Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 5(8), 48-52, August (2015) Res. J. Chem. Sci. International Science Congress Association 48 Synthesis of 2-Ethylhydroanthraquinone for the Production of Hydrogen Peroxide in a Catalytic Slurry Reactor: Design CaseFayyaz Khan M., Qudsia Ramzan, Ahmad Mukhtar, Umar Shafiq and Ali Feroz Khan2 Material Division, Pakistan Institute of Nuclear Science and Technology, PAKISTAN Department of Chemical Engineering, NFC Institute of Engineering and Fertilizer Research Faisalabad, PAKISTANAvailable online at: www.isca.in, www.isca.me Received 20th July 2015, revised 4th August 2015, accepted 16th August 2015 AbstractThe demand of hydrogen peroxide in the international market is increasing because of its one of the most environment friendly chemical feature which is available in different grades with a wide range of applications. According to the demand in international market 3000kt/year is being produced by a traditional autoxidation method which is known as 2-ethylanthraquinone process. The purpose of this research is to design a catalytic slurry reactor which give maximum efficiency of hydrogenation reaction for this purpose we perform a list of experiments inthe synthesis of 2-ethylhydroanthraquinone for the hydrogen peroxide production in a catalytic slurry reactor in the lab. Catalyst is available in the spherical form and some useful data is collected some from experiment and some from literature and a design of slurry type catalytic hydrogenator is present in this paper. Keywords: Hydrogen peroxide, 2-Ethylanthraquinone, catalyst, slurry reactor. Introduction Hydrogen peroxide (H) in widely used in almost all industrial areas, particularly in chemical industry and environment protection. One of the most important feature of the hydrogen peroxide is that is usage does not yields any secondary pollution and it has a wide range of applications as rocket propulsion fuel, paper making, chemical synthesis, environmental protection, food processing, medical sterilization and other fields. It is the only one germicidal agent composed of hydrogen and oxygen. 2-Ethylanthraquinone (2-EAQ) is a key component of anthraquinone process for the production of hydrogen peroxide, pharmaceuticals, and many other useful chemicals. With the increasing demands of hydrogen peroxide in the international market it needs to increase the production of 2-ethylanthraquinone (2-eaq). Slurry reactors are three phase reactors, meaning that they can be react solids, liquids and gases simultaneously. They can operate in either semi batch or continuous mode. In this well-established Anthraquinone process for the production of hydrogen peroxide first of all the key component 2-ethylanthraquinone is hydrogenated in a catalytic slurry reactor which produce 2-ethylhydroanthraquinone and the further air oxidation of 2-ethylhydroanthraquinone yields hydrogen peroxide along with the regeneration of the key component 2-ethylanthraquinone. We use palladium-alumina supported catalyst in the spherical form is used in this research. Previous research shows that when we use palladium alumina-silica catalyst then results shows that activation energy increases as the particle diameter of the catalyst which is available in the spherical is decreases. The hydrogenation of 2-ethylanthraquinone in a catalytic reactor that the reaction rate is very high and the mass transfer layers are come into existences due to three phase catalytic reaction. we calculate the gas-liquid and liquid-solid co-efficient are calculated. Reaction Mechanism Previous research shows that the hydrogenation of 2ethylanthraquinone is zero order reaction with respect to hydrogen and 1st order reaction with respect to the 2-ethylanthraquinone7-10. The reaction on silica-alumina supported palladium catalysts PD/AL-SI (pd 2%) is very fast. previous research on the 2-ethylanthraquinone hydrogenation demonstrate that when we use hydrogen as a key component it follows zero order kinetics and when we use 2-ethylanthraquinone as a key component it follows the 1st order kinetics11. A 2-ethylhydroanthraquinone (2-EHAQ) which is generated before from the corresponding 2-ethylanthraquinone (2-EAQ) by catalytic hydrogenation with silica-alumina supported palladium catalysts pd/al-si (pd 2%) and the organic phase react under formation of the anthraquinone and hydrogen peroxide12. Research Journal of Chemical Sciences ___ ______________________________ Vol. 5(8), 48-52, August (2015) International Science Congress Association Design Calculations We select a slurry type semi batch reactor for this research Figure-1 Following catalysts can be used: Raney Nickel catalyst Palladium– alumina catalyst, Chromium Nickel catalyst The selected catalyst is Palladium– alumina catalyst. properties of the selected catalyst are given in table Table-1 Mass Transfer Resistances Name 5% Palladium Alumina Catalyst Particle Diameter d 25×10 Catalyst Density p 1500 Kg/m Catalyst Loading W 0.0001 Kg Kg The Mass Transfer Resistance is given by this relation ______________________________ ___________________ Association We select a slurry type semi batch reactor for this research Following catalysts can be used: Raney Nickel catalyst alumina catalyst, Chromium Nickel catalyst alumina catalyst. The properties of the selected catalyst are given in table -1 Mass Transfer Resistances 5% Palladium - Alumina 25×10 - 6 m 1500 Kg/m 3 0.0001 Kg Cat Kg Liquid-1 The Mass Transfer Resistance is given by this relation 13. Also we know that: 1/W = 1/0.0001 = 10000, For 5% palladium-alumina catalyst, 1/w = 10000 × 0.05 so: 1/w = 500 and for 1000 rpm, from graph 0.032 m mole-1 sec. Also: H enry constant for hydrogen = h = 1.2821 m mole-1 atm. P artial pressure of hydrogen gas = p 1.2 atm. P ut all of these values in above equation we get \r  \r\r   \r\r \r  \r \r  \r Specific Surface Area: The specific surface area of catalyst is given by this relation13.  "   ! " As we know that: catalyst loading = w catalyst particle diameter = d = 25×10 density of ethyl-anthraquinone =  # catalyst density =  = 1500 kg/m Put all of these values in above equation we get  \r &  "  & "  \r'%'&    \r (%  (\r% )+\n,\n-.,01231 Thiele Modulus: Thiele Modulus is given by the formula 57 9::\r As we know that14: L = R/3 = d /6 = 25×10 Rate Constant14 = k = 3.2×10-6 m Kg Now also we know that15:  \r Reaction Temperature = T = 60 C = 333.15 K So put the value in the above equation in order to calculate the diffusivity of hydrogen gas ___________________ _______ ISSN 2231-606X Res. J. Chem. Sci. 49 (1) = 1/0.0001 = 10000, For 5% = 10000 × 0.05 = 500 and for 1000 rpm, from graph 13. We find c = enry constant for hydrogen = h = artial pressure of hydrogen gas = p h2 = ut all of these values in above equation we get specific surface area of catalyst is (2) catalyst loading = w = 0.0001 kgcat kgliquid-1, = 25×10 -6 m # = 1231 kg/m, Put all of these values in above equation we get " Thiele Modulus is given by the formula 13. (3) /6 = 25×10 -6/6 = 4.1666×10-6 Kg -1 sec.-1 \r & *=?@AB D = 333.15 K the value in the above equation in order to calculate the Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(8), 48-52, August (2015) Res. J. Chem. Sci. International Science Congress Association 50 \r & *=E*F///\rE \r & *=H\rE*E\r & * \r  \r  & *) or  \r  & Now put all of these values in the above equation in order to calculate the Thiele Modulus we get \r%%% \r & \r  &  \r%%% & \r \r  & \r%%% &'\r&' \r%%% %'%\r'\r&  \r Effectiveness Factor: The effectiveness factor is given by the formula13. ,\nLM4 (4) Put the value of thiele modulus in above equation in order to calculate the effectiveness factor of catalyst. OPQ \r  \r  \r Rate of Reaction: Basis = 1 hour Operation, The Rate of Reaction is given by the Formula16. STU%&\r%=?@V\rBW@XC D (5) Where: General gas constant = R = 8.314 J mole-1 K-1, Partial pressure of hydrogen gas = PH2 = 1.2 atm, reaction temperature = T = 60 C = 333.15 K, Put all these values in above equation in order to calculate the rate of reaction we get STU%&\r%=Y\rFHZ\r/H///\rE D\r*STU%&\r%=*F\rHH[*Z*YYZ\rZF STU%&\r%=F\rFFY/ESTU%&\r% \r((%STU%&\r(( )\] )/QROr STU \r  )\] )/Volume of Reactor: The volume of reactor is given by the formula14. d (6) We want to design our Reactor for 80% Conversion so. Conversion = X = 80% = 0.8 Hydrogen Flow Rate = V = 2 L/min = 0.0000333 m/sec. Initial concentration of ethyl-anthraquinone = CAo= 2.795×10-4mole/cm = 2.795×10 mole/cm = 2.795 mole/mAs we know that Molar feed rate = FAo = CAo × V = 0.0000333×2.795 = 0.0093 mole/sec. Now put the values in the above equation in order to calculate the volume of reactor we get. \r ( \r \r  \r \r   \r ( \r ' \r  \r ' \r   \r)Area of Cooling Jacket: The Area of Jacket which is in the form of Annulus can be calculated by this formula17. iR(7) Also we know that. eQ (8) For reactor the rule of thumb is. L/D = 3 L = 3D Put in volume formula we get Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(8), 48-52, August (2015) Res. J. Chem. Sci. International Science Congress Association 51 e;Put D = 2r we get e%Re%Put the values we get. \r%\rR \r\rR \r\r  \r R \r  R \r'( )Let the inner diameter of outer pipe is: R = 0.5 m Put in the above equation to fine out the area of jacket we get. \r \r&i \r'(\r \r&i \r '\r \r' \r&  )As we know that: lnoioq (9) Where: Overall heat transfer co-efficient18 = U = 65 Btu/hr.ftF (for cooling water and organics), area of jacket = = 0.54008 m, water entering temperature = TJ1 = 301K, water leaving temperature = tj2 = 312k, average temperature = T = (TJ1 + TJ2)/2 = (301 + 312)/2 = 306k, reaction temperature = = 60 c = 333.15 K Put the value in above equation we get %& \r& \r&i %&\r &'\r&(&\r % rOsQR Now as we know that )nog*iogq (10) Put the values we get (&\r %)\ri (&\r %)&\r()(&\r %&\r( ) \r' tQR Material of Construction: The selection criteria for the reactor construction material are tensile strength, temperature conditions, corrosion resistance, cost. Because of better tensile strength, useful at temperature greater than 700F, good corrosion resistance and cheaper we select stainless steel (ss) as a reactor construction material19. Specification Sheet Hydrogenation efficiency increase with the increase in the pressure anddecrease with the increase in liquid hourly space velocity (LHSV)20. Table-2 Effect of Pressure and LHSV Reactor Name Slurry Stirred Semi Batch Reactor Mass Transfer Resistance  \r     Specific Surface Area ( \r % ) * +\n,\n-., ) / 01231 Thiele Modulus \r  Effectiveness Factor  \r Rate of Reaction \r  )\] )  /    Volume of Reactor \r  ) / Area of Jacket \r &  ) Flow Rate Through Jacket  \r ' t u QR Material of Construction Stainless Steel Results and Discussion We find a reactor size of 0.411m for 80% conversion of the hydrogenation reaction at 60c at atmospheric pressure. Which the optimized reactor size with construction material stainless steel (SS) and catalyst silica-alumina supported palladium catalysts Pd/Al-Si (Pd 2%). Conclusion In this research we conclude that we got maximum conversion of 2-Ethylanthraquinone in to 2-Ethylhydroanthraquinone with the optimized reactor size of 0.411m in the presence of Palladium Alumina-Silica (Pd 2%) supported catalyst in a Slurry Reactor. Due to three phase chemical reaction we recommend Slurry Reactor with the catalyst in spherical form having effectiveness factor 1. Due to multiphase chemical reaction Gas-Liquid and Liquid-Solid Mass Transfer layers are also come into existences which are measured accurately. Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(8), 48-52, August (2015) Res. J. Chem. Sci. International Science Congress Association 52 References 1.Jose M., Campose-Martin, Gema Blanco-Brieva and Jose L.G. 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