The application of selected activated carbons to dye wastewater treatment (Wykorzystanie wybranych węgli aktywnych do oczyszczania ścieków farbiarskich)

DO7\VLłFOHFLD3DŐVWZD3ROVNLHJR .LHOFH3RODQG

THE APPLICATION OF SELECTED ACTIVATED

CARBONS TO DYE WASTEWATER TREATMENT

Keywords: activated carbon, dye wastewater, sorption, crystal violet

1. Introduction

Activated carbon is obtained by carbonization and activation of raw materials such as charcoal, lignite, semi-coke, coke, peat, wood, lignin, fruit seeds, nuts shells, organic polymers, industrial waste (rubber, rubber Bakelite or overburden).

The materials named above are subjected to carbonization i.e. pyrolysis of source material. As a result a carbonized product with a disordered structure is obtained. This disordered structure leads to formation of slots, which transform into pores. These SRUHVDUH¿OOHGZLWKWKHWDUU\PDWWHURUWKHSURGXFWV of decomposition (or at least blocked partially by disorgan-ized carbon). The obtained product has a low absorption activity, with the surface area of several m2J ,Q WKH QH[W VWDJH WKH FDUERQL]HG SURGXFW LV further developed and enhanced during the activation process. It converts the carbonized raw material into a form that contains the greatest possible number of randomly distributed pores of various sizes and shapes, JLYLQJULVHWRDQH[WHQGHGVXUIDFHDUHDRIWKHSURGXFW The activation process is usually carried out in an air, CO₂, or water vapour in the temperature ranges from 800° to 900°C. Finally, the activated carbon with VSHFL¿FSK\VLFRFKHPLFDOSURSHUWLHVLVREWDLQHG>@

Activated carbons have a developed porous structure and the resulting high area surface with

VSHFL¿FFKHPLFDOSURSHUWLHV7KDWPDNHVLWVXLWDEOHIRU SXUL¿FDWLRQSXUSRVHV7KH\DUHXVHGIRUSXUL¿FDWLRQ RIJDVSXUL¿FDWLRQRIWDLOJDVHVUHPRYDORIYRODWLOH organic com-pounds, Hg, SO₂, NO_[, polychlorinated ELSKHQ\O GLR[LQ VHSDUDWLRQ RI JDV PL[WXUHV ZDWHU and sewage (drinking water treatment, preparation of process water, preparation of medi-cated baths, SXUL¿FDWLRQ RI JURXQGZDWHU LQGXVWULDO ZDVWH ZDWHU ODQG¿OOV OHDFKDWH DQG RWKHU SXUL¿FDWLRQ RI substrates and products in the sugar industry, food industry, pharma-ceutical industry, cosmetic industry, chemical industry and acquisition of high grade purity substances). Activated carbons are also used as catalyst carriers in heterogeneous reactions in gas and OLTXLGSKDVHV>@

As mentioned above, one of the important applications of activated carbons is water waste treatment, particularly industrial waste treatment. 'XH WR GLYHUVL¿HG LQGXVWU\ W\SHGHSHQGHQW VHZDJH composition and different technologies used, industrial ZDVWHZDWHUWUHDWPHQWLVDFRPSOH[SURFHVV$VVXFK it has been a subject of numerous research projects >   @ $Q H[DPSOH RI LQGXVWULDO ZDVWHZDWHU LV WKDW RI WH[WLOH DQG SDLQW DQG G\H LQGXVWULHV ,W contains dyes (more than 100 000 industrial dyes with DQHVWLPDWHGRXWSXWRI[±[WRQD\HDU [8]), mineral and silicon oils, polycyclic aromatic

hydrocarbons, pesticides, detergents, inorganic acids, VWURQJR[LGDQWVXVHGDVEOHDFKLQJVXEVWDQFHVJOXHV DQG DONDOLV 7KHLU FKDUDFWHULVWLF IHDWXUH LV WR[LFLW\ WRZDWHURUJDQLVPVWKH\DOVRGHOD\VHOISXUL¿FDWLRQ processes by decreasing the light permeability in the water environment. Typical feature of such wastewater is the presence of hard-biodegradable compounds and their high loading. Depending on the dye class, &2'&KHPLFDO2[\JHQ'HPDQGRIH[KDXVWHGG\HV EDWKVUHDFKHVWKHYDOXHEHWZHHQDQGPJ O₂/dm [9]. High requirements related to wastewater discharge into the municipal sewer facilities [9], JURXQGZDWHUDQGJURXQG>@UHYHDOLQHI¿FLHQF\RI WUDGLWLRQDOSXUL¿FDWLRQPHWKRGV7KHUHIRUHLWVHHPV necessary to search for more effective solutions, for LQVWDQFHWKHVRUSWLRQSURFHVV>@:HOOGHYHORSHG porous structure and large number of pores (micro, mezo- and macro pores) of activated carbons, as well as chemical properties of surface facilitate the dyes retention on the surface of activated carbons. The combination of sorption and traditional processes of waste water treatment makes it possible to remove diluted organic impurities. That w produces colour and smell, contribute to reducing the concentration RI E\ SURGXFWV RI R[LGDWLRQ DQG GLVLQIHFWLRQ DQG to removing substances which pose direct threat to human health [11].

7KLVSDSHUSUHVHQWVWKHLQYHVWLJDWLRQLQHI¿FLHQF\ of eliminating crystal violet from a water solution by means of activated carbons. Crystal violet, i.e., KH[DPHWK\OSURVDQLOLQH K\GURFKORULQH EHORQJV WR triphenylmethane dyes called aniline dyes. It is used for fabric dying and production of paper products and printing paste. The dye is listed as harmful and dangerous to the environment. For that reason it has to be removed from the waterwaste.

Assessment of sorption capacity is one of the stages of research on wastewater treatment in the presence RI DFWLYDWHG FDUERQV DQG XVH RI DGYDQFHG R[LGDWLRQ processes (AOP).

2. Experimental part

The research was focused on WD_H[ and WG-12 activated carbons, commercially used as sorbents.

2.1. Characteristics of investigated activated carbons The porous structure was determined on basis of low temperature absorption of nitrogen (77 K). Absorption and desorption isotherm was determined by the volumetric method with Sorptomatic 1900

and ASAP 2010 Micromeritics apparatus. Moreover, for the investigated carbons the following factors, qualities and properties were determined: the porous structure, the dechlorination capacity (determined DFFRUGLQJ WR ',1  LRGLQH DGVRUSWLRQ QXPEHU GHWHUPLQHGDFFRUGLQJWR31&WKHDVK FRQWHQWGHWHUPLQHGDFFRUGLQJWR31& the methylene number (determined according to 31&DQGGHWHUJHQWQXPEHUDFFRUGLQJ WR31&

Acidic-basic character of surface (the total content of acidic groups was determined by titration with 0.01M solution of HCl against the unreacted 0.01 M 1D2+ZKLFKKDGEHHQXVHGIRUÀRRGLQJWKHWHVWHG samples of carbons. The total content of basic groups was determined by titration with 0.01 M solution of NaOH against the unreacted 0.01 M HCl, which had EHHQXVHGIRUÀRRGLQJWKHWHVWHGVDPSOHVRIFDUERQV and the content of soluble substances (according to 31&ZHUHGHWHUPLQHG7KHUHVXOWVDUH presented in Table 1.

Table 1. Physicochemical characteristics of investigated activated carbons A cti va te d c arb on Parameter S [m 2J @ V p [c m 3J @ 'H FK ORUL QD WLR QF DS DF LW\ >F P @ )H UUX P FR QWH QW>P JJ @ 0 HWK \OH QH Q XP EH UV >F P 3@ ,R GLQ HD GV RUS WLR QQ XP EH UV >P JJ @ 'H WH UJ HQ WQ XP EH U>P JJ @ $V KF RQ WH QW>@ : DWH UV ROX EOH VX EV WD QF HV >@ WD_ex 5 0.5 36 990 20.62 20.64 1.07 1050 0.95 WG-12 6 0.44 32 1230 32 8.85 2.48 980 0.89

2.2. Crystal violet sorption on investigated activated carbons a) Sorption kinetics.

,Q  FP_{FRQLFDO ÀDVNV  J RI HDFK RI WKH} activated carbons WD_H[ and WG-12 were weighed RXW7KHZHLJKHGVDPSOHVZHUHÀRRGHGZLWK cm of crystal violet solution of concentration of about 20 g/dm and shook for 12 hours. In solutions from above the activated carbons, the concentration of crystal violet was determined at hourly intervals.

b) Sorption isotherms

DFWLYDWHG FDUERQV :'H[ DQG :* ZHUH ZHLJKHGRXWLQFP_{FRQLFDOÀDVNVDQGÀRRGHG} with crystal violet solution of concentration of about 20 mg/dm and shook for 12 hours.

The concentration of crystal violet was determined by the use of UV/VIS Marcel Media spectrophotometer at the wave length O QP

3. Analysis of the results

The assessment of physicochemical properties of chosen activated carbons determined by FIBDM (F – phenol, I – iodine, B – methylene blue, D – sodium lauryl sulphate, M – molasses) indicator was done in WKH ¿UVW VWDJH 7KLV LQGLFDWRU H[SUHVVHV WKH UHODWLYH adsorption capacity of investigated activated carbons LQWHUPVWR¿YHLQGH[VXEVWDQFHV7KRVHVXEVWDQFHV represent different groups of impurities occurring in waters, which vary in terms of chemical character, structure, and molecule size. The following substances are used as indicators: F – phenol (a simple ring, GLPHQVLRQQP-±LRGLQHDVSKHULFDOPROHFXOH GLDPHWHUQP%±PHWK\OHQHEOXHFRPSOH[ULQJ OHQJWKQP'±VRGLXPODXU\OVXOSKDWHOHQJWK FKDLQQPDQG0±PRODVVHVPL[WXUHRIFKDLQ and ring molecules, about 2.8 nm average size) are used as indicators. The FIBDM indicator has a form RI¿YHGLJLWQXPEHUHDFKRIWKHPLQDFRQYHQWLRQDO scale from 0 to 9, (the higher number, the better carbon), indicates the activated carbon class in terms of its adsorption capacity in relation to the standard substance [11].

Data presented in Table 1 show that among the investigated activated carbons: WD_H[ and WG-12, WD_H[ is characterized by the bigger area surface and higher total volume of pores. The parameters for WD_H[DUHP2JDQGFP_{/g respectively. This} carbon has also the higher value of methylene number  FP_{ 7KLV FOHDUO\ FRQ¿UPV LWV JRRG VRUSWLRQ} capacity. WG-12 carbon has lower area surface, 980 cm/g and the volume of pores, 0.89 cm/g, which together with other parameters, indicates its weaker sorption capacity.

The established sorption kinetics shows that contact-time of activated carbon-crystal violet lasts 12 hours. The investigated carbons were used as sorbents of crystal violet from water solution. The sorption isotherms presented in Figure 1 prove that WD_H[KDVDEHWWHUVRUSWLRQFDSDFLW\PJJDQGWKH highest surface acidity of 0.98 mval/g. This means that factors which foster crystal violet sorption include not only the surface area and availability of

pores (which is indicated by the methylene number FP_{) and the detergent number (21 mg/g), but also} negative charge of activated carbon surface resulting IURP WKH HIIHFW RI LRQL]DWLRQ RI VXSHU¿FLDO DFLGLF groups and from the interaction between positive charge of resonant structure of crystal violet and GHORFDOL]HGʌHOHFWURQVRIDFWLYDWHGFDUERQJUDSKLWH VWUXFWXUH7KLVH[SODLQVORZHUVRUSWLRQFDSDFLW\RI the second carbon, WG-12, which is 12 mg/g. It is GHVSLWHWKHH[WHQGHGVXUIDFHDUHDDQGDYDLODELOLW\RI pores, which is showed by the methylene number FP_{DQGWKHGHWHUJHQWQXPEHUPJJ}

Fig. 1. Sorption isotherms of crystal violet on investigated activated carbons

The sorption process from the water solution can be described

– by the Langmuir equation:

(1)

where: y – the amount adsorbed, m – sorbent mass,

C – concentration, a ± H[SHULPHQWDOO\ FDOFXODWHG

constant, b±H[SHULPHQWDOO\FDOFXODWHGFRQVWDQW – and the Freundlich equation:

(2)

where: K±H[SHULPHQWDOO\GHWHUPLQHGYDOXHRIWKH FRHI¿FLHQWn ± H[SHULPHQWDOO\ GHWHUPLQHG YDOXH RI WKHFRHI¿FLHQW

Calculated parameters presented in Table 2 indicate better matching of the results of crystal violet sorption on the investigated carbons to the Langmuir isotherm, which means that the saturation rate of carbon with the dye was achieved.

Table 2. &RHI¿FLHQWV RI WKH )UHXQGOLFK DQG /DQJPXLU equation for crystal violet adsorption on investigated activated carbons.

Activated carbon

Freundlich isotherm Langmuir isotherm

K n R2 _{a b R}2

WD_ex 9.73 1.92 0.956 50 0.33 0.997

WG-12 6.30 3.70 0.933 14.29 1.00 0.996

4. Summary

Activated carbons are commonly used as sorbents. Fresh, commercial active carbons and a crystal violet (as a dye) were used for the investigation. When removing crystal violet for the water solution with the use of the given activated carbon, the sorption capacity GHFLGHV RQ WKH UHPRYDO HI¿FLHQF\ 7KH VRUSWLRQ capacity depends on porous surface parameters, chemical properties of the surface, and the conditions of reaction. WD_H[ activated carbon shows better VRUSWLRQFDSDFLW\PJJWKDQWKHRWKHUDFWLYDWHG carbon, WG-12, which is characterized by both higher VXUIDFHDUHDP2_{/g), the total volume of pores}  FP_{/g) and the high value of the methylene} QXPEHUFP_).

The presented results of the study related to the removal of the dye from the water solution with WKH XVH RI WKH VRUSWLRQ SURFHVV VKRZ WKH HI¿FLHQF\ of the process. Long contact-time, however, causes a necessity to search for even better solutions, for LQVWDQFHWKHDGYDQFHGR[LGDWLRQ

$QQD 3LFKHWD2OHĞ D 3K' VWXGHQW UHFHLYHV D VFKRODUVKLS funded from the Kielce University of Technology Didactic Potential Development Programme: Education for Success, XQGHUWKHDJUHHPHQW1R8'$32./ FRIXQGHGIURPWKH(XURSHDQ6RFLDO)XQGZLWKLQWKHIUDPHZRUN RI32./3ULRULW\,90HDVXUH6XEPHDVXUH The study employed Statistica software, the purchase of which ZDV¿QDQFHGIURPWKHIXQGVRIWKHSURMHFWPHQWLRQHGDERYH References

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>@0LNXáND 0 SRG UHG HG Charakterystyka

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 RQ WKH REOLJDWLRQV ZDVWH JHQHUDWRUV DQG on standards of wastewater discharge into the sewer V\VWHP']8

[11] Regulation of the Minister for Environment of  RQ UHTXLUHPHQWV UHODWLQJ WR ZDVWHZDWHU discharge into the water or the ground and a list of substances particularly hazardous to water HQYLURQPHQW']81RLWHP>LQ3ROLVK@ >@1DZURFNL - %LáR]RUD 6 UHG Uzdatnianie wody.

Procesy chemiczne i biologiczne, (Water treatment, Chemical and biological processes),

Warszawa-3R]QDĔ3:1>LQ3ROLVK@

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Process – AOP).

2.&]ĘŒýGRŒZLDGF]DOQD

3U]HGPLRWHP EDGDĔ E\á\ ZĊJOH DNW\ZQH ĞZLHĪH handlowe o symbolu WD_H[ i WG-12, powszechnie wykorzystywane jako sorbenty.

2.1.&KDUDNWHU\VW\NDEDGDQ\FKZĘJOLDNW\ZQ\FK

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