CHINESE UNIVERSITIES 2009, 25(4), 451—454
Degradation of Furfural by UV/O3 Technology
KANG Chun-li*, TANG Xiao-jian, JIAO Xin-qian, GUO Ping, QUAN Fu-min and LIN Xue-yu
College of Environment and Resources, Jilin University, Changchun 130021, P. R. China Abstract Furfural in aqueous solution was treated by UV/O3 method. The results show that the removal rate of furfural is severely enhanced and the synergism phenomenon appears when ultraviolet and ozone are present together. The influences of experimental parameters such as pH, the intensity of light and the negative-positive ions on furfural degradation were investigated. The results indicate that furfural(300 mg/L) is almost completely degraded after 3 h under the optimum conditions. The intermediate in the furfural degradation was characterized by GC-MS and IR spectrum and the degradation mechanism of furfural by UV/O3 technology was proposed. Keywords Ozone; Ultraviolet (UV); Furfural; Degradation Article ID 1005-9040(2009)-04-451-04
Furfural manufacturing is one of the main industrial activities in Jilin Province, China. Furfural is made from the agriculture wastes(such as corn cob grits, sorghum straws) through hydrolyzing and refining. Furfural and its derivates are important chemicals because it is a selective solvent for separating compounds in petroleum refining, gas, oil and diesel furl. Furfural wastewater is khaki and feculent, and contains a great deal of organic acids, especially acetic acid is present in furfural wastewater and the pH value of the wastewater is in the range of 2.0―3.0. In the wastewater there is 1%―2.5% of acetic acid and 0.05% of furfural. The discharge of untreated furfural wastewater can cause severe environment pollution. Now, the furfural wastewater treatment commonly adopts biological method and chemical method at home and abroad. Compared with these traditional methods, advanced oxidation processes have the characteristics of low cost and simple operation[1―5]. Advanced oxidation processes(AOPs) are defined as the processes that generate hydroxyl radicals in sufficient quantity to be able to oxidize majority of the complex chemicals present in the effluent water. These processes include cavitation, photocatalytic oxidation and Fenton chemistry. In recent years the application of photo-oxidation techniques in the decomposition of complex and heavy molecules has been considered, which involve the application of
various combinations of O3, such as UV/O3 and UV/H2O2. These combinations are widely used in the decomposing of organic products in industrial wastewater and groundwater owing to their great ability of oxidizing and high reaction rate[6―18]. In order to study the feasibility of furfural wastewater treatment by UV/O3 technology, the main pollutants(acetic acid and furfural) in furfural wastewater were separately investigated. The degradation of furfural in its wastewater under UV/O3 system was explored and the furfural decomposition mechanism in UV/O3 system was also discussed.
Furfural, phosphoric acid, sodium hydroxide, copper sulfate, sodium chloride, sodium bicarbonate, ferric chloride, manganese chloride were of analytical grade. All the reagents were obtained from Beijing Chemical Reagent Co., China. The solutions were prepared with distilled water. Put 500 mL furfural solution(300 mg/L) into a quartz reactor. Ozone was produced by an ozone producer(BW-400A Tidynet) with the initially produced concentration of 0.1 mg/L, and diffused by a glass ball in the bottom of the reactor. The reactor was exposed to an incident UV radiation of 1.5×105 Lx from a high-pressure mercury and the distance of the lamp from the center of the solution was 10 cm. Samples were taken at regular intervals. The concentration of the furfural in the photodegradation was determined at
——————————— *Corresponding author. E-mail: email@example.com Received September 16, 2008; accepted October 13, 2008. Supported by the Jilin Scientific Research Committee Foundation, China(No.20010422).
500. These indicate that UV/O3 system got the best result.1 mg/L.1430 0. b.395 ρ0–ρt = –0. in the systems of O3. USA) analyses.84 127. 100.1430t+31. The calculated results indicate that the zero order kinetic model gives a good fit.25
λmax=275 nm on an UV-Vis spectrophotometer(7530. The photodegradation efficiency(η) was calculated by equation: η(%)=(ρ0–ρt)/ ρ0×100% .3
Effects of the initial furfural concentrations on degradation of furfural
Fig. It also supports that the degradation rate decreases with the increasing of furfural concentration. more OH was produced and hence the degradation of furfural was accelerated. The concentration of the TOC was analyzed by TOC analyzer(TOC-vcph.19 k/min-1 0. The furfural solution(500 mL) was extracted with 30 mL of petroleum ether after 2.3). Table 1 shows the reaction followed the zero kinetic law.1838 0. Nevertheless.
Ozone decomposes to produce hydroxyl radical.7%.4 shows the effects of the intensities of light on the degradation of furfural. k is the zero-order reaction rate constant(min–1). With the increasing of initial concentration of furfural solution.2046 0. The effect of pH value on the degradation of furfural in the system of UV/O3 was investigated over a pH range of 2. O3 or UV/O3 Fig.7. ozone and UV/ozone systems
pH=4. CHINESE UNIVERSITIES
Vol.02 r 0. As the intensity of light is increased.2) that the degradation rate of furfural was higher
Kinetic parameters obtained from experimental runs at different initial concentrations
Equation ρ0–ρt = –0. the degradation rate of furfural decreased (Fig. t1/2 is the half life period.11 332. the ozone concentration was 0. China).1649 t1/2/h 87. 200. the ozone concentration was 0.5 h irradiation for GC-MS and IR(5PC Nicolet.0898 0.
Fig. ρ0 is the initial concentration of furfural.1 mg/L.0898t+15. respectively.3―12.261 ρ0–ρt = –0. With increasing pH · value. The degradation rates were 18.992
3. China). In Table 1. The pH value of the furfural solution was measured with a pH-meter(pHS-3C. Shangfen.509 ρ0–ρt = –0. The concentration of furfural was unchanged in the dark reaction.
3.2046t+53.1838t+75. 47% and 91%. ozone de· composes and produces OH. RES. Japan). e.1
Degradation of furfural in UV. d.999 0. 3. which is strong oxidative but its quantity is limited. ρt is the concentration of furfural at time t.42 110. Therefore.826 ρ0–ρt = –0. initial furfural concentration was 300 mg/L. The intensity of light was adjusted by altering the distance between the reactor and the lamp.2
Effects of pH values on degradation of furfural
Initial furfural concentration was 300 mg/L.81 208. UV and UV/O3 after 240 min.998 0. and r is the correlation coefficient.998 0. the removal of furfural is accelerated because the more the intensity of light.
Fig. The results show (Fig. It is known that the oxidizing potentials of ozone are 2.452
CHEM.1 mol/L) were used to adjust the pH value of the furfural.1649t+112. where ρ0 is initial concentration of furfural. pH=4. c. ρt is the concentration at reaction time t.1 shows the degradation of furfural(300 mg/L) in three different systems. 700. the ozone concentration was 0.3 Effects of Initial Furfural Concentrations
Results and Discussion
3.1 Degradation of Furfural under UV.1 mg/L. the degradation rate increased.
in alkaline solution.7. the more the radicals were produced under the action of UV/O3.8 V.996 0. and UV and O3 show a synergetic effect in this system.08 or 1.1 mol/L) and/or sodium hydroxide(0.4 V separately under acidic or alkaline condition.2
Effects of pH on Degradation of Furfural
ρ0/(mg·L–1) 100 200 300 500 700
Phosphoric acid(0. 300. which has a higher oxidizing potential of 2.4
Effects of Light Intensities
Effects of light intensities on degradation of furfural
3. Fig. the light khaki aqueous solution was finally changed into red-brown in color. This is because the irradiated Fe3+ in aqueous solution undergoes a photoredox process. initial furfural concentration was 300 mg/L.7. In the furfural degradation process in
Fig. the ozone concentration was 0. · Fe2++ OH Fe(OH)2++hv Simultaneously. 7500 Lx.6
Effects of cations on degradation of furfural
pH=4. As has been pointed before. the ozone concentration was 0.7. H2O2 or · HO2 offers an interesting catalytic effect on the process mentioned above and larger amounts of oxi· dizing OH can be formed.
Fig. c. the furfural degradation rate was almost unchanged.
There are some anions and cations in the natural water such as SO42–. b.4
KANG Chun-li et al. In the presence of Cu2+ and Mn2+. So. initial furfural concentration was 300 mg/L.7.7
Mineralization of Furfural
As seen in the Fig. under higher light intensity. As the spectrum of high-pressure xenon lamp is similar to the solar spectrum and it is usually used to simulate solar light. the concentrations of TOC and furfural gradually decrease with increasing
. it can be deduced that the furfural will be degraded effectively in the solar light/O3 system and this is significant for saving energy when this technology is used to treat actual furfural wastewater.1 mg/L. respectively. the degradation of furfural increases in the presence of Fe3+.7
Effects of different light sources on degradation of furfural
pH=4. the re-oxidation of Fe2+ into Fe3+ by oxidizing species in solutions such as O3. It is due to the difference between the emission spectra of the two lamps. 10040 Lx.89×104 Lx. · Under the light some ions can produce OH and increase the degradation of organic compounds[20. initial furfural concentration was 300 mg/L.
Effects of Anions and Cations
Fig.5 mmol/L) on the furfural degradation were researched. Therefore.
As seen in Fig. Cu2+.
3. the higher furfural removal rate could be achieved. 5230 Lx.5 shows that the presence of HCO3– could accelerate the degradation of furfural. In the presence of Cl– and SO42–. the ozone concentration was 0. The light intensities of high-pressure mercury lamp and high-pressure xenon lamp are 1.
It can be seen from Fig. the furfural degradation rate is almost not changed. but the efficiency of high-pressure xenon lamp is about 5/8 that of the high-pressure mercury lamp. the degradation rate was accelerated. pH=4.6. The intensity of the light of the high-pressure mercury lamp is 4 times that of the high-pressure xenon lamp. Mn2+ and Fe3+.
the UV/O3 system with Fe added.7.5×105 and 3.1 mg/L. HCO3–. The effects of six kinds of ions(0. initial furfural concentration was 300 mg/L.8. respectively.1 mg/L.No. which gives rise to Fe2+ and hydroxyl radicals via photo-Fenton reaction. It’s probably because of the increasing of pH value in aqueous solution when HCO3– is added. Cl–. But some other ions have been proved as the scaven· ger of OH and are unfavorable to the degradation of organic compounds.21].1 mg/L.5
Effects of anions on degradation of furfural
Effects of Different Light Sources
Fig. 2820 Lx.7 that the removal of furfural under the high-pressure mercury lamp is faster than that under the high-pressure xenon lamp. the ozone concentration was 0. d.
2004. the whole degradation process of furfural in the UV/O3 system can be described as follows(Scheme 1). 2. 151 Xia X. 127   Sun Z. Juan C.. 2003.. Hosseini S. Y. 65. A. Q.. 25(8)... Environ. Wang H. B. 1999.. Zhang H. Sci.. 11.124 Tong S. Sci. Dyes and Pigments... Environ... Technol. Fu J. Zhu Y.. Meng Y.. Chemical Engineering Journal.. B.. 22.9.. 11(2). Ma J. 1. 2004. 2004. this absorption is attributed
Fig.. Acta Scientiae Circumstantiae. M. Industrial Water Treatment. 1. Yu Z.
Fig. T. 28 Yang G. Guan X..7. extract with petroleum ether.
. Luo J. Y.. Adv. Veronica G.. 2008. 25(1).1 mg/L
3.. Willlam H.. R. 2004. 482 Muthukumar M.... This result also indicates that intermediate is a kind of hydrocarbon. A. Kestioglu K. Sci. P.. 139
Fig. 2005.. China Environ.. Environ.. b. M.. 1034 Zhong L.. Selvakumar N. B. 2005. Petroleum ether.25
reaction time under the optimum condition. 2002. 25(11).. 2004. the ozone concentration was 0. Environ. 14 Jia D. 2000.9 GC-MS spectrum of intermediate of furfural degradation
The intermediate was extracted with petroleum ether and analyzed by IR spectrum(Fig.. Contreras S. Guangxi Sci. 2005. Zhu Y.
          Wang R. P.8
Scheme 1 Photodegradation mechanism of furfural
The chromatogram of the intermediate by GCMS analyses is shown in Fig.. X...
to the C―H(―CH2. Gao N. 2004. 2005. Miguel A.1-dimethyl cyclopropane. 8. which coincides with the result by GC-MS. 1041 James D. Hence. B. 139(3). Nigel J. 1457           Shi F. 2008. M. Yun Y. Gimenez J. initial furfural concentration was 300 mg/L. Sci.. Shi W. Ma C. H. RES.. Xiao X...553 Zhong W. 50 Gogate P. Eng... 568 Borghei S.8
Comparison between the rates of TOC removal and furfural degradation
pH=4.. University(Natural Science). L...7% and 100% after 300 min. 35 Mare P. CHINESE UNIVERSITIES
Vol.. 113 Cristina C. Water Res. 43... N.. B. Technol..10 IR spectra of intermediates of furfural degradation
a. 2008. Res. Acta Scientiae Circumstantiae. ―CH3) wagging motion and in regions there are not any absorption peaks. 219 Gary R.. 25(3). 55. Beijing Norm. 22(1). the intermediate should be 1. Pandit A... G. Xu B... Yonar T. 72 Zhang W. The result shows that the intermediate of the furfural degradation is cycloalkane and its molecular weight is 70. F.. M.454
CHEM. Y. 761 Rui M. 366 Tong S.. P... Heilongjiang Environmental Journal. Santiago E.10). 33. 5.. Ma C... 2005. R. On the basis of the analysis above. 2007.. Sargunamani D.. 32 Azbar N. This means the degradation rate of TOC is slower than that of furfural and it can be deduced that furfural is not directly mineralized into CO2 and H2O and the intermediate products are formed during the degradation process. Zhu X. Henan Chemical Industry. Environ. Technol. 3. Shanghai Environ. 36. Chemosphere. Yu H. Y. 47.. J. 19(12). Q. H. H. Sci. There is only one absorption peak in a range of 2880―2978 cm–1 on the spectrum. 1453 Esplugas S. F. 2000. The degradation rate of TOC and furfural are separately 73. Chem. 1988.. et al.. 25 Zhang S. H.. Zhu Y.. Environ. 2005. Journal of the Gradute School of the Chinese Academy of Sciences. H. Environ.