Ind. Eng. Chem. Res.

2009, 48, 35053512

3505

Chemical Plant Flare Minimization via Plantwide Dynamic Simulation

Qiang Xu,* Xiongtao Yang, Chaowei Liu, Kuyen Li, Helen H. Lou, and John L. Gossage
Department of Chemical Engineering, Lamar UniVersity, Beaumont, Texas 77710

Flaring is crucial to chemical plant safety. However, excessive aring, especially the intensive aring during the chemical plant start-up operation, emits huge amounts of volatile organic compounds (VOCs) and highly reactive VOCs, which meanwhile results in tremendous industrial material and energy loss. Thus, the are emission should be minimized if at all possible. This paper presents a general methodology on are minimization for chemical plant start-up operations via plantwide dynamic simulation. The methodology starts with setup and validation of plantwide steady-state and dynamic simulation models. The validated dynamic model is then systematically transformed to the initial state of start-up and thereafter virtually run to check the plant start-up procedures. Any infeasible or risky scenarios will be fed back to plant engineers for operation improvement. The plantwide dynamic simulation provides an insight into process dynamic behaviors, which is crucial for the plant to minimize the aring while maintaining operational feasibility and safety. The efcacy of the developed methodology has been demonstrated by a real start-up test.
Introduction
Downloaded by LAMAR UNIV on October 7, 2009 | http://pubs.acs.org Publication Date (Web): February 27, 2009 | doi: 10.1021/ie8016219

Chemical plant start-up operations can be considered as plantwide dynamic operations, by which the whole plant operating status is transferred from one steady state to another. Apparently, the start-up operation is a highly nonlinear, complex operation that usually involves discontinuous and/or parallel operating procedures, as well as a wide change of many controllers set points. Such complex operations would inevitably generate huge amounts of off-spec product streams that have to be sent to aring systems for destruction, if the plant start-up could not be completed promptly. Flaring can protect chemical plant personnel and equipments, as well as protect the local environment from direct emission pollutions. Thus, aring is crucial to the chemical process industry (CPI). Excessive aring, however, will also cause negative environmental and social impacts and result in tremendous material and energy losses.1 The aring emissions during chemical plant start-up operations generate huge amounts of CO, CO2, NOx, volatile organic compounds (VOCs), highly reactive VOC (HRVOCs) (dened in Texas air quality regulation as ethylene, propylene, isomers of butene, and 1,3-butadiene), and partially oxygenated hydrocarbons (such as formaldehyde). It has been estimated that an ethylene plant with a capacity of 1.2 billion pounds of ethylene production per year will easily are about 5.0 million pounds of ethylene during one single start-up.2 Given the 98% aring efciency (destruction efciency), the resultant air emission will include at least 40.0 klb CO, 7.5 klb NOx, 15.1 klb hydrocarbon, and 100.0 klb HRVOCs. The aring emission will cause highly localized and transient air pollution events, which are harmful to peoples health. For instance, the industrial are emission of HRVOCs mixed with NOx has been identied with high concentrations of ozone observed in the Houston/Galveston area of Texas, which violates the National Ambient Air Quality Standards (NAAQS) for ozone.3-7 Note that the aring emission not only causes dangerous environmental pollution but also results in tremendous raw material and energy loss that could generate much needed products from the industry. As a result of the increasingly strict environmental regulations and economic competition, are
* To whom correspondence should be addressed. Telephone: 409880-7818. Fax: 409-880-2297. E-mail: Qiang.xu@lamar.edu.

minimization has become one of the major concerns for the chemical process industry. Current practice of are minimization in CPI plants is not standardized due to the complexity of the different process and operating procedures. This causes are minimization to depend almost exclusively on the experienced and well trained operators, engineers, and administrators.8,9 The focal point for are minimization is to reduce the number of instances when the plant has to are and the quantity of the materials to be ared. However, the industrial-experience based methods are often limited, when they have to confront complex plantwide dynamic operations (e.g., start-up) with critical control and safety issues.10 Consequently, virtual models are employed to study the startup behaviors. Some studies have tried steady-state simulation (SS) for start-up operation, based on a set of predicted steadystate operating points to project the system dynamic response.11 The methods have inherent deciency because they could not reveal the real dynamic behaviors between two adjacent steady states and thus lack the capability to guide critical process control and operation.12 To provide more accurate dynamic information, plantwide dynamic simulation (DS) methods have recently become popular.13 It is used to virtually test plant start-up operations according to the operating strategies that will be undertaken by the plant operating personnel.14-17 It examines critically the potential process operational risks and infeasibilities. Based on the DS results, the feedback will help the plant improve the start-up operating strategies and thus reduce are emissions. The methodology is cost-effective and proved very successful in real application. Based on the previous studies, this paper for the rst time generalizes a systematic methodology for are minimization during CPI plant start-up operations via plantwide dynamic simulation. It covers the modeling of recent practice for start-up operations with total recycles. Meanwhile, modeling experience and required industrial data are also summarized. A eld test for are minimization during an ethylene plant startup is presented to demonstrate the efcacy of the methodology. Scope of the Dynamic Simulation Model The amount of aring emission during a plant start-up normally increases with the start-up duration. To shorten the

10.1021/ie8016219 CCC: $40.75 2009 American Chemical Society Published on Web 02/27/2009

3506 Ind. Eng. Chem. Res., Vol. 48, No. 7, 2009

Downloaded by LAMAR UNIV on October 7, 2009 | http://pubs.acs.org Publication Date (Web): February 27, 2009 | doi: 10.1021/ie8016219

Figure 2. General methodology framework. Figure 1. General sketches of normal operation and the initial status for start-ups.

changes when full-recycle start-ups are considered, which makes the simulation task extremely complex. General Methodology for Plantwide Dynamic Simulation To conduct the plantwide dynamic simulation for total-recycle start-ups, a systematic modeling methodology has been developed in this paper, which considers more general and complex situations than previous methods. The plantwide dynamic simulation is performed based on the integration of rigorous process models, plant design data, P&ID, DCS historian, and industrial expertise. Generally, the developed methodology is the integration of modeling activities among three interactive stages as shown in Figure 2. Steady-State Modeling and Validation. In the rst stage, model development starts with the setup of the SS model for the plant process system that needs to be investigated during the start-up. The sequential modular approach is used in this methodology, by which each subsystem will be modeled and solved independently. The reasons for selecting sequential modular approach instead of the equation oriented approach are mainly because the whole plantwide simulation task is more convenient to be decomposed into small subsystems for validation and troubleshooting. Although the modeling process will be slower, it does not inuence too much as the start-up simulation task is conducted ofine. The developed SS model is usually validated by plant design data rst, which are collected from plant design documents. Then the model will be further validated by normal steady-state operating conditions, where DCS (distributed control system) historian will be used. Sometimes, the real plant data are not in mass or energy balance due to unpredicted reasons such as sensor drifting, malfunction, or the negligence of some input/output streams. Under such

start-up time, the important plant units are usually commissioned at some designated steady states before initiating the start-up, which is called the initial state for start-up. For instance, distillation columns need to run with total reux, and reactors need to be controlled at certain temperature levels. Recent are minimization practices have shown the total-recycle start-up may signicantly reduce the are emission. This suggests that the plant should start with full-recycled streams from downstream process as system input, which can capture, recycle, and reuse large amounts of off-spec products that would otherwise be sent to the are system as waste streams. To model the total-recycle start-up without losing the generality, the proposed methodology will address the dynamic simulation of the process system dened in Figure 1. For comparison, the plantwide dynamic simulation model at normal operations is shown in Figure 1a, where normal feed means the raw material input at normal operating conditions. Note that Figure 1a includes all the internal recycles at normal working conditions. Figure 1b shows the initial state of the dynamic simulation model for start-ups. Based on a general case, the DS model contains all the designated outer and inner loops of recycled streams, which are only used for plant start-up. Here, a recycled stream is called an outer-loop stream because it recycles the off-spec materials to the very beginning of the system input; otherwise, it is called an inner-loop stream. With the help of Figure 1, the DS model for a plant start-up can be dened as simulating the transient behaviors from the initial condition of start-up (Figure 1b) to the normal working condition (Figure 1a). Note that the topology of the simulation model

Ind. Eng. Chem. Res., Vol. 48, No. 7, 2009 3507

Downloaded by LAMAR UNIV on October 7, 2009 | http://pubs.acs.org Publication Date (Web): February 27, 2009 | doi: 10.1021/ie8016219

Figure 3. General model for plant start-ups.

conditions, data verication, data reconciliation, and the support from industrial expertise will be extensively involved. Typical model turning parameters in this stage include column tray efciency, heat transfer efciency, reaction kinetic parameters, etc. Dynamic Modeling and Validation. If the plantwide SS is satised, the validated SS model is then transferred to the DS model. Three types of information must be involved to support such a model transition. First, equipment dimension data (such as initial equipment hold-up level, vessel type and geometry, hydraulics, and tray geometry and details) from updated mechanical drawings is required, which provides the process capacity information. Second, control strategy and controller parameters from current plant P&ID (piping and instrument diagram) are needed, which provides process control information. Third, process and equipment heat-transfer methods should be given for the dynamic simulation model, which provides the thermodynamic information. When the plantwide DS model has been built, the plant DCS historian of some process upset scenarios will be used again for further model validation. This is a nontrivial task, because lots of data preprocessing and postprocessing, as well as modeling troubleshooting activities, are induced. Meanwhile, it is also unrealistic to expect the DS results will exactly match the real measurements even if all possible modeling efforts have been made. The success of the DS validation depends on whether or not the timing and amplitude of the dynamic responses of each subsystem will match the real DCS historian. Sometimes, the plant may lack some transient concentration, temperature, or pressure information, which really provides difculties for DS model validation. Therefore, it is always better to collaborate with experienced plant engineers to judge the validation results, so as to improve the modeling quality. Note that this is the last chance to validate the plantwide DS model. Identication of Start-up Initial Status. Before the validated plantwide DS model is applied for start-up simulation, the whole model should be adjusted to run at the initial state of start-up. This step actually highlights the most important difference between normal DS and start-up DS. The initial state of startup usually involves low-load running equipment, zero inow and outow rate, and full reux of distillation columns, as well as temporary multiple recycles and auxiliary streams at the

beginning of start-up. Meanwhile, the transfer procedure from the normal status to its initial start-up status oftens lacks supporting information, such as real plant data, parameter estimations, and operating guidance. Thus, the activities of model status adjustment present the most challenging step for plantwide start-up simulation, where sufcient care is needed to prevent the divergence of the modeling process. Figure 3 shows a general model system to illustrate the transformation, where the initial feed for start-up represents the feed used for commissioning the system to its initial state for start-up. Note that the transition of model status requires not only system model input changes but also process topology changes (recycle and auxiliary streams) and operating status changes (e.g., temperature, pressure, concentration, and control parameters changes). A general algorithm to accomplish the status-adjusting task, which was completely ignored in previous studies, is presented below. Step 1. Make the plantwide DS model run at the normal steady state. At this step, the ow rates of the entire inner and outer loop streams for start-up are zero. The normal feed (stream A in Figure 3) will be exactly equal to system input (stream C in Figure 3), while the ow rates of initial feed for start-up (stream B in Figure 3), system recycle (stream D in Figure 3), total recycle (stream E in Figure 3), and purge (stream F in Figure 3) are all zero. Step 2. According to the plant start-up procedure, add additional dynamic models into the plantwide DS model. The additional models include mixers, splitters, and outer and inner loop streams (heat exchanger models may also be needed). Step 3. Identify the operation conditions for the key units at the initial status for start-up, such as the composition of stream B, controller set points, reux ratios, and heating and cooling duties. Step 4. Gradually reduce the ow rate of A and meanwhile gradually increase the ow rate of B, which will make the system input of C gradually transform from A to B. During the input transform, the ow rates of the entire inner and outer loop streams for start-up should be gradually increased from zero to the designated value. The controller set points for all the key units should be gradually adjusted accordingly. At the end of this step, the ow rate of A will be zero; the ow rate of B will

3508 Ind. Eng. Chem. Res., Vol. 48, No. 7, 2009

Table 1. Major Information for Plantwide Dynamic Simulation modeling level targets major supporting data from plant SS validation model capability check set point identication plant PFD and P&ID plant design data nominal operating data industrial expertise Aspen Plus Hysis Pro II 1 DS validation model capability check equipment capacity control strategy and parameters process upset data industrial expertise Aspen Dynamics Dynsim Hysis 23 DS for start-up operation feasibility test safety check start-up procedure improvement turnaround operating data industrial expertise Aspen Dynamics Dynsim Hysis 34

typical simulators normalized time expense

reach the desired value, which will make the system run close to the initial status for start-up. Step 5. Gradually increase the splitter ratio of D and make its ow rate increase. Meanwhile gradually decrease the ow rate of B. At the end of this step, the ow rates of B and purge stream F will be zero. Thus, the total recycle ow rate of E will exactly equal the system recycle ow rate of D, which also equals the system input ow rate of C. Step 6. Check the entire DS model to see if every unit is running at the expected initial state of start-up. If yes, the model system has reached the initial state of start-up. Otherwise, the model system needs further ne-tuning. First, make sure all the controller set points are xed at the specied values in step 2. Then increase the ow rate of B from zero to some small value, and meanwhile reduce the ow rate of D by the same value by reducing its split ratio, and go to step 5. Note that in steps 4 and 5, the system input transformation needs sufcient care to avoid computational divergence, because such transformation inuences the dynamic simulation result of every unit of the model system. Except the small changes at every input adjustment, the most important is to make the plantwide system reach the steady state at some intermediate transformation points (e.g., 50%, 70%, and 90% completion of full recycles), and then continue the model tuning. Thus, the system input transformation in steps 4 and 5 actually suggests the acquisition of a series of steady states. Because of that, the identication of start-up initial status is considered as the most critical and time-consuming task during the dynamic simulation. Also note that this general algorithm is a hypothetical modeling procedure without any real implementation assumption. It presents a systematic way to obtain the initial state of the plantwide DS model for the start-up simulation. Dynamic Simulation for Flare Minimization. After the initial state of a start-up is obtained, the DS model is ready to virtually test the start-up operating procedures provided by the plant. The nal modeling activity is to schedule all the dynamic operating procedures as the input of the DS model and let it run. Note that a chemical plant start-up undergoes a number of stages. At each start-up stage, specic objectives and constraints must be obtained, which usually involves process inputs, temperature, pressure, ow rate, and stream components of each unit changing nonlinearly.18-20 Thus the controller set points and even control strategy should be changed accordingly. To model the dynamic process inputs and dynamic start-up operation procedure, a set of program scripts, or so-called startup tasks, have to be developed and embedded into the DS.21 Then, the DS model is ready to run, while the simulation results will be fully repeatable. Supposedly, the dynamic simulation results will identify unexpected or unsafe operation conditions. This will be fed back to the plant operation group to recheck their previous operating procedures. The modied operating procedures will be virtually

tested again by rerunning the DS model with modied input. Similarly and iteratively, the DS model will help the plant identify viable or even optimal operating strategies for its startup operations. Note that when simulation meets an infeasible problem, two possibilities may exist: either the model itself has some problems, which are not detected in previous model validation, or the plant operating procedures do have uncontrollable operations. Thus, troubleshooting should be conducted with the help of both theoretical analysis and industrial expertise. Also note that all the developed methodology is based on rstprinciples models. Therefore, commercial simulators such as Aspen Plus, Aspen Dynamics, PRO/II, Dynsim, or Hysys are recommended. The developed methodology is applicable in general and is not limited to one particular plant or process. It is also a cost-effective approach for are minimization. Table 1 gives a summary about the major supporting information needed from a real plant. It is worth noting that although the focal point of the developed methodology is dynamic DS, SS is absolutely necessary. This is not only because DS models are generated from the SS models but also because SS can identify the controller set point information, which determines the settling point of a dynamic response. Therefore, the controller set points at the end of start-up operations should be identied through SS before the DS validation and application. Due to the inherent complexity of plantwide dynamic simulation and the possible data incompleteness, on-site industrial expertise is required at every stage. It helps validate the simulation result and facilitate troubleshooting. Two groups, operation group and simulation group, usually work together for the DS based are minimization project. The operation group from the plant includes experienced operators and engineers. They provide alternative start-up procedures based on their planning and experience. Then the simulation group virtually tests the proposed procedures with the plantwide DS model to check the operational feasibility, reliability, and safety issues. The plantwide DS model will be validated or modied based on the simulation results and joint discussions. The time cost generally increases as the modeling activity goes to the next stage. Based on the experience, if time expense for steady-state modeling is normalized as one unit, dynamic modeling activity will cost two to three units. The nal start-up simulation for are minimization will take three to four units, which is because considerable troubleshooting and improvement efforts will be involved at this stage. Case Study Ethylene plant start-ups emit huge amounts of VOCs and HRVOCs that may cause highly localized and transient air pollution events and also result in tremendous raw material and energy loss. Thus, one are minimization project based on the

Downloaded by LAMAR UNIV on October 7, 2009 | http://pubs.acs.org Publication Date (Web): February 27, 2009 | doi: 10.1021/ie8016219

Ind. Eng. Chem. Res., Vol. 48, No. 7, 2009 3509

Figure 4. Sketch of the entire modeling system for the case study.

developed methodology has been conducted. A general ethylene plant starts with thermal cracking of raw feedstock in furnaces. The efuent cracked charge gas is cooled and partially condensed and then sent to a charge gas compression system. Charge gas from the nal stage compression is dried prior to the chilling train. After the majority of hydrogen is removed from the chilling train, the cold charge gas is then fed to the fractionation section, which consists of a demethanizer (DeC1), deethanizer (DeC2), depropanizer (DeC3), and debutanizer (DeC4). In the demethanizer, methane and hydrogen are separated from the charge gas mixture as overhead vapor. The bottom stream with the enriched mixture of C2+ (ethylene, ethane, propane, and heavier hydrocarbons) is then sent to the recovery section for further separation. The recovery section employs a deethanizer, depropanizer, and debutanizer to separate the products of C2s, C3s, C4s, and C5s plus heavier components, respectively. All the products have to meet the product specications or purity at normal operation conditions. To reduce are emission, the start-up with total recycle has been implemented. Figure 4 presents a sketch of the entire modeling system for the case study, where some subsystems are simplied for easy illustration. It should be noted that since the furnace operations are not within the total-recycled start-up process, the charge gas ow rate and component concentrations from furnaces only functioned as the simulation inputs. Meanwhile, because the charge gas concentrations from a specic furnace are xed (for either heavy or light naphtha cracking), in this case study only the furnace ow rate is changed dynamically according to increased number of activated furnaces. Thus, the furnace simulation is unnecessary to be dynamic. To reduce the computational load without the sacrice of simulation accuracy, the furnace simulation is conducted independently and is not included in the dynamic simulation of the case study. Note that four major outer recycles are considered during start-up, which include the recycles of H2 from the chilling train: H2 and methane from the top of DeC1, C2s from the top of DeC2, and C3s from the top of DeC3. A major inner recycle is the stream of C4s from the top of DeC4 fed back to the bottom of DeC2. With these recycles, the start-up emissions are expected to be greatly reduced due to two reasons: one is that the huge amounts of components from H2 though C4 will be reused instead of being ared during start-up; the other is that with the help of these recycled streams, the key units of DeC1

Downloaded by LAMAR UNIV on October 7, 2009 | http://pubs.acs.org Publication Date (Web): February 27, 2009 | doi: 10.1021/ie8016219

Figure 5. Depropanizer temperature prole at normal steady state.

through DeC4 can gear toward their normal operation conditions quickly, which means the start-up aring time will be reduced compared with the start-up without recycles. This daring start-up indeed presents considerable challenges for modeling and dynamic simulation. With the developed methodology, the plantwide dynamic simulation has successfully helped the plant validate the conceptual start-up procedure. In accordance with the developed methodology, the simulation results at different modeling stages are shown below. Model Development and Validation. After the SS model has been developed, model validation is needed. If the SS test is not satised, it needs to be calibrated with plant data by adjusting different model parameters to match the steady-state model results with plant data measurements. For instance, Figure 5 shows the comparison between SS model prediction and real measurements for DeC3 tray temperature prole, which are key factors for evaluating separation performance of these distillation columns. It is clear that the simulation results match well with the real measurements. As examples of dynamic model validation, Figures 6-8 show the ow rate dynamic response for DeC2, DeC3, and DeC4 product streams under a recorded disturbance from the DCS historian. The disturbance was caused by a cracking furnace shutdown for decoking, which caused upstream process upset. As a result, the disturbance was propagated to the downstream process. The response time and trend

3510 Ind. Eng. Chem. Res., Vol. 48, No. 7, 2009

Figure 6. Dynamic response for the deethanizer.

Downloaded by LAMAR UNIV on October 7, 2009 | http://pubs.acs.org Publication Date (Web): February 27, 2009 | doi: 10.1021/ie8016219

Figure 9. Start-up procedure for the case study.

Figure 7. Dynamic response for the depropanizer.

Figure 8. Dynamic response for the debutanizer.

predicted by the DS model match the DCS historian quite well, except for some system biases. Through troubleshooting, it is identied that this is because the DCS data does not satisfy mass balance while the dynamic model does. It actually reminded the plant that the ow rate sensors might have problems during that period. The simulation results and

analysis are also acknowledged by the plant engineers based on their industrial expertise. DS for Flare Minimization. Once the steady-state and dynamic model validation has been completed, the plantwide DS model needs to be transformed to its initial state for startup. At this initial state, the whole process system runs stably with the total recycle. A light hydrocarbon mixture containing hydrogen, methane, ethane, ethylene, and propylene with the composition ratio of 1.5:15:1.5:73:9. in mole percent is circulated in the system. There are no system inputs and outputs at the initial state of start-up, but only the inner and outer recycles are fully open. Based on the plant operation strategy, the startup is made up of two different feeds: heavy naphtha and light naphtha. One studied start-up procedure in terms of feed input is shown in Figure 9, which is also the input of the DS model. It shows the charge gas feed from heavy naphtha cracking furnaces (the rst two furnaces) is incremented in two ramps for each of the rst two furnaces with a half-hour duration in between. The feeds from light naphtha cracking furnace (the third through the seventh furances) are also incremented in two ramps for each furnace but without any idle waiting between two furnaces. Based on this start-up procedure, the dynamic simulation for product streams of DeC1, DeC2, DeC3, and DeC4 are shown in Figures 10-13. The overall dynamic responses show the startup will take about 14 h to reach the normal steady-state operation, during which all the product streams are within specication. Historically, the plant start-up took about at least one day. Based on the simulation prediction, the new start-up procedure will help the plant save more than 44% of the startup time. The predicted start-up time has been really ac-

Ind. Eng. Chem. Res., Vol. 48, No. 7, 2009 3511

Figure 10. Dynamic response of demethanizer top products during the startup.

Figure 13. Dynamic response of debutanizer bottom products. Table 2. Flare Minimization Results for the Case Study
amount of ared raw materials (klb) C1 2163 C2 5569 C3 3017 C4+ 2782 major emitted pollutantsa (klb) NOx 19.5 HC 270.6 101.2 62.6

Downloaded by LAMAR UNIV on October 7, 2009 | http://pubs.acs.org Publication Date (Web): February 27, 2009 | doi: 10.1021/ie8016219

start-up duration (h) shortest start-up in the pastb DS assisted start-up saved percentage (%) 25 14 44

904 2237 1001 58.0 59.8 66.8

918 7.4 67.0 62.1

a Assuming 98% aring efciency and based on U.S. EPA Flare Efciency Study, 1983.22 b The amounts of ared raw materials are estimated based on the plant start-up time and feedstock ow rate.

Figure 11. Dynamic response of deethanizer top products.

Figure 12. Dynamic response of depropanizer top products.

complished on site with the help of the developed plantwide DS model. The dynamic simulation provided an insight into process dynamic behaviors, which really helped the plant beforehand start-up material preparations and process operation, and meanwhile increased the plant engineers condence level. As an example, Figure 10 shows that during the start-up DeC1 top stream temperature will decrease continuously, while ow rate will generally decrease rst and then increase. This is because the temperature of DeC1 feed from the chilling train will continuously decrease during the start-up, which makes the top temperature also decrease from -150 to -250 F. Because of that, the top ow rate of C1 will decrease initially. However,

as the system feed from cracking furnace increases, the total amount of methane in DeC1 feed increases with each furnace feeding in. The combined effects result in the obtained ow rate response. It helps operators avoid potential inappropriate control to increase the top ow rate, as the ow rate will come back automatically to the expected level after some time. As another example, Figure 13 shows that the DeC4 bottom ow rate will be zero during the rst hour of start-up. The reason is that at the initial start-up state, C5s or heavier components do not exist in the system. As the charge gas is fed in the system, the C5s or heavier components will gradually accumulate in the sump of DeC4. The simulation predicts that the bottom ow rate will increase after 1 h of sump accumulation. This information helps the plant prepare the downstream units operation for start-up. With the plantwide dynamic simulation, the are emission data is summarized in Table 2. For simplication, the ared raw materials are aggregated and classied as C1 (methane), C2 (ethane and ethylene), C3 (propane, propylene), and C4+ (butane, butylene, butadiene, etc.). The aring emissions are aggregated as NOx and hydrocarbons, the calculation for which is based on 98% aring efciency and the U.S. EPA Flare Efciency Study in 1983.22 For comparison, the emission data for the plant best start-up in the past are also calculated and shown in Table 2. The simulation shows C2 are the major aring materials for both cases. The DS assisted start-up can save 58.0%-66.8% of ared raw materials under different categories. As a result, the total NOx and hydrocarbons emissions of the DS assisted start-up are estimated as 7.4 and 101.2 klb, receptively. These are signicant reduction by 62.1% and 62.6%, respectively, compared with 19.5 and 270.6 klb of emissions from the historical best start-up. It should be indicated that the aring sources and thus emissions in the case study have been signicantly reduced because of the novel start-up procedure with total recycles (see

3512 Ind. Eng. Chem. Res., Vol. 48, No. 7, 2009

Figure 4) and operation strategies (see Figure 9). The DS plays the important role to virtually verify the applicability of the startup procedures and the operation conditions, which helps reduce aring during the plant start-up. The DS shows, due to various recycles during a plant start-up, that the majority of off-spec product streams (recycled H2/C1, C2, C3, and C4 streams in Figure 4) from DeC1 through DeC4 have been reused instead of ared. Meanwhile, start-up time is signicantly reduced (11 h less compared with the shortest start-up in the past). Note that the reduction of aring time means the increase of normal manufacturing time. It also means the saving of raw materials from aring for future production. Furthermore, the salient environmental and societal benets from are minimization are priceless. The predictions of the start-up time and dynamic responses are in good agreement with reality. Conclusions Plant-wide dynamic simulation serves as a powerful tool in aiding are minimization for CPI plants today. This paper developed a general methodology on are minimization for chemical plant start-up operations via plantwide dynamic simulation. The plantwide dynamic simulation is performed based on the integration of rigorous process models, plant design data, P&ID, DCS historian, and industrial expertise. It can predict accurately the dynamic behavior of a process prior to any real plant changes, which gives insight into the process behavior that is not apparent through SS or operational experience. It helps test plant operating procedures and support decision making during plant start-up. It is also a cost-effective approach for industrial emission source reduction. The benets from this study are not only for environment and society but also for the economics and sustainability for the chemical process industry. Acknowledgment This work was in part supported by the Texas Commission on Environmental Quality (TCEQ), Texas Air Research Center, and Texas Hazardous Waste Research Center. Literature Cited
(1) Pohl, J.; Lee, J.; Payne, R. Combustion efciency of ares. Combust. Sci. Technol. 1986, 50, 217. (2) Xu, Q.; Li, K. Y. Dynamic simulation for chemical plant turnaround operation. Integrated Environmental Management Consortium Meeting, Houston, TX, June 25, 2008. (3) Nam, J.; Webster, M.; Kimura, Y.; Jeffries, H.; Vizuete, W.; Allen, D. T. Reductions in ozone concentrations due to controls on variability in industrial are emissions in Houston, Texas. Atmos. EnViron. 2008, 42, 4198.

(4) Vizuete, W.; Kim, B.; Jeffries, H.; Kimura, Y.; Allen, D. T.; Kioumourtzoglou, M.; Biton, L.; Henderson, B. Modeling ozone formation from industrial emission events in Houston, Texas. Atmos. EnViron. 2008, 42, 7641. (5) Webster, M.; Nam, J.; Kimura, Y.; Jeffries, H.; Vizuete, W.; Allen, D. T. The effect of variability in industrial emissions on ozone formation in Houston, Texas. Atmos. EnViron. 2007, 41, 9580. (6) Murphy, C. F.; Allen, D. T. Hydrocarbon emissions from industrial release events in the Houston-Galveston area and their impact on ozone formation. Atmos. EnViron. 2005, 39, 3785. (7) EPA, National Ambient Air Quality Standards. http://www.epa.gov/ air/criteria.html, accessed March 8, 2008. (8) Doe, K.; Coppard, D. Process simulation and ethylene cracker for operation training. Proceedings of the 13th Ethylene Producers Conference, Houston, TX, April 23-26, 2001; p 656. (9) Chenevert, D.; Harry, C.; Walker, J.; Unterbrink, B.; Cain, M. Flare minimization practices improve olens plant start-ups. Oil Gas J. 2005, 103, 54. (10) Greg, D. The use of dynamic simulation to develop control strategies for emergency situations. Comput. Chem. Eng. 2000, 24, 1181. (11) Vinod, P.; Jeffrey, Y.; Surajit, D.; Prakash, R.; Jihong W. Application of dynamic simulation in the design, operation, and troubleshooting of compressor. Systems Proceedings of the 36 Turbomachinery Symposium, 2007. (12) Mario, R. E.; Arne, K. l.; Louis, H.; Sten, B. J. Dynamics and control during start-up of heat integrated distillation column. Comput. Chem. Eng. 2000, 24, 1091. (13) Luyben. W. L. Plantwide Dynamic Simulators in Chemical Processing and Control, 1st ed.; CRC Press: Boca Raton, FL, 2002. (14) Bernard, A. Start-up planning and support Following a plant revamp, 2007. AIChE Spring National Meeting, Houston, TX, 2007. (15) Singh, A.; Li, K. Y.; Lou, H. H.; Hopper, J. R.; Golwala, H.; Ghumare, S. Flare minimization via dynamic simulation. Int. J. EnViron. Pollut. 2007, 29, 19. (16) Li, K.; Xu, Q.; Lou, H. H.; Gossage, J. L.; Singh, A.; Vragolic, S.; Kelly, T. Flare minimization during plant start-up via dynamic simulation. PSE ASIA 2007, Xian, China, 2007. (17) Gore, S., Plant start-up in CPI via dynamic simulation: Case study. Master Thesis, Lamar University, Beaumont, TX, 2005. (18) Rajagopalan, S.; Pradeep, V.; Hiranmayee, V.; Ananthanarayanan, N. A framework for managing transitions in chemical plants. Comput. Chem. Eng. 2005, 29, 305. (19) Wang, L.; Makita, H.; Kano, M.; Hasebe, S. Dynamic start-up model of heat integrated distillation column. PSE ASIA 2007, Xian, China, 2007. (20) Joao, A. F.; Arrude, L. V. R.; Flavo, N., Jr. Startup of a distillation column using intelligent control techniques. Comput. Chem. Eng. 2005, 30, 309. (21) Rutherford, P.; Persad, W.; Lauritsen, M. Consider dynamic simulation tools when planning new plant start-up. Hydrocarbon Process. 2003, 82, 75. (22) U.S. Environmental Protection Agency, Flare Efciency Study, EPA-600/2-83-052, Cincinnati, OH, 1983.

Downloaded by LAMAR UNIV on October 7, 2009 | http://pubs.acs.org Publication Date (Web): February 27, 2009 | doi: 10.1021/ie8016219

ReceiVed for reView October 24, 2008 ReVised manuscript receiVed January 19, 2009 Accepted January 22, 2009 IE8016219