SOLIDIFICATION/STABILIZATION OF PAINT BOOTHS SLUDGES

Arce, R.; Andrs A.; Irabien J.A.; Viguri J. Dpto. Ingeniera Qumica y Qumica Inorgnica, Universidad de Cantabria . ETSIIyT . Avda. de los Castros s/n 39005 Santander, Spain E-mail: arcer@unican.es
Subject : Enviromental and sustainable development Introduction Wastewater from the paint of metallic pieces (Figure 1) may be treated by overspray coagulation and continuosly extracting the paint slurry as floating or settling sludge . These sludges represent an important environmental problem due to their hazardous characteristiques being necessary a previous treatment before final management . In this work a solidificaton/stabilization (S/S) process has been developed in order to obtain a non hazardous and workable material Material and Methods The basis of the S/S process is the mixture of the waste with micronized lime as a binder, and sepiolite as additive in controlled atmosphere of N2 or CO2 . The stabilization process is carried out in two phases : 1) Organic compounds in the mixture waste-sepiolite are absorbed by the micronized lime , the sludge-water in this phase does not take part in the mixture. 2) The VOCs are removed and adsorbed using activated carbon . A dry-solid product is formed due to the heat of hydratation of lime .
Energy Energy Boothwater Boothwater Solid Wastes Solid Wastes Toluene Paint Water Toluene Paint Water VOCs VOCs

Metallic Pieces Metallic Pieces

WATER-WASHED WATER-WASHED PAINT SPRAY BOOTH PAINT SPRAY BOOTH

Painted Metallic Pieces Painted Metallic Pieces

Figure 1.- Paint Spray Booth Flowsheet Figure 1.- Paint Spray Booth Flowsheet

Paint waste characterization characterization Paint waste Direct characterization Direct characterization % Toluene ...................... 5,95 % Toluene ...................... 5,95 % Ethylbenzene ............. 2,40 % Ethylbenzene ............. 2,40 % Xylenes ..................... 5,65 % Xylenes ..................... 5,65 Flash Point ...................... << 21 C Flash Point ...................... 21 C Lecheate characterization Leachate characterization TCLP lecheate : : EC 4.132 mg/l TCLP leachate EC50 4.132 mg/l DIN 38414-S4 lecheate :COD 8.400 mg/l DIN 38414-S4 leachate :COD1 8.400 mg/l DIN 38414-S4 lecheate : : TOC2 4.850 mg/l DIN 38414-S4 leachate TOC 4.850 mg/l 1) COD= Chemical Oxygen Demand 2)TOC = Total Organic Carbon
50

Experimental Flowsheet

Additive and binder Additive and binder

VOCs total ..................... 14 % VOCs total ..................... 14 %

S/S Product characterization S/S Product characterization Direct characterization Limits Direct characterization Limits % Toluene % Toluene % Ethylbenzene % VOCs > 3% (Non stabilised) % Ethylbenzene % VOCs > 3% (Non stabilised) S/S Product S/S Product % Xylenes % Xylenes Flash Point Flash Point <<55 CC ( flammable) 55 ( flammable)

N22 CO22 N CO

Gas stream

Water Water Mixer Mixer Waste Waste S/S Product S/S Adsorption tower Adsorption tower Scrubber Scrubber

Lecheates characterization Leachates characterization TCLP lecheate : : EC << 3.000 mg/l (ecotoxic) TCLP leachate EC50 3.000 mg/l (ecotoxic)
50

Clean air Clean air

DIN S-4 lecheate : : TOC , COD DIN S-4 leachate TOC COD

RESULTS SAMPLE S/S SEPIOL 1 SEPIOL 2 SEPIOL 3 SEPIOL 4 SEPIOL 5 H2O % 20 20 20 20 20 CaO SEPIOLITE % % 0 72 66 54 42 50 6 12 24 36
SEPIOLITE - VOCs
2

TOLUENE ETHYLBENZENE XYLENES % % % 0,72 0,56 0,55 0,59 0,32 0,27 0,14 0,16 0,17 0,05 2,06 1,25 1,44 1,47 0,640

COVs % 3,05 Non stabilized 1,95 Stabilized 2,15 Stabilized 2,23 1,01 Stabilized Stabilized
OCa-VOCs

FLASH POINT C < 55C Flammable > 55C Non flammable > 55 C Non flammable > 55C > 55C Non flammable Non flammable

EC50 LEACHATE TCLP (mg/l) 7.515 Non ecotoxic 6.125 Non ecotoxic 6.550 Non ecotoxic 6.300 Non ecotoxic 6.900 Non ecotoxic
40 40 40 35 35 36 35 30 30 30 25 2542 25 20 20 20 15 15 15 10 10 10 5 5 5 0 0 0

TOC LEACHATE DIN S-4 (mg/l) 1.189 1.969 2.453 2.399 1.760
80 80

COD LEACHATE DIN S-4 (mg/l) 2.700 4.300 5.950 6.510 3.660

72
36 66

72

% CAL % SEPIOLITE

OCa- VOC's

72 36

66

70 70

80 70 60

% SEPIOLITE

y = -0,1755Ln(x) + 2,4128

24

42

24

54

50 50

42

% VOCs % VOC's

24

50
40 40

% VOCs

40

10
1,96 2,16 2,24 1,02 2,06

10 1,5
1 0,5

12 6
6

12

30 30

30 20 10

12 6

20 20 1 10 0

2,24 1,02
40

2,16 1,96

1 0 30
50

00 0
0
0, 5

1 0 5 10 15 20 25 30 35 40 45 50 55 % SEPIOLITE

50

60

% OCa

70

70

90

01

0,5

1 ,5 1,5

2 2

2, 10 5 2,5

% OCa

% VOCs % VOCs % VOCs

Figure 2. % VOCs versus at % sepiolite

Figure 3 . % VOCs versus at % CaO

Figura 4 . % VOCs versus at % of sepiolite and % CaO

CONCLUSIONS 1.- Sludges generated in water-washed paint spray booth from an automotive components industry has been characterized . These sludges are hazardous wastes, because its high VOCs content (14%) and its flash point . 2.- The S/S process developped of paint booths sludges using different percentages of micronized lime ( 0%-72%) as binder, and different percentages of sepiolite as additive (6%-50%) allowing to reduce the organic content and to obtain dry-solid product. The direct characterization of %VOCs and leachate characterization of the S/S products show a non flammable and non ecotoxic product . 3.- The best results has been obtained with the formulation Sepiol 4 (100 g. of waste , 20% of water, 36% of sepiolite and 40% of micronized lime). 4.- The S/S products obtained are adequate to disposal take into account the catalan regulation in relation to the organic content , < 3% VOCs .

Adknowledgements This work has been carried out thanks to the financing of the Project I + D of the Department of Education and Spanish Culture. It programs FEDER N: 1FD97-2013-C02-02.

% CaO

100

100

y = -0,0037x + 0,4464x - 11,254 R2 = 0,9828y = 1,7638Ln(x) - 5,295 2,5

54

54

% OCa %SEPIOLITA

66

60 60