Executive Summary In September of 2004, the ALPHA Consultancy entered into a bidding agreement to design a Methanol Production plant

with special requirements to produce methanol from Syngas, using natural gas. The following outlines the major factors being considered and the investment cost necessary for the plant to be manufactured. With the availability of 99% purity natural gas the Syngas is to be produced using gas via steam reforming process. Under a required production of 1000 tonne per year this method of Syngas was deemed most suitable as alternative methods involves air purifiers, which are more suited for methanol production capacities above 2500 tonnes per year. The table shows a Financial Summary of the major results from the design of the process.
Natural Gas Cost Yearly Operation Daily Cost 300 days 1604500/7200 37483 x 50 7200 hrs £ 1836630 h-1 £230 £ 15454965 £ 372035 £ 6132567 £231,773,550

Total Variable cost Fixed Cost Insurance 1% fixed capital Total Fixed cost Direct production cost Price of Methanol £17640983 + £ 6,132,567 £158.34/tonne

Sales revenue £158.34 x 1000 x 300 Profit Sales revenue – direct production cost = Profit = 47 502 000 – 15 454 965 = £ 23, 728,450

£47,502,000 £23,728,540

The basis of producing methanol from Syngas is to be using a multi tubular isothermal reactor. This reactor would operate at low temperatures and pressure with the use of Cu/Zn/AL2O3/CrO as catalyst. This method of methanol production is a modern process which would give up to a conversion of 85% CO, which determines the actual amount of Methanol produced. Shell and tube reactors were chosen because the reactions are exothermic. Therefore heat needs to be removed from the reaction system. Shell and tube reactors not only allow heat to be removed from the process by circulating a cooling medium on the shell side of the reactor, but also reduce hot spot formation in the reactor. In the shell and tube reactors, process fluid flows through the tubes while cooling fluid, saturated water, which is boiling to saturated steam, flows through the shell. The main issue of environmental effect of methanol is the production and removal of carbon dioxide. The Alpha Consultancy is proposing to inject the carbon dioxide into the ground. This requires very extensive research and we are in the process of seeing it through.

Table of Contents Page 1. 2. 3. 4 5. 6. 7. 8. 9. 10. 11. 12. Introduction HYSIS – Process Simulation Energy Recovery Methanol Reactor Design Chemical Engineering Design Mechanical Design Process Control and Instrumentation HAZOP Cost Estimation and Economic Appraisal Critical Review Reference Appendix Phase1 Report Phase 2 Report Phase 3Report HYSIS material and Energy Balance 3 4-6 7-9 10 10-19 20-23 24-26 27-29 30-32 33-34 35 36

Introduction Phase 4 of the design report represents the last in a series of 4 reports on the design of the Alpha Consultancy Methanol Plant. The previous covered aspects of design routine, the methanol market, environmental issues and sustainability. Phase 4 is a summary of the entire report as well as detail reports on the methanol reactor design, simulation of process using HYSIS and a final cost estimation appraisal. The major part of the entire process is the reactors, this is where initially Syngas is produced in the process, and secondly where methanol is produced. This report will cover all the aspects considered when designing a methanol reactor, with special interest in the multi-tubular isothermal methanol reactor. Issues of both chemical and mechanical design are covered as well as cooling medium for the reactor. Also covered in this report is a detailed Hazard Analysis Syngas reformer. It is necessary fro a standard as well as management point of view to understand the steps taken in analyzing a process for risks and hazards to estimate any unforeseeable accident. This detailed study gives more depth to process control, which is also considered in this report fort the Methanol Synthesis reactor.

with the water gas shift reaction. simulates and put an actual process into theoretical operation. as the basis for the production was. This type of reactor was chosen because detailed knowledge was obtained prior to simulation and data was collected for specific conversion of CO and CO2 to methanol. HYSIS was used to do a simulation and design with reference to hand calculations that were done in phase 2 of these reports. User knowledge is always the key however as all simulation package can only give an output. Simulation packages do as the term suggests. With these packages getting more user friendly and capable to do more than normal. only some basis had to be specified for HYSIS. PFD The two main areas of methanol production are the Syngas production and methanol synthesis. The Peng-Robinson SV basis of fluid package was chosen since the PRSV is a two-fold modification of the PR equation of state that extends the application of the original PR method for highly nonideal systems. (Fro phase2) defined by an equilibrium relationship between the CO and steam reaction. and other control software packages. These were the only two areas in the process where reaction actually occurred. even though ideality was assumed for much part of the phase 2 report calculations. The first obvious difference was the principle by which HYSIS does the calculations. reaction type and where necessary process conditions. The use of simulation packages in chemical plants over the past 3 decades has grown rapidly and more companies buy into the idea each day. For this reactor the reaction and conversion had to be defined in the reaction manager in HYSIS. based on an input. a user-friendly computer software package developed by Hyprotech is one of these packages. simulation packages can set up an entire production with a few user specified variable. The goal of programs like HYSYS is to provide users with the capability to design an entire process as completely and accurately as possible. reaction equations with appropriate stoichiometry. HYSIS. Unlike the hand calculation. these including components.HYSIS In the modern methanol and other chemical industries. Methanol synthesis reactor was of the converter type. In the ALPHA Consultancy. and because of this showed a difference in calculated conditions. Gibbs free is the basis of its calculations. the initially process flow of a plant is usually defined by simulation packages. . Syngas was produced with the use of an equilibrium reactor.

Table 7 gives a short description to some the major units and streams in the PFD.Fig 7 – Process Flow Diagram ‘ALPHA Methanol Process’ HYSIS METHANOL PRODUCTION PROCESS. simulation package. the inlet ratio of CO to steam was found to be 3:1. APLHA©2005 Fig 7 shows the final PFD of the methanol production process simulated through the HYSIS TM. The SET operation set the value of one stream variable (the independent variable) to meet a required ratio (the dependent variable) in another stream or operation. From Phase2 in these reports. and a SET block was use to set this ratio. .

Separator used to condense the gas mixture.water MIX-2 HX-1 RX-100 CLR-1 SEP -1 x27 RX-200 MIX-100 CMPR-1 HX-2 Sep 2 Mixer used to mix the process flow water with the treated and recycled water from the process Heater used to raise the temperature of the process water to form steam Used to set the inlet flow of steam to 3 times the molar flow rate of natural gas Raw methane feed. Produces syngas at very high temperature and low pressure. the separator maintained at a pressure and temperature below BP of methanol. The mixing of the fresh feed and recycled feed to the synthesis reactor. To obtain gas for recycling. Water is very corrosive to compressors etc. which exchanges heat between the cold. which are responsible for adequately exchanging heat while making HP. Stream x27 is the recycled stream. MP and LP steam from the useful energy from the reactor. while the stream rich methanol concentration is distilled for purification. so the gases could evaporate and be recycled. Steam Reformer.Table 8 – HYSIS equipment unit and streams explained. low temperature (260˚C) reactions of CO 2. In the form of a converter reactor. Beyond HX-1 also would be an array of heat exchangers. Heat Exchanger. Representing a series of heat exchangers and cooling system. suitable for water separation. Unit/ Streams MIX-1 HTR-1 SET-1 n. CO and H2. so as much water can be removed from the process as possible. this set of heat exchangers also produces LP steam with the useful energy from the reactor. the purpose of the cooler is to bring the temperature of stream from reformer. by recombining with fresh feed before entering the synthesis reactor. . of 99% purity at ambient temperature and pressure at a flow rate of at 2000kgmol/hr Pure uncontaminated water at 2O˚C and ambient pressure Mixer used to mix steam and natural gas before entry into the steam reformer. Also a representation of compressors in series as one compressor would need too much of an unrealistic volume to yield correct pressure increase. this is where methanol is produced from high pressure (70bars). Reaction highly exothermic. The compressor increases the pressure of the reactor inlet feed to the reactor operating pressure 70bars.gas p. in the form of an equilibrium reactor. Also used to decrease the temperature of the exit stream from the reactor. of gases rich in CO concentration. where 1st set of reaction occurs in the process. feed mixture of natural gas and steam with hot outlet syngas. Reaction highly endothermic so a considerable amount of energy is needed to drive reaction. used to improve the efficiency of the process. under a temperature (60˚C).

. through optimization produced on average more methanol than using hand calculations. the inlet pressure of the reactor was varied. and by hand calculations this would take a very long time to examine the effect on methanol production and other downstream processes. and this was seen as major source of energy recovery for the Alpha Consultancy..HYSIS Selected HYSIS simulated data comparison with results from PHASE 1. The principles and basis for the HYSIS calculations has to be taken into account as well as the nature by which optimizations are done.29E+09 From the above data comparison it can be seen that the HYSIS package. These exchangers use the useful heat from in the stream to produce HP.74E+09 HYSIS Simulated 2000 6000 3:1 94 1273 16 3.6 : 1 533 70 77 0 1340 2.g. Units Inlet Natural Gas Molar Flow Inlet Steam Molar Flow CH4: Steam Ratio CH4 conversion Reformer Temperature Reformer Pressure CO: H2 ratio in Synthesis Reactor Inlet Reactor Temperature Reactor Pressure CO conversion in synthesis reactor CO2 conversion Methanol Production Overall Energy usage (kgmol/hr) (kgmol/hr) % K bar K bar % % Kgmol/hr KJ/hr Phase-1 Report 1803 5410 3:1 85 1273 16 15 : 1 533 100 74 5 995 5. Energy Recovery The area of Syngas production produced a considerable amount of heat. For e. With added units also. the heat flow throughout the process was almost halved comparing with that of the phase 1 calculation. The heat from the exiting feed stream from the reformer is cooled through a series of heat exchangers. IP and LP steam. Hand Calculated results.

-4- . Design Approach Kinetics Various personnel have studied the complex chain reaction of the methanol synthesis process over the years and many theories have been made for the actual rate kinetic equations that correctly define the mechanism. CO + H2O ↔ H2 + CO2 CO2 + 3H2 ↔CH3OH + H2O -1-2- Bussche and Froment showed that for the rate of methanol synthesis and the inverse water gas shift reaction the following expressions are accepted: -3- And. CO + H2O ↔ H2 + CO2 CO2 + 3H2 ↔CH3OH + H2O ∆H298 = -41.5 KJmol-1 -1-2- These two reactions will be considered for the major unit design of an Isothermal Multitubular Methanol Synthesis Reactor. namely conversion of CO via the water gas shift reaction to CO2 followed by hydrogenation of CO2 to methanol. 1996) have reported a proposed model of the kinetic relationship based on production of methanol in the presence of high selective Cu/ZnO/Al2O3 catalyst. Bussche and Froment (Journal of Coal and Petroleum. The proposed model takes into consideration only reaction from carbon dioxide and inverse water-gas shift reaction.Methanol Reactor Design Methanol synthesis is believed a combination of two exothermic reactions.2 KJmol-1 ∆H298 = -49. which permits operation at lower pressure than classic pressure process. the two also been considered for ALPHA methanol synthesis reactor design.

442E+16 540 2.0 0 0 0 1 0 450 500 550 600 650 700 750 T e m p e r a tu r e ( K ) .717E+16 550 2.0 0 0 0 2 0 .898E+16 530 2.00291 8 41 9E+16 5E-07 0.095646752 3E+19 2E-05 0.0375 0.029071 253 4E+18 5E-06 0.294791858 0.055261 18.8E-06 4.4E-05 4.1168 0.0155 0. Table 1 – Values of Rate Constants at various Temperatures T (K) 500 520 530 540 550 560 570 580 590 600 630 670 700 720 k1 31.011 0. k2. k1.726E+14 R(Me O HV) a r a itio n w ith T e m p e r a tu r e 0 .9E-05 9.1E-06 5.501E+15 700 6. Fig 1 – Graph of Temperature Effect on Rate of Methanol Formation T (K) R1(CH3OH) R 2(RWGS) 500 7. their own laboratory data and detailed researches.01 04099 91 2E+18 3E-06 0.057848774 1E+19 1E-05 0.Where.995372 21.8258283 k2 613.6321622 113.6897535 194.945E+15 630 1.0182 0. Buscche and Froment proposal was based on combined the work of past research models.9E-05 3.718835 22.259E+15 670 9.363E+14 720 5.455324218 4.CH3OH at 70 bars 1E+20 3E-05 0.0861 0.008936821 3E+17 1E-06 0.3E-05 1. Buscche and Froment. k3.CH3OH KRWGSE Ke.621204 15.2E-06 1.0076 0.2302838 67.9E-06 7.0212 0.685527 9.01 5650074 9E+17 2E-06 0.985840212 6.234157985 1.1E-05 5.1412 0.0 0 0 0 4 Rxn Rate (r)/kgmol/hr 0 .304296 10.875E+16 560 2. k5.121078146 0.677848 13.7E-05 5.240907 26.1E-05 1. and have had the credibility authorization from worldrenowned researchers.656863 16.03904186 15.004577578 1E+17 6E-07 0.77E+16 520 2.0247 0.5808217 8.0022021 64 Rate of reaction obtained from equations 3 and 4.796878 17. 5 -12 These reaction and equilibrium constant were based on detailed research.645431 24.066954877 k3 3454 3454 3454 3454 3454 3454 3454 3454 3454 3454 3454 3454 3454 3454 k4 7297 5196 4427 3794 3270 2834 2468 2159 1898 1676 1180 777 586 492 k5 Ke.20841007 40.345E+16 580 2. and Ke2 at various reactor temperatures are given below.328E+16 600 1.0 0 0 0 3 0 .93614 9. k4.074032437 2E+19 1E-05 0.0285 0.9E-05 4.0328 0.0131 0.771E+16 590 2.314623736 0.1 64632807 4E+19 2E-05 0.056E+16 570 2.6E-05 2.023481 362 3E+18 4E-06 0.65579223 25. Using Eqn 5-12 the following values of pi. Ke1.04561 85 01 8E+18 8E-06 0.8E-05 3.0548 0.448369 20.036267397 6E+18 6E-06 0. which spanned across companies institutions.

by calculating the Equilibrium constant of the Reverse Water Gas shift Reaction from the Gibbs Energy model. 26 00 8 0 . 06 00 1 3 . (530°C and 70 bars) Table-3 shows the K values obtained for the RWGSR (Reverse Water Gas Shift Reaction) compared with values using Bussche Kinetic Model. 11 00 5 9 .0 6 0 39 .0 5 0 19 .0 3 0 19 . 18 01 1 0 .0 C 4 H -7 .0 8 0 12 . Equilibrium Constants Although obtained from the Bussche model of methanol reaction kinetics.0 6 0 48 .Fig1 shows the variation MeOH formation rate with temperature. and specifically at the ALPHA methanol synthesis reactor temperature and pressure.5 2 1 .6 8 5 3 5 . 1999 McGraw Hill’. 11 00 1 4 . 25 00 2 7 .6 6 9 8 -2 . we obtain ∆G298.0 2 0 24 .1 -1 9 6 2 . 42 G B E E G M DL I S NR Y O E B 0 09 .2 4 7 -1 . ∆S298 obtained from ‘Chemical Properties Handbook by Yaws. 22 00 4 7 . 35 00 4 7 . The equilibrium constants Kp1 (RWGSR) and Kp2 (MeOH) are carried with the use of Gibbs Energy Relationship and Hoff’s Law. From this evidence the reactor temperature of 530K.8 4 5 -8 .0 1 0 70 . the aim is the understand the validity of the rate constants proposed. we obtain values for ln K.1 6 . was confirmed as an ideal temperature to be used with the Bussche kinetic model. 37 00 7 0 . ∆ H R298 − T ∆ S R298 = ∆ G R298 lnK = -13-14- ∆ R G RT 298 ln K = ln K298 − ∆ H R 298 1 1(Hoff’s ( − ) RT T T298 Equation) 15 ∆H298. From 13.1 H2 0 0 .8 -4 .0 0 0 . 80 01 6 3 .L. 14 00 8 9 . and 14.1 6 0 65 . Kp1 and Kp2 at different range of temperatures.9 8 R GR WS MO e H C O -1 0 1 . Beyond 530-540K. 10 00 3 1 .0 2 0 12 .0 8 0 24 .6 6 R GR WS MO e H H2 -2 1 0 4 .5 5 1 6 1 7 . the reaction rate slows and is an indication of the shift in conversion of Co2 being produced while the methanol being produced decreases in the reaction.2 3 From Hoff’s equation (15).0 1 0 48 . Calculated Values ∆H J o ) 298 (K /m lK ∆S298 (J o ) /m lK ∆G298 (K /m lK J o ) C 2 O -3 3 9 . Table-2. 57 00 6 9 . values were obtained for the equilibrium constants.5 8 .5 0 0 3 L K n L K n 1 2 C 3O H H -2 1 7 0 .1 0 0 91 .0 0 0 31 . T M (K EP ) 50 0 50 2 50 3 50 4 50 5 50 6 50 7 50 8 50 9 60 0 60 3 60 7 70 0 70 2 B S CE OE U S H M DL 00 7 4 . C.

theses are the number of moles of each species at any time in the reaction. into equations 23 and 24. since уi = ni /nT for a system of j reactions having an equilibrium extent xj: ni = nio + ∑νij xj -16- The initial model I started preparing for the design of the reactor consisted of both the reverse water gas shift reaction as well as the decomposition of carbon dioxide to methanol.86 CH4 0.x1 + x2) (nT-2x2)2 / (nCO2° .x1) (nH2O° .e. representing the extent of reaction in both equations: nCO nH2O nH2 nCO2 nCH3OH nT = = = = = = nCO°. Kprwgsr = (nH2° + x1 – 3x2) (nCO2° . Kprwgsr = (nCO2 nH2)/ nH2O nCO Ky1 KpMEOH = (nCH3OH nH2O nT2)/ nCO2 nH23 PT2 Ky2 -23-24- Substituting for number of moles of each species in terms of initial moles and extents of reactions from equations 17-22. and correction for non-ideality.5 CO 0.x1 – x2 nCH3OH°+ x2 nT – 2x2 -17-18-19-20-21-22- An equation can now be written for the equilibrium expression in terms of the number of moles.x1 – x2) (nH2° + x1 – 3x2)3 PT2 -25- 26- Inlet mole ratio.27 CH3OH 0.Conversions The equilibrium constant Kp can be expressed as the product of the equilibrium constant Ky in terms of mole fractions and a function of pressure. obtained from HYSIS.171 1739. Equilibrium expression can be set up in terms of mole fractions уi. in terms of ni.x1 – x2) / (nCO°.03 .044 447. equilibrium constant K in terms mole fractions.x1 nH2O° .03 H2 0. For both reactions being considered for the design.x1 + x2 nH2° + x1 – 3x2 nCO2° .34 CO2 0. sets up simultaneous equations with x1 and x2 as unknowns.631 6417. Table 4 – Values Obtained fron Hysis Simulation Basis Species Mol Fraction # Moles H2O 0.x1 + x2) KpMEOH = (nCH3OH°+ x2) (nH2O° . i. Kp = Ky∏PT∑νi.03 Total 1 10170.105 1067.002 20.047 478.

The conversions in CO and CO2 were found. of moles.7 -28- When solved using Math Cad at 530K.7 . Addition Reaction Approach Form the reaction rate data in Fig1. the actual conversion of carbon monoxide to methanol is observed rather than. With this theory the overall assumption is made that the Methanol forming from CO2 is the actual controlling step. to obtain expressions with only x1 and x2 as unknowns. This would have being the better approach. Values of Ky1 & Ky2 were obtained from generalized fugacity tables (Perrys). Kp constants. are added to form one reaction.03+ x − y ) ⋅ ( 6417. initial no of moles and total no. At 530˚C Where x1= x and x2 = y ( 6417.56510 ⋅ ( 478.27+ x − 3⋅ y ) ⋅ .86− x + y ) ⋅ . Both reactions affect the rate and extent of reaction on the other. the following expressions are found.03− x) ⋅ ( 1067.27+ x − 3y ) ⋅ ( 478. To include an overall mechanism. but to obtain corresponding reaction rates at other conversions would involve very complex mathematics. the following values of y and x. the reverse water gas shift reactions and the CO2 decomposition to methanol.Using Kp values from Table 1. .  x   772. every other short reaction. were obtained. which would be a better but simpler mechanism. and total pressure we can substitute into equations 25 and 26. but a mathematical model has to be developed to integrate both equations with respect to the conversion. and later in the model this proved to be very difficult.03− x − y ) ( 1739.02 ) 3 2 1. it was observed that the rate of the Reverse water gas shift reaction happens much quicker than the Methanol formation reaction and therefore would suggest the reaction-forming methanol is the rate-limiting step. This way.5+ y ) ⋅ ( 1067 − x + y ) ⋅ ( 10170. Substituting values of moles from table 4.204  By definition of conversion: Xi = (ni° – ni) / ni° XCO = x/nCO° XCO2 = (x+y)/nCO2° -29- The inconsistency in this approach was a matter of complexity than feasibility. This kinetic concept was also highlighted by Bussche and Froment. and Ky.037 -27−5 ( 447. as the direct relationship on both reactions and their effect on reactor sizing would be more acceptable in practice.229  =   y   −294.

0.2x nTº-2x -31-32-33-34- Substituting equations 31-34 into equation 30 yields: KpMEOH = (nCH3OH°+ x) (nTº – 2x) 2 / (nCO° .00056356 -36-37- Using this value of Kp for the Ke. for the purpose of reactor design. That is the reason why. but the time this would take would not be economically feasible. Kp.27 -2x) 3 702 *0.1 = .2 KJmol-1 ∆H298 = -49.CH3OH at 530K and 70bars. KpMEOH is found over a range of reactor temperature at 70 bars. will be considered.3 . This figure represents entire conversion. therefore backward-calculations were doing using equation 38 to . which present a more simplistic design. nCH3OH nCO nH2 nT = = = = nCH3OHº + x nCOº -x nH2º .6 KJmol-1 The equilibrium expression for this reaction can be written as follows can be written KpMEOH = (nCH3OH nT2)/ nCO nH22 PT2 Ky2 -30- From mass balance the following is obtained.x) (6417. Recall: CO + H2O ↔ H2 + CO2 CO2 + 3H2 ↔CH3OH + H2O ∆H298 = -41.x) (nH2° -2x) 3 PT2Ky2 -35- From the Bussche Model of Kinetic equations.In the methanol synthesis industry.7 -38- The overall extent showed a value of x to be 1738. It is important to pinpoint that the RWGSR occurs very quickly.5 + x) (nTº – 2x) 2 / (1739. but does have some effect on the sizing of the reactor. the extent of reaction was calculated in Excel. The conversion associated with this extent in reaction was calculated for carbon monoxide.592 Kp. and equation 35. using equation 11.1 = 10 3066/533 – 10. a combination of both equations.98. very complex relationships on the mechanism and action of one reaction on the other are considered (Journal of Advanced Catalysis).074324 = (447.5 KJmol-1 -1-2- Combining both equations gives the following CO + 2H2 ↔CH3OH ∆H298 = -90.

and setting predicted values so new extent of conversions and Kp values could be obtained.5529E-07 1.65 0.4303E-07 1.95 Conversion .35 0.9388E-07 1.37 1043.9871E-08 6. catalyst volume.77 62886.0658E-07 2.90 86.45 0.1003E-05 4. a graph corresponding to the function expressed in equation 39.48 287223.30 0. and conversion.18 1391. the following values were obtained for extent of reaction and Equilibrium constants.95 0.97 142906. F0 being the inlet molar flow rate to the reactor. With the defined values of conversion and rate of reaction in Table5. . the reaction rate corresponding to the respective conversions.2459E-07 9.9023E-07 3.7092E-06 2.20 0.36 10186.3470E-08 4.76 347.51 802521.32 1130.11 39093.08 1565.X CO 0.8726E-08 Xxnt rctn 1652.13 1478.9909E-08 7.50 0.47 869.25 0.10 0.75 0.85 0. This was done by specifying a conversion with the associated extent of reaction calculated from equation 29.27 1217.43 Kp 1.0278E-07 3.70 0. The area under the graph within a specified conversion would relate to V/F0.52 782.80 0. so values of Kp can be obtained to specify at what rate this would occur.39 8014.81 260.7020E-06 1.61 608.55 0.36 16041.42 956.specify conversions for reactor actual conversions.67 106465.66 521.10 197975.90 0.5842E-07 5.21 20011.2157E-06 8.92 12821.85 173. Equation 3 was then used to obtain. Using the Goal-Seek function in Excel. the volume can be found from defining molar flow rate reaction rate.7518E-06 1.9947E-08 3. can be plotted.56 695.07 31167.22 1304. obtained from HYSIS and V’ corresponding to the volume of the reactor and catalyst volume. The basic design equation for ideal plug flow is utilized. -39One of the most important applications of this design equation is the determination of reactor volume and in this special case of a catalytic reactor.8130E-07 6.60 0.62 24951.43 49354.36 448474.05 Reactor/Catalyst Volume Since for a plug flow reactor.68 4710.40 0.15 0. Table 5 – Data Obtained Through Excel Goal Seek Function Rxn rate 2046529.46 81139.71 434.

00 Vol.3 0.00 Rate (-1/RA) 3000. of Reactor = 339 ~ 340 m3 0 0. the volume necessary for an almost complete conversion would not be economically feasible. for the plug flow reactor the equation 40 is used. With a desired 54% of conversion.6 0.885 = 339m3 Residence Time To obtain the residence time θ. For the reactor design therefore an industrial practiced conversion of 50-70%.00 5000.Graph Plot to Obtain Reactor Volume Graph of Reaction rate vs CO conversion 6000.00 4000.5 0.00 Conversion = V/FO As observed from the graph above.2 0.9 0. the catalyst weight and the pressure drop across the catalyst bed.4 0. V = 30×4×2. but for simplistic design and this is assumed to be constant.8 0. θplug = F0 ∫xco dxCO/-rAν(1+εAxA) -40Assuming ideal gas behaviour: . the residence time. the volume of reactor obtained from Fig2.Fig2.885 kgmol/s Number of squares counted = 30 Volume of Reactor. Volume of each square = . of squares (area under graph at 55% conversion = 30 × 4(area of unit square) = 120 m3s/kgmol Vol.00 2000.1 0. the aim was then to obtain the desired reactor volume. Using the method of counting the squares.00 1000.02 × 200 = 4m3/kgmols F0 = 1.825) Vol. the number and arrangement of pipes. of Reactor = 120 m3s/kgmol × F0 = (120 × 2. Assumption – The molar flow rate of would expect to change during the reaction.07E+04 kgmol/hr=2.7 0. is used. was calculated.

9 1 Volume of each square = .07E+04 kgmol/hr=2.171×70.02 ×100000 = 2000 kgmol/s F0 = 1. Graphical Solution of Reac tor Residenc e Time 3000000 θplug =F x ?co -41- Rate(kmol/s ) 2000000 0 dC x O /-rC .825/270 = 0.4 gcm-3.5 Conv ersion 0 .PV = nRT.314×530) = 270 kgmol/m3 εA = Expansion coefficient.001867xCO) The integral of this graph was found graphically.2 gcm-3 = 1200kg/m3 Mass of catalyst therefore = ρb × catalysis volume Mass of catalyst therefore = 1200 × 339 = 406800 kg . n/V = C.885 = 28350 sec = 7.7 0 . 00.2 0 . Fig 3 shows the graph and the corresponding area.0 0 (1 . ρb for design purpose is 1. (Fundamentals of Industrial Catalytic Processes pg 276).8 0 . θplug = F0 ∫xco dxCO/-rCO .1 – 1.001876K-1 ν = F0/CCO = 2. C = P/RT or Ci = yiP/RT At 70 bars and Temp of 530 K CCO = (0.825 kgmol/s Number of squares counted = 4 Residence Time = 2000×4×2.0 1 6 x 14 + 087 O C O ) 2 1000000 =T /F 0 0 0 0 .6 0 .4 0 .000) / (8.84 hr Catalyst Weight Bulk densities (ρb) of Cu/Zn/Al2O3 catalysts are typically 1.3 0 .0104(1+. = 1/T ν = Space Velocity = F0/CCO εA = 1/T = 1/533 = .1 0 .01403 m3/s Equation 40 now becomes. which relates directly to the residence time. P/RT = n/V.

Q = -3.84 2. at boiling.55 Specific enthalpy of steam (total heat) kj/kg 2706. The concept of cooling in the reactor is brought about by the difference in temperature of the boiling water and reactor tubes.1208(280 – 120) m = 2. The flow rate of boiling water required for this purpose is calculated by dividing the required duty of the reactor by the latent heat of vaporization for steam at 10 bars. the inlet water is to be maintained at 120˚C. m = 3. A driving force is therefore created which removes heat from the reactor tubes to the boiling water creating LP steam at 280˚C Table7. The assumed outlet coolant temperature is 280˚C.29 Kcal/kg 646.Coolant Requirements The reactor tubes are to be cooled using boiling water.129 kj/kg 504.54 kg/s or.s 0.71 Kcal/kg 120. m = 9146. This temperature provides a reasonable log mean driving force for heat transfer. m = Q [λ + cp(T2-T1)] Substituting.THERM EXCEL physical data of water Specific Specific enthalpy Absolute Boiling Density volume of liquid water (sensible pressure point (steam) (steam) heat) bar 2 °C 120. At these conditions the latent heat of vaporization is 2201. and 2 bar.59 + 2.878E+04 [2201.23 m3/kg 0. The mass flow rate of the boiling water is calculated as follows: From equation 43.844 kg/h .1208 The required duty of the reactor is given by Q = mλ + mcpΔT Where λ = latent heat of vaporization m = mass flow rate of boiling water cp = specific heat capacity ΔT = change in temperature of coolant Also obtained from Hysis.59 Kcal/kg Specific Dynamic heat viscosity kj/kg kg/m. and heat capacity.878E+04 kW Q = -38.000013 525.59 kJ/kg.39 Latent heat of vaporization kj/kg 2201. mounted near the top of the reactor.885 kg/m3 1.78 MW -43- From table above. produced from a boiling water tank.

347 2.01 0.1237 0.156 22083.351 588.07 0.6569 134.091 199.007 0.07 0.01 0. the tubes is constructed of stainless steel (304).091 399. Of tubes = 3850 Diameter of catalyst pellet = 0.495 1. and tube diameter.091 149. Erguns equation was used to calculate the pressure drop.414 3.091 349.262 3847.0530 0.149 4.701 798. Reactor Length = 5m Internal Tube Diameter = 0.091 299.6867 From the iterative length and pressure drop. with the corresponding pressure drops.497 5.15 0.696 2748.4580 559.972 12619.1414 0.15 0.523 798.224 3206.Reactor Tubes Since the reactor tubes will be in contact with carbon monoxide methane.351 399.260 5410.945 29445.005 0.3734 367.012 1.01 0.089 8656.15 0.678 2.630 17667.1883 167. Where.996 1.10 0.0269 0.677 1.0471 0.701 798.15 0.005 0. To obtain the number of reactor tubes.4978 514.906 10821.07 0.2510 234.0192 0.2489 220.351 399.01 0.9356 441.10 Vol of tubes No of 0.10 0.514 4809.701 798.392 6412. the tube dimensions chose is below.8111 294.567 6183.01 0.397 14722.10 0.007 0.07 0.3496 559.0550 0.15m No.993 2. -42- ∆P = Pressure drop ε = porosity ρg = gas density.07 0.007 0.6748 399.0308 0.0628 0.10 0.07 0.1328 559.10 0.01m Pressure Drop in Reactor Tubes (70 bars) = 2 bars .1255 100.207 11041.2412 559. and a small quantity of water during normal operations. kg/m3 Ug = gas apparent velocity.351 399.005 0.1060 0.15 0.005 0.0314 0.885 5.133 14428.991 3.0231 0.5941 bar 2.0236 tubes Re 2404.007 0.0393 0.005 0.492 2.005 Internal Diameter(m) 8 7 6 5 4 3 8 7 6 5 4 3 8 7 6 5 4 3 0.0707 0.0115 0.942 2.007 0.341 1.007 0. a spreadsheet was used to timely calculate the pressure drop in pipes of different length corresponding to the reactor volume.701 798.683 2.177 559.01 0.351 399.15 0.5664 559.0154 0.091 249. m νg = kinematics gas viscosity z = length of the reactor Table 6 – Iterative Pressure Drop Optimization .Excel diameter of ctalyst pellet de(m) Length(m) 0. m/s de = ekvivalent diameter of catalyst pellet.351 399.006 3.701 P drop (KPa) 268.7196 201.0884 0.701 798.505 7214.

the only fluid to come in contact with the reactor shell will be industrial water.25*0. bst st304 (260˚C) = 110 N/mm2. et al. is shown below. at reactor temperature of 260˚C.3 times the height of the reactor tubes. from data (Coulson and Richardson) should be at least 1. During normal operations. N/mm2 Design stress found for stainless steal 304. mm id = pipe inside diameter.77 ~ 5mm Outside diameter of tubes = 160 mm or 0. t = [70 * 150]/[20*110] t = 4. (…) From equation 44.25 length of the tube outside diameter. bar d = pipe outside diameter.The pipe thickness is calculated from the British Standard (Coulson and Richardson Vol 6) Pd 20b + P t Pid t or 20b -43- Where P = internal pressure. the diameter across the bed is calculated as follows. 1 Australian Standards 1210 . D = √ ((4/∏)*3850*(1. the resulting shell height is 16. Assuming pitch of 1.15)2)/0. Carbon steel is cheap and can easily withstand the pressures and temperatures required for the shell side of the reactor.95) = 14.5m.6 the length of the tubes.4 m For reactor length. The reactor is to be constructed of carbon steel with a 1. using an equation based on circumferential difference.16m Given 4 no ⋅ of ⋅ tubes ⋅ ( pitch ) π Diameter across reactor bed = packing ⋅ efficiency (Martyn) -45- Assumed packing efficiency = 95% Pitch. The wall thickness can be specified in accordance with 1AS1210 for class 1 pressurevessel. Since the reactor tube height calculated was 5m.25 corrosion allowance. mm b = design stress at working temperature. the height of reactor shell based on maintenance area and catalyst entry area is estimated 3. thickness‘t’ obtained.

t = D = P = f = n = minimum shell wall thickness (mm) Shell inside diameter Design Pressure MPa Tensile strength of carbon steel et al.t := P⋅ D 2. joint efficiency D for shell diameter is estimated to be at least 1.*14. (Brownell and Young 1959) Thickness = 7/17 * 37 = 15mm Support The reactor is to be supported by four (4) saddles at the bottom of the reactor.4 = 15. 46. (Coulson and Richardson Volume 6) Thickness of hemispherical head using rule of thumb which states it should be at least 7/17 the thickness of the shell. equal distance apart. This gives: 1.4m Joint efficiency estimated to be 100% Tensile stress of carbon steel (304) = (290) N/mm2 Substituting into equation. .1 times the diameter across the tubes cross-section.7) = 37mm Shell Heads The Reactor shell will be closed with a hemispherical head. and used generally for high pressures. f ⋅ n − P -46- Where. t is: t := 0. × 540⋅ ( 1 − 0. This is the strongest shape.7⋅ 16200 2.

Fig4.5m) Tube outer dia 0.05m Reactor length (16.4m Shell thickness 37mm MECHANICAL DESIGN PROCESS CONTROL AND INSTRUMENTATION .0.2m Shell inner dia 15. Mechanical Design -Schematic Diameter across Bed (14.4m) REACTOR Tube inner dia 0.15m No. of Tubes 3850 Tube length 5m Catalyst pellet dia 0.

Feed forward control actions will be utilized to detect changes in the reactor feed rate before they impact on the temperature control loop. 4) the water tank level and 5). with the flow rate of coolant changing with respect to reactor outlet temperature. The coolant supply temperature to the reactor will be controlled via the water flow from the boiling feed tank. . Another feedback-feed forward controller will be used to maintain the level of water in the boiling tank. the pressure of the steam stream. and hence temperature and pressure in the reactor. The diagram in Fig 8 illustrates the process control scheme discussed above. A control system is established to regulate the flow of coolant through the reactor shell. This controller will maintain the correct level by monitoring the boiling water production rate from addition of steam inlet flow rate and process water inlet flow rate to the tank. Temperature indicators are also inserted to monitor the coolant. If the flow rate increases the flow rate of the outlet stream (product) will increase the remove any excess build up of feed. The system consists of 5 control loops with control 1). and to detect any abnormal pressure build ups.Tight process control of the reactor temperature is essential in order to maintain isothermal conditions. Pressure indicators are placed at the inlet and outlet of the gas streams to provide a continuous record of the pressure drop over the catalyst. An increase in temperature of the coolant will automatically cause the flow from the water tank to decrease. Temperature indicators are positioned at several positions along the reactor tubes to monitor the temperature profile and the peak temperature. The reactor feed rate. 2) the reactor outlet temperature. and product quality. A simple PI controller is used to control the feed stream rate. Set-point ramping will be used to smooth changes to the reactor feed. The entire system will also be fitted with alarms to warn of any excess or malfunction in process variables and control. A feedback-feed forward controller will be used to control the reactor outlet temperature. 3) the coolant temperature.


Increased suction pressure More Pressure More Temperature 11.Ambient conditions Increased in temperature.Exchanger tube leaks 7.Thermal expansion 12.More quantity 9.HAZOP The unit chosen by the Alpha Consultancy for Hazard Analysis is the reformer reactor.Defective Pump 18. with the addition of a Fault Tree Analysis which outlines the route of unforeseeable accidents.Ambient conditions 14.c) 5. Material loss Pump overheats b) Maintenance of control valves & instrumentations a) Institute regular patrolling & inspection of transfer line Possible Causes Consequences Action Required .Control faults 8.Leaking line 17.Line fracture 4. HAZOP ALPHA CONSULTANCY LIMITED Pre-heated inlet (600 o C. build up of materials in the reactor Less conversion of reactants in the reactor Line fracture or flange leak Line subjected to full pump delivery Deactivation of catalyst High risk of thermal runaway due to high energy demand Less conversion of reactants in reactor Material loss adjacent to public highway Reduced output Deactivation of catalyst Covered by b) d) Install thermal expansion relief on valve section e) Install kick-back on pumps Covered by c) Covered by b).Increased pumping capacity 10.Wrong routing 2. Hazards analysis are very important in engineering design as this is where unforeseen process hazards are identified which could cause major accidents.Isolation in error with pump running 13.Equipment failure (control valve. In compliance with the British Heal Standards.Isolation in error 3.Higher energy from machines 15.t. isolation valve e. the hazard analysis on the Alpha reformer is detailed below.Blockage More Of More Flow 6. 16bar) Guide None Deviation No Flow 1.Cooling water failure Less Of Less Flow Less Temperature 16. f) emergency shutdown procedures Covered by c) Covered by a) Covered by b) Covered by c) Covered by b) c) Regular checks No feed in the reactor.

Guide None More Of Deviation No Flow More Flow More Pressure More Temperature Possible Causes 19. Undesired reactions might occur As for 21. As for 8. Covered by c) More Pressure . Thermal runaway 24. As for 8. As for 21 30. Low Syngas formation High formation of CO2 Poison to catalyst Accumulation in reactor Table () Steam reformer Outlet (1000oC 16bar) Covered by b) Covered by c) Covered by c) Action Required g) Install high level alarm and locking off procedure for control valves. 28. undesired reaction might occur As for 13. 34. Outlet line blockage Consequences Material loss to atmosphere As for 32. Action Required Covered by f). Sulphur in raw materials 31. h) Immediate evacuation Less Of Less Pressure Less Temperature Part Of More than As well as Other Lower Ratios Higher Ratios Impurities Maintenance 27. Coke formation i) check ratios for optimum Syngas formation Covered by i) Covered by c) Covered by f) Guide None Deviation No flow Possible Causes 32.Failure operation of valves 22.Transfer line fracture 20. Condensation 26. As for 7. 23. Vessel drainage Consequences Covered by a) No feed in the reactor. As for 3. As for 21. As for 13. Risk of explosion Less conversion in reactor As for 24. 36. As for 21. As for 6.h) Covered by b) More Of More Flow 35. Vessel Rupture 3. 29.Blockage 21. As for 32. 37. Covered by g) and c) Covered by f). Material loss Ruptured vessel As for 21. Material loss. Vacuum conditions 25.

Reactor Explodes FAULT TREE ANALYSIS Damage to reactor Reactor runs out Of control Physical damage to reactor Thermal damage to reactor Thermal runaway Fire Sparks Leakage Mechanical damage to reactor Explosive power damage to reactor Poor design of Heat removal Inadequate control & safety systems Inadequate Training Piping failure Valve failure Mechanical failure Technical failure .

05 0.2 0.15 0.5 0. For a number of unit and operation pricing.05 0.7 0.4 0. Major Equipment Reactor Heat Exchanger Cooler Compressor Heater Separator Mixer Distillation column Quantity 2 15 2 1 2 4 2 1 450000 34000 654709 4150741 282487 6032 6190 74709 Total (£) £Total 900000 510000 1309418 4150740 564974 24128 12380 74709 7546349 Estimation of Fixed Capital Cost Item Equipment erection Piping Instrumentation Electrical Buildings. The flow rates were obtained from HYSIS.45 0.9 1131952 3773175 1131952 377317.05 7546349 3018540 5282444 1509270 754634. the Chemical Engineering Cost Index was used to find the modern cost in pound sterling.1 1.FINAL COSTING & COMMERCIAL RISK ASSESMENT The following calculation describes the entire cost associated with the start up of the ALPHA methanol plant if the proposal goes through. as the optimized process.15 Total (£) PCE 0.1 0. process Utilities Storages Site development ancillary Buildings PCE 0.5 1131952 25657587 Total Physical Plant Cost Design and Engineering Contractor's Fee Contingency Total (£) working capital Total investment required for project 5% Total (£) 25657587 7697276 1282879 2565759 37203501 1860175 39063676 Variable Cost .3 0.15 0.


000 £23.550 Direct production cost Price of Methanol £17640983 + £ 6.34/tonne Sales revenue £158.05 Operating labor Plant overheads Laboratory Capital changes Insurance Total Fixed cost Assumed 50 % of Operating labor 30 % of Operating labor 10 % fixed capital 1% fixed capital £ 10.502.05 £186018 5 % of fixed capital cost 10 % of maintenance cost Miscellaneous Materials Material UTILITIES Steam mass flow rate Therefore steam cost Cooling water Cost Power total ( HYSIS) 108100 kgh-1 £7/tonne 7200x (108100/1000) x 7 62260 kg/h 1 .34 x 1000 x 300 Profit Sales revenue – direct production cost = If we were to assume that the electricity bill is 10 million therefore new var cost = 15454965 pounds Profit = 47 502 000 – 15 454 965 = £ 23.540 CRITICAL REVIEW Methanol production in the modern era is a challenge for industries worldwide.Methane Flow rates obtained from HYSIS CH4 mass flow rate 40000 kg h-1 CH4 Cost Yearly Operation 300 days Daily Cost Maintenance Cost 1604500/7200 £50/kg 37483 x 50 7200 hrs £ 1836630 h-1 £230 37203501 × 0.728.5/100 x 62260/1000 x 7200 384942 kW 1.1 × 1860175.773.05 0. .360 £ 15454965 £1860180 £ 100000 £ 50000 £ 30000 £ 3720352 £ 372035 £ 6132567 £231.732.567 £158.05 £ 1860175.2/100 ×300×9238608 Total Variable cost Fixed Cost Maintenance 37203501 x 0. 728.450 £47.2p/MJ 384942 × 7200 = 9238608 kWh / d 300 1.132.5p/tonne £ 6725 £ 5448240 1.

There has not been much discussion of the pollutants that are associated with methanol production. and using steam reforming as the most economically feasible method to generate steam was considered. and in fact nowhere in the UK. these challenges at a minute glimpse were observed. The difference in results from the HYSIS package and hand calculation was down to the basis of calculations. the process was designed to facilitate a production capacity of 1000 tonnes of methanol per year. With an annual profit of just over £23 million. areas close to natural gas resources. labor and operation cost is cheap. high pressure conditions for methanol production. while several methods and assumptions were used in the hand calculation. The prime locations from research are areas close to the sea for transportation purposes. and scientist has proved this harmless. The plant to be located in South Cambridgeshire would in actuality not be economically feasible to compete. and having secure major contract for product. . Because of this the nature in the difference in the results were observed. The methanol synthesis type reactor used was a multi-tubular isothermal reactor. by effective research and development. the competition would probably be a huge driver in investment. The most harmful situation identified by Alpha Methanol Plant is carbon dioxide being emitted into the atmosphere. With other competitors operating at lower costs. The choice of Syngas production is also one of great importance in the Alpha methanol production. As a promoter on science and new technology the Alpha Consultancy approach the issues of carbon dioxide in a similar mode. For process simulation. qualifies on these basis. With our total dedication to abide with the Protocol Agreement and British Air regulation. These include the partial oxidation method and auto thermal methods. A larger plant can facilitate additional components which could in turn do more for a process financially than smaller plants. the package chosen was HYSIS. our aim is to reduce the emission of carbon dioxide through large scale research and development. From research however I most case this is done on the principle heat balance rather than reaction kinetics. since it is meant to be a kept at constant temperature throughout its operation. In Sweden. The challenges most encountered by this type of reactor is temperature control. Mega methanol plant structures are considered because other means of producing Syngas then becomes feasible. on either a European or International level in the methanol market. The practicality of the HYSIS package is extensive and used industrially. Cambridge. areas where mass methanol is required and most importantly areas where the maintenance. The Alpha Consultancy methanol reactor was designed based on kinetics and reaction approach to equilibrium. from phase 1-4. the venture to invest in the plant would be economically beneficial and would be more profitable than fixing money in a bank account. Of all the methanol plants worldwide only very few has capacities below 1500 tonnes per year. With the ALPHA Consultancy initial selection for methanol production down to steam reforming and low temperature. The calculations within the HYSIS package are deemed more consistent as the PRSV basis of component calculation was used.Throughout the design of the Alpha Methanol Plant. the latest approach to discharge carbon dioxide was to inject the gas in the earth.

Fundamentals of Industrial Catalytic Processes. Of great interest is the method of using steam to control the temperature of the reactor. Reference 1. 1997 . but other issues would have to be considered. especially in areas of high pressure reaction. It was expected that the height would be least 50% greater than the width but. Farrauto and Bartholomew. The reactor height and width obtained were 14 and 17m respectively. All the calculated data found for the reactor design seemed to go in similarity with theory except for the reactor width compared with its height.Obtaining data to follow through with the design of the reactor was almost impossible to obtain. other sources shows these dimensions area acceptable. Where the relevant data could not de found. This ‘in theory’ gives a better control of the temperature of the reactor. as that would be a very confidential issue. The structure would prevent environmental effects such as high wind and ‘sight blockage’ issues. After designing the reactor it was observed that newer processes of temperature control are now being adapted by methanol production plants. assumptions were made and clearly marked.

http://www. 6th Edition. Chemical Properties Handbook by Yaws. D. 1. Ray and Martin. Chemical Engineering Design. pp 1-10. C. 10. 1971 7.thermexcel. 1984 6.L. Lieu 1984. (Chinchem 1998. 1982). Coulson and Richardson. Vol.2. Chemical Engineering Design Project. Martyn S.htm 8.com/english/tables/vap_eau. Chemical Engineering Volume 3. 1999 McGraw Hill 5.W. 1996 4. Volume 6. Klier. Journal of Catalysis. Journal of Petroleum and Coal. G Sneesby 9. . Green. 161. 43. Coulson and Richardson. Perry’s Chemical Engineers’ Handbook. 31-34 3.

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