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TABLE 3
HIGH RESOLUTION MASS SPECTRAL HYDROCARBON ANALYSIS FOR FEED MATERIAL
HYDROCARBON TYPE Z NUMBER 390 F.-455 F. 455 F.-510 F. 510 F.575 F. 575 F.-625 F. 625" F.-650 F.
PARAFFIN +2 11.2 14.8 18.0 20.3 20.6
4,640,764
7 8
TABLE 3-continued
man RESOLUTION MASS SPECTRAL HYDROCARBON ANALYSIS FOR FEED MATERIAL
HYDROCARBON TYPE 2 NUMBER 390' 12455 F. 455' F.SIO" F. 510' F.S75 F. 575' F.625' F. 625' F.-65o' F.
: o 19.2 24.7 29.6 26.8 26.6
: -2 45 4 23 6 11.3 14 5 14 2
: 6 4s 2.5 14 11 11
_ , _1o 03 0.3 49 s6 53
' : : - 12 o7 2.9 56 36 27
i?) - 14 ~ 02 2.3 13 1 15 o
: : : 18 12 35
NOT OBSERVED.
This data shows a surprisingly increased cetane value above target speci?cations, i.e. 40.0. In conclusion, this
for Catalyst A, B and C versus the original cetane value 30 data shows that current diesel fuel is hydrocracked and
of the feed. All cetane values derived from treatment hydrogenated to selectively eliminate tricyclic feed
with the platinum impregnated interlayered clay were components.
inured with unexpectedly high cetane qualities above In the lightest two fractions, hydrogenation rather
target speci?cations. In order to further analyze the than cracking is clearly the predominant reaction mech
results achieved in this case, the product produced from 35 anism. For example, in the 4555 10 F. fraction, the
Catalyst B was analyzed in detail. This analysis is set number of tetralins (Z: 8) is reduced while the num
forth in Table 5 as follows with feed data being shown her of dicyclic naphthenes (Z: 2) is increased. Again,
parenthetically. the tricyclic naphthenes (Z: 4) increase is attributed
TABLE 5
DISTILLATION AND CETANE NUMBER DATA FOR PRODUCT OF CATALYST B
DISTILLATION API GRAVITY WT. PERCENT CETANE A CETANE YIELD RELATIVE
curs F. @ 60' F. YIELD NUMBER NUMBER T0 FEED
11313-390 39.9 (35.6) 15.6 (5.3) * * 2.94
390-455 33.8 (30.4) 21.7 (22.2) 34.4 (26.9) 7.1 0.95
455-510 31.9 (28.1) 22.0 (22.7) 36.7 (27.3) 9.4 0.97
510-575 29.0 (24.9) 23.6 (24.3) 41.0 (31.6) 9.4 0.97
575-625 21.8 (28.2) 9.4 (14.1) 45.5 (33.1) 12.4 0.67
625-650 20.0 (30.1) 3.2 (5.2) 51.4 (35.1) 16.3 062
650+ 17.8 (30.9) 3.5 (5.0) ' ' 0.70
NOT MEASURED.
FEED DATA ARE SHOWN PARENTHETICALLY.
CETANE NUMBER CATALYST B COMPOSITE = 42.2.
CETANE REFERENCE = DECALIN = 36.5.
This data show that the greatest improvement in to the cascading of the hydrogenated products from
cetane quality occurs in the heaviest end of the feed and higher boiling fractions. In the fraction boiling between
then the amount of relative increase begins to decrease 55 390-455 F., a large increase is noted in the number of
as the product becomes lighter. The heavier ends also decalins (Z: 2) and a decrease in total tetralins
appear to have been hydroconverted to a much larger (Z: 8), while cetane quality is improved by the small
extent than the lighter fractions. The conversion data est amount of all the product fractions. In summation,
must also be analyzed with the knowledge that hydro- the cetane value of the higher boiling fractions are more
genation and/or cracking of the hydrocarbons results in 60 improved versus the smaller, yet unexpected improve
a cascading of hydrocarbon products to a lower boiling ment achieved in the lower boiling fractions.
fraction. In furtherance thereof, a high resolution mass
TABLE 6
HIGH RESOLUTION MASS SPECTRAL I-IYDROCARBON ANALYSIS FOR CATALYST B
HYDROCARBON TYPE Z NUMBER 390" F.455 F. 455 F.-5l0 F. 510 F.575 F. 575' F.625 F. 625 F.650 F.
PARAFFIN +2 9.0 (11.2) 16.3 (14.3) 13.7 (111.0) 27.6 (20.3) 33.5 (20.6)
4,640,764
11 12
TABLE (i-continued
HIGH RESOLUTION MASS SPECTRAL HYDROCARBON ANALYSIS FOR CATALYST B
HYDROCARBON TYPE Z NUMBER 390' F.-455' F. 455' F.-510' F. 510' F.-575 F. 575' F.-625' F. 625' F.-650' F.
O 16.1 (19.2) 18.5 (24.7) 17.6 (29.6) 19.9 (26.8) 17.8 (26.6)
(I ~2 60.1 (45.4) 30.2 (23.6) 14.3 (17.13) 16.0 (14.5) 16.5 (14.2)
G31 -4 3.3 (2.9) 17.9 (6.3) 33.3 (5.9) 13.6 (4.6) 8.8 (2.5)
CCU -6 4.9 (4.8) 4.7 (2.5) 3.4 (1.4) 4.8 (1.1) 3.8 (1.1)
-8 6.3 (15.4) 11.0 (24.1) 7.0 (13.9) 2.5 (3.3) 1.3 (1.6)
@O -
~10 3 (0.3) 0.3 (0.13) 3.6 (4.9) 10.9 (8.6) 7.9 (5.3)
_
: -12 3 (0.7) 0.4 (2.9) 0.9 (5.6) 2.1 (3.6) 4.8 (2.7)
(2(0) ~14 3 3 0.3 (0.2) 0.7 (2.8) 1.4 (13.1) 1.6 (15.0)
@210)
. _20 3 3 3 3 3 3 0.4 (3) 0.2 (0.2)
NOT OBSERVED.
I claim as my invention:
1. A selective hydrocracking and hydrogenation pro- 65
cess to upgrade the cetane value of a hydrocarbon distil paraf?ns, tetralins, decalins and undesirable tricyclic
late boiling in the range of from 300 to 700 F. and hydrocarbons which process comprises contacting said
containing C10 to C13 normal paraf?ns, C10 to C13 iso hydrocarbon distillate with a catalytic metal or metals
4,640,764
13 14
containing intercalated clay at hydrocracking and hy 16. The process of claim 1 wherein catalytic metal or
drogenation conversion conditions to selectively crack metals are placed in said intercalated clay by means of
said tricyclic hydrocarbons in preference to said C10 to ion exchange or impregnation.
C13 normal paraf?ns, Clo-C18 isoparaf?ns, tetralins and 17. The process of claim 1 wherein said catalytic
decalins and to produce a hydrocarbon distillate having metal or metals is present in a quantity of from about 0.5
an increased cetane value. to about 10 percent by weight.
2. The process of claim 1 wherein said hydrocarbon 18. The process of claim 1 wherein said hydrocrack
distillate is selected from the group consisting of a kero ing and hydrogenation conditions comprise a tempera
sene fuel, a turbine fuel and a diesel fuel. ture of from about 300 to 700 F., a pressure of from
3. The process of claim 2 wherein said diesel fuel has 700 to 2100 psig, a hydrogen content of about 30 to
a boiling point of from 300 to 550 F. and wherein said
about 75 SCFB and a weight hourly space velocity of
from about 0.5 to about 2.5.
increase in said cetane value is greater than 10 percent. 19. A process for the selective hydrocracking and
4. The process of claim 3 wherein said increase in said hydrogenation of tricylic hydrocarbons in the presence
cetane value is as high as 25 percent. of normal paraf?ns, isoparaf?ns, tetralins and decalins
5. The process of claim 1 wherein said tricyclic hy which comprises contacting an admixture of said hy
drocarbons comprise aromatic, cycloparaf?nic and drocarbon components, at hydrocracking and hydroge
combinations of aromatic and cycloparaf?nic mole nation conditions, including a temperature of from 300
cules. to 700 F ., a hydrogen pressure of from 700 to 2100 psig,
6. The process of claim 1 wherein said metal contain 20 a hydrogen content of 30 to 75 SCFB and a weight
ing intercalated clay comprises a synthetically layered hourly space velocity of from 0.5 to 2.5, with a pillared
bentonite clay. bentonite clay having channels formed therein as a
7. The process of claim 6 wherein said bentonite clay result of said pillaring, which channels contain metals
is layered by treatment of natural or synthetic bentonite having catalytic activity and which are selected from
clay by a layering agent comprising aluminum trichlo 25 the group consisting of metals chosen from Group VIII,
ride hydrate. Group VIB and combinations of metals from Group
8. The process of claim 6 wherein said bentonite clay VIII and Group VIB to selectively hydrocrack and
is layered to form a clay having multiple layers of clay hydrogenate said tricyclic hydrocarbons to hydrocar
selectively and uniformly separated by a multitude of bons having higher intrinsic cetane values in preference
heat stable pillars. to hydrocracking or hydrogenating said normal paraf
9. The process of claim 8 wherein said layers of clay ?n, isoparaf?n, tetralin and decalin hydrocarbons.
are uniformly separated by a distance of from 7 to 10 A 20. The process of claim 19 wherein said tricyclic
and which are receptive to said catalytic metal or met hydrocarbons comprise triaromatic hydrocarbons and
als. saturated cycloparaf?nic substituted naphthalene hy
10. The process of claim 9 wherein said catalytic 35 drocarbons and wherein said normal paraf?ns and iso
metal or metals are selected from Group VIII and
paraf?ns possess from 10 to 18 carbon atoms.
21. The process of claim 19 wherein said pillared
Group VIB of the Periodic Table. bentonite clay comprises silica pillars intercalated be
11. The process of claim 10 wherein said catalytically tween layers of an expandable, swelling layer, lattice
active metals are a combination of catalytically active clay mineral or synthetic analogue thereof, wherein said
metals selected from Group VIII and Group VIB of the silica pillars comprise at least two silicon atom layers.
Periodic Table. 22. The process of claim 19 wherein said intercalated
12. The process of claim 11 wherein said combination clay has layers separated by a distance of greater than 6
of catalytically active metals comprises a combination
of metals of Group VIII. 45 23. The process of claim 19 wherein said metals se
13. The process of claim 10 wherein said Group VIII lected from the combination of Group VIII and Group
catalytically active metal is platinum. VIB comprise nickel and molybdenum.
14. The process of claim 12 wherein said combination 24. The process of claim 19 wherein said metal se
of catalytically active metals comprises platinum and lected from Group VIII is platinum.
palladium. 25. The process of claim 19 wherein said combination
15. The process of claim 11 wherein said combination of Group VIII metals comprises platinum and palla
of catalytically active metals selected from Group VIB dium.
# i * it I!
and Group VIII comprises molybdenum and nickel.
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60
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