly higher probability. However, for the specific application described here, the intensified process turned out to be safer but because of other reasons which are mostly just indirectly related to reactor volume: Intensification leads to a solvent-free operation, which avoids risk scenarios associated with a flammable solvent of high vapour pressure. These scenarios have shown to be most problematic for the batch reactor or following (separation) units. Intensification in terms of high pressure leads to a massive reactor construction which delays thermal runaway and provides more time for intervention. Smaller reactor size allows for additional measures of loss prevention such as instant drainage and blockhouse installation, which are infeasible or too expensive for large scale processing. Due to very different designs the safety of intensified processes has to be evaluated technology specific. In best case results obtained for one technology can be generalized for a reaction class. The results of this study, for example, should be transferrable to other gasliquid reactions. In many other cases, however, the question whether or not intensification leads to safer processes will be not only technology but also highly application specific. Acknowledgements The authors would like to thank the ANR (Agence Nationale de la Recherche, France) for financial support in connection with the project PropreSur (french acronym for clean and secure processes towards future chemical plants) with grant number ANR-06-BLAN-0381. References [1] V. Hessel, C. Knoblauch and H. Loewe Review on Patents in Microreactor and Micro process Engineering Recent Pat. Chem. Eng. 2008, 1, 1-16. [2] M. Goedde Sicherheit in der Mikroreaktionstechnik Chem. Ing. Techn. 2009, 81, 73-78. [3] U. Krtschil, V. Hessel, D. Kralisch et al. Cost analysis of a Commercial Manufacturing Process of a Fine Chemical Compound Using Micro Process Engineering Chimia 2006, 60, 611-617. [4] S. Lomel, L. Falk, J.M. Commenge et al. The Microreactor A Systematic and Efficient Tool for the Transition from Batch to Continuous Process Chem. Eng. Res. Des. 2006, 84, 363-369. [5] L. Falk, S. Machefer, F. de Panthou et al. The Raptor An Intensified continuous minireactor for bulk and fine chemical production, in preparation. [6] T. Obein Caractrisation dun microracteur film tombant et tude de la fluoration directe de lAnisole dans ce microracteur. 2006, phD-thesis INPL/Rhodia. [7] L. Luyben, D.C. Hendershot Dynamic Disadvantages of Intensification in Inherently Safer Process Design Ind. Eng. Chem. Res. 2004, 43, 384-396. [8] R.K. Sinnott Chemical Engineering Chemical Engineering Design ButterworthHeinemann, Oxford, 1999. [9] J. Steinbach Safety Assessment for Chemical Processes Wiley-VCH, Weinheim, 1999 [10] H. Hichri, A. Accary and J. Andrieu Kinetics and Slurry-type Reactor Modelling during Catalytic Modelling of o-Cresol on Ni/SiO2 Chem. Eng. Process. 1991, 30, 133-140. [11] S. Bahroun, C. Jallut, C. Valentin et al. Dynamic modelling of a three-phase catalytic slurry intensified chemical reactor. International Symposium on Advanced Control of Chemical Processes (ADCHEM09), 2009.