UNIVERSITI TEKNOLOGI MARA FAKULTI KEJURUTERAAN KIMIA REACTION ENGINEERING LABORATORY (CHE506) NAME: STUDENT NO : KHAIRUL AMIRIN BIN KHAIRUL ANUAR 2017632082 PUTERA NAJMEEN FARITH BIN ABDUL RAZAK 2017632096 NURUL AMIRAH BINTI MUSDAFA KAMAL 2017632124 NURUL AIDA BINTI MOHAMMAD 2017632132 NURUL KAMILAH BINTI KHAIROL ANUAR 2017632192 NURLINA SYAHIIRAH BINTI MD TAHIR 2017632214 GROUP : EH2205I EXPERIMENT : PLUG FLOW REACTOR (BP101) DATE PERFORMED : 8th OCTOBER 2018 SEMESTER :5 PROGRAMME / CODE : CHEMICAL ENGINEERING / EH220 SUBMIT TO : DR. FARID MULANA No. 1 2 3 4 5 6 7 8 9 10 11 12 13 Title Abstract/Summary Introduction Aims Theory Apparatus Methodology/Procedure Results Calculations Discussion Conclusion Recommendations Reference Appendix TOTAL MARKS Allocated Marks (%) Marks 5 5 5 5 5 10 10 10 20 10 5 5 5 100 Remarks: Checked by: Rechecked by: --------------------------- --------------------------- Date: Date: TABLE OF CONTENT 1.0 ABSTRACT ................................................................................................................... 2 2.0 INTRODUCTION......................................................................................................... 3 3.0 OBJECTIVES ............................................................................................................... 3 4.0 THEORY ....................................................................................................................... 5 5.0 MATERIALS & APPARATUS ................................................................................... 5 6.0 METHODOLOGY ....................................................................................................... 8 7.0 RESULTS .................................................................................................................... 11 8.0 CALCULATIONS ...................................................................................................... 15 9.0 DISCUSSION .............................................................................................................. 15 10.0 CONCLUSION ........................................................................................................... 21 11.0 RECOMMENDATIONS............................................................................................ 22 12.0 REFERENCES ............................................................................................................ 23 13.0 APPENDICES ............................................................................................................. 24 LAB REPORT ON PLUG FLOW REACTOR (L5) 1 1.0 ABSTRACT The goals of the experiment is to investigate the effect of residence time towards the conversion of the saponification process between Sodium Hydroxide, NaOH and ethyl acetate, Et(Ac). The saponification process is done using the SOLTEQ Plug Flow Reactor BP – 101. The product sample is taken for every flowrate of sodium hydroxide, NaOH and ethyl acetate, Et(Ac) which is at 250mL/min, 200mL/min, 150mL/min, 100mL/min and 50mL/min for titration process in Experiment 2 for the manual conversion determination. The residence time for each flowrate is 8 min, 10 min, 13.3333 min, 20 min and 40 min, respectively. The conversion of the reactant to product is 68%, 64%, 57.2%, 56.8% and 54.4%, respectively. The reaction rate constant, k is 2.6563 L/mol.min, 2.2222 L/mol.min, 1.6706 L/mol.min, 1.6435 L/mol.min and 1.4912 L/mol.min, respectively. The rate of reaction, -rA is 0.002720 mol/L.min, 0.002879 mol/L.min, 0.003060 mol/L.min, 0.003067 mol/L.min and 0.003100 mol/L.min, respectively. The rate of reaction decreases as the reaction rate constant decreases. Higher flowrate of reactant increases the rate of reaction and thus, increasing the conversion rate of the reactant to product. LAB REPORT ON PLUG FLOW REACTOR (L5) 2 2.0 INTRODUCTION In the industry, reactors are one of the most important equipment to create a desired products from the raw materials. The design of a certain reactors are crucial. There are three types of basic reactor which is Batch Reactor, Continuous Stirred Tank Reactor (CSTR), and Plug Flow Reactor (PFR). Plug flow reactor (PFR) or Tubular flow reactor consist of long hollow tube in which the reactant would flow in an axial direction in the shape of plug (Cylindrical shape) as shown in Figure 1. These tube usually encased inside the tank to maintain the temperature of the system. In the PFR, we would consider the reactant is perfectly mixed and the composition of the reactant is different along the tube. The streams are opposite of a batch reactor, which is a reactor that has a constant volume and has no incoming or outgoing streams. Figure 1 - Plug Flow Reactor Where the Reactant Flow In an Axial Direction in the Shape of Plug PFR become main choice for certain chemical process in the industry due to its nonmixing property of the reactors. It is also very helpful in the continuous production of the product. Flow of plug flow reactor is laminar, as with viscous fluids in small-diameter tubes, and greatly deviate from ideal plug-flow behaviour. Basically, for chemical reactions, it is impossible to proceed to 100% completion. This is because due to the rate of reaction decreases when percent completion gradually increases until the point where the system achieve dynamic equilibrium (no net reaction occurs). In fact, the equilibrium point mostly is less than 100% complete. Thus, distillation is used as a separation process, in order to separate any remaining reagents or by products from the desired product. Sometimes the reagents may be reused at the beginning of the process as a recycle back, such as in the Haber process. LAB REPORT ON PLUG FLOW REACTOR (L5) 3 3.0 OBJECTIVES The objectives of the experiment are:1) To carry out a saponification reaction between sodium hydroxide, NaOH and ethyl acetate, Et(AC). 2) To determine the reaction rate constant. 3) To determine the effect of residence time on the conversion. LAB REPORT ON PLUG FLOW REACTOR (L5) 4 4.0 THEORY Plug Flow Reactor (PFR) is one of the ideal reactor in industry. Many plants and company used PFR as the site for their reactants to react in producing valuable desired product. This reactor mainly famous for process that involves gas or fast reactions process. This is because, in PFR the reactants are fed continuously and products are also continuously removed. PFR becomes favourable because it is easy to maintain, as it does not have any moving parts. Additionally, the most favourable reason is it has the highest conversion per reactor volume of flow reactor. In designing and modelling a PFR, an ideal condition are assumed in order to ease the calculation. The PFR behaviour are assumed to be perfect mixing at all times without dead time occurs in any corner or area in the PFR. This composition is a function of residence time and rate of reaction. Figure 2 - The Schematic Diagram of A PFR The ideal PFR mole balance with assumptions can be written as follows: (Accumulation) = (in) − (out) + (generation) Assumption made: π― πππ = π ππ − π π + ∫ π«π ππ ππ π dNA (ππͺ. π) = 0 but only in the radial direction (Rodgers, 2013). 1. In steady state condition, 2. No axial mixing. 3. For a flow system, FA can be given in terms of entering molar flow rate FA0 and the conversion, X. dt FA = FA0 − FA0 X Thus, rearranging the equation would obtained this equation, FA0 X = FA0 − FA LAB REPORT ON PLUG FLOW REACTOR (L5) 5 Rearranging eq.1, π£ 0 = πΉπ΄0 π + ∫ ππ΄ ππ π£ 0 π[∫ −ππ΄ ππ] = ππΉπ΄0 π 0 −ππ΄ ππ = πΉπ΄0 ππ π π£ ∫ ππ = πΉπ΄0 ∫ 0 Ideal equation of a PFR is shown as below: 0 πΏ π½ = ππ¨π ∫ π ππ −ππ΄ π πΏ −ππ¨ (ππ. π) 4. In this experiment, the reaction order is second order thus it depends on concentration of both solution πΆπ΄0 and πΆπ΅0 (Engineering). However, to ease the calculation and analysis, the concentration being fed to the reactor in in equimolar. Thus, the initial concentrations of reactants is CA0 = CB0 . The rate law can be written as follow: −rA = kCA CB = kCA2 π (π − π)π −π«π = π€πππ (ππͺ. π) Rearranging in terms of residence time, X X dX dX = v0 CA0 ∫ 2 V = FA0 ∫ −rA kCA0 (1 − X)2 0 X 0 v0 dX V= ∫ kCA0 (1 − X)2 0 V= π= v0 X ( ) kCA0 1 − X π π π = ( ) π―π π€πππ π − π (ππͺ. π) For constant PFR volume, flow rate and initial concentrations, the reaction rate constant is, π€= π―π π ( ) ππππ π − π LAB REPORT ON PLUG FLOW REACTOR (L5) (ππͺ. π) 6 5.0 MATERIALS & APPARATUS 5.1 Materials 1) 0.25M Hydrochloric Acid, HCl 2) 0.1M Sodium Hydroxide ,NaOH 3) 0.1M Sodium Acetate, Na(Ac) 4) Deionized Water, H2O 5.2 Apparatus 1) Burette 2) Conductivity Meter 3) Plug Flow Reactor Plug flow reactor Figure 3 - Set Up Of Plug Flow Reactor LAB REPORT ON PLUG FLOW REACTOR (L5) 7 6.0 METHODOLOGY 6.1 General Start Up 1) Ensure all the valves are initially closed except valves V4, V8 and V17. 2) The solutions are prepared for each experiment. 3) The power for the control panel is turned on. Task Experiment 1&2 Experiments 3&4 B1 Deionized water 0.1M NaOH solution B2 0.05M NaCl solution 0.1M Et(Ac) solution 4) The water jacket B4 and preheater B5 is filled with a clean water. The valves V13 and V18 is opened. Pump P3 is switch on to calculate the water through preheater B5. 5) A stirrer motor M1 is switched on and the speed is set for about 200 rpm. 6) Valve V2, V4 and V10 is opened. Pump P1 is switched on. P1 is adjusted to flow rate of 150 ml/min at flow meter, FI-01. Valve V10 is closed and pump P1 is switched off. 7) Valve V6, V8, V12 is opened. Pump P2 is switched on. P2 is adjusted to flow rate 150 ml/min at flow meter FI-02. Valve V12 is closed and pump P2 is switched off. 8) The unit is now ready for the experiments. 6.2 Experiment 1 – Preparation of Calibration for Conversion vs. Conductivity 1) The following solutions are prepared: i. 1 liter of sodium hydroxide, NaOH (0.1M) ii. 1 liter of sodium acetate, Na(Ac) (0.1M) iii. 1 liter of deionised water, H2O 2) The conductivity and NaOH concentration for each conversion values is determined by mixing the following solutions into 100ml of deionised water: i. 0% conversion : 100 ml NaOH ii. 25% conversion : 75 ml NaOH + 25 ml Na(Ac) iii. 50% conversion : 50 ml NaOH + 50 ml Na(Ac) iv. 75% conversion : 25 ml NaOH + 75 ml Na(Ac) v. 100% conversion : 100 ml Na(Ac) LAB REPORT ON PLUG FLOW REACTOR (L5) 8 6.3 Experiment 2 – Back Titration for Manual Conversion Determination 1) The burette is filled up with 0.1M NaOH solution. 2) 10 ml of 0.25M HCl is measured in flask. 3) 50 ml of sample from the experiment is obtained and the sample is immediately added to the HCl in the flask to quench the saponification reaction. 4) A few drops of pH indicator is added into the mixture. 5) The mixture is titrated with NaOH solution from the burette until the mixture is neutralized. The amount of NaOH titrated is recorded. 6.4 Experiment 3 – Effect of Residence Time on the Reaction 1) The general start-up procedures are performed as above. 2) Valve V9 and V11 are opened. 3) Both NaOH and Et(Ac) solutions are allowed to enter the plug flow reactor R1 and empty into the waste tank B3. 4) P1 and P2 are adjusted to give a constant flow rate of about 300ml/min at flow meters FI-01 and FI-02. Make sure that both flow rates are the same. The flow rates are recorded. 5) The inlet (QI-01) and outlet (QI-02) conductivity values are being monitored until they do not change over time. This is to ensure that the reactor has reached steady state. 6) Both inlet and outlet steady state conductivity values are recorded. The concentration of NaOH exiting the reactor and extent of conversion from the calibration curve is obtained. 7) Optional : sampling valve V15 is opened and 50 ml of sample is collected. A back titration procedure to manually determine the concentration of NaOH in the reactor and extent of conversion is carried out. 8) The experiment steps 4 to 7 is repeated for different residence time by reducing the feed flow rates of NaOH and Et(Ac) to about 250, 200, 150, 100 and 50 ml/min. Make sure that both flow rates are the same. LAB REPORT ON PLUG FLOW REACTOR (L5) 9 6.5 General Shut Down 1) Pump P1, P2 and P3 is switched off. Valve V2 and V6 is closed. 2) The heaters is switched off. 3) The cooling water is kept circulating through the reactor while the stirrer motor is running to allow the water jacket to cool down to a room temperature. 4) All liquid is drained from the unit by opening valve V1 to V19 if the equipment is not going to be used for a long period of time. 5) The power is turned off for the control panel. LAB REPORT ON PLUG FLOW REACTOR (L5) 10 7.0 RESULTS Table 1 - Data Collection for Calibration Curve Preparation in Experiment 1. Solution Mixture Concentration Conductivity of NaOH (M) (mS/cm) 100 mL 0.0500 23.6000 25 mL 100 mL 0.0375 14.9000 50 mL 50 mL 100 mL 0.0250 9.2100 75% 25 mL 75 mL 100 mL 0.0125 4.2300 100% - 100 mL 100 mL 0.0000 0.0654 Conversion 0.1 M 0.1 M NaOH Et (Ac) 0% 100 mL - 25% 75 mL 50% H2 O Conversion, X Conversion vs. Conductivity y = -0.0424x + 0.9406 R² = 0.9783 y = -0.0424x + 0.9406 R² = 0.9783 Conductivity (ms/cm) Figure 4 - The graph of Conversion, X, against Conductivity, Q, obtained from calibration curve preparation in experiment 1. The graph shows the graph of conversion versus conductivity. The conversion is decreasing linearly as the conductivity increase. LAB REPORT ON PLUG FLOW REACTOR (L5) 11 Experiment 2: Effect of Residence Time on the Reaction Table 2 - A Constant Flowrate Recorded At Flowmeters FI-01 and FI-02 Initial Flowrate Of Solutions Inlet Conductivity, Q1 (mS/cm) Outlet Conductivity, Q2 (mS/cm) (mL/min) Pump 1 250 10.4 7.0 Pump 2 250 10.6 6.9 β Information added: a) Reactor Volume, VPFR :4L b) Concentration of NaOH in feed vessel, CNaOH,f : 0.1 M c) Concentration of NaOH in the reactor, CNaOH : 0.1 M d) Concentration of HCl for quenching, CHCl,s : 0.25 M e) Volume of HCl for quenching, VHCl,s : 10 f) Volume of sample, Vs : 50 mL LAB REPORT ON PLUG FLOW REACTOR (L5) mL 12 Table 3 - Data Collection Obtained From Experiment 3 Flowrate of NaOH (mL/min) Flowrate of Et (Ac) (mL/min) Total feed flowrate of solutions, vo (mL/min) Residence Time, τ (min) 250 250 500 200 200 150 Conductivity (mS/cm) Volume of NaOH (mL) Conversion , X (%) Reaction Rate Constant, k (L/mol.min) Rate of Reaction, -rA (mol/L.min) Q1 Q2 8.00 9.5 8.3 17.0 68.0 2.6563 0.002720 400 10.00 9.4 7.7 16.0 64.0 2.2222 0.002879 150 300 13.33 8.9 7.3 14.3 57.2 1.6706 0.003060 100 100 200 20.00 8.1 6.1 14.2 56.8 1.6435 0.003067 50 50 100 40.00 7.8 5.2 13.6 54.4 1.4912 0.003100 13 Conversion vs. Residence Time Conversion, X (%) 50 45 40 35 30 25 20 15 10 5 0 Residence Time, τ (min) 0 10 20 30 40 50 Figure 5 - The graph of Conversion, X, against Residence time, τ, obtained from the calculations in experiment 3. The graph shows the plot of conversion versus residence time. The curve shows a decreasing pattern until t = 20 min, before increasing as the curve approaching to t = 40 min. 14 8.0 CALCULATIONS β These calculations were determined for the flowrates of 250 mL/min: A. Calculation for Residence Time, τ. Residence Time, τ = Reactor volume, VPFR (L) L Total feed flowrate, vo ( min) 1. Total flowrates of sodium hydroxide, NaOH, and ethyl acetate, Et (Ac) are, Total flowrate, Vo = Flowrate of NaOH + Flowrate of Et (Ac) = 250 mL/min NaOH + 250 mL/min Et (Ac) = 500 mL/min = 0.5 L/min 4L Thus, Residence Time, τ = 0.5 L/min = 8 min B. Calculation for Conversion, X. 1. Concentration of NaOH entering the reactor, CNaOH,o CNaOH,o = CNaOH,f 2 = 0.1 M 2 = 0.05 M LAB REPORT ON PLUG FLOW REACTOR (L5) 15 2. Volume of unreacted quenching HCl, V2 V2 = = CNaOH,s × V1 CHCl,s 0.1 M × 17.0 mL 0.25 M = 6.8 mL 3. Volume of HCl reacted with NaOH in the sample, V3 V3 = VHCl,s − V2 = (10 − 6.8) mL = 3.2 mL 4. Moles of HCl reacted with NaOH in the sample, n1 = 0.25 n1 = CHCl,s × V3 mol 1L × 3.2 mL × L 1000 mL = 0.0008 mol 5. Moles of unreacted NaOH in sample, n2 n2 = n1 = 0.0008 mol 6. Concentration of unreacted NaOH in the reactor, CNaOH = CNaOH = n2 Vs 0.0008 mol 1000 mL × 1L 50 mL = 0.016 M LAB REPORT ON PLUG FLOW REACTOR (L5) 16 7. Conversion of NaOH in the reactor, XNaOH Xunreacted = = CNaOH CNaOH,o 0.016 M = 0.32 0.05 M Xreacted = (1 − Xunreacted ) × 100% = (1 − 0.32) × 100% = 68% C. Calculation for Reaction Rate Constant, k. k= 1. Total feed flowrate, vo X vo ( ) VTFR CAo 1 − X = 0.5 L/min 2. Volume of reactor, VTFR =4L 3. Inlet concentration of NaOH, CAo, in the reactor = 0.1 M 4. Conversion, X = 0.68 β All the values above are substituting into the rate constant equation where, L L min ] ( 0.68 ) = 2.6563 k=[ (4 L)(0.1 M) 1 − 0.68 mol. min 0.5 LAB REPORT ON PLUG FLOW REACTOR (L5) 17 D. Calculation for Rate of Reaction. -rA. −rA = kCA CB CA = CAo (1 − X) Since CAo = CBo , CB = CBo (1 − X) 2 −rA = k(CAo ) (1 − X)2 β From the equation above, the rate of reaction obtained is, L mol mol 2 −rA = (2.6563 ) (0.1 ) (1 − 0.68)2 = 0.002720 mol. min L. min L NOTE: The same way of calculations was used to evaluate the residence time, conversion, reaction rate constant and rate of reaction for different flowrates of 200 mL/min, 150 mL/min, 100 mL/min and 50 mL/min. LAB REPORT ON PLUG FLOW REACTOR (L5) 18 9.0 DISCUSSION In this plug flow reactor (PFR) experiment it is primarily to carry out a saponification reaction between NaOH and Et(Ac). At the end of the experiment, the reaction rate constant is determined by using formula and the effect of residence time on the conversion in the PFR. This experiment are conducted using the SOLTEQ Plug Flow Reactor (Model BP 101) where NaOH and Et(Ac) solution are fed into the reactor by varying the feed flow rates to obtain several residence time and the effect of each one is studied. Besides, a calibration curve for conductivity versus conversion is also prepared for saponification reaction of ethyl acetate Et(Ac) and sodium hydroxide NaOH. For the calibration curve of conductivity versus conversion, the slope and y-axis intercept value is determined from the equation of the curve yield using excel. Based on Figure 4, the slope = 0.0424, while the y – axis intercept = 0.9406. In this experiment, different initial feed flowrates, conductivity value and the volume of NaOH used in the titration process is organized in Table 3. From the data, the residence time, conversion of the reactions and the reaction rate constant is determined through a series of calculation by using formula for plug flow reactor experiment. A graph of conversion against residence time is plotted and it is shown in Figure 5. The residence time and the conversion of the reaction is obtained from the calculation using formula. The reactors residence time is defined as the reactor volume divided by the total feed flow rates while conversion is a property that shows how much of the reaction take place which is the number of moles of A that reacted per mole of A fed to the system. From the graph plotted in Figure 5, the conversion of the reaction is inversely proportional to the residence time of the reactant in the reactor. It shows that when the residence time of the reactor increases, the conversion of the reactant will decreases. Residence time shows the average amount of time that a particle spends in a particular system and conversion is a direct function of time spent for reaction. Apparently, the higher the residence time, the higher conversion. This may be due to the error of total feed flowrate of solutions occurred while conducting the experiment. The reaction rate constant, k for every different initial feed flowrate is 2.6563 L/mol.min for flow rate 250 mL/min. For flow rate 200 mL/min the k-value is 2.2222 L/mol.min and reaction rate constant for 150 mL/min is 1.6706 L/mol.min. For flow rate 100 LAB REPORT ON PLUG FLOW REACTOR (L5) 19 and 50 mL min the reaction rate constant is 1.6435 and 1.4912. We can see that the reaction rate constant is decreased when the feed flowrate is decreased as well. Thus, showing that the rate of chemical reaction at constant temperature depends only on the concentrations of the substances that influence the rate according to the law of mass action. The rate of reaction, -rA is also determined after the rate of reaction has been calculated. The rate of reaction for 250 mL/min is 0.0002720 mol/L.min while 0.002879 mol/L.min is the rate of reaction for 200 mL/min. For flow rate 150 mL/min, the rate of reaction is 0.003060 mol/L.min, 0.003067 and 0.003100 mol/L.min is the rate of reaction for flow rate 10 and 50 mL/min. It indicates that when the reaction rate constant is decreases, the rate of reaction is also decreases. The specific rate constant is proportionally constant relating the rate of the reactions to the concentrations of reactants. A rate law is an expression showing the relationship of the reaction rate to the concentrations of each reactants. LAB REPORT ON PLUG FLOW REACTOR (L5) 20 10.0 CONCLUSION From the experiment above, the flowrate of the sodium hydroxide, NaOH and ethyl acetate, Et(Ac) is 250mL/min, 200mL/min, 150mL/min, 100mL/min and 50mL/min. The residence time for each flowrate is 8 min, 10 min, 13.3333 min, 20 min and 40 min, respectively. The conversion of the reactant to product is 68%, 64%, 57.2%, 56.8% and 54.4%, respectively. The reaction rate constant, k is 2.6563 L/mol.min, 2.2222 L/mol.min, 1.6706 L/mol.min, 1.6435 L/mol.min and 1.4912 L/mol.min, respectively. The rate of reaction, -rA is 0.002720 mol/L.min, 0.002879 mol/L.min, 0.003060 mol/L.min, 0.003067 mol/L.min and 0.003100 mol/L.min, respectively. The rate of reaction decreases as the reaction rate constant decreases. Higher flowrate of reactant increases the rate of reaction and thus, increasing the conversion rate of the reactant to product. LAB REPORT ON PLUG FLOW REACTOR (L5) 21 11.0 RECOMMENDATIONS There are several precautions and recommendations that we can do to ensure more accurate and reliable results. Which is: 1) Repeat the trials at least three times and calculate the average results to get a more accurate data. 2) Always make sure that the start-up procedure and shut down procedure was done correctly to prevent damage at the equipment. 3) The flow rates of the inlet need to be kept constant by monitor it at all times because the flow rates will affect the collected data. 4) Glass apparatus need to be handle carefully to prevent it from broken while conducting experiment. 5) Make sure to wear the Personal Protective Equipment (PPE) while conducting the titration as we handling the chemicals. LAB REPORT ON PLUG FLOW REACTOR (L5) 22 12.0 REFERENCES Alqurri, S. (7 Jun, 2017). Tubular reactor. Retrieved from Slide Share: https://www.slideshare.net/saidalqurri/tubular-reactor Engineering, F. o. (n.d.). Lab Report Plug Fow Reactor. UiTM Shah Alam. Fogler, H. S. (2006). Element of Chemical Reaction Engineering. Michigan: Prentice Hall. Plug flow reactor model. (n.d.). Retrieved from Wikipedia: https://en.wikipedia.org/wiki/Plug_flow_reactor_model Rodgers, T. (2013). Chemical Reaction Engineering. Retrieved from https://personalpages.manchester.ac.uk/staff/tom.rodgers/documents/CRE_Notes.pdf LAB REPORT ON PLUG FLOW REACTOR (L5) 23 13.0 APPENDICES LAB REPORT ON PLUG FLOW REACTOR (L5) 24