Based on successful experiences on batch scale, from Table 4.5: the efficient protocol condition of modified UAOD process on diesel fuels, the amount of catalyst usage is 0.3 gram per gram of diesel. Therefore, with 1,000 gram of Valley oil, the amount of catalyst require were 300 gram of catalyst. Due to the economical concern, it may not necessary need that much catalyst to run the entire process, therefore, in this section, different amount of catalyst usage and catalyst concentration has been test.

Based on successful experiments on batch scale (illustrated in Table 4.5) it is observed that with the efficient protocol condition of modified UAOD process on diesel fuels, the amount of catalyst usage is 0.3 gram per gram of diesel. Therefore, with 1,000 gram of Valley oil, the amount of catalyst required for the procedures were 300 gram of catalyst. Due to the feasibility of economical concerns, much catalyst may not be necessarily needed to run the entire process; henceforth, in this section, different amounts of catalyst usage and catalyst concentration have been put to the procedural testing.

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The different amount usage of acid catalyst has applied to batch type continuous flow system for Valley oil, shown as Table A1 and Figure A1. The sulfur reduction reached 7ppm in 140 minutes with 300g of catalyst. However, with 35g of catalyst, sulfur reduction was reach to 15 ppm at 200 minutes, this shows that almost one tenth of catalyst can achieve same desulfurization efficiency compare to the batch scale. The only drawback is need extra hour to reach minimum requirement of sulfur regulation.

The different amounts usages of acid catalyst have been applied to batch type continuous flow system for Valley oil which is illustrated in Table A1 and Figure A1. In the present process, the sulfur reduction reached 7ppm in 140 minutes with 300g of catalyst. However, with 35g of catalyst, the sulfur reduction reached to 15 ppm at 200 minutes. This shows that almost one tenth of catalyst can reach up to the same desulfurization efficiency as compared to the batch scale. The only drawback found here is that it needs an extra hour to reach the minimum requirement of sulfur regulation.

 

Reaction Time (min)
5g catalyst
25g catalyst
35g catalyst
300g catalyst
Ppm
ppm
ppm
ppm
0
8,100
8,100
8,100
8,100
10
3,145
1,344
914
841
20
2,889
1,141
779
588
30
2,457
1,020
642
476
40
2,180
890
564
311
60
1,874
612
314
206
80
1,544
489
227
76
140
1,317
279
84
7 (99.9%)
200
984 (87.9%)
129 (98.4%)
15 (99.8%)

Although, as the amount of catalyst usage increase, from 5 gram to 35 gram, the desulfurization efficiency increase significantly, this phenomena prove in this modified UAOD process that acid catalyst play a very important role for oxidation. Also, it indicate that using more cata;yst can fulfill the requirements of practical applications and permit much fast operation time.

Although the amount of catalyst usage increases, that is, from 5 gram to 35 gram, the desulfurization efficiency also increases to a significant degree. These phenomena prove in this modified UAOD process that acid catalysts play a very important role for the process of oxidation. Besides this, the present procedure indicates that using more catalyst can fulfill the requirements of practical applications; it also comes to the observation that it can permit much faster operation time.

 

 

 

 

 

With kinetic study of catalyst usage, since oxidant is excess amount, the reaction data was fitted to a first order rate equation. A plot of ln(Ct/Co) versus reaction time showed as Figure ASC. The result displayed a linear relationship that confirm the pseudo first order reaction kinetics. With 35 gram catalyst usage, it gives the highest rate constant of K=0.0211 min-1.

With kinetic study of catalyst usage, (registering the fact that oxidant is in excess amount) the reaction data were tailor-made to fit to a first order rate equation. A plot of ln(Ct/Co) versus reaction time is illustrated with the help of Figure ASC. The result displays a linear relationship that confirms the pseudo first order reaction kinetics. With 35 gram catalyst usage, it gives the highest rate constant of K=0.0211 min-1.

 

 

Another parameter that may affect the desulfurization efficiency were acid catalyst concentration, Table A2 and Figure A2 shows the data of desulfurization efficiency of different acid catalyst concentration with 10%, 20% and 40%. From batch study, by using 20% TFA as the concentration can reduce sulfur concentration to 15 ppm, but in pilot study, the result shows sulfur reduction can only reach to 189 ppm after 200 minute reaction time. This is because on the continuous flow system, using lower TFA concentration, it needs relatively longer time to reach the equivalent (high sulfur reduction). However, with 40% TFA, 15 ppm sulfur concentration can be achieve. The results clearly shows that higher the TFA concentration can fulfill the requirement of pilot study at given time.

Illustrations in Table A2 and Figure A2 display the data of desulfurization efficiency of different acid catalyst concentrations with 10%, 20% and 40%, in a respective order. From the batch study, by using 20% TFA, it is found that the concentration can reduce sulfur concentration to 15 ppm. However, in the pilot study, the outcome manifests that sulfur reduction can only reach to 189 ppm after 200 minute of reaction time. This is because of the fact that on the continuous flow system, using lower TFA concentration, it needs relatively longer time to reach the equivalent (high sulfur reduction). However, with 40% TFA, 15 ppm sulfur concentration can be obtained. The point worth the notice here is that the results clearly make it known that higher TFA concentration can fulfill the requirements of a pilot study at a given time.

 

Table A2

Reaction Time

(min)
10% TFA
20% TFA
40% TFA
ppm
Ppm
ppm
0
8,100
8,100
8,100
10
1,754
1,159
914
20
1,547
909
779
30
1,424
842
642
40
1,315
745
564
60
1,222
621
314
80
1,054
555
227
140
901
444
84
200
787 (90.3%)
279 (96.6%)
15 (99.8%)
Figure A2

With kinetic study of catalyst concentration, since oxidant is excess amount, the reaction data was fitted to a first order rate equation. A plot of ln(Ct/Co) versus reaction time showed as Figure ASD. The result displayed a linear relationship that confirm the pseudo first order reaction kinetics. With 40% TFA concentration, it gives the highest rate constant of K=0.0211 min-1. Therefore, to treat 1000 gram of Valley oil, it require 35 gram of 40% TFA catalyst to add into the continuous flow system that allow 99.9% (15 ppm) desulfurization.

With kinetic study of catalyst concentration, (registering the fact that oxidant is in excess amount), the reaction data were adapted to fit to a first order rate equation. A plot of ln(Ct/Co) versus reaction time is illustrated in Figure ASD. The result displays a linear connection which endorses the pseudo first order reaction kinetics. With 40% TFA concentration, it gives the highest rate constant of K=0.0211 min-1. Therefore, to treat 1000 gram of Valley oil, it require 35 gram of 40% TFA catalyst to add to the continuous flow system which lets go of 99.9% (15 ppm) of desulfurization.

 

 

Figure ASD