ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING Asia-Pac. J. Chem. Eng.

2010; 5: 191206 Published online 10 September 2009 in Wiley InterScience (www.interscience.wiley.com) DOI:10.1002/apj.369

Special Theme Review

Remarks on studies for direct production of phenol in conventional and membrane reactors
Raffaele Molinari* and Teresa Poerio
Department of Chemical and Materials Engineering, University of Calabria, Via P. Bucci, 44/A, I-87036 Rende (CS)-Italy

Received 29 December 2008; Revised 5 March 2009; Accepted 18 March 2009

ABSTRACT: The great interest in the oxidation reaction of benzene to phenol is linked to some disadvantages of the cumene process, such as environmental impact, production of an explosive intermediate, a multi-step process (which involves (1) difculty to achieve high phenol yield, in relation to the benzene used and (2) high capital investment), and a high acetone production as a co-product which results in an over supply in the market. In this paper, we discuss various studies concerning a new approach based on a one-step and acetone-free method for phenol production. Particular attention is devoted to phenol production processes using various congurations of membrane reactors (MRs) and a photocatalytic membrane reactor (PMR). In particular, the biphasic MR allowed to achieving high selectivity values (9798%). The described studies have been classied according to oxidant type such as N2 O, O2 , and H2 O2 . Each of them shows that direct oxidation of benzene to phenol is a difcult task and further efforts are needed to search and replace the three step traditional process of converting benzene into phenol with a process of direct oxidation. 2009 Curtin University of Technology and John Wiley & Sons, Ltd. KEYWORDS: cumene process; one-step phenol production; membrane reactor; nitrous oxide; oxygen; hydrogen peroxide; phenol by photocatalysis

INTRODUCTION
Phenol is an important raw material for the synthesis of petrochemicals, agrochemicals, and plastics. Examples of employment of phenol as an intermediate are production of bisphenol A, phenolic resins, caprolactam, alkyl phenols, aniline, and other useful chemicals. Current worldwide capacity for phenol production is nearly 7 million metric tonnes per year.[1] Today, almost 95% of the worldwide phenol production is based on the so called cumene process (described afterwards in more detail) which is based on a three-step process. Despite its great success, the cumene process has some disadvantages: poor ecology, an explosive intermediate (cumene hydroperoxide (CHP)), and a multisteps character, which makes difcult to achieve high phenol yields with respect to benzene. For example, as reported by Niwa et al .[2] the benzene conversion is about 20% in the rst step (concerning the production of cumene from benzene and propylene) using the traditional supported phosphoric acid catalyst, while in the second step it is about 25% for the oxidation of cumene to CHP
*Correspondence to : Raffaele Molinari, Department of Chemical and Materials Engineering, University of Calabria, Via P. Bucci, 44/A, I-87036 Rende (CS)-Italy. E-mail: r.molinari@unical.it
2009 Curtin University of Technology and John Wiley & Sons, Ltd.

with air. In the third step the decomposition of CHP to phenol and acetone with sulphuric acid gives phenol in a yield over 93%. Accordingly, in this traditional process, the one-pass yield of phenol, based on the amount of benzene initially used, is less than 5%. The presence of acetone, produced as by-product in a 1 : 1 stoichiometry, is the greater inevitable disadvantage. This problem brings serious issues since the economics of this process signicantly depends on the marketability of the acetone by-product.[3] In order to solve this problem the Mitsui Company ventured into phenol production with a modied cumene process making use of acetone recycling. The acetone recycling included two additional steps to convert acetone into propylene, via hydrogenation and dehydration, which is then reused in the rst step of the cumene process. The Mitsui 5-step technology increases the process complexity. The search for new routes for phenol production based on the direct benzene oxidation became more intensive in the last decade. Many studies emphasize the innovative potentialities and the emerged role of the membrane reactors (MRs)[4 6] for improving existing industrial processes and for introducing new production methodologies. MRs can improve the efciency of chemical conversion processes reducing reactants consumption and by-product formation (and also reducing

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polluting emissions). Higher energy efciency, modularity, and easy scale-up are some other advantages of MRs with respect to conventional xed bed reactors.[7] In this work, after an in depth description of the cumene process, the main studies for alternative methods of phenol production are presented. Particular attention is devoted to the phenol production processes studied by our research group using various congurations of MRs and a photocatalytic membrane reactor (PMR). The described studies have been classied according to oxidant type, such as N2 O, O2 , and H2 O2 , employed for the direct oxidation of benzene to phenol in both traditional and membrane processes.

CUMENE PROCESS
The aim of all the described innovative processes being replacement of the multi-step processes of phenol production, a wide description of the cumene process is reported below, in order to use it as a comparison for other processes. The cumene process was developed and rst realised in the former Soviet Union, where in 1949 a rst industrial plant was put into operation. The same process, sometimes referred to as Hocks process, was developed independently in the Western Countries. The rst plant was commissioned in 1952 in Canada.[8] Between 1939 and 1945 the cumene was produced to be used for aviation fuel during the World War II. In 1989, more than 90% of cumene demand was for use as an intermediate for the phenol production. The rst step of the cumene process is the alkylation of benzene with propylene to cumene. This alkylation reaction is performed using different processes. A process, named SPA (solid phosphoric acid) process, currently licensed by UOP, uses as catalyst a complex mixture of orthosiliconphosphate and polyphosphoric

acid supported on kieselguhr. The small amounts of water, that continuously are fed into the reactor in order to maintain the desired level of activity, develop H3 PO4 causing some downstream corrosion. Pressures and temperatures employed in the SPA process are in the range 2940 bar and 200260 C, respectively. A typical reactor output yield contains 94.8 wt% cumene, 3.1 wt% diisopropylbenzene (DIPB) and 2.1 wt% heavy aromatics. More than 40 SPA plants have been licensed worldwide.[8] Another process developed by Monsanto uses an AlCl3 and hydrogen chloride catalyst. This process permitted to obtain the highest overall yield: almost 99 wt% based on benzene and 98 wt% based on propylene. SPA and AlCl3 processes offer different features but both suffer from a variety of drawbacks such as high environmental impact, corrosive catalysts and formation of oligomers and other impurities. To overcome the limitations of the SPA process, UOP began searching for a new cumene catalyst. More than 100 different catalyst materials were screened, including mordenites, MFIs, Y-zeolites, amorphous silicaaluminas, and -zeolite. UOP selected the most promising catalyst, based on -zeolite, for cumene production and then began to optimize the process design around this new catalyst. The result of this study was the UOP Q-Max process. The Q-Max process represents a new generation of cumene technology based upon a highly selective zeolitic catalyst. It provides excellent cumene product quality (99.97 wt% purity) and nearstoichiometric cumene yield (>99.7 wt%). The rst Q-Max process unit came on stream at JLM Chemicals, Blue Island, IL, USA in August 1996. The JLM project was a revamp of an existing UOP Catalytic Condensation unit (SPA catalyst). A Q-Max unit consists (Fig. 1) of an alkylation reactor, a distillation section, and a transalkylation reactor.[10] The alkylation reactor is divided into four catalyst beds contained in a single reactor shell. Propylene

Propylen Benzene Propane Benzene

Cumene

Alkylation reactor

Depropanizer column Transalkylation reactor

Benzene column

Cumene column

DIPB Column

Heavies

Figure 1. Q-MAX process scheme for cumene production (Elaborated from Schmidt 2005).[10] .
2009 Curtin University of Technology and John Wiley & Sons, Ltd.

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Cumene

PRODUCTION OF PHENOL IN CONVENTIONAL AND MEMBRANE REACTORS

193

Acetone Purification Decomposition /Neutralisation Phenol purification Air Acid Neutralizing agent Phenol Recovery

Acetone

Cumene

Oxidation

Concentration

Phenol Residue

Cumene

AMS Hydrogenation

(AMS)

Figure 2. Sunoco/UOP Phenol process scheme for phenol and acetone production (Elaborated from Schmidt 2005).[10] .

feed and a mixture of fresh and recycle benzene are charged into the alkylation reactor, where the propylene reacts to form mainly cumene. The stream from the alkylation reactor ows into the depropanizer column, which removes the propane that entered the unit with the propylene feed. The bottoms stream of the depropanizer column is sent to the benzene column where excess benzene is collected overhead and recycled. The bottom stream of the benzene column is sent to the cumene column where cumene produced is recovered overhead. The bottom stream from the cumene column, containing mostly DIPB, is sent to the DIPB column where it is recovered and recycled to the transalkylation reactor. In this reactor, DIPB and benzene are converted to additional cumene. The efuent from the transalkylation reactor is then sent to the benzene column. Other processes for the cumene production, licensed by Dow Chemical, Mobil Bagder, CdTech, and Eni, have been converted to more efcient and environmentally friendly zeolite-based processes.[9] The last steps of the cumene process are the cumene conversion to CHP and then the decomposition of concentrated CHP to phenol and acetone using the Sunoco/UOP Phenol process (Fig. 2). The key process steps in the Sunoco/UOP Phenol process include (1) liquid-phase oxidation of cumene to CHP performed using oxygen from air; (2) concentration of CHP and recycling of unreacted cumene to oxidation; (3) decomposition of concentrated CHP to phenol and acetone, accompained by dehydration of dimethylphenylcarbinol (DMPC) to alphamethylstyrene (AMS) catalyzed by sulphuric acid at 60100 C; (4) neutralization of the decomposition catalyst; (5) fractionation of the neutralized decomposition product for recovery of acetone, phenol, AMS, and residue; (6) recovery and purication of acetone and phenol, and rejection of by products as heavy residue; and (7) AMS hydrogenation back to cumene for recycle to oxidation, or AMS rening for sale as a by product.
2009 Curtin University of Technology and John Wiley & Sons, Ltd.

The high overall yield from oxidation and decomposition achieved is 1.31 cumene wt/phenol wt without tar cracking.[10] Despite its great success, the cumene process has some disadvantages such as the production of an explosive intermediate (CHP); indeed the oxidation of cumene to CHP occurs at conditions close to its ammability limits and CHP is a potentially unstable material, which can violently decompose under certain conditions. It is a multi-step process, which makes it difcult to achieve high phenol yields in relation to the benzene used and which leads to a high capital investment. It requires the use of aggressive media (dilute sulphuric acid at 60100 C) and has a high acetone production as a co-product which results in an over supply in the market.[11] Besides, current predictions show that phenol demand will be signicantly higher than the demand of acetone and that the co-product supply of acetone will soon exceed the demand of acetone. Phenol plants using the cumene process need expensive control equipments and involve increased operation complexity owing to the complex and highly energy consuming three-stage cumene process. As a result, a great number of modern phenol companies are searching for a manufacturing method independent on acetone production. The above arguments justify the great interest to approach a onestep and acetone-free method for the phenol production.

ONE-STEP OXIDATION USING N2 O AS OXIDANT

A new route for producing phenol directly from benzene was the use of N2 O as an oxidizing agent in the gas phase. The mechanism of oxidation of benzene to phenol by means nitrous oxide, a very selective oxidant, is still controversial. According to Panov et al .[8] the so-called -sites, which are formed in an iron-containing zeolite matrix
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can dissociate N2 O at low temperature (300 C)[12 23] . This would produce (O) species responsible for the selective oxidation of benzene to phenol. Other researchers attribute the catalytic activity to surface acidity only (Bronsted sites or extra framework aluminabased Lewis acid sites).[24 27] The rst ones to use N2 O as oxidant for the oxidation of benzene to phenol were, in 1983, Iwamoto et al .[28] This reaction achieved, at 550 C, selectivity over vanadium catalyst exceeding 70%. In 1988, Suzuki et al .[24] in Japan (Tokyo Institute one of Technology), Gubelmann et al .[26] in France (Rh Poulenc Co.), and Kharitonov et al .[29] in Russia at the Boreskov Institute of Catalysis (BIC), discovered independently, that ZSM-5 zeolites are the best catalysts for this reaction. On this basis zeolites of various chemical compositions were tested: AlSi[30 34] , GaSi[35,36] , TiSi[37] , and Si (silicalite).[38,39] . The new phenol synthesis process based on zeolite catalyst was developed jointly by Solutia Inc. (formerly a chemical business unit of Monsanto) and the BIC. The phenol process, called the AlphOx process after the name of -oxygen, was successfully transferred to a pilot plant that was built by Solutia in Pensacola (Florida). The reaction parameters of AlphOx pilot plant, operating at 400450 C with a contact time of 12 s are reported in Table 1. In Fig. 3, a owsheet
Table 1. plant. Reaction parameters of the AlphOx pilot

of the AlphOx pilot plant[40] shows a simple adiabatic reactor, where the reaction is performed. This process shows several advantages compared to the cumene process, i.e. one step only, no acetone byproduct, and no explosive intermediates. Despite the advantages, it is associated with serious problems: the prohibitively high cost of N2 O that could hinder its industrial application[4] and the rapid deactivation of the catalyst that results in lower yield and short lifespan of the catalyst.[41,42] The major cause of catalyst deactivation is the accumulation of phenol inside the pores of ZSM-5 crystals with consequent coke formation.

ONE-STEP OXIDATION USING O2 AS OXIDANT

The most available chemical element on the Earth is the oxygen (53.6 atomic %) and from economical and environmental point of view it represents an attractive and challenging agent for selective oxidation of hydrocarbons. Generally, the selective oxidation of hydrocarbons with oxygen can be performed in two different ways: activation of oxygen to generate the active oxygen species or activation of substrate. The substrate activation is very difcult for the hydroxylation of benzene to phenol, because the bond energy of the CH bond of benzene is about 472.2 kJ/mol[43] which is much higher than that of other kinds of CH bond.[44] . In order to perform the oxidation reaction, the activation of oxygen is necessary. One method to generate the activated oxygen species in the benzene hydroxylation reaction is the reductive activation process that reduces molecular oxygen by using reducing agents such as H2 , CO, NH3 , ascorbic acid, dithioalcohols, zinc, and iron.[4,45 51] Hydrogen as reducing agent was used in

Catalyst Phenol productivity (kg/kgcat h) Benzene conversion to phenol (mol%) N2 O conversion to phenol (mol%)

Fe-ZSM5 0.4 9798 85

Figure 3. A owsheet of the AlphOx pilot plant (Elaborated from Parmon et al ., 2005).[40] .
2009 Curtin University of Technology and John Wiley & Sons, Ltd.

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195

numerous studies summarized by Kuznetova et al .[52] In these works, catalysts of Pt or Pd and transition metal oxides were utilised with a mixture of O2 and H2 in the liquid phase providing 90% selectivity and 0.10.6% conversion of benzene to phenol. Kuznetsova et al .[52] employed the oxygen-hydrogen mixture over silica supported bi-component catalysts containing group VIII metals and heteropoly compounds, obtaining a benzene conversion of 4.4% and a phenol production of 0.96 mmol/h. Ehrich et al .[53] reported that in gas phase, using platinum catalysts, benzene conversion was equal to 1.0% (Selectivity, Sphenol = 97%) at 413 K, whereas palladium catalysts reached a conversion of only 0.2% (Sphenol = 86%) for the same contact time and temperature. Although oxygen is an ideal oxidant, oxygen and hydrogen mixture is dangerous. In the literature alternative ways to avoid explosion, and successfully control the hydroxylation process, involve supplying oxygen and hydrogen separately. These modes are based on the use of a membrane reactor that is an effective method to produce active oxygen species.[2,54 57] . Indeed, Niwa et al .[2] reported a single stage method of benzene oxidation to phenol using a palladium MR (Fig. 4). In this reactor, hydrogen and oxygen are separately supplied on opposite sides of the membrane. The active hydrogen species, formed by the permeation from one side of the Pd membrane, produces active oxygen species on the opposite side by reacting with oxygen gas. Then, the active oxygen species reacts with the adsorbed benzene on Pd and the benzene is directly converted into phenol. This one-step process attained phenol formation selectivities of 8097% and benzene conversions of 216% below 250 C (phenol yield: 1.5 kg/kg of catalyst per hour at 150 C). Otsuka et al .[58,59] were the rst to study another kind of membrane reactor, a fuel cell, to perform the onestep oxidation of benzene to phenol using H2 O2 fuel cell both in liquid phase and in gas phase. The fuel cells

are electrochemical reactors that allow direct conversion of the chemical energy of a fuel into electricity. In the H2 O2 fuel cell system reactor, oxygen is activated by the permeated hydrogen from the electrolyte membrane (Fig. 5). Further studies were carried out by Cai et al .[56] using a H2 O2 proton exchange membrane fuel cell (PEMFC) with Naon1 membrane as the electrolyte. In this system it was found that phenol was the only product detected with a yield equal to 0.35% at 100 mA/cm2 at 80 C. The activation of oxygen by carbon monoxide was reported by Tani et al .[60] who developed a direct synthetic method for producing phenol from benzene using air in presence of CO and molybdovanadophosphoric acids as catalysts, obtaining a phenol yield of 27.3% along with a small amount of 1,4-benzoquinone (3.4% yield) and a benzene conversion of 41.6%. Various studies in which ascorbic acid was used as reducing agent for the benzene hydroxylation are summarized in Table 2. Direct oxidation of benzene to phenol by O2 without any reducing agent would be of great interest for the industry. Some studies, indeed, have been reported using heteropolyacid (HPA) catalysts having both strong acidity and redox properties.[68,69] Passoni et al .[70] performed the benzene hydroxylation using molybdovanadophosphoric HPAs, producing 12 mmol of phenol with a selectivity of 75%. However, after 4 h of reaction time, the HPA was irreversibly reduced and fresh addition of HPA promoted unselective oxidation.

ONE-STEP OXIDATION USING H2 O2 AS OXIDANT

Hydrogen peroxide, H2 O2 , is a very attractive oxidant for liquid-phase reactions. It can oxidize organic compounds with the generation of water as the only theoretical co-product. It is relatively cheap, <0.7 US dollar per kg (100% H2 O2 ), and about 2.4 million metric tons are produced for use, mainly as a bleaching agent.[71] Thus, the discovery of an efcient catalyst and the choice of reaction conditions are the keys to realize an ideal oxidation procedure. The H2 O2 oxidation is particularly useful for the synthesis of high-value ne chemicals, pharmaceuticals or agrochemicals, and electronic materials which require high chemical purity. Generally, the reactions of hydrogen peroxide with aromatic compounds proceed in the presence of transition metal ions of variable oxidation state, Mn+ /M(n1)+ . Many studies, summarized in Table 3, have been made with the aim to develop more efcient and environmentally friendly one-step benzene hydroxylation processes using H2 O2 as oxidant.
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O2 H

Phenol Benzene OH

H Palladium Membrane

H2

Figure 4. Scheme of the reductive oxidation of benzene to phenol using catalytic palladium membrane (Elaborated from Itoh et al . 2003).[57] .
2009 Curtin University of Technology and John Wiley & Sons, Ltd.

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Figure 5. Reaction scheme for the phenol synthesis using a fuel cell reactor (Elaborated from Cai et al. 2005).[56] .

Table 2. Catalytic systems reported in the literature using ascorbic acid as reducing agent.

Catalyst CuO/Al2 O3 (Cu = 3 wt%) VCl3 CuO/Al2 O3 (Cu = 2 wt%) Polyoxometalate [(C4 H9 )4 N]m [PW11 CuO39 (H2 O)]nH2 O V/Al2 O3 VOx /CuSBA-15 LaOx/HZSM5 (0.5 wt%)

Conditions 80 vol% acetic acid, T = 80 C, PO2 = 1 atm, benzene = 22.5 mmol, ascorbic acid = 4 mmol 50% Water/CH3 CN, T = 50 C, PO2 = 1 atm, benzene = 11.3 mmol, ascorbic acid = 0.1 mmol 80 vol% acetic acid, T = 30 C, PO2 = 1 atm, benzene = 22.5 mmol, ascorbic acid = 4 mmol Benzene : acetone : sulfolane : water = 1 : 7 : 1 : 1, T = 50 C, PO2 = 10 atm, benzene = 11.3 mmol, ascorbic acid = 0.8 mmol 80 vol% acetic acid, T = 30 C, PO2 = 4 atm, benzene = 5.6 mmol, ascorbic acid = 1 mmol Acetic acid: water = 2 : 1 T = 80 C, PO2 = 7 atm, benzene = 11.3 mmol, ascorbic acid = 11.9 mmol 80 vol% acetic acid, T = 80 C, PO2 = 4 atm, benzene = 5.6 mmol, ascorbic acid = 1 mmol

Yield of Benzene phenol conversion Selectivity (%) (%) (%) References 1.3 3.6 2.5 9.2 98.1 91.8 [61] [62] [63] [64]

8.4 27 4.2

100

[65] [66] [67]

Recently, Bianchi et al .[85] reported a water acetonitrile (1 : 1) biphasic reaction medium in which the produced phenol was extracted into the organic phase and the Fenton catalyst was soluble in the aqueous phase. The selectivity of the benzene hydroxylation was obtained by reducing the contact time between phenol and catalyst. The oxidation of benzene and its derivatives by Fentons reagent has been known for a long time.[89] The classical oxidation process utilizes the reaction of aqueous iron(II) with hydrogen peroxide to generate hydroxyl radicals, which are then used to carry out the substrate oxidation.
2009 Curtin University of Technology and John Wiley & Sons, Ltd.

However, the selectivity of this process is rather poor since phenol is more reactive towards oxidation than benzene itself, and formation of oxidation by-products (catechol, hydroquinone (HQ), benzoquinones (BQ), biphenyl, and tars) usually occurs. Molinari et al .[90,91] , in order to avoid the phenol over-oxidation, employed a different conguration of membrane reactors. The major advantage to use the membrane technology in catalytic processes is the separation of products from the reaction mixture. The product separation is one of the most common tasks in using a membrane to build a reactor and permits
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Table 3. Catalytic systems reported in the literature using H2 O2 as oxidant.

Catalyst Solvent: acetic acid/CH3 CN; T = 80 C Benzene: 11.28 mmol; H2 O2 : 33.95 mmol Solvent: acetic acid; T = 70 C 10.1 26.6 20.5

Conditions

Yield of phenol (%)a Benzene conversion (%)

Selectivity(%)b

References

Pyridine modied molybdovanadophosphate PyPMo10 V2 O40

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98

[72]

93 91.2

[73] [74]

Benzene: 22.50 mmol; H2 O2 : 47 mmol Solvent: acetic acid; T = 25 C Benzene: 22.56 mmol; H2 O2 : 38.8 mmol

2009 Curtin University of Technology and John Wiley & Sons, Ltd.

28

70 8.6 28

98 94c 100d

[75] [76, 77] [78]

Vanadium substituted heteropolymolybdic acid H4 PMo11 VO40 Vanadium-substituted heteropolymolybdates Mixture of H4 PMo11 VO40 , H5 PMo10 V2 O40 , H6 PMo9V3O40 Mesoporous titanosilicate Ti-MCM-41 Modied Titanio-Silicalite TS-1B Cu2+ -substituted molecular sieves Cu-AlPO4 Iron-porphyrin encapsulated in PMAA (Polymethacrylic acid) Solvent: CH3 CN; T = 60 C Benzene: 4.8 mmol; H2 O2 : 32.6 mmol Solvent: sulfolane; T = 100 C ratio H2 O2 /Benzene = 0.1 Solvent: CH3 CN/H2 O; T = 60 C Benzene: 10 mmol; H2 O2 : 27.4 mmol Solvent: Benzene/H2 O2 ; T = 70 C Benzene: 22.50 mmol; H2 O2 : 9.4 mmol Solvent: acetic acid; T = 25 C 0.13

100

[79]

Water washed manganese nodule leached residue (WMNLR) Powder containing: Mn, Fe, Al2 O3 , SiO2 , H2 O

12.7

98

[80]

Ferric tri(dodecanesulfonate) Fe(DS)3

PRODUCTION OF PHENOL IN CONVENTIONAL AND MEMBRANE REACTORS

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Benzene: 11.25 mmol; H2 O2 : 22.50 mmol Solvent: Ionic liquid (1-n -octyl-3-ethylimidazolium hexauorophosphate (OMImPF6 ); T = 50 C Benzene: 11.25 mmol; H2 O2 : 11.25 mmol

54

100

[81]

197

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Table 3. (Continued ).

Catalyst Solvent: CH3 CN; T = 20 C 3.2 23.1

Conditions

Yield of phenol (%)a Benzene conversion (%)

Selectivity(%)b

References

Vanadium (IV) complexes with N -hydroxyiminodicarboxylic acids, Ca[V(hida)2] [hida = ON(CH2COO )2 ]

[82] [83]

Na3 VO4

2009 Curtin University of Technology and John Wiley & Sons, Ltd.

Oxovanadium(V) hydroxamate C26 H20 N2 O5 ClV FeSO4 , 5-carboxy-2-metylpyrazine-N-oxide 75 27

100

[84]

8.6 30.8 14 27

97c 79.8 94 100

[85] [86] [87] [88]

Copper hydroxyphosphate Cu2 (OH)PO4 Clay-supported vanadium oxide

Fe

3+

Al2 O3

Benzene: 5 mmol; H2 O2 : 4 mmol Solvent: acetic acid; T = 55 C Benzene: 270 mmol; H2 O2 generated from Na2 O2 = 270 mmol Solvent: CH3 CN; T = 80 C Benzene: 22.50 mmol; H2 O2 : 53 mmol Solvent: H2 O/(CH3 CN-Benzene); T = 3550 C Benzene: 180 mmol; H2 O2 : 18 mmol Solvent: acetone; T = 60 C Benzene: 11.2 mmol; H2 O2 : 11.2 mmol Solvent: acetic acid; T = 60 C Benzene/H2 O2 = 1.4 Solvent: CH3 CN/H2 O; T = 60 C Benzene: 22.50 mmol; H2 O2 : 9.4 mmol

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b c

Phenol yield(%) = mol phenol/mol initial benzene 100. Selectivity (%) = (mol phenol/mol of all oxidation products detected) 100. Calculated as mol of phenol/mol of reacted benzene 100. d Calculated by dividing the yield with the conversion.

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Membrane

199

TC

Aqueous phase

Organic phase Thermostated bath Stirrers

Hydrophobic membrane Aqueous phase

Organic phase

C6H6 C6H6+ H2O2 + cat. C6H5OH + H2O C6H5OH

Figure 6. Scheme of the biphasic membrane reactor.

to obtain advantages in terms of yield and selectivity in equilibrium-limited reactions and in consecutive catalytic reactions.

DIRECT OXIDATION OF BENZENE IN CATALYTIC MEMBRANE REACTORS USING H2 O2 AS OXIDANT

Biphasic membrane reactor
The rst approach studied[89] in our work was the liquidphase catalytic benzene oxidation using a biphasic system (Fig. 6). The two phases consist of an aqueous phase, containing the catalyst (FeSO4 ) and hydrogen peroxide (oxidant), and an organic phase containing initially only benzene. They were placed in a two compartment cell separated by a hydrophobic membrane to avoid phase mixing during the oxidation reaction and to extract phenol from the reaction at ambient conditions. This system showed a high selectivity to phenol, avoiding its over-oxidation in the organic phase. Indeed, benzene permeation, across the membrane from the organic phase, feeds the reaction interface, and then the formed phenol permeates back across the membrane to the organic phase taking shelter from over oxidation.
2009 Curtin University of Technology and John Wiley & Sons, Ltd.

The high value of phenol selectivity (98%) is obtained thanks to its extraction into the organic phase, thereby avoiding further contact with the catalyst, which is soluble in the aqueous phase. To optimize the performance of the biphasic membrane reactor the following parameters were studied: (1) feeding-mode and amount of hydrogen peroxide, (2) various organic acids to promote phenol extraction into the organic phase, (3) different kinds of membrane as perm-selective barrier for separating the two phases. A constant amount of hydrogen peroxide of 18 mmol was added by three different methods: (1) one step mode, meaning that all H2 O2 was added at the beginning of the experimental run; (2) pump top mode, i.e. by adding the H2 O2 slowly in 4 h by means of a peristaltic pump with a ow rate of 4.2 ml h1 ; and (3) pump bulk mode, similar to the previous one but the difference was the oxidant injection in the bulk of the aqueous phase of Fig. 6. By adding the hydrogen peroxide slowly (in 4 h) into the aqueous phase (mode iii)), a higher conversion based on hydrogen peroxide (96.8%) and phenol production (13.3 g l1 ) were achieved (Table 4). This difference can be explained with the high reactivity of phenol in the aqueous phase: indeed, when the oxidant is added slowly, the interfacial reaction is
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Table 4. Inuence of the addition of hydrogen peroxide mode on the benzene hydroxylation in the biphasic membrane reactor.

Mode of hydrogen peroxide feeding One step Pump top Pump bulk
a b c

Selectivity to phenola (%) 98 98 98

Benzene conversion to phenolb (%) 0.49 0.81 1.20

Hydrogen peroxide conversion to phenolc (%) 39.25 65.06 96.78

Phenol concentration g1 5.1 8.5 13.3

selectivity to phenol = [mmol phenol/(mmol phenol + mmol biphenyl + mmol benzoquinone)] 100. benzene conversion to phenol = (mmol phenol/mmol benzene initial) 100. hydrogen peroxide conversion to phenol = (mmol phenol/mmol hydrogen peroxide initial) 100.

Table 5. Inuence of hydrogen peroxide amount on the benzene hydroxylation in the biphasic membrane reactor.

Amount of hydrogen peroxide 9 18 36

Selectivity to phenol (%) 98 98 98

Benzene conversion to phenol (%) 0.25 1.20 1.12

Hydrogen peroxide conversion to phenol (%) 40.87 96.78 45.17

Phenol concentration g l1 2.7 13.3 11.8

the limiting step, so that phenol can permeate through the membrane without over oxidation caused byfurther attack from hydroxyl radical. Instead, when the hydrogen peroxide is fed by one step mode, the permeation of produced phenol across the membrane becomes the limiting step, so that a certain amount of phenol suffers over oxidation. Thus a higher by-product formation in the aqueous phase takes place, resulting in lower phenol production and uncontrolled consumption of oxidant. Regarding to the amount of hydrogen peroxide added in the aqueous phase, the results evidenced an optimal amount of 18 mmol (Table 5). Indeed, an increase from 9 to 18 mmol increased the benzene and hydrogen peroxide conversion to phenol and phenol production. A further increase to 36 mmol gave the following results: (1) the benzene conversion decreased (1.12 vs 1.20) promoting over-oxidation of a small amount of phenol; (2) the hydrogen peroxide conversion decreased at half of its optimal value (45.2 vs 96.8); and (3) the phenol production decreased slightly (11.8 vs 13.3 g l1 ). This behaviour can be explained considering that too much oxidant in the aqueous phase provokes an increase of oxidant capacity of the system. Thus the fraction of produced phenol that did not permeate in the organic phase through the membrane was converted to over oxidation products which remained in the aqueous phase. This result conrms that the oxidant must be fed in appropriate amount and slowly. Acidic pH is necessary to promote phenol extraction in the organic phase. In particular, acetic acid (pKa = 4.76) and triuoroacetic acid (pKa = 0.6)
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were considered to investigate the inuence of acidic strength on phenol transport in the organic phase. Next, ascorbic acid was tested because it could promote phenol extraction and it should be able to nd and neutralize the hydroxyl radicals in excess. The results (Table 6) showed that best system performance was obtained by using acetic acid. The inuence of porous membrane material (polypropylene (PP), polytetrauoro ethylene (PTFE) hydrophobic; polyacrylonitrile (PAN) hydrophilic) was also investigated to compare system performance in changing membrane interface where oxidation reaction takes place (Table 7). When a hydrophobic support is employed, the reaction happens at membrane interface on the aqueous side, while with hydrophilic support the oxidation takes place at membrane interface on the organic side. Obtained results showed that hydrophobic PP porous support was the best. Summarizing, the results showed that iron(II) sulphate as the catalyst, 18 mmol of hydrogen peroxide pumped in 4 h in the bulk of the aqueous phase as oxidant, acetic acid for pH control, and polypropylene hydrophobic porous support as separation barrier gave the best system performance in terms of phenol productivity (38.2 mmol gcat 1 h1 ), selectivity to phenol (98%), benzene conversion to phenol (1.2%), and hydrogen peroxide conversion to phenol (96.8%). The drawback of this system was the low rate of phenol extraction into the organic phase. Indeed, the phenol that does not cross the membrane rapidly to reach the organic phase reacts further to generate over-oxidation products and forms a black solid. Further studies are in progress to solve or reduce this problem.
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Table 6. Inuence of acid type on the benzene hydroxylation in the biphasic membrane reactor.

Acid Acetic Ascorbic Triuoroacetic

Selectivity to phenol (%) 98 98 98

Benzene conversion to phenol (%) 1.20 0.30 0.22

Hydrogen peroxide conversion to phenol (%) 96.78 49.06 17.82

Phenol concentration g l1 13.3 3.2 1.5

Table 7. Inuence of membrane materials on the benzene hydroxylation in the biphasic membrane reactor.

Membrane material PP PTFE PAN

Selectivity to phenol (%) 98 98 98

Benzene conversion to phenol (%) 1.20 0.84 0.22

Hydrogen peroxide conversion to phenol (%) 97 67 36

Phenol concentration g l1 13.3 8.8 2.4

(a)

(b)

Figure 7. Cross section images of PVDF membranes prepared with DMAc and (a) copper oxide nanopowder catalyst (PVDF2CuOnanop); (b) copper oxide powder catalyst (PVDF2CuOp).

Ultraltration membrane reactor

A further approach based on the control of the contact time of phenol with the catalyst was investigated in order to avoid/reduce by-product formation.[91] The catalyst was entrapped in polymeric membranes and the solution containing the reactants (the oxidant and the substrate) permeated through the membrane at different permeation ow rates. Various at-sheet polyvinylidene uoride (PVDF) catalytic membranes were prepared by the phase inversion process induced by a nonsolvent. Dimethylacetammide (DMAc), dimethylformammide (DMF), and 1methyl-2-pyrrolidone (NMP) were used as solvents and distilled water as the nonsolvent. For each solvent a polymer solution (20 wt%) in the solvents was prepared at room temperature; then the catalyst, a CuO powder or CuO nanopowder (16 wt%), was added and the solution was cast on a glass plate to obtain the membrane. By scanning electron microscopy (SEM) a uniform catalyst distribution was observed in all the
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polymeric membranes prepared using the copper oxide nanopowder (Fig. 7a). In contrast, no uniform catalyst distribution was observed in PVDF membranes prepared using the copper oxide powder (Fig. 7b). The membrane properties were affected by the addition of CuO particles in terms of morphological properties such as membrane thickness and pore size, and in terms of membrane performance such as the membrane permeability. The membrane characterization tests evidenced that the best solvent was the DMAc. The prepared catalytic membranes were tested using an ultraltration membrane reactor (Fig. 8). It is composed of an ultraltration membrane where a peristaltic pump fed a dead-end permeation cell with the feed solution. The permeation cell containing the membrane had an exposed surface area of 4 cm 6 cm = 24 cm2 . This system permits to control the contact time of feed solution with the catalytic membrane by varying the permeate ow rates changing the transmembrane pressure.
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Catalytic membrane

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TC Permeate

Feed

Figure 8. Scheme of the ultraltration membrane reactor.

Calculation of contact times were performed by using the following equations: Contact time = v= Membrane thickness (cm) v (cm min1 )
2

Permeate ow rate (cm3 min1 ) membrane surface (cm )

cm (2) min

where v is the permeation velocity of the reacting solutions across the membrane.

A typical procedure for oxidation tests in the membrane reactor was as follows. A solution containing 100 ml of an acetonitrile-benzene mixture of 8 : 1 v/v ratio and hydrogen peroxide of 1 : 1 molar ratio with benzene was pumped into the permeation cell at different transmembrane pressures corresponding to different contact times. The permeated solution was collected and analysed for determining the concentrations of phenol and byproducts. The preliminary catalytic tests were performed at two temperatures (35 and 50 C); the effect of acetic and ascorbic acid addition in the reacting media was also studied. The obtained results (Tables 8 and 9) showed a higher phenol concentration using the PVDF membrane lled with the CuO nanopowder rather than CuO powder catalysts. In particular a phenol yield of 2.3 (%) was obtained in a single pass using a contact time with the catalyst of 19.6 s at 35 C. The by-products such as benzoquinone and biphenyl were detected as traces. Further research is in progress to improve system performance by testing other more efcient catalysts able to increase the phenol yield and to maintain high selectivity value for longer time.

Table 8. Phenol Yield (%)a at different contact times using the catalytic membranes prepared with DMA copper oxide nanopowder catalyst (PVDF2CuOnanop).

Contact time (s) 4 4.5 5.1 6.9 10.6 19.4

Yield (%) at 35 C 0.19 0.21 0.25 0.29 0.43 0.44

Yield (%) at 50 C 0.34 0.27 0.27 0.25 0.24 0.53

Yield (%) at 35 C with acetic acidb 0.24 0.22 0.21 0.19 0.17 0.18

Yield (%) at 35 C with ascorbic acidc 0.25 0.27 0.36 0.41 0.88 2.3

a Phenol yield (%) = Ph/Bz 100, Ph is the mol numbers of phenol in the permeated solution, Bz is the mol number of benzene in the feed solution, Bz = 113 mmoles. b 4 mmol of acetic acid. c 4 mmol of ascorbic acid.

Table 9. Phenol yield (%)a at different contact times using the catalytic membranes prepared with DMA copper oxide powder catalyst (PVDF2CuOp).

Contact time (s) 33.4 47.7 66.8

Yield (%) at 35 C 0.1 0.1 0.1

Yield (%) at 50 C 0.34 0.27 0.27

Yield (%) at 35 C with acetic acidb 0.98 1.13 1.38

Yield (%) at 35 C with ascorbic acidc 1.1 1.3 1.7

a Phenol yield (%) = Ph/Bz 100, Ph is the mol numbers of phenol in the permeated solution, Bz is the mol number of benzene in the feed solution, Bz = 113 mmoles. b 4 mmol of acetic acid. c 4 mmol of ascorbic acid.

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ONE-STEP CONVERSION OF BENZENE TO PHENOL WITH COUPLED PHOTOCATALYTIC AND MEMBRANE TECHNOLOGIES
A direct synthesis of phenol from benzene was also studied using a photocatalytic reaction coupled with a membrane. In photo-catalysis the only difference with conventional catalysis is the mode of activation of the catalyst that happens by a photonic activation.[92,93] Indeed the absorption of a photon by semiconducting solids excites an electron (e ) from the valence band to the conduction band if the photon energy, h , equals or exceeds the band gap of the semiconductor/photocatalyst. Simultaneously, an electron vacancy or a positive charge, called a hole (h+ ), is also generated in the valence band (Fig. 9). Ultraviolet (UV) or near-ultraviolet photons are typically required for this kind of reactions. Generally, the hole oxidizes water to hydroxyl radicals and the electron can be donated to an electron acceptor such as an oxygen molecule (leading to formation of superoxide radical) or a metal ion (with a redox potential more positive than the band gap of the photocatalyst). In particular, for the benzene hydroxylation the formed hydroxyl radical adds directly to benzene to produce a hydroxycyclohexadienyl (HCHD) radical which rapidly undergoes an H-atom abstraction by oxidants (O2 , Fe3+ , Cu2+ , etc.) leading to phenol. Several photocatalytic systems using TiO2 as heterogeneous photocatalyst and polyoxometalate (POM) as homogeneous photocatalyst were studied by Park et al .[94] investigating on the effects of various electron acceptors such as O2 , Fe3+ , H2 O2 , Ag+ , N2 O, and surface-modied TiO2 (platinization, uorination, and silica loading). They observed that phenol production yield and selectivity were enhanced with the addition

of Fe3+ , H2 O2 , or Fe3+ + H2 O2 or modifying the surface of the catalyst, but the highest yield observed in this study was obtained with the addition of POM to TiO2 suspension. Selective photo-oxidation of liquid benzene was studied, also, using cation-exchanged zeolites dispersed in C6 H6 /CH3 CN/H2 O mixtures at room temperature by using molecular oxygen,[95] Mo complexes with Mo1Mo4 nuclearities grafted on mesoporous silica FSM-16[96] , and bis- and tris-(bipyridine) Ru complexes grafted on mesoporous FSM-16[97] using hydrogen peroxide as an oxidant under the irradiation of UV-light.

One step oxidation in a Photocatalytic Membrane Reactor

The photocatalytic process coupled with a membrane system for the direct hydroxylation of benzene was studied by Molinari et al .[98] In a PMR, the one-step synthesis of phenol and its simultaneous separation happen. The experimental plant used (Fig. 10) was realized by connecting a photocatalytic batch reactor with the biphasic separation system described in Fig. 6 in which the aqueous reactive phase was constituted by 700 ml of an acidic solution containing suspended TiO2 as catalyst and benzene as substrate. Preliminary dark reactions and photolytic tests were performed on benzene dispersions in water, in absence of UV light and the catalyst, respectively. They showed that the oxidation reaction occurs in a true photocatalytic regime. Besides, by means of batch tests, the inuence of some photocatalytic parameters (initial substrate amount, catalyst concentration, pH, etc.) were studied in order to choose the optimal operative conditions to employ in the photo membrane contactor (PMC). A rst set of experiments was performed varying the initial volume of benzene added to the TiO2 suspension to investigate the inuence of the amount of substrate on the rate of phenol production. The obtained results

O2O2 Conduction band e-

UV
L

MC aq phase org phase

Band Gap (Eg)

Valence band

h+ P TB OH-/H2O PR

OH

Figure 9. Band-gap diagram: formation of holes (h+ ) and electrons (e ) upon UV irradiation of semiconductor surface.
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Figure 10. Scheme of the PMC: PR, photoreactor system; MC, membrane contactor; L, UV lamp; TB, thermostatic bath; P peristaltic pump.
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showed that oxidation kinetics did not depend on the undissolved substrate but on its concentration in solution (460 50 mg l1 with 5 and 10 ml vs 60 10 mg l1 with 1 ml after 2 h), showing the need to realize a system that provides benzene continuously. Besides, by changing the pH of the aqueous suspensions it was observed that the system productivity increased at alkaline values, due to a lower phenol adsorption on the catalyst surface which reduced its subsequent oxidation reactions. Moreover, on using sulphuric or hydrochloric acid to reduce the pH, it was observed that the oxidation was also inuenced by the type of anion present. In particular, the sulphate ion increased the productivity but reduced the selectivity of the process. Negligible variations were obtained in the rate of phenol production in a range of catalyst concentration of 0.11 g l1 , with values of 0.13 vs 0.18 mg l1 min1 , respectively, in the rst 100 min. By means of extraction and transport tests the efciency of the realized system was veried in terms of ux and extraction degree of phenol in the organic phase. From the slope of the equilibrium isotherm (25 C) of the water/benzene system, a distribution coefcient of phenol between the two phases of 2.1 was obtained, while an extraction percentage value (E%) of 24 2% was measured at the steady state (after 360 min) in the transport tests. Although these values were lower than those of other extractants reported in the literature, a constant benzene concentration of about 200 50 mg l1 was measured in the aqueous phase assuring a constant feeding of the substrate to the reactive environment. In a rst set of photooxidation tests in the PMC the effect of the pH of the aqueous phase on the efciency of the process was investigated. The data obtained at pH values of 5.5 and 3.1 showed that the more acidic pH condition allows to obtain a slight increase in the phenol production in the aqueous phase (Fig. 11) and a constant ux (after 2 h) in the organic phase of 1.27 mmol h1 m2 (compared to the value of 1.06 mmol h1 m2 obtained at pH 5.5).

During the reaction runs, three main intermediate products were observed in the high performance liquid chromatography (HPLC) chromatograms. Two of them were identied by GC-MS (gas chromatography-mass spectrometry) measurements as BQ and HQ, while the other oxidation product (Ox3.6) is under study. By the area of these by-products it was observed that the membrane system allowed to maintain HQ in the aqueous phase, but it was not able to reject the other oxidation products, which pass completely into the organic phase due to their greater solubility in that phase. However, the acidic pH led to a lower extent of formation and extraction of these intermediates (Fig. 12). Another set of experiments was performed investigating the effects of some parameters, such as catalyst concentration and light intensity, on the photocatalytic and separation performance of the PMC. Comparing the results obtained with higher TiO2 amounts and lower irradiation power with those using 0.1 g l1 of catalyst and an irradiation of 6.0 mW cm2 (Fig. 13), only a negligible increase of phenol production and extraction was observed with a catalyst concentration of 1 g l1 , while a marked decrease of the system efciency was found with a light intensity of 4.7 mW cm2 .

180 pH 5.5 Area (mAU) 120

Aqueous phase Organic phase

pH 3.1

60

0 HQ Ox3.6 BQ HQ Ox3.6 BQ

Figure 12. Comparison of the HPLC peaks of three intermediates in the two phases measured in the photocatalytic oxidation tests at pH 3.1 and 5.5.

20 C phenol (mg L-1) Cphenol (mg L-1) 16 12 8 4 0 0 100 200 300 Time (min) 400 500
pH 3.1 pH 5.5

CAT0.1 I6.0

CAT1.0 I6.0

CAT0.1 I4.7

20 15 10 5 0 Aqueous phase Organic phase

Figure 11. Phenol concentration in the aqueous phase versus the time in the photocatalytic oxidation tests performed in the PMC at pH 3.1 and 5.5.
2009 Curtin University of Technology and John Wiley & Sons, Ltd.

Figure 13. Phenol concentration in the aqueous and organic phases in oxidation experiments in the PMC (CTiO2 = 0.1 g l1 and I = 6.0 mW cm2 ; CTiO2 = 1.0 g l1 and I = 6.0 mW cm2 ; CTiO2 = 0.1 g l1 and I = 4.7 mW cm2 ).
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PRODUCTION OF PHENOL IN CONVENTIONAL AND MEMBRANE REACTORS [10] R. Schmidt. J. Appl. Catal. A Gen., 2005; 280, 89103. DOI:10.1016/j.apcata.2004.08.030. [11] M.H. Sayyar, R.J. Wakeman. Chem. Eng. Res. Des., 2008; 86, 517526. DOI:10.1016/j.cherd.2008.02.00.9. [12] L.V. Pirutko, V.S. Chernyavsky, A.K. Uriarte, G.I. Panov. Appl. Catal. A Gen., 2002; 227, 143157. [13] V.I. Sobolev, G.I. Panov, A.S. Kharitonov, V.N. Romannikov, A.M. Volodin, K.G. Ione. J. Catal., 1993; 139, 435443. [14] G.I. Panov, G.A. Sheveleva, A.S. Kharitonov, V.N. Romannikov, L.A. Vostrikova. Appl. Catal. A Gen, 1992; 82, 3136. [15] M. Mauvezin, G. Delahay, B. Coq, S. Kieger, J.C. Jumas, J. Olivier-Fourcade. J. Phys. Chem. B, 2001; 105, 928935. [16] G. Berlier, G. Spoto, G. Ricchiardi, S. Bordiga, C. Lamberti, A. Zecchina. J. Mol. Catal. A Chem, 2002; 182-183, 359366. [17] G. Berlier, A. Zecchina, G. Spoto, G. Ricchiardi, S. Bordiga, C. Lamberti. J. Catal., 2003; 215, 264270. DOI:10.1016/S0021-9517(03)000046. [18] L. Kiwi-Minsker, D.A. Bulushev, A. Renken. J. Catal., 2003; 219, 273285. DOI:10.1016/S0021-9517(03)00222-7. [19] B. Louis, C. Tezel, L. Kiwi-Minsker, A. Renken. Catal. Today, 2001; 69, 365370. [20] I. Yuranov, D.A. Bulushev, A. Renken, L. Kiwi-Minsker. J. Catal., 2004; 227, 138147. DOI:10.1016/j.jcat.2004. 06.014. [21] G.D. Pirngruber. J. Catal., 2003; 219, 456463. DOI:10.1016/ S0021-9517(03)00220-3. [22] P.K. Roy, G.D. Pirngruber. J. Catal., 2004; 227, 164174. DOI:10.1016/j.jcat.2004.07.004. [23] S. Komeoka, T. Nobukova, S.-I. Tanaka, I. Shin-ichi, K. Tomishige, K. Kunimori. Phys. Chem. Chem. Phys., 2003; 5, 33283333. [24] E. Suzuki, K. Makashiro, Y. Ono. Chem. Soc. Jap. Chem. Commun., 1988; 953959. [25] V. Zholobenko. Mendeleev 0043ommun., 1993; 1, 2829. [26] M.H. Gubelmann, P.J. Tirel. Fr. Patent 2 630 735, 1988. [27] J.L. Motz, H. Heinichen, W.F. H olderich. Stud. Surf. Sci. Catal., 1997; 105, 10531060. [28] M. Iwamoto, J. Hirata, K. Matsukami, S. Kagawa. J. Phys. Chem., 1983; 87, 903905. [29] A.S. Kharitonov, T.N. Aleksandrova, L.A. Vostrikova, V.I. Sobolev, K.G. Ione, G.I. Panov. USSR Patent 1805127, 1988. [30] V.I. Bogdan, L.M. Kustov, D.B. Batizat, A.M. Sakharov, V.B. Kazansky. Stud. Surf. Sci. Catal., 1995; 94, 635642. [31] A. Ribera, I.W.C.E. Arends, S. De Vries, J. Perez-Ramires, R.A. Sheldon. J. Catal. A, 2000; 195, 287297. [32] P.P. Nott` e. Top. Catal., 2000; 13, 387394. [33] S.N. Vereshchagin, N.P. Kirik, N.N. Shishkina, A.G. Anshits. Catal. Lett., 1998; 56, 145148. [34] B. Louis, L. Kiwi-Minsker, P. Reuse, A. Renken. Ind. End. Chem. Res., 2001; 40, 14541459. [35] M. H afele, A. Reitzmann, E. Klemm, G. Emig. Stud. Surf. Sci. Catal., 1997; 110, 847856. [36] M. H afele, A. Reitzmann, D. Roppelt, G. Emig. Appl. Catal. A, 1997; 150, 153164. [37] L.V. Pirutko, A.K. Uriarte, V.S. Chernyavsky, A.S. Kharitonov, G.I. Panov. Micropor. Mesopor. Mater., 2001; 48, 345353. [38] A.S. Kharitonov, G.A. Sheveleva, G.I. Panov, V.I. Sobolev, Y.A. Paukshtis, V.N. Romannikov. Appl. Catal. A, 1993; 98, 3343. [39] R. Monaci, E. Rombi, M.G. Cutrufello, V. Solinas, G. Berlier, G. Spoto. Stud. Surf. Sci. Catal., 2000; 130, 16791684. [40] V.N. Parmon, G.I. Panov, A. Uriarte, A.S. Noskov. Catal. Today, 2005; 100, 115131. DOI:10.1016/j.cattod.2004. 12.012. [41] S. Gopalakrishnan, S. Yada, J. Muench, T. Selvam, W. Schwieger, M. Sommer, W. Peukert. Appl. Catal., 2007; 327, 132138. DOI:10.1016/j.apcata.2007.03.003. [42] D. Meloni, R. Monaci, V. Solinas, G. Berlier, S. Bordiga, I. Rossetti, C. Oliva, L. Forni. J. Catal., 2003; 214, 169178. DOI:10.1016/S0021-9517(03)00013-7. [43] K.M. Ervin, V.F. Deturi. J. Phys. Chem. A, 2002; 106, 99479956. [44] X. Gao, J. Xu. Catal. Lett., 2006; 111, 203205. DOI: 10.1007/s10562-006-0148-1. Asia-Pac. J. Chem. Eng. 2010; 5: 191206 DOI: 10.1002/apj

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CONCLUSIONS
The cumene process for making phenol is today unsustainable in terms of environmental impact and energyconsumption. In this context much effort is devoted to new processes that produce phenol using a direct route with high yield and selectivity. Direct oxidation has been studied by many authors in both gas and liquid phases, under low and high pressure, and with and without catalysts, making this reaction more studied both for the variety of approaches and number of tested catalysts; nevertheless, relatively few catalytic processes have successfully been developed. One example of advanced direct oxidation process is the Alphox process developed by Solutia based on nitrous oxide oxidation of benzene with phenol selectivities of 97100% at 100% N2 O conversion. However, the catalyst, at present, requires frequent regeneration driving up capital costs. When oxygen was used as the oxidant, it usually needs reducing agents to activate the oxygen and this not only consumes the oxidant but also increases the possibility of explosion. An interesting process based on the oxygen as oxidant is represented by the employment of a palladium membrane reactor using O2 /H2 as the oxidant, where a high phenol yield was obtained and the possibility explosion was avoided. The development of biphasic systems using H2 O2 as oxidant has allowed to getting high selectivity values (9798%) thanks to the selective role of the membrane. Currently, further efforts are in demand to search and replace the three step traditional process to convert benzene into phenol with a process of direct oxidation. However, too much resistance is encountered to substitute the old with the new.

Acknowledgements
The authors thank the MIUR within the FIRB 2005 2009 programme for the nancial support.

REFERENCES
[1] Y. Liu, K. Murata, M. Inaba. J. Mol. Catal. A, 2006; 256, 247255. DOI:10.1016/j.molcata.2006.05.015. [2] S. Niwa, M. Eswaramoorthy, J. Nair, A. Raj, N. Itoh, H. Shoji, T. Namba, F. Mizukami. Science, 2002; 295, 105107. DOI: 10.1126/science.1066527. [3] G. Bellussi, C. Perego. CATTECH, 2000; 4, 416. [4] J. Coronas, J. Santamaria. Catal. Today, 1999; 51, 377389. [5] J.N. Armor. J. Mem. Sci., 1998; 147, 217233. [6] G. Saracco, V. Specchia. Cat. Rev. Sci. Eng., 1994; 36, 305384. [7] A. Sengupta, K.K. Sirkar. In Membrane Separations Technology, Principles and Application (Eds.: R.D. Noble, S.A. Stern), Elsevier Science: Amsterdam, 1995; pp.499501. [8] G.I. Panov. CATTECH, 2000; 4, 1832. [9] J.T.F. Degnan, C.M. Smith, C.R. Venkat. J. Appl. Catal. A Gen., 2001; 221, 283294.
2009 Curtin University of Technology and John Wiley & Sons, Ltd.

206

R. MOLINARI AND T. POERIO [45] A. Kunai, T. Kitano, Y. Kuroda, J. Li-Fen, K. Sasaki. Catal. Lett., 1990; 4, 139144. [46] N. Hideyki, N. Mitiyki, K. Motohiro. Japan Patent 6256241, 1994. [47] M. Hamada, Y. Sasaki, T. Mitake. Japan Patent 54935, 1993. [48] M. Hamada, H. Niwa, M. Oguri, T. Miyake. USA Patent 5,426,245, 1993. [49] T. Miyake, M. Hamada, Y. Sasaki, M. Oguri. Appl. Catal. A Gen., 1995; 131, 3342. [50] T. Tatsumi. Japan Patent 5320082, 1993. [51] J.E. Remias, T.A. Pavlosky, A. Sen. J. Mol. Catal. A Chem., 2003; 203, 179192. DOI:10.1016/S1381-1169(03)00212-7. [52] N.I. Kuznetsova, L.I. Kuznetsova, V.A. Likholobov, G.P. Pez. Catal. Today, 2005; 99, 193198. DOI:10.1016/j.cattod. 2004.09.040. [53] H. Ehrich, H. Berndt, M.-M. Pohl, K. J ahnisch, M. Baerns. Appl. Catal. A Gen, 2002; 230, 271280. [54] G.D. Vulpescu, M. Ruitenbeek, L.L. van Lieshout, L.A. Correia, D. Meyer, P.P.A.C. Pex. Catal. Commun., 2004; 5, 347351. DOI:10.1016/j.catcom.2004.04.002. [55] K. Sato, T. Hanaoka, S. Niwa, C. Stefan, T. Namba, F. Mizukami. Catal Today, 2005; 104, 260266. DOI:10.1016/ j.cattod.2005.03.067. [56] R. Cai, S. Song, B. Ji, W. Yang, G. Sun, Q. Xin. Catal. Today, 2005; 104, 200204. DOI:10.1016/j.cattod.2005.03.052. [57] N. Itoh, S. Niwa, F. Mizukami, T. Inoue, A. Igarashi, T. Namba. Catal. Commun., 2003; 4, 243246. DOI:10.1016/ S1566-7367(03)00046-3. [58] K. Otsuka, K. Hosokawa, I. Yamanaka, Y. Wada, A. Morikawa. Electrochim. Acta, 1989; 34, 14851488. [59] I. Yamanaka, T. Akimoto, K. Otsuka. Electrochim. Acta, 1994; 39, 25452549. [60] M. Tani, T. Sakamoto, S. Mita, S. Sakaguchi, Y. Ishii. Angew. Chem. Int. Ed., 2005; 44, 25862588. DOI: 10.1002/anie.200462769. [61] T. Miyahara, H. Kanzaki, R. Hamada, S. Kuroiwa, S. Nishiyama, S. Tsuruya. J. Mol. Catal. A Chem, 2001; 176, 141150. [62] E. Battistel, R. Tassinari, M. Fornaroli, L. Bonoldi. J. Mol. Catal. A Chem, 2003; 202, 107115. DOI:10.1016/S13811169(03)00259-0. [63] H. Kanzaki, T. Kitamura, R. Hamada, S. Nishiyama, S. Tsuruya. J. Mol. Catal. A Chem, 2004; 208, 203211. DOI:10.1016/S1381-1169(03)00516-8. [64] Y. Liu, K. Murata, M. Inaba. Catal. Commun., 2005; 6, 679683. DOI:10.1016/j.catcom.2005.06.015. [65] Y.-K. Masumoto, R. Hamada, K. Yokota, S. Nishiyama, S. Tsuruya. J. Mol. Catal. A Chem., 2002; 184, 215222. [66] Y.-Y. Gu, X.-H. Zhao, G.-R. Zhang, H.-M. Ding, Y.K. Shan. Appl. Catal. A Gen, 2007; 328, 150155. DOI:10.1016/j.apcata. 2007.06.002. [67] Y. Ichihashi, T. Taniguchi, H. Amano, T. Atsumi, S. Nishiyama, S. Tsuruya. Top Catal., 2008; 47, 98100. DOI 10.1007/s11244-007-9027-2. [68] Y. Liu, K. Murata, M. Inaba. J. Mol. Catal. A Chem., 2006; 256, 247255. DOI:10.1016/j.molcata.2006.05.015. [69] Y.J. Seo, Y. Mukai, T. Tagana, S. Goto. J. Mol. Catal. A Chem, 1997; 120, 149154. [70] L.C. Passoni, A. Tadini Cruz, R. Buffon, U. Schuchardt. J. Mol. Catal. A Chem, 1997; 120, 117123. [71] R. Noyori, M. Aoki, K. Sato. Chem. Commun., 2003; 19771986. DOI: 10.1039/b303160h.

Asia-Pacic Journal of Chemical Engineering [72] Y. Leng, H. Ge, C. Zhou, J. Wang. Chem. Eng. J., 2008; 145, 335339. DOI:10.1016/j.cej.2008.08.015. [73] Y. Tang, J. Zhang. Transition M. Chem., 2006; 31, 299305. DOI 10.1007/s11243-005-6412-1. [74] J. Zhang, Y. Tang, G. Li, C. Hu. Appl. Catal. A Gen., 2005; 278, 251261. DOI:10.1016/j.apcata.2004.10.009. [75] Y.-W. Chen, H.-Y. Lin. J. Porous Mater., 2002; 9, 175184. [76] L. Balducci, D. Bianchi, R. Bortolo, R. DAloisio, M. Ricci, R. Tassinari, R. Ungarelli. Angew. Chem. Int. Ed., 2003; 42, 49374940. DOI: 10.1002/anie.200352184. [77] D. Bianchi, L. Balducci, R. Bortolo, R. DAloisio, M. Ricci, G. Span, R. Tassinari, C. Tonini, R. Ungarelli. Adv. Synth. Catal., 2007; 349, 979986. DOI: 10.1002/adsc.200600371. [78] B. Chou, J.-L. Tsai, S. Cheng. Micropor. Mesopor. Mater., 2001; 48, 309317. [79] H. Nur, H. Hamid, S. Endud, H. Hamdan, Z. Ramli. Mater. Chem. Phys., 2006; 96, 337342. DOI:10.1016/j. matchemphys.2005.07.023. [80] K.M. Parida, S.S. Dash. J. Colloid Interface Sci., 2007; 316, 541546. DOI:10.1016/j.jcis.2007.08.054. [81] J. Peng, F. Shi, Y. Gu, Y. Deng. Green Chem., 2003; 5, 224226. DOI: 10.1039/b211239f. [82] P.M. Reis, J.A.L. Silva, J.J.R. Frausto da Silva, A.J.L. Pombeiro. J. Mol. Catal. A Chem., 2004; 224, 189195. DOI:10.1016/j.molcata.2004.08.048. [83] N.I. Rudakova, M.V. Klyuev, Y.G. Erykalov, D.N. Ramazanov. Russ. J. Gen. Chem., 2006; 76, 14071409. DOI: 10.1134/S107036320609009X. [84] T.K. Si, K. Chowdhury, M. Mukherjee, D.C. Bera, R. Bhattacharyya. J. Mol. Catal. A Chem., 2004; 219, 241247. DOI:10.1016/j.molcata.2004.05.006. [85] D. Bianchi, R. Bortolo, R. Tassinari, M. Ricci, R. Vignola. Angew. Chem. Int. Ed., 2000; 39, 43214323. [86] F.S. Xiao, J. Sun, X. Meng, R. Yu, H. Yuan, D. Jiang., S. Qiu, R. Xu. Appl. Catal. A Gen., 2001; 207, 267271. [87] X. Gao, J. Xu. Appl. Clay Sci., 2006; 33, 16. DOI:10.1016/j. clay.2005.12.002. [88] H.H. Monfared, Z. Amouei. J. Mol. Catal. A Chem., 2004; 217, 161164. DOI:10.1016/j.molcata.2004.03.020. [89] J.R.L. Smith, R.O.C. Norman. J. Chem. Soc., 1963; 28972899. [90] R. Molinari, T. Poerio, P. Argurio. Italy Patent CZ A000029, 2006. [91] R. Molinari, T. Poerio, P. Argurio. Catal. Today, 2006; 118, 5256. DOI:10.1016/j.cattod.2005.11.089. [92] M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemannt. Chem. Rev., 1995; 95, 6996. [93] J.-M. Herrmann. Top. Catal., 2005; 34, 4965. DOI: 10.1007/s11244-005-3788-2. [94] H. Park, W. Choi. Catal. Today, 2005; 101, 291297. DOI:10.1016/j.cattod.2005.03.014. [95] K. Shimizu, H. Akahane, T. Kodamab, Y. Kitayama. Appl. Catal. A. Gen., 2004; 269, 7580. DOI:10.1016/j.apcata.2004. 04.001. [96] K. Zama, A. Fukuoka, Y. Sasaki., S. Inagaki., Y. Fukushima, M. Ichikawa. Catal. Lett., 2000; 66, 251253. [97] K. Fujishima, A. Fukuoka, A. Yamagishi, S. Inagaki, Y. Fukushima, M. Ichikawa. J. Mol. Catal. A Chem., 2001; 166, 211218. [98] R. Molinari, T. Poerio, A. Caruso, P. Argurio, S.M. Carnevale. In Future Feedstocks for Fuels and Chemicals (Eds.: S. Ernst, A. Jess, F. Nees, U. Peters, M. Ricci, E. Santacesaria), DGMK: Berlin, 2008; pp.217224.

2009 Curtin University of Technology and John Wiley & Sons, Ltd.

Asia-Pac. J. Chem. Eng. 2010; 5: 191206 DOI: 10.1002/apj