Experiment 2 Elimination of heavy metals by means of a precipitation process

1. Introduction [1] Heavy metals are critical elements for human health and the environment because they show a distinctive capability for accumulation in organisms and other environmental spheres. The maximum limits for some important heavy metals, following the regulations on safe drinking water is given in table 1 sind, [ , !]. Tab. 1" Nr. 1 ! ) & + , . / #aximum limits of important heavy metals in drinking water Parameter antimony, $b arsenic, 's lead, (b cadmium, *d chromium, *r copper, *u nickel, -i mercury, Hg selenium, $e regulation on safe drinking water [mg/L] %,%%& %,%1 %,%1 %,%%& %,%& ,% %,% %,%%1 %,%1

*urrent problems with trace metals in drinking water appear exclusivly from the output of materials 0copper and lead1 which belong to the distribution system The elimination of heavy metals is an elementarily process step in waste water treatment.. 2eside the avoidance of emissions in the a3uatic environment it is utili4ed to recycle valueable products [) 5 +]. Heavy metal containing waste waters are derived from the chemical industrie, the metallurgy, the mining and especially the metal5working industry. (ossible processes for removal of heavy metals in drinking water treatment is summariced in Tab. . 6locculation and precipitation are the most important techni3ues.

Tab. " process

review of processes for heavy metal removal 0drinking water treatment1 [1] Al 77 Sb 77 08881 6e 7 ;x. As 77 091 6e 7 ;x. 5 7 091 7 091 77 091 7 5 77 7 7 5 7 77 77 = 77 77 = 77 0981 Pb 77 Cd 77 Cr 77 Ni 77 :alk g 7 Se 7 !n 7

precipitation/flocculation oxidation/reduktion exchange of cations exchange of anions activated alumina aktive carbon geosorption
77 7 5 =

77 <ed. 77 77 = 77 =

7 5 7 77 77 77 =

good removal moderate removal unsuitable weak basic exchanger

1.1 Neutralizing precipitation for heavy metal removal [)] -eutrali4ation is in most cases the last chemical process in waste water treatment. This process means the alkali4ation of the metall containing water under consideration of the specific precipitation conditions. The prevalent part of the waste water originate in the metal5 working industrie is acidic and has to neutrali4e with bases. Higher pH5values 0> 1%1 are re3uired for 3uantitative precipitation. $trong bases like sodium hydroxide solution and lime milk 0calcium oxid5solution1 are normally used. The advantages of sodium hydroxide solution are caused by a high solubility and good proportioning properties. ?isadvantages are represented in higher costs and in the worsend filterability. The solubility of suspended lime milk @ust amounts by 1,, gAB at % C* and decreases with higher temperatures. Bime milk dissolves and neutrali4es very fast if its mixed with acidic waste water. 'dvantages of the lime milk utili4ation are not only caused by lower costs 0&,, times cheaper then -a;H1, but also by a better process engineering. $o the bivalent calciumion influences the coagulation in a convinient way and its precipitation products have a better filterability. Heavy metals react to nearly dissoluble hydroxids or dissoluble basic salts. The formation and the stoechiometry of this products depend on the precipitation5pH5value. The constitution of these products can verify in big range. $everal modifications of the hydroxids, the basic salts and of common mixtures can originate in dependance of the precipitation conditions. The basicity of the different hydroxids effectuats different pH5values. ' 3uantitative precipitation process needs a sufficient number of hydroxide ions [1.1].

Me z + + zOH Me0OH 1 z

[1.1]

The pH5value for 3uantitative precipitation has to be higher when the hydroxid is more basic. $o a ph5range between !,& for 8ron 08881 and 1%,& for *admium is observed. ' decrease of pH5values in the solutions is determined after 3uantitative precipitation. This effect is caused by metal oxidation 06e88 6e8881 or by slow transformation of basic salts into hydroxids. Hydroxids of the trivalent metals are highly voluminous. Therfore they are used in waste water treatment for the process step flocculation. 'n oversaturation of the precipitant in the solution is necessary before the precipitation can start. 't first nuclei have to form. They further grow to bigger particles until a filterable precipitate is originated. The ratio of concentrations is ad@usted according to the corresponding solubility product after the precipitation. The precipitat properties strongly depend on the rate of nuclei formation and the rate of cristallisation. The nuclei formation is substantially faster then the cristal growth. 8f the oversaturation is formed very fast the rate of nuclei formation will be increased by formation of many nucleis. The cristal growth is ended when the concentration gradient in the limiting diffusion layer is low. 's a result many small particles are formed which create a fine disperse participate with an unsufficient filterability. <ough disperse paticipates with a close particle5si4e distribution are produced by using of an appropriate process engineering. The following preciptation conditions for the generation of rough disperse paticipates with a close particle5si4e distribution 5 like avoidance of variations in concentration, steady hydraulic conditions and constant temperatures 5 should maintain. The following rules summari4e the facts around the neutrali4ing precipitation of heavy metals" 1. ?ilute solution with mainly one sort of metal ions should neutrali4e by the precipitation pH5value or higher. . $ome amphoteric metals can precipitate with lime milk by higher pH5values, some bivalent ions can precipitate with sodium hydroxid by deeper ph5values. !. ?eeper residual solubilities are reached in presence of several metal ions. The better precitable element promotes the precipitation of the more difficult ones. ). The residual solubility of the metals is increased by higher concentration of neutral salts. This effect can compensate by using of an increased pH5value. &. ' decrease of the pH5value after the neutrali4ing precipitation is considered. Therfore stronger basic hydroxids can redissolved again. This effect has to compensate by using of higher pH5values. Tab. ! summari4es the pH5values, when the precipitation begins, the pH5values for 3uantitative precipitation and the pH5value of the beginning redissolution of amphoteric metal hydroxids. 'lso the several solubility products and the dissociation constants of the hydroxide complexes are represented comparartivly.

tab. !" metal

important parameters for precipitation of metals with sodium hydroxide [)] p "#alue begin of precipitation 'uantitati#e precipitation !,& ),! ),. +,. ,,+ .,/ /,% /,/ 1%,! 1%,) redissolution 5 /, .,, .,! 5 5 1%,. 5 5 5 solubilit$ product %issociation constant of $dro&ide comple& 5 , 1%5 & ) 1%5!) &,+ 1%5!. 5 5 + 1%51/ 5 5 5

6e08881 $n0881 'l *r *u 6e0881 Dn -i (b *d

,. !,. ),! &,. &,. ,,% ,,+ ,,. +,& /,1

.,, 1%5!. + 1%5 & 1%5! ! 1%5 . 1%51/ 1%51& ) 1%51, &,. 1%51& ca. 1%51! 1,! 1%51)

The consumption of neutrali4er is negatively influenced by certain water ingredients, e.g." the buffer capacity, the presence of complexing agents. Especially the influence of complexing agents can generate a high transgression of the limiting values. -evertheless a 3uantitaive precipitaion is reached by using of an excess of lime milk 0overbased1. 2eside the higher pH5values the yielded calcium5ions can influence the precipitation positively by" creation of poorly soluble calcium compounds with the complexing agents 0e. g. poly5 phosphates1, replacement of heavy metal complexes by creation of calcium complexes, reduction of the complex stability by an increase of total ion concentration. *opper can precipitate with lime milk in presence of E?T' by ad@usting pH5values of more then 11,,. The residual concentrations are higher by reaching pH5values over 1 ,&. 'lso good results with citrate or tartrate containing water were achieved by using of higher concentrations of lime milk [,]. 'ddition of drop chalk to lime milk is able to moderate the alkali4ation effect [.]. The 6erro5Bime milk5(rocess can furtherly improve the removal of copper in complexing agents containing water. The success of this process is based on the reduction of the bivalent copper ion with iron 0881. The precipitation of the generated monovalent copper ion is more effective. 'lso copper ions can incorporate into the isomorph iron08815hydroxid5lattice [/]. $o residual concentrations of copper under %,& mgAB by an ad@usted pH5value of 1%,, are achieved. 'dding of 6e08881 supports the *opper elimination via flocculation and

(. Aim 2asic processes for the treatment of heavy metal containing waste water 0neutrali4ing precipitation1 should carry out. The influence of complexing agents on the removal of heavy metals is analy4ed. ). Sub*ect 8n this practical course a two5stage process for waste water treatment is demonstrated. The neutrali4ing precipitation with sodium hydroxide represents the main step for the elimination of the heavy metal copper. 6urther treatment of the residual copper should carry out by using iron088815salt, lime and drop chalk. The influence of complexing agents on the removal of heavy metals by precipitation is demonstrated by the example of the copperAtartrate5system. +. Instruments measuring graduated flask 01B1, beakers 01&%% mB, .%% mB, 1&% mB1 Erlenmeyer flask %% mB, graduated cylinder, 8mhoff funnel, transfer pipettes 0 & mB, 1% mB, & mB1, dropping pipette, funnel, tap funnel 0 &% mB with precision divison1, filters 0hard1, magnetic stirrer, funnel rack, stop watch, pH5meter.

,. C-emicals a) Synthetic waste water $tock solution 8 mit % gAB *u 7 0F %,!1& molAB1" ,.,&/ g *u$;)=&H ; 0#G )/,+. gAmol1 dissolved in destilled water and fill up to 1 B $tock solution 88 mit & gAB tartrate 0F %,1+, molAB1" ),,% g :5-a5tartrate=)H ; 0#G . , + gAmol1 dissolved in destilled water and fill up to 1 B b) Chemicals for waste water treatment sodium hydroxide 1 # iron chloride5solution 0c F !% gAB 6e*l =+H ;1 calcium carbonate 0drop chalk1 Bime milk &% gAB *a0;H1 hydrochloric acid 01% Hig1 c) Atomic Absorption Spectroscopy (AAS) copper5standard solution 01%%% mgAB1 dilution water 0 mB kon4. H-;! AB <einstwasser1 .. Completion &

$ynthetic waste water will be produced from stock solutions 8A88 according to the descriptions in tab. ) for a total volume of %,& B 0pH ) I &, H*l1. Tab )" production of the waste water models 0 & % [mgAB] 1%%% 1&,,& % % % ( & ,& 1%%% 1&,,& 1 & %,.! %,%& ) & ,,& 1%%% 1&,,& !,& ,& %,1+ + & 1& 1%%% 1&,,& ,&% & %,! , & )% 1%%% 1&,,& %%% 1!,! %,.&

/odel"number. $tock solution 8 [mBAB]] $tock solution 88 [mBAB] *opper08815concentration tartrate5concentration mole ratio tartrate " *u 7 *opper08815concentration [mmolAB] [mgAB] tartrate5concentration [mmolAB]

The influence of complexing agents will be tested by using five several tartrate5 concentrations. 't first the chief portion of copper will be reduced by using neutrali4ing precipitation untill a pH5value of ,. The residual copper is eliminated by using of an additional treatment step. Therefore the copper complexes have to destabili4ed. 1. possibility" . possibility" ?estabili4ation can reached by addition of iron088815ios. The treatment will be finnished by addition of lime milk and drop chalk. The complexing agents can be destroyed by using of advanced oxidation processes like o4oni4ation, J9, H ; , 6enton5process etc.

The waste water models will be treated by a precipitation with sodium hydroxide 0 molAB1 until a pH5value of , is reached. ' dropwise addition of the base will be performed to record a titrion curve. Then the mixture will be filled in an 8mhoff funnel. The settled sludge volume will be determined after half an hour. %% mB of destilled water should be given to the sample before a filtration will be carried out. *opper concentration will be determined by using 'tomic 'bsorption spectroscopy. ' calibration should be performed before the measurement of the samples begin. &% ml will be taken from the sample and mixed with 8ron chloride5solution 0!% gAB 6e*l!=+H ;1. The concentration of iron will be originated by +% mgAB. The pH5value will be under &. ;therwise it will be ad@usted with H*l 01% H1. Then 1%% mgAB drop chalk 01 tip of a spatula1 will be added to the solution. ' pH5value of . I / will be ad@usted by addition of lime milk 0& H1. 't the end the solution will be mixed carefully for ! minutes and then has to settle.

 ' small sample will be filtrated and the copper concentration is determined by 'tomic 'bsorption spectroscopy. work flow for precipitation of waste water model ( 1record titration cur#es model ( 2 +34 &%% mB5volumetric flask 7 & mB stock solution 8 0copper08815sulfate5solution1 7 ,& mB stock solution 88 0:5-a5tartrate5solution1

5
pH5ad@ustment with hydrochloric acid 01% H1 between ) I & transfer in a beaker in %.& mB intervals addition of -a;H 0c F 1 molAB1 until pH , caution" at pH &,& dosing carefullyKK please note the pH after every intervalKK Jse this pair of values to generate a titration curve

5
after precipitation transfer the solution complete in an 8mhoff cone after !% min measure the volume of the settled sludge filtrate nearly %% mB of the supernatant solution over a filter paper

5
&% mB of the filtrate is to analy4ed by atomic absorption spctrometrie

5
postprecipitation of the filtrate by dosing of an iron088815solution that in the filtrate is a c[6e08881] F +% mgAB at pH L & add 1 spit of spatula of precipitated chalk to the filtrate ad@ust the pH by dosing lime milk 0& H1 between . I / agitate carefully for ! min and settle

5
filtrate nearly %% mB of the supernatant solution over a filter paper copper residues is to analy4e by ''$ L %, & mgAB 6. 7#aluation 1. The measured titration curves should be depictedK Explain the curves in dependance of the content of the complexing agent. . The measured contents of copper should be represented in tables and should be discussed under consideration of the process steps and the complexing agent concentrations. !. Mhy is the removal of heavy metals from waste water so importantN

). *all several chemicals for the precipitation of heavy metals which are applied in waste water treatment. &. Mhy is the metal precipitation with sulfide criticalN +. The residual concentration of metals in the solution increase with higher contents of neutral salts. Mhat is the reason for this effectN

,. Explain the measuring principle of 'tomic 'bsorption $pectroscopyK [1] [ ] [!] [)] [&] [+] [,] [.] [/] 8. Literature Gimbel, <.O Pekel, #.O BieQfeld, <." Masseraufbereitung I Grundlagen und 9erfahren, ;ldenbourg 8ndustrieverlag #Rnchen5Mien, %%), &&1 I &., 9erordnung 4ur -ovellierung der Trinkwasserverordnung 0Trinkw91. 2undesgeset45 blatt Pahrgang %%1, Teil 8 -r. ), ..%&. %%1, /&/5/.% <ichtlinie des <ates Rber die SualitTt von Masser fRr den menschlichen Gebrauch, -r. /.A.!AEG vom !. -ov. 1//. 0'2B.EG -r. B !!%, ! Hartinger, B." Handbuch der 'bwasser5 und <ecyclingtechnik fRr die metallverarbeiten5 de 8ndustrie, . 'ufl., *arl Hanser 9erlag, #Rnchen, Mien, 1//1 :un4, (." 2ehandlung von 'bwasser, ). 'ufl., 9ogel59erlag, MRr4burg, 1//& :ermer, :." (hysikalisch5chemische 9erfahren 4ur Masser5, 'bwasser5, $chlammbe5 handlung und MertstoffrRckgewinnung, Teil 17 , . 'ufl., 9erlag fRr 2auwesen, 2er5 lin, 1/.) Ming, <. E.O et al." Treatment (rocesses for some <inse Maters from Electroless (lating of copper, (lating and $urface 6inishing, Pune, 1/,,, &, 5 + $chilling, H.O 6ischwasser, :." Eliminierung von $chwermetallen aus komplexbildner5 haltigen 'bwTssern durch :alk5:reide56Tllung. 'cta hydrochim. Et hydrobiol., 1,, 1/.+, + Hartinger, B." *hemische 9erfahren 4ur Entfernung von #etallen aus komplexbildner5 haltigen BUsungen in der Beiterplattentechnik, Galvanotechnik, ,1, 1/.%, ,/, I .%&