Thermogravimetric study and kinetic model on pyrolysis of medical waste compositions

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1 Acta Scientiae Circumstantiae Vol. 25,No. 11 Nov., 2005,,,. [J ].,2005,25 (11) : DENG Na, ZHANG Yufeng, et al. Thermogravimetric study and kinetic model on pyrolysis of medical waste compositions[j ]. Acta Scientiae Circumstantiae,2005, 25 (11) : , 3,,,, : : : :,., 14,.,, , ;, 800.,1168 %,. : ; ; ; : (2005) :X705 :A Thermogravimetric study and kinetic model on pyrolysis of medical waste compositions DENG Na, ZHANG Yufeng 3, NIU Baolian, SUN Yuexia, CHEN Jing School of Environmental Engineering, Tianjin Uninversity,Tianjin, , China Received 15 April 2005 ; received in revised form 6 September 2005 ; accepted 8 September 2005 Abstract : To obtain thermal decomposition and kinetic reaction mechanism of medical waste, thermogravimetric study of the 14 kinds of the typical medical waste compositions was carried out using the thermogravimetric analyser ( TGA) with N2. The mathematics model with two steps and four reactions was established to simulate the pyrolysis process. The results showed that : a) within the temperature range between 160 to 290, medicine, plastic, protein, biomass, synthetic fibre and rubber started to enter pyrolysis process in succession ; b) there was at least one or two decompositing stages for the these materials ; c) pyrolysis processes of all waste samples ended basically at about 800 ; d) the model could describe satisfactorily the weight loss and differential process of all waste samples within its maximum deviation 1168 %. The effect of the original waste compositions and all their product with different pyrolysis temperature in process could be estimated based on the model. Keywords :medical waste ; pyrolysis ; thermogravimetric analysis ; model,,,.,, (Lee et al.,1996 ;Mato et al.,1997 ;Lee et al., 2004).,,,,, (Zhang et al.,2003). ([ 2003 ]41 ).,,., ( Reina et al., 1998 ;, 2001 ; Raveendran et al., 1996 ;, 2003 ) ( Sgrum et al.,2001 ; Garc a et al.,1995 ;,1999) : (No ) ;(No ) ; (No. TD200111) : (1978 ),,,E2mail com ; 3 ( ),E2mail edu. cn Foundation item : National Natural Science Foundation of CHINA ( No ), Key Technologies R&D Programme of Tianjin S&T Commission ( No ), Tianjin University and Nankai University Shared Research Item (No. TD200111). Biography :Deng Na (1978 ), female, Ph. D candidate, E2mail : com ; 3 Corresponding author,e2mail edu. cn

2 11 : 1485 (Conesa et al.,1996 ; Marcilla et al.,1995).,, (2003) (2004) 5 8,.,., : (1) :a) (Reina et al.,1998 ; Li et al.,2004) ;b) (,1999 ;,2004) ;c) (, 2003 ;Conesa et al.,1996). (2) : d) ( Sgrum et al., 2001 ; Garc a et al.,1995 ; Font et al.,1995).,a,,, ;b,,, ;c,,, ;d,,.,,,, ;,,,,,,., ;,,.,, 14 ;,. 1 ( Experiments) , 6 : ( ) ( ) ( ) ( ) ( ) () (). 1 (,,).,.,. 112 SHIMADZU DTG260H. 20 ml min - 1 N 2 ; Al 2 O 3 Al 2 O 3, ;, 20 min - 1, 2,;,, 2 9 mg,2 ; 015 mm, ;, (Antal et al.,1980). 2 ( Results) min - 1 TG DTG, 14.,.,,. 150, ; ,,, ; 600,, ; , 800,.

,a,,, ;b,,, ;c,,, ;d,,.,,,, ;,,,,,,., ;,,.,, 14 ;,. 1 ( Experiments) 111 14., 6 : ( ) ( ) ( ) ( ) ( ) () (). 1 (,,).,.,. 112 SHIMADZU DTG260H.

3 Table 1 1 Major constituent and ultimate analysis of typical medical waste compositions C H O 3 N S Cl Si 1 (PVC) % % % NA % % 2 (PVC) % % % NA % % 3 (LDPE) % % % NA NA 4 (NR) % % % % % % 5 (NR) % % % % % % % % % NA % % % % NA % % % % NA % % % % NA % % % % % 11 (PVA) % % % NA % O 3 : O,; NA : ; :; 1 TG( a)2dtg( b) (1.,2.,3.,4.,5., 6.,7.,8.,9.,10.,11.,12.,13.,14. ;m t, m 0 ) Fig. 1 TG(a)2DTG(b) curves of typical medical waste compositions(12tube for transfusion, 22sample collector for urine, 32one2off medical glove, 42operating glove, 52catheter, 62a cotton swabs, 72toilet paper, 82gauze, 92absorbent cotton, 102absorbable catgut suture, 112filling of dressing, 122adhesive plaster, 132dressing, 142medicine ; Annotation : m2sample weight at time t, m 0 2initial sample weight),1a,;, DTG( 1b),2,.,. PVC, HCl,,, (Marcilla et al.,1995 ; Varma et al.,1999). PE, PE,,,,(Conesa et al., 1996).,

43 % 47. 09 % NA 0. 22 % 7 41. 63 % 5. 71 % 52. 35 % NA 0. 31 % 8 42. 51 % 6. 35 % 51. 01 % NA 0. 13 % 9 42. 90 % 6. 69 % 50. 19 % NA 0. 22 % 10 43. 16 % 7. 60 % 34. 85 % 13. 59 0. 80 % 11 (PVA) 54.

4 11 : 1487.,40 % (,1999), 700.,,2. 1,3 DTG,, ;,DTG,.,,40 100, ;,,,,. 2 Table 2 Thermal analysis data of typical medical waste compositions 2,M, T, T onset, T endset, T max DTG, T. 2,,;. 800, 80 % 85 %90 %, 95 %,. d Πd t max, T max. 2, T max ,.,,,. Πmg M T Π T T onset Π T endset Π T max Π d d t max Πs % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % : 3,DTG() DTG. 3 ( Pyrolysis kinetic modeling) 311,, ;,,. 2, 2 ;,c,. (a),s,2

43 % 428 541 14. 99 % 461. 92 491. 27 470. 41 3 0. 11 % 230 388 58. 21 % 295. 34 329. 97 309. 93 0. 55 % 403 568 24. 52 % 454. 58 493. 00 472. 31 3 0. 19 % 210 0. 1 272 513 95. 14 % 429. 40 493.

5 ( k 1 k 2 ), :V 1 S 1, 1 ; S 1, ( k 3 k 4 ), V 2 S 2,S 2,, 2. S k 2 V 1 k 1 S 1 k 4 V 2 k 3 S 2 (a) (a) :1) ;2), ;3),. : : d SΠd t = - k 1 S n 1 - k 2 S n 2 (1) d S 1 Πd t = k 1 S n 1 - k 3 S n k 4 S n 4 1 (2) d S 2 Πd t = k 3 S n 3 1 (3) [ S, S 1, S 2 ] t = t0 = [1,0,0 ] ;, k i = A i exp ( - E i ΠRT), k i,a, E, n ;,: T = t + T 0 ; w,w cal = S + S 1 + S 2., x = [ A 1, A 2, A 3, A 4, E 1, E 2, E 3, E 4, n 1, n 2, n 3, n 4 ], : m OF = ( w cal ( t j, x) - w exp ( t j ) ) 2, (4) j = 1,OF, w cal ; w exp ; x ; m ; j j, t j j. 2 3, Levenberg2Marquardt,,.,,, : 5, 10, 30, 50 min - 1,Ozawa, ; ( Conesa et al., 1996 ; Marcilla et al.,1995 ; Kim et al.,1998 ; Williams et al., 1995 ; Dollimore et al.,1996 ; Rao et al.,1998), min - 1, 3 (, ). (4) D OF, gw exp VC(5). VC = OFΠ( D - P) gw exp 100 % (5), P,12. 3 Table 3 Kinetic parameters obtained by two2step, four2reaction, comprehensive model E A OF Π(kJ mol - 1 ) Πmin - 1 n D gw exp Π VC % % % % % % ,,,. 2 3 ( ) ( ),. 2 3

E, n ;,: T = t + T 0 ; w,w cal = S + S 1 + S 2.

6 11 : 1489,, DTG. 2 3 w 0 w f, w t ( ).,. 3 TG( a)2dtg( b) Fig. 3 Experimental and calculated TG(a)2DTG( b) curves in the decomposition of gauze 2 TG( a)2dtg( b) Fig. 2 Experimental and calculated TG(a)2DTG( b) curves in the decomposition of tube for transfusion 4 ( Conclusions) 1) ,,600,; ,800. 2),,;, , %,. 3),,,,.,. :(1954 ),,,. :,. E2mail edu. cn ( References) : Antal MJ, Friedman H L, Rogers F E Kinetics of cellulose pyrolysis in nitrogen and steam [J ]. Combustion Science and Technology, 21 : Chen G Y, Fang M X, Andries J, et al Study on biomass wastes pyrolysis for fuel gas production [J ]. Acta Energiae Solaris Sinica, 24 (3) : (in Chinese) Conesa J A, Marcilla A, Font R, et al Thermogravimetric studies on the thermal decomposition of polyethylene[j ]. Journal of Analytical and Applied Pyrolysis, 36 (1) : 1 15 Dollimore D, Tong P, Alexander K S The kinetic interpretation of the

E2mail :yufengfa @tju. edu. cn ( References) : Antal MJ, Friedman H L, Rogers F E. 1980. Kinetics of cellulose pyrolysis in nitrogen and steam [J ].

7 decomposition of calcium carbonate by use of relationships other than the Arrhenius equation[j ]. Thermochimica Acta, :13 27 Font R, Marcilla A, Conesa J A, et al Kinetic models for thermal degradation of heterogeneous materials [ J ]. Journal of Analytical and Applied Pyrolysis, 32 : Garc a A N, Marcilla A, Font R Thermogravimetric kinetic study of the pyrolysis of municipal solid waste [J ]. Thermochimica Acta, 254 : Kim S W, Cho Y S, Shim MJ Thermal degradation kinetics of PE by the Kissinger equation [J ]. Materials Chemistry and Physics, 52 (1) : Lee B K, Ellenbeckerb M J, Rafael M E Alternatives for treatment and disposal cost reduction of regulated medical wastes [ J ]. Management, 24 (2) : Waste Lee C C, Huffman G L. Medical waste managementπincineration : review[j ]. Journal of Hazardous Materials, 48 (123) :1 30 Li B, Gu YL, Yan J H Thermal decomposition kinetics model of the Li J. representative composition of municipal solid waste [J ]. Acta Scientiae Circumstanctiae, 19 (5) : (in Chinese) Study on Pyrolysis & Gasification Characteristics of Typical Components in Medical Waste [ D ]. Hangzhou : Zhejiang University, (in Chinese) Li Sh Y, Yue Ch T Study of different kinetic models for oil shale pyrolysis[j ]. Fuel Processing Technology, 85 (1) : Liu N A, Fan W C, Dobashi Ritsu, A novel thermogravimetric kinetic model of thermal degradation of biomass[j ]. Chinese Science Bulletin, 46 (10) : (in Chinese) Marcilla A, Beltran M Thermogravimetric kinetic study of poly(vinyl chloride) pyrolysis[j ]. Polymer Degration and Stability, 48 (2) : Mato R R A M, Kassenga G R A study on problems of management of medical solid wastes in Dar es Salaam and their remedial measures [J ]. Resourse, Conservation and Recycling, 21 (1) :1 16 Ran J Y Numerical Simulation and Experiment on the Gas Solid Flow and Combustion character in Circulating Fluidized Bed Combustion for Solid Medical Waste[D]. Chongging Chongqing University :40 45 (in Chinese) Rao T R, Sharma A Pyrolysis rates of biomass materials[j ]. Energy, 23 (11) : Raveendran K, Ganesh A, Khilar K C Pyrolysis characteristics of biomass and biomass components[j ]. Fuel, 75 (8) : Reina J, Velo E, Puigjaner L Thermogravimetric study of the pyrolysis of waste wood [J ]. Thermochimica Acta, 320 (122) : Sgrum L, Grgnli M G, Hustad J E Pyrolysis characteristics and kinetics of municipal solid wastes[j ]. Fuel, 80 (9) : Varma A J, Deshpande S V, Kondapalli P A comparative study of the thermal behavior of PVC, a series of synthesized chlorinated polyethylenes and HDPE [ J ]. Polymer Degradation and Stability, 63 (1) :1 3 Williams P T, Besler S Pyrolysis2thermogravimetric analysis of tyres and tyre components[j ]. Fuel, 74 (9) : Xie Z L, Yang M F Applied formula manual of fabricated rubber product[m]. Beijing : Chemical Industry Press, 645 (in Chinese) Zhang Y F, Deng N, Ling J H, et al A new pyrolysis technology and equipment for treatment of municipal household garbage and hospital waste [J ]. Renewable Energy, 28 (15) : :,,Andries J [J ].,24 (3) : ,,, [J ].,19 (5) : ,2004. [ D]. :,29 48,, Dobashi Ritsu [J ].,46 (10) : [D]. :,40 45, [M]. :,645

Thermogravimetric kinetic study of the pyrolysis of municipal solid waste [J ]. Thermochimica Acta, 254 : 277 304 Kim S W, Cho Y S, Shim MJ. 1998.

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