SUPPLEMENTARY INFORMATION
Procedure for generation of catalyst-free PE-TG profiles and its consequence on calculated activation energies
Gorazd Berčiča,[*], Petar Djinovićb, Albin Pintarb
aDepatment of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19, SI-1001 Ljubljana, Slovenia
bDepartment for Environmental Sciences and Engineering, National Institute of Chemistry, Hajdrihova 19, SI-1001 Ljubljana, Slovenia
a) b)
Fig. S1 Demonstration of smoothing efficiency for different smoothing algorithms by comparison of calculated DTG curves from smooth raw TG data. Catalyst: M300, heating rate 5 Kmin-1 (a) and 25 Kmin-1 (b)
Fig. S2 Comparison between observed degradation rates during PE depolymerization runs
Table S1 Calculated mixing ratios from experimentally measured TG profiles and TG profile of pure catalyst sample for measurements carried out at different heating rates
/Kmin-1 / PE : MAl / PE : M300 / PE : ASA
5 / 0.5097 : 0.4903 / 0.5055 : 0.4945 / 0.5115 : 0.4885
10 / 0.4909 : 0.5091 / 0.5164 : 0.4836 / 0.5174 : 0.4826
15 / 0.4877 : 0.5123 / 0.4986 : 0.5014 / 0.5129 : 0.4872
20 / 0.4905 : 0.5095 / 0.5382 : 0.4618 / 0.5112 : 0.4888
25 / 0.4985 : 0.5015 / 0.5397 : 0.4603 / 0.5099 : 0.4901
Table S2 Calculated values of activation energies from the extracted PE profiles for the case of PE depolymerization in the presence of MAl catalyst
Conversion / Activation energy/kJmol-1 / Correlationfactor / Ea /kJmol-1 / Correlation
factor
AICM / Friedman / rFriedman / KAS / rKAS
.025 / 387.90 / 399.51 / 0.989 / 422.66 / 0.985
.05 / 291.36 / 290.73 / 0.988 / 311.54 / 0.99
.1 / 284.27 / 284.39 / 0.990 / 278.74 / 0.992
.15 / 300.22 / 300.01 / 0.995 / 286.09 / 0.993
.2 / 309.88 / 309.99 / 0.996 / 294.75 / 0.995
.25 / 322.76 / 322.73 / 0.997 / 304.31 / 0.996
.3 / 333.29 / 333.18 / 0.997 / 314.08 / 0.996
.35 / 345.71 / 345.66 / 0.997 / 324.00 / 0.996
.4 / 352.74 / 352.68 / 0.996 / 333.04 / 0.996
.45 / 356.55 / 356.51 / 0.996 / 340.29 / 0.996
.5 / 356.32 / 355.92 / 0.996 / 345.26 / 0.996
.55 / 354.26 / 353.86 / 0.996 / 348.18 / 0.996
.6 / 349.52 / 349.88 / 0.996 / 349.35 / 0.996
.65 / 344.45 / 344.29 / 0.997 / 348.95 / 0.996
.7 / 337.08 / 337.2 / 0.998 / 347.31 / 0.997
.75 / 326.94 / 327.26 / 0.998 / 344.13 / 0.997
.8 / 312.68 / 312.81 / 0.999 / 338.85 / 0.998
.85 / 292.89 / 293.06 / 0.999 / 330.65 / 0.998
.9 / 270.79 / 270.78 / 0.999 / 318.88 / 0.999
.95 / 254.13 / 253.72 / 0.999 / 302.47 / 0.999
.975 / 265.56 / 264.69 / 0.998 / 291.86 / 0.999
Table S3 Calculated values of activation energies from the extracted PE profiles for the case of PE depolymerization in the presence of M300 catalyst
factor / Ea/kJmol-1 / Correlation
factor
AICM / Friedman / rFriedman / KAS / rKAS
.025 / 113.11 / 113.28 / 0.977 / 121.95 / 0.986
.05 / 120.16 / 119.70 / 0.986 / 117.66 / 0.995
.1 / 154.93 / 155.29 / 0.999 / 126.92 / 0.997
.15 / 167.38 / 167.39 / 0.995 / 139.77 / 0.997
.2 / 167.26 / 167.31 / 0.998 / 147.06 / 0.997
.25 / 174.63 / 174.64 / 0.997 / 152.16 / 0.997
.3 / 182.01 / 182.26 / 0.994 / 156.90 / 0.996
.35 / 188.09 / 188.37 / 0.994 / 161.87 / 0.996
.4 / 196.97 / 196.42 / 0.996 / 166.79 / 0.996
.45 / 205.97 / 205.71 / 0.998 / 171.88 / 0.996
.5 / 212.49 / 213.26 / 0.999 / 177.10 / 0.996
.55 / 219.19 / 219.14 / 0.999 / 182.32 / 0.997
.6 / 223.41 / 224.49 / 0.999 / 187.43 / 0.997
.65 / 227.95 / 228.64 / 0.999 / 192.35 / 0.997
.7 / 230.52 / 230.49 / 0.999 / 196.91 / 0.998
.75 / 228.74 / 229.18 / 0.998 / 200.87 / 0.998
.8 / 226.92 / 225.06 / 0.999 / 203.90 / 0.998
.85 / 216.91 / 215.79 / 0.998 / 205.56 / 0.998
.9 / 202.30 / 199.5 / 0.998 / 205.02 / 0.998
.95 / 179.35 / 178.52 / 0.996 / 200.90 / 0.998
.975 / 176.35 / 175.27 / 0.99 / 196.96 / 0.999
Table S4 Calculated values of activation energies from the extracted PE profiles for the case of PE depolymerization in the presence of ASA catalyst
Conversion / Activation energy/kJmol-1 / Correlationfactor / Ea/kJmol-1 / Correlation
factor
AICM / Friedman / rFriedman / KAS / rKAS
.025 / 102.11 / 102.14 / 0.999 / 101.60 / 0.995
.05 / 104.51 / 104.31 / 1 / 101.41 / 0.998
.1 / 112.89 / 112.84 / 1 / 104.27 / 0.999
.15 / 120.65 / 120.62 / 1 / 108.49 / 1
.2 / 129.35 / 129.31 / 1 / 113.86 / 1
.25 / 137.37 / 137.32 / 0.999 / 119.54 / 1
.3 / 145.65 / 145.58 / 0.998 / 125.56 / 1
.35 / 154.68 / 154.64 / 0.998 / 132.00 / 0.999
.4 / 162.57 / 162.59 / 0.997 / 138.80 / 0.999
.45 / 170.65 / 170.59 / 0.997 / 145.68 / 0.998
.5 / 177.79 / 177.79 / 0.996 / 152.50 / 0.998
.55 / 184.32 / 184.38 / 0.996 / 159.11 / 0.997
.6 / 188.48 / 188.54 / 0.995 / 165.19 / 0.997
.65 / 191.61 / 191.55 / 0.995 / 170.49 / 0.996
.7 / 194.10 / 194.05 / 0.994 / 174.94 / 0.996
.75 / 195.92 / 196.00 / 0.993 / 178.78 / 0.995
.8 / 197.73 / 197.82 / 0.99 / 182.06 / 0.995
.85 / 202.72 / 202.66 / 0.983 / 185.26 / 0.993
.9 / 216.74 / 216.61 / 0.963 / 189.71 / 0.988
.95 / 293.76 / 292.88 / 0.905 / 205.75 / 0.961
.975 / 625.52 / 600.98 / 0.977 / 308.77 / 0.956
Table S5 Calculated values of activation energies from the TG profiles measured during non-catalytic PE depolymerization
factor / Ea/kJmol-1 / Correlation
factor
AICM / Friedman / rFriedman / KAS / rKAS
.025 / 214.84 / 214.03 / 0.971 / 285.86 / 0.955
.05 / 198.06 / 197.52 / 0.989 / 239.57 / 0.978
.1 / 204.80 / 205.24 / 0.99 / 217.23 / 0.987
.15 / 216.83 / 216.66 / 0.991 / 214.50 / 0.989
.2 / 231.01 / 230.62 / 0.992 / 217.01 / 0.991
.25 / 243.17 / 242.91 / 0.993 / 221.72 / 0.992
.3 / 249.81 / 250.68 / 0.994 / 226.75 / 0.993
.35 / 252.58 / 254.94 / 0.995 / 231.42 / 0.993
.4 / 255.66 / 256.82 / 0.998 / 235.44 / 0.994
.45 / 258.04 / 259.44 / 0.999 / 239.14 / 0.995
.5 / 264.24 / 265.89 / 0.999 / 242.84 / 0.996
.55 / 269.66 / 273.12 / 0.999 / 246.66 / 0.997
.6 / 276.42 / 278.65 / 0.999 / 250.5 / 0.998
.65 / 281.44 / 282.11 / 0.998 / 254.28 / 0.999
.7 / 285.13 / 284.77 / 0.998 / 257.88 / 0.999
.75 / 288.48 / 287.32 / 0.998 / 261.31 / 0.999
.8 / 289.94 / 288.49 / 0.999 / 264.56 / 0.999
.85 / 294.76 / 286.28 / 0.999 / 267.51 / 1
.9 / 287.80 / 279.71 / 0.999 / 270.06 / 1
.95 / 266.06 / 266.05 / 0.999 / 272.71 / 1
.975 / 257.56 / 254.45 / 0.999 / 278.08 / 0.999
Table S6 Calculated values of activation energies from measured TG profiles for PE degradation in the presence of MAl catalyst according to postulated presumptions
Conversion / Presumption I / Presumption II / Presumption IIIEa/kJmol-1 / r / Ea/kJmol-1 / r / Ea/kJmol-1 / r
.025 / 399.51 / 0.989 / 254.9 / 0.992 / -11.62 / .045
.05 / 290.73 / 0.988 / 246.74 / 0.993 / 297.98 / .863
.1 / 284.39 / 0.99 / 259.78 / 0.995 / 275.71 / 0.989
.15 / 300.01 / 0.995 / 283.84 / 0.995 / 292.14 / 0.996
.2 / 309.99 / 0.996 / 296.36 / 0.997 / 305.31 / 0.996
.25 / 322.73 / 0.997 / 309.27 / 0.998 / 316.01 / 0.997
.3 / 333.18 / 0.997 / 322.06 / 0.998 / 329.98 / 0.998
.35 / 345.66 / 0.997 / 334.35 / 0.998 / 342.07 / 0.997
.4 / 352.68 / 0.996 / 343.31 / 0.997 / 352.22 / 0.997
.45 / 356.51 / 0.996 / 348.54 / 0.997 / 357.50 / 0.997
.5 / 355.92 / 0.996 / 349.68 / 0.997 / 358.11 / 0.997
.55 / 353.86 / 0.996 / 348.01 / 0.996 / 356.05 / 0.996
.6 / 349.88 / 0.996 / 343.95 / 0.997 / 351.27 / 0.996
.65 / 344.29 / 0.997 / 339.63 / 0.998 / 346.38 / 0.997
.7 / 337.20 / 0.998 / 333.08 / 0.998 / 339.30 / 0.998
.75 / 327.26 / 0.998 / 323.54 / 0.999 / 329.29 / 0.999
.8 / 312.81 / 0.999 / 310.62 / 0.999 / 315.67 / 0.999
.85 / 293.06 / 0.999 / 291.27 / 0.999 / 295.58 / 0.999
.9 / 270.78 / 0.999 / 264.49 / 1 / 271.68 / 1
.95 / 253.72 / 0.999 / 235.34 / 1 / 265.25 / 0.999
.975 / 264.69 / 0.998 / 219.34 / 0.997 / 349.5 / 0.994
Table S7 Calculated values of activation energies from measured TG profiles for PE degradation in the presence of M300 catalyst according to postulated presumptions
Ea/kJmol-1 / r / Ea/kJmol-1 / r / Ea/kJmol-1 / r
.025 / 113.28 / 0.977 / 95.15 / 0.985 / 13.29 / .017
.05 / 119.70 / 0.986 / 127.41 / 0.991 / 94.41 / 0.985
.1 / 155.29 / 0.999 / 146.69 / 0.997 / 131.72 / 0.993
.15 / 167.39 / 0.995 / 166.38 / 0.994 / 163.06 / 0.995
.2 / 167.31 / 0.998 / 164.75 / 0.999 / 164.32 / 0.998
.25 / 174.64 / 0.997 / 172.03 / 0.997 / 170.46 / 0.998
.3 / 182.26 / 0.994 / 180.54 / 0.994 / 179.51 / 0.995
.35 / 188.37 / 0.994 / 186.48 / 0.994 / 185.77 / 0.993
.4 / 196.42 / 0.996 / 194.2 / 0.996 / 192.9 / 0.995
.45 / 205.71 / 0.998 / 203.88 / 0.998 / 203.56 / 0.997
.5 / 213.26 / 0.999 / 211.29 / 0.999 / 212.22 / 0.998
.55 / 219.14 / 0.999 / 216.76 / 0.999 / 218.42 / 0.999
.6 / 224.49 / 0.999 / 221.87 / 0.999 / 224.09 / 0.999
.65 / 228.64 / 0.999 / 226.03 / 0.999 / 228.82 / 0.999
.7 / 230.49 / 0.999 / 227.85 / 0.998 / 231.12 / 0.999
.75 / 229.18 / 0.998 / 226.47 / 0.999 / 230.52 / 0.999
.8 / 225.06 / 0.999 / 222.07 / 0.998 / 226.48 / 0.999
.85 / 215.79 / 0.998 / 212.26 / 0.998 / 217.10 / 0.999
.9 / 199.50 / 0.998 / 193.45 / 0.999 / 198.73 / 0.999
.95 / 178.52 / 0.996 / 161.55 / 0.998 / 176.87 / 0.998
.975 / 175.27 / 0.990 / 144.78 / 0.997 / 225.10 / 0.995
Table S8 Calculated values of activation energies from measured TG profiles for PE degradation in the presence of ASA catalyst according to postulated presumptions
Conversion / Presumption I / Presumption II / Presumption IIIEa/kJmol-1 / r / Ea/kJmol-1 / r / Ea/kJmol-1 / r
.025 / 102.14 / 0.999 / 102.04 / 1 / 81.55 / 0.962
.05 / 104.31 / 1 / 103.25 / 0.999 / 102.69 / 1
.1 / 112.84 / 1 / 111.17 / 1 / 110.64 / 0.999
.15 / 120.62 / 1 / 119.51 / 1 / 117.29 / 1
.2 / 129.31 / 1 / 127.2 / 0.999 / 126.61 / 0.999
.25 / 137.32 / 0.999 / 134.96 / 0.998 / 134.99 / 0.998
.3 / 145.58 / 0.998 / 143.21 / 0.998 / 143.53 / 0.998
.35 / 154.64 / 0.998 / 151.86 / 0.997 / 152.30 / 0.997
.4 / 162.59 / 0.997 / 159.17 / 0.996 / 161.01 / 0.997
.45 / 170.59 / 0.997 / 167.10 / 0.996 / 169.57 / 0.996
.5 / 177.79 / 0.996 / 173.68 / 0.995 / 176.75 / 0.996
.55 / 184.38 / 0.996 / 180.23 / 0.995 / 183.95 / 0.996
.6 / 188.54 / 0.995 / 184.63 / 0.994 / 188.92 / 0.995
.65 / 191.55 / 0.995 / 187.14 / 0.995 / 191.81 / 0.995
.7 / 194.05 / 0.994 / 189.43 / 0.993 / 194.63 / 0.994
.75 / 196.00 / 0.993 / 190.97 / 0.992 / 197.03 / 0.993
.8 / 197.82 / 0.990 / 191.30 / 0.989 / 198.74 / 0.990
.85 / 202.66 / 0.983 / 193.50 / 0.981 / 204.76 / 0.983
.9 / 216.61 / 0.963 / 199.93 / 0.960 / 221.08 / 0.962
.95 / 292.88 / 0.905 / 229.89 / 0.867 / 327.82 / 0.919
.975 / 600.98 / 0.977 / 309.82 / 0.940 / 937.5 / 0.921
1
[*]Corresponding author. Tel.: +386 1 47 60 282; fax: +386 1 47 60 300. E-mail address:
(G. Berčič).