Bio-based olefin oligomerization with chabazite catalysts
A catalyst, chabazite technology, applied in the direction of catalyst regeneration/reactivation, catalyst, molecular sieve catalyst, etc., can solve the problems of poor cold flow characteristics, decreased fluidity, filter blockage, etc.
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Embodiment 1
[0064] Example 1: No Oxygenates and No Recycle Feed
[0065] Catalyst: Clariant TiAPSO-34, total WHSV=2; reactor top temperature 180-185°C; P(psig)=250; 2.9g Client TiAPSO-34 (granular particles)+glass beads; mass ratio=97.4%; Feed: 88% iC4, 6% cis-2-butene, 6% trans-2-butene.
[0066] As shown in Table 1 below, C 8 The percentage of oligomers is about 40%, C 12 The percentage of oligomers is about 50%. In addition, C 8 And the percentage of higher carbon chain (C8+) oligomers is about 95%. C 8 relative C 12 and larger oligomers with a selectivity of 0.69:1, and C 8 -C 24 The yield of hydrocarbons is greater than 95%. C 8 Hydrocarbon yield greater than 39%, C 12 The yield of hydrocarbons was greater than 49%.
[0067] Table 1: Reaction oligomer product distribution:
[0068] %C4 %C5-C7 %C8 %C9-C11 %C12 %C13-C15 %C16 %C20 %C24 3.96 0.42 39.04 0.35 49.26 0.12 6.43 0.41 0.01
Embodiment 2
[0069] Example 2: Presence of oxygenates and recycled feed
[0070] Catalyst: Clariant TiAPSO-34, total WHSV=3.2, recycle feed: the mass ratio of fresh feed is 3: 1; Reactor top product concentration 180-185 ℃, P (psig)=250; 2.9g Clariant TiAPSO-34 ( Granular particles) + glass microspheres; mass ratio = 97.0%; oxygenates in recycled feed: 200ppm water, 6070ppm (isobutanol and tert-butanol); feed: 88% iC4, 6% cis-2- Butene, 6% trans-2-butene.
[0071] Table 2 illustrates the distribution of carbon oligomers where the feed stream contains oxygenates such as alcohols and water and about 25% of the feed stream contains recycle feed. The recycle feed contains about 37% C 8 oligomers and about 47% C 12 Oligomer. In the recycle feed C 8 The percentage of + oligomers was greater than 92%, lower than the overall yield in Example 1. In the product stream, C 8 The amount of oligomers decreased slightly, while C 12 The amount of oligomers increased slightly. This example illustr...
Embodiment 3
[0077] Example 3: Extended On Time (TOS) in the Presence of Oxygenates and Multiple Catalyst Regenerations
[0078] Catalyst: Clariant TiAPSO-34, total WHSV=2.6, recycle feed: the mass ratio of fresh feed is 2: 1; Reactor top temperature 180-185 ℃, P (psig)=250; 2.9g Clariant TiAPSO-34 (granular Granules) + glass microspheres; typical mass proportion = 97.0%; total oxygenates in feed: 100 ppm water, 1800 ppm (mass ratio of isobutanol and tert-butanol is 85 / 15).
[0079] Table 3 below shows that C 8 and C 12+ The percentages of oligomers are in the range of 30%-45% and 50%-65%, respectively. Surprisingly, the catalyst can be used for at least 10 days without regeneration and still produce acceptable yields of C 8 and C 12 Oligomer. Also surprisingly, the catalyst is also regenerable in air and can be used for long periods of time without the need for regeneration. C 8 +Oligomer selectivity and high yield, long catalyst life without replacement and long catalyst regenerat...
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