Clean Techn Environ Policy (2008) 10:6779 DOI 10.

1007/s10098-007-0127-2

ORIGINAL PAPER

An integrated approach for water minimisation in a PVC manufacturing process

Jun Hoa Chan Dominic Chwan Yee Foo Sivakumar Kumaresan Ramlan Abdul Aziz Mohd Arifn Abu-Hassan

Received: 23 July 2007 / Accepted: 12 October 2007 / Published online: 30 November 2007 Springer-Verlag 2007

Abstract This paper presents a water minimisation study carried out for a polyvinyl chloride (PVC) resins manufacturing plant. Due to the complexity of the mixed batch and continuous polymerisation process, an integrated process integration approach, which consists of process synthesis, analysis and optimisation was used for this work. A simulation model was rst developed in a batch process simulation software, SuperPro Designer V6.0, based on the operating condition of a PVC manufacturing process. The batch simulation model captured the essential information needed for a water minimisation study, e.g. process

duration, water mass ow, etc. Data extracted from the simulation model was later used in the water minimisation study, utilising the widely established process synthesis technique of water pinch analysis. Two water saving scenarios were presented. Scenario 1 reports a fresh water and wastewater reduction of 28.5 and 90.1% respectively, for the maximum water recovery scheme without water storage system. In Scenario 2, higher fresh water and wastewater reduction are reported at 31.7 and 100% respectively, when water storage tank is installed in the water network. Keywords Process integration Water minimisation Pinch analysis Process modelling Batch processes Polymer manufacturing

J. H. Chan GTC Process Technology (Singapore) Pte. Ltd, 3 Science Park Drive, #01-08/09, The Franklin 118223, Singapore e-mail: jhchan_gtcsg@yahoo.com D. C. Y. Foo (&) School of Chemical and Environmental Engineering, University of Nottingham Malaysia, Broga Road, 43500 Semenyih, Selangor, Malaysia e-mail: Dominic.Foo@nottingham.edu.my S. Kumaresan School of Engineering and Information Technology, University Malaysia Sabah, Locked Bag 2073, 88999 Kota Kinabalu, Sabah, Malaysia e-mail: shiva@ums.edu.my R. A. Aziz Chemical Engineering Pilot Plant, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia e-mail: ramlan@cepp.utm.my M. A. Abu-Hassan Chemical Engineering Department, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia e-mail: m.arifn@fkkksa.utm.my

Introduction Recent development has seen the shift of the process industries from conventional end-of-pipe waste treatment to more sustainable pollution prevention or waste minimisation practises. Some of the factors that drive this shift include environmental sustainability and stringent emission legislations, as well as increasing cost of resources and waste treatment. One of the active areas for waste minimisation activities has been that of in-plant water recovery. The benets of implementing water recovery are twofold. Apart from the reduction of fresh water (and its associated treatment), smaller volume of wastewater is generated. The seminal work on insight-based techniques for water network synthesis was initiated by Wang and Smith (1994), who presented a two-stage pinch analysis technique for xed load problems, based on the more generalised mass exchange network synthesis problems (El-Halwagi and

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Manousiouthakis 1989). In the rst synthesis stage, limiting composite curve is used to locate the minimum fresh water and wastewater owrate targets prior to detailed network design (second stage of network synthesis). Flowrate constraints and multiple water sources were considered in their later work (Wang and Smith 1995a). The basic concept underlying these works is that all processes that use water are modelled as mass transfer operations. However, later works (e.g. Dhole et al. 1996; Hallale 2002; Manan et al. 2004) showed that representing all processes that use water with mass transfer model might not be always adequate. Some processes that use water e.g. boiler blowdown, cooling tower make-up and reactor efuent are typical examples where water quantity is more important than the quality (always termed as xed owrate problems). New graphical and numerical approaches have been later developed to handle the xed owrate problems. Some promising techniques in locating the minimum water targets for the xed owrate problems include the graphical tools of water surplus diagram (Hallale 2002), material recovery pinch diagram (El-Halwagi et al. 2003; Prakash and Shenoy 2005a), source composite curve (Bandyopadhyay et al. 2006; Bandyopadhyay 2006) and the improved limiting composite curve (Agrawal and Shenoy 2006), as well as the numerical targeting tools such as cascade analysis techniques (Manan et al. 2004; Almutlaq et al. 2005; Foo et al. 2006a; Almutlaq and El-Halwagi 2007; Foo 2007a, b). Apart from the targeting stage, numerous techniques have also been proposed for the systematic design of water network, i.e. second stage of the synthesis task. This includes water grid diagram (Wang and Smith 1994), load table (Olesen and Polley 1996, 1997), water main method (Kuo and Smith 1998; Castro et al. 1999; Feng and Seider 2001), water source diagram procedure (Gomes et al. 2007) for xed load problems; as well as source sink mapping diagram (El-Halwagi 1997), nearest neighbour algorithm (Prakash and Shenoy 2005a) as well as the load problem table (Aly et al. 2005) for xed owrate problems. Once the owrate targets are established, the water network is designed to achieve the minimum targets using any of the above-mentioned design tools. Subsequently, a preliminary synthesised network can be evolved to yield a simplied network (Prakash and Shenoy 2005b; Ng and Foo 2006). In contrast to the active evolvement of water network synthesis techniques in continuous processes, water minimisation for batch processes has received far less attention due to its nature of complexity. Only recently, similar work has received considerable attention for batch water network. Wang and Smith (1995b) initiated the work in batch water network synthesis that focused on mass transferbased processes that use water. Majozi et al. (2006) developed a similar technique to account for batch

processes where no water intake and discharge are permitted during the operation. The shortcoming of both these approaches is their limitation in handling xed load problems. To overcome the limitation of the xed load problems, Foo et al. (2005) proposed the use of water cascade analysis technique that was originally developed for water network for continuous processes (Manan et al. 2004; Foo et al. 2006a) in handling the xed owrate problems. Other works on batch water network synthesis are mainly dominated by various mathematical optimisa et al. 1997, 1999a, 1999b; tion approaches (Almato Puigjaner et al. 2000; Kim and Smith 2004; Li and Chang 2006; Majozi 2005a, 2005b, 2006; Shoaib et al. 2007). It should be noted that most of the reported works on batch water network synthesis have utilised hypothetical examples for demonstration. To date, limited numbers of industrial cases have been reported, in both pinch-based and mathematical-based works. This includes production et al. 1997) and agroof concentrated fruit juice (Almato chemicals (Majozi et al. 2006). More industrial case studies are needed to help in the development of new water minimisation techniques that are of practical use. This is the subject of this paper. El-Halwagi (1997) describes that a process integration study consists of three elements: i.e. process synthesis, analysis and optimisation. In this work, an integrated process integration approach has been used. The process synthesis element consists of water network synthesis, via pinch analysis technique while process analysis and optimisation were carried out by batch process simulation and modelling studies. In the following section, the water cascade analysis technique (Manan et al. 2004; Foo et al. 2006a) for locating the minimum targets for a water network is rst described. This is followed by the description of a PVC manufacturing case study. A simulation model that was developed based on the plant operation data is next described. Batch process simulation overcomes the constraint of the mixedbatch and continuous operation mode in the polymer manufacturing process. Data extracted from the simulation model are later used in the water minimisation study carried out using pinch analysis technique.

Water cascade analysis technique The generic water cascade table (WCT) in Table 1 summarises how WCA is carried out for water targeting in the reuse/recycle scheme (Manan et al. 2004; Foo et al. 2006a). The rst step in conducting a WCA is to locate the various water sinks and sources at their respective concentration levels. As shown in the rst two columns of Table 1, the concentration levels (Ck) are arranged in an ascending order (k = 1, 2, , n), and the ow of water sink (Fj) and

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An integrated approach for water minimisation in a PVC manufacturing process Table 1 The generic water cascade table (WCT) k Ck RjFj RiFi RiFi - RjFj FC,k FFW k k+1 . . . n-2 n-1 n Ck Ck+1 . . . Cn-2 Cn-1 Cn (RjFj)k (RjFj)k+1 . . . (RjFj)n-2 (RjFj)n-1 (RiFi)k (RiFi)k+1 . . . (Ri Fi)n-2 (RiFi)n-1 (RiFi - RjFj)k FC,k (RiFi - RjFj)k+1 . . . (RiFi - RjFj)n-2 FC,n-2 (RiFi -Rj Fj)
n-1

69

Dmk

Cum. Dmk

FFW,k

Dmk Cum. Dmk+1 FFW,k+1 . . . Dmk+1 . . . Dn-2 Cum. Dm

n-1

FC,k+1 . . .

. . .

FFW,n-1 FFW,n

FC,n-1 = FWW

Dmn-1 Cum. Dmn

source (Fi) are summed at their respective concentration level k in columns 3 and 4. Column 5 represents the net ow, (RiFi - RjFj) between water sources and sinks at each concentration level k; with positive indicating surplus, negative indicating decit. Next, the net water ow surplus/decit is cascaded down the concentration levels to yield the cumulative surplus/decit ow (FC, k) in column 6 with an assumed zero fresh water ow (FFW = 0). This assumed ow is to facilitate the search for the minimum water ow and will later be replaced once the rigorous fresh water target is located. Two important parameters to full in water network targeting are the water ow and impurity load constraints (Foo et al. 2006a). Water ow constraints are fullled once the above-described ow cascading is carried out. The next step involves setting up the cumulative impurity load cascade (Cum. Dm) to full the load constraint. Impurity load in column 7 (Dmk) is obtained via the product of cumulative ow (FC, k) and the concentration difference across two subsequent concentration levels (Ck+1 - Ck). Cascading the impurity load down the concentration levels of column 8 yields the cumulative load (Cum. Dmk), which is essentially the numerical equivalent of graphical targeting tool of water surplus diagram (Hallale 2002). A feasible water network is characterised by the presence of only positive values of Cum. Dm in column 8. A negative Cum. Dmk means the impurity load is transferred from lower to higher concentration level, which is infeasible. In such a case, an interval fresh water ow (FFW, k, column 9) is calculated by dividing Cum. Dmk by the concentration difference between level k (Ck) and the fresh water concentration (CFW) i.e., FFW;k Cum. Dmk : Ck CFW 1

cumulative ow (column 6) to obtain a new set of feasible ow cascade and hence a feasible load cascade. This new fresh water ow represents the minimum fresh water ow (FFW) of the network; while the nal row in column 6 represents the wastewater ow (FWW) generated from the network. The network pinch concentration is the impurity concentration with zero Cum. Dmk, while the water source that exists at the pinch is called the pinch-causing source (Manan et al. 2004; Foo et al. 2006a). Note that once the ow and impurity load cascading are carried out using the minimum fresh water ow, the nal column of Table 1 is omitted. The above-described procedure for locating the minimum water targets was original developed for water networks operated in continuous mode (Manan et al. 2004; Foo et al. 2006a), in which water owrate is used instead of water ow. Foo et al. (2005) later extended the targeting tool for batch water network known as time-dependent water cascade analysis. By segregating water sinks and sources into the time interval when they exist, cascade analysis is carried out in each time interval to locate the minimum water targets. More recently, the targeting technique was extended to multiple fresh resources (Foo 2007a) and threshold (Foo 2007b) problems.

Case study on PVC manufacturing Figure 1 shows the process ow diagram for PVC resins manufacture. It consists of ten parallel batch polymerisation reactors, blow-down vessel, and two parallel trains of downstream processing equipment. Each downstream processing train consists of a stripper, two decanters and a uid bed dryer. The plant is operated in a semi-batch mode where upstream polymerisation reactors are scheduled to match the downstream processing trains that are operated in continuous mode. The polymerisation process is carried

The absolute value of the largest negative FFW, k will then replace the earlier assumed zero fresh water ow in the

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Gas Holder

J. H. Chan et al.

Condenser

Compressor

R ec y c l e d VCM

Recovered VCM vapour

Fresh VCM

Bat ch R ea ctor s (10 Units)

Blowdown V es s el

Slurry Stripper

Stea m P VC R es ins

Sh i ft er

Dryer Hot air

Decanter

Fig. 1 Process ow diagram of a PVC manufacturing plant

out subsequently in ten parallel batch reactors. Raw materials for the polymerisation process include demineralised water, mixture of fresh vinyl chloride monomer (VCM) and recycled VCM (mainly from blowdown vessel and stripper), initiators and suspending agents, which are charged into the reactor in sequence. The suspending agent is diluted to approximately 4.0 wt% and is charged into the reactor together with demineralised water. This is mainly due to the high viscosity of the suspending agent solution. Upon completion of the suspending agent charge, primary and secondary initiators are added into the reactor. It shall also be noted that, due to piping constraints, demineralised water can only be charged into the reactors one at a time. Charging procedure in each of the reactor will only start after the end of charging in an earlier reactor. The same situation occurs to the charging of VCM and the blowdown operation after the reaction ends. Upon completion of water charge, the reactor is purged by nitrogen and then vacuumed before charging of VCM is commenced. This is to ensure that no oxygen is present in the reactor, as reaction between VCM and oxygen might result in an explosion. Upon the completion of VCM charge, heating is commenced to raise the reactor to the operating temperature and pressure. Exothermic polymerisation process next commences for a duration of 7.5 h. Continuous cooling is needed to remove excess heat and to maintain the reactor temperature. A huge amount of chilled water is added towards the end of the polymerisation process to maintain the reactor temperature. PVC polymer is the main product at the end of the polymerisation process. Other by-products of the reaction are the unreacted VCM, initiators, suspending agent and some trace amount of contaminant. The nal reactor content is in slurry form (mainly consists of PVC and water). The blowdown vessel receives batches of slurry, which are intermittently discharged from the reactors. The blowdown vessel acts as buffer storage so that slurry can be continuously fed to the two parallel downstream processing

trains. As the slurry enters the blowdown vessel, the major portion of the unreacted VCM trapped in the PVC particles ashes off and is vented to the gas holder for recovery. The VCM vapour is next compressed and condensed into liquid form before it is sent for reuse in the polymerisation reactors. As the efuent from the blowdown vessel enters the downstream processing trains, the stripper column further removes the unreacted VCM from the PVC slurry. Steam is introduced at the base of the stripping column and the VCM is removed as an overhead product to the gas holder. The stripped slurry is then directed to two parallel decanters for water removal. Approximately 80% of water is removed by these decanters from the PVC slurry. Wet cake from the decanters is dried in the uidised bed dryer. Dried PVC resins are transported to the shifter. Fine resins that pass through the shifter are sold as product, while the course resins are ground and sold as low-grade resins.

Process simulation model Figure 2 shows the base case process simulation model that has been developed based on the operating condition of the PVC manufacturing process using SuperPro Designer V6.0 (Intelligen 2005). The annual operating time of the process model is taken as 7920 h. In the modelling environment of SuperPro Designer, a few operations take place sequentially in a single unit procedure (Intellegen 2005). For instance, vessel procedure P-1 in Fig. 2 is used to model the batch polymerisation procedure that takes place in vessel K-207A. The polymerisation procedure consists of sequential operations of raw material charges, vacuum operation, material heating, polymerisation as well as product blowdown. The modelling of these single operations is described next. The raw material charged into the reactor during the start of procedure P-1 includes demineralised water (CHARGE-H2O), suspending agent (CHARGE-PVA), primary initiator (CHARGE-Init1) and secondary initiator (CHARGE-Init2). Note that the model was developed based on the operating condition of the manufacturing process, where the charging of demineralised water for a subsequent reactor is scheduled to start after the water charging of the preceding reactor ends. Suspending agent and initiators are charged into the reactor during the charging of water. The vacuum operations (VACUUM) in procedure P-1 include a vacuum air purge, followed by a nitrogen gas purge and nally another vacuum purge. The vacuum operations were carried out before the charging of VCM (CHARGE-VCM), to avoid the mixing of VCM with air, which will lead to explosion.

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An integrated approach for water minimisation in a PVC manufacturing process

71

Fig. 2 Simulation owsheet of PVC manufacturing

During the heating operation, hot water is used to raise the reactor temperature (HEAT-1) to 60C where the polymerisation process (REACT-1) is carried out. The polymerisation reaction operation takes an overall duration of 7.5 h. Chilled water is added to the reactor (CHARGEChilled H2O) in the last half-an-hour just before the polymerisation reaction ends. Stoichiometric reaction model is used and the reaction stoichiometric is dened as the conversion of one mass of VCM to one mass of PVC, as follows: nVCM ! PVCn : 2

Upon the completion of the polymerisation process, the slurry reactor content is discharged (TRANS-OUT) to the blowdown procedure P-14 (in vessel V-101). Similar to the case of demineralised water charge, blowdown operation of a subsequent reactor is also scheduled to start after the completion of a preceding reactor, due to the piping constraint in the PVC plant. The last operation in the vessel procedure is the cleaning process. The scheduling summary for all reaction procedures (P-1 to P-10) is displayed in the process Gantt chart as shown in Fig. 3. From the blowdown vessel, the slurry product enters into two parallel identical and continuous downstream processing trains, which individually consist of a stripper, slurry tank, two parallel identical decanters and a uid-bed dryer. Thus, no scheduling is needed in these processes. The modelling specications of each unit procedure in these downstream processing trains are next described.

Stripper procedures (P-16 and P-17) are used for VCM removal. Steam at 110C is introduced into the strippers to achieve a VCM removal of 99.9%, before the PVC slurry enters into two parallel identical decanters (P-18 and P-19, each represents two identical decanters). Solid removal in the decanters is specied as 99% for PVC, with water loss of 21%. Efuent emits from these decanter units (WW A-D) is the main wastewater of the process, while the wet lter cake is sent to uidised-bed dryers for moisture removal. In the uidised-bed dryers (P-20 and P-21), hot air at 95C is used to dry the wet lter cake. Evaporation rate of water and the nal solid temperature are set at 916 kg H2O/h and 60C respectively. As a result, 99.8% of the moisture (the component of water and chilled water) is removed. From the simulation model, the minimum cycle time for the process is determined to be 11.78 h corresponds to the completion of the last reactor (P-10/K-207J). Based on the annual operating time of 7,920 h, this translates into 671 batches/year. It should also be noted that all vessel procedures (P-1 to P-10) are observed to have different cycle times (see Gantt chart in Fig. 3). This is mainly due to the scheduling of the TRANS-OUT operations in each of the reactor procedures (P-1 to P-10). Since TRANS-OUT operation in each of the reactor is scheduled to start after the TRANS-OUT operation of the preceding reactor ends, this creates a lag time for the product to be discharged from the subsequent reactor before the preceding reactor completes its TRANS-OUT operation. A good example is shown in Fig. 3. As shown, the polymerisation reaction

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Fig. 3 Process Gantt chart for base case simulation

(REACT-1) in P-2/K-207B is completed at 9.62 h. However, due to the TRANS-OUT operation of P-1/K-207A being still in operation, TRANS-OUT operation in P-2/K207B cannot be started until the TRANS-OUT operation in P-1/K-207A ends at 9.78 h.

single water source. The main impurity that is of concern for water reuse/recycling activity is the suspended solid content in the wastewater at a concentration of 50 ppm. Water sinks that are considered for water reuse/recycle include the PVC manufacturing process (mainly for reactor feed), utility section (boiler and cooling tower make-up) and miscellaneous usage (e.g. oor cleaning, etc.).

Water minimisation study This section presents water minimisation study carried out for the PVC manufacturing process. Figure 4 shows the water usage diagram for the process. This includes the PVC manufacturing as well as the utility sections. As shown in Fig. 4, the process receives fresh water supply from the state water supplier. Since the PVC manufacturing process requires feed water that is free of hardness, the fresh water is further treated in a deionised plant (DI plant). Feed water to the utility section (boiler and cooling tower make-up) and general cleaning purposes tolerate a lower quality of water, and hence treatment in the DI plant has been avoided. The only water source for the process originates from the continuous discharge of the four parallel decanters (WW A-D), which are used to dewater the slurry efuent from the strippers. The total owrate of these water sources are determined to be 9,243.9 kg/h. Since the four water sources have the same characteristics, they are treated as a Limiting water data extraction Data extraction is considered to be the most essential step of a water minimisation study. Incorrect extraction of data leads to sub-optimal water network with reduced water saving targets (Foo et al. 2006b). For a batch water network, apart from the limiting water ow and concentration, the occurrences of the processes that use water are to be identied. In this work, the start and end time as well as the duration for each processes that use water are identied with the aid of the base case simulation model. Table 2 summarises the limiting data for a single batch of polymerisation process. However, if one were to use this set of limiting data for the analysis, one may lose the greater water saving potential. This is because the raw data extracted from the simulation study does not reect how the batch polymerisation process are carried out in actual operation. For most industrial batch processes, the

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An integrated approach for water minimisation in a PVC manufacturing process Fig. 4 Water usage diagram
Fresh water Miscellaneous usage (Floor Washing) Miscellaneous usage (Manual Flushing) Water Filter Filtered Water Tank
Chemicals

73

Chiller
Water to Steady Bearing R e a ct or Fe e d Chilled Water

Flushing Flushing F l us h i ng

D. I. Plant

P ure Water T an k
Chemicals

S tead y B e ar i n g
Line Flushing

Re a c t o r
R ea ct or C l ea n i n g

Blow down

Stripper

Slurry Tank

Cooling Tower Make Up

C o o l in g T o w er
Cooling Water Circulation

Ja cke t
Hot Water Circulation

S te a m

Decanter

Wastewater

Steam

Hot Water Tank Hot Water Tank

Steam

Hot Water Circulation

D ry er

PVC Resins

Boiler make up water

Chemicals

Bo iler
Co nd en sate

Air Heater

Hot Air Co l d A i r

operations are repeated (as cyclic mode) once the equipment has completed its earlier operation. Figure 5 shows such a situation, where three consequent batches of processes occur simultaneously within the time frame of a single batch N. As shown, batch (N - 1) completed its operations after 4.5 h batch N commences its operation; while batch (N + 1) begins its operations 4.5 h before batch N ends. The revised limiting data is summarised in Table 3. It should also be noted that some operations in Fig. 5 and Table 3 are carried out in sequence. For instance, reactor feed operation (SK1) for one reactor takes 20 min to complete (CHARGE-H2O as in Fig. 3), hence a total of 200 min or 3.33 h would be needed for 10 reactors to complete their reactor feed operations carried out
Table 2 Raw data extracted from base case simulation Sinks SKj 1 2 3 4 5 6 7 8 9 RjSKj Sources SRi RjSRi Decanter Operation Operation Reactor feed Line ushing Boiler make-up 1 Boiler make-up 2 Reactor cleaning Cooling tower Flushing Floor cleaning 1 Floor cleaning 2 Flowrate (kg/h) 31,531.53 3,125.00 13,200.00 13,200.00 1,200 6,300.00 2,000.00 6,000.00 6,000.00 82,556.53 Flowrate (kg/h) 9,243.90

subsequently (Fig. 5). The same situation occurs to line ushing (SK2), reactor cleaning (SK5) and ushing (SK7), in which each individual operation for each reactor takes 0.5 h to complete. Two water saving scenarios with and without water storage system were analysed using the time-dependent water cascade analysis technique (Foo et al. 2005). The rst stage of the analysis corresponds to the allocation of the water sinks and sources in their respective time intervals. The time interval table in Table 4 is utilised for this preliminary analysis. As shown, there are 13 time intervals and all water sinks are located in their respective time intervals according to their occurrence time. The sum of the individual water ow of the water sinks gives the total water requirement of each time interval. The owrate of

Concentration Cj (ppm) 10 10 10 10 20 50 200 500 500 Concentration Ci (ppm) 50

Start time tS (h) 0 9.28 0 8 9.78 0 9.28 0 8 Start time tS (h) 0

End time tT (h) 3.33 14.28 0.25 8.25 14.78 14.78 14.28 0.25 8.25 End time tT (h) 14.78

Mass ow Fj (kg) 105,000 15,625 3,300 3,300 6,000 93,114 10,000 1,500 1,500 239,339 Mass ow Fi (kg) 136,625

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Batch (N 1) ends operation at 4.5 hr

J. H. Chan et al.

10

15

Scenario 1: water network without water storage system In Scenario 1, no water storage tank is installed for the batch water network. Hence, water saving can only be carried out via direct integration, i.e. when both water sinks and sources present together within the same time interval. Table 5 shows two examples of ow targeting for time interval 00.25 h and 9.289.78 h. Due to the overlapping between two consequent batches, water sinks from the earlier batch (SK2, SK5, SK6 and SK7) and current batch (SK1, SK3, SK6 and SK8) operations are observed between 0 and 0.25 h. The water source for this interval is available at 2,311 kg and 50 ppm ( column 3 in Table 4). Without considering for water reuse/recycle, this interval requires 17,414 kg of fresh water and generates 2,311 kg of wastewater. As shown in Table 5, maximum water recovery enables the fresh water (FFW) to be reduced to 15,103 kg and wastewater is completely eliminated (FWW = 0 kg). Another characteristic to be noted in Table 5 is that water targeting this time interval exhibits a threshold problem. Hence, ow adjustment is needed for the ow cascade, as reected in the adjusted cumulative ow (Adj. FC) column in Table 5. Detailed description for the threshold problem is outlined in Foo (2007b).

Batch (N 1)
2 5 6 7

1 3

B a tc h N
4

5 6 7 8 9

1 3 6 8

Batch (N + 1) 0 5
Batch cycle time = 14.78 hr

10

Batch (N + 1) starts operation at 10.28 hr

15

Fig. 5 The overlap of three consequent batches of polymerisation processes (only water sinks are shown)

the continuous water source (SR1 from decanter) is also scaled according to the duration of each time interval. Both water saving scenarios are analysed as follows.

Table 3 Limiting data that takes into consideration repeated batch processes Number of batches N-1 Sinks SKj 2a 5a 6a 7a 1b 2b 3b 4b N 5b 6b 7b 8b 9b 1c N+1 3c 6c 8c RjSKj Sources SKi Operation Continuous 1 RjSKi Decanter Operation Line ushing Reactor cleaning Cooling tower Flushing Reactor feed Flowrate (kg/h) 3,125.00 1,200 6,300.00 2,000.00 31,531.53 Concentration Cj (ppm) 10 20 50 200 10 10 10 10 20 50 200 500 500 10 10 50 500 Start time tS (h) 0 0 0 0 0 9.28 0 8.00 9.78 0 9.28 0 8.00 10.28 10.28 10.28 10.28 End time tT (h) 4 4.5 4.5 4 3.33 14.28 0.25 8.25 14.78 14.78 14.28 0.25 8.25 13.61 10.53 14.78 10.53 Mass ow Fj (kg) 12,500 5,400 28,350 8,000 105,000 15,625 3,300 3,300 6,000 93,114 10,000 1,500 1,500 105,000 3,300 28,350 1,500 431,739 50 0 14.78 136,625 136,625

Line ushing 3,125.00 Boiler make-up 1 13,200.00 Boiler make-up 2 13,200.00 Reactor cleaning Cooling tower Flushing Floor cleaning 1 Floor cleaning 2 Reactor feed Cooling tower Floor cleaning 1 1,200 6,300.00 2,000.00 6,000.00 6,000.00 31,531.53 6,300.00 6,000.00 152,213 9,243.90 9,243.90

Boiler make-up 1 13,200.00

Flowrate (kg/h) Concentration Ci (ppm) Start time tS (h) End time tT (h) Mass ow Fi (kg)

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An integrated approach for water minimisation in a PVC manufacturing process Table 4 Time interval table for case study on PVC manufacturing SKj Flowrate (kg/h) Start time, tS (h) 0
2a 5a 6a 7a 1b 2b 3b 4b 5b 6b 7b 8b 9b 1c 3c 6c 8c SRi 1 3,125 1,200 6,300 2,000 31,532 3,125 13,200 13,200 1,200 6,300 2,000 6,000 6,000 31,532 13,200 6,300 6,000 Flowrate 9,244 781 300 1,575 500 7,883 3,300 3,300 1,575 1,500 1,500 7,883 3,300 1,575 1,500 2,311 28,471 6,193 4,622 32,354 2,311 9,521 4,622 4,622 2,311 97,117 19,404 4,221 19,404 4,221 3,150 22,050 1,575 6,489 3,150 1,000 600 3,150 1,000 300 1,575 500 3,696 19,404 6,160 804 4,221 1,340

75

0.25
9,625 3,696 19,404 6,160 97,117

3.33
2,094 804 4,221 1,340

4
600 3,150

4.5

8.25

9.28

9.78

10.28

10.53

13.61

14.28

1,563

1,563

781

9,625

2,094

600 3,150

3,150

28,471

6,193

4,622

Table 5 Cascade analysis for water ow targeting (00.25 h) Ci (ppm)

0 0 10 20 50 200 500 1,000,000 11,964 300 3150 500 1,500 -11,964 -11,964 -119,641 -300 -12,264 -367,924 2,311 -839 -13,103 -1,965,474 -500 -13,603 -4,080,947 -1,500 -15,103 -15,095,605,921 -15,102,139,907 -15,102 -6,533,986 -13,068 -1 FWW = 0 0 1,017,593 -2,453,039 -12,265 1,499 1500 450,000 1,017,593 -487,565 -9,751 1,999 2000 300,000 567,593 -119,641 -5,982 2,838 2839 85,171 267,593 3,138 3139 31,390 182,422 15,102 FFW = 15,103 151,032 151,032

RjFj (kg)

RiFi (kg)

RiFi - RjFj (kg)

FC (kg)

Dm (mg)

Cum. Dm (mg)

FFW,k (kg)

FC (kg)

Adj. FC (kg)

Dm (mg)

Cum. Dm (mg)

Table 6 Cascade analysis for water ow targeting (9.289.78 h) Ci (ppm)

0 0 10 20 50 200 500 1,000,000 3,150 1,000 4,622 1,563 -1,563 -1,563 0 -1,563 1,472 -91 -1,000 -1,091 0 -1,091 -1,090,004,725 -1,090,407,973 -1,090 -327,165 -403,248 -806 FWW = 159 159,370,275 159,592,028 -13,583 -76,083 -380 159 47,835 221,753 -46,875 -62,500 -1,250 1,159 173,918 -15,625 -15,625 -781 -313 -9,375 0 (PINCH) 173,918 -313 FFW = 1,250 12,500 12,500 -3,125 9,375

RjFj (kg)

RiFi (kg)

RiFi - RjFj (kg)

FC (kg)

Dm (mg)

Cum. Dm (mg)

FFW,k (kg)

FC (kg)

Dm (mg)

Cum. Dm (mg)

123

76

Table 7 Minimum ow targeting for Scenario 1: without water storage 0.253.33 h RiFi - RjFj (kg) FC (kg) FC (kg) FC (kg) FC (kg) FC (kg) RiFi - RjFj (kg) RiFi - RjFj (kg) RiFi - RjFj (kg) RiFi - RjFj (kg) RiFi - RjFj (kg) 3.334.00 h 4.004.50 h 4.508.00 h 8.008.25 h 8.259.28 h FC (kg)

123
126,935 -106,742 20,193 -3,696 16,497 -10,337 6,160 -6,160 0 0 0 0 0 0 0 0 10,304 0 0 -1,340 0 0 10,304 -1,500 0 1,340 0 10,304 0 1,500 0 3,032 -2,249 -1,678 10,304 736 1,500 0 3,032 3,589 1,678 0 -804 -600 0 0 764 3,032 3,032 4,393 2,278 0 -2,094 0 0 -3,300 764 0 0 6,486 2,278 0 4,064 0 0 0 9.7810.28 h RiFi - RjFj (kg) FC (kg) FC (kg) FC (kg) RiFi - RjFj (kg) RiFi - RjFj (kg) 10.280.53 h 10.5313.61 h 13.6114.28 h RiFi - RjFj (kg) FC (kg) 14.2814.78 h RiFi - RjFj (kg) FC (kg) 1,690 -1,563 128 -600 -472 1,472 1,000 -1,000 0 0 0 -1,500 0 -500 1,500 0 0 -839 2,000 -6,160 0 0 0 2,839 -10,337 6,160 -1,340 0 0 0 RFWW = 13,495 -300 3,139 -3,696 16,497 -2,249 1,340 0 0 -11,964 15,103 -106,742 20,193 -804 3,589 -1,678 0 126,935 -2,094 4,393 -600 1,678 6,486 0 2,278 2,278 RFFW = 308,609

00.25 h

Ci (ppm)

RiFi - RjFj (kg)

FC (kg)

(a) 09.28 h

15,103

10

-11,964

3,139

20

-300

2,839

50

-839

2,000

200

-500

1,500

500

-1,500

1,000,000

9.289.78 h

Ci (ppm)

RiFi - RjFj (kg)

FC (kg)

(b) 9.2814.78 h

1,250

10

-1,563

-313

20

-313

50

1,472

1,159

200

-1,000

159

500

159

J. H. Chan et al.

1,000,000

Table 8 Minimum ow targeting for Scenario 2: with water storage 0.253.33 h RiFi - RjFj (kg) FC (kg) FC (kg) FC (kg) FC (kg) FC (kg) RiFi - RjFj (kg) RiFi - RjFj (kg) RiFi - RjFj (kg) RiFi - RjFj (kg) RiFi - RjFj (kg) 3.334.00 h 4.004.50 h 4.508.00 h 8.008.25 h 8.259.28 h FC (kg)

00.25 h

Ci (ppm)

RiFi - RjFj (kg)

FC (kg)

(a) 09.28 h 126,935 -106,742 20,193 -3,696 16,497 -10,337 6,160 -6,160 0 0 0 0 9.7810.28 h RiFi - RjFj (kg) FC (kg) FC (kg) FC (kg) RiFi - RjFj (kg) RiFi - RjFj (kg) 10.2810.53 h 10.5313.61 h 0 0 0 0 0 10,304 13.6114.28 h RiFi - RjFj (kg) FC (kg) 0 0 0 0 0 0 -1,500 0.00 -1,424 14.2814.78 h RiFi - RjFj (kg) FC (kg) -1,340 0 0 0 1500.00 0 0 3,032 1,340 0 0 -2,249 -1,678 10,304 736 1500.00 0 0 3,589 1,678 0 -804 -600 0 0 -660.00 3,032 0 4,393 2,278 0 -2,094 0 0 -3,300 -660.00 0 0 6,486 2,278 0 2640 0 0 0

15,103

10

-11,964

3,139

20

-300

2,839

50

-839

2,000

200

-500

1,500

500

-1,500

1,000,000

FST

An integrated approach for water minimisation in a PVC manufacturing process

9.289.78 h

Ci (ppm)

RiFi - RjFj (kg)

FC (kg)

(b) 9.2814.78 h 1610 -1,563 48 -600 -553 1,472 1000 -1,000 0 0 0 -81 -1,500 0 -5,252 -500 1500 0 0 -6,739 -839 2000 -6,160 0 0 0 0 -300 -2413 -10,337 6,160 -1,340 0 0 0 0 RFWW = 0 77 -2113 -3,696 9,758 -2,249 1,340 0 0 -11,964 9851 -106,742 13,454 -804 3,589 -1,678 0 120,196 -2,094 4,393 -600 1,678 6,486 0 2,278 2,278 RFFW = 295,114

1,250

10

-1,563

-313

20

-313

50

1,472

1,000

200

-1,000

500

1,000,000

123

FST

159

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J. H. Chan et al.

reduction of 28.5% fresh water and 90.1% of wastewater, compared to current water network without any water reuse/recycle practice. Scenario 2:water network with water storage system In Scenario 1, due to the absence of a water storage tank, wastewater are discharged at certain time intervals without being further utilised. This includes time intervals of 4.50 8.00, 8.259.28 and 9.289.78 h. By utilising a water storage tank, wastewater at these time intervals may be stored for further usage at time intervals that exhibit water decit. Table 8 shows how this indirect integration scheme is materialised. The last row of Table 8 displays the water ow (FST) that enters or leaves the water storage. As shown, water is stored between intervals that generate wastewater (given as positive FST value) and utilised at other intervals (given as negative FST value) to reduce their fresh water demand. As such, the fresh water ow is reduced to 295,114 kg (31.7% reduction), while wastewater ow is completely removed. A cumulative water mass chart is shown in Fig. 6, indicating that a tank with a capacity of 12 tons is needed to achieve the maximum water recovery as in Scenario 2. The ow sheet for the nal water reuse/recycling scheme is shown in Fig. 7.

Fig. 6 Cumulative mass in water storage tank

On the other hand, only three water sinks from current operation are observed between 9.28 and 9.78 h (observed from Table 4). As shown in Table 6, targeting for this time interval yields fresh water and wastewater ows of 1,250 and 159 kg, respectively, with a pinch concentration observed at 50 ppm. Similar water ows targeting were carried out for all other time intervals, and the summary is shown in Table 7 (only net water ow and cumulative ow are shown). The nal column of Table 7 shows that the total fresh water and wastewater ows for the network are determined to be 308,609 and 13,495 kg respectively. This corresponds to a

Fig. 7 Flow sheet after water reuse/recycling

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An integrated approach for water minimisation in a PVC manufacturing process

79

The decision as to which scenarios would be implemented eventually will rely on the decision of the plant authority after a detailed economic assessment of each scenario, which is beyond the scope of this work.

Conclusion A water minimisation scheme was developed for a PVC manufacturing case study. An integrated approach that consists of process synthesis, analysis and optimisation steps was utilised to identify the true minimum water targets for the water network that is operated in mixed batch and in continuous mode. Two water saving scenarios were presented to analyse the maximum water saving potential of the process.
Acknowledgment The technical assistance of Mr. Yoeng Chee Nyok is gratefully acknowledged.

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