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Removal of lead from aqueous solution

Nanotechnology

KING FAHD UNIVERSITY OF PETEROLEUMS AND MINERALS DHARAN KSA


Special Topics in Chemical Engineering Authored by: KAMAL SIDDIQUE Presented by : Kamal Siddique G201207340

Removal of lead from aqueous solution


Special Topics in Chemical Engineering

ABSTRACT Iron oxide, titanium oxide, silver oxide and zinc oxide coated carbon nanotubes were used to remove Pb(II) from aqueous solution. Carbon nanotubes (CTNs) show exceptional adsorption capability and high adsorption eciency for lead removal from water .Adsorption is a method for removing lead from wastewater. The adsorption of lead on new adsorbent different types of carbon nanotubes has been investigated using a series of batch adsorption experiments. To a significant extent, pH influenced the extraction of lead from aqueous solutions. The lead removal efficiency was checked by varying pH value and contact hours. The adsorption capacity of lead calculated at different dosage of lead and similarly by varying the runs per hour. Our results suggest that CNTs can be good Pb2 absorbers and have great potential applications in environmental protection

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Removal of lead from aqueous solution


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TABLE OF CONTENTS
Introduction ..................................................................................................................................................................3 SAFETY MEASURES WHILE HANDLING LEAD AND NANO PARTICLES ............................................................................4 1. 2. Inductively Coupled Plasma Mass Spectrometry or ICP-MS: ..............................................................................5 Method .................................................................................................................................................................8 2.1 3. a. b. c. d. 4. 5. 6. Experiment: ...............................................................................................................................................10

Effect of different parameters ...........................................................................................................................10 Effect of contact time ....................................................................................................................................10 Effect of CNT dose ..........................................................................................................................................11 Effect of solution pH ......................................................................................................................................11 Effect of agitation ..........................................................................................................................................12 Optimum conditions for removal of lead ..........................................................................................................12 Comparative analysis of various cnts ...............................................................................................................12 Conclusions .........................................................................................................................................................15

Acknowledgment .........................................................................................................................................................16 References ...................................................................................................................................................................17

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INTRODUCTION
The eects of heavy metals such as lead, mercury, copper, zinc and cadmium on human health have been studied extensively. Excessive ingestion of them can causes accumulative poisoning, cancer, nervous system damage. Lead is ubiquitous in the environment and is hazardous at high levels. It is a general metabolic poison and enzyme inhibitor and can accumulate in bones, brain, kidney and muscles. Long-term drinking water containing high level of lead can cause serious disorders, such as anemia, kidney disease and mental retardation. Lead in wastewater comes mainly from battery manufacturing, printing, painting, dying and other industries. Unlike organic compounds, lead is non-biodegradable and, therefore, must be removed from water. Various methods of lead removal from wastewater have been developed and ad-sorption with activated carbon is a common used method. Increasingly stringent standard on the quality of drinking water has stimulated a growing e ort on the exploiter of new high ecient ad-sorbents. Out of the wastewater treatment methods involving lead, precipitation, coagulation sedimentation, reverse osmosis, ion exchange, cementation, and adsorption onto activated carbon, adsorption is considered quite attractive in terms of its efficiency of removal from dilute solutions, economics, and handling . Various adsorbents such as activated carbon, iron oxides, filamentous fungal biomass and natural condensed tannin have been explored . EPA drinking water standards for lead are 0.05 mg/l, but a level of 0.02 mg/l has been proposed and is under review. Increasingly stringent standard on the quality of drinking water has stimulated a growing effort on the exploiter of new high efficient adsorbents. So the necessity to exploit new high efficient adsorbents is great. Carbon nanotubes (CNTs), a novel kind of carbon, were first reported by Iijima in 1991. CNTs can be thought of as cylindrical hollow micro-crystals of graphite. Because of relatively large specific area, CNTs have attracted researchers interest as a new type of adsorbent and offer an attractive option for the removal of metals, fluoride, organic pollutants. CNTs can also be used as supports for adsorption materials. Zinc, silver. Titanium and iron oxide-coated CNTs for metal removal have been proved successful for the enhancement of treatment capacity Carbon nanotubes (CNTs), a new form of carbon, are attracting researchers great interest due to their exceptional absorption properties, mechanical properties and unique electrical property. Although carbon nanotubes exhibit great potential for the adsorption of heavy metal ions from aqueous solutions, the removal efficiency, selectivity, and sensitivity remain limited. The modification of carbon nanotubes is therefore considered to be an important route for the enhancement of removal efficiency, selectivity, and sensitivity of heavy metals. The surfaces of multi-walled carbon nanotubes (MWCNTs) can be modified in a variety of ways, such as chemical bond formation between the modifying species and MWCNTs surfaces or physical adsorption of the modifier to MWC-NTs surface. Many studies have focused on the removal of heavy metal ions by modified carbon nanotubes, including cadmium , nickel and strontium , lead chromium , uranium , copper , and copper, zinc, cadmium, and nickel ions from aqueous solution
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SAFETY MEASURES WHILE HANDLING LEAD AND NANO PARTICLES

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Removal of lead from aqueous solution


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1. INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY OR ICP-MS: Inductively Coupled Plasma Mass Spectrometry or ICP-MS is an analytical technique used for elemental determinations. The technique was commercially introduced in 1983 and has gained general acceptance in many types of laboratories. Geochemical analysis labs were early adopters of ICP-MS technology because of its superior detection capabilities, particularly for the rare-earth elements (REEs). ICP-MS has many advantages over other elemental analysis techniques such as atomic absorption and optical emission spectrometry, including ICP Atomic Emission Spectroscopy (ICP-AES), including:

Detection limits for most elements equal to or better than those obtained by Graphite Furnace Atomic Absorption Spectroscopy (GFAAS) Higher throughput than GFAAS The ability to handle both simple and complex matrices with a minimum of matrix interferences due to the high-temperature of the ICP source Superior detection capability to ICP-AES with the same sample throughput The ability to obtain isotopic information.

An ICP-MS combines a high-temperature ICP (Inductively Coupled Plasma) source with a mass spectrometer. The ICP source converts the atoms of the elements in the sample to ions. These ions are then separated and detected by the mass spectrometer. Figure 1 shows a schematic representation of an ICP source in an ICP-MS. Argon gas flows inside the concentric channels of the ICP torch. The RF load coil is connected to a radio-frequency (RF) generator. As power is supplied to the load coil from the generator, oscillating electric and magnetic fields are established at the end of the torch. When a spark is applied to the argon flowing through the ICP torch, electrons are stripped off of the argon atoms, forming argon ions. These ions are caught in the oscillating fields and collide with other argon atoms, forming an argon discharge or plasma.
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Figure.1

The sample is typically introduced into the ICP plasma as an aerosol, either by aspirating a liquid or dissolved solid sample into a nebulizer or using a laser to directly convert solid samples into an aerosol. Once the sample aerosol is introduced into the ICP torch, it is completely desolvated and the elements in the aerosol are converted first into gaseous atoms and then ionized towards the end of the plasma. The most important things to remember about the argon ICP plasma are:

The argon discharge, with a temperature of around 6000-10000K, is an excellent ion source. The ions formed by the ICP discharge are typically positive ions, M+ or M+, therefore, elements that prefer to form negative ions, such as Cl, I, F, etc., are very difficult to determine via ICP-MS. The detection capabilities of the technique can vary with the sample introduction technique used, as different techniques will allow differing amounts of sample to reach the ICP plasma. Detection capabilities will vary with the sample matrix, which may affect the degree of ionization that will occur in the plasma or allow the formation of species that may interfere with the analyte determination.

Once the elements in the sample are converted into ions, they are then brought into the mass spectrometer via the interface cones. The interface region in the ICP-MS transmits the ions traveling in the argon sample stream at atmospheric pressure (1-2 torr) into the low pressure region of the mass spectrometer (<1 x 10-5 torr). This is done through the intermediate vacuum region created by the two interface cones, the sampler and the skimmer

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Figure 2. The interface region of an ICP-MS. The sampler and skimmer cones are metal disks with a small hole (1mm) in the center. The purpose of these cones is to sample the center portion of the ion beam coming from the ICP torch. A shadow stop (see Figure 2) or similar device blocks the photons coming from the ICP torch, which is also an intense light source. Due to the small diameters of the orifices in the sampler and skimmer cones, ICP-MS has some limitations as to the amount of total dissolved solids in the samples. Generally, it is recommended that samples have no more than 0.2% total dissolved solids (TDS) for best instrument performance and stability. If samples with very high TDS levels are run, the orifices in the cones will eventually become blocked, causing decreased sensitivity and detection capability and requiring the system to be shut down for maintenance. This is why many sample types, including digested soil and rock samples must be diluted before running on the ICP-MS. The ions from the ICP source are then focused by the electrostatic lenses in the system. Remember, the ions coming from the system are positively charged, so the electrostatic lens, which also has a positive charge, serves to collimate the ion beam and focus it into the entrance aperture or slit of the mass spectrometer. Different types of ICP-MS systems have different types of lens systems. The simplest employs a single lens, while more complex systems may contain as many as 12 ion lenses. Each ion optic system is specifically designed to work with the interface and mass spectrometer design of the instrument. Once the ions enter the mass spectrometer, they are separated by their mass-to-charge ratio. The most commonly used type of mass spectrometer is thequadrupole mass filter. In this type, 4 rods (approximately 1 cm in diameter and 15-20 cm long) are arranged as in Figure

fig.3. Schematic of quadrupole mass filter.

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In a quadrupole mass filter, alternating AC and DC voltages are applied to opposite pairs of the rods. These voltages are then rapidly switched along with an RF-field. The result is that an electrostatic filter is established that only allows ions of a single mass-to-charge ratio (m/e) pass through the rods to the detector at a given instant in time. So, the quadrupole mass filter is really a sequential filter, with the settings being change for each specific m/e at a time. However, the voltages on the rods can be switched at a very rapid rate. The result is that the quadrupole mass filter can separate up to 2400 amu (atomic mass units) per second! This speed is why the quadrupole ICP-MS is often considered to have simultaneous multi-elemental analysis properties. Spectrum showing copper isotopes by ICP-MS.The ability to filter ions on their mass-to-charge ratio allows ICP-MS to supply isotopic information, since different isotopes of the same element have different masses. Once the ions have been separated by their mass-to-charge ratio, they must then be detected or counted by a suitable detector. The fundamental purpose of the detector is to translate the number of ions striking the detector into an electrical signal that can be measured and related to the number of atoms of that element in the sample via the use of calibration standards. Most detectors use a high negative voltage on the front surface of the detector to attract the positively charged ions to the detector. Once the ion hits the active surface of the detector, a number of electrons is released which then strike the next surface of the detector, amplifying the signal. In the past several years, the channel electron multiplier (CEM), which was used on earlier ICP-MS instruments, has been replaced with discrete dynode type detectors (see Figure 6). Discrete dynode detectors generally have wider linear dynamic ranges than CEMs, which is important in ICP-MS as the concentrations analyzed may vary from sub-ppt to high ppm. The discrete dynode type detector can also be run in two modes, pulse-counting and analog, which further extends the instrument's linear range and can be used to protect the detector from excessively high signals

2. METHOD
All chemicals and reagents used for experiments were of analytical grades. Stock solutions of 1 ppm Pb(II) were prepared from Pb(NO3)2 in deionized water. The initial PH of the solution was 3.5. One molar buffer solution was prepared from sodium acetate to prepare the various sample of PH ranging from 4 to 5. Four different types of Carbon Nano tubes were used as an strong absorbent to remove the lead from the aqueous solution. These are iron oxide coated, zinc oxide coated, silver oxide coated, titanium oxide coated. The concentrations of Pb(II) were measured using an ICP-MS . The pH measurements were made on a pH meter. The final Pb(II) concentrations remaining in solution were analyzed. The equilibrium metal adsorption capacity was calculated for each sample of Pb(II) by using the following expression: q = C1- C2

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Where q is the percentage Oxides/CNTs adsorption capacity ppm , C1 the initial concentration 1ppm,C2 the final Pb(II) concentration 1ppm.

Pb(II)

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2.1 EXPERIMENT: All glassware used in this work was rinsed with 10% nitric acid to remove all impurities that might be present and to prevent further adsorption of heavy metals to the walls of the glassware. 50 gm. of zinc, silver, iron and titanium coated multiwall carbon nanotubes been prepared for the experiments. Stock solutions of 1 ppm Pb(II) were prepared from Pb(NO3)2 in deionized water. 1ppm aqueous lead solutions of PH 4,5,6,7 were prepared to check the effect of these four carbon nanotubes absorption ability. Each for types of CNTs of mass 25 mg. were dissolved in 4,5,6,7 PH of 25 ml lead aqueous solution. All these samples were stirred at 150 rpm for 3 hr. but the contact time given to these samples was 24 hr. all these samples than filtered through filter paper and the final concentration of lead in all these samples were measured in ICP-MS. The final concentration of lead was compared with the initial 1ppm lead concentration in aqueous solution and the absorbed percentage of lead is calculation and graphically presented at the end. To check the effect of runs per hour 6 PH of lead solution was prepared and these four cnts of each 25 mg dissolved in 50 ml lead solution. The contact time was 3 hr. All these samples were run at 50, 100 and 150 rpm. Filtration of these samples carried out. Final concentration of lead is measured by ICP-MS and compared with the initial concentration and the percent absorbed lead is calculated. Similarly to check the effect of dosage of these cnts on adsorption of lead different dosage of 15, 25, 35 mg were dissolved in 50 ml of 1ppm aqueous lead solution. RPM were set to be at 150.And at the end different contact time was given ranging from 1 hr. to 3 hr. for each different type of cnts (Fe, Ag, Ti Zn coated) and the final concentration was measured by ICPMS after filtering the cnts.

3. EFFECT OF DIFFERENT PARAMETERS


a. EFFECT OF CONTACT TIME The time needed for the interaction between the adsorbate and adsorbent is crucial ( i.e., the faster the removal, the better the adsorbent). Hence, it is important to study the effect of contact time on the removal of the target heavy metals with all four types of cnts (Fe, Ti, Ag, Zn) shows the effect of contact time on the adsorption of Pb(II) on to cnts. In general, the % adsorption of metals ions increased significantly within the first 10 min. Pb(II) absorbed for the silver coated ct increased linearly with time up to 3 hr in the experiment. The maximum removal of lead by silver coated cnt observed to be 58%. The removal of Pb(II) by iron coated cnt increased linearly with time and the maximum removal was 85.5%. Similarly for the other two the adsorption increases with time.

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b. EFFECT OF CNT DOSE The effect of the coated cnts dosage on the percentage of metal ions adsorbed from aqueous solutions was studied using metal ion concentrations of lead 1ppm .The experimental results revealed that the removal efficiencies of metal ions increased gradually with increasing amounts of CNTs. Increasing the masses of CNTs from 15 mg to 25 mg increased the % adsorption of Pb(II) from 89% to 98%. This increase in % adsorption might have been attributed to the fact that increasing the adsorbent dose provided a greater surface area or more adsorption sites for the metal ions. Additional increases in the amount of CNTs used from 25 mg to 35 mg did not significantly affect the removal percentage of metal ions. c. EFFECT OF SOLUTION P H Solution pH is one of the main influences on the adsorption process, especially for heavy metal ions, such as Cu(II), Pb(II), Cd(II) and Zn(II), as they exist in different species depending on the pH. The effects of solution pH on the adsorption of Pb(II) by coated CNTs were studied in the pH range of 4.07.0, and the results are presented in graph . In general, the removal of metal ions by CNTs was highly dependent on the pH of the solution. For all metals, the % adsorption increased gradually with increasing pH. The minimum adsorption observed at low pH values might have been due to the fact that the higher concentration and mobility of hydrogen ions (H+ ) present at lower pH favored the preferential adsorption of hydrogen ions than metal ions. In addition, at low pH values the surfaces of the MWCNTs are predominantly covered by H+ , which prevents metal ions from approaching the binding sites. This was also in agreement with the surface complex formation (SCF) theory, which states that an increase in the pH decreases the competition for adsorption sites between protons and metal species but up to specific range. Moreover, lower positive surface charge leads to less Columbic repulsion of the metal ions. Further increases in the solution pH were shown to exhibit different effects on the adsorption process, especially approaching the basic region up to 6 PH the adsorption found to be maximum. But going to basic region again decrease the adsorption due to OH ion surround the surface of the the cnts and form strong attraction. When the pH of the solution increased from 6.0 % absorption of lead ions decreased and decreased with CNTs. This decrease in the % adsorption at pH values higher than 6.0 could potentially be due to precipitation in the form of Pb(OH)2 . It is commonly agreed that the absorption of metal ions increases with increasing pH because the metal ionic species become less stable in solution. However, at higher pH values (i.e., pH 6.010.0), the adsorption capacity decreased, which may have been due to the precipitation of lead. The exact and experimentally observed removal of lead by all four types of coated cnts is graphically and numerically attached here.
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d. EFFECT OF AGITATION In the previous parameters the RPM were kept constant at 150. So see the effect of different rpm the experiments were run at three different RPM from 50 to 150.the general trend observed was, by increasing the rpm the absorption of lead increases due to increased turbulence and mixing of the solution except for the silver. At 150 rpm the maximum adsorption for zinc oxide coated carbon nanotube was observed and similarly for titanium was 97% and for iron was 93%.

4. OPTIMUM CONDITIONS FOR REMOVAL OF LEAD The highest predictive percentage removal is 99% . The parameters that contribute to these optimal conditions are PH 6, dosage 25mg, rpm 150, contact time 2 hr. and using the solution volume of 50 ml. the control of carbon surface chemistry through the exclusive introduction of certain surface group is a natural goal for the lead removal using carbon structures. It is highly challenging as most method gives a surface covered with a mixture of acidic and basic groups. Therefore the deposition of metal particles is usually achieved through multistep and timeconsuming procedures. 5. COMPARATIVE ANALYSIS OF VARIOUS CNT S In comparison with the adsorption kinetics of various adsorbents it was concluded that most of the removal process occurred with in the first 10 min. it can be concluded that the adsorption capability of the adsorbent is highly dependent on many factors such as surface functional group, the specific surface area and the solution components. Cnts coated with zinc oxide and titanium oxide shows the maximum removal of lead while the silver shows the minimum in comparison to these. Iron oxide cnt also show the good absorption capability.

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Silver coated cnt 80 conc absorbed ppm 60 40 20 0 50 100 rpm 150

Iron coated cnt 95

conc absorbed ppm

90 85 80 50 100 rpm 150

Titanium coated cnt conc absorbed ppm 100 98 96 94 92 90 50 100 rpm 150

Zinc coated cnt conc absorbed ppm 100 98 96 94 92 90 88 50 100 rpm 150

silver coated cnt 120 conc absorbed ppm 100 80 60 40 20 0 4 5 PH 6 7


conc absorbed ppm

Iron coated CNT 120 100 80 60 40 20 0 4 5 PH 6 7

Titanium coated CNT

Zinc coated CNT 120 100 80 60 40 20 0 4 5 PH 6 7 conc absorbed ppm

conc absorbed ppm

100 98 96 94 92 4 5 PH 6 7

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100 conc absorbed ppm 80 60 40 20 0 15

Ag coated cnt

Ti coated cnt 100 conc absorbed ppm 98 96 94 92

25 dosage mg Zn coated cnt

35

15

25 dosage mg Fe coated cnt

35

98.5 conc absorbed ppm conc absorbed ppm 15 25 dosage mg Ag coated cnt conc absorbed ppm 35 98

96 94 92 90 88 15 dosage25 mg Fe coated cnt 86 84 82 80 78 1 2 time hr Ti coated cnt conc absorbed ppm 100 95 90 85 1 2 time hr 3 3 1 2 time hr Zn coated cnt 3 35

97.5 97

96.5

60 conc absorbed ppm conc absorbed ppm 50 40 30 20 10 0

105 100 95 90 85 80 1

2 time hr

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6. CONCLUSIONS The optimum PH is 6 which give the maximum result for the removal of lead from the aqueous solution. The percentage uptake increased with an increase of the agitation speed in which 150 rpm give the maximum result. The percentage removal of lead was observed to be optimal for the intermediate dosage of 25 mg. the effect of contact time experiment indicated the higher fraction of the lead migrates from the bulk solution through the adsorbent boundary layer onto the active sites of the active sites of the adsorbent. The results obtained from these analyses proved that this method of adsorption of lead using CNTs are the promising for the further development of water and waste water treatment.

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ACKNOWLEDGMENT

I am very thankful to Dr. Mautaz Ali Atieh and KFUPM for giving me an opportunity to work in a professional environment to perform the project on the laboratory scale. I learnt alot during the supervision of Dr. in my analytical and technical skills to understand the nanotechology work, principle and its industrial application

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REFERENCES

Nassereldeen, AK,Mautaz A A , Abdullah A.M, Mohamed E S migrhami, MD Z Alam ,Noorahayu Yahhya, 2008, kinetic adsorption of carbon nanotubes for lead removal from aqueous solution. Journal of Environmental Science 21(2009)539-544. Reed BE, Arunachalam S. Use of granular activated carbon columns for lead removal. J Environ EngASCE 1994;120:41636 Li YH, Wang SG, Wei JQ, Zhang XF, Xu CL, Luan ZK, Wu DH, Wei BQ. Lead adsorption on carbon nanotubes. Chem Phys Lett 2002;357:2636 Shu-Guang Wang , Wen-Xin Gong, Xian-Wei Liu,Ya-Wei Yao, Bao-Yu Gao, Qin-Yan Yue. Removal of lead(II) from aqueous solution by adsorption onto manganese oxide-coated carbon nanotubes, School of Environmental Science and Engineering,, 58 (2007) 1723 Y.H. Li, Z.C. Di, J. Ding, D.H. Wu, Z.K. Luan, Y.Q. Zhu, Adsorption ther-modynamic, kinetic and desorption studies of Pb2+ on carbon nanotubes, Water Res. 39 (2005) 605609.

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