Professional Documents
Culture Documents
Sameer Ranjan
11CH10039
1
Contents
2
1.0) Introduction
Despite these advantages, photochemical reactions are not very widely used in
industrial practice. They have been adopted when no alternative thermal or catalytic
process is available or the manufacturing scale is small and, very often, dedicated to
high added value products; then, the processing difficulties and the negative effects of
the operating and equipment costs are greatly reduced. In the past, one of the reasons
set forward to explain this situation was the lack of suitable reactor models and design
procedures and sufficient quantitative information regarding the pertinent physical and
chemical parameters
3
2.0) Theory
• When a photon with energy equal to or greater than the materials’ band gap is
absorbed by semiconductor, an electron is excited from valence band to the
conduction band generating a positive hole in the valence band
• Exciton recombination is prevented through structural features such as
heterojunction, noble metal nanoparticles, silicon nanowires and substitutional
cation doping.
• Transition metals show variable valency and a strong tendency to form
coordination compounds.
• Some of the physiochemical properties of TiO2 which make it a good catalyst: -
(a) High surface area;
(b) Small crystalline size;
(c) Anatase form of TiO2;
(d) High crystallinity;
4
(e) Porous structure;
(f) Activation light source.
5
• Recently Metal-organic-frameworks have emerged as novel catalysts due to
catalytically active metal centers, functional organic linkers, easily tunable
properties in addition to large surface areas and well oriented porous structure.
• Stability of MOFs during the photocatalytic reaction is important because
reactions like pyrolyzation may destroy the framework.
• Generally thermal stability of MOFs is determined by the coordination number
and the local coordination environment.
• Another drawback is poor electronic conductivity which hampers charge transfer
from organic linker to metal cluster. Doping can largely boost electrical
conductivity and also one and two dimensional MOFs exhibit higher electronic
conductivity that three dimensional framework.
• Heterojunction photocatalysis is another way to prevent recombination. In this
method two semi-conductor metal oxides are coupled. It is also helpful to
increase visible light absorption of semiconductor photocatalyst.
6
2.1) Degradation of phenol by photocatalysis.
A wide variety of organic pollutants are introduced into the water system from various
sources, such as industrial effluents, agricultural run-off and chemical spills. Their
toxicity, stability to natural decomposition and persistence in the environment has been
the cause of much concern to the societies and regulation authorities around the world.
Phenol is a kind of refractory organic compound, having the toxicity of carcinogenesis,
teratogenesis and mutagenicity. The treatment of phenol in micro-polluted water has
always been paid attention by many researchers.
The traditional purification technique has been not suitable for the existing water
source and water quality standards. Therefore, it is necessary to develop low cost and
high efficient treatment technique.
Several specific new technologies, called Advanced Oxidation Processes (AOP), have
been developed to eliminate dangerous chemicals such as organics from polluted
waters. The photocatalytic process, based on UV irradiated semiconductor, represents
one of AOP that provide an interesting route to the destruction of many organic
substances to CO2, H2O and corresponding mineral acids.
TiO2 is doped with Fe (III) to increase its activity under visible light.
7
2.2) Eley Riedel model
8
9
2.3) Eley Rieldel for Phenol degradation derivation
A+B→C+D
A + S ⇌ AS
AS + B → C + D
r= (k.Co.Ka.Ca.Cb)/(1+Ka.Ca)
AS + B ⇌ CS + DS
r= kf .Cas.Cb-kb.Ccs.Cds
CS → C + S
DS → D + S
Ccs= Kc.Cc.Cv
Cds= Kc.Cd.Cv
Cv= Co/(1+Ka.Ca+Kc.Cc+Kd.Cd)
Cas= Ka.Ca.Co/(1+Ka.Ca+Kc.Cc+Kd.Cd)
Ccs= Kc.Cc.Co/(1+Ka.Ca+Kc.Cc+Kd.Cd)
Cds= Kd.Cd.Co/(1+Ka.Ca+Kc.Cc+Kd.Cd)
So, r= kf .Cas.Cb-kb.Ccs.Cds
r= (kf.Ka.Ca.Co.Cb)-(kb.Kd.Kc.Cc.Cd.Co2)/(1+Ka.Ca+Kc.Cc+Kd.Cd)
10
3.0) Data Extraction for Phenol degradation.
pH = 3
11
Data extraction by Web Plot Digitizer
12
117.627 0.477296
121.4976 0.466749
124.6604 0.460441
128.5273 0.452022
132.3867 0.447858
136.2536 0.439439
140.1205 0.431019
144.3301 0.426864
149.24 0.422724
153.1069 0.414305
156.2697 0.407997
160.4719 0.408096
164.6703 0.410323
168.526 0.408287
172.7356 0.404131
175.5408 0.40207
178.7036 0.395761
182.9095 0.393733
186.7689 0.389569
190.2782 0.385397
193.0908 0.37908
195.5569 0.370628
199.0587 0.370711
203.2683 0.366555
206.7813 0.360255
210.9872 0.358227
13
4.0) Calculations for this data set.
Time C/CO Phenol CO2 H2O O2 moles Rate
(min) moles moles moles (moles/L(min))
0 1 1.06383 0 0 100 -
17.31156 0.768542 0.817598 1.477393 0.738697 98.27637 0.01422357
18.40308 0.745163 0.792727 1.626617 0.813309 98.10228 0.014731387
20.53396 0.728192 0.774673 1.734942 0.867471 97.9759 0.014081892
22.31839 0.709086 0.754346 1.8569 0.92845 97.83362 0.013866742
24.46045 0.685732 0.729502 2.005966 1.002983 97.65971 0.01366809
26.23743 0.67088 0.713703 2.100763 1.050382 97.54911 0.013344571
28.02186 0.651774 0.693376 2.222721 1.111361 97.40683 0.013220165
30.14901 0.63693 0.677585 2.317466 1.158733 97.29629 0.012811177
33.32299 0.624239 0.664084 2.398472 1.199236 97.20178 0.011996083
36.84341 0.613684 0.652856 2.465845 1.232922 97.12318 0.011154616
41.07538 0.596763 0.634854 2.573852 1.286926 96.99717 0.010443615
44.93108 0.594727 0.632688 2.586851 1.293426 96.98201 0.009595627
49.48342 0.594834 0.632802 2.586165 1.293082 96.98281 0.008710542
53.70048 0.586423 0.623855 2.639851 1.319926 96.92017 0.008193134
58.62163 0.575901 0.612661 2.707013 1.353506 96.84182 0.007696285
61.79188 0.565338 0.601423 2.774439 1.387219 96.76316 0.007483288
65.65131 0.561174 0.596994 2.801018 1.400509 96.73215 0.007110845
70.21855 0.552771 0.588054 2.854652 1.427326 96.66957 0.006775635
76.52924 0.548665 0.583686 2.880861 1.440431 96.639 0.006273988
82.49721 0.540296 0.574782 2.934284 1.467142 96.57667 0.005928047
88.46144 0.534054 0.568142 2.974126 1.487063 96.53019 0.005603432
84.95964 0.533971 0.568054 2.974655 1.487327 96.52957 0.005835427
79.33813 0.544476 0.57923 2.907599 1.453799 96.6078 0.006108031
72.66981 0.552829 0.588116 2.854282 1.427141 96.67 0.006546235
91.98187 0.523498 0.556913 3.041499 1.52075 96.45158 0.005511048
94.79821 0.515054 0.54793 3.095397 1.547699 96.3887 0.005442081
98.65764 0.51089 0.5435 3.121976 1.560988 96.35769 0.005274091
102.1706 0.50459 0.536798 3.162189 1.581094 96.31078 0.005158347
104.6331 0.498266 0.53007 3.20256 1.60128 96.26368 0.005101255
107.4457 0.491949 0.52335 3.242878 1.621439 96.21664 0.005030259
110.6085 0.485641 0.516639 3.283143 1.641571 96.16967 0.004947094
14
114.1214 0.479341 0.509937 3.323355 1.661678 96.12275 0.004853536
117.627 0.477296 0.507762 3.336407 1.668203 96.10753 0.004727384
121.4976 0.466749 0.496542 3.403727 1.701863 96.02899 0.004669129
124.6604 0.460441 0.489831 3.443992 1.721996 95.98201 0.0046045
128.5273 0.452022 0.480874 3.497732 1.748866 95.91931 0.004535655
132.3867 0.447858 0.476445 3.524311 1.762156 95.8883 0.00443689
136.2536 0.439439 0.467488 3.578051 1.789025 95.82561 0.004376706
140.1205 0.431019 0.458531 3.63179 1.815895 95.76291 0.004319843
144.3301 0.426864 0.45411 3.658317 1.829158 95.73196 0.00422448
149.24 0.422724 0.449707 3.684738 1.842369 95.70114 0.004115001
153.1069 0.414305 0.44075 3.738477 1.869239 95.63844 0.004069572
156.2697 0.407997 0.434039 3.778742 1.889371 95.59147 0.00403015
160.4719 0.408096 0.434145 3.778108 1.889054 95.59221 0.003923957
164.6703 0.410323 0.436514 3.763894 1.881947 95.60879 0.003809525
168.526 0.408287 0.434348 3.776893 1.888446 95.59362 0.003735223
172.7356 0.404131 0.429927 3.803419 1.90171 95.56268 0.003669789
175.5408 0.40207 0.427734 3.816577 1.908288 95.54733 0.003623637
178.7036 0.395761 0.421023 3.856842 1.928421 95.50035 0.003597057
182.9095 0.393733 0.418865 3.869788 1.934894 95.48525 0.003526142
186.7689 0.389569 0.414435 3.896367 1.948184 95.45424 0.003476995
190.2782 0.385397 0.409997 3.923 1.9615 95.42317 0.003436197
193.0908 0.37908 0.403277 3.963318 1.981659 95.37613 0.003420945
195.5569 0.370628 0.394285 4.017269 2.008634 95.31319 0.003423784
199.0587 0.370711 0.394373 4.01674 2.00837 95.3138 0.003363111
203.2683 0.366555 0.389952 4.043267 2.021633 95.28286 0.003315212
206.7813 0.360255 0.38325 4.083479 2.041739 95.23594 0.003291302
210.9872 0.358227 0.381092 4.096425 2.048213 95.22084 0.003235919
15
5.0) Graph for above rate calculation
Rate vs Time
0.016
0.014
0.012
Rate (moles/L(min))
0.01
0.008
0.006
0.004
0.002
0
0 50 100 150 200 250
Time (minutes)
16
6.0) Data Arrangement for regression
17
0.004536 0.276751 0.00022 0.480874 3.497732 1.748866
0.004437 0.274113 0.000224 0.476445 3.524311 1.762156
0.004377 0.268784 0.00023 0.467488 3.578051 1.789025
0.00432 0.263462 0.000237 0.458531 3.63179 1.815895
0.004224 0.260837 0.000241 0.45411 3.658317 1.829158
0.004115 0.258225 0.000244 0.449707 3.684738 1.842369
0.00407 0.252916 0.000252 0.44075 3.738477 1.869239
0.00403 0.248943 0.000257 0.434039 3.778742 1.889371
0.003924 0.249005 0.000257 0.434145 3.778108 1.889054
0.00381 0.250408 0.000255 0.436514 3.763894 1.881947
0.003735 0.249125 0.000257 0.434348 3.776893 1.888446
0.00367 0.24651 0.00026 0.429927 3.803419 1.90171
0.003624 0.245213 0.000262 0.427734 3.816577 1.908288
0.003597 0.241247 0.000268 0.421023 3.856842 1.928421
0.003526 0.239973 0.00027 0.418865 3.869788 1.934894
0.003477 0.237358 0.000273 0.414435 3.896367 1.948184
0.003436 0.234739 0.000277 0.409997 3.923 1.9615
0.003421 0.230778 0.000283 0.403277 3.963318 1.981659
0.003424 0.225483 0.00029 0.394285 4.017269 2.008634
0.003363 0.225535 0.00029 0.394373 4.01674 2.00837
0.003315 0.222934 0.000294 0.389952 4.043267 2.021633
0.003291 0.218995 0.0003 0.38325 4.083479 2.041739
0.003236 0.217728 0.000302 0.381092 4.096425 2.048213
18
7.0) Code for regression approximation in R
19
8.0) Compiled Results in R
20
21
22
9.0) Results summary
K-terms Values
kf.Ka 3.057e-02
kb.Kd.Kc -1.608e+01
Ka 0.34460
Kc 0.064076
Kd 0.12815
R-squared 0.9741
p-value < 2.2e-16
Standard Error 10-3
Rate vs Time
0.016
0.014
→Actual curve
Rate (moles/L(min))
0.012
0.01
↑
0.008 ER- Model
0.006
0.004
0.002
0
0 50 100 150 200 250
Time (minutes)
23
10.0) Basic Design for photo-reactor.
From the extracted data, time for 99% conversion is 328 minutes.
rA= {[3.057e-02.Cao(1-X).Co.(Cbo-7CaoX)]-[1.608e+01.6(CaoX).(3CaoX).Co2]
(1+0.34460.Cao(1-x)+(0.064076.6CaoX)+(0.12815.3CaoX))
On solving using Wolfram Alpha, we get V=505 mL (this is the minimum area required
for 1.06 moles of Phenol)
If we take this as the minimum concentration for phenol, then in 505 ml of reactor only
0.537 moles of Phenol will be present instead of 1.06, so twice the volume calculated
above is taken. Also, for maximum concentration where in 1 litre 1.06 moles of phenol
are present, we do not want the reactor to be fully filled and have a clearance of atleast
20-25%.
We are considering the reactor as an annular cylindermade of glass, with the annulus
space for the reactor and the inner cylinder for light.
For the light, we use CFL lamp with λ>400nm, to cutoff wavelength lesser than 400nm,
we use a cutoff filter inside the inner quartz tube cylinder.
Say, Ro = Outer diameter and Ri = Inner diameter and keeping height of reactor H as 15
cm
24
Photo-reactor Summary
Total Volume 1.2 L
Outer Radius 5.15 cm
Inner Radius 1.03 cm
Height 15 cm
Material Glass
Type Annular
Wavelength λ > 400 nm
Phenol Concentration 100g/L
25
11.0) References
[1] TiO2 photocatalysis: Design and applications by Kazuya Nakata, Akira Fujishima in
the Journal of Photochemistry and Photobiology C: Photochemistry Reviews 13 (2012)
169– 189.
26
[10] Photoreactor Analysis and Design: Fundamentals and Applications by Alberto E.
Cassano, Carlos A. Martin, Rodolfo J. Brandi, and Orlando M. Alfano in Ind. Eng. Chem.
Res. 1995, 34, 2155—2201.
[11] Photoreactors for Wastewater Treatment: A Review by Ewa Kowalska and Sven Rau
in Recent Patents on Engineering · November 2010.
[13] NPTEL Course: Catalyst Science and Technology, Module 2 Heterogeneous Catalysis,
Lecture 19 Reaction Mechanisms and Kinetics, page 7.
[14] NPTEL Course: Nano structured materials- synthesis, properties, self assembly and
applications, Module 4, Photocatalysis – III.
27