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Title: Low severity upgrading of F-T waxes with solid superacids

Technical Report ·
DOI:https://doi.org/10.2172/6704063· OSTI ID:6704063

In the last quarters a new class of solid superacids, including sulfated zirconium-hafnium oxides and ZrO[sub 2]/SO[sub 4] modified by Mn and Fe, were synthesized and shown to be active for isomerization and hydrocracking of hexadecane (n-C[sub 16]H[sub 34]). The reaction was carried out in a tubing bomb under mild conditions: 2.5 MPa and 433 K. Pt/HfO[sub 2]S0[sub 4] catalyst exhibited a low activity for hydrocracking of n-C[sub 16], but the addition of ZrO[sub 2] to the sulfated hafnium improved its activity considerably. An 85 wt % conversion level was achieved when the molar ratio of ZrO[sub 2] to HfO[sub 2] reached 1:1, indicating the possibility of a synergistic effect between zirconium and hafnium. It has recently been reported that Mn,Fe/ZrO[sub 2]/SO[sub 4] is about three orders of magnitude more active than ZrO[sub 2]/SO[sub 4] for isomerizing n-butane. As a result, an 0.5%Mn1.5%Fe/ZrO[sub 2]/SO[sub 4] catalyst was prepared according to a procedure given in a patent. It was found that, without Pt, the catalyst was inactive for hydrocracking of n-C[sub 16], possibly by deactivation due to coking. It is interesting that a 68 wt % conversion level was achieved after incorporation of Pt along with a product distribution that was shifted towards longer chain paraffins. ZrO[sub 2]/SO[sub 4]has been reported to be a superacid with H[sub 0] < [minus]16 as measured by the Hammett indicator method. However, the acid strength of some ZrO[sub 2]/SO[sub 4] based catalysts, such as the mentioned catalysts, could not be measured by using Hammett indicators because the catalysts are colored gray. We successfully modified an in situ FT-IR analytical system to characterize the acidity of these catalysts. We have applied the method using pyridine as adsorbate to demonstrate their acid strength. Preliminary results indicated a level of acidity of our catalysts which is consistent with their performance in hydrocracking of n-C[sub 16].

Research Organization:
Pittsburgh Univ., PA (United States). Dept. of Chemical and Petroleum Engineering
Sponsoring Organization:
USDOE; USDOE, Washington, DC (United States)
DOE Contract Number:
FG22-91PC91304
OSTI ID:
6704063
Report Number(s):
DOE/PC/91304-T5; ON: DE93011453
Country of Publication:
United States
Language:
English