doi 10.1515/ijcre-2013-0061 International Journal of Chemical Reactor Engineering 2013; 11(1): 469–477 Raquel De María, Ismael Díaz*, Manuel Rodríguez, and Adrián Sáiz Industrial Methanol from Syngas: Kinetic Study and Process Simulation Abstract: In this study, a detailed rigorous kinetic model is proposed for the industrial production of methanol taking into account changes in total mole flowrate. The kinetic model proposed is compared with the one proposed in literature (Rezaie et al., Chem Eng Process Process Intensification 2005;44:911–21), showing significant differences in terms of compositions and total mole flow. A complete simulation of the methanol production process is developed with a commercial software. The rigorous reactor model is integrated in the simulation using the CAPE OPEN standard. Flowsheet simulation is carried out, and results show small differences with those found in previous studies (Luyben, Ind Eng Chem Res 2010;49:6150–63). Keywords: methanol, reactor model, process simulation got some good results using copper dispersed on zincbased catalysts (1960s). This development allowed the use of milder conditions, strongly decreasing both costs and process risks. This is still the base of the catalysts employed today. Methanol from syngas synthesis involves hydrogenation of CO (1) and CO2 (2) and reversed water–gas shift reactions (3): CO þ 2H2 $ CH3 OH ΔH298 ¼ 90:55kJ=mol ð1Þ CO2 þ 3H2 $ CH3 OH þ H2 O ΔH298 ¼ 49:43kJ=mol ð2Þ CO2 þ H2 $ CO þ H2 O ΔH298 ¼ 41:12kJ=mol ð3Þ *Corresponding author: Ismael Díaz, Chemical Technology Laboratory, School of Industrial Engineering, Technical University of Madrid, C/José Gutiérrez Abascal 2, 28006, Madrid, Spain, E-mail: [email protected] Raquel De María: E-mail: [email protected], Manuel Rodríguez: E-mail: [email protected], Adrián Sáiz: E-mail: [email protected], Chemical Technology Laboratory, School of Industrial Engineering, Technical University of Madrid, C/José Gutiérrez Abascal 2, 28006, Madrid, Spain 1 Introduction Nowadays, methanol is one of the most consumed commodities around the world with an expected global demand of 61.4 million metric tons [1]. Its main applications are as fuel, additive or reactant in the fine chemical industry, but others are emerging such as hydrogen carrier for fuel cell technology applications or denitrification agent for wastewater treatment. So its importance in the chemical industry is clearly demonstrated. Initially, methanol was produced by wood distillation which was proved a very inefficient method [2]. The first industrial methanol production process needed a highpressure (around 300 atm) syngas reaction, and it was patented by BASF in 1923. Catalysts used in these early processes were based on ZnO/Cr2O3. The ICIs company As shown in the heats of reaction, the global process is exothermic, reaching highest conversions at low temperatures. This fact, coupled with the high capacity of the process, makes the reactor design to be the sticking point in the process. Therefore, companies have invested great efforts in the development of their own reactors. Most of the designed industrial reactors are packed bed reactors (i.e. ICI, Kellogg and Linde processes) where the catalyst is fixed inside the tubes and cooling is provided through a reactor jacket. Another design is the threephase reactor carried out by Chem Systems, where the catalyst is fluidized in an inert liquid and the gas phase is composed of reactants and products except methanol which is absorbed by the liquid phase. This design improves heat transfer and catalyst deactivation aspects [3]. The aim of this study is to investigate the influence of different kinetic approaches on the results of a validated process simulation model. The remainder of this article is organized as follows: Section 2 presents two kinetic models (one from literature and one provided by the authors), Section 3 describes the process simulations where the previous developed reactor model is integrated along with the whole model performance, and finally, Section 4 draws some conclusions. Brought to you by | University of Maryland - College Park Authenticated Download Date | 2/13/15 9:41 PM 470 R. De María et al.: Industrial Methanol from Syngas 2 Kinetic modelling (c) Gas-phase mole balance 2.1 Literature models εB Ct dyi Ft dyi ¼0¼ þ av Ct kgi ðyi ys Þ dt Ac dz i ¼ 1; 2; . . . ; N ð6Þ The key aspect in the simulation of the methanol process is the reactor behaviour. Many efforts have been done for the correct modelling of the kinetic processes involved. Mainly, two kinds of models are proposed depending if the solid is taken or not into account for the model. If only mole and energy balances are applied to the fluid phase, then the model is called homogeneous. If both solid- and gas-phase molar and energy balances are carried out, then we have a heterogeneous model. The expressions here adopted for the two models are adapted from the work of Rezaie et al. [4] and Yusup et al. [5]. 2.1.1 Heterogeneous model The model considers mass and energy transfers between solid and fluid phases as well as energy exchange between reactor fluid phase and the coolant in reactor jacket. Pressure drop was computed by Ergun’s equation [6]. Some other assumptions were taken: – Time independence (stationary condition). – Neither axial nor radial dispersion. – Coolant temperature keeps constant. – Effectiveness factor (η) value equal to 1. This is a conservative assumption because it has been reported values higher than 1 for this factor, as in Ref. 7. – Intraparticular diffusion and catalyst deactivation has not been taken into account. – Ideal gas phase. – Constant molar flux along the reactor. Last assumption will be discussed later on Section 2.1.3 where the author’s model is proposed. Basic equations of this model are: (a) Solid-phase mole balance ε B Ct dyis ¼ 0 ¼ kgi ðyi ys Þ þ ηri ρB a i ¼ 1; 2; . . . ; N dt ð4Þ (b) Solid-phase energy balance ρB Cps N X dyis ηri ΔHfi ¼ 0 ¼ av hf ðT Ts Þ þ ρB a dt i¼1 ð5Þ d) Gas-phase energy balance εB Ct Cpg dT Ft dT ¼0 ¼ Cpg þ av hf ðT Ts Þ dt dz Ac πDi þ Ushell ðTshell T Þ Ac ð7Þ e) Ergun’s equation dP 1 εB 1 εB u2g ρg 6 1:75 þ 150 ¼ L 10 dz Re ε3B Dp ð8Þ The resolution can be carried out, because it is a so-called initial value problem with known boundary conditions at the entrance of the reactor: z ¼ 0 ! yi ¼ yi0 z ¼ 0 ! T ¼ T0 ð9Þ 2.1.2 Homogeneous model This model is essentially the same than before with the particularity that there is neither a temperature nor a concentration gradient between the solid and fluid phase. This means that yi ¼ yis and T ¼ Ts . 2.2 Mass homogeneous model (author’s model) Previous models were adopted from literature [4, 5], and it was observed an imperfection in their basis. Both of them supposed that total molar flux (Ft) remains constant along the reactor. As it can be observed from reactions involved, all the compounds are gases at reaction temperature and pressure. Besides, it can be seen that there are net changes in the mole number of chemical substances. So, under these conditions, the assumption of constant Ft is not valid. To overcome it, a new model based on mass fractions and fluxes is proposed. In the new model, total mass flow (Wt) remains constant. Brought to you by | University of Maryland - College Park Authenticated Download Date | 2/13/15 9:41 PM 471 R. De María et al.: Industrial Methanol from Syngas The model is derived from the homogeneous model of Section 2.1.2, where Fi ½i mole flow ¼ h i 3=2 k3 KCO pCO pH2 pCH3 OH pH2 O = pH2 Kp2 h i r3 ¼ 1=2 1=2 ð1 þ KCO pCO þ KCO2 pCO2 Þ pH2 þ KH2 O =KH2 pH2 O ð16Þ wi ½mass fractioni Wt ½total mass flow Mi ½molecular weighti ð10Þ 2.4 Mass-transfer correlations Model balances are expressed at follows: (a) Gas-phase mass balance 0¼ Values of mass-transfer coefficient (kgi) were computed in the reactor using the Cussler correlation [11]. Wt dwi þ Mi ηρB a i ¼ 1; 2; . . . ; N Ac dz ð11Þ kgi ¼ 1:17Re0:42 Sci0:67 ug ð17Þ (b) Gas-phase energy balance 0¼ Mixture diffusivity was estimated attending to Wilke’s equation [12], and binary diffusivities were calculated using the Fuller–Schetter–Giddins method [13]. Wt dT πDi þ Cpg Ushell ðTshell T Þ dz Ac Ac þ ρB a N X ð12Þ ηri ΔHfi 2.5 Heat-transfer correlations i¼1 The overall heat-transfer coefficient was estimated neglecting the wall effect as follows: (c) Ergun’s equation dP 1 εB 1 εB u2g ρg 6 ¼ L 10 1:75 þ 150 dz Re ε3B Dp ð13Þ 1 1 1 ¼ þ Ushell hi ho ð18Þ Where shell side heat-transfer coefficient can be estimated by Holman [14]: 2.3 Kinetics In this model, kinetic expressions were taken from the work of Graaf et al. [8]. Heat of formation correlations for the species were calculated from bibliographic correlations [9, 10] in order to predict the change of the heat of reaction with temperature. Values of both kinetics and equilibrium temperature-dependent parameters were taken from Graaf et al. [8]. Eqs [14–16] show the kinetic expressions for the three existing reactions. ho ¼ 7:96ðTshell Tsat Þ3 Pshell 0:4 Patm Values of Pshell and Tshell are 41.2 bar and 525 K, respectively, as reported in literature for these reactors [15]. Tube side heat-transfer coefficient can be calculated by conventional correlations Nu ¼ f ðRe; PrÞ [16]. For example, hi Cpg μ 2=3 0:458 ρuDp 0:407 ¼ k εB Cpg ρμ μ h i 3=2 1=2 k1 KCO pCO pH2 pCH3 OH = pH2 Kp1 h i r1 ¼ 1=2 1=2 ð1 þ KCO pCO þ KCO2 pCO2 Þ pH2 þ KH2 O =KH2 pH2 O ð14Þ h i 3=2 1=2 k2 KCO pCO pH2 pCH3 OH pH2 O = pH2 Kp2 h i r2 ¼ 1=2 1=2 ð1 þ KCO pCO þ KCO2 pCO2 Þ pH2 þ KH2 O =KH2 pH2 O ð15Þ ð19Þ ð20Þ 2.6 Models comparison Based on data collected from industrial plants [17], Rezaie et al. [4] studied the influence of using the more sophisticated heterogeneous model instead of the simple homogeneous one. Conditions of the study are presented Brought to you by | University of Maryland - College Park Authenticated Download Date | 2/13/15 9:41 PM 472 R. De María et al.: Industrial Methanol from Syngas Table 1 Catalyst and reactor specifications. Parameter Value Pressure (bar) Inlet temp. (K) Total molar flowrate (mol/s) Composition (mol%): CH3OH/CO2/CO/H2O/H2/N2/CH4 ρs (kg/m3) dp (m) Cps (kJ/kg·K) λc (W/m·K) av (m2/m3) εS/τ Number of tubes Tube length (m) 76.98 503 0.64 the molar-based homogeneous model. In essence, the model is the same than the molar homogeneous one, but assuming mass basis for all the terms in eqs [11] and [12], so total mass flow can be treated successfully as invariant. As shown in Figure 2, there are significant differences in the resulting profiles, being higher for H2 and CH4 for which more than 10% difference is computed. The results show that a global decreasing in mole flowrate is obtained (final value of 0.59 mol/s in comparison with 0.64 mol/s from literature) as expected from the reaction pathway (1–3). It makes all compositions higher than for the mole-based case. The influence of choosing a kinetic model over both temperature and pressure profiles is negligible. So, henceforth, the mass homogeneous model is employed for simulating the methanol synthesis process. 0.5/9.4/4.6/0.04/65.9/9.3/10.26 1,770 5.47 10−3 5 4 10−3 627 0.123 2,962 7.022 in Table 1. Obtained results were in agreement with Rezaie’s findings. It means, a simple homogeneous model, which neglects differences of gas and solid phases, can be employed satisfactorily as it can be seen from Figure 1. In a new approach, we try to solve the weakest point of both homogeneous and heterogeneous models: they are developed assuming that total molar flowrate keeps constant. Therefore, a mass homogeneous model (Section 2.1.3) is proposed, evaluated and compared with CH3OH 1 2 3 Mole fraction 5 6 7 0.075 H 2O 0.01 0.005 0 1 2 3 4 5 6 Temperature (K) 0.15 0.1 0.05 0 1 0 1 2 3 2 3 4 5 Reactor length (m) 6 7 4 5 6 7 H2 0.02 0.2 0.62 0.15 0.6 0.1 0.58 0.05 0 1 2 3 4 5 6 0 7 530 80 520 79.95 510 500 490 0 1 0 1 2 3 2 3 4 5 Reactor length (m) 6 7 4 5 6 7 4 N2 0.25 0.64 7 CH4 0.2 0 0.03 0.66 0.015 0.25 Mole fraction 4 Homogeneous Heterogeneous 0.04 0.08 0.02 0 Homogeneous Heterogeneous 0.09 0.085 0 CO 0.05 0.095 0.02 0 CO2 0.1 Homogeneous Heterogeneous 0.04 Methanol synthesis process simulation has been previously studied in literature [18–20]. Validated results were presented in detail by Luyben [18] and are the basis of this work. The main difference is in how the reactor is modelled. Luyben modelled this reactor by changing the original Pressure (bar) Mole fraction 0.06 3 Process simulation 0 1 2 3 5 6 7 0 1 2 3 4 5 Reactor length (m) 6 7 79.9 79.85 79.8 79.75 Figure 1 Comparison between heterogeneous and homogeneous kinetic models for methanol synthesis. Brought to you by | University of Maryland - College Park Authenticated Download Date | 2/13/15 9:41 PM 473 R. De María et al.: Industrial Methanol from Syngas CH3OH 0.04 0.02 0 Molar homogeneous Massic homogeneous 0 2 Mole fraction 0.02 0.08 0.03 2 0.66 4 H2 0.02 6 0 2 4 N2 6 0 2 4 6 0 2 4 Reactor length (m) 0.105 0.64 0.1 0.62 0.01 0.6 0.005 0.095 0.58 0 2 4 6 0 CH4 0.112 Temperature (K) 0.108 0.106 0.104 0 2 4 Reactor length (m) 2 4 0.09 6 530 0.11 0.102 0.04 0 CO 0.05 0.09 6 0.015 0 Mole fraction 4 H2O CO2 0.1 6 80 520 Pressure (bar) Mole fraction 0.06 510 500 490 0 2 4 6 79.9 79.8 79.7 Reactor length (m) 6 Figure 2 Comparison between mass and molar homogeneous kinetic models for methanol synthesis. kinetic expressions to meet the process simulator format and including the reactor as a standard unit simulation block. In our work, we have also developed the process model using Aspen Plus, but we have integrated an external model of the reactor into the simulation flowsheet instead of using a reactor block. So, we have modelled the reactor rigorously by solving the ODE system of equations keeping the original kinetic formulations coupled with the mass homogeneous balance equations. The reactor model developed in Matlab has been integrated into the Aspen Plus flowsheet using the CAPE OPEN standard [21]. The process flowsheet (Aspen Plus PFD) is depicted in Figure 3, where syngas feed is firstly compressed from 1 to 110 bar in two-stage compressions with intermediate cooling (38°C). The resulting stream is adiabatically mixed with vapour distillate from the methanol purification column (loop 1). Stream 8 is again mixed with unreacted gases, separated and compressed after flash separations (loop 2). Main stream (10) goes to the reactor being preheated in a feed-effluent heat exchanger (FEHE) with the product stream of the reactor (loop 3). A stream containing raw methanol from the bottom of the flash separators is then fed to the distillation column. RK-Aspen properties package was chosen for the whole simulation except for the distillation column (atmospheric pressure), where NRTL-RK package was employed. Today generated Matlab code cannot yet be directly embedded in the Aspen simulation flowsheet being necessary to use a simulator interface. In this work, we have used the COCO simulator interface application [22]. Matlab code, using CAPE OPEN was integrated in the COCO simulator, and the flowsheet generated in this simulator was embedded in the Aspen flowsheet. Figure 4 shows the integration process. The obtained reactor profiles (Figure 5) show a decrease on hydrogen composition and an increase in methanol concentration as expected. Temperature rapidly increases due to the high heat-transfer coefficient computed (U ~ 3,000 W/m2 K), and pressure decreases as predicted by Ergun’s equation. Conversion per pass (reactor outlet related with reactor inlet) of hydrogen is 22%, 39% for carbon monoxide and 15% for carbon dioxide, these values are slightly different from literature ones, showing the influence of reactor modelling assumptions. However, total carbon conversion is marginally higher (for the same feed syngas stream) resulting in 3,142 kmol/h of methanol at the end Brought to you by | University of Maryland - College Park Authenticated Download Date | 2/13/15 9:41 PM 474 R. De María et al.: Industrial Methanol from Syngas Figure 3 Methanol synthesis process flowsheet. Figure 4 Scheme of reactor modelling implementation. Brought to you by | University of Maryland - College Park Authenticated Download Date | 2/13/15 9:41 PM 475 R. De María et al.: Industrial Methanol from Syngas CH3OH Mole fraction 0.1 0.08 0.08 0 2 4 6 8 10 12 0.075 0 2 4 6 8 10 0.06 12 0.6 0.032 0.01 0.55 0.03 0.005 0.5 0.028 0 2 4 6 8 10 CH4 0.22 0.21 0 2 0 2 4 6 8 10 12 0.026 550 Temperature (K) 0.23 0.2 0.45 12 2 4 4 6 8 Lenght of reactor (m) 10 12 500 450 400 6 8 10 12 8 10 12 10 12 N2 0 2 0 2 4 6 110 Pressure (bar) 0 0 H2 H2O 0.015 Mole fraction CO 0.12 0.1 0.05 0 Mole fraction CO2 0.085 0 2 4 6 8 Lenght of reactor (m) 10 12 109 108 107 4 6 8 Lenght of reactor (m) Figure 5 Reactor composition, temperature and pressure profiles. of the process instead of 3,274 kmol/h obtained in Ref. 18, representing a 3.8% of change. Differences in total mole flowrates of the main outlet stream are reported in Table 2. Detailed results of all process streams are included in Table 3. Some temperature differences (5°C in the inlet and around 15°C in the outlet) have been observed in the reactor-FEHE system regarding Luyben’s work. In our simulations, we have calculated a heat duty of 40.9 MW instead of 44.3 MW from literature (8% change). It is due to the higher overall heat exchanger coefficient calculated taking into account equipment hydrodynamic by eqs [18–20]. Global heat duties do not differ very much Table 2 Differences in molar flowrates (kmol/h). Stream ID Ref. 13 This work Vent Methanol Water F1 872 3,311 707 4,019 1,034 3,203 738 4,098 between both works, being for total heat consumed below 10% (209 MW vs 229 MW). 4 Conclusions A conventional methanol synthesis reactor was modelled by using three different approaches: molar homogeneous, molar heterogeneous and mass homogeneous models. It was shown that both heterogeneous and homogeneous models resulted in similar compositions for the tested reactor. Significant differences were obtained when applying the proposed mass approach for the reactor, allowing changes for the total mole flowrate along the reactor. The model is rigorously implemented in commercial process simulation software showing small differences in terms of the final amount of methanol obtained. Acknowledgements: The authors gratefully acknowledge Jasper van Baten comments and support when dealing with the implementation of Matlab model into process simulation software. Brought to you by | University of Maryland - College Park Authenticated Download Date | 2/13/15 9:41 PM 74.0 Pressure 248.5 CH4 0.069 0.23 0.002 0.675 0.003 0.022 CO2 CO H2O H2 N2 CH4 CH3OH 0 34.4 Mole frac 7,724.9 26.3 H2O N2 2,630.3 CO H2 785.5 CO2 CH3OH (kmol/h) Mole Flow 0.0 371.4 Temp. (K) (atm) 4 0.022 0.003 0.675 0.002 0.23 0.069 0 248.5 34.4 7,724.9 26.3 2,630.3 785.5 0.0 74.0 311.1 5 Stream results. Stream ID Table 3 0.022 0.003 0.675 0.002 0.23 0.069 0 248.5 34.4 7,724.9 26.3 2,630.3 785.5 0.0 108.6 358.2 6 0.089 0.002 0 0.003 0.006 0.372 0.528 14.1 0.3 0.0 0.4 0.9 58.6 83.1 108.6 800 7 0.023 0.003 0.666 0.002 0.227 0.073 0.007 262.6 34.6 7,724.9 26.8 2,631.3 844.2 83.1 108.6 369.1 8 0.244 0.033 0.54 0.001 0.063 0.112 0.008 11,375.6 1,528.2 25,203.7 23.4 2,923.6 5,247.5 369.9 108.6 334.9 9 0.2 0.027 0.565 0.001 0.095 0.105 0.008 11,638.1 1,562.8 32,928.6 50.1 5,554.9 6,091.6 453.0 108.6 341 10 0.2 0.027 0.565 0.001 0.095 0.105 0.008 11,638.1 1,562.8 32,928.6 50.1 5,554.9 6,091.6 453.0 108.6 414.7 11 0.225 0.03 0.498 0.014 0.058 0.105 0.071 11,638.1 1,562.8 25,780.1 723.0 2,990.0 5,418.7 3,690.8 105.9 545.4 13 0.225 0.03 0.498 0.014 0.058 0.105 0.071 11,638.1 1,562.8 25,780.1 723.0 2,990.0 5,418.7 3,690.8 105.9 471.8 14 0.225 0.03 0.498 0.014 0.058 0.105 0.071 11,638.1 1,562.8 25,780.1 723.0 2,990.0 5,418.7 3,690.8 105.1 311.1 15 0.24 0.033 0.557 0 0.063 0.102 0.004 11,104.3 1,536.6 25,780.1 11.2 2,924.0 4,715.4 178.2 105.1 311.1 16 0.096 0.005 0 0.128 0.012 0.127 0.632 533.8 26.3 0.0 711.8 66.0 703.3 3,512.6 105.1 311.1 17 0.24 0.033 0.557 0 0.063 0.102 0.004 10,856.0 1,502.2 25,203.7 11.0 2,858.6 4,610.0 174.2 105.1 311.1 19 0.24 0.033 0.557 0 0.063 0.102 0.004 10,856.0 1,502.2 25,203.7 11.0 2,858.6 4,610.0 174.2 108.6 314.7 20 0.357 0.018 0 0.009 0.045 0.438 0.134 519.6 26.0 0.0 12.4 65.0 637.5 195.7 2.0 311.1 21 0.003 0 0 0.171 0 0.016 0.809 14.3 0.3 0.0 699.4 0.9 65.8 3,316.9 2.0 311.1 22 0.357 0.018 0 0.009 0.045 0.438 0.134 519.6 26.0 0.0 12.4 65.0 637.5 195.7 108.6 759.1 23 0.2 0.027 0.565 0.001 0.095 0.105 0.008 11,638.1 1,562.8 32,928.6 50.1 5,554.9 6,091.6 453.0 108.6 423.1 24 0.089 0.002 0 0.003 0.006 0.372 0.528 14.1 0.3 0.0 0.4 0.9 58.6 83.1 1.0 323.1 26 0 0 0 0.016 0 0.002 0.981 0.2 0.0 0.0 52.5 0.0 7.2 3,142.8 1.0 323.1 Methanol 0.022 0.003 0.675 0.002 0.23 0.069 0 248.5 34.4 7,724.9 26.3 2,630.3 785.5 0.0 50.5 323 Syngas 0.24 0.033 0.557 0 0.063 0.102 0.004 248.3 34.4 576.4 0.3 65.4 105.4 4.0 105.1 311.1 Vent 0 0 0 0.877 0 0 0.123 0.0 0.0 0.0 646.5 0.0 0.0 91.0 1.0 358.7 Water 476 R. 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De María et al.: Industrial Methanol from Syngas 477 Nomenclature εB Ct yis kgi yi η ri ρB a Cps av hf Ts T ΔHfi Ft Ac Di Bed porosity Total mole concentration Molar fraction of i component in the solid phase Mass-transfer component of i component Molar fraction of i component in the gas phase Effectiveness factor Reaction rate of i component Bed density Catalytic activity Heat capacity of solid phase Catalyst surface area Heat-transfer coefficient Temperature of the solid phase Temperature of the gas phase Enthalpy of formation of component i Total mole flowrate Cross-section area of each tube Tube diameter Ushell Tshell L Re Dp ug ρg Wt wi Mi ki Ki Kpi N P Sci hi ho Overall heat-transfer coefficient Shell side temperature Length of reactor Reynolds number Particle diameter Gas velocity Gas density Total mass flow Mass fraction of component i Molecular weight of component i Reaction rate constant for the ith rate equation Adsorption equilibrium constant for component i Equilibrium constant based on partial pressure for component i Number of components Total pressure Schmidt number for component i Tube side individual heat-transfer coefficient Shell side individual heat-transfer coefficient References 1. 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