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Energy 32 (2007) 983998 www.elsevier.com/locate/energy

Step-by-step process integration method for the improvements and optimization of sodium tripolyphosphate process plant
Predrag Raskovic
, Bulevar OsloboXenja 124, 18000 Leskovac, Serbia Faculty of Technology, University of Nis

Abstract Improvement and optimization of a complex chemical plant motivated by energy savings is presented in this paper. The reference object of the research is the sodium tripolyphosphate plant in IHP-Prahovo, the biggest factory for producing chemical products in Serbia and Montenegro. The research is done by using a step-by-step process integration approach, which combines several computerbased simulation/optimization methodologies. The evaluation of obtained results indicates considerable possibilities for plant efciency improvement. r 2006 Elsevier Ltd. All rights reserved.
Keywords: Energy efciency; Process integration; Sodium tripolyphosphate; Software tool

1. Introduction The improvement of energy system efciency is covering a variety of actions and approaches. These operations in general can be described by the tasks of changing the manufacture procedures and improvement of control, unit operations and system integration. One of the methods, which play an important role in the effort to improve the energy efciency of industrial plants is Process Integration (PI). PI can be dened very widely as design, operation and management of industrial processes with system-oriented and integrated methods, models and tools. Such denition insinuates that proper use of PI methods includes on one hand the fundamental knowledge of thermodynamics, chemical reactions, process control, unit operations, and on the other hand, an understanding and experience in optimizations methods and technical objectives. Major projects in the chemical industry are rarely motivated by energy savings. If the energy is not taken into consideration before late in the design project, the possibilities of its savings will be reduced. The restrictions in choices (originate from the fact that other parts of the
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projects with inuence on the energy consumption have been xed) do not enable a procedure, which handles the PI task in a general manner. Instead of that, in the case of chemical industry, when reduction of the energy consumption is investigated the optimal objectives for PI are often a subjective decision. The PI task for the improving energy efciency of sodium tripolyphosphate manufacture, one of the most complex processes in the chemical industry, possesses the lot of qualications described in previous paragraphs. In the literature review the author has found only one paper concerning exergy analysis of sodium trypolyphosphate manufacture [1], unfortunately with different production route and without use of computer-aided methods. In spite of this difference, that work was of great help. This paper will be dedicated to a more detailed description of process and plant conguration, as well as the explanation of PI methods and software tools, used for the energy efciency improvement. Detailed description of the mathematical models and the research results will be presented in future papers. 2. Properties and the use of sodium tripolyphosphate Sodium tripolyphosphate (STPP)Na5P3O10, is a solid inorganic compound, which belong to the group of

E-mail address: buki@bankerinter.net. 0360-5442/$ - see front matter r 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.energy.2006.10.004

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Nomenclature A c E G h HRAT Hd I {i} J {j } K p : Q t T : W area (m2) velocity (m/s) exergy (W) mass ow rate (kg/s) specic enthalpy (J/kg) heat recovery approach temperature (1C) lower heating value (kJ/kg) process units process streams thermal conductivity (W/mK) pressure (Pa) heat ow (W) temperature (1C) temperature (K) work ow(power) (W)

Greek symbols d l x thickness (m) coefcient of excess air () height (m)

Subscripts cal Fl FU IN OUT ORT calciner fuel ring unit inlet outlet orthophosphate

condensed inorganic phosphates. The general term condensed inorganic phosphates is applied to phosphorus compounds in which various numbers of PO4 groups are linked together by oxygen bridges. Condensed inorganic phosphates can be classied into three classes: cyclic, linear and cross-linked condensed phosphates. Linear condensed phosphates, also called polyphosphates have the general elementary composition [PnO3n+1](n+2) and the most important of them are presented in Table 1. Sodium tripolyphosphate have the stable form as the hexahydrated salt. Identity and physical/chemical properties of sodium tripolyphosphate are presented in Table 2. STPP is widely used in regular and compact laundry detergents, automatic dishwashing detergents, toilet and surface cleaners, where it provides a number of functions including:

    

sequestration of water hardness enabling surfactants to function effectively, pH buffering, dirt emulsication and prevention of deposition, hydrolysis of grease, dissolving-dispersing dirt particles.

environmental risk related to its use in detergents is indicated in soil, air or sewage treatment plants.1 Sodium tripolyphosphate exists in two major crystalline forms, known as Phase I (or Form I) and Phase II (or Form II). Phase I material is formed if the process temperature is maintained above 450 1C, while Phase II material is formed at temperatures below 450 1C. The nal product of STTP in practice, according to its composition, is named as: Low Term (Form I is the major component in product), Middle Term (Form I and Form II has nearly the same percentage in product) and High Term (Form II is the major component in product). The price of the product is directly proportional to the percentage of Form II. Typical composition of STPP includes 4% impurity due to presence of sodium pyrophosphate, sodium orthophosphate and sodium metaphosphate. A production plant for STTP, based on wet manufacturing route2, essentially consists of:

 

neutralization part (Wet process part) where phosphoric acid is neutralized to an orthophosphate solution, heating part (Dry process part) where, by drying and calcination, the solution is converted into sodium tripolyphosphate.

Generally speaking, the use of STPP in detergents could be replaced only by a great number of different chemicals, as no one substitute offers all its functions. The amount of STPP which was used in household cleaning products in Europe in 2000, is estimated to be about 300 000 t, since its consumption in household detergents varies considerably between different countries in Europe. It should be pointed out that in some countries the STPP use in detergents is almost exclusively concentrated on automatic dishwashing products while in other countries the use in laundry detergents is the overwhelming application. The United States Food and Drug Administration lists STPP as generally recognized as safe, no

The raw material for sodium tripolyphosphate manufacture is obtained by recovering the phosphate values from phosphoric ore, in the form of phosphoric acid H3PO4. In this process, phosphate rock is acidulated with sulfuric acid H2SO4, either alone, or in conjunction with
1 A primary environmental concern of sodium phosphates is their release into water. Phosphate may be a limiting nutrient in some aquatic environments and in some countries the use of phosphate in detergents has been discouraged to prevent unsustainable plant growth and oxygen starvation (eutrophication) of lakes and waterways. 2 The alternative one, named as thermal route, is not used in the production of STPP for detergent applications.

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phosphoric acid. The result of this operation is formation of precipitate, which contains the calcium values as calcium sulfate, and recovering the impure phosphoric acid, termed wet acid. The resulting wet acid is contaminated [2] with:

Such wet acid is unsuitable for use in sodium tripolyphosphate production, because the presence of soluble cationic/anionic impurities and uoride contamination, which would end up in the nal product. 3. Process description of sodium tripolyphosphate manufacture The reference object, in this paper, is the sodium tripolyphosphate manufacture in IHP-Prahovo, the biggest factory for producing base chemical products in Serbia and Montenegro. This company production plant essentially consists of two parts:

 

process impurities originate from the reagents used in the production of phosphoric acid, like sulfuric acid and process water, common impurities in the phosphate rock, like aluminum (Al3+), iron (Fe3+), magnesium (Mg2+), calcium (Ca2+), potassium (K+), strontium (Sr2+), chlorides (Cl) and uoride (F), common trace elements in the phosphate ore, like arsenic, cadmium, mercury, uranium, copper, zinc and lead.

Table 1 Condensed phosphates Number of P atoms 1 Type Example CAS no.

 

wet process part, where the raw material is primarily treated with chemical reactions and dry (nal) process part, based on thermal treating of seminished product from previous part.

Monophosphates/ Orthophosphates Biphosphates/ Pyrophosphates

Na3PO4 NaH2PO4 Na2HPO4 Na4P2O7 Na3HP2O7 Na2H2P2O7 NaH3P2O7 Na5P3O10 Na4HP3O10 Na3H2P3O10 Na6P4O13

7601-54-9 7558-79-4 7558-80-7 7722-88-5 14691-80-6 7758-16-9 13847-74-0 7758-29-4 24616-37-3

Triphosphates

Tetraphosphates

The Wet process plant (Fig. 1) comprising: Primary treatment stagewhere the wet acid is introduced in storage tanks in order of removing process impurities by precipitation. Major fraction of the sludge formed in this operation is calcium sulfate dihydrate (gypsum) CaSO4d2H2O. The process of sludge thickening is done by the use of centrifugal pumps. Deuorization stageoperation for separating the insoluble uorides (like hydrouoric acid HF or sodium uoride NaF, present in the wet acid as uorosilicate acid H2SiF6) from wet acid by adding sodium carbonate

Table 2 Identity and physical/chemical properties of sodium tripolyphosphate Formula

Symonimus

Macro-molecular description Physical state/particle size Molecular weight Melting point Vapor pressure at 25 1C Water solubility other*

Density pH-value PKa

Sodium triphosphate; Triphosphoric acid, pentasodium salt; Sodium Phosphate Tripoly; STPP; Tripolyphosphate de sodium; Pentasodium triphosphate; Pentasodium Tripolyphosphate; Natriumtripolyphosphat; Pentanatriumtriphosphat (German); Trifosfato de pentasodio (Spanish);Triphosphate de pentasodium (French) Solid, inorganic Slightly hygroscopic granules 367.86 (g/mol) Decomposes at 620 1C 1 Negligible At 20 1C 140 (g/kg) At 25 1C 145 (g/l) At 40 1C 160 (g/kg) At 100 1C 325 (g/l) 0.45 1.15 (g/cm3) at ambient temp. 4 At 25 1C : 9.010 in 1% aqueous solution H5P3O102H++H4P3O 10 (pK1 1) + 2 H4P3O 102H +H3P3O10 (pK2 1:1) + 3 H3P3O2 10 2H +H2P3O10 (pK3 2:3) + 4 H2P3O3 2 H +HP O 10 3 10 (pK4 6:3) + 5 HP3O4 10 2H +P3O10 (pK5 8:9)

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Fig. 1. Process ow diagram of wet process plant sodium tripolyphosphate manufacture.

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Na2CO3, which reacts with uoride as H2 SiF6 Na2 CO3 ! Na2 SiF6 H2 O CO2 2HF Na2 CO3 ! 2NaF H2 O CO2 (1) (2)

The result of these reactions is made up of sodium uorosilicate Na2SiF6 and sodium uoride NaF, which precipitates in the solution and substantially reduces the uoride concentration of the wet acid. Filtration stageoperation for removing the residual contaminants from acid, by its passing through the lter (impregnated by cellulose ber). This production step ensures the complete removal of Na2SiF6 and NaF from acid. Decolorization stageadsorption process for removing the organic compound from the acid, by passing through active coal layer. The adsorbate is desorbed in regeneration stage by the use of NaOH solution. Extraction stagein this stage, the acid is introduced on the top of an extraction column and extracted in counterow by an organic extraction solution (water insoluble). Extraction column allow efcient liquid to liquid contact between the wet acid and the organic extracting solution (made up of alkyl phosphate, tri-n-butylphosphate (C4H9)3PO4 (TBP)). The TBP is diluted with an organic solvent (low boiling petroleum hydrocarbons-kerosene) that has limited solubility in water to improve phase separation. In the extraction stage of the process, phosphorous pentoxide P2O5 values, present in the wet acid, are loaded into the organic extract, leaving behind the bulk of the mineral impurities in a resulting rafnate. The rafnate is an aqueous solution, which can be employed in producing fertilizer. The extraction step is normally carried out at temperatures 5055 1C. Washing stageoperation, which is used to remove the soluble impurities in TBP (H2SO4, H2SiF6 and Fe salt), by adding water in mixers. Reextraction stageprocess for separating TBP from the acid by neutralization (adding the sodium dihydrogen phosphate NaH2PO4) and precipitation. In this phase wet acid is transformed in the primal salt. From the top of decanter 87% of the light phase (TBP) ows to a storage tank and the rest of this phase goes to the Regeneration stage. On the other side 20% of the hard phase from the bottom of decanter ows to centrifugal separators (Centrifugation stage) in order to separate the residual TBP from this compound. Remaining 80% of this phase is going back to the Reextraction stage. Neutralization stageoperation of mixing NaH2PO4 with sodium carbonate Na2CO3 in order to form a sodium orthophosphate solution having a Na:P mole ratio of 1.67:1. This reaction is presented as 3NaH2 PO4 Na2 CO3 ! 2Na2 HPO4 NaH2 PO4 H2 O CO2 3 Neutralization result is the formation of an aqueous mixture named orthophosphate solution, containing mono-

sodium orthophosphate and disodium orthophosphate in a mole ratio of about 1:2. Evaporation stagewhere the concentration of salt in orthophosphate solution is rising up from 43% to 50%. The orthophosphate solution also called make up liquor is stored in storage tank, which presents the link to the heating part of the process. The dry process plant (Fig. 2) comprising: Drying stagethe orthophosphate solution is rst dried in spray drier. Atomization of the feed is done in multiple nozzles at the top of the drier, where the solution is injected using the high-pressure rotary pumps (pE100 bars). Solution in nely atomized state is heated by a parallel downward ow of hot (ue) gases from a heavy oil-ring unit, which are employed in drier as the mixture of recirculated and fresh ue gases from mixing chambers. After drying, orthophosphate solution is transformed in orthophosphate powder (mixture 2Na2HPO4/NaH2PO4). Dehydration (calcining) stagewhere sodium tripolyphosphate is produced from the sodium orthophosphate mixture. The moisturized material from spray drier is calcined in rotary kiln (calciner) in order to made reaction: 4Na2 HPO4 s 2NaH2 PO4 s ! 2Na4 P2 O7 s Na2 H2 P2 O7 s 3H2 O 4

at temperature within the range from about 300 to 600 1C. The temperature is selected in order to produce the desired Form I and/or Form II content in the nal STPP product. Heating agents in calciner is the ue gas from another heavy oil ring unit. Cooling stagewhere the product is cooled in a recuperative water-cooled rotary tubular cooler for solids. Final product stagethe product coming from the previous stage is generally in agglomerated form. The agglomerates are sized by crushing and screening to a desired size range or distribution (granules size about f 1 mm). The ue gas streams, emanating from either the spray dryer or the calciner, are passing through a solid recovery zone (cyclone battery of centrifugal separators) to remove the bulk of any orto/sodium tripolyphosphate powder that has been entrained in the streams. Such treated streams are then passing through a scrubber, containing a liquid scrubbing solution, which cleans the ue gas. The scrubber also takes up remaining amounts of nally powdered sodium tripolyphosphate, which were not caught in the centrifugal separators.

4. Step-by-step PI approach The improvement and the optimization of a chemical process plant, motivated by energy savings, cover a wide range of alternatives. In other word, denition of the problems, improvements, optimization of objectives as well as nal evaluations, involve a large number of choices.

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Fig. 2. Process ow diagram of dry process partsodium tripolyphosphate manufacture.

In order to constrain the problem and limit the improvement/optimization possibilities, Step-by-Step PI Approach (SSPIA) is developed. Simplied ow chart of the approach is presented in Fig. 3. This approach is based on the combined use of mathematical and thermodynamic optimization techniques [3], which are arranged for the improvement/optimization of reference, sodium tripolyphosphate plant. The prex, step-by-step, denotes the presence of more than one phase in the route of this approach. The results obtained by the use of SSPIA yielded a wide range of possible improve-

ments and acceptable solutions, which could be t into the existing plant design. 4.1. Process modeling phase In the common practice, study for energy efciency improvement in chemical industry does not necessarily depend on the complete mapping of the factory. In the effort of limiting the range of research, it has been recognized, that the most signicant part in plant production cost is the heavy oil consumption (approximately

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Fig. 3. Flowchart of step-by-step process integration approach.

7000 t crude oil per year). As more than 90% of the oil consumption is executed in the nal part of process (dry process part), the PI task is focused on it. In the rst stage of this SSPIA phase, the physical model of dry process plant (Fig. 4) is dened, by the use component-oriented approach, as the network of interconnected component (process units). This kind of approach usually generates many equations, but it is very user friendly and enables quick representation of the plant for possible recongurations. In order to create appropriate mathematical model of the plant, some assumptions were added after an analysis of the available parameters. The most signicant are the following:

ural consequence of that selection is demand for mathematical model of each component by the using mass end energy balance equations, which are in general form presented as: Mass balance equation: X X Gj G j 0; 8 i 2 I . (5)
j 2IN i;j j 2OUT i;j

Energy balance equation:     X X c2 c2 G j hj gx G j hj gx 2 2 j 2IN i;j j 2OUT i;j

: :

W i Q i 08

i 2 I,

  

connections between components are assumed to be without losses, model is steady state, because the processes in the plant can be dened as time independent, some of the streams are the ideal mixtures of air, dry ue gases, water vapor in ue gases and sodium tripolyphosphate powder. For such streams, balance equations are created for each component, bulk mass ow and the water vapor content in ue gases are the functions of mass ow rate of stream and fuel specication, respectively.

where W i 0; 8i 2 fCL; CBA ; CBK ; SP; ST ; AT ; KC ; CC ; LA ; LK g, Qi 0; 8i 2 fCL; CBA ; CBK ; SP; ST g,

Qi f K ; A; d; DT 8i 2 fAT ; KC ; CC g, Qi f GFl ; Hd ; l; ZFU 8i 2 fLA ; LK g,

The method, chosen for handling the inter-connections, was direct componentcomponent connections. The nat-

Qi f GORT ; pH ; T cal 8i 2 fKC g.

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Fig. 4. Physical model of dry process part.

4.2. Process simulation phase The second phase of SSPIA, Process simulation phase, can be noted as the most difcult and the most important part in the research route. Difcult, because in this phase, two different software tools were developed; important, since the results obtained by the use of these software tools, point out the distance of mathematical models from real thermodynamic parameters of the plant. This phase has two stages. In the rst stage, numerical model of plant (based on sequential modular approach) is implemented in the spreadsheet software tool named ExP, developed on Microsoft Excel programming platform. Thermodynamic properties of the vapor present in the ue gas streams are calculated by the use of water/steam properties simulator, settled in the Excel Add-in component. Validation of the result, obtained by simulation (presented in the Table 3), is achieved by comparison with operating data from technical documentation. The research in this phase enabled some very important conclusion and accomplishments:

construction of mass and energy ows (Fig. 5) diagrams of the plant. Simulation results were the base for polynomial tting of some equations concerning chemical reaction in calciner and re units, as well as thermodynamic properties of the ue gas streams. The participation of kinetic and potential energy in streams (except input stream of orthophosphate solution) is negligible in respect to overall energy balance.

Previously, this software tool was used for exergyefciency analysis of the plant, but its sequential modular nature has limited the range of possible improvements. Still, its results encouraged the author for the next more complicated research steps. In the next stage, the mathematical model is integrated in software tool named Prahovo Sim, by equation-oriented approach. Numerical model of this software can be classied as the non-linear optimization problem (DOF40)3, but it could be easily transformed for solving the non-linear simulation problems (DOF 0).
3

Results of software tool conrmed the proposed mathematical models of process units and enabled the

DOFnumber of degrees of freedom.

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/ Energy 32 (2007) 983998 P. Raskovic Table 3 Stream parameters obtained by sequential modular simulation by ExP Stream 1 2 3 4 5Aa 5Bb 6 7 8 9 10 11 12 13 14B 14A 15 16 17 18 19 20A 20B 21A 21B 22 23A 23B 24 25 26 27 28 29
a b

991

Gdry (kg/s) 1.93 12.89 1.78 1.35 14.67 0.58 6.89 6.00 3.77 3.04 0.09 2.00 1.45 0.092 9.10 7.65 1.74 5.69 2.14 9.10 0.003 3.09 0.003 0.56 14.67 0.013 17.76 0.02 0.00 0.00 0.00 1.74

Gwet (kg/s) 1.93 0.53 0.01 0.07 2.37 0.03 0.23 0.30 0.02 0.01 0.00 0.10 0.01 0.00 0.45 0.17 0.00 0.02 0.01 0.45 0.00 0.15 0.00 0.03 2.37 0.00 1.44 28.86 27.78 13.89 13.89 0.00

SG (kg/s) 3.86 13.42 1.79 1.42 17.04 0.61 7.12 6.30 3.79 3.05 0.16 0.09 2.10 1.46 0.09 9.55 7.82 1.74 5.71 2.15 0.11 9.55 0.00 3.25 0.00 0.59 17.04 0.01 19.20 28.88 27.78 13.89 13.89 1.74

t (1C) 80.00 523.30 10.00 80.00 160.00 160.00 790.03 213.53 10.00 10.00 10.00 220.00 109.01 10.00 220.00 220.00 525.51 350.00 10.00 10.00 10.00 213.53 213.53 213.53 213.53 160.00 159.04 159.04 65.63 80.00 40.00 25.00 36.20 50.00

c (m/s) 70.00 8.80 0.50 0.30 14.70 14.70 1.40 18.00 22.00 22.00 0.12 0.30 0.50 14.00 14.00 1.40 0.00 22.00 22.00 18.00 18.00 18.00 18.00 0.12 14.70 14.70 7.00 2.00 5.00

x (m) 30.00 32.00 33.00 5.00 5.00 5.00 32.00 30.00 30.00 30.00 12.00 3.00 2.00 5.00 5.00 1.60 3.00 3.00 3.00 20.00 20.00 20.00 20.00 12.00 20.00 20.00 32.00 26.00 31.00

G c2/2 (kW) 801.96 8999.55 38.19 133.42 8985.93 113.89 6837.45 2161.72 77.87 62.58 6759.79 19.68 265.80 30.41 20.44 3337.96 4890.99 607.64 121.45 45.75 4768.124 3283.35 0.73 1121.63 0.73 111.27 8914.02 2.60 5024.34 9665.75 4651.11 1453.47 2104.81 87.33

G x (kW) 9.45 0.52 0.00 0.00 1.84 0.07 0.01 1.02 0.91 0.74 0.00 0.00 0.00 0.01 0.94 0.01 0.00 1.38 0.52 1.55 0.00 0.53 0.00 0.00 1.84 0.00 0.47 0.06 0.35

G h (kW) 1.13 4.21 0.58 0.07 0.84 0.03 2.23 1.85 1.11 0.89 0.01 0.06 0.03 0.00 0.47 0.12 0.05 0.17 0.06 1.87 0.00 0.64 0.00 0.03 0.17 0.00 6.03 7.36 8.45

SE (kW) 812.54 9004.29 38.77 133.49 8988.61 113.98 6839.69 2164.60 79.89 64.21 19.69 265.86 30.44 20.45 3339.36 4891.12 607.69 123.00 46.33 3286.77 0.73 1122.79 0.73 111.30 8916.03 2.61 5033.73 9673.17 4659.91 1453.47 2104.81 87.33

A-ue gas in the stream. B-orto/tripolyphosphate powder in the stream.

The solving procedure for this problem is based on Sequential Linear Programming (SLP) method [4,5]. This method belongs to the group of mathematical programming strategies for constrained optimization problems. The SLP method was developed in the early 1960s and in the literature is also known as Kelleys cutting plane method or as Stewart and Grifths method of approximate programming. Although SLP is considered unattractive by theoreticians its concept has proven to be quite powerful and efcient for engineering design. As the name implies, SLP use linear programming search technique. This technique can be applied to non-linear mathematical models, very often in energy project designs. The general formulation of a SLP problem could be expressed as optimize f x; x fx1 ; x2 ; . . . ; xN g, j 1; 2; . . . ; P, (7) (8) (9)

subject to gj xp0; zj x 0;

j P 1; . . . ; P M ,

where f(x) is a non-linear objective function, gj(x) and zj(x) are non-linear inequality and equality constraints, respectively. The idea of SLP is based on linear approximations of the objective function and constraints, usually by using the rst term of a Taylor series expansion. In that way the mathematical model is transformed to a linear problem, which can be solved by the Simplex method. In the numerical model of Prahovo Sim, equality constraints are presented as the mass and energy balance equations of process units, since inequality constrain is the ratio of ue gasses mass ow rates in splitter SP (Fig. 4). In order to simulate the existing plant ratio of ue gasses mass ow rates in splitter is xed to 0.667, which is the usual value in existing operating regime. The variables that describe a numerical model are divided into two groups: decision variables (variables that are under the control of the decision maker) and design variables (which are varied by the simulation/optimization process). Software is developed on Visual Studio C++ programming platform,

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Fig. 5. Mass (a) and energy ow (b) diagrams of dry process part.

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Fig. 6. Flowchart of Prahovo Sim.

with user-friendly interfaces. The Prahovo Sim owchart is presented on Fig. 6. As it can be seen from the gure, software consists of three parts:

4.3. Optimization of the reference plant The optimization phase is realized in two research levels. On the rst level, the SLP software tool Prahovo Sim, amplied by two new numerical modules, got his nal form Prahovo Target. On the second level Prahovo Target is rearranged for application to three different scenarios (plant congurations):

 

Input part, part under the control of operator, which is used for input of decision variables and preassigned parameters. Solver part, which comprises: the linearization of constraints, denitions of starting values of design variables, move limits, stopping criteria and Simplex solver. This stage is under the programmer control, invisible for operator. During the execution solver checks the convergence and feasibility of the solutions, so in a case of failure the program is automatically returned in the Input part. Output part, where the simulation/optimization results are rst checked (percent error due to non-linearity of the problem) and then classied for analyses, either in the appropriate software menu, or in the ole-com connected Microsoft Excel Worksheets.

  

NR scenarioconguration without heat recovery option. FRG scenariosconguration with heat recovery option accomplished by the ue gas recirculation. HENS scenariosconguration where heat recovery option are realized by the use of recuperative heat exchangers network.

Scenarios are realized on the seven different owsheets (named model) of the plant as:

In the stage of data validation, the simulation results are compared with real plant parameters (presented in the Table 4). For that purpose, temperature and pressure values, obtained from plant-operating measurements, have become the decision variables in the input part of the software. The result obtained from simulationheavy oil consumption4is then compared with operating plant data. Data validations, based on oil consumption, are presented in Fig. 7. The author concluded that the average error of about 5.84% can be good starting point for the next, optimization phase.
4 There is a wide range of data validation but author decided to present only one, in his opinion the most important.

 

Model 1.0 for NR scenario. Model 1.1 (scenario with one stage gas recirculation, existing plant conguration), and Models 2.0, 2.1, 2.2 (scenarios with multistage gas recirculation) for FRG scenarios. Models 3.0 and 3.1 for HENS scenarios.

The ow sheets of some models are presented in Fig. 8, and important facts about their mathematical models are presented in Table 5. Scenario for the Model 1.0 is simplied conguration of existing plant in which the recirculation of ue gasses is excluded. This scenario can be named the base scenario, since there is no heat recovery operation. According to the

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994 Table 4 Plant operating parameters Date Sort 18. 1 29.1 30. 6 26.7 1.8 8.8 27.7 19.8 5.9 21.7 25.7 25.9 M T-1 M T-2 M T-3 M T-4 M T-5 M T-6 H T-1 H T-2 H T-3 L T-1 L T-2 L T-3 p1 (bar) t1 (1C) t2 (1C) t5 (1C) t6 (1C) t14 (1C) t15 (1C) t16 (1C) t24 (1C) t28 (1C) t29 (1C) Prod. (t/h) Fuel cons. (kgG/tpr) 100 90 80 100 98.6 100 100 110 111.7 100 100 95 98.8 108.4 92 101.5 101 102 94 93.2 89.3 100 97 94.4 395 488 418 501.7 415.7 420 429.4 422.9 368.3 608.3 458 407.5 160.6 160.4 151 160.8 160 159.2 158.8 154.8 158.7 157.3 153.6 135.6 685 802 653 846.7 715.7 725 551.7 759.8 750.4 720 686 752.5 237.5 233 244 240 240.7 240 260.4 236.1 173.3 175 211 233.1 432.5 402 530 443.3 417.1 421.7 611.3 631.9 591.7 480 519 574.4 349.9 349.2 347.6 371.5 364.6 368.5 402.3 445.3 360.2 346.3 376 364.5 50.8 56.8 67.8 66 63.6 62.2 63.8 63.2 63.1 59 62 60.5 14.9 17.8 53.6 45.5 40.9 41.3 55.6 65.1 47.9 45.3 59 66.9 6.5 6.6 30.2 32.3 33.6 33.2 27.7 45.9 29.7 32 33.2 41 5.5 5.9 4.5 6.8 5.6 5.5 5 5.1 6.2 6.3 5.06 4.3 175 175 150 170 170 170 185 185 185 140 140 140 / Energy 32 (2007) 983998 P. Raskovic

MTmiddle term sodium tripolyphosphates. LTlow term sodium tripolyphosphates. HThigh term sodium tripolyphosphates.

Fig. 7. Data validation.

number of inequality constrains its mathematical model is transformed into non-linear simulation. Second scenario for the Model 1.1 is existing plant conguration, explained in previous part of the paper. This

time the xed value, dened by the ratio of mass ow rates in splitter, is substituted by additional inequality constrain. Such exchange transformed this problem into a non-linear optimization task.

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Fig. 8. Flowsheets of plant conguration scenarios. Table 5 Important facts about SLP mathematical models of different plant congurations Model 1.0 Variables Decision variable Design variables Equality constrains Inequality constrains 62 31 31 31 0 Model 1.1 71 33 41 40 1 Model 2.0 83 28 56 55 1 Model 3.0 84 34 50 50 0

Scenario for the Model 2.0 is developed by considering the new possibilities of the ue gasses recirculation in existing plant. In order to remove the moisture from ue gasses, the gas uid separators modules are included in ow sheet (new splitter and mixture chambers, too). Although a lot of energy could be regenerated in these units, their main purpose is to remove the vapor from the ue gases stream. Mathematical model of this process unit is expressed by the same equitation as for the other units (5, 6). The outlet temperature of condensate and dry gasses is the dew point of rened ue gasses. Model 2.0 has two modications (Model 2.1 and Model 2.2) which represent their simplications but with the same DOF 1. Scenario for the Model 3.0 (and its simplied modication Model 3.1) is developed on the basis of Model 1.0, and rearranged for PI by the use of pinch design method.

PI of existing dry process plant, by the use of pinch design method, is limited for only 3 streams. Target temperature of these streams can be changed in order to create heat exchanger network for possible heat recovery. This operation would be in accordance with global mass and energy balance equation, and the nal result of such PI can be qualied as correct, from physical point of view. However, in this way the energy efciency of the plant will be improved just slightly. The situation is quite different for the others; let me call them promising5 streams. If the target temperature of these streams is changed (and these streams are involved in pinch design task), the result of such PI would be mathematically correct and quite better, according to the energy efciency improvement. On the other side, that change will disturb the global mass and energy balance of the plant, thus from the physical point of view, the obtained results can be qualied as incorrect.6 In order to exceed this limitation, new heat exchangers are added on every promising stream which exists in the Model 1.0. Such added heat exchangers present physically
5 Promising, from pinch design point of view. Streams, which can be used for the creation of heat exchangers network, such as primary and secondary air streams in combustion chambers of ring units. 6 The main reason for this is the fact that pinch design method does not respond to complex chemical operation in examined energy system (combustion, spray drying, calcining, scrubbing).

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ctive elements, the balance equations of which are settled in the mathematical model of the plant (HENS scenarios). They enable possible heating/cooling of those streams and

changing of their target temperatures, this time in accordance with mass and energy balance. In SLP software, target temperatures of such streams become the new

Fig. 9. Flowchart of Prahovo Target.

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decision variables, since the rest of the program stay the same as for the other scenarios. Another update of HENS scenario was done by plugging the pinch design module [6] in SLP software tool (Prahovo Sim). After simulation (the problem DOF 0) by SLP software, the data (which includes all promising streams) for pinch task are automatically generated. New added numerical module enables the execution of targeting, network design and network optimization, by choosing different possibilities for external heating/cooling and different HRAT. The operating cost in rst two scenarios (NR and FRG) is primarily depending on heavy oil fuel consumption. In the case of HENS scenario the optimal solution (heat exchanger network) indicates the need for new utilities (hot and cold), which means the new energy source/sink in existing plant. As in the rst part of research, the intention was to compare the solutions of all scenarios on the base of heavy oil fuel consumption, new utilities are excluded from the nal HENS solution by moving the composite curves in threshold problem statement. Operating and investment costs for such states are loaded and classied in intermediate (Targeting results) database. The solutions, this time with real heat exchangers network, which had the best energy performance, is then presented in the grid and process ow diagrams. A more detailed owchart of Prahovo Target is presented in Fig. 9. As may be seen from the picture, the numerical module for calculation of exergy rates is common to all scenarios, and enabled their evaluation by exergy efciency analysis in the last phase of the research. Pinch design module is used only in the case of HENS scenarios.

4.4. Evaluation of possible improvements The development of all phases, by presented step-by-step PI approach, makes a wide range for possible project improvements with respect to energy, environmental and economic objectives. The assessment of the improvement potential is generated by:

  

identifying the most important design variables through sensitivity analyses, investigating the effect of these variables on the performance, evaluating the improvement potential.

As the authors intention is to promote the general ideas and methods of sodium tripolyphosphate project design, detailed presentation and description of obtained results are excluded in this paper. Instead of that one general evaluation of energy efciency improvement potential, with respect to retrot project cost and fuel consumption is presented on Fig. 10. Values presented in the diagram were calculated by comparing the oil consumption and total cost (which include the investment cost) of existing plant conguration (Model 1.1) versus consumption and cost in the new-formed scenarios. Comparison was done on the basis of the same important energy inputs, and the same physicochemical properties of raw and nal materials. Presented results lead to three important conclusions:

The most effective gas recirculation is the one in existing plant conguration (Model 1.1). Scenarios without that

Fig. 10. Evaluation of energy efciency improvement potential.

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recirculation possibility (Models 1.0, 2.1) indicate increase of fuel consumption and cost. The results clearly indicate better possibilities for the project improvements in the case of HENS models than in the case of FRG and NR models. Investment cost for NR and FGR cases can be rated as negligible in comparison to the case of HENS cases.

References
[1] Atanasova L, Rasheva D. In: Hirs GG, editor. Exergy analysis of sodium tripolyphosphate manufacture. Proceedings of the international conference ECOS 2000. Efciency, costs, optimization, simulation and environmental aspects of energy and process systems, vol. 3. the Netherlands: University of Twente Enschede; 2000. p. 13218. [2] Becker P. Phosphates and phosphoric acid: raw materialstechnology, and economics of the wet-process. New York: Marcel Dekker Inc; 1989. [3] Gundersen T. Process integration PRIMER, Trondheim, Norway. SINTEF energy research, 2000. See also: /http://www.tev.ntnu.no/ iea/pi/primer.htmlS. M, Lukic N, Trnobranski K. Linear programming applied to an [4] Bojic industrial building with several available hot refuse ows. Energy 1995;20(10):106774. M, Raskovic P, Radojkovic N. An inuence of boiler-recovery[5] Bojic heat exchanger to boiler sizea tool shop example. Facta UnivSer Mech Eng 1997;1(4):44757. P. In: Signe Kjelstrup, Johan E. Hustad, Truls Gundersen, [6] Ras kovic Audun Rsjorde George Tsatsaronis, editors. Process integration case study sodiumtripolyphosphate manufacture. Proceedings of the international conference ECOS 2005; 18th international conference on efciency, cost, optimization, simulation and environmental impact of energy systems, vol. 1. Trondheim, Norway; 2005. p. 493501.

5. Conclusion The need of increasing production and energy efciency of plants as well as the improvements of their environmental performance are the most important future challenges for chemical industry. The paper presents an approach, which collects a few process integration methods for achieving these goals. The use of a computer-based simulation/optimization methodology has been applied to energy efciency improvement of the sodiumtripolyphosphate production plant. Preliminary evaluation of obtained results indicates considerable possibilities for plant efciency improvement.