5.

2 Resins

Resins are organo-polymeric material which possesses the high surface area, high ion-exchange capacities and a typical functionality

Table 1
Synthesis of fuel-additive levulinate compounds from biomass derived levulinic acid using various catalytic systems.

Entry LVA Catalyst and other reaction conditions Mole ratio Temp Time Yield Reuse Ref.

Silica catalyst
1 EL Silica included Wells-Dawson heteropoly acid 1:64 78 °C 10 h 93 3 51
2 EL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 5h 99 5 52
3 BL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 5h 90 – 52
4 ISPL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 6h 85 – 52
5 ISAL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 6h 70 – 52
6 TBL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 5h 68 – 52
7 BENL HClO4/SiO2 nanoporous solid-acid (10% w/w) 1:86 100 °C 10 h 45 – 52
8 ML Tungsten oxide incorporated SBA-16 catalyst (0.5 g), flow: 30 mL min−1, liquid feed flow: 1 mL h−1 1:7 250 °C – 96 – 53
9 EL Tungsten oxide incorporated SBA-16 catalyst (0.5 g), flow: 30 mL min−1, liquid feed flow: 1 mL h−1 1:7 250 °C – 95 – 53
10 PL Tungsten oxide incorporated SBA-16 catalyst (0.5 g), flow: 30 mL min−1, liquid feed flow: 1 mL h−1 1:7 250 °C – 94 – 53
11 BL Tungsten oxide incorporated SBA-16 catalyst (0.5 g), flow: 30 mL min−1, liquid feed flow:1 mL h−1 1:7 250 °C – 94 – 53
12 ISBL Tungsten oxide incorporated SBA-16 catalyst (0.5 g), flow: 30 mL min−1, liquid feed flow:1 mL h−1 1:7 250 °C – ~65 – 53
13 EL Sulfonic mesostructured silica (7 wt%) 1:4.86 117 °C 2h 100 3 54
14 ML Sulphated silica (30%) 1:20 64 °C 4h 69 3 55
15 BL Aluminum-containing MCM-41 (1%) 1:5 120 °C 8h 90 10 56
16 ISBL Aluminum-containing MCM-41 (3%) 1:5 110 °C 8h 98 – 56
17 EL Silica supported sulfonic acid catalyst (1 mol%) 1:1 75 °C 2h 94 6 57

Resin catalyst
18 PENL Aquivion mP98 (10 mol%) 1:10 90 °C 24 h 92 5 58
19 ML Amberlyst-15 (30%) 1:20 64.7 °C 5h 82 – 59
20 EL Amberlyst-15 (30%) 1:20 78.4 °C 5h 71 – 59
21 BL Amberlyst-15 (30%) 1:20 117.74 °C 5h 55 5 59
22 EL Amberlyst-15 (2.5 wt%) 1:5 343 K 5h ~54 4 60
23 BL Amberlyst-15 (20 wt%) 1:4 397 K 75 min 97.03 – 61
24 BL Dowex 50Wx2, gel-type resin (0.8%) 1:3 80 °C 8h 94 – 62

Heteropolyacid catalyst
25 EL 3D Graphene aerogel anchored tungstophosphoric acid (45 wt%) 1:10 80 °C 9h 89.1 5 63
26 EL Dodecatungstophosphoric acid supported on desilicated H-ZSM-5 as catalyst (0.25 wt% to LVA), speed of 1:8 351 K 4h 94 4 64
agitation: 250 rpm
27 BL Ammonium co-doped phosphotungstic acid (1.5%) 1:2 120 °C 2h 99 4 65
28 BL Silver co-doped phosphotungstic acid (1.5%) 1:2 120 °C 2h 92 – 65
29 HL Dodecatungstophosphoric acid anchored to Al-MCM-41 (25 wt%) 1:5 100 °C 10 h 100 6 66
30 EL Zirconia supported phosphotungstic acid (1 g) 1:17 150 °C 3h 97.3 4 67
31 EL Porous solid acid consisting of tungstophosphoric acid supported on reduced graphene oxide (0.50 g) 1:7.5 80 °C 11 h 96.9 5 68
32 EL Tungstophosphoric acid based mesoporous material anchored on MCM-41 (25 wt%) 1:5 80 °C 10 h 77.1 5 69
33 EL Organic-salt of H4SiW12O40 (4 mol%) 1:5 Reflux 5h 98.6 – 70
34 ML Organic-salt of H4SiW12O40 (4 mol%) 1:5 Reflux 5h 100 – 70
35 ISBL Organic-salt of H4SiW12O40 (4 mol%) 1:5 Reflux 5h 87.8 5 70
36 BL Dodecatungston phosphoric acid supported on K10 (10 mol%) 1:6 120 °C 4h 97 3 71
37 EL H4SiW12O40 (8 mol%) 1:18 25 °C 8h ~90 3 72
38 ML H4SiW12O40 (8 mol%) 1:18 25 °C 8h 92 – 72
39 PL H4SiW12O40 (8 mol%) 1:18 25 °C 8h 90 – 72
40 BL H4SiW12O40 (8 mol%) 1:18 25 °C 8h 91 – 72
41 SBL H4SiW12O40 (8 mol%) 1:18 25 °C 8h 72 – 72
42 TBL H4SiW12O40 (8 mol%) 1:18 25 °C 8h 14 – 72
43 PL Heteropoly acid supported on silicalite-1 (100 mg) 1:5 100 °C 5h 90 4 73
44 BL Heteropoly acid supported on silicalite-1 (100 mg) 1:5 100 °C 5h 93 – 73
45 HEL Heteropoly acid supported on silicalite-1 (100 mg) 1:5 100 °C 5h 76 – 73
46 EL Hetero poly acid supported STA-AlSBA-15 (20 wt%) 1:10 75 °C 5h 87.4 3 74
47 ML Tungstosilicic acid (104 mg), LVA: 205 mg, AL:2 mL, cyclohexane 5 mL, Temp 65 °C, Time 6 h. – 65 °C 6h 73 4 75
48 EL Tungstosilicic acid (104 mg), LVA: 205 mg, AL:2 mL, cyclohexane 5 mL, Temp 75 °C, Time 6 h. – 75 °C 6h 67 4 75

Zeolite catalyst
49 ML Micro/Meso-HZ-5 catalyst (20 wt%) 1:8 393 K 5h 91 – 76
50 EL Micro/Meso-HZ-5 catalyst (20 wt%) 1:8 393 K 5h 95 – 76
51 BL Micro/Meso-HZ-5 catalyst (20 wt%) 1:8 393 K 5h 96 – 76
52 OL Micro/Meso-HZ-5 catalyst (20 wt%) 1:8 393 K 5h 98 6 76
53 EL Bimodal micro–mesoporous H/BEA zeolites catalyst (20 wt%) 1:6 78 °C 5h 40 4 77
54 BL Desilicated H-ZSM-5 catalyst (20% to LVA) 1:6 393 K 5h 95 6 78
55 BL H-BEA catalyst (10 wt%) 1:7 120 °C 4h 82.2 5 79
56 BL H-MOR catalyst (10 wt%) 1:7 120 °C 4h 29.5 – 79
57 BL H-Y catalyst (10 wt%) 1:7 120 °C 4h 32.2 – 79

(continued on next
PAGE)

4
58 BL H-SM-5 catalyst (10 wt%) 1:7 120 °C 4h 30.6 – 79
59 EL Modified H-ZSM-5 catalyst (20 wt%) 1:8 393 K 5h 98 7 80
60 HL Hierarchical H-ZSM-5 catalyst (24 wt%) 1:9 401 °C 5h 97.2 5 81
61 OL Modified H-ZSM-5 catalyst (25.4 wt%) 1:7.56 393 K 4h 99 7 82

Carbonaceous catalyst
62 EL Sulphonic carbon (Bagasse carbonized) based catalyst (0.3 g) 1:5 120 °C 9h 88.2 5 83
63 EL Sulfonated hydrothermal carbons catalyst (5 wt%) 1:5 60 °C 1h 91.5 – 84
64 EL Loofah sponge-derived carbon (5 wt%) 1:5 80 °C 10 h 91 4 85
65 EL Starbon (0.1 g) 1:30 80 °C ~6 h 85 – 86
66 EL Calcined carbon cryogel crystal (25 wt%) 1:15 150 °C 4h 86.5 – 87

(continued on next
PAGE)

5
Entry LVA Catalyst and other reaction conditions Mole ratio Temp Time Yield Reuse Ref.

67 EL Carbonized carbon cryogel crystal (15 wt%) 1:19 78 °C 10 h 61.4 – 87

68 EL Craboncryogel crystal (25 wt%) 1:15 150 °C 4h 86.5 – 88

Zirconia catalyst
69 ML Mesoporous H3PW12O40/ZrO2–Si(Ph)Si hybrid catalyst (2 wt%) 1:7 65 °C 3h ~100 3 89
70 EL Sulphated mesoporous zircon-silicates (5 wt%), 700 rpm 1:10 70 °C 24 h 79 5 90
71 EL Sulphated Si-doped ZrO2 solid (5 wt%), 700 rpm 1:10 70 °C 10 h 65.6 5 91
72 ML Mesoporous H3PW12O40/ZrO2–Si(Ph)Si 1.0 hybrid catalyst (2 wt%) 1:7 Reflux 3h 99.9 3 92
73 EL Mesoporous H3PW12O40/ZrO2–Si(Ph)Si 1.0 hybrid catalyst (2 wt%) 1:7 Reflux 3h 91.5 – 92
74 BL Mesoporous H3PW12O40/ZrO2–Si(Ph)Si 1.0 hybrid catalyst (2 wt%) 1:7 Reflux 3h 82.8 – 92
75 EL Sulphated zirconia coated hydroxyethyl cellulose catalytic membrane (8 g/L) 1:3 70 °C 7h 95 – 93
76 EL Powder sulphated zirconia catalyst (8 g/L) 1:3 70 °C 7h 39.92 5 93
77 ML Mesoporous super acidic zirconia catalyst UDCaT-5 (catalyst loading 0.01 g/cm 3), speed of agitation: 1:20 160 °C 3h 100 6 94
1000 rpm
78 EL Mesoporous super acidic zirconia catalyst UDCaT-5 (catalyst loading 0.01 g/cm 3), speed of agitation: – 160 °C 3h 100 – 94
1000 rpm
79 PL Mesoporous super acidic zirconia catalyst UDCaT-5 (catalyst loading 0.01 g/cm 3), speed of agitation: – 160 °C 3h 95 – 94
1000 rpm
80 BL Mesoporous super acidic zirconia catalyst UDCaT-5 (catalyst loading 0.01 g/cm 3), speed of agitation: – 160 °C 3h 98 – 94
1000 rpm
81 PENL Mesoporous super acidic zirconia catalyst UDCaT-5 (catalyst loading 0.01 g/cm 3), speed of agitation: 160 °C 3h 94 – 94
1000 rpm

Acid catalyst
82 EL Bio-glycerol derived carbon–sulfonic-acid (50 mg) 1:5 Reflux 3h 99 5 95
83 ML Bio-glycerol derived carbon–sulfonic-acid (50 mg) 1:5 Reflux 3h 99 – 95
84 PL Bio-glycerol derived carbon–sulfonic-acid (50 mg) 1:5 Reflux 3h 95 – 95
85 BL Bio-glycerol derived carbon–sulfonic-acid (50 mg) 1:5 Reflux 3h 44 – 95
86 EL PTSA (2.5 mol%) 1:10 120 °C 5 min 100 – 96

Metal salt catalyst

87 ML Al2(SO4)3 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 99.4 5 97
88 ML CrCl3 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 91.5 – 97
89 ML SnCl4 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 96.8 – 97
90 ML SnSO4 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 15.7 – 97
91 ML FeCl3 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 89.6 – 97
92 ML CuSO4 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 49.5 – 97
93 ML CuCl2 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 66.1 – 97
94 ML AlCl3 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 83.9 – 97
95 ML ZnCl2 (20 mmol%), LVA: 1 mmol, AL 14 mL, microwave 400 W – 110 °C 0.5 h 8.1 – 97
96 EL Fe2(SO4)3 (3 mol%) 1:6 333 K 4h ~94 4 98
97 ML Fe2(SO4)3 (3 mol%) 1:6 333 K 4h ~94 – 98
98 BL Fe2(SO4)3 (3 mol%) 1:6 333 K 4h ~90 – 98
99 PL Fe2(SO4)3 (3 mol%) 1:6 333 K 4h ~88 – 98
100 EL FeCl3 (3 mol%) 1:3 333 K 4h ~85 – 98
101 EL CuSO4 (3 mol%) 1:3 333 K 4h 15 – 98
102 EL FeSO4(3 mol%) 1:3 333 K 4h 12 – 98
103 EL ZnSO4(3 mol%) 1:3 333 K 4h 10 – 98
104 EL NiSO4(3 mol%) 1:3 333 K 4h 2 – 98
105 EL MnSO4(3 mol%) 1:3 333 K 4h 2 – 98

Metal organic framework catalyst

106 EL MOF supported ployoxometalates Cu BTC [HPM] (40 mg) – 120 °C 4h 100 3 99
LVA: 0.5 mmol, AL: 10 mL
107 ML Sulphonic acid functionalized hafnium based MOF (0.8 mol%), LVA: 1 mmol, AL: 20 mL – 120 °C 2.5 h 94 4 100
108 EL Sulphonic acid functionalized hafnium based MOF (0.8 mol%), LVA: 1 mmol, AL: 20 mL – 120 °C 2h 90 – 100
109 PL Sulphonic acid functionalized hafnium based MOF (0.8 mol%), LVA: 1 mmol, AL: 20 mL – 120 °C 2h 87 – 100
110 ISPL Sulphonic acid functionalized hafnium based MOF (0.8 mol%), LVA: 1 mmol, AL: 20 mL – 120 °C 2h 88 – 100
111 BL Zirconia containing MOF UIO-66 (1.8 mol%) 1:6 120 °C 5h 99 3 101
112 BL Zirconia containing MOF UIO-66-NH 2 (1.8 mol%) 1:6 120 °C 5h 99 3 101
113 LL Zirconia containing MOF UIO-66 (9 mol%) 1:1 80 °C 20 h ~90 3 101
114 CL Zirconia containing MOF UIO-66 (9 mol%) 1:1 80 °C 20 h ~82 3 101
115 OLL Zirconia containing MOF UIO-66 (9 mol%) 1:1 80 °C 20 h ~62 3 101