US 8,927,766 B2  46  45  TABLE 16-continued  TABLE 17  TABLE 17 -continued  Examples 144-147  Overall Feed Molar Ratios and Reaction Conditions  co  Flow  F0  Ex  SCCM Type  118  998.0  PF  119  998.0  PF  120  998.0  PF  121  998.0  PF  122  998.0  PF  123  998.0  PF  124  998.0  PF  125  998.0  PF  126  998.0  PF  127  998.0  PF  128  998.0  PF  129  998.0  PF  130  998.0  PF  131  498.0  PF  132  498.0  PF  133  498.0  PF  134  498.0  PF  135  498.0  PF  136  498.0  PF  137  498.0  PF  138  498.0  PF  139  498.0  PF  140  498.0  PF  141  498.0  PF  142  498.0  PF  143  498.0  PF  Res  ___  F_e_ed_M_o_lar_Ra_t_io ___ Press  Temp  Time  HFR  AS  Gl Water  Triflic  Psig  Celsius  min  1.0  0.7  1.0  0.70  0.054  1497  180  1.0  0.7  1.0  0.70  0.054  1503  180  1.0  0.7  1.0  0.70  0.054  1497  180  1.0  0.7  1.0  0.70  0.054  1498  180  1.0  0.7  1.0  0.70  0.054  1504  180  1.0  0.7  1.0  0.70  0.054  1504  180  1.0  1.0 0.6  0.70  0.054  1492  180  1.0  1.0 0.6  0.70  0.054  1003  180  1.0  1.0 0.6  0.70  0.054  500  180  1.0  1.0 0.6  0.70  0.054  995  170  1.0  1.0 0.6  0.70  0.054  502  170  1.0  1.0 0.6  0.70  0.054  1000  160  1.0  1.0 0.6  0.70  0.054  498  160  1.0  0.7  1.0  0.30  0.054  1507  170  1.0  0.7  1.0  0.30  0.054  1499  180  1.0  0.7  1.0  0.30  0.054  1503  180  1.0  0.7  1.0  0.30  0.054  1498  180  1.0  0.7  1.0  0.30  0.054  1003  160  1.0  0.7  1.0  0.30  0.054  1501  170  1.0  1.0 0.8  0.30  0.054  1500  180  1.0  1.0 0.8  0.30  0.054  999  180  1.0  1.0 0.8  0.30  0.054  500  180  1.0  1.0 0.8  0.30  0.054  999  170  1.0  1.0 0.8  0.30  0.054  500  170  1.0  1.0 0.8  0.30  0.054  1004  160  1.0  1.0 0.8  0.30  0.054  500  160  80  80  80  83  80  80  80  80  80  80  80  80  80  80  80  80  80  80  80  76  76  76  76  76  76  76  Selectivity, Conversion, and Space-Time Yield Results  Exam› ple  97  98  99  100  101  102  103  104  105  106  107  108  109  110  111  112  113  114  115  116  117  118  119  120  121  122  123  124  125  126  127  128  129  130  Space  % F0  Time  Molar  Con- Yield  Selectivity  version  gmol/1-hr  G 1  94.7  93.0  93.5  92.5  87.1  90.3  96.3  75.3  56.3  89.4  67.5  86.2  91.3  93.5  95.2  90.9  62.6  54.5  86.6  84.4  80.7  90.2  90.4  90.1  89.1  90.0  90.2  91.7  85.7  76.4  75.5  59.9  66.5  53.4  1.51  1.44  1.42  0.93  1.36  1.32  1.37  1.59  1.22  1.41  1.89  1.42  1.55  1.60  1.59  1.55  1.79  1.84  2.72  2.84  2.56  2.24  2.49  2.69  2.66  2.47  2.60  2.37  2.13  1.44  2.40  1.78  0.92  0.57  96.42  96.71  96.41  96.22  96.17  96.92  96.90  91.30  85.32  96.55  92.15  94.31  96.12  96.32  96.10  96.71  91.65  91.64  92.16  93.10  94.18  89.72  90.79  94.24  92.90  93.07  93.35  93.41  91.14  79.78  90.60  83.27  70.09  58.03  Al  DG  MGH  MeOH  1.02  1.55  0.00  0.93  1.42  0.00  1.23  1.13  0.00  1.36  1.06  0.00  1.41  0.80  0.43  1.09  0.91  0.00  0.87  1.36  0.00  3.85  0.99  0.00  7.16  0.10  0.50  1.05  1.34  0.00  3.56  0.72  0.00  2.33  0.98  0.12  1.26  1.36  0.00  1.05  1.58  0.00  1.13  1.64  0.00  0.93  1.42  0.00  2.07  4.07  0.19  0.47  7.42  0.00  2.45  2.62  0.56  1.93  3.03  0.00  1.38  2.88  0.37  2.00  5.69  0.73  1.67  5.85  0.00  1.47  2.82  0.00  1.02  0.93  1.23  1.36  1.19  1.09  0.87  3.85  6.91  1.05  3.56  2.26  1.26  1.05  1.13  0.93  1.97  0.47  2.17  1.93  1.19  1.64  1.67  1.47  1.83  3.07  0.31  1.68  1.67  3.10  0.72  1.31  1.69  2.94  0.66  1.36  1.71  3.11  0.11  1.66  3.20  2.01  0.90  2.75  8.41  2.09  1.83  7.49  3.53  2.16  0.36  3.35  7.20  1.43  0.85  6.78  11.5  2.31  7.69  7.75  20.1  0.93  0.86  19.68  Selectivity, Conversion, and Space-Time Yield Results  Exam› ple  131  132  133  134  135  136  137  138  139  140  141  142  143  Space  % F0  Time  Molar  Con- Yield  Selectivity  version  gmol/1-hr  Gl  89.5  94.9  95.2  92.9  83.0  92.5  93.0  93.6  87.1  90.4  80.0  82.0  71.6  2.25  2.87  2.46  2.46  1.92  2.53  2.62  2.82  2.35  2.48  2.12  2.28  2.05  89.86  92.05  91.01  92.89  89.48  91.90  93.77  94.21  89.56  93.64  87.08  90.50  86.67  Al  DG  MGH  MeOH  2.62  3.94  1.49  1.87  1.47  4.53  0.79  1.07  1.71  4.98  0.92  1.25  1.43  4.02  0.37  1.24  3.19  3.45  1.21  2.58  1.63  4.28  0.72  1.27  1.51  2.95  0.53  1.24  1.37  2.96  0.17  1.29  3.53  2.91  0.81  3.13  1.72  2.84  0.00  1.72  4.91  2.46  0.88  4.47  3.24  2.44  1.13  2.68  5.24  2.30  0.48  5.00  These examples illustrate the effect of feed water content,  temperature, pressure, and catalyst level on the hydrocar› boxylation of formaldehyde (trioxane) with triflic acid as  catalyst, with n-butyric acid and glycolic acid as solvent/  reactant.  Example 97 was repeated with only one feed at 0.91 g/min.  The feed contained 14.6 wt% paraformaldehyde, 6.2% water,  28.8 wt% butyric acid, 48.2 wt% glycolic acid, and 2.2 wt%  triflic acid. The feed molar ratio was paraformaldehyde (1.0),  water (0.7), glycolic acid (1.5), and triflic acid (0.03). The  hold-up time was 95 minutes. The feed rate of carbon mon› oxide was 498 SCCM. The operating pressure and tempera- ture, along with conversion, space-time yield, and selectivity  of reacted formaldehyde to end products are summarized in  Table 18. 