Method for conversion of waste plastics to lube oil

The invention includes a process of making a lubricating oil composition including: a process for making a high VI lubricating oil composition including the steps of (1) contacting a waste plastics feed including mainly polyethylene in a pyrolysis zone at pyrolysis conditions, whereby at least a portion of the waste plastics feed is cracked, thereby forming a pyrolysis zone effluent including 1-olefins and n-paraffins; (2) passing the pyrolysis zone effluent, including a heavy fraction and a middle fraction, the pyrolysis effluent middle fraction including 1-olefins, to a separations zone; where the pyrolysis effluent heavy fraction portion is separated from the pyrolysis effluent middle fraction; (3) passing the pyrolysis effluent heavy fraction to a hydrogenation zone; and (4) passing at least a portion of the hydrogenation zone effluent to a catalytic isomerization dewaxing zone, where at least a portion of the hydrogenation zone effluent is contacted with a isomerization dewaxing catalyst at isomerization dewaxing conditions thereby forming a high VI lubricating oil composition.

FIELD OF THE INVENTION 
The present invention relates to a process for making a lubricating 
composition and other useful products from polymers/plastics, especially 
from waste polymers/plastics, particularly polyethylene. 
BACKGROUND OF THE INVENTION 
Manufacturers of mechanical and hydraulic equipment regularly increase the 
viscometric requirements for lubricating compositions used in such 
equipment. These increases are driven by a desire for reduced maintenance 
and lubricating composition replacement, a desire for and laws and 
regulations for reduced environmental emissions, and by the closer 
tolerances of moving parts, higher operating temperatures, and other 
changes in new equipment designs. 
Manufacturing a lubricating composition that meets more stringent 
viscometric requirements is typically more expensive than manufacturing a 
lubricating composition meeting less stringent viscometric requirements. 
This may be due to both a higher priced feed to such a process and 
additional or more expensive processing involved in such manufacturing. A 
high viscosity index ("VI") is a key measure of a superior lubricating 
composition. "High VI" is defined in detail later in this specification. 
High VI lubricating compositions have traditionally been manufactured 
synthetically from polymers. The addition of polymeric VI improvers also 
has been traditionally employed to improve the VI performance of mineral 
oils. These are expensive ways, however, to obtain a lubricating 
composition having a high VI. 
It would be advantageous to have a relatively inexpensive process for 
producing high VI lubricating compositions. Such a process would ideally 
utilize a readily available inexpensive feedstock. Waste plastics/polymers 
have been used in known processes for the manufacture of some synthetic 
hydrocarbons, typically fuels or other polymers. 
According to the latest report from the Office of Solid Waste, USEPA, about 
62% of plastic packaging in the U.S. is made of polyethylene, the 
preferred feed for a plastics to lubes process. Equally important, 
plastics waste (after recycling) is the fastest growing waste product with 
about 18 million tons/yr in 1995 compared to only 4 million tons/yr in 
1970. This presents a unique opportunity, not only to acquire a useful 
source of high quality lube, but also address a growing environmental 
problem at the same time. 
Dewaxing is required when highly paraffinic oils are to be used in products 
which need to remain mobile at low temperatures, e.g., lubricating oils, 
heating oils and jet fuels. The higher molecular weight straight chain 
normal and slightly branched paraffins which are present in oils of this 
kind are waxes which cause high pour points and high cloud points in the 
oils. If adequately low pour points are to be obtained, these waxes must 
be wholly or partly removed. 
Methods are known for upgrading to lubricating compositions various waxy 
feeds by dewaxing. Various solvent removal techniques are known, such as 
propane dewaxing and MEK dewaxing but these techniques are costly and time 
consuming. Solvent dewaxing removes waxes by dissolving them in the 
solvent, then separating the solvent containing the dissolved wax from the 
lube oil range material. Where a major portion of the feed is wax, solvent 
dewaxing leaves only the minor portion of lube oil remaining. 
Catalytic dewaxing, on the other hand, does not separate out waxes, but 
rather converts them to light products boiling below the lube oil range. 
The conversion is achieved by selectively cracking the longer chain waxy 
molecules to produce lower molecular weight products, some of which may be 
removed by distillation. Isomerization catalytic dewaxing is another form 
of catalytic dewaxing. It is superior to other dewaxing methods. 
Isomerization catalytic dewaxing achieves a lower pour point neither by 
removing the wax nor by cracking the wax. Rather, it achieves a lower pour 
point by isomerizing the wax. Isomerization dewaxing is taught in U.S. 
Pat. No. 5,135,638 (the '638 patent). However, the '638 patent does not 
teach the use of isomerization dewaxing for a feed derived from a waste 
plastics feed. 
EP patent application 0620264A2 discloses a process for making a lube oil 
from waste plastics. The process utilizes a cracking process in a 
fluidized bed of inert solids and fluidized with, e.g., nitrogen. The 
product of the cracking is hydrotreated over an alumina catalyst or other 
refractory metal oxide support containing a metal component, and then 
optionally catalytically isomerized. The overall yield, however, is lower 
than desired. The isomerization catalysts taught partially cause this 
result. There is no teaching of using better isomerization catalysts. 
Also, EP 0620264A2 does not teach a process of producing a high yield of 
heavy lube oils. 
It would be advantageous to have a process using readily available waste 
plastics to produce a high yield of high VI lubricating oil compositions, 
especially heavy high VI lubricating oil compositions. The process of the 
present invention meets this need. 
SUMMARY OF THE INVENTION 
The invention includes a process of making a lubricating oil composition 
including: a process for making a high VI lubricating oil composition 
including the steps of (1) contacting a waste plastics feed containing 
primarily polyethylene in a pyrolysis zone at pyrolysis conditions, 
whereby at least a portion of the waste plastics feed is cracked, thereby 
forming a pyrolysis zone effluent including 1-olefins and n-paraffins; (2) 
passing the pyrolysis zone effluent, including a heavy fraction and a 
pyrolysis effluent middle fraction (each defined in the detailed 
description), including normal alpha olefins, to a separations zone; where 
the pyrolysis effluent heavy fraction heavy fraction is separated from the 
pyrolysis effluent middle fraction; (3) passing the pyrolysis effluent 
heavy fraction to a hydrotreating zone; and (4) passing at least a portion 
of the hydrotreating zone effluent to a catalytic isomerization dewaxing 
zone, where at least a portion of the hydrotreating zone effluent is 
contacted with a isomerization dewaxing catalyst at isomerization dewaxing 
conditions, where at least a portion of the hydrotreating zone effluent is 
converted to a high VI lubricating oil composition.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
A. Process Overview 
FIG. 1 is a schematic flow drawing of one embodiment of the process of the 
invention. Waste PE feed stream 5 is fed to pyrolysis zone 10. The 
pyrolysis zone effluent 15 is passed to separations zone 20. The lube 
boiling range material in the pyrolysis zone effluent has a BP from about 
650.degree. F. to about 1200.degree. F. In separations zone 20 pyrolysis 
zone effluent 15 is separated into 2 or more streams as shown by 
350.degree. F.-boiling point ("BP") stream 22, i.e., light fraction, 
350-650.degree. F. BP stream 25, i.e., middle fraction, and 650.degree. 
F.+ BP stream 30, i.e., heavy fraction. Heavy fraction stream 30 is passed 
to hydrotreating zone 35, thereby producing hydrotreating zone effluent 
stream 40. Stream 40 is passed to catalytic isomerization dewaxing zone 
45. The isomerization dewaxing zone effluent 50 is a high VI lubricating 
oil composition. An additional separation zone (not shown) optionally 
follows isomerization zone 50 for fractionating the lube into fractions of 
various viscometric properties. 
B. Pyrolysis 
The first step in the process for making a high VI lubricating oil 
composition according to the invention is contacting a waste plastics feed 
containing polyethylene in a pyrolysis zone at pyrolysis conditions, where 
at least a portion of the waste plastics feed is cracked, thus forming a 
pyrolysis zone effluent comprising 1-olefins and n-paraffins. The 
percentage of 1-olefins in the pyrolysis zone effluent is optionally from 
about 25 to 75 wt. %, preferably from about 40-60 wt. %. Pyrolysis 
conditions include a temperature of from about 500-700.degree. C., 
preferably from about 600-700.degree. C. 
Conventional pyrolysis technology teaches operating conditions of 
above-atmospheric pressures. See, e.g., U.S. Pat. No. 4,642,401. It has 
been discovered that by adjusting the pressure downward, the yield of a 
desired product can be controlled. For a Neutral stock range lubricating 
oil composition, the pyrolysis zone pressure is about atmospheric, 
preferably from about 0.75 atm to about 1 atm. For a bright stock range 
lubricating composition, the pyrolysis zone pressure is preferably 
sub-atmospheric, preferably not greater than about 0.75 atmospheres or 0.5 
atmospheres. It has been discovered that sub-atmospheric pressures in the 
pyrolysis zone results in a greater yield of bright stock range 
lubricating composition, since the thermally cracked waste plastic goes 
overhead and out of the pyrolysis zone before secondary cracking can 
occur. 
The pyrolysis zone pressure is optionally controlled by vacuum or by 
addition of an inert gas (i.e., acts inert in the pyrolysis zone), e.g., 
selected from the group comprising nitrogen, hydrogen, steam, methane or 
recycled light ends from the pyrolysis zone. The inert gas reduces the 
partial pressure of the waste plastic gaseous product. It is this partial 
pressure which is of interest in controlling the weight of the pyrolysis 
zone product. 
The pyrolysis zone effluent (liquid portion) is very waxy and has a too 
high pour point. It comprises n-paraffins and some olefins. Further 
processing according to the invention is needed to convert it to a high VI 
lubricating oil composition. 
The feed may contain some contaminants normally associated with waste 
plastics, e.g., paper labels and metal caps. Typically, from about 80 wt. 
% to about 100 wt. % of the waste plastics feed consists essentially of 
polyethylene, preferably about 95 wt. % to about 100 wt. %. Typically, the 
feed is prepared by grinding to a suitable size for transport to the 
pyrolysis unit using any conventional means for feeding solids to a 
vessel. Optionally, the ground waste plastics feed is also heated and 
initially dissolved in a solvent. The heated material is then passed by an 
auger, or other conventional means, to the pyrolysis unit. After the 
initial feed, a portion of the heated liquefied feed from the pyrolysis 
zone is optionally removed and recycled to the feed to provide a heat 
source for dissolving the feed. 
The feed may contain chlorine, preferably less than about 20 ppm. 
Preferably, a substantial portion of any chlorine in the feed is removed 
by the addition to the feed of a chlorine scavenger compound, e.g., sodium 
carbonate. It reacts in the pyrolysis zone with the chlorine to form 
sodium chloride which becomes part of the residue at the bottom of the 
pyrolysis zone. Preferably, the chlorine content is removed to less that 
about 5 ppm. 
C. Separations Step 
The pyrolysis zone effluent typically contains a broad boiling point range 
of materials. The pyrolysis zone effluent is passed to a conventional 
separations zone, e.g., distillation column; where it is separated in 
typically at least three fractions, a light, middle, and heavy fraction. 
The light fraction contains, e.g., 350.degree. F.-BP, gasoline range 
material, and gases. The middle fraction is typically a middle distillate 
range material, e.g., diesel fuels range, e.g., 350-650.degree. F. BP. The 
heavy fraction is lube oil range material, e.g., 650.degree. F.+ BP. All 
fractions contain n-paraffins and 1-olefins. 
D. Hydrotreating 
Prior to catalytic isomerization dewaxing, the pyrolysis effluent is 
preferably hydrotreated to remove compounds, e.g., N, S or O containing 
compounds, that could deactivate the isomerization dewaxing catalyst or 
produce an unstable lubricating oil composition, e.g., color instability. 
Hydrotreating is typically conducted by contacting the pyrolysis effluent 
heavy fraction with a hydrotreating catalyst at hydrotreating conditions. 
A conventional catalytic hydrotreating process may be used. 
The hydrotreating is done under conditions to remove substantially all 
heteroatoms, while minimizing cracking. Typically, hydrotreating 
conditions include temperatures ranging from about 190.degree. C. to about 
340.degree. C., pressures of from about 400 psig to about 3000 psig, space 
velocities (LHSV) of from about 0.1 to about 20, and hydrogen recycle 
rates of from about 400 to about 15000 SCF/bbl. 
Suitable hydrogenation catalysts include conventional, metallic 
hydrogenation catalysts, particularly the Group VIII metals such as Co, 
Mo, Ni, and W. The metals are typically associated with carriers such as 
bauxite, alumina, silica gel, silica-alumina composites, and crystalline 
aluminosilicate zeolites and other molecular sieves. If desired, non-noble 
Group VIII metals can be used with molybdates or tungstates. Metal oxides, 
e.g., nickel/cobalt promoters, or sulfides can be used. Suitable catalysts 
are disclosed in U.S. Pat. Nos. 3,852,207; 4,157,294; 4,921,594; 3,904,513 
and 4,673,487, the disclosures of which are incorporated herein by 
reference. The S and N levels of the hydrotreated pyrolysis effluent heavy 
fraction portion are preferably not greater that about 5 ppm S and 1 ppm 
N. 
E. Catalytic Isomerization Dewaxing 
The pyrolysis zone effluent (liquid portion) is very waxy and has a too 
high pour point. To reduce the pour point while maintaining high yield, 
the hydrotreating zone effluent is passed to a catalytic isomerization 
dewaxing zone. Optionally, the hydrotreating zone effluent is first passed 
to a second separations zone for separation out of the heaviest material, 
e.g., 1000.degree. F.+ BP. The fraction having a lower BP is the one sent 
to the isomerization dewaxing zone. The 1000.degree. F.+ BP fraction is 
the most difficult to isomerize. Thus, optionally, it is not isomerized, 
but is useful as a high grade heavy wax. 
For the portion of the hydrotreating zone effluent isomerized, after 
isomerization catalytic dewaxing, at least a portion of the feed to the 
isomerization catalytic dewaxing zone is converted to a high VI 
lubricating oil composition. Unlike solvent dewaxing which is a 
separations process, isomerization catalytic dewaxing converts the 
n-paraffins into iso-paraffins, thereby reducing the pour point to form a 
high VI lubricating oil composition with a much higher yield. Preferably, 
a portion of such high VI lubricating oil composition has a BP in the 
bright stock range (may be referenced as "composition in some of the 
claims portion of this specification). More preferably, a substantial 
portion (i.e., &gt;10 wt. %) or major portion (i.e., &gt;50 wt. %) has a BP in 
the bright stock range. The pour point (as measured by ASTM D97) of the 
high VI lubricating oil composition is not more than about 20.degree. F., 
preferably not more than about 15.degree. F. The cloud point (as measured 
by ASTM D2500) is preferably not more than about 10.degree. F. higher than 
the pour point. Preferably, either or both of the first and second high VI 
lubricating oil compositions include a lube fraction having a kinematic 
viscosity at 100.degree. C. of at least about 8 cSt. This and other 
fractions can be separated by conventional separation processes. 
Preferably the 8 cSt fraction is at least about 10 wt. % (a substantial 
portion), more preferably at least about 50 wt. % (a major portion) of the 
high VI lubricating composition. 
The isomerization catalytic dewaxing zone is operated as taught in U.S. 
Pat. No. 5,135,638, which disclosure is incorporated herein by reference. 
In brief, the dewaxing zone is practiced as discussed below. The process 
includes any solid catalyst capable of isomerization dewaxing. Preferably, 
the catalyst is an intermediate pore size molecular sieve. The phrase 
"intermediate pore size", as used herein, means an effective pore aperture 
in the range of from about 5.3 to about 6.5 Angstroms when the porous 
inorganic oxide is in the calcined form. Molecular sieves having pore 
apertures in this range tend to have unique molecular sieving 
characteristics. Unlike small pore zeolites such as erionite and 
chabazite, they will allow hydrocarbons having some branching into the 
molecular sieve void spaces. Unlike larger pore zeolites such as the 
faujasites and mordenites, they can differentiate between n-alkanes and 
slightly branched alkanes, and larger branched alkanes having, for 
example, quaternary carbon atoms. 
The effective pore size of the molecular sieves can be measured using 
standard adsorption techniques and hydrocarbonaceous compounds of known 
minimum kinetic diameters. See Breck, Zeolite Molecular Sieves, 1974 
(especially Chapter 8); Anderson et al., J. Catalysis 58, 114 (1979); and 
U.S. Pat. No. 4,440,871, the pertinent portions of which are incorporated 
herein by reference. 
In performing adsorption measurements to determine pore size, standard 
techniques are used. It is convenient to consider a particular molecule as 
excluded if it does not reach at least 95% of its equilibrium adsorption 
value on the molecular sieve in less than about 10 minutes (p/po=0.5; 
25.degree. C.). Intermediate pore size molecular sieves will typically 
admit molecules having kinetic diameters of 5.3 to 6.5 Angstroms with 
little hindrance. Examples of such compounds (and their kinetic diameters 
in Angstroms) are: n-hexane (4.3), 3-methylpentane (5.5), benzene (5.85), 
and toluene (5.8). Compounds having kinetic diameters of about 6 to 6.5 
Angstroms can be admitted into the pores, depending on the particular 
sieve, but do not penetrate as quickly and in some cases are effectively 
excluded. Compounds having kinetic diameters in the range of 6 to 6.5 
Angstroms include: cyclohexane (6.0), 2,3-dimethylbutane (6.1), and 
m-xylene (6.1). Generally, compounds having kinetic diameters of greater 
than about 6.5 Angstroms do not penetrate the pore apertures and thus are 
not absorbed into the interior of the molecular sieve lattice. Examples of 
such larger compounds include: o-xylene (6.8), 1,3,5-trimethylbenzene 
(7.5), and tributylamine (8.1). 
The preferred effective pore size range is from about 5.5 to about 6.2 
Angstroms. While the effective pore size as discussed above is important 
to the practice of the invention, not all intermediate pore size molecular 
sieves having such effective pore sizes are advantageously usable in the 
practice of the present invention. Indeed, it is essential that the 
intermediate pore size molecular sieve catalysts used in the practice of 
the present invention have a very specific pore shape and size as measured 
by X-ray crystallography. First, the intracrystalline channels must be 
parallel and must not be interconnected. Such channels are conventionally 
referred to as 1-D diffusion types or more shortly as 1-D pores. The 
classification of intrazeolite channels such as 1-D, 2-D and 3-D is set 
forth by R. M. Barrer in Zeolites, Science and Technology, edited by F. R. 
Rodrigues, L. D. Rollman and C. Naccache, NATO ASI Series, 1984, which 
classification is incorporated in its entirety by reference (see 
particularly page 75). Known 1-D zeolites include cancrinite hydrate, 
laumontite, mazzite, mordenite and zeolite L. 
None of the above listed 1-D pore zeolites, however, satisfies the second 
essential criterion for catalysts useful in the practice of the present 
invention. This second essential criterion is that the pores must be 
generally oval in shape, by which is meant the pores must exhibit two 
unequal axes referred to herein as a minor axis and a major axis. The term 
oval as used herein is not meant to require a specific oval or elliptical 
shape but rather to refer to the pores exhibiting two unequal axes. In 
particular, the 1-D pores of the catalysts useful in the practice of the 
present invention must have a minor axis between about 3.9 Angstroms and 
about 4.8 Angstroms and a major axis between about 5.4 Angstroms and about 
7.0 Angstroms as determined by conventional X-ray crystallography 
measurements. 
The catalyst used in the isomerization process of the invention has an 
acidic component and a platinum and/or palladium hydrogenation component. 
In accordance with one embodiment of the invention, the acidic component 
can suitably comprise 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. 
The most preferred intermediate pore size silicoaluminophosphate molecular 
sieve for use in the process of the invention is SAPO-11, especially SM-3 
(as taught in U.S. Pat. No. 5,208,005, which reference is incorporated 
herein by reference in its entirety). SAPO-11 comprises a molecular 
framework of corner-sharing [SiO.sub.2 ]tetrahedra, [AlO.sub.2 
]tetrahedra, and [PO.sub.2 ]tetrahedra, [i.e., (Si x Al y P z )O.sub.2 
tetrahedral units]. When combined with a platinum or palladium 
hydrogenation component, the SAPO-11 converts the waxy components to 
produce a lubricating oil having excellent yield, very low pour point, low 
viscosity and high viscosity index. 
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 x Al y P z)O.sub.2 (l) 
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 x Al y P 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 phosphorous. The silicoaluminophosphate 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(.ANG.) 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. 
These values were determined by standard techniques. The radiation was the 
K-alpha doublet of copper and a diffractometer equipped with a 
scintillation counter and an associated computer was used. The peak 
heights, I, and the positions as a function of 2 .theta., where .theta. is 
the Bragg angle, were determined using algorithms on the computer 
associated with the spectrometer. From these, the relative intensities, 
100 I/I.sub.o, where I is the intensity of the strongest line or peak, and 
d (obs.) the interplanar spacing in Angstroms, corresponding to the 
recorded lines, were determined. In the Tables, the relative intensities 
are given in terms of the symbols vs=very strong, s=strong, m=medium, 
w=weak, etc. 
TABLE II 
______________________________________ 
2.theta. d(.ANG.) 100 .times. I/I.sub.0 
______________________________________ 
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 sieve 
preferably used in the process of the invention is SAPO-31. SAPO-31 
comprises a silicoaluminophosphate 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: mR: (Si x Al 
y P 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 x Al y P 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 phosphorous. 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(.ANG.) 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 3.823-2.814 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(.ANG.) 100 .times. I/I.sub.0 
______________________________________ 
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. 
SAPO41, also suitable for use in the process of the invention, comprises a 
silicoaluminophosphate having a three-dimensional microporous crystal 
framework structure of [PO.sub.2 ], [AlO.sub.2 ] and [SiO.sub.2 
]tetrahedral units, and whose unit empirical formula on an anhydrous basis 
is: mR: (Si x Al y P 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 x Al y P 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 phosphorous. The 
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 0.03. 
TABLE V 
______________________________________ 
Relative 
2.theta. d(.ANG.) 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 SAPO41 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(.ANG.) 100 .times. I/I.sub.0 
______________________________________ 
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 process of the invention may also be carried out using a catalyst 
comprising an intermediate pore size non-zeolitic 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 
non-zeolitic molecular sieves are set forth in European patent Application 
No. 158,977 which is incorporated herein by reference. 
The group of intermediate pore size zeolites of the present invention 
include ZSM-22, ZSM-23, SSZ-32 (as taught in U.S. Pat. No. 5,252,527, 
which reference is incorporated herein by reference in its entirety), and 
ZSM-35. These catalysts are generally considered to be intermediate pore 
size catalysts based on the measure of their internal structure as 
represented by their Constraint Index. Zeolites which provide highly 
restricted access to and egress from their internal structure have a high 
value for the Constraint Index, while zeolites which provide relatively 
free access to the internal zeolite structure have a low value for their 
Constraint Index. The method for determining Constraint Index is described 
fully in U.S. Pat. No. 4,016,218 which is incorporated herein by 
reference. 
Those zeolites exhibiting a Constraint Index value within the range of from 
about 1 to about 12 are considered to be intermediate pore size zeolites. 
Zeolites which are considered to be in this range include ZSM-5, ZSM-11, 
etc. Upon careful examination of the intermediate pore size zeolites, 
however, it has been found that not all of them are efficient as a 
catalyst for isomerization of a paraffin-containing feedstock which are 
high in C.sub.20 + paraffins, and preferably which are high in C.sub.22 + 
paraffins. In particular, it has been found that the group including 
ZSM-22, ZSM-23 and ZSM-35 used in combination with Group VIII metals can 
provide a means whereby a hydrocarbon feedstock having a paraffinic 
content with molecules of 20 carbon atoms or more undergoes unexpectedly 
efficient isomerization without destroying the ultimate yield of the 
feedstock. 
It is known to use prior art techniques for formation of a great variety of 
synthetic aluminosilicates. These aluminosilicates have come to be 
designated by letter or other convenient symbols. One of the zeolites of 
the present invention, ZSM-22, is a highly siliceous material which 
includes crystalline three-dimensional continuous framework silicon 
containing structures or crystals which result when all the oxygen atoms 
in the tetrahedra are mutually shared between tetrahedral atoms of silicon 
or aluminum, and which can exist with a network of mostly SiO.sub.2, i.e., 
exclusive of any intracrystalline cations. The description of ZSM-22 is 
set forth in full in U.S. Pat. No. 4,556,477, U.S. Pat. No. 4,481,177, and 
European Patent Application No.102,716, the contents of which are 
incorporated herein by reference. 
As indicated in U.S. Pat. No. 4,566,477, the crystalline material ZSM-22 
has been designated with a characteristic X-ray diffraction pattern as set 
forth in Table VII. 
TABLE VII 
______________________________________ 
Most Significant Lines of ZSM-22 
Interplanar d-spacings (.ANG.) 
Relative Intensity (I/I.sub.0) 
______________________________________ 
10.9 +/- 0.2 M-VS 
8.7 +/- 0.16 W 
6.94 +/- 0.10 W-M 
5.40 +/- 0.08 W 
4.58 +/- 0.07 W 
4.36 +/- 0.07 VS 
3.68 +/- 0.05 VS 
3.62 +/- 0.05 S-VS 
3.47 +/- 0.04 M-S 
3.30 +/- 0.04 W 
2.74 +/- 0.02 W 
2.52 +/- 0.02 W 
______________________________________ 
It should be understood that the X-ray diffraction pattern of Table VII is 
characteristic of all the species of ZSM-22 zeolite compositions. Ion 
exchange of the alkali metal cations with other ions results in a zeolite 
which reveals substantially the same X-ray diffraction pattern with some 
minor shifts in interplanar spacing and variation in relative intensity. 
Furthermore, the original cations of the as-synthesized ZSM-22 can be 
replaced at least in part by other ions using conventional ion exchange 
techniques. It may be necessary to pre-calcine the ZSM-22 zeolite crystals 
prior to ion exchange. In accordance with the present invention, the 
replacement ions are those taken from Group VIII of the Periodic Table, 
especially platinum, palladium, iridium, osmium, rhodium and ruthenium. 
ZSM-22 freely sorbs normal hexane and has a pore dimension greater than 
about 4 Angstroms. In addition, the structure of the zeolite provides 
constrained access to larger molecules. The Constraint Index as determined 
by the procedure set forth in U.S. Pat. No. 4,016,246 for ZSM-22 has been 
determined to be from about 2.5 to about 3.0. 
Another zeolite which can be used with the present invention is the 
synthetic crystalline aluminosilicate referred to as ZSM-23, disclosed in 
U.S. Pat. No.4,076,842, the contents of which are incorporated herein by 
reference. The ZSM-23 composition has a characteristic X-ray diffraction 
pattern as set forth herein in Table VIII. 
Other molecular sieves which can be used with the present invention 
include, for example, Theta-1, as described in U.S. Pat. Nos. 4,533,649 
and 4,836,910, both of which are incorporated in their entireties by 
reference, Nu-10, as described in European Patent Application 065,400 
which is incorporated in its entirety by reference and SSZ-20 as described 
in U.S. Pat. No. 4,483,835 which is incorporated in its entirety by 
reference. 
TABLE VIII 
______________________________________ 
d(.ANG.) I/I.sub.0 
______________________________________ 
11.2 +/- 0.23 
M 
10.1 +/- 0.20 W 
7.87 +/- 0.15 W 
5.59 +/- 0.10 W 
5.44 +/- 0.10 W 
4.90 +/- 0.10 W 
4.53 +/- 0.10 S 
3.90 +/- 0.08 VS 
3.72 +/- 0.08 VS 
3.62 +/- 0.07 VS 
3.54 +/- 0.07 M 
3.44 +/- 0.07 S 
3.36 +/- 0.07 W 
3.16 +/- 0.07 W 
3.05 +/- 0.06 W 
2.99 +/- 0.06 W 
2.85 +/- 0.06 W 
2.54 +/- 0.05 M 
2.47 +/- 0.05 W 
2.40 +/- 0.05 W 
2.34 +/- 0.05 W 
______________________________________ 
The ZSM-23 composition can also be defined in terms of mole ratios of 
oxides in the anhydrous state as follows: 
EQU (0.58-3.4)M.sub.2 /.sub.n O: Al.sub.2 O.sub.3 : (40-250)SiO.sub.2 
wherein M is at least 1 cation and n is the valence thereof. As in the 
ZSM-22, the original cations of as-synthesized ZSM-23 can be replaced in 
accordance with techniques well known in the art, at least in part by 
ionic exchange with other cations. In the present invention, these cations 
include the Group VIII metals as set forth hereinbefore. 
The third intermediate pore size zeolite which has been found to be 
successful in the present invention is ZSM-35, which is disclosed in U.S. 
Pat. No. 4,016,245, the contents of which are incorporated herein by 
reference. The synthetic crystalline aluminosilicate known as ZSM-35 has a 
characteristic X-ray diffraction pattern which is set forth in U.S. Pat. 
No. 4,016,245. ZSM-35 has a composition which can be defined in terms of 
mole ratio of oxides in the anhydrous state as follows: 
EQU (0.3-2.5)R.sub.2 O: (0-0.8)M.sub.2 O:Al.sub.2 O3:&gt;8SiO.sub.2 
wherein R is organic nitrogen-containing cation derived from 
ethylenediamine or pyrrolidine and M is an alkali metal cation. The 
original cations of the as-synthesized ZSM-35 can be removed using 
techniques well known in the art which includes ion exchange with other 
cations. In the present invention, the cation exchange is used to replace 
the as-synthesized cations with the Group VIII metals set forth herein. It 
has been observed that the X-ray diffraction pattern of ZSM-35 is similar 
to that of natural ferrierite with a notable exception being that natural 
ferrierite patterns exhibit a significant line at 1.33 Angstroms. 
X-ray crystallography of SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23 and 
ZSM-35 shows these molecular sieves to have the following major and minor 
axes: SAPO-11, major 6.3 Angstroms, minor 3.9 Angstroms; (Meier, W. M., 
Olson, D. H., and Baerlocher, Ch., Atlas of Zeolite Structure Types, 
Elsevier, 1996), SAPO-31 and SAPO-41, believed to be slightly larger than 
SAPO-11, ZSM-22, major 5.5 Angstroms, minor 4.5 Angstroms (Kokotailo, G. 
T., et al, Zeolites, 5, 349(85)); ZSM-23, major 5.6 Angstroms, minor 4.5 
Angstroms; ZSM-35, major 5.4 Angstroms, minor 4.2 Angstroms (Meier, W. M. 
and Olsen, D. H., Atlas of Zeolite Structure Types, Butterworths, 1987). 
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. Most 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 preexisting 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 catalyst may also contain metals which reduce the number of strong acid 
sites on the catalyst and thereby lower the selectivity for cracking 
versus isomerization. Especially preferred are the Group IIA metals such 
as magnesium and calcium. 
It is preferred that relatively small crystal size catalyst be utilized in 
practicing the invention. Suitably, the average crystal size is no greater 
than about 10 mu, preferably no more than about 5 mu, more preferably no 
more than about 1 mu, and still more preferably no more than about 0.5 mu. 
Strong acidity may also be reduced by introducing nitrogen compounds, e.g., 
NH.sub.3 or organic nitrogen compounds, into the feed; however, the total 
nitrogen content should be less than 50 ppm, preferably less than 10 ppm. 
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 catalytic isomerization 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 catalytic isomerization conditions employed depend on the feed used and 
the desired pour point. Generally, the temperature is from about 
200.degree. C. to about 475.degree. C., preferably from about 250.degree. 
C. to about 450.degree. C. The pressure is typically from about 15 psig 
and to about 2000 psig, preferably from about 50 to about 1000 psig, more 
preferably from about 100 psig to about 600 psig. The process of the 
invention is preferably carried out at low pressure. The liquid hourly 
space velocity (LHSV) is preferably from about 0.1 to about 20, more 
preferably from about 0.1 to about 5, and most preferably from about 0.1 
to about 1.0. Low pressure and low liquid hourly space velocity provide 
enhanced isomerization selectivity which results in more isomerization and 
less cracking of the feed thus producing an increased yield. 
Hydrogen is preferably present in the reaction zone during the catalytic 
isomerization 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 10,000 SCF/bbl. Generally, hydrogen will be 
separated from the product and recycled to the reaction zone. 
The intermediate pore size molecular sieve used in the isomerization step 
provides selective conversion of the waxy components to non-waxy 
components. During processing, isomerization of the paraffins occurs to 
reduce the pour point of the oil below that of the feed and form lube oil 
boiling range materials which contribute to a low pour point product 
having excellent viscosity index properties. Because of the selectivity of 
the intermediate pore size molecular sieve used in the invention, the 
yield of low boiling products is reduced, thereby preserving the economic 
value of the feedstock. 
The intermediate pore size molecular sieve catalyst 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. 
The molecular sieve can be composited with other materials resistant to 
temperatures and other conditions employed in the isomerization 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 isomerization 
process so that products can be obtained economically without employing 
other means for controlling the rate of reaction. The 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 
powderlike materials which cause problems in processing. 
Naturally occurring clays which can be composited with the molecular sieve 
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, diokite, nacrite or anauxite. Fibrous clays such 
as halloysite, sepiolite and attapulgite can also be use 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 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-aluminatitania, silica-alumina-magnesia and 
silica-magnesia-zirconia. The matrix can be in the form of a cogel. 
The catalyst used in the process of this invention can also be composited 
with other zeolites such as synthetic and natural faujasites, (e.g., X and 
Y) erionites, and mordenites. It can also be composited with purely 
synthetic zeolites such as those of the ZSM series. The combination of 
zeolites can also be composited in a porous inorganic matrix. 
It is often desirable to use mild hydrogenation referred to as 
hydrofinishing after isomerization to produce more stable lubricating 
oils. 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 1500 
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 (color 
bodies). 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. Since yield decreases with increasing 
viscosity index in either hydrocracking or solvent refining, the use of an 
isomerized wax to increase the viscosity index improves yield. 
F. High Viscosity Index Lubricating Oil Composition 
The process of the invention includes a process for making a high viscosity 
index lubricating oil composition. The terms "high viscosity index" 
lubricating oil composition and "unconventional base oil" do not have 
strict definitions. In general, they refer to base oils having desirable 
viscometric properties not typically found in mineral oils and generally 
only available in expensive synthetic base oils. The marketplace 
recognizes the desirability of viscometric properties of high-viscosity 
index and unconventional base oils in that they command a higher price 
than "conventional" oils. Thus, the relative price is also an indicator of 
unconventional and high viscosity index base oils. 
To avoid ambiguity, the term "high viscosity index" mineral oil or 
lubricating oil composition as used in this specification and appended 
claims means (1) a viscosity index of at least 90 for a mineral oil having 
a viscosity of 3.0 centistokes at 100.degree. C.; (2) a viscosity index of 
at least 105 for a lubricating oil composition having a viscosity of 4 
centistokes at 100.degree. C.; (3) a viscosity index of at least 115 for a 
lubricating oil composition having a viscosity of 5.0 centistokes at 
100.degree. C.; and (4) a viscosity index of at least 120 for a 
lubricating oil composition having a viscosity of 7.0 centistokes at 
100.degree. C. "High" viscosity indices for other viscosities between 3.0 
and 7.0 can be determined by conventional interpolation. 
The viscosity indices of the high VI base oils made in the present 
invention are much higher than those commonly used in conventional oils in 
the industry. Known methods of manufacturing high VI base oils, using a 
mineral oil feed, use a combination of hydrocracking followed by catalytic 
isomerization dewaxing. Two such processes are licensed under the names of 
ISOCRACKING and ISODEWAXING. 
ILLUSTRATIVE EMBODIMENTS 
The invention will be further clarified by the following Illustrative 
Embodiments, which are intended to be purely exemplary of the invention. 
The results are shown in Tables IX-XVI below. 
Example 1 
High density polyethylene (HDPE) was pyrolyzed in a pyrolysis reactor at 
atmospheric pressure and different temperatures, as shown in Table IX, 
which also gives yields of gas, residue, and waxy oil, as well as boiling 
point distributions of the waxy oil. This table shows that most of the oil 
in the lube boiling range was in the range of 650-1000.degree. F., with 
little boiling in the bright stock range above 1000.degree. F. 
The waxy oil fraction of the material pyrolyzed at 650.degree. C. was 
evaluated by high pressure liquid chromatography followed by GC-MS. It was 
found to be composed almost entirely of n-paraffins and 1-olefins, as 
shown in Table X. 
Example 2 
HDPE was pyrolyzed in the pyrolysis reactor, as in Example 1, except at 
sub-atmospheric pressure, as indicated in Table XI and FIG. 2. This shows 
not only an increase in the yield of lube range waxy oil (650.degree. 
F.+), but also a large increase in bright stock range waxy oil 
(950-1200.degree. F.). 
Example 3 
Waste HDPE, obtained from a recycling center, was pyrolyzed at 650.degree. 
C. and 0.5 atm pressure. Table XII shows the results are very similar to 
those obtained with the virgin HDPE of Examples 1 and 2. 
Example 4 
The waxy oil produced in Example 1 at atmospheric pressure and 650, 675, 
and 700.degree. C. was composited. The waxy oil yield of the composite was 
86.5 wt %. This oil was distilled at 650.degree. F. to give 59.1 wt % 
650.degree. F.+ bottoms (51.1 wt % based on HDPE feed). The 650.degree. 
F.+ bottoms were then hydrotreated over a Ni--Mo hydrotreating catalyst at 
600.degree. F., 1950 psig, 1 LHSV, and 5 MSCF/bbl once-through H2 to 
reduce the nitrogen level to below 1 ppm. Conversion of 650.degree. F.+ 
material in the feed to 650.degree. F. - was less than 1%. The 
hydrotreated oil was then processed at 1000 psig and 4 MSCF/bbl 
once-through H2 over an isomerization dewaxing catalyst at 610.degree. F. 
and 0.63 LHSV followed by a hydrofinishing catalyst at 450.degree. F. and 
1.6 LHSV. The isomerization catalyst was Pt on SAPO-11 (made according to 
U.S. Pat. No. 5,135,638) and the hydrofinishing catalyst was Pt/Pd on 
SiO2-Al2O3. This gave a 4 cSt oil (viscosity measured at 100.degree. C.) 
with a pour point of-8.degree. C. and a viscosity index of 153, as shown 
in Table XIII. The 650.degree. F.+ yield through the isomerization step 
was 67 wt %. A flow diagram of the process, based on 1000 pounds of HDPE, 
is given in FIG. 3. 
Example 5 
HDPE was pyrolyzed in the pyrolysis reactor at sub-atmospheric pressure, as 
shown in Table XIV to again give a large amount of both lube and bright 
stock range waxy oil. 
Example 6 
The waxy oil produced in Example 2 at 0.10 atm pressure and 600, 650, and 
700.degree. C. was composited (distillation analysis shown in Table XV) 
and hydrotreated over a Ni--Mo hydrotreating catalyst at 600.degree. F., 
1950 psig, 1 LHSV, and 5 MSCF/bbl once-through H2 to reduce the nitrogen 
level to below 1 ppm. Conversion of 650.degree. F.+ material in the feed 
to 650.degree. F.- was less than 1%. The waxy oil was then isomerized as 
in Example 4, but at an isomerization temperature of 685.degree. F., to 
give a 9 cSt oil with a pour point of 0.degree. C. and a 137 VI, as shown 
in Table XVI. 
Example 7 
The waxy oil produced in Example 2 at 0.5 atm pressure and 550, 600 and 
650.degree. C. was composited (distillation analysis shown in Table XV) 
and hydrotreated over a Ni--Mo hydrotreating catalyst at 600.degree. F., 
1950 psig, 1 LHSV, and 5 MSCF/bbl once-through H2 to reduce the nitrogen 
level to below 1 ppm. Conversion of 650.degree. F.+ material in the feed 
to 650.degree. F.- was less than 1%. The waxy oil was then isomerized as 
in Example 4, but at an isomerization temperature of 648.degree. F., to 
give a 3.7 cSt oil with a pour point of -22.degree. C. and a 153 VI, as 
shown in Table XVI. 
TABLE IX 
__________________________________________________________________________ 
HPDE PYROLYSIS RESULTS 
AT 1 ATM 
550 575 600 625 650 675 700 
__________________________________________________________________________ 
Pyrolysis Temp, .degree. F. 
Oil Yield, Wt % 85.2 88.8 88.8 87.4 87.0 86.0 86.5 
650.degree. F. + Yield, Wt % 35.8 39.1 41.6 47.1 53.5 52.1 53.6 
700.degree. F. + Yield, Wt % 
29.2 32.3 34.7 41.0 44.8 44.9 
46.4 
Oil Inspections 
Sim. Dist., LV %, .degree. F. 
ST/5 80/201 75/253 80/201 87/208 186/338 188/328 188/328 
10/30 253/443 253/449 256/458 280/487 403/588 390/588 394/596 
50 580 598 620 660 711 715 722 
70/90 714/872 729/877 743/898 796/952 803/892 808/902 818/908 
95/EP 934/1027 938/1021 954/1032 1003/1089 928/1224 931/1224 940/1224 
__________________________________________________________________________ 
TABLE X 
______________________________________ 
ANALYSIS OF WAXY OIL PYROLYZED AT 1 ATM AND 650.degree. C. 
Wt % 
______________________________________ 
N-Paraffins 
.about.50 
1-Olefins .about.49 
Aromatics 0.7 
Polars 0.4 
______________________________________ 
TABLE XI 
__________________________________________________________________________ 
HDPE PYROLYSIS RESULTS AT REDUCED PRESSURE 
Pyrolysis Pressure, Atm 
0.5 0.5 0.5 0.1 0.1 0.1 
__________________________________________________________________________ 
Pyrolysis Temp, .degree. C. 
600 650 700 550 600 650 
Oil Yield, Wt % 88.8 90.1 89.7 83.5 88.0 89.1 
Residue, Wt % 1.8 0 0 3.0 0 0 
Gas Yield, Wt % 5.9 6.3 6.7 6.5 7.3 10.6 
650.degree. F. + Yield, Wt % 45.6 58.8 63.9 50.9 74.4 82.7 
700.degree. F. + Yield, Wt % 38.7 50.2 56.2 41.4 70.0 80.4 
Oil Inspections 
Sim. Dist., Wt %, .degree. F. 
ST/5 308/317 182/385 181/402 183/366 194/478 184/605 
10/30 342/521 457/626 486/658 442/604 573/792 704/925 
50 658 730 760 702 948 1052 
70/90 777/928 807/889 837/910 777/864 1068/1098 1085/1103 
95/99 992/1181 922/1224 941/1071 897/997 1106/1224 1107/1149 
__________________________________________________________________________ 
TABLE XII 
______________________________________ 
COMISON OF WASTE HDPE VERSUS 
PLANT HDPE FOR PYROLYSIS AT 
650.degree. C. AND 0.5 ATM 
Feed HDPE Waste HDPE 
______________________________________ 
Oil Yield, Wt % 90.1 86.7 
Residue, Wt % 0 0.9 
Gas Yield, Wt % 6.3 11.7 
Oil Inspections 
ST/5 182/385 186/368 
10/30 457/626 442/619 
50 730 723 
70/90 807/889 810/900 
95/99 922/1224 939/1224 
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TABLE XIII 
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INSPECTIONS IN CONERVERSION OF HDPE TO LUBE OIL 
Pyrolyzed PE 
HDT'd 
650-700.degree. C. 650.degree. F. + Isomerized 
Identification HDPE Feed Comp. Feed Oil 
______________________________________ 
Gravity, API 40.0 40.0 
Nitrogen, ppm 53 29 0.2 
Oxygen, ppm 147 297 
Pour Pt, .degree. C. -8 
Cloud Pt, .degree. C. +12 
Viscosity, 17.07 
40.degree. C., cSt 
100 C., cSt 4.155 
VI 153 
Sim. Dist., 
TGA, LV %, 
.degree. F. 
ST/5 186/341 193/701 362/559 
10/30 422/625 759/850 621/711 
50 752 906 781 
70/90 847/935 950/997 860/959 
95/EP 961/ 1014/ 993/1034 
______________________________________ 
TABLE XIV 
__________________________________________________________________________ 
HPDE PYROLYSIS RESULTS 
AT REDUCED PRESSURE 
__________________________________________________________________________ 
Pyrolysis Temperature, .degree. C. 
650 650 650 650 700 700 
Pyrolysis Pressure, Atm 0.5 0.25 0.25 0.1 0.5 0.25 
+0.5% Na.sub.2 CO.sub.3 No No Yes No No No 
Gas, Wt % 9.63 8.92 7.23 8.04 4.9 6.3 
Naphtha, Wt % 14.39 5.00 5.71 6.18 20.9 11.38 
Oil, Wt % 75.98 86.08 86.70 85.78 68.04 82.32 
Residue, Wt % 0 0 0.25 0 0.28 0 
650 F+ Yield, Wt % 68.9 78.7 79.0 82.8 64.4 82.20 
1000 F+ Yield, Wt % 26.8 43.4 44.9 57.4 5.7 71.39 
Inspections 
Naphtha 
Sim. Dist., LV %, .degree. F. 
ST/5 64/147 82/148 139/177 75/148 81/150 92/157 
10/30 155/252 171/251 206/261 178/262 174/266 203/293 
50 340 336 339 376 375 379 
70/90 432/605 420/621 414/546 482/650 479/628 472/627 
95/EP 693/893 727/941 651/944 730/894 713/913 710/893 
Oil 
Sim. Dist., Wt %, .degree. F. 
ST/5 189/554 186/569 183/573 187/674 192/597 188/831 
10/30 640/812 670/876 665/870 784/978 671/810 949/1077 
50 921 1003 1016 1077 885 1093 
70/90 1037/1094 1083/1105 1085/1106 1098/1111 941/995 1104/1115 
95/EP 1103/ 1109/ 1112/ 
1117/ 1018/ 1119/ 
Chloride, ppm &lt;10 &lt;10 
__________________________________________________________________________ 
TABLE XV 
______________________________________ 
PYROLYZED/HDT'D FEEDS 
Identification 0.5 Atm Composite 
0.1 Atm Composite 
Sim. Dist., Wt %, .degree. F. (600,650,700.degree. C.) (550,600,650.degr 
ee. C.) 
______________________________________ 
ST/5 197/523 186/542 
10/30 585/700 605/737 
50 778 833 
70/90 837/903 928/1054 
95/ 932/ 1078/ 
______________________________________ 
TABLE XVI 
______________________________________ 
ISOMERIZATION OF HDT'D PYROLYZED HDPE AT 0.62 LHSV, 
1950 PSIG, AND 4 MSCF/BBL OVER Pt/SAPO-11 
Feed 0.5 Atm Composite 
0.1 Atm Composite 
______________________________________ 
Temperature, .degree. F. 
648 685 
Pour Point, .degree. C. -22 0 
Cloud Point, .degree. C. +22 +59 
Viscosity, 40.degree. C., cSt 14.15 57.24 
100.degree. C., cSt 3.672 9.034 
VI 153 137 
Sim. Dist., Wt %, .degree. F. 
ST/5 460/562 504/586 
10/30 602/693 622/720 
50 770 822 
70/90 855/966 980/1308 
95/EP 1004/1088 1353/1400 
______________________________________