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    Chinese J. Chem. Bng., 18 (1) 74 —80 (2005) Dynamic Modeling and Simulation of a Commercial Naphtha Catalytic Reforming Process’ HU Yongyou(#i#)"**, XU Weibua( tt #4), HOU Weifeng(‘t 24), SU Hongye( ## W)"* and CHU Jian(##() Notional Laboratory of Industrial Control Technology, inatitute of Advanced Process Control, Zhejiang University, Hangzhou 810027, China Abstract _A fret principler-based dynamic model for a continuous catalyst regeneration (COR) platforming pro- ‘ets, the UOP commercial naphtha catalytic reforming process, is developed in this paper. The lumping details ‘of the naphtha feed and reaction scheme of the reaction model are given. ‘The process modal is composed of the ‘reforming reaction model with catalyst deactivation, the furnace model and the separstor model, which is capable ‘of capturing the major dynamics that occurs in this process system. Dynamic simulations are performed based ‘on Gear numerical algorithm and method of lines (MOL), a numerical technique dealing with partial differential ‘equations (PDEs). The results of simulation are also presented. Dynauic reaponsee coused by disturbances in the process system can be correctly predicted through simulations Keywords eatalytic reforming, dynamic mode 1 INTRODUCTION Catalytic reforming of naphtha isa very important process for producing high octane gasoline or aromat- ies im petsuleuu teiueries aad petrucianical industiy Because of its impact on overall plant profits, the cat- alytic reforming of naphtha is the better unit to ap- ply advanced process control and process optimization strategies. The base for these profitable applications is always a good mathematical model that can repro- duce reasonably well main dynamics and stationary sins of the process system ‘The naphtha feed to reformers usually consists of about three hundred hydrocarbons with the carbon number ranging from 5 to 9+. A detailed model con- sidering all components and reactions is infeasible, so attempts had been made to split naphtha into kinetic Jumps and some notable static models had been de- veloped in past decadesl'~4]. Generally speaking, de- tailed models are theoretically sound but. quite com- plicated, and consequently dificult for application be- cause of very complex lumping scheme and paraine- ter estimation. To maintain a good balance between Kinetics and applicability of the model, in the previ- cous work), we presented a simple but sound first- principle model with 17 lumps involving only 17 re- Actions, which decreases the complexity of the model and proves to be reasonable by applying to the com- mercial reformers. Unfortunately, all of these models in the litera ture are static models that do not eapture the dy- Received 2004-02-27, accepted 2008-09-02, simulation, method of lines, process control namics of the process system and give very limited guide for process control or other fields related to pro- cess dynamics. Recently Tian et al. first developed a dyuauie model for a semiregeneration vatalytiv r= forming process successfully but it is based on only 10 lumps and did not consider catalyst coking!” In this work, a dynamic model of continuous catalyst regener- ation (CCR) platforming process, the UOP commer- cial continuous catalyst regeneration naphtha reform- ing process which includes four stacked reformers, one furnace with four heaters integrated, and one separa tor, is proposed for dynamic analysis, process control, and optimization of this process system. This work is an extension of our previous work that developed a static model, 2. PROCESS DESCRIPTION ‘The naphtha catalytic reforming is adiabatically carried out in four stacked reformers, at high temper- atures, building up aromatics, liquefied petroleum gas (LPG), hydrogen, fuel gas, and coke. The coke de- posits on the spent catalyst surface causing its deac- tivation. To recover its activation, the catalysts with coke are moved continuously and slowly through the reactors, withdrawn from the last reactor, regener- ated in a regeneration section, and returned to the first reactor as fresh catalysts. ‘The catalyst used in reformers is commonly a bifunctional bimetallic cat- alyst such as Pt-Sn/Al,Os providing the metal func- tion and the acid function. In the catalytic reform- * supported by the National Outstanding Youth Science Foundation of China (No. 602938) and National Key Technologies R&D Program in the 10th Five-Year Plan (No.2001BA204B01), "To whom correspondence should be addressed. 160516, USA. E-mail: huyongyGit-edu His current addreea is Department of Chemical and Environmental Engineering, Illinois Institute of Technology, Chicago, TL. Dynamic Modeling and Simulation of a Commercial Naphtha Catalytic Reforming Process 6 ing process occur many complicated reactions such as, dehydrogenation of naphthenes, dehydrocyclization of paraffins, hydeorvacking and jsamerizntion of paraffins and naphthenes, and hydrodealkylation of aromatics. ig.1 shows the UOP CCR platforming process flow sheet consisting of four stacked reformers, a catalyst regeneration section, and a furnace with four heaters integrated, and a flash separator. A flow diagram for UOP COR platforming. ‘process with controllers 1 regeneration section; 2—furnace; 3—exchanger; ‘4-air cooler; S—water cooler; 6—flash separator, RI—Ré—reformer Figure 1 In this model, the naphtha feed is character- ized into PNA (paraffins, naphthenes and aromatics) lumps of each carbon number from 6 to 94+ and light paraffins (C;—Cs). ‘The reforming reaction network undergone by all 17 lumps is shown in Fig.2. Corre- sponding rate equations are presented as follows. Dehydrogenation Ni + Ay + 3H, 6,7,8,9+ 15 = AYR, /A(Ve/ Fire) = (Ws, Ya, Kops) jai-4 @ Dehydrocyclization Pi + Nit Ha, 6.7.8.9+ 175 = d¥p,/(Ve/ Fac) = ks - (Y, ~ Ys /Kep.j) j=5-8 (2) Hydrocracking Ceti xe s 1 Ports g(22 +0) 1 5 Pro Ha — 3(Pe+ 2G) 1 5 Ps tH — 5(Pr+ Pot SOG. + Ca) Po+ Ha i(Pe+Pr+Pe+3°Gi) & 15 = d¥p,/8(Ve/ Fac) = hy “Yous f=o-94, ja9-as ®) Hydrodealkylation Ar + Hy Ag+ Ci, Ag + Hy Ar+Ca, Apt Ha 9 Ar $C, Ag+ Ha 9 As $C (4) ‘The rate equation for hydrogen balance is ein /A(V./Fac) =3 045+ Do-Lory () Ss ss as Ne Ave fn Ne Av] , NA aN cs . ¢; cr Figure 2 Reaction scheme for naphtha reforming ‘The reaction rate coefficients of Eqs. (1)—(4) obey- ing the Arrhenius law can be given by a {Fos exp (-E/RT)- Fy’ 6/08, p= 1—4 fos -exp(-E;/RT)- Ph! -@/P, j=5-A7 (6) ‘where @ is the deactivation function of catalysts due to the coke deposition on the reforming catalysts. Some of the model kinetic parameters, E;, 6), %, I are taken from the references) and others are bench- imarked with plant data. The static simulation results of the UOP CCR Platforming process are summarized in Table 1. Chinese J. Ch. B. 18 (1) 74 (2008) 18 Chinese J. Ch. B. (Vol.13, No.1) ‘Table 1 Comparivon af predicted and actual waloe al a . Ter Tea Tears Tia Pe Tha Pre ‘Component i the reactant (bj Tas), To He 687 635 962 8837.89 7.88 C245 lat 2ar 262254192 GIS ag In Figure 8 A block diagram for catalytic Cp Ral Rs? Om 9m RAK TT reforming process Cy BAT 868-909 973 959 9s (Fr tuensees RTretormer) Cy 441 360-423 4405.5 667 BC 2863 27.18 30.30 3211 90.45 B1.66, energy balance on the system of reforming reactions. Po SST 520 835 346 465 449 ‘The mass balance provides the variation of the con- Pr 182 263353 335255 231 centrations of the components along the reactors, and Ps ost om 182 175 0.89 O19 the energy balance gives the variation of temperature. Poy 000 000 0.16 000 0.00 9.00 Mass and energy balances for each radial flow reactor BP G16 804 S87 886 = 8.00 6.90 ted in COR are hoth nonlinear partial differential Ne 002 049 002 036002037 ‘ . No oot 018 010 017 008 O24 ‘equations (PDEs) in space and time as follows. in O14 013 045 0080.29 46 Ney 000 0.00 0.01 000 0.00 0.00, oy oy EN 0.28 O77 058 062 040 OT a Oe 7 Ae 657 610-385 343 5425.57 ar__ar Ar 1477 1631 1207 11811805 14.58. Ri -h heie Ag 1852 1768 1647 1668 17.99 1650 ‘ve 1925 199 184 7916611057 here ¥ isa vector of molar flow rates including Ha; a An aght ST $068 WS S8OT 5522. factor used to adjust the residence time; v=LHSV; Rm us moe K,=C-K. Kis the matrix of reaction rate constants Ry 76 73) 85S given by Eq, (6) and Cis the matrix of reaction coefi- ee cients. The initial and boundary conditions for Eq. (7) R 6 1% ” 19 are given by BR owe 247 a2 Liquid mase vield. % ee %8 768 Tl 707 7712 770 ¥(40) fer te fey, 70) -T Purity of recycle gas (by Ha volume), % ¥@2)=¥., T(,2)=T (8) 851 810 BTS 8686S BTS Mass yield of aromatic, % where ay is the naphtha feed mole composition; ris the 686 60.1 ToAT 691 66.9 685 hydrogen-to-hydrocarbon molar ratio; y is the mole Coke ma content on he aa, implored us coming eo thee 56 55 5253588 From this table, the obtained agreement is satisfac- tory in view of the scatter observed generally in plant, data. So the lumping and reaction schemes in this static model are adequately reasonable, which is an important precondition of building a precise dynamic model. 3 DYNAMIC MODELING ‘The catalytic reforming process shown in Fig. 1 can be also described concisely by Fig.3. This block di- agram is composed of four reformers, four furnaces and one separator. Here, fy is the mole flowrate of the byproduct hydrogen (net gas) and fy is the mole flowrate of the reformate. A part of reformed gas (fa) coming from the separator is recycled into the reaction system by merging into the naphtha feed. 3.1 Kinetic reaction model ‘A dynamic mathematical model with kinetics de- sctibed above is developed by assembling the mass and February, 2005 arator; T; is the entry reaction temperature of the reformer. 3.2. Catalyst deactivation model During the running of reformers the catalyst gets deactivated by coke deposition blocking the active sites and reducing the selectivity of catalyst and the products yields. For predicting the behavior of such reactions subject to catalyst deactivation, the coking rate equation is also included in the kinetic dynamic model. The coking rate equation and deactivation function of catalyst can be written asl") acK __, ret) = Ge Fee = exp(-3-CK) (9) where 72 is the average coking rate at fresh catalyst correlating with feed composition, hydrogen partial pressure and reforming severity. In the dynamic pro- cess, FZ is the function with time t, so the dynamic models of catalyst coking and deactivation function Dynamic Modeling and Simulation of a Commercial Naphtha Catalytic Reforming Process 7 in four radial reactors are given by I F2(t)de] CK (ht) = 5 In| +8 6(4,t) = 1 14a f weejae O

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