Process for preparing low pour middle distillates and lube oil using a catalyst containing a silicoaluminophosphate molecular sieve

The present invention relates to a hydrocracking and isomerization process for preparing low pour point middle distillate hydrocarbons and lube oil from a hydrocarbonaceous feedstock boiling above about 600.degree. F. by contacting the feedstock with a catalyst containing an intermediate pore size silicoaluminophosphate molecular sieve and a hydrogenation component.

BACKGROUND OF THE INVENTION 
The present invention relates to a process for preparing low pour point 
middle distillate hydrocarbons and lube oil. More specifically, the 
invention relates to a hydrocracking and isomerization process for 
selectively preparing low pour point middle distillate hydrocarbons and 
lube oil from a hydrocarbonaceous feedstock boiling above about 600.F by 
contacting the feedstock with a catalyst comprising an intermediate pore 
size silicoaluminophosphate molecular sieve and a hydrogenation component. 
DESCRIPTION OF THE PRIOR ART 
Hydrocracking, used either in a one-step process or in a multi-step process 
coupled with hydrodenitrogenation and/or hydrodesulfurization steps, has 
been used extensively to upgrade poor-quality feeds and produce middle 
distillate materials. Over the years, much work has been done to develop 
improved cracking conditions and catalysts. Tests have been carried out 
using catalysts containing only amorphous materials and catalysts 
containing zeolites composited with amorphous materials. 
Large pore size zeolites such as zeolites X and Y are presently considered 
the most active hydrocracking catalysts. However, high activity is not the 
only essential characteristic of midbarrel cracking in catalysts. 
Midbarrel selectivity, namely, the percentage of total conversion 
accounted for by products boiling within the midbarrel range of from about 
300.degree. F. to about 725.degree. F. is also important. As noted in U.S. 
Pat. No. 3,853,742, many commercial midbarrel hydrocracking processes do 
not use zeolitic catalysts due to their relatively low midbarrel 
selectivity. 
Also, middle distillates conventionally serve as fuels such as diesel oils, 
jet fuels, furnace oils, and the like. For convenience in the handling and 
use of these middle distillates, it is desirable for the pour point to be 
as low as practical consistent with the temperatures to which they may be 
exposed. Specifications for these products often include a requirement 
that the pour point or freeze point not exceed a certain maximum value. In 
some instances, it is necessary to subject these distillate fuels to 
additional processing, the principle purpose of which is to reduce the 
pour point of the feed stream. Pour point can also be lowered by lowering 
the distillate end point, however this reduces yield. 
As noted in U.S. Pat. No. 4,486,296, although zeolite catalysts have been 
employed in hydrocracking processes and may be effective in providing 
distillate yields having one or more properties consistent with the 
intended use of the distillate, these catalysts suffer the disadvantage of 
providing product yields that do not have good low temperature fluidity 
characteristics, particularly reduced pour point and viscosity. 
The prior art has utilized a separate dewaxing process to reduce the pour 
point of middle distillates wherein selective intermediate pore size 
zeolites such as ZSM-5 (U.S. Pat. No. RE. 28,398), and ZSM-23 (European 
Patent Application No. 0092376) are employed. 
Other methods in the art for producing middle distillates possessing 
acceptable viscosity and pour point properties include processes wherein 
the hydrocarbon feeds are concurrently or sequentially subjected to 
hydrocracking and dewaxing in a continuous process using a large pore size 
zeolite hydrocarbon cracking catalyst such as zeolite X or zeolite Y and 
an intermediate pore size zeolite dewaxing catalyst such as ZSM-5 (U.S. 
Pat. No. 3,758,402). 
These processes have two drawbacks. The first is that while the pour point 
is reduced, the viscosity is increased, possibly above acceptable limits. 
The second drawback is that the process operates by cracking wax primarily 
to light products (e.g., C.sub.3 -C.sub.4) thereby significantly reducing 
distillate yield. PCT International Application WO86/03694 discloses a 
hydrocracking process to produce high octane gasoline using a catalyst 
comprising silicoaluminophosphates, either alone or in combination with 
traditional hydrocracking catalysts such as zeolite aluminosilicates. 
As set forth in co-pending application Ser. No. 07/002,087, now U.S. Pat. 
No. 4,859,312 applicant has discovered that middle distillate products can 
be selectively produced in a simplified process over a single catalyst in 
high yields which exhibit reduced pour points and viscosities as compared 
to prior art processes. Applicant has found that heavy hydrocarbon oils 
may be simultaneously hydrocracked and hydrodewaxed to produce a midbarrel 
liquid product of improved yield and satisfactory pour point and viscosity 
by using a catalyst containing an intermediate pore size 
silicoaluminophosphate molecular sieve component and a hydrogenation 
component to promote isomerization. 
High-quality lubricating oils are critical for the machinery of modern 
society. Unfortunately, the supply of natural crude oils having good 
lubricating properties, e.g., Pennsylvania and Arabian Light feedstocks, 
is not enough to meet present demands. Additionally, because of 
uncertainties in world crude oil supplies, it is necessary to be able to 
produce lubricating oils efficiently from ordinary crude feedstocks. 
Numerous processes have been proposed to produce lubricating oils by 
upgrading the ordinary and low-quality stocks which ordinarily would be 
converted into other products. 
The desirability of upgrading a crude fraction normally considered 
unsuitable for lubricant manufacture into one from which good yields of 
lube oils can be obtained has long been recognized. Hydrocracking 
processes have been proposed to accomplish such upgrading. U.S. Pat. Nos. 
3,506,565, 3,637,483 and 3,790,472 teach hydrocracking processes for 
producing lubricating oils. 
Hydrocracked lubricating oils generally have an unacceptably high pour 
point and require dewaxing. The bottoms from distilling the hydrocracked 
product are generally recycled back to the hydrocracker for further 
conversion to lower boiling products. It would be of utility if the 
hydrocracking process produced a distillation bottoms fraction of low pour 
point and high viscosity index which could therefore be used as a lube 
oil. 
Solvent dewaxing is a well-known and effective process but is expensive. 
More recently, catalytic methods for dewaxing have been proposed. U.S. 
Pat. No. Re. 28,398 discloses dewaxing petroleum charge stocks using ZSM-5 
type zeolites. U.S. Pat. No. 3,755,145 discloses a process for preparing 
low pour point lube oils by hydrocracking a lube oil stock using a 
catalyst mixture comprising a conventional cracking catalyst and ZSM-5. 
It has also been suggested that in order to improve the oxidation 
resistance of lubricants it is often necessary to hydrogenate or 
hydrofinish the oil after hydrocracking, with and without catalytic 
dewaxing as illustrated in U.S. Pat. Nos. 4,325,805; 4,347,121; 4,162,962; 
3,530,061; and 3,852,207. U.S. Pat. Nos. 4,283,272 and 4,441,097 teach 
continuous processes for producing dewaxed lubricating oil base stocks 
including hydrocracking a hydrocarbon feedstock, catalytically dewaxing 
the hydrocrackate and hydrofinishing the dewaxed hydrocrackate. These 
patents teach the use of catalysts comprising zeolite ZSM-5 and ZSM-23, 
respectively, for the dewaxing phase. 
European Patent Application No. 225,053 discloses a process for producing 
lubricant oils of low pour point and high viscosity index by partially 
dewaxing a lubricant base stock by isomerization using a large pore, high 
silica zeolite dewaxing catalyst followed by a selective dewaxing step. 
The prior art does not provide a process whereby both low pour 
mid-distillate hydrocarbons and lube oil can be prepared in the same 
reactor. 
Generally, the high boiling bottoms from distilling the hydrocracked 
product are high in pour point and therefore are of limited value without 
further processing. These bottoms therefore are generally recycled back to 
the hydrocracker for further conversion to lower boiling products. It 
would be of utility if the hydrocracking process were to produce a 
distillation bottoms fraction of low pour point and high viscosity index 
which could therefore be used as a lube oil. 
SUMMARY OF THE INVENTION 
The present invention overcomes the disadvantages of the prior art by 
providing a process for simultaneously preparing low pour and freeze point 
mid-distillate hydrocarbons and low pour point lube oil base stock in the 
same reactor. 
It is an object of the invention to provide a process for preparing both 
low pour mid-distillates and lube oil base stock wherein the amount of 
bottoms recycled is reduced or eliminated thereby providing increased 
throughput. 
It is a further object of the invention to provide a process for producing 
low pour middle distillate hydrocarbons and low pour, high viscosity index 
lube oil in the same reactor. 
Additional objects and advantages of the invention will be set forth in 
part in the description which follows, and in part will be obvious from 
the description or may be learned by practice of the invention. The 
objects and advantages of the invention will be realized and attained by 
means of the instrumentalities and combinations, particularly pointed out 
in the appended claims. 
To achieve the objects and in accordance with the purpose of the invention, 
as embodied and broadly described herein, the invention provides a process 
for selectively preparing low pour middle distillate hydrocarbons and low 
pour, high viscosity index, low viscosity lube oil comprising (a) 
contacting under hydrocracking conditions a hydrocarbonaceous feed wherein 
at least about 90% of said feed has a boiling point greater than about 
600.degree. F., with a catalyst comprising an intermediate pore size 
silicoaluminophosphate molecular sieve and at least one hydrogenation 
component; (b) recovering a hydrocarbonaceous effluent wherein greater 
than about 40% by volume of said effluent (1) boils above 300.degree. F. 
and below from about 675.degree. F. to about 725.degree. F. (2) and has a 
pour point below about 0.degree. F.; and (c) distilling the 
hydrocarbonaceous effluent to produce a first fraction containing middle 
distillate products having a boiling point below from about 675.degree. F. 
to about 725.degree. F., and a second fraction containing a lube oil 
having a boiling point above about 700.degree. F. 
In the process of the invention, the hydrocarbon feedstock is contacted 
with the intermediate pore size silicoaluminophosphate molecular sieve 
catalyst under conversion conditions appropriate for hydrocracking. During 
conversion, the aromatics and naphthenes present in the feedstock undergo 
hydrocracking reactions such as dealkylation, ring opening, and cracking, 
followed by hydrogenation. The long-chain paraffins present in the 
feedstock undergo mild cracking reactions to yield non-waxy products of 
higher molecular weight than products obtained using prior art dewaxing 
zeolitic catalysts such as ZSM-5. At the same time, a measure of 
isomerization occurs so that not only is the pour point reduced by the 
cracking reactions described above, but in addition, the n-paraffins 
become isomerized to isoparaffins to form liquid-range materials which 
contribute to low viscosity, low pour point products. In the bottoms 
portion of the effluent, a measure of hydrocracking and isomerization 
takes place which contributes not only to the low pour point and viscosity 
of the lube oil base stock but also to its high viscosity index, since 
isoparaffins are known to have high viscosity indices. 
The process of the invention enables heavy feedstock, such as gas oils, 
boiling above about 600.degree. F. to be more selectively converted to 
middle distillate range products having improved pour points than prior 
art processes using large pore catalysts, such as zeolite Y. Further, in 
the process of the invention, the consumption of hydrogen will be reduced 
even though the product will conform to the desired specifications for 
pour point and viscosity. Further, the process of the invention provides 
bottoms having a low pour point, low viscosity and high viscosity index 
which are suitable for use as lube oil. 
In comparison with prior art dewaxing processes using shape selective 
catalysts such as zeolite ZSM-5, the yields of the process of the 
invention will be improved and the viscosity kept acceptably low. The 
latter is ensured because the bulk conversion involves not only the 
cracking of low viscosity paraffins but high viscosity components (e.g., 
multi-ring naphthenes) as well. In addition, unlike the prior art ZSM-5 
catalyst, the process of the invention provides low pour point middle 
distillates and high viscosity index lube oil base stock due to a measure 
of isomerization which produces isoparaffins which contribute not only to 
the low pour point and viscosity, but also to the high viscosity index in 
the bottoms. Thus, the present process is capable of effecting bulk 
conversion together with simultaneous dewaxing. It is also possible to 
operate at partial conversion, thus effecting economies in hydrogen 
consumption while still meeting pour point and viscosity requirements. 
Overall, the present process reduces or eliminates the amount of bottoms 
recycled, thereby increasing throughput. 
The accompanying drawings, which are incorporated in and constitute a part 
of this specification illustrate several exemplary embodiments of this 
invention and together with the description, serve to explain the 
principles of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS 
Reference will now be made in detail to the preferred embodiments of 
applicant's invention. 
Feedstocks 
The feedstock for the process of the invention comprises a heavy 
hydrocarbon oil such as a gas oil, coker tower bottoms fraction, reduced 
crude, vacuum tower bottoms, deasphalted vacuum resids, FCC tower bottoms, 
or cycle oils. Oils of this kind generally boil above about 600.degree. F. 
(316.degree. C.) although the process is also useful with oils which have 
initial boiling points as low as 436.degree. F. (260.degree. C.). 
Preferably, at least 90% of the feed will boil above 600.degree. F. 
(316.degree. C.). Most preferably, at least about 90% of the feed will 
boil between 700.degree. F. (371.degree. C.) and about 1200.degree. F. 
(649.degree. C.). These heavy oils comprise high molecular weight 
long-chain paraffins and high molecular weight ring compounds with a large 
proportion of fused ring compounds. During processing, both the fused ring 
aromatics and naphthenes and paraffinic compounds are cracked by an 
intermediate pore size silicoaluminophosphate molecular sieve catalyst to 
middle distillate range products. A substantial fraction of the paraffinic 
components of the initial feedstock also undergo conversion to 
isoparaffins. 
The process is of particular utility with highly paraffinic feeds because 
with such feeds, the greatest improvement in pour point may be obtained. 
The degree of paraffinicity will depend to some degree on the viscosity 
index desired in the product. For example, when the paraffinic content is 
greater than about 50% by weight, a viscosity index of at least about 130 
can be obtained. The higher the paraffinic content, the higher the 
viscosity index. Preferably, the paraffinic content of the feed employed 
is greater than about 20% by weight, more preferably greater than about 
40% by weight. The most preferable paraffinic content of the feed will be 
determined by the viscosity index requirements of the product. 
The feedstocks employed in the process of the present invention may be 
subjected to a hydrofining and/or hydrogenation treatment, which may be 
accompanied by some hydrocracking, prior to use in the present process. 
Silicoaluminophosphate Molecular Sieve Catalysts 
As set forth above, the process of the invention combines elements of 
hydrocracking and isomerization. The catalyst employed in the process has 
an acidic component and a hydrogenation component. The acidic component 
comprises an intermediate pore size silicoaluminophosphate molecular sieve 
which is described in U.S. Pat. No. 4,440,871, the pertinent disclosure of 
which is incorporated herein by reference. 
Among other factors, the present invention is based on my discovery that 
the use of a catalyst containing a silicoaluminophosphate intermediate 
pore size molecular sieve and a Group VIII metal in a hydrocracking and 
isomerization reaction of hydrocarbonaceous feeds boiling above about 
600.degree. F. results in unexpectedly high yields of middle distillates 
and lube oil base stock having excellent pour point characteristics. 
The most preferred intermediate pore size silicoaluminophosphate molecular 
sieve for use in the process of the invention is SAPO-11. When combined 
with a hydrogenation component, the SAPO-11 produces a midbarrel liquid 
product and a lube oil base stock of improved yields and satisfactory pour 
point and viscosity. 
SAPO-11 comprises a silicoaluminophosphate material having a 
three-dimensional microporous crystal framework structure of [PO.sub.2 ], 
[AlO.sub.2 ]and [SiO.sub.2 ] tetrahedral units whose unit empirical 
formula on an anhydrous basis is: 
EQU mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2 (I) 
wherein "R" represents at least one organic templating agent present in the 
intracrystalline pore system; "m" represents the moles of "R" present per 
mole of (Si.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 
about 0.3, "x", "y" and "z" represent respectively, the mole fractions of 
silicon, aluminum and phosphorus, said mole fractions being within the 
compositional area bounded by points A, B, C, D and E on the ternary 
diagram of FIG. 1 or preferably within the area bounded by points a, b, c, 
d and e on the ternary diagram of FIG. 2. The silicoaluminophosphate 
molecular sieve has a characteristic X-ray powder diffraction pattern 
which contains at least the d-spacings (as-synthesized and calcined) set 
forth below in Table I. When SAPO-11 is in the as-synthesized form, "m" 
preferably has a value of from 0.02 to 0.3. 
TABLE I 
______________________________________ 
Relative 
2.THETA. d Intensity 
______________________________________ 
9.4-9.65 9.41-9.17 
m 
20.3-20.6 4.37-4.31 
m 
21.0-21.3 4.23-4.17 
vs 
22.1-22.35 4.02-3.99 
m 
22.5-22.9 (doublet) 
3.95-3.92 
m 
23.15-23.35 3.84-3.81 
m-s 
______________________________________ 
All of the as-synthesized SAPO-11 compositions for which X-ray powder 
diffraction data have been obtained to date have patterns which are within 
the generalized pattern of Table II below. 
TABLE II 
______________________________________ 
2.THETA. d 100 .times. I/I.sub.o 
______________________________________ 
8.05-8.3 10.98-10.65 
20-42 
9.4-9.65 9.41-9.17 36-58 
13.1-13.4 6.76-6.61 12-16 
15.6-15.85 5.68-5.59 23-38 
16.2-16.4 5.47-5.40 3-5 
18.95-19.2 4.68-4.62 5-6 
20.3-20.6 4.37-4.31 36-49 
21.0-21.3 4.23-4.17 100 
22.1-22.35 4.02-3.99 47-59 
22.5-22.9 (doublet) 
3.95-3.92 55-60 
23.15-23.35 3.84-3.81 64-74 
24.5-24.9 (doublet) 
3.63-3.58 7-10 
26.4-26.8 (doublet) 
3.38-3.33 11-19 
27.2-27.3 3.28-3.27 0-1 
28.3-28.5 (shoulder) 
3.15-3.13 11-17 
28.6-28.85 3.121-3.094 
29.0-29.2 3.079-3.058 
0-3 
29.45-29.65 3.033-3.013 
5-7 
31.45-31.7 2.846-2.823 
7-9 
32.8-33.1 2.730-2.706 
11-14 
34.1-34.4 2.629-2.607 
7-9 
35.7-36.0 2.515-2.495 
0-3 
36.3-36.7 2.475-2.449 
3-4 
37.5-38.0 (doublet) 
2.398-2.368 
10-13 
39.3-39.55 2.292-2.279 
2-3 
40.3 2.238 0-2 
42.2-42.4 2.141-2.132 
0-2 
42.8-43.1 2.113-2.099 
3-6 
44.8-45.2 (doublet) 
2.023-2.006 
3-5 
45.9-46.1 1.977-1.969 
0-2 
46.8-47.1 1.941-1.929 
0-1 
48.7-49.0 1.870-1.859 
2-3 
50.5-50.8 1.807-1.797 
3-4 
54.6-54.8 1.681-1.675 
2-3 
55.4-55.7 1.658-1.650 
0-2 
______________________________________ 
Another intermediate pore size silicoaluminophosphate molecular siever 
preferably employed in the process of this invention is SAPO-31. SAPO-31 
comprises a silicoaluminophosphate material having a three-dimensional 
microporous crystal framework of [PO.sub.2 ], [AlO.sub.2 ] and [SiO.sub.2 
] tetrahedral units whose unit empirical formula on an anhydrous basis is: 
EQU mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2 
wherein R represents at least one organic templating agent present in the 
intracrystalline pore system; "m" represents the moles of "R" present per 
mole of (Si.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 
0.3; "x", "y" and "z" represent respectively, the mole fractions of 
silicon, aluminum and phosphorus, said mole fractions being within the 
compositional area bounded by points A, B, C, D and E on the ternary 
diagram of FIG. 1, or preferably within the area bounded by points a, b, 
c, d and e on the ternary diagram of FIG. 2. The silicoaluminophosphate 
has a characteristic X-ray powder diffraction pattern (as-synthesized and 
calcined) which contains at least the d-spacings set forth below in Table 
III. When SAPO-31 is in the as-synthesized form, "m" preferably has a 
value of from 0.02 to 0.3. 
TABLE III 
______________________________________ 
Relative 
2.THETA. d Intensity 
______________________________________ 
8.5-8.6 10.40-10.28 
m-s 
20.2-20.3 4.40-4.37 m 
21.9-22.1 4.06-4.02 w-m 
22.6-22.7 3.93-3.92 vs 
31.7-31.8 2.823-2.814 
w-m 
______________________________________ 
All of the as-synthesized SAPO-31 compositions for which X-ray powder 
diffraction data have presently been obtained have patterns which are 
within the generalized pattern of Table IV below. 
TABLE IV 
______________________________________ 
2.THETA. d 100 .times. I/I.sub.o 
______________________________________ 
6.1 14.5 0-1 
8.5-8.6* 10.40-10.28 
60-72 
9.5* 9.31 7-14 
13.2-13.3* 6.71-6.66 1-4 
14.7-14.8 6.03-5.99 1-2 
15.7-15.8* 5.64-5.61 1-8 
17.05-17.1 5.20-5.19 2-4 
18.3-18.4 4.85-4.82 2-3 
20.2-20.3 4.40-4.37 44-55 
21.1-21.2* 4.21-4.19 6-28 
21.9-22.1* 4.06-4.02 32-38 
22.6-22.7* 3.93-3.92 100 
23.3-23.35* 3.818-3.810 
2-20 
25.1* 3.548 3-4 
25.65-25.75 3.473-3.460 
2-3 
26.5* 3.363 1-4 
27.9-28.0 3.198-3.187 
8-10 
28.7* 3.110 0-2 
29.7 3.008 4-5 
31.7-31.8 2.823-2.814 
15-18 
32.9-33.0* 2.722-2.714 
0-3 
35.1-35.2 2.557-2.550 
5-8 
36.0-36.1 2.495-2.488 
1-2 
37.2 2.417 1-2 
37.9-38.1* 2.374-2.362 
2-4 
39.3 2.292 2-3 
43.0-43.1* 2.103-2.100 
1 
44.8-45.2* 2.023-2.006 
1 
46.6 1.949 1-2 
47.4-47.5 1.918 1 
48.6-48.7 1.872-1.870 
2 
50.7-50.8 1.801-1.797 
1 
51.6-51.7 1.771-1.768 
2-3 
55.4-55.5 1.658-1.656 
1 
______________________________________ 
*Possibly contains peak from a minor impurity. 
SAPO-41, an intermediate pore size silicoaluminophosphate molecular sieve, 
also preferred for use in the process of the invention, comprises a 
silicoaluminophosphate material having a three-dimensional microporous 
crystal framework structure of [PO.sub.2 ], [AlO.sub.2 ] and [SiO.sub.2 ] 
tetrahedral units whose unit empirical formula on an anhydrous basis is: 
mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2 
wherein "R" represents at least one inorganic templating agent present in 
the intracrystalline pore system; "m" represents the moles of "R" present 
per mole of (Si.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from 
zero to 0.3; "x", "y", and "z" represent respectively, the mole fractions 
of silicon, aluminum and phosphorus, said mole fractions being within the 
compositional area bounded by points A, B, C, D and E on the ternary 
diagram of FIG. 1, or preferably within the area bounded by points a, b, 
c, d and e on the ternary diagram of FIG. 2, said silicoaluminophosphate 
having a characteristic X-ray powder diffraction pattern (as-synthesized 
and calcined) which contains at least the d-spacings set forth below in 
Table V. When SAPO-41 is in the as-synthesized form, "m" preferably has a 
value of from 0.02 to 0.3. 
TABLE V 
______________________________________ 
Relative 
2.THETA. d Intensity 
______________________________________ 
13.6-13.8 6.51-6.42 w-m 
20.5-20.6 4.33-4.31 w-m 
21.1-21.3 4.21-4.17 vs 
22.1-22.3 4.02-3.99 m-s 
22.8-23.0 3.90-3.86 m 
23.1-23.4 3.82-3.80 w-m 
25.5-25.9 3.493-3.44 
w-m 
______________________________________ 
All of the as-synthesized SAPO-41 compositions for which X-ray powder 
diffraction data have presently been obtained have patterns which are 
within the generalized pattern of Table VI below. 
TABLE VI 
______________________________________ 
2.THETA. d 100 .times. I/I.sub.o 
______________________________________ 
6.7-6.8 13.19-12.99 
15-24 
9.6-9.7 9.21-9.11 12-25 
13.6-13.8 6.51-6.42 10-28 
18.2-18.3 4.87-4.85 8-10 
20.5-20.6 4.33-4.31 10-32 
21.1-21.3 4.21-4.17 100 
22.1-22.3 4.02-3.99 45-82 
22.8-23.0 3.90-3.87 43-58 
23.1-23.4 3.82-3.80 20-30 
25.2-25.5 3.53-3.49 8-20 
25.5-25.9 3.493-3.44 
12-28 
29.3-29.5 3.048-3.028 
17-23 
31.4-31.6 2.849-2.831 
5-10 
33.1-33.3 2.706-2.690 
5-7 
37.6-37.9 2.392-2.374 
10-15 
38.1-38.3 2.362-2.350 
7-10 
39.6-39.8 2.276-2.265 
2-5 
42.8-43.0 2.113-2.103 
5-8 
49.0-49.3 1.856-1.848 
1-8 
51.5 1.774 0-8 
______________________________________ 
The above silicoaluminophosphates are generally synthesized by hydrothermal 
crystallization from a reaction mixture comprising reactive sources of 
silicon, aluminum and phosphorus, and one or more organic templating 
agents. Optionally, alkali metal(s) may be present in the reaction 
mixture. The reaction mixture is placed in a sealed pressure vessel, 
preferably lined with an inert plastic material, such as 
polytetrafluoroethylene, and heated, preferably under autogenous pressure 
at a temperature of at least about 100.degree. C., and preferably between 
100.degree. C. and 250.degree. C., until crystals of the 
silicoaluminophosphate product are obtained, usually for a period of from 
two hours to two weeks. While not essential to the synthesis of SAPO 
compositions, it has been found that in general, stirring or other 
moderate agitation of the reaction mixture and/or seeding of the reaction 
mixture with seed crystals of either the SAPO to be produced or a 
topologically similar composition, facilitates the crystallization 
procedure. The product is recovered by any convenient method such as 
centrifugation or filtration. 
After crystallization the SAPO may be isolated and washed with water and 
dried in air. As a result of the hydrothermal crystallization, the 
as-synthesized SAPO contains within its intracrystalline pore system at 
least one form of the template employed in its formation. Generally, the 
template is a molecular species, but it is possible, steric considerations 
permitting, that at least some of the template is present as a 
charge-balancing cation. Generally, the template is too large to move 
freely through the intracrystalline pore system of the formed SAPO and may 
be removed by a post-treatment process, such as by calcining the SAPO at 
temperatures of between about 200.degree. C. and about 700.degree. C. so 
as to thermally degrade the template, or by employing some other 
post-treatment process for removal of at least part of the template from 
the SAPO. In some instances the pores of the SAPO are sufficiently large 
to permit transport of the template, and, accordingly, complete or partial 
removal thereof can be accomplished by conventional desorption procedures 
such as are carried out in the case of zeolites. 
The SAPOs are preferably formed from a reaction mixture having a mole 
fraction of alkali metal cation that is sufficiently low to not interfere 
with the formation of the SAPO composition. Although the SAPO compositions 
will form if alkali metal cations are present, reaction mixtures, having 
the following bulk composition are preferred: 
EQU aR.sub.2 O(Si.sub.x Al.sub.y P.sub.z)O.sub.2 bH.sub.2 O 
wherein "R" is a template; "a" has a value great enough to constitute an 
effective concentration of "R" and is within the range of from greater 
than zero to about 3; "b" has a value of from zero to 500; "x", "y" and 
"z" represent the mole fractions, respectively, of silicon, aluminum and 
phosphorus wherein x, y and z each have a value of at least 0.01. The 
reaction mixture is preferably formed by combining at least a portion of 
the reactive aluminum and phosphorus sources in the substantial absence of 
the silicon source and thereafter combining the resulting reaction mixture 
comprising the aluminum and phosphorus sources with the silicon source. 
When the SAPOs are synthesized by this method the value of "m" is 
generally above about 0.02. 
Though the presence of alkali metal cations are not preferred, when they 
are present in the reaction mixture, it is preferred to first admix at 
least a portion of each of the aluminum and phosphorus sources in the 
substantial absence of the silicon source. This procedure avoids adding 
the phosphorus source to a highly basic reaction mixture containing the 
silicon and aluminum source. 
The reaction mixture from which these SAPOs are formed contain one or more 
organic templating agents (templates) which can be most any of those 
heretofore proposed for use in the synthesis of aluminosilicates. The 
template preferably contains at least one element of Group VA of the 
Periodic Table, more preferably nitrogen or phosphorus and most preferably 
nitrogen. The template contains at least one alkyl, aryl, araalkyl, or 
alkylaryl group. The template preferably contains from 1 to 8 carbon 
atoms, although more than eight carbon atoms may be present in the 
template. Nitrogen-containing templates are preferred, including amines 
and quaternary ammonium compounds, the latter being represented generally 
by the formula R'.sub.4 N+ wherein each R' is an alkyl, aryl, alkylaryl, 
or araalkyl group; wherein R' preferably contains from 1 to 8 carbon atoms 
or higher when R' is alkyl and greater than 6 carbon atoms when R' is 
otherwise. Polymeric quaternary ammonium salts such as [(C.sub.14 H.sub.32 
N.sub.2)(OH).sub.2 ].sub.x wherein "x" has a value of at least 2 may also 
be employed. The mono-, di- and tri-amines, including mixed amines, may 
also be employed as templates either alone or in combination with a 
quaternary ammonium compound or another template. 
Representative templates, phosphorus, aluminum and silicon sources as well 
as detailed process conditions are more fully described in U.S. Pat. No. 
4,440,871, which is incorporated herein by reference. 
The process of the invention may also be carried out by using a catalyst 
comprising an intermediate pore size nonzeolitic molecular sieve 
containing AlO.sub.2 and PO.sub.2 tetrahedral oxide units, and at least 
one Group VIII metal. Exemplary suitable intermediate pore size 
nonzeolitic molecular sieves are set forth in European Patent Application 
No. 158,977 which is incorporated herein by reference. 
The intermediate pore size molecular sieve is used in admixture with at 
least one Group VIII metal. Preferably, the Group VIII metal is selected 
from the group consisting of at least one of platinum and palladium, and 
optionally, other catalytically active metals such as molybdenum, nickel, 
vanadium, cobalt, tungsten, zinc, and mixtures thereof. More preferably, 
the Group VIII metal is selected from the group consisting of at least one 
of platinum and palladium. The amount of metal ranges from about 0.01% to 
about 10% by weight of the molecular sieve, preferably from about 0.2% to 
about 5% by weight of the molecular sieve. The techniques of introducing 
catalytically active metals into a molecular sieve are disclosed in the 
literature, and pre-existing metal incorporation techniques and treatment 
of the molecular sieve to form an active catalyst such as ion exchange, 
impregnation or occlusion during sieve preparation are suitable for use in 
the present process. Such techniques are disclosed in U.S. Pat. Nos. 
3,236,761; 3,226,339; 3,236,762; 3,620,960; 3,373,109; 4,202,996; 
4,440,781 and 4,710,485 which are incorporated herein by reference. 
The term "metal" or "active metal" as used herein means one or more metals 
in the elemental state or in some form such as sulfide, oxide and mixtures 
thereof. Regardless of the state in which the metallic component actually 
exists, the concentrations are computed as if they existed in the 
elemental state. 
The physical form of the catalyst depends on the type of catalytic reactor 
being employed and may be in the form of a granule or powder, and is 
desirably compacted into a more readily usable form (e.g., larger 
agglomerates), usually with a silica or alumina binder for fluidized bed 
reaction, or pills, prills, spheres, extrudates, or other shapes of 
controlled size to accord adequate catalyst-reactant contact. The catalyst 
may be employed either as a fluidized catalyst, or in a fixed or moving 
bed, and in one or more reaction stages. 
The intermediate pore size molecular sieve can be manufactured into a wide 
variety of physical forms. The molecular sieves can be in the form of a 
powder, a granule, or a molded product, such as an extrudate having a 
particle size sufficient to pass through a 2-mesh (Tyler) screen and be 
retained on a 40-mesh (Tyler) screen. In cases wherein the catalyst is 
molded, such as by extrusion with a binder, the silicoaluminophosphate can 
be extruded before drying, or dried or partially dried and then extruded. 
In a preferred embodiment, the final catalyst will be a composite and 
includes an intermediate pore size silicoaluminophosphate molecular sieve, 
a platinum or palladium hydrogenation metal component and an inorganic 
oxide matrix. The most preferred silicoaluminophosphate is SAPO-11, the 
most preferred metal component is palladium, and the most preferred 
support is alumina. A wide variety of procedures can be used to combine 
the molecular sieve and refractory oxide. For example, the molecular sieve 
can be mulled with a hydrogel of the oxide followed by partial drying if 
required and extruding or pelletizing to form particles of a desired 
shape. Alternatively, the refractory oxide can be precipitated in the 
presence of the molecular sieve. This is accomplished by increasing the pH 
of the solution of a refractory oxide precursor such as sodium aluminate 
or sodium silicate. The combination can then be partially dried as 
desired, tableted, pelleted, extruded, or formed by other means and then 
calcined, e.g., at a temperature above 600.degree. F. (316.degree. C.), 
usually above 800.degree. F. (427.degree. C.). Processes which produce 
larger pore size supports are preferred to those producing smaller pore 
size supports when cogelling. 
The molecular sieves may be composited with other materials resistant to 
temperatures and other conditions employed in the process. Such matrix 
materials include active and inactive materials and synthetic or naturally 
occurring zeolites as well as inorganic materials such as clays, silica 
and metal oxides. The latter may be either naturally occurring or in the 
form of gelatinous precipitates, sols or gels including mixtures of silica 
and metal oxides. Inactive materials suitably serve as diluents to control 
the amount of conversion in the hydrocracking process so that products can 
be obtained economically without employing other means for controlling the 
rate of reaction. The silicoaluminophosphate molecular sieve may be 
incorporated into naturally occurring clays, e.g., bentonite and kaolin. 
These materials, i.e., clays, oxides, etc., function, in part, as binders 
for the catalyst. It is desirable to provide a catalyst having good crush 
strength, because in petroleum refining, the catalyst is often subjected 
to rough handling. This tends to break the catalyst down into powder-like 
materials which cause problems in processing. 
Naturally occurring clays which can be composited with the catalyst include 
the montmorillonite and kaolin families, which families include the 
sub-bentonites, and the kaolins commonly known as Dixie, McNamee, Georgia 
and Florida clays or others in which the main mineral constituent is 
halloysite, kaolinite, dickite, nacrite or anauxite. Fibrous clays such as 
halloysite, sepiolite and attapulgite can also be used as supports. Such 
clays can be used in the raw state as originally mined or initially 
subjected to calcination, acid treatment or chemical modification. 
In addition to the foregoing materials, the molecular sieve can be 
composited with porous inorganic oxide matrix materials and mixtures of 
matrix materials such as silica, alumina, titania, magnesia, 
silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, 
silica-beryllia, silica-titania, titania-zirconia, as well as ternary 
compositions such as silica-alumina-thoria, silica-alumina-titania, 
silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in 
the form of a cogel. 
The hydrocracking step of the invention may be conducted by contacting the 
feed with a fixed stationary bed of catalyst, with a fixed fluidized bed, 
or with a transport bed. A simple and therefore preferred configuration is 
a trickle-bed operation in which the feed is allowed to trickle through a 
stationary fixed bed, preferably in the presence of hydrogen. 
The hydrocracking conditions employed depend on the feed used and the 
desired pour point. Generally, the temperature is from about 260.degree. 
C. to about 482.degree. C., preferably from about 316.degree. C. to about 
482.degree. C. The pressure is typically from about 200 psig to about 3000 
psig, preferably from about 500 psig to about 3000 psig. The liquid hourly 
space velocity (LHSV) is preferably from about 0.05 to about 20, more 
preferably from about 0.2 to about 10, most preferably from about 0.2 to 
about 5. 
Hydrogen is preferably present in the reaction zone during the 
hydrocracking process. The hydrogen to feed ratio is typically from about 
500 to about 30,000 SCF/bbl (standard cubic feet per barrel), preferably 
from about 1,000 to about 20,000 SCF/bbl. Generally, hydrogen will be 
separated from the product and recycled to the reaction zone. 
The crystalline catalyst used in the hydrocracking step provides selective 
conversion of the waxy components to non-waxy components as well as 
conversion of 700.degree. F. + boiling feed components to middle 
distillate hydrocarbons. During processing, isomerization of the oil 
occurs to reduce the pour point of the unconverted 700.degree. F.+ 
components below that of the feed and form a lube oil which has a low pour 
point and excellent viscosity index. 
Because of the selectivity of the intermediate pore size molecular sieve 
used in this invention, the yield of product boiling below middle 
distillate made by cracking is reduced, thereby preserving the economic 
value of the feedstock. 
Process Conditions 
Although the catalyst used in this method exhibits excellent stability, 
activity and midbarrel selectivity, reaction conditions must nevertheless 
be correlated to provide the desired conversion rates while minimizing 
conversion to less desired lower-boiling products. The conditions required 
to meet these objectives will depend on catalyst activity and selectivity 
and feedstock characteristics such as boiling range, as well as 
organonitrogen and aromatic content and structure. The conditions will 
also depend on the most judicious compromise of overall activity, i.e., 
conversion and selectivity. For example, these systems can be operated at 
relatively high conversion rates on the order of 70, 80 or even 90% 
conversion. However, higher conversion rates generally result in lower 
selectivity. Thus, a compromise must be drawn between conversion and 
selectivity. The balancing of reaction conditions to achieve the desired 
objectives is part of the ordinary skill of the art. 
The overall conversion rate is primarily controlled by reaction temperature 
and liquid hourly space velocity. However, selectivity is generally 
inversely proportional to reaction temperature. It is not as severely 
affected by reduced space velocities at otherwise constant conversion. 
Conversely, selectivity for pour point reduction of lube oil is usually 
improved at lower pressures. Thus, the most desirable conditions for the 
conversion of a specific feed to a predetermined product can be best 
obtained by converting the feed at several different temperatures, 
pressures, space velocities and hydrogen addition rates, correlating the 
effect of each of these variables and selecting the best compromise of 
overall conversion and selectivity. 
The conditions should be chosen so that the overall conversion rate will 
correspond to the production of at least about 40%, preferably at least 
about 50%, of the products boiling below from about 675.degree. F. 
(343.degree. C.) to about 725.degree. F. (385.degree. C.) in the middle 
distillate range. Midbarrel selectivity should be such that at least about 
40%, preferably at least about 50% of the product is in the middle 
distillate range, preferably below from about 675.degree. F. to about 
725.degree. F. and above about 300.degree. F. The process can maintain 
conversion levels in excess of about 50% at selectivities in excess of 60% 
to middle distillate products boiling between 300.degree. F. (149.degree. 
C.) and about 675.degree. F. (343.degree. C.) to about 725.degree. F. 
(385.degree. C.). Preferably, the hydrocarbonaceous effluent contains 
greater than about 40% by volume boiling above about 300.degree. F. and 
below from about 675.degree. F. to about 725.degree. F. and has a pour 
point below about 0.degree. F., more preferably below about -20.degree. F. 
The lube oil produced by the process of the invention has a low pour 
point, for example, below about 30.degree. F., and a high viscosity index, 
for example, from about 95 to about 150. In another embodiment, the pour 
point of the lube oil is from about 30.degree. F. to about -70.degree. F. 
The process can be operated as a single-stage hydroprocessing zone. It can 
also be the second stage of a two-stage hydrocracking scheme in which the 
first stage removes nitrogen and sulfur from the feedstock before contact 
with the middle distillate-producing catalyst. 
Nitrogen Content of Feedstocks 
While the process herein can be practiced with utility when the feed 
contains organic nitrogen (nitrogen-containing impurities), for example as 
much as several thousand parts per million by weight of organic nitrogen, 
it is preferred that the organic nitrogen content of the feed be less than 
50 ppmw, more preferably less than 10 ppmw. Particularly good results, in 
terms of activity and length of catalyst cycle (period between successive 
regenerations or start-up and first regeneration), are I0 obtained when 
the feed contains less than -0 ppmw of organic nitrogen. This is 
surprising in view of the art (see, for example, U.S. Pat. No. 3,894,938). 
Sulfur Content Feedstocks 
The presence of organic sulfur (sulfur-containing impurities) in the 
feedstock does not appear to deleteriously affect the desired 
hydrocracking of the feed, for example, in terms of activity and catalyst 
life. In fact, hydrodesulfurization of the feed of organic sulfur is in 
large part a significant concurrent reaction. However, the resulting 
product will usually contain at least some thiols and/or thioethers as a 
result of inter-reaction of hydrogen sulfide and olefinic hydrocarbons in 
the effluent product stream. Thus, it may be desirable in some instances 
that the feed prior to use in the process herein by hydrofined or 
hydrotreated for at least substantial removal of both organic sulfur- and 
nitrogen-containing compounds. 
Upstream hydrodenitrogenation can be performed in the reactor with the 
molecular sieve-containing catalyst or preferably in a separate reactor. 
When a separate hydrodenitrogenation reactor is used, it may be desirable 
to remove, e.g., flash, light gaseous products such as NH3 upstream of the 
reactor containing the molecular sieve-containing catalyst. If the 
hydrotreating is performed in the same reactor, the molecular 
sieve-containing catalyst is disposed in one or more layers downstream of 
an active hydrodenitrogenation catalyst. The single reactor should 
preferably be operated under hydrotreating conditions sufficient to reduce 
the organic nitrogen of the feed to 10 ppmw or less before the feed 
encounters the molecular sieve-containing layer. The volume of 
hydrodenitrogenation catalyst relative to molecular sieve-containing 
catalyst can vary over a wide range, such as from about 0.1 to 1 to 20 to 
1, preferably at least 0.2 to 1 and more preferably at least 0.5 to 1. The 
ratio depends upon such parameters as: (a) the organic nitrogen content of 
the feedstock; (b) the hydrodenitrogenation and hydrocracking activities 
of the upstream hydrotreating catalyst; and (c) the degree of overall 
hydrocracking desired. 
The upstream hydrotreating catalysts can be any of the conventional 
catalysts having hydrodenitrogenation and hydrocracking activity. See, for 
example, U.S. Pat. No. 3,401,125 incorporated herein by reference. In 
general, such hydrotreating catalysts are porous composites or inorganic 
matrix oxides such as alumina, silica, and magnesia, which contain one or 
more hydrogenation components such as transition elements, particularly 
elements of Group VIB or Group VIII of the Periodic Table of the Elements. 
Handbook of Chemistry and Physics, 45th Ed., Chemical Rubber Company. The 
Group VIB and/or Group VIII or other transition elements can be present as 
metals, oxides, or sulfides. The hydrotreating catalyst can also contain 
promoters such as phosphorus, titanium and other materials known in the 
art, present as metals, oxides or sulfides. The upstream hydrotreating 
catalyst need not contain a silicoaluminophosphate component. Typical 
upstream hydrogenation catalysts suitable for use herein contain 10 to 30 
wt.% amorphous silica, 20 to 40 wt.% amorphous alumina, 15 to 30 wt.% 
Group VIB metal oxide, such as WO.sub.3, 5 to 15 wt.% Group VIII metal 
oxide, such as NiO and 2 to 15 wt.% of a promoter oxide, such as 
TiO.sub.2. The hydrotreating catalyst should have an average pore size in 
the range of about 30 to 200 Angstroms and a surface area of at least 
about 150 square meters per gram. 
Following the hydrocracking step over the silicoaluminophosphate catalyst, 
the middle distillate and lighter boiling products are separated from the 
lube oil base stock by distillation. It is often desirable to then treat 
this base stock by mild hydrogenation referred to as hydrofinishing to 
improve color and produce a more stable oil. Hydrofinishing is typically 
conducted at temperatures ranging from about 190.degree. C. to about 
340.degree. C., at pressures from about 400 psig to about 3000 psig, at 
space velocities (LHSV) from about 0.1 to about 20, and hydrogen recycle 
rates of from about 400 to about 15,000 SCF/bbl. The hydrogenation 
catalyst employed must be active enough not only to hydrogenate the 
olefins, diolefins and color bodies within the lube oil fractions, but 
also to reduce the aromatic content. The hydrofinishing step is beneficial 
in preparing an acceptably stable lubricating oil. 
Suitable hydrogenation catalysts include conventional metallic 
hydrogenation catalysts, particularly the Group VIII metals such as 
cobalt, nickel, palladium and platinum. The metals are typically 
associated with carriers such as bauxite, alumina, silica gel, 
silica-alumina composites, and crystalline aluminosilicate zeolites. 
Palladium is a particularly preferred hydrogenation metal. If desired, 
non-noble Group VIII metals can be used with molybdates. Metal oxides or 
sulfides can be used. Suitable catalysts are disclosed in U.S. Pat. Nos. 
3,852,207; 4,157,294; 3,904,513 and 4,673,487, which are incorporated 
herein by reference. 
The high viscosity index lube oil produced by the process of the present 
invention can be used as a blending component to raise the viscosity index 
of lube oils to a higher value. The lube oil is particularly suitable for 
use as a blending component when the lube oil has a high viscosity index, 
for example, greater than 130. Since yield decreases with increasing 
viscosity index in either hydrocracking or solvent refining, the use of an 
ultra-high viscosity oil to increase the viscosity index improves yield. 
The invention will be further clarified by the following examples, which 
are intended to be purely exemplary of the invention. 
EXAMPLE 1 
SAPO-11 was prepared as described below and identified as such by x-ray 
diffraction analysis. More specifically, 115.6 g of 85% H.sub.3 PO.sub.4 
were added to 59 g of H.sub.2 O and cooled in an ice bath. To this were 
slowly added 204.2 g of aluminum isopropoxide ([(CH.sub.3).sub.2 
CHO].sub.3 Al) and mixed until homogeneous. 120 g of H.sub.2 O were added 
to 30 g of Cab-O-Sil M-5 silica and the mixture added to the above with 
mixing until homogeneous. 45.6 g of di-n-propylamine were then slowly 
added with mixing, again until homogeneous. Synthesis was carried out in a 
Teflon bottle in an autoclave at 200.degree. C. for 5 days. 
The anhydrous molar composition of the calcined sieve was 
EQU 0.4 SiO.sub.2 :Al.sub.2 O.sub.3 :P.sub.2 O.sub.5 
The sieve was bound with 35% Catapal alumina and made into 1/10-inch 
extrudate. The extrudate was dried in air for 4 hours at 250.degree. F., 
then calcined 2 hours at 450.degree. F. and 2 hours at 1000.degree. F. The 
extrudate was then impregnated by the pore-fill method with 0.5 wt.% Pd 
using an aqueous solution of Pd(NH.sub.3).sub.4 (N03).sub.2. The catalyst 
was dried for 2 hours at 250.degree. F., then calcined in air for two 
hours at 450.degree. F. and two hours at 900.degree. F. It was then 
crushed to 24-42 mesh. 
EXAMPLE 2 
The catalyst of Example 1 was used to hydrocrack a hydrodenitrified vacuum 
gas oil (Table VII) at 700.degree. F., 2200 psig, 1.3 LHSV, and 8M SCF/bbl 
once-through H.sub.2 at a conversion below 725.degree. F. of 60 wt.%, 
where percent conversion is defined as 
##EQU1## 
Inspections of the 725.degree. F.- products are given in Table VIII. 
Inspections of the 725.degree. F.+ products are given in Table IX, showing 
this oil to have both very high VI and very low pour point. 
TABLE VII 
______________________________________ 
Hydrodenitrified Vacuum Gas Oil 
______________________________________ 
Gravity, .degree.API 
38.2 
Aniline Point, .degree.F. 
246.4 
Sulfur, ppm 1.0 
Nitrogen, ppm 1.8 
Pour Point, .degree.F. 
+125 
Distillation, ASTM D1160, .degree.F. 
ST/5 688/732 
10/30 751/782 
50 815 
70/90 856/928 
95/EP 966/1024 
______________________________________ 
TABLE VIII 
______________________________________ 
Inspections of 725.degree. F. - Product from Hydrocracking 
Hydrodenitrified Vacuum Gas Oil over Pd/SAPO-11 at 
700.degree. F., 2200 psig, 1.3 LHSV, and 8M SCF/bbl H.sub.2 
______________________________________ 
Conversion &lt;725.degree. F., Wt. % 
60 
Product Selectivity, Wt. % 
C.sub.4 - 10.6 
C.sub.5 -230.degree. F. 
14.0 
230-284.degree. F. 6.2 
284-482.degree. F. 22.4 
482-725.degree. F. 46.8 
482-725.degree. F. 
Pour Point, .degree.F. 
-55 
Distillation, D86, LV %, .degree.F. 
ST/10 467/522 
30/50 572/618 
70/90 646/673 
EP 712 
______________________________________ 
TABLE IX 
______________________________________ 
Inspections of 725.degree. F. + Product from 
Hydrocracking Hydrodenitrified Vacuum Gas 
Oil over Pd/SAPO-11 at 700.degree. F., 2200 psig, 
1.3 LHSV, 8M SCF/bbl H.sub.2 and 60% Conversion &lt;725.degree. F. 
______________________________________ 
Pour Point, .degree.F. 
-30 
Cloud Point, .degree.F. 
0 
Viscosity, St, 40.degree. C. 
25.76 
100.degree. C. 5.172 
VI 135 
Simulated Distillation, LV %, .degree.F. 
ST/5 718/733 
10/30 745/784 
50 822 
70/90 872/963 
95/99 1007/1085 
______________________________________ 
EXAMPLE 3 
A. Comparative Example 
The hydrodenitrified vacuum gas oil of Table VII was hydrocracked over a 
sulfided cogelled nickel-tungsten-silica-alumina catalyst containing 7.7 
wt.% Ni and 19.4 wt.% W. The conditions were a catalyst temperature of 
670.degree. F., a reactor pressure of 2200 psig, a liquid hourly space 
velocity (LHSV) of 1.3, and a once-through hydrogen rate of 8 MSCF/bbl. 
The conversion below 700.degree. F. was 56 wt.%, where percent conversion 
is defined as 
##EQU2## 
The liquid product was distilled into fractions boiling in the following 
ranges: C.sub.5 --230.degree. F., 230-284.degree. F., 284-482.degree. F., 
482-698.degree. F., and 698.degree. F.+, where the middle distillate 
fractions are those with the ranges 284-482.degree. F. and 482-698.degree. 
F. The yields of the 698.degree. F.-fractions are shown in FIG. 3, which 
shows a diesel (482-698.degree. F.) yield of 36 wt.%. The inspections of 
the diesel cut are given in Table X below, showing a pour point of 
+5.degree. F. 
B. SAPO-11 was prepared as described below and identified as such by X-ray 
diffraction analysis. More specifically, 115.6 g of 85% H.sub.3 PO.sub.4 
were added to 59 g of H.sub.2 O. To this were slowly added 204.2 g of 
aluminum isoproxide ([(CH.sub.3).sub.2 CHO].sub.3 Al) and mixed until 
homogeneous. 8 g of H.sub.2 O were added to 60.2 g of Ludox AS-30 (30% 
silica aqueous sol) and the mixture slowly added to the above with mixing 
until homogeneous. 45.6 g of di-n-propylamine were then slowly added with 
mixing, again until homogeneous. Synthesis was carried out in a Teflon 
bottle in an autoclave at 150.degree. C. for 5 days. 
The anhydrous molar composition of the calcined sieve was 
EQU 0.2SiO.sub.2 :Al.sub.2 O.sub.3 :P.sub.2 O.sub.5 
The sieve was bound with 35% catapal alumina and made into 1/10-inch 
extrudate. The extrudate was dried in air for 4 hours at 250.degree. F., 
then calcined 2 hours at 450.degree. F. and 2 hours at 1000.degree. F. The 
extrudate was then impregnated by the pore-fill method with 0.5 wt.% Pd 
using an aqueous solution of Pd(NH.sub.3).sub.4 (N03).sub.2. The catalyst 
was dried for 2 hours at 250.degree. F., then calcined in air for two 
hours at 450.degree. F. and two hours at 900.degree. F. It was then 
crushed to 24-42 mesh and used to hydrocrack the feed of the above example 
at 750.degree. F., 2200 psig, 1.0 LHSV, and 8M SCF/bbl once-through 
H.sub.2 to give 44 wt.% conversion below 700.degree. F. Product yields are 
compared to those for the Comparative Example catalyst in FIG. 3 showing 
the 482-698.degree. F. diesel yield to be 7 wt.% higher. The inspections 
of the diesel cut are given in Table X below showing a pour point of 
-40.degree. F. 
C. The catalyst of Example B was also run at 750.degree. F., 1.3 LHSV, 2200 
psig, and 8M SCF/bbl once-through H.sub.2 to give 47 wt.% conversion below 
725.degree. F. The diesel end point was extended from 698.degree. F. to 
725.degree. F., thereby increasing diesel yield another 11 wt.%. Despite 
the higher end point, the pour point was still exceedingly low 
(-50.degree. F.). The inspections of the diesel cut are given in Table X 
below. 
TABLE X 
______________________________________ 
Diesel Cut from Hydrocracking 
Hydrodenitrified Vacuum Gas Oil 
______________________________________ 
Catalyst Ni--W/ Pd/SAPO-11 Pd/SAPO-11 
SiO.sub.2 --Al.sub.2 O.sub.3 
Conversion, Wt. % 
56&lt;700.degree. F. 
44&lt;700.degree. F. 
47&lt;725.degree. F. 
Selectivity, Wt. % 
35.8 42.5 53.4 
Selectivity to Total 
64.7 75.4 77.3 
Middle Distillate, 
Wt. % 
Pour Point, .degree.F. 
+5 -40 -50 
Cloud Point, .degree.F. 
+34 -20 -14 
Calculated 81.7 78.7 78.3 
Cetane Index 
Distillation, D86, 
LV %, .degree.F. 
ST/10 474/508 480/510 481/526 
30/50 541/576 540/572 578/623 
70/90 612/645 604/640 647/666 
EP 691 690 693 
______________________________________ 
EXAMPLE 4 
SAPO-5 was grown according to U.S. Pat. No. 4,440,871 and identified as 
such by X-ray diffraction analysis. The anhydrous molar composition of the 
calcined sieve was 
EQU 0.1SiO.sub.2 :Al.sub.2 O.sub.3 :P.sub.2 O.sub.5 
The sieve was extruded with 35% Catapal alumina, impregnated with 0.5 wt.% 
Pd, and calcined in the same manner as the catalyst of Example 3B. This 
catalyst was then used to hydrocrack the same vacuum gas oil at 1.3 LHSV, 
2200 psig, and 8M SCF/bbl once-through H.sub.2. At 775.degree. F., the 
conversion below 725.degree. F. was 51 wt.%. The product yields are given 
in Table XI. The pour point of the 482-725.degree. F. diesel cut was 
+48.degree. F. 
TABLE XI 
______________________________________ 
Diesel Cut from Hydrocracking Hydrodenitrified 
Vacuum Gas Oil over Pd/SAPO-5 at 51%&lt; 725.degree. F. 
______________________________________ 
Selectivity, Wt. % 47.0 
Pour Point, .degree.F. 
+48 
Cloud Point, .degree.F. 
+61 
Calculated Cetane Index 
83.1 
Distillation, D86, LV %, .degree.F. 
ST/10 486/523 
30/50 570/617 
70/90 645/669 
EP 713 
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EXAMPLE 5 
To further show the uniqueness of SAPO-11 in hydrocracking for low pour 
middle distillates, the following two catalysts were tested for dewaxing a 
+ 100.degree. F. pour point lube oil (Table XII) to +30.degree. F. pour 
point at 1 LHSV, 2200 psig, and 8M SCF/bbl H.sub.2. 
EXAMPLE 5 
(a) 0.8 wt. % Pt impregnated on HZSM-5 bound with 35% Catapal alumina. 
(b) 1.0 wt. % Pt impregnated on SAPO-11 bound with 35% Catapal alumina. 
FIG. 4 shows that while ZSM-5 catalyst dewaxed the feed, it produced 
essentially no 350-800.degree. F. liquid, making mostly C.sub.3 
-350.degree. F. The SAPO-11 catalyst, on the other hand, produced mainly 
liquid boiling in the 350-800.degree. F. range. 
TABLE XII 
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+100.degree. F. Pour Point Lube Oil 
______________________________________ 
Gravity, .degree.API 34.0 
Aniline Point, .degree.F. 
244.0 
Sulfur, ppm 0.4 
Nitrogen, ppm 0.1 
Pour Point, .degree.F. 
+100 
Viscosity, cS, 100.degree. C. 
6.195 
Flash Point, .degree.F. 
420 
P/N/A/S, LV % 25.0/62.1/12.8/0 
Simulated Distillation, LV %, .degree.F. 
ST/5 313/770 
10/30 794/841 
50 873 
70/90 908/968 
95/EP 998/1061 
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