Recent Patents on Engineering 2010, 4, 000-000 1

Photoreactors for Wastewater Treatment: A Review

Ewa Kowalska* and Sven Rau

Friedrich-Alexander University of Erlangen-Nuremberg, Institute of Inorganic Chemistry, 91058 Erlangen, Germany

Received: August 10, 2010; Accepted: November 2, 2010; Revised: October 30, 2010

Abstract: Photochemical oxidation of organic and inorganic pollutants is rapidly becoming an attractive technique for
water purification and wastewater treatment. Since artificial sources of light require much energy delivery, this method is
recommended for toxic contaminants in a specific concentration range below the recommended levels for recovery and
above the levels for conventional biological treatment. Selection of a light source and an oxidation system and determina-
tion of key-parameters play an important role in the treatment efficiency. Sufficient UV penetration into the radiated liq-
uid is of crucial importance; especially for an opaque environment the UV radiation is only available very close to the UV
lamp surface. High mass transfer rates for efficient interaction between the pollutant and the photocatalyst and for high
oxygen uptake at the gas-liquid interface is another requirement for practical applications. In this regard, reactor design
for efficient wastewater treatment has been a challenging problem. Many types of photoreactors have already been stud-
ied, reported and patented. This paper presents a revision of some conventional and novel photoreactors equipped with
UV/vis lamps or working under solar radiation for wastewater treatment in laboratory and industrial scales.
Keywords: Advanced Oxidation Processes (AOPs), catalyst immobilization, photocatalysis, photoreactor, wastewater treat-
ment, UV/H2O2, UV/TiO2.

INTRODUCTION UV penetration into the radiated liquid is of crucial impor-

Advanced oxidation processes (AOPs) including pho-
tolysis and photocatalysis, are regarded as environmentally
attractive technologies for degradation of toxic organic pol-
lutants in an aquatic and air environment [1]. AOPs involve
generation and subsequent reaction of hydroxyl radicals
(•OH). The hydroxyl radicals are capable of oxidizing or-
ganic compounds mostly by hydrogen abstraction, generat-
ing organic radicals which, by addition of molecular oxygen,
yield peroxyl radicals. These intermediates initiate chain
reactions of oxidative degradation leading eventually to car-
bon dioxide, water and inorganic salts. Thus the efficiency of
degradation depends on the energy needed to homolyze a
given chemical bond and on the availability of dissolved
molecular oxygen. The rate of chemical oxidation of the pol-
lutants is controlled by the rate of formation of hydroxyl
radicals.
Since artificial sources of light require much energy de-
livery, this method is recommended for toxic contaminants
in a specific concentration range below the recommended
levels for recovery and above the levels for conventional
biological treatment. Selection of a light source (natural or
artificial) and an oxidation system (UV, UV/H2O2, UV/O3,
UV/TiO2, UV/Fe+3/H2O2, etc.), determination of key-
parameters, such as pollutant concentrations, distribution and
amount of oxidant, amount and form (suspended or immobi-
lized) of photocatalyst, pH, residence time and flow rates,
play an important role in the treatment efficiency. Sufficient
*Address correspondence to this author at the Friedrich-Alexander Univer-
sity of Erlangen-Nuremberg, Institute of Inorganic Chemistry, Egerlandstr.
1, 91058 Erlangen, Germany; Tel: (+49-9131) 85 27398; Fax: (+49-9131)
85 27367; E-mail: Ewa.Kowalska@chemie.uni-erlangen.de
tance; especially for an opaque environment (often occurring
in the case of real wastewater) the UV radiation is only
available very close to the UV lamp surface. High mass
transfer rates for efficient interaction between the pollutant
and the photocatalyst and for high oxygen uptake at the gas-
liquid interface is another requirement for practical applica-
tions. In this regard, reactor design for efficient wastewater
treatment has been a challenging problem. Many types of
photoreactors has been already studied, reported and pat-
ented. This paper presents a revision of some conventional
and novel photoreactors equipped with UV/vis lamps or
working under solar radiation for wastewater treatment in
laboratory and pilot-plan scales.
CONSTRUCTION OF PHOTOREACTORS
Source of Irradiation
Photochemical reactions may be carried in the most of
the reactor types used for thermal or thermal-catalytic proc-
esses [2]. The driving force is a significant difference be-
tween them and other reactions, since they are activated by
absorption of light. Thus, the distribution of electromagnetic
radiation must be the integral part of photoreactor design.
Two kinds of irradiation systems may be used to carry out
photoreactions: artificial (lamps) and natural (the Sun)
sources of light. The oldest, and at the same, the most popu-
lar lamp is a low-pressure mercury lamp (LPML) which is a
gas discharge lamp. The LPML composes of tungsten fila-
ments, located inside each end of the lamp, and a jacket
filled with inert gas (argon) and mercury vapor under nega-
tive pressure (<13 hPa). Thus, these lamps are also known as
vacuum ultraviolet (VUV). Mercury is excited by glow dis-
charge emitting line spectrum at 185 and 253.7 nm. The

1872-2121/10 $100.00+.00 © 2010 Bentham Science Publishers Ltd.

2 Recent Patents on Engineering 2010, Vol. 4, No. 3
LPML is similar to a common fluorescent lamp (FL) but its
jacket, made of quartz, allows transmitting ultraviolet rays.
In the case of FL a jacket is covered with luminophore which
absorbs whole radiation at 253.7 nm emitting radiation at
longer wavelengths in the visible range. The mercury is often
replaced by amalgam (AFL) to avoid the influence of envi-
ronment temperature on lamp capacity (for mercury FLs
15ºC is recommended). The next, often used lamp is a mid-
dle pressure mercury lamp (MPML) often called polychro-
matic lamp, since it emits light from 200 nm till IR. The
pressure inside quartz tube is higher and equals 1300 hPa.
The lamp is working under high temperature and the tem-
perature of its surface may reach 800°C, the temperature of
insulating jacket usually does not exceed 60°C. Emerging
LED technologies might in the future become more impor-
tant as they represent a more energy efficient means of prov-
ing irradiation than conventional techniques. However, con-
tinuous sources of light are still more stable than line
sources.
Photo-reactions are usually carried out under UV part of
electromagnetic radiation. Conventionally UV is divided into
four ranges: Vacuum Ultravolet (VUV), Ultraviolet C
(UVC), Ultraviolet B (UVB) and Ultraviolet A (UVA). Far,
mid and near UV instead of VUV/UVC, UVB and UVA,
respectively, are also often used. In the literature different
ranges for specific UV types have been used. The usage of
unified radiation ranges based on ISO International Standard
[3] are recommended and presented in Table 1. Here we are
presenting only main classification, the specified ranges are
not shown in this Table, i.e. Vacuum Ultraviolet (VUV) con-
tains also Extreme Ultraviolet (EUV, 10-121 nm), Hydrogen
Lyman-alpha (H Lyman-
, 121-122 nm) and Far Ultraviolet
(FUV, 122-200 nm), X-rays can be divided into Hard and
Soft, Microwave into W, V, Q, K, X, C, S, L and P, and Ra-
dio (0.1 mm - 100 m) into EHF, SHF, UHF, VHF and HF. In
this review we will focus on processes based on UV and/or
visible light irradiation as these processes seem easier for
commercial application. However we do not exclude the
application of processes using different radiation ranges, e.g.
ionizing radiation, since some preliminary cost analyses
showed the potential of this high energy irradiation espe-
cially with regards to substantial economic advantages for
sewage-sludge treatment [4].
Wavelength/Lamp Selection
Microorganisms can be destructed by direct UV irradia-
tion. Therefore UV radiation is usually applied for disinfec-
tion as an alternative to traditional chlorination methods [83]
since Cl2, NaClO, Ca(ClO)2 usage causes generation of can-
cerogenic substances [84]. Disinfection is usually carried out
under irradiation with 253.7 nm [84, 85] since majority of
organic components of bacterial cells is resistance to irradia-
tion under longer wavelengths [85]. The main mechanism of
elimination of bacteria cells is based on photon absorption
by DNA (263-275 nm) which causes splitting of hydrogen
bonds and thus generated break in DNA chain or other irre-
versible changes of the DNA precluding its transcription.
The more energetic wavelengths (shorter) may be absorbed
by cell membrane precluding regulation of osmotic pressure.
The mechanism of bacteria deactivation depends on wave-
length range, and thus UVA destroys non-nuclear cellular
Kowalska and Rau
components, while UVB and UVC usually destruct nucleus
[85]. Disinfection by UV radiation is applied for liquids
(drinking water, emulsions and brines in food and pharma-
ceutical industry, process water and swimming pool water),
air (ventilation chambers, hospitals) and surfaces (packing
materials).
Alternatively to direct destruction of bacteria, photocata-
lytic processes and photolysis of reactive compounds may be
employed as well. In the resent years the application of UV
and/or vis irradiation for water/wastewater treatment has
been widely studied [26, 28, 42, 47, 86-91]. Many types of
lamps have been used for examination of contaminants deg-
radation and some of them are presented in Table 1. The
choice of lamp used for photodegradation is made on the
basis of wavelength requirement for AOPs, and thus LPMLs
(254.7 nm) are usually used for disinfection and H2O2 pho-
tolysis, MPMLs, HPMLs, FLs and xenon lamps for photo-
catalysis on the surface of common TiO2 photocatalyst
which requires UVA/vis activation (< 400 nm). While tung-
sten lamps, halogen lamps and LEDs are often applied for
photocatalysis on the surfaces of novel photocatalysts with
ability of working under visible-light irradiation, e.g. modi-
fied TiO2, Pt/WO3, Au/CeO2.
Placement of Light Source and Light Distribution
Photoirradiation can be carried out from outside the reac-
tor (external illumination) [57, 90, 92] or by lamps immersed
in the liquid (placed in the reactor, internal illumination) [28,
90, 93, 94]. External illumination can be carried out by one
or a few lamps placed in parallel or perpendicularly to the
side walls of the reactor [95], lamps placed at the focal axis
of a parabolic reflector [30, 96], screens surrounded the reac-
tor or point source of light [57, 97].
In the case of external illumination (often point irradia-
tion), the light passes through focusing or collimating lens
(silicate glass, fused silica [92], quartz [98]; lamp can be also
installed inside light condensing lamp housing [99]), an IR
absorption filter filled with water or other solution, e.g. UV
absorbing (Ni-Co sulfate [92], potassium chromate (> 500
nm), sodium nitrite (> 400 nm) [56, 100]), an interference
filter (band-pass or cut-off) or simple Pyrex glass (to cut off
the light of < 300 nm) [17, 101] to a reaction cell. The UV
light with the desired intensity can be obtained by applica-
tion of neutral density filters [92] or stainless-steel screens
with different mesh sizes [102]. A reaction cell often is made
of quartz to enable UV transmission or a cell made of glass
equipped with quartz window is used. When IR filter is in-
sufficient or when temperature inside cell increases due to
exothermic reaction, additional cell cooling is applied. Usu-
ally a cell is placed in thermostated bath filled with water
(distilled water is recommended for constant radiation inten-
sity). The cell cooling by flow of air [32, 103], application of
cold mirror [104] or direct lamp cooling by compressed air
[32] have been also reported. Within this context it is very
important to note that concentration of light (by application
of focusing lens) as well as flat surface of front wall of the
reactor can be the reason of increase of experimental error
since every, even very small, change of reactor position (e.g.
after cleaning) is connected with large change in light inten-
sity and its distribution. Thus, the position of irradiated cell
Photoreactors for Wastewater Treatment: A Review Recent Patents on Engineering 2010, Vol. 4, No. 3 3

Table 1. Categories, Sources and Application of Electromagnetic Radiation

Spectral Cate- Wavelength Common

Radiation Source Oxidation System/Application for Wastewater Treatment
gory/Subcategory Range/nm [3] Name [3]
60
Gamma-rays 0.00001- 0.001 - Co gamma source [5-8] - sewage-sludge: solubilization, neutralization and improved
filterability [4, 9],
- wastewater treatment: elimination of bacterial flora; BOD,
COD, ammonia nitrogen, toxicity and TSS decrease [4, 5, 8,
10, 11]; biodegradability increase (BOD/COD) [6, 12]; degra-
dation of thebaine [13]; dechlorination of PCE [7]

X-rays 0.001 - 10 - Cu K, Synchrotron radia- -

tion [14],
HHG [14], Ne-ZnL (21.2
nm) [15]

Ultraviolet (UV): 100 - 400 Ultraviolet

VUV 10 - 200 Vacuum Xe2*L [16], XeL [17], VUV: germicidal [16], photolysis (VOCs [21])
Ultraviolet LPML [18, 19], W-MDEL VUV/H2O/O 2•OH, 1O2, O3: 2,4-D, BPA [20] VUV/O2 O3:
[20] phenol [18], surfactants [19]

UVC 100 - 280 Ultraviolet XeL [17], KrCl*L [16], UV: germicidal [11, 16, 24]; UV/H 2O2: germicidal [24], de-
C TUV [22], ML [23], LMPL colorization of river water [25], decomposition of: phenol
[24], W-MDEL [20] [26], DMDT [27], real pesticide wastewater [28]; UV/O3:
phenol degradation [23],

UVB 280 - 315 Ultraviolet XeL [17, 29], FL [30], ML UV: pesticide photolysis [29]
B [23]

UVA 315 - 400 Ultraviolet HPML [31, 32], FL [30, UV/TiO2 :organic and inorganic pollutants [41-43], dyehouse
A 33], Bl [34], BlB [35, 36], effluents [33], phenol [17, 32], 4-CP [32], 4-NP [32], salicylic
XeL [17], MVL [37], BLFL acid [38], chloroform [44], chloroorganic pesticides [45-47],
[38], MPML [39], ML [23], cyanide [48], BSA [30], dodecane [49]; Fe+3 /H2O2 /UV-vis:
TL[40] fenitrothion [50]

Visible (VIS): 380 – 760: Optical: XeL [17], THL [51],LED model wastewater treatment by: Vis/modified-TiO2 [55]:
[52], OLEDs [53], - nonmetal/TiO2: C [56, 57], S [58], N [59-61], F [62], B [63],
360 - 450 Purple
PHOLEDs [53], I [64]
450 - 500 Blue FL [30, 36], WL [40, 54], - metal/TiO 2: Fe [36], Pt [65, 66], Au [67, 68], Ag [45], La
MVL [37] [64], Cr, V, Ni [69];
500 - 570 Green
Vis/Fe2O 3 [51], Fe+3/H 2O2/UV-vis [50], Vis/Pt@WO3 [70],
570 - 591 Yellow Vis/Bi2 WO6 [71], Vis/Bi2O 3 [72, 73]
591 - 610 Orange

610 - 760 Red

Infrared (IR): 760 - 1 000 000 WL [74, 75], HL [76], IR-L

[77], IR-PF [78]

IR-A 760 - 1400 Near Infra- IR lamp [79] IR-A, IR-A/vis, IR-A/UV decomposition of: -Carotene,
red Chlorophyll a [79]

IR-B 1400 - 3000 Middle PM-IR TS [80]

Infrared

IR-C 3000 - 1000 Far Infra- LWIRE [81], Heater [79] IR-C: decomposition of: -Carotene, Chlorophyll a [79]
000 red

Microwave 1 - 15 mm Microwave-induced oxidation, e.g. microwave-induced ClO2-

CuOx/Al2O3 process for phenol removal [82]

should be fixed, e.g. by using cell holder stationary mounted Sometimes round testing tubes as photoreactors and no
as shown in Fig. (1) [97, 105]. focusing lens are used to avoid the influence of change in
4 Recent Patents on Engineering 2010, Vol. 4, No. 3 Kowalska and Rau

light intensity [68, 106]. Similarly, a round testing tube with

a water cooling jacket located along one of the focal axes of
a cylindrical mirror with an elliptic base and a fluorescent
lamp located along the other focal axis has been proposed for
efficient usage of incident light (the number of photons re-
ceived by the suspension is almost proportional to the irradi-
ated volume) [30].
Several testing tubes placed at the same distance from
centered lamp and immersed with one joint thermostated
bath have been also reported and are shown in Fig. (2) [68,
106]. The advantageous of this solution is ability of simulta-
neous irradiation of different samples at the same conditions,
i.e. temperature, mixing speed and light intensity. A horizon-
tal device consists of a few identical beakers exposed to UV
light under the same conditions has been also proposed [30]. Fig. (1). Schematic diagram of experimental set-up with point irra-
For safety the photodegradation setup is placed in a black diation: 1 - UV/VIS lamp (XeL), 2 – IR water filter, 3 – UV cut-off
box [23, 32], often wooden box [31, 32]. Another purpose of filter, 4 - diaphragm, 5 – oxygen supply (needle), 6 – stand for reac-
black box (often wooden, inside covered with black material tion cuvette, 7 – magnetic stirrer, 8 – laboratory lift, 9 – optical
or painted black), dark room, covering reactor walls with bench.
black adhesive tape [40], aluminum foil [107] or closing
reactor with a mirror cover [52] is to avoid the influence of
stray light (natural or artificial), often unfavorable (e.g. UV-
rays for testing the activity under visible light irradiation of
modified titania photocatalysts), which can reach a reactor.
Usually external illumination (mainly point irradiation) is
used for testing activity of novel photocatalysts under visible
light irradiation (Fig. 1). Sometimes UV separation by appli-
cation of cut-off filters on the way of incident light is not
sufficient and some scattered UV-rays (especially in the case
of non focused light) can reach reaction mixture [68]. Thus
reaction tubes are placed in additional sample tube holders
equipped with an irradiation window with cut-off filter. Due
to tightness of sample-holder housing temperature of cooling
water inside the holder can increase [68]. In this case a spe-
cial set-up with circulating cooling water and well separated
UV radiation is proposed and shown in Fig. (3) [45, 68]. The
set-up is composed of two parts: A and B. In the part A, light
from a xenon lamp (1) passes through water bath (8) and
then through a UV cut-off filter (3) to eliminate IR and UV
radiation, respectively. To achieve water circulation through
two parts and to prevent leakage of UV light to part B, a
separating wall (5) has been mounted in part A to make cir-
culating water flow over it and then through a hole (9) in the
bottom of partition wall between two parts. In the part B,
two test-tubes (12) are placed behind the filter at the same
distance from the light source. Their content is stirred (13)
and cooled by circulating water. Fig. (2). A photograph of experimental set-up with 12 simultane-
In the case of internal illumination, the lamp equipped ously irradiated testing tubes: 1 - UV/VIS lamp (MPML), 2 – ther-
with quartz jacket is immersed in treated liquids. Three kinds mostated lamp cooling water, 3 – testing tubes holder, 4 – thermo-
of lamp cooling systems are applied: i) the lamp is placed in stated water bath, 5 – magnetic stirrer [Photo taken in Ohtani’s
an additional jacket filled with circulating distilled water laboratory, Catalysis Research Center, Hokkaido University].
(Fig. 4) [28, 90], ii) the reactor is equipped with a jacket in
which water is circulated [108], iii) the whole reactor slurry (LFFS) photoreactor [110], zero reflectance model
equipped with immersed lamp is placed in a water bath (ZRM) and two-flux model (TFM) for the prediction of ra-
[109]. diation fields inside heterogeneous photocatalytic reactor
The models concerning emission/absorption of light and [113, 114]. For novel, thin-film, slurry “fountain” photocata-
reaction run inside a photoreactor have been also examined lytic reactor two models: a flat fountain model and a para-
[2, 110-112], e.g. LSSE-LSPP model for laminar falling film bolic fountain model [115] have been proposed. The thin-
film, slurry (TFS) flat plate and annular photoreactors of (i)
Photoreactors for Wastewater Treatment: A Review
Fig. (3). Experimental setup for photocatalytic activity tests under visible-light irradiation: schematic drawing (side view, on the left) and a
photograph taken in Ohtani’s laboratory, Catalysis Research Center, Hokkaido University (on the right): 1 - UV/vis lamp (XeL), 2 - pyrex
glass window, 3 - cut-off filter, 4 - filter holder, 5 - separating wall for water circulation, 6 - water inlet, 7 - water outlet, 8 - water bath, 9 -
hole for circulating water, 10 - reactor covers, 11 - sample tubes holder, 12 - sample tubes (two), 13 – stirrers (two) [68].
Fig. (4). Schematic diagram of Heraeus photoreactor: 1-UV/vis
lamp (MPML) inside quartz tube filled with cooling water, 2 - glass
reactor, 3 - UV lamp cooling system, 4 - porous frit for sparging
gas, 5 – liquid phase, 6 - magnetic stirrer [28].
falling film design or (ii) double-skin design was modeled
for three ideal flow conditions: failing film laminar flow,
plug flow and slit flow has been applied [116]. Solving the
radiative transfer equation with the discrete ordinate method
resulted in the radiation field model for cylindrical slurry
reactor [117]. Monte Carlo model of UV-radiation interac-
tion with TiO2-coated silica-fused sphere beds was also ap-
plied for a fixed bed photocatalytic reactor [118]. The mod-
Recent Patents on Engineering 2010, Vol. 4, No. 3 5
eling of photocatalytic reactors requires the definition of four
submodels: (i) a light emission model, (ii) a light absorption
model, (iii) a reaction kinetic model, and (iv) a fluid-
dynamic model [110]. In general, rigorous modeling is based
on the analysis of the radiation field in the photoreactor re-
sulting in a complex set of integro-differential equations and
elaborate numerical treatment to produce a solution [110].
Often models fit the experimental data, e.g. during photo-
catalytic oxidation of salicylic acid in a pilot-scale LFFS
photocatalytic reactor [111] and in a pilot plant “fountain”
photocatalytic reactor [119], during degradation of 4-
chlorophenol in a cylindrical slurry reactor [117], for hydro-
dynamic calculation by computational fluid dynamics (CFD)
with visualization data by particle image velocimetry (PIV)
[120]. However for long reaction time (>120 min), realistic
reactors may have a performance very different than pre-
dicted one by theoretical calculation [40]. Romero et. al.
examined an annular, tubular reactor inside a recycle for
three different modes: (i) perfectly mixed, (ii) operating at
pseudo-steady-state, and (iii) operating at transient state, and
only the third one, after consideration of deposition and ag-
glomeration effects, fitted to the experimental results [40]. It
is thought that insufficient amount of research on photoreac-
tor modeling, and thus a lack of readily applicable mathe-
matical models to reactor design and scale-up, is the reason
of impeding application of photocatalytical method for
wastewater treatment on an industrial scale [116]. Fortu-
nately, recently large amount of research on modeling differ-
ent kind of photoreactors has been performed, mainly by the
group of Cassano and Alfano [2, 112, 121-129].
6 Recent Patents on Engineering 2010, Vol. 4, No. 3
TYPES OF PHOTOREACTORS USED DURING EX-
AMINATION OF WATER/WASTEWATER TREAT-
MENT
The examples of chemical reactors used for photodegra-
dation are presented in Table 3. Almost all photoreactors run
in a periodic operation mode. Different names are used even
for the same reactor depending on feature intended to be
exposed, e.g.
- Construction: photocatalytic reactor system containing
two parts [130], spiral [36, 131] and specially design
[132] reactor,
- Shape: cylindrical [117, 133-135], annular [24, 40, 134],
round-shaped [101], vertical [30], horizontal [30], flat
[136], rectangular [51], tubular [137, 138], round-
bottom [35], flat-surfaced [54, 139] and round flask
[140] reactor,
- Material: glass [133], quartz [17, 138, 141], Pyrex [35,
39], Teflon and stainless steel [142] reactor,
- Type of mixing: recirculating [143], concurrent down-
flow contactor [144] and completely mixed batch
(CMBR) [142] reactor,
- Cooling system: jacket cooling, water jacketed [17] and
double jacket [145] reactor
- Introducing of a gas phase: gas-sparged cyclone reactor
[26, 28, 46], reactor equipped with an oxygen-permeable
membrane [146], bubble reactor [147],
- Flow: cocurrent downflow contactor reactor (CDCR)
[148], laminar falling film slurry (LFFS) [110], fountain
[115], pulsed baffled tubular photochemical (PBTPR)
[149] and thin-film [116] reactor
- Operating mode: batch [24, 39, 52, 141], semi-batch
[32] and STEP [150] reactor
- Producer: Rayox [151-153], Rayoney [138], Rayonet
[154] and Heraeus [28, 29] reactor,
- Light source: solar simulator [50], parabolic round con-
centrator (PRCR) [155], Suntest [29] and vis-LED [52]
reactor
- Irradiation mode: collimated beam apparatus [156],
double-wall (lamp placed in the inner tube) [137], and
multilamp [95, 157] reactor,
- Photocatalyst arrangement: with thin film, membrane
[158], suspension, packed-bed [112, 137], TiO2-
immobilised [131], slurry [36, 116, 117], fixed bed
[118] and heterogeneous [113] reactor,
- Experiment scale: photocatalytic cell [35], laboratory-
scale [134, 135], bench-scale [134] and pilot-size [40]
reactor,
- Multifunctional (cooperating with other processes): ul-
trasonic [38] and sonuv [18] reactor.
The most typical photoreactors used for wastewa-
ter/water treatment are shortly described below.
The photodegradation experiments are usually carried out
for very small volume of liquid (2-5 cm3), often in quartz
cuvette under outside irradiation. Demanded radiation is
Kowalska and Rau
achieved by application of different filters made of fused
silica, Pyrex glass, Corning glass filters [91]. Light intensity
is measured by either chemical actinometry (e.g. using po-
tassium ferrioxalate [101], uranyl oxalate [95]) or instrumen-
tal analysis (using radiometers [23], photomultipiers [113],
power meters [159]). Gas phase (air, O2, N2, Ar) is intro-
duced by bubbling using syringes or Pasteur pipettes. Some-
times gas is not introduced to a reactor and oxygen, needed
for reaction, dissolved in the liquid is taken from the sur-
rounding atmosphere when reactor is open. Mixing is usually
carried out by magnetic stirrers. Rotation of reaction vessel
has been also reported [37]. Reaction temperature is con-
trolled by IR filters filled with stationary or circulating water
[91].
The “cylindrical reactor” is the most often used type of
photoreactor for testing of organics photo-decomposition.
Usually its volume is larger than cuvette and equals 20-1000
cm3. The UV lamp is either immersed in the liquid phase or
placed outside the reactor. Usually the reactors with smaller
volume (20-100 cm3) have external source of light. While
centrically immersed lamp is used for larger liquid volumes
(1-4 dm3). The reactor is cooled by water jacket (“cylindrical
jacketed reactor”) or thermostated. Usually liquid is mixed
by magnetic stirrers. For larger volumes mechanic stirrers
with blade producing axial and upwardly directed flow has
been also reported [160]. A reactor with circulating liquid
phase has been also reported [161]. The simples home-made
photoreactor can be composed of a glass beaker equipped
with a magnetic stirring setup and a lamp positioned above
the beaker [31, 162].
Often the differences between cylindrical reactor and
other photoreactors (shown in Table 3) used for laboratory
tests are almost negligible. Considering different construc-
tion, “horizontal reactor” and “reactor with flat surface”, in
which source of light is placed above [31] or below [160]
liquid surface, have been reported. A photocatalytic reaction
system, containing two or more parts, composed of a ba-
sic/principal reactor and peripheral parts of reactor (for sam-
pling, aeration and mixing) has been also tested [163].
Sometimes whole reactor is rotated to mix the suspension
[37] and the liquid phase can be preliminary aerated and then
introduced to a reactor.
More advanced reactor designs aimed to higher mass
transfer efficiency have been also reported [28, 46, 148]. An
example is a pilot scale cocurrent downflow contactor reac-
tor (CDCR) operated in closed loop recycle mode [148]. The
CDCR gives unusually large gas hold-up of approximately
50%. Other examples are shown in successive parts of this
manuscript.
The names of photoreactors applied to homogeneous and
heterogeneous systems do not usually differ from each other,
e.g. reaction cuvette, quartz reactor, cylindrical reactor, glass
reactor, batch reactor, tubular reactor. There are only a few
examples of photoreactors with names emphasized the appli-
cation of heterogeneous photocatalyst, usually in the case of
immobilized ones, e.g. photocatalytic membrane reactor
[158], reactor with packing [133], packed-bead reactor [137].
In this case, a lamp is usually placed outside a photoreactor.
The system with an immersed lamp was only reported for
photocatalyst coated on the photoreactor walls and on
Photoreactors for Wastewater Treatment: A Review Recent Patents on Engineering 2010, Vol. 4, No. 3 7

Table 2. Recommended Dose of Photocatalyst for Various Compounds and Photoreactors

Compound C0/ mM Volume/ mL Photoreactor//Light Intensity/ mW cm-2 Kind of TiO 2 Photocatalyst Amount/ g dm-3 Ref.

Suspended Photocatalyst

P25 or anatase
3-NBSA vertical & horizontal//
0.04 (Millennium PC50, PC100, PC105, [30]
2,5-ADSA 5.6 x 10-9 Einst cm-2 s-1 >2
PC500)

Cr (VI) 100 flat reactor inside Solarbox [136]

DBS 0.1 5 [172]

3000 PRC (25-70 suns) and a round flask photore-
BS 0.1 9 [140]
actor, circulation
MB 0.025 2 [155]
P25
4-NP 0.144 18.3 3
semi-batch with two circular glass
4-CP 0.16 13 [32]
plates// 2
0.2 17.5

100 flat reactor inside Solarbox 0.65 [136]

Phenol
-1 -6
batch, circulation 0.8 mL min // 8.7 x 10
1 anatase 1 [39]
Einst dm-3 s-1

double-wall tubular reactor//

HCOOH 0.95 500 2 [137]
4 x 10-6 Einst s-1
P25
Cellulose
bleaching TOC 487 1100 cylindrical// 5.9 x 10-5 Einst L-1 s-1 1 [195]
effluent

K-TiO2(anatase) 0.8-1.2
Oils 6 ppm 500 batch, magnetic stirring //4.9 [141]
TiO2(anatase)/KOH 0.5-0.8

Supported photocatalyst

4-NP 1 semi-batch//16.2 P25 on a glass plate 7.5 g m-2 [32]

-2
650 P25 on a reactor wall 2.8 g m
double-wall tubular reactor//
HCOOH 1.1 1.3 0.2-0.6 g [137]
380 4 x 10-6 Einst s-1 P25 on a glass beads of d/mm
2 >0.46 g

packed glass beads [137]. The gas phase is introduced simi-
lar as in the case of suspended photocatalysts or by oxygen
membrane [146].
Commercial application of artificial source of light is
connected with high investment and operating costs. Thus in
recent years usage of solar radiation for wastewater treat-
ment has been widely studied. Laboratory photoreactors usu-
ally use several cut-off or band-pass filters or solar simula-
tor. Direct Sun’s radiation in not common used for labora-
tory experiments, because of low repeatability of experimen-
tal data, due to large changes in solar radiation, as well as
low intensity of solar radiation, and thus necessity of very
long irradiation. Photoreactors based on solar simulator
(usually “home made”) are composed of a lamp (or set of
lamps [33]) and a parabolic reflector [143, 164]. The front of
the light source can be also covered with a light homogenizer
to obtain uniform light output [33]. Within this context it is
very important to note, that often in such experiments the
authors are using UV/vis lamps (xenon arc [29, 143], fluo-
rescent [33], metallic vapor discharge [164]), and thus only
distribution of light (homogeneous), but not its spectrum, is
the same as in the case of natural solar radiation. More re-
cently solar simulators [50, 107, 165, 166] with the same
radiation as the Sun spectrum at the Earth surface have been
also applied. The solar simulators are either “home made”
equipped with xenon lamp and special glass filters (e.g.
Oriel, AM0 and AM1.0) or with solar simulator lamp (e.g.
Leybold Didactic Ltd.) or commercial ones (e.g. Solarbox,
Cofomegra [166]; PEC-L 11, Peccell technologies, Inc.
[165]; Oriel, Model 81160-1000 [50]).
The photochemical systems based on direct solar radia-
tion are composed of focusing/concentrating solar collectors
[167] and a photoreactor. The reviews on decontaminations
of water by solar photocatalysis and on recent patents on
solar energy collectors and their applications have been re-
cently published by Malato [168] and Kalogirou [169], re-
spectively. The Compound Parabolic Collector (CPC) and
the Parabolic Sunlight Round Concentrator (PRC) are the
8 Recent Patents on Engineering 2010, Vol. 4, No. 3 Kowalska and Rau

Table 3. Examples of Photoreactors Applied for Wastewater Teratment

Photo- Liquid Irradiation Arrangement of Kind of Oxidant, Cata- Gas Phase Kind and Cooling/ Ref-
Reactor Volume/ L Source/ Irradiation Source Mixing/ lyst (g L-1) / Supply Amount of gas Reaction erence
Name Power and Applied Fil- Circulation Support Phase (L min-1) Temperature
ters (L min-1)

SUSPENSION/SLURRY PHOTOREACTORS
circulation
MPML internal inside (1) & 2 H 2O 2 thermostatic
Annular 1.5 - - [147]
125W quartz jacket stirrers in a (3-13mM) circuit/ 25°C
reactor
stirring in cooling water
reservoir and titania
Annular,
and recircu- suspension
tubular, TL(FL) low flow
12.5 internal, centerline lation (two TiO2 (
1) O2 circulation [40]
inside a /80W rate
streams to through 2 heat
recycle
improve exchangers
mixing) /20°C
eccentri-
cally- H 2O 2 thermostated
Annular, LPMLs/
2 internal, centerline operated, - - cooling jacket [24]
batch 15W, 40W (0.045-0.350)
orbital shak- /20°C
ing device

H2O2 (0.008- sparged [26,

internal inside
0.08 % v/v) through 46,
MPML quartz tube, center- recirculation cooling coil in
ASH 100-200 porous tube Air (40-120) 94,
2.5kW line, 5mm liquid (190) TiO2 (0.01- a reservoir
(bub- 97,
layer 0.03) ble<300m) 226]
2 x UVA, B
external (7cm dis- O2 (to have 15mg electrical/25 ±
Batch 0,5 or C 15W - H2O2 (0.05) - [227]
tance) dissolved O2/L) 2°C
(x2)
mixed in cooling coil in
UV 1kW, recirculation TiO2 (0.01-
CDCR 15 internal “T” configu- O2 (0.005-0.2) the reser- [148]
2kW (10) 0.03% w/w)
ration voir/50°C
HPML internal in quartz tap wa-
Cylindrical 1.1 magnetic TiO2 (0.5-1.5) - - [195]
125W tube ter/25°C
Cylindrical
ML 100W, TiO2 colloidal water circula-
glass 0.07 internal + bubbling N2 lub O2 [228]
HL 500W (5mM) tion
vessel
internal inside
quartz sleeve
Cylindri- Rayox
equipped with
cal, Rayox, 40 MPML mechanical H2O2 (0.01-0.3) - - cooling coil [151]
transmittance con-
batch 1kW
troller and steel
shutter
Double
HPXeL external, band-pass thermostated/
jacket 0.06 + TiO2 (0.5) - - [145]
450W filter (320 nm) 25°C
quartz
external, from both
Flat plate, recirculation
sides, 2 tubular heat
circular TUV 15W; and me- H2O2 (50-250
1 lamps placed at the - open storage tank exchanger/25° [25]
cross UVC 40W chanical in ppm
focal axis of 2 C
section storage tank
parabolic reflectors
Flat-
WL 50W/ external, 20 cm [54,
surfaced 0.05 magnetic TiO2 (2) pre-aerated air -
XeL 150W from the reactor 139]
glass
Horizontal - 2-4 FL 15W external from top + - - - - [30]
Photoreactors for Wastewater Treatment: A Review Recent Patents on Engineering 2010, Vol. 4, No. 3 9

(Table 3) Contd….

Photo- Liquid Irradiation Arrangement of Kind of Oxidant, Cata- Gas Phase Kind and Cooling/ Ref-
Reactor Volume/ L Source/ Irradiation Source Mixing/ lyst (g L-1) / Supply Amount of gas Reaction erence
Name Power and Applied Circulation Support Phase (L min-1) Temperature
Filters (L min-1)

H2O2 (0.008-0.8 cooling water

magnetic [28]
% v/v) in lamp jacket
Laboratory MPML internal inside air, O2 , Ar (0.15-
0.8 bubbling
Heraeus 150W quartz jacket magnetic 0.3) thermostated
and circula- TiO2 (1) water bath/ 20 [48]
tion (0.3) or 35ºC
MPML
0.5 internal - TiO2 (1.4) O2 ca. 27°C [229]
125W
Pyrex
barbotage
cylindrical MPML external/6 lamps magneti- TiO2 (1), thermostated /
0.17 O2 or N2 (8·10-4) [39]
(6x6W) around reactor cally H2O2 0.01M 25 ± 0.5ºC

cooling water
MPML internal inside O2 dissolved in
Pyrex glass 0.4 - TiO2 (0.4) open to air in lamp [230]
300W quartz jacket water
jacket/20°C
glass fibber external
external/ through a
filter placed chamber by
0.15 ML quartz window 450 rpm TiO2 (0.15) O3 (0.05) [23]
Pyrex glass at the bot- water circula-
placed in the top
batch tom tion/25°C
ML 15W
5 internal, 4 lamps magnetic H2O2 (5mM) - - - [231]
(x4)
external/ perpen-
Pyrex glass HPML
0.1 dicularly above the magnetic ZnO (>3.5) - - - [31]
beaker 125W
beaker
magnetic
Photocata-
(2nd part) + jacketed glass
lytic reac- external, parallel to
MPML circulation prior irradia- tube with
tor system 0.3 the Pyrex glass tube TiO2 O2 [163]
300W (30) be- tion water circula-
containing (1st part)
tween two tion
two parts
parts
Quartz placed in Rayoney thermostated/
0.05 UV 300 nm no TiO2 (0.2) barbotage O2 (2) [138]
tubular (PRP-100) 20 ± 2°C
Quartz
0.5 Hg 370W external magnetic TiO2 (0.5-1.2) open air No [141]
batch
Rayonet
external inside
(merry-go- 0.004 LPML magnetic acetone - - cooling fan [154]
Rayonet
round)
MPML internal inside Circulation H2O2 (1.5-15.7 heat ex- [152,
Rayox 28 - dissolved oxygen
1kW quartz sleeve (40-110) mM) changer 153]
external, IR and
XeL 300W cut-off (
>450 magnetic TiO2 (0.5-1) bubbling air - [66]
nm) filters
0.005 external, light con- tempered
denser (quartz aluminum
Reaction Xe 150W - TiO2 (1) - saturated with air [98]
cell lens), filtr UV block/ 30 ±
(>320 nm) 1ºC
external, colli-
mated, band-pass
0.055 XeL 1000W - - - O2 IR filter [92]
filter (310-330 nm),
neutral density filter
Fe+3 (0.017- cocurrent
1.6-2.5 [95]
0.26) gas and
Recircula-
external, 4 x lamps liquid
ting LPML flowrate exterior cool-
parallel to reactor phases O2/O3 (1)
tubular 15W (4x) (1.67) ing [147,
2.5 axis H 2O 2 mixed with
batch 157]
diffuser
valve
10 Recent Patents on Engineering 2010, Vol. 4, No. 3 Kowalska and Rau

(Table 3) Contd….

Photo- Liquid Irradiation Arrangement of Kind of Oxidant, Cata- Gas Phase Kind and Cooling/ Ref-
Reactor Volume/ L Source/ Irradiation Source Mixing/ lyst (g L-1) / Supply Amount of gas Reaction erence
Name Power and Applied Circulation Support Phase (L min-1) Temperature
Filters (L min-1)

Slurry/
external, 15 cm reactor cooling bath/
quartz 0.1 MVL TiO2 (0.2) - - [37]
above rotation 30ºC
vessel
Static
external from bot-
batch, HPML O2 dissolved in
0.02 tom, IR filter, cut- magnetic TiO2 (3.5) open to air IR filter [159]
Pyrex, 125W water
off filter >340nm
cylindrical
external, in one of
water cooling
Vertical 0.05 FL 15W the focal axes of magnetic - - [30]
jacket
cylindrical mirror
TiO2 (0.5-2)
cooling
LED flexi-
Vis-LED 0.4 internal magnetic bubbling air jacket/30 ± [52]
ble strip
5°C
lamp cooling
internal in suprasil-
circulation and reactor
(Reactor) 0.5 LPML 20W glass filled with TiO2 (1) barbotage air/N2 [109]
(3.33) inside water
cooling water
bath
PHOTOREACTORS WITH IMMOBILIZED PHOTOCATALYST
silica micro-
- LPML external, above magnetic - - - [162]
spheres
Beaker external, solar

0.1 XeL 50W simulator with magnetic sand open reactor air thermostated [107]
concentration lens
TiO2 or ZnO on
Cylindrical currency
0.15 hp Hg internal no glass rashing fritted glass O2 (0.2) [133]
glass water/ 20°C
rings
25 thermo-
rector
0.6 35-120 ml
Double- wall glass sieve& stated
circula- sparger in s-1 supply
wall UVA/15W internal O2 [137]
tion/ml s-1 the supply 80 vessel
tubular Glass
0.38 8-32 vessel ml /20°C
beads
s-1
external, perpen-
HPML aerated
Glass tube 0.005 dicular to the SSM - SSM or FGC air - [146]
400W solution
and FGC
Labo- MPML saturated thermostated,
internal, coaxial recirculation PHOTOPERM [135,
ratory- 4 500W prior irradia- O2 water jack-
membrane (3.1) membrane 232]
scale HPML tion eted/ 35 ± 2°C
external, concen- thermostated
MPML 11 types of
Membrane trated by aluminum recirculation bubbling O2 or air water bath/ [158]
500W membrane
cone 30°C
external through a circulation teflon mem- O2 (120μmol/h),
Membrane 2.5 BL FGC - [146]
Pyrex window 140ml/min brane Ar, air
Quartz placed in Rayoney zeolites, mo- thermostated/
0.05 UV 300 nm - barbotage O2 (2 ml/min) [138]
tubular (PRP-100) lecular sieve 20 ± 2°C
stainless steel,
Quartz Ti-4V-6Al thermostated/
external through
water 0,008 XeL 150W magnetic alloy, titanium - O2 water jacket/ [17]
Pyrex filter
jacketed foil, tin oxide 20ºC
coated glass
Round-
thermostatic
shaped HPML external/Pyrex glass
0.1 - silica - - water bath// [101]
glass 375W filter
20 ± 1°C
reactor
Photoreactors for Wastewater Treatment: A Review Recent Patents on Engineering 2010, Vol. 4, No. 3 11

(Table 3) Contd….

Photo- Liquid Irradiation Arrangement of Kind of Oxidant, Cata- Gas Phase Kind and Cooling/ Ref-
Reactor Volume/ L Source/ Irradiation Source Mixing/ lyst (g L-1) / Supply Amount of gas Reaction erence
Name Power and Applied Circulation Support Phase (L min-1) Temperature
Filters (L min-1)

Rectangu- -Fe2O3 film on water bath,

external, IR water magneti-
lar glass 0.03 THL 250W fused quartz bubbling O2 water changed [51]
filter cally
vessel plate periodically
circulation lamp cooling
HPML external/underneath
Semi-batch (60-450 pyrex glass O2 saturated by com- [32]
125W the photoreactor
ml/min) pressed air
ML 400W
external, 30 cm
- (200-800 magnetic HA films - - - [190]
from the samples
nm)
PHOTOREACTORS USING SOLAR RADIATION OR SOLAR SIMULATORS
Round
external/ the Sun circulation bubbling in [155,
bottom 1.3 PRC TiO2 (2÷5) O2 no
(70 suns) 2-8.3 l/min reservoir 172]
flask
Solar simu-
Recirculat- lator external/XPXL and TiO2 (0.001- sintered no
0.25 recirculation air [143]
ing batch (HPXL parabolic reflector 0.01) glass tip
1000W )
heating (elec-
CPC (4x 5 tric resistance)
borosili- H2O2 (0.3), Fe or cooling [233,
44.6 recirculation open to air air
cate-glass (0.02) (heat- 234]
tubes) ex-
changer)/30°C
CPC (3x 8 The
external, 37° angel
Pyrex 40 Sun/PSA flow (20) - - - [186]
tubes) TiO2 (0.2)
recirculation cooling sys-
CPC 247 in reservoir O2
(58) tem
[235]
Flat, cylin-
100 by air diffuser air
drical tank
Pyrex TiO2 (2)
horizontal 0.1 The Sun external - - - no [30]
tube

flow 20 TiO2 (0.05)

CPC 3.09 m2 The Sun external - - - [161]
l/min H2O2 (0.3ml/l)
Discon-
solar simulator
tinous
“Solarbox”, XeL in
cylindrical 0.12 XeL 1.5kW magnetic TiO2 (0.05-5) syringe compressed air - [147]
the axis of para-
micro-
bolic mirror
reactor
external, glass
Solar FeCl3 (0.05),
0.06 XeL 300W filters (Oriel AM0, magnetic - - 20°C [50]
simulator H2O2 (0.05%)
AM1.0)
Flat pho- exter-
toreactor in 0.1 XeL 1500W nal/perpendicular magnetic TiO2 (0-2) - - - [136]
Solarbox rays to the reactor
Suntest XeL 500W
0.25 external magnetic cyclodextrines - - - [29]
CPC m-2
external/Light
Solar UVA (FL)
0.15 source covered with TiO2 (1) - air (35) - [33]
simulator (16x40W)
a light homogenizer
12 Recent Patents on Engineering 2010, Vol. 4, No. 3
(Table 3) Contd….
Photo- Liquid Irradiation Arrangement of
Reactor Volume/ L Source/ Irradiation Source
Name Power and Applied
Filters
MULTIFUNCTIONAL REACTORS
Ultrasonic
BLFL
with UV 1 immersed
/7x4W
lamps
Sonuv
(sono-
chemical 0.05 LPML partially immersed
and photo-
chemical)
most often applied collectors for wastewater treatment [87,
155, 166, 170-173]. The CPC photoreactor is composed of
several collectors, one tank and one pump. Each collector
consists of a few Pyrex tubes, filled with flowing treated
wastewater, connected in series and mounted on a fixed plat-
form. The CPC photoreactor has been used in the most fa-
mous place of solar light application for wastewater treat-
ment, named Platforma Solar de Almeria (PSA) in Spain
[87, 91, 171, 173-177]. The PRC is composed of one reactor
on which solar light is concentrated by a parabolic round
mirror (geometric concentration of sunlight equivalent to 25
or 70 suns in dependence on mirror area and aperture diame-
ter), one pump and one tank [155]. To eliminate necessity of
photocatalyst separation in slurries, a novel solar STEP pho-
toreactor using TiO2-coated paper has been invented and
mounted in PSA [150]. The constructions of solar collectors
[169] and photoreactors based on solar collectors have been
already reviewed [178, 179].
The usage of direct, non-concentrated solar radiation has
been also reported, e.g. a photoreactor consists of only pho-
tocatalyst deposited on a glass wool mat spread over a wide
area on the ground [180]. Such system is very simple, i.e. the
wastewater is poured onto mats, cheap, efficient (TOC val-
ues of one thousand ppm decreased to nearly zero in one
week), and thus highly recommended in developing coun-
tries for water purification. Another application of photocata-
lysis under direct solar radiation has been reported for to-
mato hydroponic culture system [180]. This system allows
decomposition of organic compounds with simultaneous
recovery of nutrients using porous ceramic plates coated
with titania photocatalyst in recycling system.
Multifunctional photoreactors use photoirradiation and
additional processes, e.g. ultrasounds. They are named in
dependence of the main reaction mechanism, e.g. ultrasonic
reactor [38], “Sonuv” (ultrasounds and UV). The lamp is
immersed in treated liquid of usually small volume (36-1000
cm3). Incomplete immersion of UV lamp in the liquid phase
allowing ozone generation (UV radiation below 200 nm
causes ozone generation from oxygen in a gas phase) has
been also reported [18].
HOMOGENOUS AND HETEROGENOUS SYSTEMS
Photochemical processes are carried out in homogeneous
or heterogeneous systems. Application of hydrogen peroxide
Kowalska and Rau
Kind of Oxidant, Cata- Gas Phase Kind and Cooling/ Ref-
Mixing/ lyst (g L-1) / Supply Amount of gas Reaction erence
Circulation Support Phase (L min-1) Temperature
(L min-1)
thermostated/
stirrer and stainless
TiO2 (0.1-0.25) O2 (0.5) water jacket/ [38]
ultrasounds steel bubbler
30 ± 2ºC
thermo-
ultrasounds - - air above liquid stated/water [18]
jacket/ 30ºC
allows carrying out the process in one liquid phase, restrain-
ing mass transport limitations. Hydrogen peroxide is usually
added once, prior to irradiation [26, 28, 93, 98, 135, 151,
181, 182]. Only a few examples of continuous addition of
oxidant during photoirradiation have been reported [183].
The dose of oxidant controls the process and its amount must
be experimentally determined [28, 97]. At high concentra-
tion, hydrogen peroxide acts as a trap for radicals thus com-
petes with pollutants resulting in lower degradation rates
according to equation: HO· + H2O2 = HOO· + H2O. At low
H2O2 concentration, absorption of UV radiation becomes
insignificant causing impaired generation of hydroxyl radi-
cals.
In the case of heterogeneous photocatalysis two types of
reactor design are considered:
- Fixed-bed or packed-bed photoreactors,
- Suspension or slurry photoreactors.
Heterogenous Photocatalyst Arrangement
The most typical system which applied heterogenous
photocatalysis uses suspended photocatalyst mixed by
magnetic, mechanical or barbotage stirring. Suspension or
slurry type reactors are efficient due to large surface area of
photocatalysts and high mass transfer rates within such
systems [184]. However, application of photocatalyst
particles, due to their small sizes (4-200 nm) causes two
main practical problems: i) particles can adsorb on the
elements of photoreaction system and ii) a post-treatment
photocatalyst recovery stage [185] involving sedimantation
or microfiltration must be done [146, 186]. Such post-
treatment would be undesirable at industrial scale as it would
add to the capital and operating costs of the treatment
process [17, 184]. In addition, the penetration deph of the
light into the slurry is limitted [137]. In this regard, a lot of
effort has been taken to obtain a recoverable photocatalyst,
such as
1) suspended systems where photocatalyst can be:
- immobilised on the surface of larger particles, e.g. silica
[101], silica gel microspheres [162], activated carbon
[187], microporous zeolites (NaY, Na-mordenite) [138],
mesoporous moleculra sieves (MCM-41) [138], glass
microspheres recovered from fly ashes (Fig. 5) [46, 90,
97], glass Raschig rings [133], sand [107],
Photoreactors for Wastewater Treatment: A Review
Fig. (5). A SEM image of glass microspheres recovered from coal-fired power plant fly ash coated with titanium dioxide (left) and naked
ones (central and right) after circulation in a gas-sparged reactor [97].
- in the form of larger particles: granulated, e.g. VP
AEROPERL® P-25/20 is a granulated form of well
know TiO2, Degussa P25 [186], spheres, e.g. titania
spheres synthesized through polystyrene spheres
templating [52],
2) fixed systems with photocatalyst immobilised on:
- elements of irradiation system, e.g.quartz protection tube
of UV lamps [188],
- photoreactor walls [137],
- additional elements, e.g. glass beads packed in the reactor
(PBR) [137], mesh [146], cloth [146, 189], membrane [135,
158], plates [17, 32, 35, 185], films [190] and foils [17].
The support is made of stainless steel [17, 146, 191],
alloys (Ti-4V-6Al) [17], titanium [17, 185], glass [17, 35,
137, 146], polymers [52, 158, 190], cotton [189], ceramic
[180]. The supprot can also possesses additional function,
e.g. application of Pyrex glass as a support allows cutting off
light shorter than 300 nm thereby eliminating the direct
photolysis of the organic compound [32]. The photocatalyst
can be also incorporated into the support structure, e.g.
titanium-containing zeolites [192]. It is important to note,
that activty and reaction mechanism can change after
photocatalyst immobilization as follow:
- decrease in activity, due to: mass transfer limitation for
photocatalyst deposited on reactor walls [137], surface
area decrease [17, 191], loss of a photocatalyst from a
support [17, 146, 158], decrease in adsorption of organic
compounds on photocatalysts surface [32, 138, 146],
limitation of space-charge width and mobility of the
illuminated particles [51], fast sedimentation of
granulated form of photocatalyst [186],
- comparable activity for packed-bed reactor (glass
Raschig rings [193], glass beads [137], glass slides [35],
polyacrylonitrile membranes [158]),
- increase in activity, due tu contribution of a support in
an overall reaction, e.g. a support can increase a
separation of charge carriers (holes/electrons) [90, 97],
- apperance of additional reaction, e.g. liberation of H2
from alcoholic suspension of bare TiO2 when metal
Recent Patents on Engineering 2010, Vol. 4, No. 3 13
species originating in a support (stainless steel mesh)
working as reduction catalyst [146].
To prevent activity decrease preparation of mesoporous
films of large surface area (BET=240 m2 /g) has been
proposed [191]. Deposition of photocatalyst on silica [101]
or on molecular sieves [138] can also lead to increase in
surface area and in adsorption ability of organic compounds
depending on their hydrophopic properties [101, 138]. In
contradiction, photocatalyst deposition on non-porous
surfaces has been also proposed, since that photocatalyst
inside the pores is not irradiated and thus not working [137].
To prevent mass transfer limitation an increase of liquid
flowrate has been proposed [32]. However high flowrate can
lead to detachement of photocatalyst from a support [158],
e.g. 11 and 21% loss of titania from fiberglass cloth and
stainless steel mesh, respectively has been observed after
only 1 hour of operating [146]. To reduce this problem
photocatalyst immobilization on polycarbonate, Pyrex, glass
slides, cellulose microporous membrane and aerogels has
been proposed [35, 158]. Modification of immobilization
method, e.g. several-step deposition of photocatalyst on a
support [35, 194], roughening of glass surface (support) by
sand blasting [32], as well as post-calcination of immobilised
structures [17, 32], can also increase an adherence of a
photocatalyst to a support.
Amount of Photocatalyst
Optimal amount of photocatalyst must be experimentally
determined, depends on kind of organic compound and on
geometry and working conditions of a photoreactor, and
equals to 0.15 - 8 g/dm3, as shown in Table 2 [32, 91, 136,
161, 172]. Reaction rate increases with increase of
photocatalyst amount, due to absorption of more photons by
photocatalyst, larger scattering of light by the dispersion and
larger adsorption of organic compounds on the photocatalyst
[172]. Whereas too large amount of photocatalyst can cause
decrease in reaction rate, due to “screening effect” of excess
particles, which masks part of photosensitive surface
decreasing in penetration depth of light [91, 136, 137, 141,
172]. The optimal amount of photocatalyst is the maximum
amount of photocatalyst in which all the particles, i.e. all the
exposed surface, are totally illuminated [91]. Model for
predicting the optimal photocatalyst amount in aqueous
14 Recent Patents on Engineering 2010, Vol. 4, No. 3
suspensions for different photosystems has been proposed by
Chen and Ray [194]. Though according to this model
optimal photocatalyst dose can be predicted if all necessary
parameters (e.g. the light absorption coefficient of catalyst in
suspension, influence of light intensity) have been deter-
mined prior to photocatalysis.
An optimal amount of photocatalyst exists also for
supported system and is considered as optimal thickness of
photocatalyst film [32, 137]. The interfacial area is
proportional to the thickness of photocatalyst since the film
is porous. Thus, thick film favorous photocatalytic oxidation.
In addition, similarly to a suspended system, more photons
can be absorb by larger amount of photocatalyst (thicker
film). On the other hand, the internal mass transfer resistance
for both organic species and photo-generated charge carriers
(electron/hole) increases with an increase in film thickness
since in a thicker film charge carriers recommbination
increses causing activity decrease.
Gas Delivery and Mixing
Oxygen adsorbs on titania from the liquid phase, where it
is dissolved following Henry’s law. In the case of constant
oxygen delivery its coverage at the surface of titania is
constant:
kKO2 pO2
kobs =
1+ KO2 pO2
(KO2 – adsorption constant of dissolved oxygen at the surface
of TiO2 /atm-1)
This coverage can be integrated into the apparent rate
constant [91]: (A + O2  P)
Actually, apparent rate constant is a function of the
power flux (express in mW/cm2) and of the oxygen coverage
[91].
Usually oxygen/air is introduced by bubbling [28, 105,
117, 132, 134]. However, this is not advisable in the case of
oxidation of volatile compounds (VOC, VCOC). An alterna-
tive method to decompose these compounds is to oxidize
them in gaseous phase. However, it has been reported that
unfavorable, toxic by-products such as dichloroacetyl chlo-
ride and phosgene can be produced during VCOC degrada-
tion [146]. In this regard, degradation of VOC and VCOC in
a liquid phase in a specially designed reactor equipped with
oxygen permeable membrane has been proposed [146, 196].
Oxygen/air bubbling plays often two functions: i) gas
delivery, and ii) suspension mixing, especially in the case of
gas supply through a porous frit installed in the bottom of a
photoreactor. Magnetic and mechanic stirring or liquid circu-
lation is also used for suspension mixing. The pump-driven
circulation of titania suspension provides better dispersion
than magnetically stirred systems in a cylindrical reactor
since it produces stronger axial flow mixing which is benefi-
cial for dispersing the component of different specific grav-
ity [172]. The magnetic stirring produces stronger tangential
flow mixing along the reactor wall, which does not result in
better re-dispersion of aggregated titania particles. In fact,
magnetic stirring results in greater aggregation of titania par-
ticles. However, foaming action caused by circulation of the
Kowalska and Rau
mixture is more significant than by magnetic stirring, thus
circulation is not recommended in the case of surfactants
degradation. An uniform dispersion of photocatalyst of a
wide range of particle sizes can be obtained also by oscilla-
tory flow in the PBTPR reactor [149].
An example of a photoreactor with circulation flow and
formed thin layer of intensely aerated liquid phase is shown
in Fig. (6) [26-28, 46, 97]. This photoreactor known as the
air/gas sparged hydrocyclone (ASH) was previously used as
flotator for minerals and oil, stripper and aerator due to large
gas-liquid contact area [197, 198]. The ASH /2/ with 5 m3 h-1
nominal flow rate of the aqueous phase is equipped with an
axially placed Hanovia 2500 W MPML /3/. Fig. (7) shows
more details of the reactor, cyclone header /1/ and aerating
section /2/ with the inner porous tube. The liquid phase
swirls in the space between the quartz lamp protection tube
and the porous tube of the aerating section. The gas phase is
sparged through pores, 60 μm in diameter, of the inner poly-
propylene tube, and is dispersed the swirling liquid [199].
Centrifugal forces, as well as shear stress of the swirling
liquid layer result in strong gas dispersion (gas bubbles <
300
m [199]). The 5 mm thick, aerated layer is thus favora-
bly exposed to the UV radiation allowing for it more effi-
cient utilization than in the case of an immersion lamp. Tita-
nium dioxide immobilized at the surface of hollow glass
microspheres (shown in Fig. 5) is swirling together with the
stream of liquid, close to the lamp surface. Please note that
centrifugal force inside a cyclone and a circulating pump can
destruct the photocatalyst support (Fig. 5, center and right).
Multiplication of cyclone units and/or extension of the inner
porous section diameter could increase reactor efficiency in
industrial application.
To characterize flow field, i.e. overall flow field, instan-
taneous and time-averages velocity field, PIV can be used as
effective technique in capturing large areas of velocity field
information [200]. Sozzi and Taghipour showed that per-
formance of photoreactors has been greatly influenced by the
reactor hydrodynamics [200]. The inlet position has a domi-
nant effect on the flow distribution in the annular photoreac-
tors. The flow patterns remain more stable, and thus predict-
able over a range of flow rates for L- than for U-shaped reac-
tor. In this regard, the L-shape is expected to provide a more
uniform UV dose distribution and thus better reactor per-
formance. They proved that simple changes in reactor ge-
ometry, such as rearranging the inlet position, could signifi-
cantly influence the local flow field, and therefore the ex-
pected UV-dose distribution and the reactor performance.
Kinetics of Heterogeneous Reaction
The matter of reaction type (kinetically- or diffusion-
controlled reaction) in the literature concerning photo-
catalytic wastewater treatment is not usually considered.
Chen and Ray have reported that in the case of immobilised
photocatalyst the degradation rate is controlled by mass
transfer but not by rate of chemical reaction [32]. While, for
suspended photocatalyst mass transfer resistance can be
neglected and the chemical reaction is the rate-determining
step. Dijkstra et al. has reported that for immobilised
photocatalyst the reaction can be controlled by either kinetics
or diffussion [137]. They compared three systems: a suspen-
Photoreactors for Wastewater Treatment: A Review Recent Patents on Engineering 2010, Vol. 4, No. 3 15

Fig. (6). Schematic diagram of gas-sparged photoreactor system: 1 - tank, 2 - gas-sparged reactor, 3 - UV lamp, 4 -cyclone header, 5 -
rotameter, 6 - manometer, 7 - blower, 8 - centrifugal pump, 9 - cooling coil, 10 - pH meter, 11 - pH electrode [28, 97].

Fig. (7). Design and principle of operation of gas-sparged reactor with UV-lamp as used for photocatalytic degradation: 1 - reactor header,
2 - aerating section, 3 - UV lamp, 4 - quartz lamp protection tube, 5 - porous tube [46].

ded, an immobilised with coated wall and an immobilised
system packed with coated glass beads (two bead diameters
were tested). Mass transfer limitations occurred in the
tubular reactor with the catalyst coated on the wall and
addition of air to this reactor increased the degradation rate
by decreasing mass transfer limitation. In contradistinction to
previous reports Zhang et. al. has observed that also for
suspended photocatalyst mass transfer limitation occurrs and
an optimal flowrate (inhibitting photocatalyst aggregation),
depending on kind of pollutant and its concentration, should
be experimentally determined (1.8-8.31 dm3 min-1) [155].
They have found that above limiting value (1.8 dm3 min-1),
the flowrate has only a weak influence on the reaction rate,
owing to the vigorous turbulent flow and to the optimal
particle distribution within the photoreactor. While decrea-
sing the flowrate below this value leads to mass transport
limitation which are greatly minimized at the higher rates.
Similarly Ballardi et al. used the maximum operating
flowrate intending to work without concentration gradients
in the reactor, and thus with good mixing and free of mass-
transfer limitations [132]. Minimal mass transfer limitation is
also achieved by special reactor construction, e.g. using TFS
photocatalytic reactor.
For the reactions process in a flow reactor, apparent
retention times of all reagents through the reactor may be
16 Recent Patents on Engineering 2010, Vol. 4, No. 3
expressed in terms of average retention times:
=V/FV, where
V is the reaction volume of the reactor, and FV is the volume
flowrate of the process. Average retention times are suitable
in the design of reactor volume, since V =
x FV [155]. Un-
fortunately, the distribution of retention times of every rea-
gent particle in a flow reactor is not well described by aver-
age retention times, especially for low flowrate (polydisper-
sity of the retention time distribution). By contrast, at higher
flowrates, the flow model approximates the ideal mixing
flow model and a narrower range of retention time distribu-
tion is obtained [155]. The special reactor design can highly
restrict mass transfer limitation, e.g. fluid oscillation in the
PBTPR reactor leads to vigorous mixing providing efficient
solid handling capabilities, enhance mass transfer, and nearly
plug flow residence time distribution [149].
Since the photonic activation occurs at considerably high
speeds, it is considered that the photocatalytic system is not
sensible to the temperature. The true activation energy Et is
nil, whereas the apparent activation energy Ea is very small
(a few kJ mol-1 [91, 161]) in the medium temperature range
(20-80°C). With the increase of temperature, the exothermic
adsorption of the reagents becomes unfavorable due to the
increase in the entropy of the solvent, and tends to become
the rate limiting-step. While, at very low temperatures
(<0°C) the activity decreases and the Ea increases since the
desorption of the final products becomes the rate limiting-
step [91].
Summarizing, for efficient wastewater treatment an ideal
mixing (no mass transfer limitation), introducing of neces-
sary amount of gas phase (oxidant/electron capture/reduction
of mass transfer limitation), an access of UV to whole liquid
volume (i.e. irradiation of thin liquid layer), determination of
optimal amount of photocatalyst or oxidant (e.g. H2O2) and
keeping moderate temperature (20-80°C) should be applied.
SELECTED PATENTS ON PHOTOREACTORS USED
FOR WASTEWATER TREATMENT
The main aim of laboratory experiments of wastewater
treatment is to reach the highest efficiency of degradation, at
best total mineralization. While, patent inventors are mainly
focused on cheap methods, energy efficient mineralization
with low investment and operating costs, automated and eas-
ily applicable in an industrial scale. Problems addressed in
research papers such as photocatalyst arrangement (re-use,
immobilization), light distribution, mass transfer limitation,
oxygen introduction, volatile compounds degradation are
also topics of patents. Examples of patented solutions of
photoreactor design are shortly presented below.
Devices for Photodegradation Using Heterogeneous Pho-
tocatalysis
1 Solar photoreactor with self-contained photocatalyst
recapture [201]
A system for the continuous use and recapture of a pho-
tocatalyst is composed of a novel 3-dimensionally adjustable
solar reflectors, a vertical photoreactor with downwardly
flowing liquid, and a photocatalyst recovery chamber adja-
cent the reaction zone containing a floating photocatalyst.
The liquid in reaction zone flows downward at a rate higher
Kowalska and Rau
than a rate of upward migration of photocatalyst particles,
thus photocatalyst particles are drawn downward with the
liquid. A slow flow velocity floatation chamber placed be-
low the reaction zone is configured to capture particles and
allow them to float back to the photocatalyst recovery cham-
ber.
2 Photoreactor equipped with TiO 2 membrane [202]
The photoreactor for mineralization of organic com-
pounds in a two-phase or three-phase boundary system
formed in the pores of a titania membrane has been pro-
posed. The porous membrane has pores which have a region
wherein the meniscus of the liquid varies from the molecular
diameter of water to that of a capillary tube resulting in a
diffusion layer much smaller (several orders of magnitude)
than the closest known reactors. This technique increases the
concentration of oxidant at the reaction sites on the photo-
catalyst surface increasing the heterogeneous reaction rate by
several orders of magnitude.
3 Photoreactor with intense liquid flow [203]
An annular photoreactor, in which fluids pass between
inner wall of the reactor body and an outer wall of a photon-
transmitting tube, has been proposed. The interesting design
solution is application mechanically static, fluid-dynamic
elements for passively inducing substantial turbulent flow
within a fluid. This arrangement increases uniformity of the
fluid’s exposure to photons within the tube.
4 Packed-bed photoreactor [202]
The photoreactor, filled with photocatalyst supported on
glass particles or silica gel, in flat configuration to improve
the contact time between the photocatalyst and the contami-
nants (as compared to annular photoreactor) has been pro-
posed. The oxidant (e.g. oxygen, ozone, hydrogen peroxide)
can be either mixed with the contaminants upon entering the
photoreactor or fed to the reactor in a constant stream.
5 Cyclone photoreactor equipped with carbon arc [204,
205]
This photoreactor is very similar to ASH phtoreactor [26,
28, 46, 97], described before and shown in Figs. (6) and (7).
The cyclone construction allows generation of thin liquid
film swirling around a radiation source and excellent intro-
duction of gas through porous tube. The main difference
between this reactor and ASH is the different source of irra-
diation. In ASH a medium pressure mercury lamp was used
while in patented photoreactor a carbon arc light source was
employed. Though a carbon arc allows deep UV penetration
in treated liquids it seems unnecessary in the cyclone con-
struction since UV penetration depth should be enough to
reach whole liquid as a thin liquid layer is generated in a
cyclone reactor. Thus irradiation of liquid by immersed mer-
cury lamp at longer length prolonging irradiation contact
time seems more beneficial.
6 A tube bundle photoreactor working under solar or
artificial radiation [206]
A photoreactor made up of numerous capillary, transpar-
ent (quartz glass) tubes in which liquid flows under solar or
artificial radiation. An inlet chamber connected with a tube
bundle comprises a flow distributor which distributes the
treated liquid from the fluid inlet to the tubes. The flow dis-
tributor caused a uniform pressure distribution to exist in a
Photoreactors for Wastewater Treatment: A Review
prechamber, to which the tube ends adjoin, and thus a uni-
form flow through all tubes is obtained. The flow distributor
also changes turbulent flow to laminar flow for precluding
coating at inside of the capillary tubes to be washed off.
7 Solar photoreactor [207]
A photoreactor consists of one or more transparent tubes
(glass or plastic material) irradiated with the light from the
exterior, the treated liquid flows through the tubes thus being
exposed to the external irradiation, wherein one or more
empty transparent tubes with smaller diameter are provided
in the interior of outer tubes (in a concentric arrangement),
and the treated liquid is passed through the gap between an
outer and inner tube or, in the case of several inner tubes,
through the gaps formed therebetween. For efficient treat-
ment, one or more radiation sources are placed into inner
tubes. Optical waveguide materials may be used for intro-
ducing additional sunlight or artificial light.
8 Photocatalytic reactor with immobilized titania [208]
The reactor has two tubes of different diameter placed
concentrically, the tubes thus defining an inner and an outer
channel. The inner channel contains as elongated light
source. The outer channel has at least one (preferably a num-
ber of) angled conical baskets, each basket covering all of
the channel and having a face supporting a fiber glass mesh
thereon, exposed towards the light. The basket has a plurality
of small apertures to permit water to pass through, and the
mesh is impregnated with TiO2.
9 Solar photoreactor for sewage treatment generated on
small and medium watercraft [209]
The treatment system composed of (i) at least two slop
tanks connected in parallel by mean of a pump, (ii) aeration
device and (iii) photoreactor. The photoreactor contains a
reaction chamber covered with UV/vis light permeable layer
with internally located modified titania photocatalyst (active
under visible light irradiation).
10 Photoreactor with immobilized titania on a nonwoven
cloth
A photoreactor is composed of two tubes arranged con-
centrically (spaced by 0.5 cm). A nonwoven cloth covered
with titania photocatalyst is inserted between outer and inner
quartz tube. A UV lamp is placed inside the inner tube.
Photocatalyst for Easy Application on an Industrial Scale
11 Application of particulate catalyst [210]
Metal ions (ferrous or ferric) were immobilized on a
compatible particulate support (NAFION beads) to improve
photocatalytic properties by avoiding both the pH-
dependency and the need for photocatalyst recovery. This
photocatalyst showed high activity in heterogeneous photo-
assisted Fenton treatment of indigo carmine.
12 Photoreactor equipped with immobilized titania and
on an oxygen-permeable membrane for decompo-
sition of VOCs [196, 211]
The reactor consists of an upper and lower chambers
separated by Teflon membrane. The upper chamber, made
from Teflon, is used for circulation of the reaction solution,
and the lower chamber, made from stainless steel, is used for
Recent Patents on Engineering 2010, Vol. 4, No. 3 17
gas supply (O2, Ar or air). FGC with immobilized titania is
placed on the Teflon membrane thus the loaded titania pho-
tocatalysts can be supplied with gas from the gas space
through the membrane. The solution is irradiated through a
Pyrex window fixed on the top of the liquid space. The ad-
vantage of this system for application of photodegradation of
aqueous VCOCs is that it does not require air bubbling,
which causes unfavorable volatilization into open air.
13 Application of easily separated (magnetic)
photocatalyst [212, 213]:
a) The efficient photocatalytic degradation of organic
compounds combined with easy photocatalyst recovery
by magnetic separation (series of magnetic bars) has
been proposed. The preparation method for active, sta-
ble and easily separated photocatalyst has been de-
scribed. The photocatalyst composed of: (i) a core being
at least partly formed of a magnetic material, (ii) an in-
sulative layer disposed above the core formed of an
electrically non-conductive material, and (iii) an outer
layer disposed about the insulative layer, formed of a
semiconductor having photocatalytic properties [213].
b) The photocatalyst composed of: (i) a magnetic part, such
as a magnetic core particle (Fe3O4, Fe2O3, BaO(Fe2O3)6,
SrO(Fe2O3)6 or AlNiCo) and (ii) photocatalytic part, at
least one photocatalyst particle (TiO2, ZnO or Fe3O4)
deposited onto a magnetic core. The use of such com-
posite particles in a photocatalytic fluidized bed en-
hances the contact between the photocatalyst, the light
source and the reactant, improving the kinetics for treat-
ing reactants. Magnetic properties of photocatalyst al-
low: (i) easy photocatalyst separation after treatment, (ii)
enhanced mixing and exposure by magnetic agitation,
(iii) creation restraining forces to prevent composite par-
ticles from escaping from the fluidized bed system. In
addition, the ability to fix photocatalyst particles to
magnetic compositions permits increased activity due to
ability to use smaller photocatalyst particles, being as
small as nano-sized, compared to conventional fluidized
bed systems (generally 100 μm) [212].
14 Application of zeolite and/or mesoporous material
hosted photocatalyst [214, 215]
The preparation method of new photocatalysts with abil-
ity of working under visible light irradiation and with easier
separation than particulate titania has been described. The
essence of the patent is based on effect of transition metal
ions (chromium, iron, nickel, manganese, copper, tungsten,
cobalt, molybdenum, ruthenium, vanadium, zinc, silver,
platinum, titanium or mixtures thereof) if bound the frame-
work of a zeolite (commercial: ZSM-4, ZSM-5, ZSM-11,
ZSM-12, ZSM-20, ZSM-22, ZSM-23, ZSM-35, ZSM-48,
ZSM-50, MCM-22, PSH-3, MCM-48, MCM-49, Beta, X, Y,
L and natural: ferrierite, mordenite, dachiardite, clinoptilo-
lite, offretite, erionite, gmelinite, chabazite) and/or
mesoporous molecular sieve material (MCM-9, VPI-5,
MCM-41, MCM-48, MCM-49, MCM-53). Titania is loaded
into the pores of zeolite or mesoporous molecular material
after a transition metal or titanium has been exchanged into
the framework or incorporated into the framework during
synthesis (doping of the materials with titania).
18 Recent Patents on Engineering 2010, Vol. 4, No. 3
Devices for Photodegradation in Homogeneous System
15 Automated system adjusting UV reactors modules for
both water flow and UV power
Apparatus for water and wastewater treatment using
pulsed ultraviolet light in an automatic pump driven configu-
ration has been proposed. The pump allows adjustment each
UV reactor module for both water flow and UV power (av-
erage and peak intensity) thus a wide ranges of influent con-
ditions can be applied. By matching the condition of source
water to the required amount of UV dosage, and then achiev-
ing this dosage in real time by the most practical optimal
combination of average/peak power and variable pump rate,
the method and apparatus represented a good way of achiev-
ing automated, high efficiency wastewater decontamination.
16 Set of easily replaceable lamps for wastewater
treatment [216]
A simplified construction of light irradiation device com-
posed of attached of a plurality of light-transmitting tubes
containing lamps to a frame. The light irradiating modules
are installed as detachable integral units inside a housing,
thus forming flow path in which photoirradiation treatment
of hazardous wastewater can be performed.
17 Device for UV-irradiation of flowing liquids with
reduced UV-transmission [217]
The device composes of plurality of UV modules, each
module being an immersed radiator (LPML surrounded by a
round tube permeable to UV rays). The distance between UV
modules is constructed in such a way that effective water
disinfection with short contact time can be obtained.
18 Photoreactor for disinfection of industrial fluids [218]
The apparatus comprise a flattened-tube mechanism to
enhance exposure to UV radiation and a turbulence-
generating system to increase effectiveness of treatment.
Turbulence moves target molecules/microorganisms from
UV-free zones towards UV source and also serves as a
sourcing force to prevent contaminants from adhering to tube
and lamp surfaces. Turbulent is generated either by pumping
pressurized fluids such as gas or liquid through the flow path
or by placing obstacles (ribbon, beads, cones, vanes and
combination of these structures) within the flow path.
19 A batch irradiation reactor for inactivation of
pathogens in biological fluid [219]
A batch irradiation reactor comprises an upright irradia-
tion vessel with a wall transparent to light, a stirrer within
the vessel, one or more thermostated light sources, and an
electronic monitoring device with a sensor sensitive to the
photoinactivating wavelengths. The light source may be
equipped with reflectors to reflect light onto the transparent
wall of irradiation vessel, and the light sources are
switchable individually. A monitoring radiometer signals
emitted by the sensor are summed up to a target value by
mechanical, electronic or computer-software-controlled
counter. After reaching target value of energy a lamp may be
automatically turned off.
Devices for Combined Methods
20 Photosonolysis [220, 221]
Kowalska and Rau
C. Sato is an inventor of two patents applications related
to a reactor for simultaneous photolysis and sonolysis of
halogenated organic compounds. The reactor is circular cy-
lindrical vessel equipped with ultrasonic horn. In the first
patent, UV light is provided by lamps either placed parallel
to reactor walls or immersed near the ultrasonic horn [220].
In the second patent, a hollow metal partition with a reactant
flow-through hole is placed in the reactor between the UV
light source and the ultrasonic horn [221]. These reactors
may be made mobile, and thus perfect for emergency situa-
tions, e.g. after natural disasters or accidental contaminations
of water supplies.
21 Reactor equipped with immobilized catalysts for
photocatalytic and thermocatalytic treatment of
liquids [189, 222].
A rotating fluidized bed reactor can be used for photo-
catalytic, thermocatalytic or combined photo- and thermo-
catalytic treatment of hazardous organic contaminants in
fluids (gas- and liquid- phase). The main advantages of this
reactor are: (i) rapid species mass transfer to and from the
active sites of the catalyst, (ii) uniform transport of thermal
and radiant energy to the active sites of the catalyst, (iii) de-
coupling of the conversion efficiency from process intrinsic
energy efficiency, and (iv) minimal pressure drop.
To provide an energy efficient photo-process and appara-
tus the photocatalyst has been bonded to the fabric of the
base material (i.e. flexible stocking of rigid, metallic or ce-
ramic screen). A flexible base material (stocking) can be
prepared from a natural polymeric (biopolymeric), synthetic
polymeric or a combination of both natural and synthetic
polymeric material, e.g. superior photocatalyst adhesion to
biopolymer fibers and the high degree of photocatalyst cov-
erage and coating uniformity can be achieved when titania is
deposited on cotton fabric since each anhydroglucose ring
consists of three hydroxyl and two oxygen moieties (ring and
bridge) and thus binding of titania to cotton fibers via hydro-
gen bonding is possible. A rigid metallic base material (sup-
port) can be fabricated from any suitable metal oxide, metal
oxide or an alloy such as 316 and 304 stainless steel. Thus
prepared stocking or support surrounding the light source
showed high activity for TNT degradation.
22 A photoreactor for photocatalysis/ozonation of waste-
water by producing a surface corona for emitting UV
light and for the producing of ozone [223, 224]
Process using compact embedded electron induced
ozonation and activation of nanostructured titanium dioxide
photocatalyst for photocatalytic oxidation of alcohols and
hydrocarbons has been proposed. A photoreactor produces a
surface corona for emitting UV light and for the production
of ozone by passing air or oxygen through the surface co-
rona. The emitted UV light activates a photocatalyst (thin
film of 0.02-0.2 μm deposited by a flame aerosol method)
coated on a surface facing a surface with embedded elec-
trodes which generate the surface corona. Combination of
two AOPs method (photocatalysis and ozonation) proved
twice higher efficiency and much lower (ten times) energy
consumption than conventional UV lamp photocatalysis.
23 Photoreactor for simultaneous disinfection and
detoxification of wastewater [225]
Photoreactors for Wastewater Treatment: A Review
A photoreactor contains at least two light sources detoxi-
fication (370-385 nm) and for disinfection (265-285 nm) of
wastewater has been invented. One light source activates the
photocatalytic function of a semiconductor material to de-
compose organic compounds. A second light source acts
directly on living biological entities to sterilize or kill them,
and can also active a photocatalyst causing further damage to
biological contaminants. The photocatalyst is deposited onto
an optically transmitting fiber substrate in the fluid. Sets of
plural LEDs can be used as the light sources or ML operat-
ing with single emission lines at about 254 nm and/or 365
nm together or in combination with LEDs.
CURRENT & FUTURE DEVELOPMENT
Current state of technology in photochemical decomposi-
tion of organic compounds and its application is originated
from past knowledge of thermo-catalytic processes and
wastewater treatment methods on one hand, and rapid pro-
gress in the preparation method of novel, easily recoverable
photocatalysts with ability of working under solar radiation.
Although many studies have analyzed the mechanism and
efficiency of photochemical degradation, much less research
has focused on photochemical set-ups. The reported photore-
actors characterize a huge variety of design starting from a
simple beaker under daylight irradiation, then the most typi-
cal a laboratory cuvette with point irradiation and interfer-
ence filters for photocatalyst activity testing, through a cy-
lindrical reactor with an immersed lamp, to more complex
photoreactors addressed the technological problems of pho-
tocatalyst arrangement, mass transfer limitation, gas phase
distribution, optimal irradiation conditions and connection of
photochemical reaction with other processes enhancing OCs
decomposition. The photoreactor design is also highly de-
pendent on kind of treated wastewater, and thus in some
cases problems with mass transfer limitation and insufficient
gas phase delivery can occur, e.g. when circulation of liquid
or barbotage of gas phase must be avoid, i.e. surfactants and
VOCs treatment, respectively.
Inventors also address these factors, i.e. preparation of
photocatalysts (particulate, magnetic, immobilized) or reac-
tor design for easily recovery of photocatalyst (self-
contained photocatalyst recapture, packed-bed photoreactor,
photoreactor with immobilized photocatalyst), high mass
transfer rates (a tube bundle photoreactor, photoreactors with
intense liquid flow or turbulent flow generated either by
pumping pressurized fluids flow path or by placing obsta-
cles), efficient gas phase supply (hydrocyclone reactor, pho-
toreactor with an oxygen-permeable membrane), irradiation
area increase (thin layer generated in a hydrocyclone reactor
or by flattened-tube mechanism). The inventors also com-
bine photo-processes with other methods, e.g. ultrasounds,
thermocatalytic process and ozonation, for efficient treat-
ment of particular wastewater. These combinations have
been well known in the laboratory scale, and increase the
scope of photocatalytic treatments as they are sometimes
only recommended as pre-treatment method for hazardous
wastes which are resistance to biological treatment.
Homogeneous systems, e.g. hydrogen peroxide photoly-
sis, appear more attractive than heterogeneous ones, since
mass transfer limitation and photocatalyst recovery are not
Recent Patents on Engineering 2010, Vol. 4, No. 3 19
involved. However necessity of usage of light with shorter
wavelengths and therefore artificial sources of light is the
main drawback of these methods. In this regard, it is under-
standable that future development will focus mainly on het-
erogeneous systems since novel photocatalysts can work
under direct radiation by the Sun. These applications even
work in regions with less intense solar radiation, e.g. in the
central Europe as has been recently patented for grey-water
phototreatment on watercraft. In this regard, photoreactors
and wastewater treatment facilities operated under direct
solar irradiation with pre- and post- treatment processes will
be the main topics of studies for future inventions, since ap-
plication of renewable energy becoming ever more impera-
tive as one of the priorities in EU. There is still need to im-
prove the photoreactor design and to invent highly active
photocatalyst. The photoreactor design will focus on low
operating costs inventions with high mass transfer rates (gas-
liquid-solid phases), highly developed irradiation area and
easily separated photocatalyst or preferably immobilized one
of high activity and thus problematic separation will be
avoided. It seems that application of photochemical treat-
ment of wastewater is impeded by still insufficient amount
of research on photoreactor modeling, and thus a lack of
readily applicable mathematical models to reactor design and
scale-up, as well as insufficient (despite huge amount of sci-
entific papers) progress of inventions in preparation of pho-
tocatalyst of high/constant activity under: i) whole visible
spectrum of solar radiation and ii) cheap photocatalyst sepa-
ration without loss in its photoactivity.
ABBREVIATIONS
2,4-D = 2,4-dichlorophenoxyacetic acid
2,5-ADSA = 2,5-anilinedisulfonic acid
3-NBSA = 3-nitrobenzenesulfonic acid
4-CP = 4-nitrophenol
4-NP = 4-chlorophenol
AFL = Amalgam fluorescent lamp
AOPs = Advanced Oxidation Processes,
ASH = Air sparged hydrocyclone
Bl = Black light tube,
BlB = Black light blue
BLFL = Black light fluorescent lamp
BOD = Biochemical oxygen demand
BPA = Bisphenol A
BSA = Benzenesulfonic acid
CDCR = Cocurrent downflow contactor reactor
CFD = Computational fluid dynamics (CFD)
CMBR = Completely mixed batch reactor
COD = Chemical oxygen demand /mg O2 L-1
CPC = Compound parabolic collector
DB = Sodium benzene sulfonate
DBS = Sodium dodecylbenzene sulfonate
20 Recent Patents on Engineering 2010, Vol. 4, No. 3 Kowalska and Rau

DMDT = Methoxychlor TOC = Total organic carbon /ppm C

DNP = 2,4-dinitrophenol TSS = Total suspended solids
FGC = Fiberglass cloth VUV = Vacuum ultraviolet (VUV).
FL = Fluorescent lamp VOC = Volatile organic compounds
HA = Hyaluronic acid WL = Tungsten lamp
HHG = High-harmonic up-conversion (of a W-MDEL = Tungsten-triggered microwave dis-
femtosecond laser) charge electrodless lamp
HPXeL = High pressure xenon lamp VCOC = Volatile chlorinated organic com-
pounds
IR-L = Infrared laser
IR-PF = Thermal emitter consisting of a XeL = Xenon lamp
*
polysilicon filament in an evacuated Xe2 L = Xe2* excilamp
cavity
ZRM = Zero reflectance model
KrCl*L = KrCl* excilamp
LEDs = light-emitting diodes ACKNOWLEDGEMENT
LFFS = Laminar falling film slurry Support via Marie Curie FP7- Reintegration Grant (IRG)
FP7-248666.
LPML = Low-pressure mercury lamp
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