Gnie des Procds et Environnement

Project: Filires

Production of Phenol KATHURIA Shubhranshu

INSA de Toulouse

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I would like to thank my tutor, M. Maria Fernandez, and my group partners Gianni Soupe, Logan who helped me finish this project with ease. Without their help and efforts it would have been a really difficult task to accomplish.

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1. Phenol...Page 1 1.a) Introduction. Page 1 1.b) Properties Page 1 1.c) Uses Page 2 1.d) Production. Page 3 2. Cumene Process. Page 4 2.a) Reactions Page 4 2.b) Raw Materials.... Page 5 2.c) Products.. Page 6 2.d) Preparation of Cumene.. Page 7 2.e) Cumene to Phenol Page 9 3. Mass Balance. Page 12 3.a) Preparation of Cumene.. Page 12 3.b) Cumene to Phenol.. Page 14 4. Energy Balance.. Page 15 4.a) Oxydation Reaction. Page 15 4.b) Cleavage Reaction. Page 16 5. Appendix. Page 18 6. Bibliographie.. Page 19

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1.a)Introduction

Phenol, also known as carbolic acid, phenic acid, is an organic compound with the chemical formula C6H5OH. It is a white crystalline solid. The molecule consists of a phenyl (-C6H5), bonded to a hydroxyl (-OH) group. Phenol was first extracted from coal tar, and its major uses involve its conversion to plastics or related materials. Phenols are key for building polycarbonates, epoxies, Bakelite, nylon, detergents and a large collection of drugs, herbicides and pharmaceuticals. It is produced on a large scale (about 7 billion kg/year) as a precursor to many materials and useful compounds. It is only mildly acidic but requires careful handling due to its propensity to cause burns.

Fig.1 Phenol Structures

1.b)Properties
Phenol has a limited solubility in water (8.3 g/100 ml). It is slightly acidic: the phenol molecule has weak tendencies to lose the H+ ion from the hydroxyl group, resulting in the highly water-soluble phenoxide anion C6H5O. Compared to aliphatic alcohols, phenol shows much higher acidity; it even reacts with NaOH to lose H+ whereas aliphatic alcohols do not. Phenol exhibits keto-enol tautomerism with its unstable keto tautomer cyclohexadienone Phenol is highly reactive toward electrophilic aromatic substitution as the oxygen atom's pi electrons donate electron density into the ring.

Molcular mass : 94,11. Density at 20 C : 1,072 g/cm3. Melting Point : 40,8C. Boiling Point : 181,7C.

Viscosity at 45 C : 4,0 mPas. Refractive Index at 45 C : 1,540 Commercial Concentration > 99,8 % by mass.

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1.c)Uses:
Major use of Phenol is as raw material for ptoduction of Bis-Phenol A. Used as a disinfectant and for chemical synthesis. Important intermediate for synthesis of many pharmaceuticals. In perfumery: thymol, estragole, eugenol, vanillin, etc.. In medicine, it is mainly used as a powerful antiseptic. In molecular biology, phenol is used to remove protein extraction protocols in nucleic acids. Preparation of phenolphthalein, a pH indicator familiar to chemists. By action of chlorine gas on phenol, chlorophenols are obtained, such as 2,4,6-trichlorophenol. Used in entomology for the conservation of insect boards against mold.

For the preservation of meat. The use in fine chemicals includes many products that are not synthesized in large quantities, but are of great importance: salicylic acid for the synthesis of aspirin, paracetamol for acetylparaaminophenol, and chlorophenols for herbicides.

1.d)Production
Phenol is one of most widely used products of petrochemical industry. Phenol was discovered in pure state in1834, when it was extracted from coal tar, which remained the primary source until the development of the petrochemical industry. Pure Phenol was first prepared in Laboratory by Laurent in 1841. Because of phenol's commercial importance, many methods have been developed for its production :

Partial oxidation of cumene (isopropylbenzene) via the Hock rearrangement:

C6H5CH(CH3)2 + O2 C6H5OH + (CH3)2CO An early commercial route begins with the reaction of strong base with benzenesulfonate: C6H5SO3H + 2 NaOH C6H5OH + Na2SO3 + H2O
Hydrolysis of chlorobenzene, using base or steam (Raschig-Hooker process):

C6H5Cl + H2O C6H5OH + HCl

Direct oxidation of benzene with nitrous oxide, a potentially "green" process:

C6H6 + N2O C6H5OH + N2

Oxidation of toluene, as developed by Dow Chemical:

C6H5CH3 + 2 O2 C6H5OH + CO2 + H2O

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In this report we are going to study the production of Phenol from Cumene. More than 95% of Phenol is produced by synthesis from Cumene. This process, developed in 1944 by Hock and Lang, has been used since the 1950s. Its advantage is its simplicity of implementation, its good performance (90%) and the fact of obtaining phenol and acetone from cumene (which is obtained in large quantities from petrochemicals). It consists of oxidation of cumene by air producing cumene hyperoxide radical as an intermediate which, in aqueous acidic medium, produces the phenol and acetone.

.CUMENE PROCESS

(THE HOCK PROCESS)

The Cumene process (Cumene-phenol process, Hock process) is an industrial process for developing phenol and acetone from benzene and propylene. The term stems from cumene (isopropyl benzene), the intermediate material during the process. It was invented by Heinrich Hock in 1944 and independently by R. dris and P. Sergeyev in 1942 (USSR). The cumene process, i. e., the proton-catalyzed cleavage of cumene hydroperoxide to Phenol and acetone, was discovered by Hock and Lang in 1944. Although the earliest commercialization was in an 8000 tonne-per-year Gulf plant in Canada in 1953. about 97% of the total synthetic phenol production in the USA until 1987, and 100% in Japan until 1990, was manufactured by this process. At that time, a new process based on toluene was introduced and this route is now used for ahout 91% of phenol production in Western Europe. The world production capacity for phenol using the Hock process is currently about 5106 tonnes per year. Despite the 0.62 tonnes of acetone produced per tonne phenol, this process has dominated because of its economics. This process converts two relatively cheap starting materials, benzene and propylene, into two more valuable ones, phenol and acetone. Other reactants required are oxygen from air and small amounts of a radical initiator. Most of the worldwide production of phenol and acetone is now based on this method. The process uses the following three exothermic reactions : Alkylation of benzene with propylene to cumene; Oxidation of cumene to cumene hydroperoxide; Splitting of cumene hydroperoxide into phenol and acetone.

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2.a)Reactions
Benzene and propylene are compressed together to a pressure of 30 standard atmospheres at 250 C (482 F) in presence of catalytic Lewis acid. Phosphoric acid is often favored over aluminium halides. Cumene is formed in the gas-phase Friedel-Crafts alkylation of benzene by propylene:

Cumene is oxidized in air which removes the tertiary benzylic hydrogen from cumene and hence forms a cumene radical:

This cumene radical then bonds with an oxygen molecule to give cumene hydroperoxide radical, which in turn forms cumene hydroperoxide (C6H5C(CH3)2-O-O-H) by abstracting benzylic hydrogen from another cumene molecule. This latter cumene converts into cumene radical and feeds back into subsequent chain formations of cumene hydroperoxides. A pressure of 5 atm is used to ensure that the unstable peroxide is kept in liquid state.

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 Cumene hydroperoxide is then hydrolysed in an acidic medium (the Hock rearrangement) to give phenol and acetone. In the first step, the terminal hydroperoxy oxygen atom is protonated. This is followed by a step in which the phenyl group migrates from the benzyl carbon to the adjacent oxygen and a water molecule is lost, producing a resonance stabilized tertiary carbocation. The concerted mechanism of this step is similar to the mechanisms of the Baeyer-Villiger oxidation and also the oxidation step of hydroboration-oxidation. In 2009, an acidified bentonite clay was proven to be a more economical catalyst than sulfuric acid as the acid medium.

As shown below, the resulting carbocation is then attacked by water, a proton is then transferred from the hydroxy oxygen to the ether oxygen, and finally the ion falls apart into phenol and acetone.

The products are extracted by distillation.

2.b)Raw Materials
Benzene Propylene Zeolite catalyst Cumene(Prepared from Bezene and Propylene) Phosphoric acid Sulfuric acid

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2.c)Products:
Phenol being the major product, the Cumene process also produces Acetone and small quantities of Methylstyrene.

Acetone:
Physicochemical properties: Molecular weight: 58.08. Commercial concentration> 99% by mass. Melting point: - 99.6C. Boiling point: 56.2 C. Solubility: Acetone is miscible with water and most solvents Uses: Acetone is used as: An industrial solvent; Feedstock for: Methyl methacrylate (MMA); Bis-phenol A; Methylisobutyl acetone; Di-acetone alcohol; Methyl-isobutyl Carbinol. Density at 20C: 8 0.789 g/cm3. Appearance: colorless liquid with sweet odor. Vapor Density: 2.00. Critical pressure: 47 bar. Critical temperature: 235C. Critical pressure: 47 bar.

Methylstyrene:
Physico-chemical properties: Molecular weight: 118.2. Commercial concentration: 99 mass%. Solidification temperature: - 23.2C. Boiling point: 165.4C Density at 25C: 0.906 g/cm3. Solubility: slightly soluble in water, soluble in organic solvents. At room temperature,it is a colorless liquid with highly aromatic odor

Uses: It is a co-monomer in the manufacture of special styrene resins.

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Fig.2 Raw materials, products and their applications

2.d)Preparation of

CUMENE

Cumene is an important chemical in the present industrial world and its uses are steadily increasing. The process followed for the production of cumene is the catalytic alkylation of benzene with propylene. The reaction can be occurred in liquid and gas phases, but high conversion are obtained at gas phase reactions, catalyst like solid phosphoric acid are replaced by zeolites and the catalytic conversion reaction are held in shell and tube reactors rather than packed fixed bed reactors. Cumene process reaction is exothermic in nature so a complex shell and tube reactor designs are not sufficient for energy conversion, tremendous research work is involved in design a rector of Cumene production from benzene and propane. As the flow sheet explains the process of a steady state system which is a continuous process and energy efficient.

Cumene plant consist of the following sections:

Storage and pumping section: Benzene (99.9%) and propane (95%) are stored in liquid state in storage tanks and propane is stored in sphere. Benzene excess reactant is mixed in the circulation tank where propane is added to the stream line of the feed inlet to the cascade of heat exchangers. Preheating and vaporization section: Benzene and propane are mixed with the 2:1 ratio and fed to preheating section where a continuous series of heat exchanger are used to heat up the feed mixture with the effluents form the Cumene reactor. Finally after the heat exchanger a fired heater is used to vaporize and raise the temperature of the mixture to the reaction condition temperature. Pressure is maintained by the compressors from pumping section.

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 Reactor section: A shell and tube reactor is designed such as to with stand pressure up to 25 atm and 350 degree centigrade. The reactor tubes are filled with catalyst and the feed is charged from the top. Gas reacts and passes over the catalyst bed with 99% conversion of propylene and outlet stream is sent to the recycle and the purification section. In the purification section side reactions generate compounds like di- iso propylbenzene (DIPB). Separation and purification section: Unreacted benzene is separated in a distillation column from the effluent obtained from the reactor and the recovered benzene is recycled to the feed stream, di- isopropylbenzene which formed as by product is separated a sieve tray distillationcolumn which is 99 percent pure. Currently, the most common Industrial process for manufacturing of CUMENE is the Q-Max Process.The Q-Max process converts a mixture of benzene and propylene to high quality cumene using a regenerable zeolite catalyst. The Q-Max process is characterized by a exceptionally high yield, better product quality, less solid waste, decrease in investment and operating costs and a corrosion free environment. The Q-Max process developed by UOP uses QZ-2000/ QZ-2001 catalyst which is a variant of - zeolite.

Fig.3 Cumene Production Process

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2.e)Cumene to Phenol via Cumene Hydro-Peroxide:

Fig.4 Process sheet for production of phenol via CHPO

Raw material:

CUMENE Air Sulfuric Acid Sodium Hydroxide

The cumene peroxidation process for the manufacture of phenol involves the liquid phase air oxidation of cumene to cumene peroxide, which in turn is decomposed to phenol and acetone by the action of acid.

Oxidation of cumene

Firstly cumene peroxide is converted to cumene hydroperoxide (CHPO) by the following reaction:

Cumene

CHPO

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The oxidation of cumene with air in CHPO is performed in solution in a stainless steel reactor. Given the risks (including explosions) and the difficulties inherent in making the CHPO, it is necessary to take certain precautions. Indeed, the CHPO, colorless liquid, is a potentially dangerous because, although stable at room temperature, it explodes to 170 C. From this point of view, the most widely used industrial option is to achieve an aqueous emulsion of air in the presence of sodium carbonate and sodium stearate. Sodium carbonate is used to make alkaline (pH = 8.5 to 10.5) in particular to avoid the decomposition of phenol CHPO (which occurs only in acidic medium), which inhibits the oxidation product of cumene. Sodium stearate in turn allows to obtain and stabilize the emulsion is a dispersion of very fine droplets of isopropylbenzene, the contact surface between the reactants is greatly increased. In industry, there is an alternative approach: it is to carry out the reaction in a homogeneous medium. This homogeneity is obtained by adding a concentrated solution of soda. This can work at temperatures slightly higher in the order of 120 C and under conditions substantially identical. In the effluent concentration CHPO can reach 35 to 50 wt%, but these proportions there, its rate of decomposition in acetophenone and phenyl-2 propanol-2 becomes important, so we limit the conversion increases to 20 -25% so that its selectivity is higher than 90 mol%. The reaction is exothermic, it removes the heat generated by the external circulation of the reaction medium in a device with pump and heat exchange or by using a cooling fluid moving in the jacket forming the wall of the reactor. This equipment is completed, upstream, by the washing with cumene charge of various waste water recovery (gas treatment, solid separation), and downstream purification of sodium carbonate and the catalyst in separator by washing with water. Subsequently, the concentrated CHPO dissolved in cumene by vacuum evaporation (7kPa) in a two-stage device by steam distillation. Unreacted cumene, recovered at the top, is recycled. The extractes stream consists of 75 to 85 wt% of CHPO, 3-6% of acetophenone and phenyl-2 propanol-2, 8-17% of cumene, the methylstyrene and various other impurities.

Cleavage of Hydro-peroxide Cumene to Phenol

It is a catalysed reaction, which involves addition of highly concentrated sulfuric acid (98 wt%) in small quantities (mass fraction of about 1%). This method has the advantage of providing good selectivity to phenol. To maximize the selectivity to phenol, the reaction must be performed at a temperature optimum of about 70C and a pressure of about 15 bars. The reaction is highly exothermic, So we use CSTR type of reactor to be able to adequately cool the system and obtain a stable temperature and pressure and homogeneity throughout the reactor. The homogenization of CSTR and the addition of phenol (or acetone) to decrease the concentration of hyper-oxidation can limit the accumulation points and hence the risk of side chain reactions and explosions in

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the reactor. These risks are minimized by an output conversion to cumene hydroperoxide equal to 100%, achieved with a residence time long enough usually about 30 minutes. The efficiency of this step is about 95%.

The separation of phenol and acetone

Now that we have synthesized the two products of interest, we'll look at how to separate impurities and purify them. This requires use of UPO in series with distillation being the most important component. The products are separated by distillation. Acetone is removed overhead in the first column and further purified by distillation. The bottoms from this column are then vacuum distilled to send unreacted cumene and by-product -methyl styrene overhead. If this impure cumene were recycled as such, the methyl styrene must be purified. This can be done by catalytic hydrogenation of the methyl styrene to cumene, by careful fractionation. In the latter case methyl styrene is available as a by-product. The bottoms from the vacuum still are further distilled to separate acetophenone and cumene from phenol. Phenol is then finally separated. However the problem of this method is that the phenol product does not have sufficient purity and is not sufficient for many applications including sulfonation or chlorination. Therefore in general it is passed through a series of OPU including distillation, crystallization and solvent extraction. They can be executed directly at the outlet of the reactor or after the first distillation. Thus we arrive industrially to produce phenol with 99.99% purity. But the problem is that we lose much of phenol at the top of the first column and the bottom of the last.

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3.a)For Synthesis of Cumene:

Basis: 300 tones per day of Cumene (=104 kmol/h)

Fig.5 Block flow diagram, Production of Cumene

Primary reaction: C3H6 + C6H6 C6H5-C3H7 Propylene Benzene Cumene 1 Kmole of benzene = 1kmole of propylene = 1kmole of cumene Selectivity: 31:1 (Cumene to DIPB) Feed Stream: Propylene in feed: 112.0071 Kmol/h Benzene in feed: 221.774 Kmol/h Feed=Benzene + Propylene +Propane = 339.6711 Kmol/h Output stream: Propylene: 1.11997 Kmol/h Benzene: 114.09 Kmol/h (which is recycled) Cumene: 104 Kmol/h Propane: 5.89 Kmol/h Total: 225.1kmol/h
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Side reaction: C3H6 + C6H5-C3H7 C3H7-C6H4-C3H7 Propylene Cumene Diisopropyl- benzene (DIPB) 1 Kmole of benzene = 2kmole of propylene = 1kmole of cumene

For cumene, propylene required is 104 kmole/hr Selectivity is 31: 1 of Cumene to DIPB, i.e., catalyst converts propylene and benzene to the ratio of 31 moles of cumene and 1 mole DIPB. Conversion of propylene is 99% Let X Kmole of DIPB formed Then, Cumene formed =31X 31 X = 104 X = 3.35 DIPB formed is = 3.35 kmole/hr Propylene Balance : Propylene Required for Cumene=104.16 kmol/h Propylene Required for DIPB=6.7 (2X3.35) Total Propylene Required =110.887 kmol/h Given: Propylene conversion=99% Propylene required=110.887/.99 =112.0071 kmol/h Propane present: 112.0071/.95 112.0071= 5.89 kmol/h Benzene Balance: Benzene required for cumene =104.16 kmol/h Benzene required for DIPB= 3.35 kmol/h Total Benzene Required= 107.51 kmol/h Benzene:Propylene=2:1 Benzene in feed= 110.8*2= 221.6 kmol/h Benzene unreacted (recycled) =221.6 -107.51 = 114.09 kmol/h Yield= (moles of product produced) (Stiochiometry Factor) /(Moles of reactant fed to the reactor) = 104.16X1/110.88 =93.93%

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3.b)Synthesis of Phenol from Cumene:

Fig.6 Block flow diagram, Production of Phenol

Reagents Cumene Introduces (g) air(g)/ O2(g) Unreacted Cumene Phenol(g) Acetone(g) Side products (g) 1746,9 1813/380,7 319,2 1000 617 191,4

Products

CALCULATIONS:
mph= 1kg = Following which we have, mO2 = = 380,7g mcumene i = F1- mO2 = 1746,9 g mside-products1=0,05*F1= 106,3g mside-products2=0,8*F1-macetone-mphenol = 85,1g This shows that the phenol produced in the first part of the process results in a molar yield of 73% (ie a mass yield of 57%). However, some of the unconsumed cumene is separated and reused in the second part (purification), ensuring a final molar yield of 92% (72 wt%). F1 = 2127,7g

macetone=

= 617g

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The focus here is the energy aspect of the main chemical reactions taking place in the training process of phenol. Both reactions are exothermic and the reactor where they occur to be maintained at constant temperatures and accurate, we will estimate the amount of heat to be exchanged for these reactions are performed in optimal conditions.

4.a)Oxidation reaction
The first reaction reagent cumene and oxygen in the air. We will assume that the water / cumene is available at 25C and 1 atm and the air is introduced at 25 C and 5 bar. The pressure of the air introduced being only 5 bar, we will consider it as a perfect mixture of oxygen and nitrogen and we neglect the influence of pressure on its enthalpy change. We take cumene conversion rate equal to 25% We calculate the value of the heat exchange per mol of cumene introduced, considering that air is introduced in stoichiometric proportion and that the molar ratio water / cumene in the liquid stream entering is 5. This gives the enthalpy diagram:

Fig. 7 Enthalpy Diagram(Oxidation Reaction) So we Q Exchanged= H1+H2 And H1 = 0.25 * Hreaction (25C, 1 atm) The literature gives: Hreaction (25C, 1 atm) = -116 kJ/mol H1 = -29 kJ/mol H2 = (0,75*Cpcumene +
25C 100C

* CpN2 + 5*Cpwater + 0,25 * CpCHPO) dT

The isobaric heat capacities are polynomial functions of temperature. Software ProSim (SRK model) has been used to calculate the integral. 15 | P a g e

The result H2 = 13 kJ/mol And therefore Q exchanged = -16 kJ/mol This represents an amount of heat to get significant, hence the importance and variety of cooling systems can be used on the entire reactor.

4.b)Cleavage reaction
In the second reactor, the CHPO product will decompose into acetone and phenol. We consider that the incoming liquid stream is available to about 70 C and 1 atm. According to the calculations of material balances performed on the first part of the installation, it is assumed that for 1 mol of cumene introduced into the process, we have, in the liquid stream entering the second reactor: nCHPO(mol) n Cumene (mol) n Side Products (mol) 0,77 0,18 0,06 We also consider that the by-products in this current were restricted to acetophenone. For lack of information and for the sake of simplification we neglect the flow of products reused in the reactor to the dilution of the CHPO. We take a conversion rate of 100% CHPO. And as above, we calculate the amount of heat exchange in the reactor per mole of cumene introduced into the process. Hence the enthalpy diagram below:

Fig. 8 Enthalpy Diagram(Cleavage Reaction)

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Similarly, we have Qexchanged= H1+H2+H3 H1 = (0,77*CpCHPO + 0,18*CpCumene+ 0,06 * Cpsp) dT

70C 25C

H1 = - 9.12 kJ/mol H2 = 0.77*Hreaction (25C, 1 atm) Is H2 = 0.77*(-253) kJ/mol = -194.8 kJ/mol Finally, H3 = (0,73*CpPhenol + 0,73*CpAcetone + 0,04 * Cpsp+ 0,18*CpCumene) dT
25C 70C

H3 = 12.9 kJ/mol Hence Q exchanged = 190.2 kJ/mol This amount of heat to be recovered is much larger due to a maximum degree of conversion and reaction much more exothermic, which requires the use of a thermal control system more important.

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Molecular Masses
The following molar masses have been used for the Calculations:
Mphenol (g/mol) Mcumene (g/mol) MO2 (g/mol) 94 120 32 MBenzene(g/mol) Mpropylene(g/mol) Macetone (g/mol) 78 42 58

Assumptions:
For Mass Balance of Cumene Production:

Conversion is 99% of propylene. Product molar selectivity cumene to p-DIPB is 31:1. Propylene feed is 95% pure and rest of propane. Benzene is about >99.9% purity. Molar feed ratio of benzene to propylene 2:1.
For energy Balances assumptions made are written with the text

Unit Operation (UPO)

In chemical engineering and related fields, a unit operation is a basic step in a process. Unit operation involves bringing a physical change such as separation, crystallization, evaporation, filtration etc. Unit operations consist of five classes: Fluid flow processes, including fluids transportation, filtration, solids fluidization Heat transfer processes, including evaporation, condensation Mass transfer processes, including gas absorption, distillation, extraction, adsorption, drying Thermodynamic processes, including gas liquefaction, refrigeration Mechanical processes, including solids transportation, crushing and pulverization, screening and sieving.

Distillation
Distillation is a method of separating mixtures based on differences in volatilities of components in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction.

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DESIGN AND SIMULATION OF CUMENE PLANT USING ASPEN PLUS A Thesis By NIRLIPT MAHAPATRA Cumene Production, Engineers guide. Information on science and technologie. Procds de ptrochimie : caractristiques techniques et conomiques . Tome 2 . Les grands intermdiaires oxygns, chlors et nitrs, 1986, par Chauvel Alain, Lefebvre Gilles, Castex Louis et Leprince Pierre, Paris Ed. Tecnhip, Cote: 665.6 CHA, Division: INP ENSIACET. Phnol. Actone. -Mthylstyrne par Jean-Marc MATHIEU Ingnieur Dveloppement procds,Rhodia Intermdiaires. http://www.educnet.education.fr/rnchimie/clpi/annales/02/gc_02_metro.pdf http://www.che.cemr.wvu.edu/publications/projects/cumene/cumene-a.PDF http://www.scribd.com/doc/30134143/Phenol The Material Balance for Chemical Reactors Copyright c 2011 by Nob Hill Publishing, LLC Phenol: Lummus Technology(Overview) http://en.wikipedia.org/wiki/Distillation http://en.wikipedia.org/wiki/Unit_operation

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