Design Lab 2

Production of Phenol

CL 457
Department Of Chemical Engineering INDIAN INSTITUTE OF TECHNOLOGY, BOMBAY

Group: A12 Sourabh Biswas Rohit Bharti Sri Vivek K Puneet Singhla 09002044 09002048 09002059 09002061

2 Uses 1.4 Cumene Oxidation process 3.2 Chlorobenzene process.3 Rasching Hooker process 2.3.4 World Market 2.1 Chemical properties 1.2 Physical properties 1.3. Kinetics . Methods of Production :2. Process Details 4. Introduction : -Phenol 1.3 Properties 1. 2.INDEX 1.1 Literature Survey 1.1 Sulphonation process 2.

The molecule consists of a phenyl group (-C6H5) bonded to a hydroxyl group (-OH). The main chemical intermediates and derivatives of phenol are bisphenol-A (BPA). The largest market for phenol is BPA which has been driven by the strong growth in polycarbonate resins. is an organic compound with the chemical formulaC6H5OH. alkylphenols. but requires careful handling due to its propensity to cause burns Uses Phenol and acetone are two basic chemicals to manufacture derivative products which eventually become essential ingredients in numerous beneficial products that consumers use every day. It is mildly acidic. aniline and adipic acid. It is a white crystalline solid at room temperature. recordable CDs and digital versatile discs (DVDs). flooring and paving . caprolactam. It has to be handled with great care because it causes immediate white blistering to the skin. Phenol also known as carbolic acid is an organic compound that contains a six-membered aromatic ring. Pure phenol is a white crystalline solid. It is produced on a large scale as a precursor to many materials and useful compounds.Literature Survey Phenol. The driving force in polycarbonate demand had been growth in optical media such as compact discs (CDs). which is used to make polycarbonate (PC) and epoxy resins. adhesives. phenolic resins. The crystals are often rather wet and discolored. smelling of disinfectant. electricalelectronic laminates. bonded directly to a hydroxyl group. BPA’s other main derivative is epoxy resins which are used in high performance coatings. The main route being practiced presently involves the partial oxidation of cumene (isopropylbenzene) via the Hock rearrangement. also known as carbolic acid and phenic acid. CD-ROMs. There is a large commercial importance of Phenol and many methods have been developed for its production.

boiling point of phenol (molecular mass = 94) is 453 K while that of toluene (molecular mass = 92) is 384 K.) 1. However. The higher boiling point of phenols is due to the presence of intermolecular hydrogen bonding in them. Phenols boil at higher temperatures than the arenes of comparable molecular masses.473415e-005 1.) 3.463(mmHG) 2. they become colored due to slow oxidation with air.09 psi ( 55 °C) n20/D 1. colorless Liquid Faint yellow 8 g/100 mL 41℃ Air & Light Sensitive Chemical reactions of Phenol :– i.071 g/mL at 25 °C(lit.24 (vs air) 0. . which is a characteristic to the existence of keto-enol tautomerism in phenols (predominantly enolic form). Phenol has characteristic odors and is sparingly soluble in water but readily soluble in organic solvents such as alcohol and ether. For example.Physical Properties of Phenol .082 9. Physical Properties :Molecular Weight (g/mol) Solubility @ 20-25 degC (mg/L) Vapor pressure @ 20-25 degC Henry's Law constant @ 20 degC Sorption coefficient (log L/kg) Koc Octanol-water partition coefficient Diffusion coefficient in air (cm^2/s) Diffusion coefficient in water 94.24 1. Reaction with FeCl3 : Phenol gives violet coloration with ferric chloride solution (neutral) due to the formation of a colored iron complex.) 182 °C(lit.5128 (log L/kg) 0.1e-006 (cm^2/s) Chemical properties Mp Bp Density Vapour density Vapour pressure Refractive index FEMA 40-42 °C(lit.11304 87000 0.53 3223 Storage temp Solubility Form Colour Water Solubility Freezing point Sensitive 2-8°C H2O: 50 mg/mL at 20 °C.    Value Phenols are colorless crystalline solids or liquids. clear.

Phenol reacts with alkyl halides in alkali solution to form phenyl ethers (Williamson’s synthesis). benzene is obtained. Reaction with PCl5 :. The phenoxide ion is a nucleophile and will replace halogenation of alkyl halide. C6H5OH + PCI5 → C6H5CI + POCI3 + HCI 3C6H5OH + POCI3 → ( C6H5 )3 PO4 +3HCl v.O .Phenol reacts with PCl5 to form chlorobenzene. C6H5OH + Zn → C6H6 + ZnO . Reaction with zinc dust : When phenol is distilled with zinc dust. Ethers are also formed when vapours of phenol and an alcohol are heated over thoria (ThO2) ThO2 C6H5OH + HOCH3 ———→ C6H5 .This is This is the test of phenol. iii. The yield of chlorobenzene is poor and mainly triphenyl phosphate is formed.CH3 Methoxy benzene iv. ii. Ether formation :.

Action of P2S5 : By heating phenol with phosphorus penta sulphide. sodium hydroxide and hydrogen gas and so are not in use. Today cumene oxidation process is the only commercially significant route for the production of phenol. Reagents : Usually NaOH. This is a useful industrial method for the synthesis of phenol. 300-350 oC followed by an Chlorobenzene process. Reagents : Usually NaOH. This process also gives a very important co-product acetone. mostly using benzene as the starting point. but the energy required and quantities produced meant this method could not be sustained. Rasching Hooker process. Chlorobenzene process. Synthesis by the sulphonation of benzene was implemented by BASF in 1899 and continued until the 1960s. The reaction occurs via the eliminationaddition mechanism via a benzyne intermediate. . Elimination of HCl creates the benzyne that then undergoes addition of H2O to produce the phenol. Reaction with ammonia : Phenol reacts with ammonia in presence of anhydrous zinc chloride at 300°C or ( NH4 )2 SO3 / NH3 at 150°C to form aniline. thiophenols are Production methods: Phenol was first manufactured commercially by distillation from coal tar. though these also used reagents like chlorine. and used aggressive reagents. iv. ii. This reaction gives very low conversions as compared to other methods hence not considered for an industrial plant. One of its main disadvantages is the poor atom economy of the reaction. a factor that has become increasingly important as the chemical industry seeks to develop more sustainable processes. were developed. Sulphonation process. Cumene Oxidation process. and so several other methods. The sulphonation route produced large quantities of waste. This conversion of phenol into aniline is called Bucherer reaction. 350 oC followed by an acidic work-up to neutralize the phenoxide. The industrially important methods of manufacture of phenol are the following : i. Zncl2 C6H5OH + NH3 ————→ C6H5NH2 + H2O 300o C vii. iii. Sulphonation process : Phenol is made from Benzene sulphonic acid:This is a useful industrial method for the synthesis of phenol.vi.

the catalyst must be regenerated frequently. all plants using this technology have been shut down. Starting with benzene and propene. . and Poland.15%. Due to carbon deposition. Italy. however. Cumene Oxidation The main method used to manufacture phenol since the 1960s has been through the oxidation of 1methylethylbenzene. In the Raschig-Hooker process. including Argentina. India. commonly called cumene. The conversion is about 10. This is one reason why alternative processes are being developed. the whole process includes three steps. hydrolysis takes place catalytically over Ca3(PO4)2/SiO2 with H2O at 400-450°C.Rasching Hooker process. Although there is a market for propanone as a solvent. combined with the fact that it is a three-step process with a potentially explosive intermediate. with an overall selectivity of 70-85% for both steps. this classical chlorobenzene/phenol route is still used to some extent in several countries. In the USA. which is made from benzene. demand for phenol is rising faster than demand for propanone. The possibility of converting excess propanone to propene for re-use is being explored by some companies. with the only other major product being propanone (acetone).

org. In a similar way the Indian installed capacity for acetone is around 50. Dynachem Inc. flooring and paving applications. The Indian demand for phenol was around 177000 per annum last year. Shell Global Solutions. accounting for 95% of production (2003). There is an ample space and growth potential for phenol and acetone.. Top Market players in phenol production Alfa Aeser.000 metric tonnes per annum and the installed capacity for acetone is 51600 metric tonnes per annum. adhesives. caprolactam. phenolic resins. The driving force in polycarbonate demand had been growth in optical media such as compact discs (CDs).htm Sulphuric acid is used as catalyst.. many methods have been developed for its production. electrical-electronic laminates. aniline and adipic acid.jazdchemicals. and composites. BPA’s other main derivative is epoxy resins which are used in high performance coatings. Cellmark US Inc. etc. Cellmark US Inc. etc. Hence new capacities have to be created to meet the new demand. involves the partial oxidation of cumene (isopropylbenzene) via the Hock rearrangement Market analysis:The main route being practiced presently involves the partial oxidation of cumene (isopropylbenzene) via the Hock rearrangement. CD-ROMs. which is used to make polycarbonate (PC) and epoxy resins.htm .greener-industry. Plant capacity: 86000 metric tons Link: http://www. The dominant current route. The main chemical intermediates and derivatives of phenol are bisphenol-A (BPA).Because of phenol's commercial importance. http://www. The projected demand supply gap for acetone is around 67500 metric tonnes per annum in 2014-2015. The largest market for phenol is BPA which has been driven by the strong growth in polycarbonate resins.com/chemyellowpages/leaf/Organic-Compounds/Phenol. The projected demand supply gap for phenol is around 152600 metric tonnes per annum in 2014-2015. The Indian demand for acetone was around 117500 per annum two years back. are some of the leading names in the production of phenol. Dynachem Inc. recordable CDs and digital versatile discs (DVDs).uk/pages/phenol/4PhenolProdMethSum. alkylphenols. Top Market players in phenol production Alfa Aeser. are some of the leading names in the production of phenol. Shell Global Solutions.

Kinetics :In the absence of external mass transfer and internal diffusion limitations. the addition of dimethylphenylcarbinol to phenol to formcumylphenol. acid. The reaction parameters. It undergoes a free radical chain reaction. other side reactions occurr such as cleavage of dicumylperoxide. The acidity is neutralised to avoid CHP cleavage and phenol formation even in limited concentration (tenths of ppm). which would trap the radicals and reduce the oxidation efficiency Cumene Hydroperoxide Concentration and Cleavage to Phenol & Acetone After the CHP concentration section is designed the solution is cleft in presence of small amount of acid catalyst to give phenol and acetone at temperature at around 60°C. further development of the actual reaction mechanism was undertaken. The various steps involved during the decomposition reaction are as follows: chemisorption of cumene hydroperoxide (A) on a vacant catalytic site (S) . acetone and phenol are purified in separate sections. like temperature. the dehydration of dimethylphenylcarbinol to alphamethylstyrene. water concentration and residence time. The by-products production is enhanced with CHP concentration and temperature increases. A Langmuir–Hinshelwood type of mechanistic model with adsorption of cumene hydroperoxide on the catalytic site was assumed to prevail on the basis of the observations. to maximise the reaction efficiency. Beside the main reaction. Alphamethylstyrene can be purified or recycled via hydrogenation to cumene. initiated by the presence of small amounts of CHP. the coupling and dehydration of acetone to mesityloxide. by phisical and extractive distillation. therefore these two parameters are carefully controlled and optimisation criteria are employed in order to maximise CHP selectivity in the proprietary natural recirculation reactors.Process Details :Cumene Oxidation to Cumene Hydroperoxide The cumene oxidation is in liquid phase with air at medium pressure and temperature around 100°C. have to be well controlled with the aid of proprietary reactor models. Distillation section After neutralisation of the cleft product. Therefore. High capacity phenol plants/lines (200 kt/y) can be implemented with a catalytic cracking section in order to minimize the amount of heavies produced. the decomposition could be controlled by one of the following steps. namely (a)adsorption (b) surface reaction or (c) desorption.

Thus.Desorption of phenol from the surface: If the rate of reaction controls then the following equation can be derived By substituting for CS. the following equation holds: where kt is a constant and w the catalyst loading If both A and B are weakly adsorbed. we get: If the reaction is far away from equilibrium. then: Typically. then summation CiKi= 1: The prices of all the raw materials involved were obtained from Sigma Aldrich . the total catalytic site concentration is proportional to the solid loading.

4 0. 204.162 64.54211 0 904.011983 64.415.026621 0 0 39.888636 0. 6.45 for 6x500ML.68 for 25G(particle size 1.38103 .53362 0. Zeolite catalysts cost Rs. Material Balance Benzene to Cumene Components m.4 0.38103 1 33.1824 3.4 0 3.621.1 0.1452 904.1.735211 225.016667 41.66 for 1L and Rs.7619 33.225686 0 96.400068 3.44 1914.4 0 39.016667 0. Cumene (98%) and Phenol(98%) are priced at Rs. H2SO4 (95-98% purity) was valued at Rs.6 mm).0344 7.2802 193.190.475.website.54211 0.888636 39.284 24.8 0.284 24.000499 3.8 0.8 0.1 0 0 R1 R2 R2 C1 mole Outlet mole molefra Inlet Outlet Inlet mo 8.695.1 0.380952 0 0 0 0 0 0 32.12 for 2.53362 0.6. Acetone costs Rs.888636 0 64.5KG respectively.4 0.49231 1914.wt (Kg) gm Propylene 42 Benzene 78 Cumene 120 Propane 44 DiPB 162 Heavies(Waste) 204 R1 Inlet 352 2534. 2.0344 7.11 for 1L.

200684191 8.48 0.380952 Benzene 0.53362 0.1 0 0 R1 Outlet moles in pro 0.wt (Kg) gm Propylene Benzene Cumene Propane DiPB Heavies(Waste) R1 Inlet 42 78 120 44 162 204 352 2534.888208 0 0 0.4 0.40114 mass in 0 225.4 moles out 0 2.0156 used 0.016667 .Components m.49231 Cumene 0 prop 0.778037169 32.02127864 0.888636 DIPB 0 Heavies(Waste) 0 41.2802 0 0 64.400068 204 0.7619 moleout 7.8 3.4 0 39.80121 0 0.wt gm 42 78 120 44 162 moles in 0 2.016667 7.001 0.950287 Reactor 2 Components (Kg) Propylene Benzene Cumene Propane DiPB Heavies(Waste) m.

PFD of the Process:- Benzene to Cumene PFD:-Cumene to phenol .

pdf http://www.mhhe.pdf http://www.uk/pages/phenol/4PhenolProdMethSum.uk/webc/HPAwebFile/HPAweb_C/1194947317663 http://www.sciencedirect.greenerindustry.[1] http://www.com/content/dam/shell/static/chemicals/downloads/productsservices/datasheet-phenol.hpa.chemsystems. Since the mid-1990s.html #chlorobenzene Commercial production of cumene is by Friedel–Crafts alkylation of benzene with propylene.References  http://www.static-shell.com/science/article/pii/S0926860X04007562 http://www.com/physsci/chemistry/carey/student/olc/ch24phenolpreparations.indian-chemicals.com/doc/70956648/Phenol-2011-World-Market-Outlook-And-Forecast         .businessstandard.scribd.yarnsandfibers.com/reports/search/docs/abstracts/0506_4_abs.com/it_IT/attachments/azienda/attivitastrategie/petrolchimica/licensing/Fenol o&Acetone-A4-lug09.com/textile_intelligence/textile-pricewatch/benzene-pricetrends-reports http://www.org.com/Technologies/Process-Technologies/KBR-Phenol/ http://www. Previously.com/india/news/petrochemicals-prices-upboiling-crude-oil-prices/186633/on http://www.htm http://www.htm http://www. commercial production has switched to zeolitebased catalysts.com/prices.org.kbr.eni.pdf http://s08. solid phosphoric acid (SPA) supported on alumina was used as the catalyst.

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