B.O.O.S.T.

advances Albemarle light olefin technology: commercial experience

large European cracking refinery operates a 2.6 million tpa UOP high-efficiency FCC unit. The complex includes an alkylation unit and has the capability for pipeline export of refinery-grade propylene to nearby petrochemical facilities.
Albemarle K-2000 was a leading-edge technology when it was first introduced in the 1990s. Since that time, significant technological advances have resulted in the development of our ZSM-5 additives, B.O.O.S.T. and Z.O.O.M. This article reviews our recent commercial experience with B.O.O.S.T. versus K-2000, illustrating our ongoing commitment to developing industry-leading technology.

ZSM-5 additive in equilibrium catalyst

Cat A Cat A = K-2000 Cat A = K-2000 Cat A = B.O.O.S.T. K-2000 wt% K-2000 B.O.O.S.T.

Oct - 04

Oct - 05

Apr - 05

Aug - 04

Jun - 04

Aug - 05

Apr - 06

Dec - 04

Dec - 05

Aug - 06

Jun - 05

Jun - 06

Oct - 06

Dec - 06

Feb - 05

The typical feedstock is pretreated in a mild hydrocracking unit to reduce sulfur and metals content to very low values. Key properties such as specific gravity and Conradson carbon residue range between 0.8900.910 and 0.010.25 wt% respectively. Operational objectives change over the course of the year. In winter, the main target is to maximize the LPG yield, especially propylene, up to the wet gas constraints. This is achieved with the addition of ZSM-5 additive. In the summer months, the unit typically operates in gasoline mode, with no addition of ZSM-5. This refinery had been using K-2000 since 2004, but in winter 2006 Albemarle proposed that they switch to the new version of B.O.O.S.T., which shares a similar crystal content but has a higher intrinsic activity, thanks to recent improvements in Albemarles ZSM-5 additive production process. Comparing B.O.O.S.T. with other additives with similar ZSM-5 contents, this FCC additive gives Better Olefins and Octane STimulation.

Figure 1: Increase ZSM-5 content in the inventory.

The comparison between the performances of the two additives has been made taking in consideration three periods:
I I I

October 2004 February 2005 October 2005 December 2006 August 2006 November 2006

Raw unit data and equilibruim catalyst data have been used in this side-by-side comparison, and all analyses of the data support the conclusion that B.O.O.S.T. has higher performance on C3= and C4= yields than K-2000.

Commercial unit performance

From the analyses of the raw unit data, B.O.O.S.T. is shown to achieve exceptional performance in C3 and C4 olefins production. Figure 2 charts the propylene yield at normalized unit conditions (same ROT, feed quality, feed rate and CAR) with increasing ZSM-5 crystal in the inventory. The results show clearly that at the same crystal content in the inventory, B.O.O.S.T. gives higher C3= yields than K-2000.

B.O.O.S.T. versus K-2000

The refinery started to add B.O.O.S.T. in the beginning of September 2006. Figure 1 charts the concentration of ZSM-5 additive in the equilibrium catalyst. It shows clearly how the ZSM-5 addition is concentrated in the winter fraction of each year. It can be observed that the level of ZSM-5 in the inventory in November 2006 was equal to that in January 2005, while ZSM-5 content in December 2005 was at a higher level.
8 Courier I Issue 68

Feb - 06

Feb - 07

FCC feedstock, operating objectives and constraints

By switching to B.O.O.S.T, the refinery has been able to reach higher performance on C3 and C4 olefins without increasing the amount of ZSM-5 additive in the inventory.

C3= corrected yield versus ZSM-5 crystal wt% Normalized conditions

7.5 82.2

MON on gasoline FBP 365oF versus ZSM-5 crystal wt% Normalized conditions

7.0 6.5

81.8

81.4

C3=, wt%

6.0 5.5 5.0 4.5

81.0

Cat A + B.O.O.S.T. Cat A + K-2000 (2004) Cat A + K-2000 (2005)

ZSM-5 crystal, wt%

80.6

Cat A + B.O.O.S.T. Cat A + K-2000 (2004) Cat A + K-2000 (2005)

80.2

ZSM-5 crystal, wt%

Figure 2: C3= yield versus ZSM-5 crystal content in inventory.

Figure 5: MON versus ZSM-5 crystal content in inventory.

B.O.O.S.T. also shows higher iC4= yields with the same crystal content in the inventory (Figure 3).
iC4= corrected yield versus ZSM-5 crystal wt% Normalized conditions
2.1

Analogous results have been observed in our laboratories through equlibrium catalyst analyses in the FST (fluidized simulation test). Figure 6 shows how at the same FST activity, the FST propylene yield with 5 wt% of B.O.O.S.T. is higher than the FST C3= yield reached with 5 wt% of K-2000.
FST C3= versus FST activity

1.7

iC4=, wt%

8 1.3

0.9

Cat A + B.O.O.S.T. Cat A + K-2000 (2004) Cat A + K-2000 (2005)

FST, wt%

0.5

ZSM-5 crystal, wt%

4 70.0 70.5 71.0 71.5

Cat A + 5 wt% B.O.O.S.T. Cat A + 5 wt% K-2000 (2004 - 2005)

72.0

72.5

73.0

73.5

Figure 3: iC4= yield versus ZSM-5 crystal content in inventory.

FST, wt%

Figures 4 and 5 illustrate the benefits achieved in RON and MON.

RON on gasoline FBP 365oF versus ZSM-5 crystal wt% Normalized condition
92

Figure 6: FST C3= versus FST activity.

A significant B.O.O.S.T. in refinery performance

By switching to B.O.O.S.T., the refinery has been able to reach higher performance on C3 and C4 olefins without increasing the amount of ZSM-5 additive in the inventory. These results have been achieved thanks to the higher intrinsic activity of the ZSM-5 crystal used in B.O.O.S.T., which achieves a relative increase in the C3= production of +2030% and in the iC4= production of +1012%.

91

90

89

Cat A + B.O.O.S.T. Cat A + K-2000 (2004) Cat A + K-2000 (2005)

ZSM-5 crystal, wt%

Figure 4: RON versus ZSM-5 crystal content in inventory.

Contact: Luca Moraca Email: luca.moraca@albemarle.com

Issue 68

Courier 9