Professional Documents
Culture Documents
I wish to express my sincere thanks and gratitude to DR. Ratna Datta, Jadavpur University, for his continuous, encouragement and supervision over my entire project work on Design a styrene plant of capacity 30 tonnes per day. His most valuable advices and the paths he showed to me helped me in completion of my work. I also express my thanks to all faculty members and my fellow students of the Department of Chemical Engineering, Jadavpur University, for their help and moral supports. Thanking you, Yours faithfully, Bappa Saha [Class: B.Ch.E. IV Sec: A-1 RollNo:000810301018] Date: 14th Oct, 2012 Place: Jadavpur, Kolkata-32
JADAVPUR UNIVERSITY
Faculty of Engineering and Technology Department of Chemical Engineering
Certificate of Approval
This is to certify that the project entitled Determination of fuel characteristics of blended and pure biodiesel, submitted by Bappa Saha, a fourth year student, bearing Roll No. 000810301018, and accepted for partial fulfillment of the degree of Bachelor of Chemical Engineering from The Department of Chemical Engineering, Faculty of Engineering And Technology, Jadavpur University, Kolkata, is prepared entirely by himself under my supervision and guidance.
Head of the Department (Prof. Chiranjib Bhattacharjee) Department of Chemical Engg. Jadavpur University, Kolkata-32
In-charge of Projet Work (Prof. Ratna Datta) Department of Chemical Engg. Jadavpur University, Kolkata-32
INTRODUCTION:
The styrene process was developed in the 1930s by BASF (Germany) and Dow Chemical (USA). Over 25106 tons/year of styrene monomer is produced worldwide.1 The annual production of styrene in the U.S.A. exceeds 6106 tons.2 The major commercial process for the production of styrene is the dehydrogenation of ethylbenzene, which accounts for 85% of the commercial production.3 The potassium-promoted iron oxide catalyst has been extensively used for styrene production. 4 The average capacity of ethylbenzene dehydrogenation plants is over 100,000 metric tons per year and plants which have a capacity of 400,000 metric ton per year is not uncommon.5 Obviously, a small improvement in the plant operation will lead to a substantial increase of returns. Nevertheless, the research towards the fundamental kinetic modeling based upon the Hougen-Watson approach has not been pursued by most styrene producers and researchers. They rely on the empirical polynomial correlations for the unit optimization.6-8 Furthermore, the reaction rates published in the most of papers are not intrinsic but effective.9, 10 An intrinsic kinetic model based upon the fundamental principles is essentially required for the optimization of the various reactor configurations with different operating conditions. The objectives of this research are to develop the mathematical kinetic model for the ethylbenzene dehydrogenation and to
investigate the effect of operating conditions on the fixed bed industrial reactor formation of styrene, benzene, and toluene, the understanding of the kinetic behavior of the minor byproducts, such as phenylacetylene, -methylstyrene, methylstyrene, cumene, n-propylbenzene, divinylbenzene, and stilbene, is also important in terms of the styrene monomer quality and separation cost of the final products. The formation of these minor by-products is not taken into account for the fundamental kinetic model. The general features of ethylbenzene dehydrogenation are briefly discussed. The theoretical and literature backgrounds are presented in each chapter. Chapter III explains the experimental methods of ethylbenzene dehydrogenation.
Problem statement :
It is proposed to design a styrene plant of capacity 30 tones par day, by vapor phase catalytic dehydrogenation of ethylbenzene, starting from ethylbenzene as raw material.
(1)
(2)
Prepare an energy balance and mass balance of the plant Design a catalytic fixed bed reactor involved in the prosess with optimum conversion
Definition:
Styrene monomer is an aromatic hydrocarbon,under normal condition it is clear,cocorless, flamableand toxic liquid.
H5 C2 H5
2.) C6 H5 C2 H5 C6 H5 C2 H3+ H2 However, styrene can be industrially produced by what is known as PO-SM Coproduction, where propylene oxide and styrene are made simultaneously. It proceeds as follows: 3.) C6H5CH2CH3 + O2
C H CH(CH
6 5
3)OOH
6H5
CH(CH3)OH +
H2COCHCH3
5.) C 6H5CH(CH3)OH
6H5
CH=CH2 +H2O
One downside to the PO-SM Coproduction is that the production capacity is dictated by the demand for propylene oxide. Since it is a more complex series of reactions makes it is less attractive to operate in industry.
The dehydrogenation reaction is usually conducted at temperatures above 600oC with an excess of steam. The ethyl benzene dehydrogenation is an endothermic and reversible reaction with an increase in the number of mole due to
reaction. High equilibrium conversion can be achieved by a high temperature and a low ethyl benzene partial pressure. The main byproducts are benzene and toluene. Ethylbenzene benzene +C2H4, kJ/mol Ethylbenzene + H2 toluene +CH4, 65.06kJ/mol Hr (620oC) =101.50
Hr (620oC) = -
Reaction thermodynamics
The dehydrogenation reaction of EB to Styrene is endothermic (DH=129.4kJ/mol) At room temperature, the reaction equilibrium is located far towards the educts side. It can be shifted towards the product side by increasing the temperature, which increases the equilibrium constant K due to the vant Hoff relationship and by reducing the pressure, since two moles of product are formed from one mole of EB. Therefore the technical St synthesis is run at around 600C with an excess of steam, the steam-EB mixtures has a molar ratios from 5:1 to 12:1. Styrene plants run their reactors under isothermal or adiabatic conditions with flow rates that ensure short contact times in order to prevent polymerization of Styrene. The equilibrium EB conversion at 600C and 0.1 bar pressure is( ~ 83% ), and conversions between 50 and 60% are obtained in technical reactors. The
typical byproducts of the EB dehydrogenation are (~1%) benzene and (~2%) toluene formed by catalytic dealkylation and hydrodealkylation of Ethylebenzene,respectively, or they also can be formed by steam dealkylation.
Flash point
Physical porperties of styrene Physical properties Molar mass Appearance Density Ethylbenzene 106.17g/mol Clear colorless 0.8670g/cm3(20 oC) o.8669 g/cm3(200 oC) .86262 g/cm3(250 oC) -94.9760 C 136.190 C 140mg/L (150 C) 152mg/l (200 C) 160mg/L (250 C) soluble in ethanol,ether,acetone 0.029 mg/L o.140 mg/l 2.3 ppm 1mg/m3=0.230ppm 0.867 at 20 oC (water = 1) 0.8(lower)vol%-6.7(upper)vol% 15oC 7 mmHg 810 oF(432 oC) 6.6*10-3 atm-m3/mol Liquid 1.49320
Solubility in organic solvent Oder threshold Water Air Conversion factor(25 oC,1atm) Specific gravity Flammability limits
Flash point
Vapor pressure at 20 c Autoignition temperature Henrys law constant Physical state Refractive Index(at 200 oC)
Latent Heat(veporizatin) Heating value(gross) Heating value(net) Kinematic viscosity(at 98.90 oC) Surface tension Specific heat capacity(idea gas, 250 oC)
335 j/kg 42999 j/kg 40928 j/kg 0.390*10-6 m2/s 28.48 mN/m 1169 -1 k-1
Physical properties Molar mass Appearance Gas Density at 70 oF Melting point Boiling point Solubility in water
Methane(CH4) 16.04g/mol Clear colorless to yellowish 0.0416lb/ft3 -296.50 F -258.70 F 280mg/L (150 C) 300mg/l (200 C) 400mg/L (400 C) soluble in ethanol,ether,acetone
Flash point
Vapor pressure at 20 c Autoignition temperature Henrys law constant Odor
Physical properties Molar mass Appearance Density at 25 oC Melting point Boiling point Solubility in water Specific heat
Toluene 92.14g/mol Clear colorless to yellowish 0.867g/cm3 -93.990 C 110-1110 C 0.052% at 25 0 C 1.72 kj/kg k 4.40 C 28.5 torr Flamable liquid
Flash point
Vapor pressure at 20 c Hazard class
Over 90% of the 12.7 billion pounds of EB produced in the U.S. during 1998 was dehydrogenated to styrene. Styrene (vinyl benzene) A liquid (b.p. 145.2C) Polymerizes easily when initiated by a free radical or when exposed to light. Dehydrogenation of ethyl benzene to styrene Catalysts: Metal oxide catalysts. Oxides of Fe, Cr, Si, Co, Zn, or their mixtures Reaction conditions: Temperature : 600-700o C Pressure : 1 atm or or lower 90% styrene yield 60-70% conversion:
Process Description
See Figure 1. The raw material is ethyl benzene, and steam is fed as an inert. In the suggested process, ethyl benzene is preheated in E-501 to a saturated vapor. This is then mixed with steam produced from the fired heater H-501. The steam provides the heat of reaction and serves as an inert diluent to help shift the reaction to the right. Steam also tends to limit side reactions and helps to extend catalyst life by reducing coke formation on the catalyst. The ratio of steam to ethyl benzene entering reactor R-501 in Stream 6 ranges between 6 and 12. The main reaction: C6H5CH2CH3 C6H5CHCH2 + H2 Ethyl benzene styrene .. (1)
is endothermic, reversible, and limited by equilibrium. The reaction occurs at high temperatures (600 700 0c) and low pressures (0.4-1.4 bar) in order to shift the equilibrium to the right to favor styrene production. In R-501, the process uses a proprietary iron catalyst that minimizes (but does not eliminate) side reactions at higher temperatures. For simplicity, assume that the only side reaction that occurs in R-501 is the hydrogenation of ethyl benzene to form toluene and methane: C6H5CH2CH3 + H2 C6H5CH3 + CH4 .(2) Ethyl benzene toluene The primary reaction is limited by equilibrium, and is assumed to approach 80% of equilibrium. The selectivity of the toluene side reaction is a function of reactor temperature.
The reactor effluent, Stream 7, is cooled in E-502 to produce steam and then enters a three-phase separator (V-501). The bottom phase of V-501 is waste water (Stream 11). This must be decanted and sent for further processing before discharge. This treatment is not shown in the PFD, but it is an expense which must be included in the economic analysis. Stream 9 leaves the top of the separator and contains all the light gases (methane and hydrogen) and can be used as a fuel gas. Stream 10 contains most of the toluene, ethyl benzene and styrene. Stream 10 flows through a pressure-reducing valve and then enters a distillation train (T-501 and T-502). The distillation columns operate at (different) constant pressures, the values of which are governed by the properties of the heating steam and cooling water used, and the composition of the top and bottom products, as described later. Most of the toluene is removed at the top of first column (T-501) in Stream 16. The remaining toluene, ethyl benzene and styrene leaving the bottom of this column in Stream 15 enter the second column (T-502). From T502, Stream 24 (containing ethyl benzene, toluene and styrene) is recycled and mixed with fresh ethyl benzene before the reactor. The bottom product of T-502 leaving in Stream 28 constitutes the styrene (with small amounts of ethyl benzene and toluene) leaving Unit 500.
Pre-Heater
Separator
99% Styrene
Styrene plant
MASS BALANCE AND ENERGY BALANCE:
C6H5CH2CH3 C6H5CHCH2 + H2. (1) Ethyl benzene styrene C6H5CH2CH3 + H2 C6H5CH3 + CH4 .(2) Ethyl benzene toluene methane
Molecular weight of Ethyl benzene = 106 Molecular weight of Styrene = 104 Molecular weight of Benzene = 78 Molecular weight of Toluene= 80
The plant capacity for ethyl benzene plant =30 tones per day
Styrene produced =
(30*1000) / 24 (kg/hr) *(104/106) (1/kg) *(1/104) (kmol)
=11.8 kmol/hr
Since we are using gas phase dehydrogenation process for styrene production, for which yield and conversion are as follows: Yield=90% Conversion=65% (w.r.t ethyl benzene) Now consider FBR for Styrene plant
It means that some of ethyl benzene had converted in to toluene and methane(side reaction will occurred <10%) rest ethyl benzene are unconverted and it is recycled. Material balance of reactor Input: Ethylbenzene : 13.4 kmol/hr Output Ethyl benzene: 1.3 kmol/hr Styrene : 11.8 kmol/hr Hydrogen : 11.5 kmol/hr Toluene : 0.27 kmol/hr Methane : 0.27 kmol/hr
Material balance over Toluene column Input Ethyl benzene: 1.3 kmol/hr Styrene :11.8 kmol/hr Toluene :0.27 kmol/hr Output Toluene
:0.27 kmol/hr
Material balance over final purification column Input Ethyl Benzene:1.3 kmol/hr Styrene Output Ethyl Benzene :1.3 kmol/hr Output Styrene:11.8 kmol/hr :11.8 kmol/hr
ENERGY BALANCE Estimated heat capacities at different temperature: In the reactor the inlet feed temp is 6600C where the outlet temp is 6000C. Hence for the energy balance about the reactor it is assumed that the physical properties are constant, Ie values at average temp (600+660)/2 = 6300C. CP of steam at 6300C= 2.223 kJ/kg k CP of EB at 6300C = 2.827 kJ/kg k CP of styrene at 6300C = 2.610 kJ/kg k Heat of raction = HR|25 =129.4 kJ/mol
Heat of formation (HR)= HR|25 + ( i* CPi)|PORDUCT -(i*CPi)|REACTANT
STEAM REQUIREMENT: Let m is the mass of steam added to the feed per hour, in order to supply the heat of reaction in the reactor .The steam and the reactant feed entered the reactor at a temperature 6600C and leave at 6000C temperature. Hence, it can be assumed that the temperature drop solely due to the reaction the approx. energy balance is made; m*CPw*T +mST* CPST*T + mEB*CPEB *T + QR = 0 From the above balance the steam flow rate been calculated as; m*2.223*(660-600) +122.97*2.613*(660-600) +1422.68*2.827*(660-600)+86.99*11.8 m= 10948.07 kg/ hr Henceforth the mol ratio of steam to hydrocarbon feed is approximately calculated = 20:1
TEMPERATURE OF THE PREHEATED STREAM: Let T be the temp of the preheated coming out of the preheater. Assume the mixing of the steam to hydrocarbon stream is adiabatic.
It is known that the temperature of the preheated steam is 8000C and after mixing with the hydrocarbon stream, the temperature is dropped to 6600C. Therefore, the heat balance can be given as: 10948.07*2.293*(800-660)=(1450.5*2.133+4638.5*2.267)(660T) i.e., T= 401.730 C TEMPERATURE DETERMINATION OF THE REACTION PRODUCT LEAVING THE PREHEATER: Again, from mass balance about the reactor the wt fraction or composition of the stream leaving the reactor can be given as: Steam= 47.64% EB = 13.95% Styrene=36.63% Toluene= 0.67% Benzene= 0.38% Hydrogen=0.73% Therefore the average Cp value been determined=2.322 kJ/kg k & the Cp value for the feed stream to the reactor= 2.235 kJ/kg k
The boiling point temp of the feed mixture at atmospheric pressure is calculated by using Roults law is=1380C And the latent heat of vaporization of the mixture= 341.03 kJ/kg. The Cp value for the liquid mixture = 1.939 kJ/kg k Let the outlet temp of the product stream from the preheater=t Therefore, the approx energy balance can be given as: 17036.97*2.322*(630-t)= 6088.9*(1.939*(13830)+341.03+2.235*(401-38)) i.e., t=472.90C WASTE HEAT RECOVERY The excess of superheat from the stream leaving the reactor and through steam preheater, is been utilized in generating steam in boiler, which further fed back to the reactor system. The temp of the product stream leaving the preheater=472.90C & Cp value of the stream is =2.322 kJ/kg k Let the boiler operated at a temp of 1000C
The water feed to the condenser is at temp= 400C The latent heat of vaporization of water at 1000C is= 2260 kJ/kg Therefore the amt. of steam generated is: 17036.97*2.322*(472.9-100) = M*(4.184*(100-40)+2260) ie, M=5874.72 kg/hr hence the amount of steam been generated= 5874.72kg/hr
ENERGY REQUIRED FOR SUPER HEATING OF STEAM: The steam is been heated to a temperature of 8000C in the super heater. The specific heat of steam at 4000C = 2.065 kJ/kg k Therefore the heat requirement in the super heater= Q= (10948.07/3600)*2.065*(800-100) = 4395.95 KW
The catalytic dehydrogenation of ethyl benzene and found that with a certain catalyst the rate could be represented by certain catalyst. C6H5CH2CH3C6H5CHCH2 + H2 (1) Ethyl benzene styrene The global rate was given as
rp= k(pe 1/k*(psph)) where, pe= partial pressure of ethylbenzene ps= partial pressure of styrene ph=partial pressure of hydrogen the specific reaction rate and equilibrium constant are logk = - 4770/T + 4.10
where k is the pound mole of styrene produced per hr/(atm)(lb catalyst) and T is degree kelvin
Temperature, T(c)
400 500 600 700
K
.0017 .0025 .0023 .0014
It is desired to estimate the volume of reactor necessary to produce 30 tones of styrene par day, using vertical tubes 4 ft in diameter, packed with catalyst pellets, consider this problem by taking into account the side reaction producing benzene and toluene. However to simplify the calculation in this inductor example, supposed that the sole reaction is the dehydrogenation to styrene, and there is no heat exchange between the reactor and the surrounding. Assumed that under normal operation the exit conversion will be 65%. However also prepare graphs conversion and temperature vs catalyst bed depth, up to equilibrium conditions. The feed rate per reactor tube is 13.5 lb moles/hr for ethylbenzene and 270lb moles/hr for stem. In addition
Temperature of mixed feed entering reactor =625 c Bulk density of catalyst as packed =90 lb/cu ft Average pressure in rector tubes =1.2 atm Heat of reaction = 60000 btu/lb mole Surrounding temperature = 70 F The reaction is endothermic, so that heat must be supplied to maintain the temperature. Energy must be supplied by adding stream to the feed to provide a reservoir of energy in its heat capacity. In this problem the operation is adiabatic and the energy balance is given by : (F/M)(-H)dx =FtCpdT .(01)
Since x refers to the conversion of ethylbenzene, F/M =13.5 lb moles/hr. As there is large access of steam, it will be satisfactory to take Cp=0.52 then the heat capacity of the reaction mixture will be FtCp=(270*18 + 13.5*106)(0.52) = 3270 Btu/F Substituting numerical value in equation (01), we obtain
Where T is in degree and 625c isthe entering temperature of the feed. The weight of catalyst expressed as :dW = pBAcdz
Ac= Cross sectional area So we get, FdX= rppBAcdz
(03) (04)
dz = F/(rppBA)
dz = 13.5dx/(90*0.78548*16)(rp) =(.0119/rp)dx
The partial pressure can be expressed in term of the conversion as follows. At any conversion x the mole of each component are Steam= 20 Ethyl benzene =1-x Hydrogen = x
Total moles = 21 + x
Then, pe= (1-x)*(1.2)/(21+x) ps = ph= x*(1.2)/(21 +x) then the total equation becomes rp =1.2*k*[(1-x) (1.2*x2)]/K*(21+x))/(21+x) ...(05) or, with the expression for k determined by wanners and Dybdal,
rp =1.2*(12600)*e-(19800/T)[(1-x) (1.2*x2)/K*(21+x)] .(06) Substituting this value of rpin equation (06) gives the expression for the catalyst bed depth in terms of the conversion and temperature, dz=((21+x) *e(19800/T)/(1270000))* [(1-x) (1.2*x2)]/K*(21+x)]-1dx (07) Equation (02) and (07) can be solved numerically for the bed depth for any conversion. If the coefficient of dx in equation (07) is designated as then we may wright eq. (07) as: z = x ..(07)
At, z =0, x=0 and T=625c o = (21/(1270000))*e12.25*(1/(1-0)) =3.30 If an increment x of 0.1 is chosen, the temperature at the end of the increment is, from equation (02), T1 = 1616 248(0.1) =1591 R =611c Then at the end of the first increment 1 =((21+0.1) *e(12.43)/(1270000))* [(1-0.1) (1.2*0.12)]/0.28*(21+0.1)]-1=4.65 (Note: In the exponential term T has been converted to degree Rankine. The value of K is estimated to be 0.28 at 1591 R from the tabulation of data. ) The bed depth required for the first increment is given by eq. (07) as z = (3.30 + 4.65)*(0.1)/2 = 0.4 ft Proceeding to the second increment, we find T2 =1616 248*(0.2) = 1566 R =597c
2 =((21+0.2) *e(12.66)/(1270000))* [(1-0.2) (1.2*0.22)]/0.22*(21+0.2)]-1= 6.60 z2-z1= x = (1 +2)*(0.1)/2 =(4.65+6.60)*(0.1)/2 =0.56 ft z2=0.4 +0.56= 0.96 The of further calculation are shown in table: Conversion 0 0.1 0.2 0.3 0.4 0.5 0.55 0.6 0.65 0.69 Temperature(c) Catalyst bed depth(ft) 625 0 611 0.4 597 0.96 584 1.75 570 2.93 556 4.84 549 6.30 542 8.5 536 13.2 530
The rate of reaction becomes zero at conversion about z=0.69 and a temperature of 530 c, as determined from equation (02) and (04) from the figure it is found that a bed depth of 3.8 ft is required for a conversion of 65%.
The production of styrene from each reactor tube would be, Production/tube = 13.5*(104)(0.65)(24)=21,902 lb/day Production/tube= 9.94 tons/day Hence three 4 ft diameter reactor tubes packed with catalyst to a depth of at least 3.8 ft would be required to produced 30 tons/day of styrene.
model developed for the ethylbenzene dehydrogenation consists of nonlinear simultaneous differential equations in multiple dependent variables. The parameters were estimated from the minimization of the multiresponse objective function which was performed by means of the Marquardt algorithm. The significance of the individual model parameters was tested by comparing the estimate bj with its standard deviation. The estimate was significantly different from zero and effectively contributes to the model. The kinetic model with set of estimated198 parameters yielded an excellent fit of the experimental data. The final estimated values of the adsorption enthalpies and entropies was tested and validated using the physicochemical criteria proposed by Boudart. The intrinsic kinetic parameters were used to simulate 3-bed adiabatic industrial reactor with axial flow and radial flow using the heterogeneous fixed bed reactor model. Kinetic experiments for the formation of minor by-products, such asphenylacetylene, -methylstyrene, -methylstyrene, cumene, npropylbenzene,divinylbenzene, and stilbene revealed that the phenylacetylene selectivity did not depend on the total ethylbenzene conversion. The selectivity of stilbene was highly increased with increasing temperature. The selectivity of divinylbenzene was so low (below0.01%) at all the reaction conditions that no correlation with the ethylbenzene conversion was made. The selectivities of other minor by-products decreased with increasing the total ethylbenzene conversion. More research efforts can be contributed to the following recommendations for future work: 1. Experimental study for the coke formation and gasification using an
electrobalance to estimate the kinetic parameters for the coke formation and gasification, which leads to determine the dynamic equilibrium coke content. 2. Process optimization of ethylbenzene dehydrogenation to determine an optimal reactor configuration and operating conditions, such as a molar ratio of steam to ethylbenzene, pressure, and temperature. 3. Empirical kinetic model for the production of minor by-products which correlates the selectivity with the total ethylbenzene conversion.
References:
Chapter 22, Introduction to Multicomponent Distillation, Unit Operations of Chemical Engineering, by McCabe-Smith-Harriott, 6th Edition, Published by McGraw . Hill International Edition, Chemical Engineering Series. Chapter 8, Process Design of distillation Column, Introduction to Process Engineering & Design, Second reprint 2009, Published by, Tata-McGraw-Hill Publishing Company limited, New Delhi. Chapter 6, Costing & Project Evaluation, Coulson & Richardsons volume 6, Third Edition, Chemical Engineering Design, By R.K.Sinnot, Publisher by Butterworth- Heinemann Publications. Chapter 11, Separation Columns, Coulson & Richardsons volume 6, Third Edition, Chemical Engineering Design, By R.K.Sinnot, Publisher by Butterworth-Heinemann Publications. Chapter 10, Process Design of Reactors, Introduction to Process Engineering & Design, Second reprint 2009, Published by, Tata-McGraw-Hill Publishing Company limited, New Delhi. Process Equipment Design, By M.V. Joshi & V.V. Mahajani, Third edition, published by McMillan India Limited. Kirk Othmer Encyclopedia of chemical Technology 4th Edition. Ullmanns Encyclopedia, Industrial Organic Chemicals, Volume 4 Chemical Weekly Buyers Guide 2005. SAXs Dangerous Properties of Industrial Materials. Hydrocarbon Processing. Basic Principals & Calculations in Chemical Engineering, David M. Himelblau, 6th Edition,