A method for making lube basestocks
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18 claims: 1 independent, 17 dependent
- 1Claims of equivalent WO 2004033596 A2 CLAIMS:1. A process to prepare lubricating oil basestocks having a VI of at least about 110 to about 130 from a lube oil boiling range feedstock comprising: a) conducting a lubricating oil feedstock to a solvent extraction zone and underex tracting the lubricating oil feedstock under conditions effective at producing at least an aromatics-lean raffinate solution;b) removing at least a portion of the extraction solvent from the aromatics-lean raffinate solution to produce a raffinate feedstock having a dewaxed oil viscosity index from about 75 to about 105 and a wax content of greater than 15 wt.%;;c) contacting the raffinate feedstock with a hydrotreating catalyst in a first reaction stage operated under effective conditions to produce at least a gaseous product and a hydrotreated feedstock;d) stripping the hydrotreated feedstock to separate at least a portion of the gaseous product from the hydrotreated feedstock to produce a stripped feedstock;and e) contacting the stripped feedstock with at least one dewaxing catalyst in a dewaxing zone operated under effective hydrodewaxing conditions, wherein said dewaxing catalyst contains at least one Group VIII noble metal and is selected from ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, Beta, SSZ-31, SAPO-11, SAPO-31, SAPO-41, MAPO-11, ECR-42, fluorided alumina, silica-alumina, fluorided silica alumina, synthetic Feπϊerites, Mordenite, Offretite, erionite, chabazite, and mixtures thereof thereby producing a lubricating oil basestock.
384 paragraphs in 9 sections, as filed
Description of equivalent WO 2004033596 A2
A METHOD FOR MAKING LUBE BASESTOCKS
FIELD OF THE INVENTION
[0001] This invention relates to a process for preparing lubricating oil
basestocks having a high viscosity index (VI) from wax containing feeds.
More particularly, a wax containing feedstock is hydrotreated under mild
conditions, catalytically hydrodewaxed and hydrofinished.
BACKGROUND OF THE INVENTION
[0002] Historically, lubricating oil products for use in applications such as
automotive engine oils have used additives to improve specific properties of
the basestocks used to prepare the finished products. With the advent of
increased environmental concerns, the performance requirements for the
basestocks themselves have increased. American Petroleum Institute (API)
requirements for Group II basestocks include a saturates content of at least
90%, a sulfur content of 0.03 wt.% or less and a viscosity index (VI) between
80 and 120. The requirements for Group III basestocks are those of Group II
basestocks except that the VI is at least 120.
[0003] Conventional techniques for preparing basestocks such as
hydrocracking or solvent extraction require severe operating conditions such as
high pressure and temperature or high solven oil ratios and high extraction temperatures to reach these higher basestock qualities. Either alternative
involves expensive operating conditions and low yields.
[0004] Hydrocracking has been combined with hydrotreating as a
preliminary step. However, this combination also results in decreased yields of
lubricating oils due to the conversion to distillates that typically accompany the
hydrocracking process.
[0005] It would be desirable to have a economical process for preparing
Group III basestocks in high yields by minimizing conversion to low boiling
distillates while at the same time producing a product having excellent low
temperature properties, high VI and high stability.
SUMMARY OF THE INVENTION
[0006] The present invention is directed at a process to prepare lubricating
oil basestocks having a VI of about 110 to about 130 from a lube oil boiling
range feedstock.
[0007] The process comprises:
a) conducting a lubricating oil feedstock to a solvent extraction zone and
underextracting the lubricating oil feedstock under conditions effective
at producing at least an aromatics-lean raffinate solution;
b) removing at least a portion of the extraction solvent from the aromatics-
lean raffinate solution to produce a raffinate feedstock having a dewaxed
oil viscosity index from about 75 to about 105 and a wax content of
greater than 15 wt.%;
c) contacting the raffinate feedstock with a hydrotreating catalyst in a first
reaction stage operated under effective conditions to produce at least a
gaseous product and a hydrotreated feedstock
d) stripping the hydrotreated feedstock to separate at least a portion of the
gaseous product from the hydrotreated feedstock to produce a stripped
feedstock; and e) contacting the stripped feedstock with at least one dewaxing catalyst in a
dewaxing zone operated under effective hydrodewaxing conditions,
wherein said dewaxing catalyst contains at least one Group VIII noble
metal and is selected from ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-
48, ZSM-57, Beta, SSZ-31, SAPO-11, SAPO-31, SAPO-41, MAPO-11,
ECR-42, fluorided alumina, silica-alumina, fluorided silica alumina,
synthetic Ferrierites, Mordenite, Offretite, erionite, chabazite, and
mixtures thereof thereby producing a lubricating oil basestock.
[0008] In one embodiment of the present invention, a hydrofinished
lubricating oil basestock is produced by contacting the lubricating oil basestock
with a hydrofinishing catalyst in a hydrofinishing zone operated under effective
hydrofininishing conditions.
DETAILED DESCRIPTION OF THE INVENTION
[0009] It should be noted that the terms "feedstock" and "feedstream" as
used herein are synonymous. Lubricating Oil Feedstocks
[0010] The feedstock used in the process of the invention are wax-
containing feeds that boil in the lubricating oil range, typically having a 10%
distillation point greater than 650°F (343°C), measured by ASTM D 86 or
ASTM 2887, and are derived from mineral sources, synthetic sources, or a
mixture of the two. Non-limiting examples of suitable lubricating oil
feedstocks include those derived from sources such as oils derived from solvent
refining processes such as raffinates, partially solvent dewaxed oils,
deasphalted oils, distillates, vacuum gas oils, coker gas oils, slack waxes, foots
oils and the like, and Fischer-Tropsch waxes.
[0011] These feedstocks may also have high contents of nitrogen- and
sulfur-contaminants. Feeds containing up to 0.2 wt.% of nitrogen, based on
feed and up to 3.0 wt.% of sulfur can be processed in the present process.
Feeds having a high wax content typically have high viscosity indexes of up to
200 or more. Sulfur and nitrogen contents may be measured by standard
ASTM methods D5453 and D4629, respectively. Raffinate Feedstocks
[0012] The raffinate feedstocks used herein are derived from a solvent
extraction process. In a solvent extraction process as contemplated herein, the
lube oil feedstocks defined above are solvent extracted. The solvent extraction
process selectively dissolves the aromatic components in an aromatics-rich
extract solution while leaving the more paraffinic components in the
"aromatics-lean raffinate solution". Naphthenes are distributed between the
extract and raffinate phases. Typical solvents for solvent extraction include
phenol, furfural and N-methyl pyrrolidone. By controlling the solvent to oil
ratio, extraction temperature and method of contacting distillate to be extracted
with solvent, one can control the degree of separation between the extract and
raffinate phases.
[0013] In the solvent extraction process, the lube oil feedstocks are
subjected to solvent extraction in a solvent extraction zone. In the solvent
extraction zone, a lube oil boiling range feedstock as defined above, is
contacted with an extraction solvent. The extraction solvent used herein is not
critical and can be any solvent known that has an affinity for aromatic
hydrocarbons in preference to non-aromatic hydrocarbons. Non-limiting examples of such solvents include suifolane, furfural, phenol, and N-methyl
pyrrolidone ("NMP"). Furfural, phenol, and NMP are preferred.
[0014] The contacting of the lube oil boiling range feedstream with the
extraction solvent can be accomplished by any suitable solvent extraction
method. Non-limiting examples of such include batch, semi-batch, or
continuous. It is preferred that the extraction process be a continuous process,
and it is more preferred that the continuous process be operated in a counter-
current fashion. In a counter-current configuration, it is preferred that the lube
oil boiling range feedstream be introduced into the bottom of an elongated
contacting zone or tower and caused to flow in an upward direction while the
extraction solvent is introduced at the top of the tower and allowed to flow in a
downward direction, counter-current to the upflowing lube oil boiling range
feedstream. In this configuration, the lube oil boiling range feedstream is
forced to pass counter-currently to the extraction solvent resulting in the
intimate contact between the extraction solvent and the lube oil boiling range
feedstock. The extraction solvent and the lube oil boiling range feedstream
thus migrate to opposite ends of the contacting zone. [0015] The contacting of the lube oil boiling range feedstream with the
extraction solvent produces at least an aromatics-lean raffinate solution. The
aromatics-lean raffinate solution is then treated to remove at least a portion of
the extraction solvent contained therein, thus producing the raffinate used as a
feedstock herein. The removal of at least a portion of the extraction solvent
can be done by any means known in the art effective at separating at least a
portion of an extraction solvent from an aromatics lean raffinate solution.
Preferably the raffinate is produced by separating at least a portion of the first
extraction solvent from the aromatics-lean raffinate solution in a stripping or
distillation tower. By at least a portion, it is meant that at least about 80 vol%,
preferably about 90 vol%, more preferably 95 vol%, based on the aromatics-
lean raffinate solution, of the extraction solvent is removed from the aromatics-
lean raffinate solution. Most preferably substantially all of the extraction
solvent is removed.
[0016] It should be noted that the phrase "aromatics-lean raffinate solution"
is not synonymous with the "raffinate". The phrase "aromatics-lean raffinate
solution" is meant to refer to the products of solvent extraction before the
solvent has been removed, i.e. distilled or stripped, from the respective phases.
Thus, "raffinate", as used herein, refers to the raffinate product after at least a portion of the solvent contained in the "aromatics-lean raffinate solution has
been removed.
[0017] It is preferred that the raffinates used herein be under extracted, i.e.,
the extraction is carried out under conditions such that the raffinate yield is
maximized while still removing most of the lowest quality molecules from the
feed. Raffinate yield may be maximized by controlling extraction conditions,
for example, by lowering the solvent to oil treat ratio and/or decreasing the
extraction temperature. The raffinate from the solvent extraction unit is
stripped of solvent and then sent to a hydrotreating unit (zone) containing a
hydrotreating catalyst.
[0018] The raffinate feedstock to the hydrotreating zone is extracted to a
dewaxed oil viscosity index of from about 75 to about 105, preferably 80 to 95,
more preferably about 80 to about 85. The raffinate feedstock will also have a
wax content greater than about 15 wt.% wax, preferably greater than about 40
wt.% wax. The wax content of a feed may be determined by nuclear magnetic
resonance spectroscopy (ASTM D5292), by correlative ndM methods (ASTM
D3238) or by solvent means (ASTM D3235). Hydrotreating
[0019] For hydrotreating, the catalysts are those effective for hydrotreating
such as catalysts containing at least one metal selected from Group VI metals,
Group VIII metals, and mixtures thereof. Preferred metals include nickel,
tungsten, molybdenum, cobalt and mixtures thereof. These metals or mixtures
of metals are typically present as oxides or sulfides on refractory metal oxide
supports. The amount of metals, either individually or in mixtures, for
supported catalysts ranges from about 0.5 to 35 wt.%, based on the catalyst,
while if a bulk or unsupported catalysts is used, the metals content can range as
high as 98 wt.%, based on the catalyst. In the case of preferred mixtures of
Group VIII metals with Group VI metals, the Group VIII metals are present in
amounts ranging from about 0.5 to 5 wt.%, based on catalyst and the Group VI
metals are present in amounts ranging from about 5 to 30 wt.%. The amounts
of metals may be measured by atomic absorption spectroscopy, inductively
coupled plasma-atomic emission spectrometry or other methods specified by
ASTM for individual metals.
[0020] The hydrotreating catalysts used herein can be either supported, or
bulk or unsupported. However, if the hydrotreating catalyst is supported, it is
important that the metal oxide support used for the hydrotreating catalysts herein be non-acidic so as to control cracking. A useful scale of acidity for
catalysts is based on the isomerization of 2-methyl-2-pentene as described by
Kramer and McVicker, J. Catalysis, 92, 355 (1985). In this scale of acidity, 2-
methyl-2-pentene is subjected to the catalyst to be evaluated at a fixed
temperature, typically 200°C. In the presence of catalyst sites, 2-methyl-2-
pentene forms a carbenium ion. The isomerization pathway of the carbenium
ion is indicative of the acidity of active sites in the catalyst. Thus weakly
acidic sites form 4-methyl-2-pentene whereas strongly acidic sites result in a
skeletal rearrangement to 3-methyl-2-pentene with very strongly acid sites
forming 2,3-dimethyl-2-butene. The mole ratio of -methyl-2-pentene to 4-
methyl-2-pentene can be correlated to a scale of acidity, which ranges from 0.0
to 4.0. Very weakly acidic sites will have values near 0.0 whereas very
strongly acidic sites will have values approaching 4.0. The catalysts useful in
the present process have acidity values of less than about 0.5, preferably less
than about 0.3. The acidity of metal oxide supports can be controlled by
adding promoters and/or dopants, or by controlling the nature of the metal
oxide support, e.g., by controlling the amount of silica incorporated into a
silica-alumina support. Examples of promoters and/or dopants include
halogen, especially fluorine, phosphorus, boron, yttria, rare-earth oxides and
magnesia. Promoters such as halogens generally increase the acidity of metal oxide supports while mildly basic dopants such as yttria or magnesia tend to
decrease the acidity of such supports.
[0021] Suitable metal oxide supports include low acidic oxides such as
silica, alumina or titania, preferably alumina. Preferred aluminas are porous
aluminas such as gamma or beta having average pore sizes from 50 to 200A,
preferably 75 to 150A, a surface area from 100 to 300 m<sup>2</sup>/g, preferably 150 to
250 m<sup>2</sup>/g and a pore volume of from 0.25 to 1.0 cm<sup>3</sup>/ g, preferably 0.35 to 0.8
cm<sup>3</sup>/g. The supports are preferably not promoted with a halogen such as
fluorine as this generally increases the acidity of the support above 0.5.
[0022] Preferred metal catalysts include cobalt/molybdenum (1-5% Co as
oxide, 10-25% Mo as oxide) nickel/molybdenum (1-5% Ni as oxide, 10-25%
Co as oxide) or nickel/tungsten (1-5% Ni as oxide, 10-30% W as oxide) on
alumina. Especially preferred are nickel/molybdenum catalysts such as KF-
840.
[0023] Effective hydrotreating conditions as used herein typically include
temperatures of from 150 to 400°C, preferably 200 to 350°C, a hydrogen partial
pressure of from 1480 to 20786 kPa (200 to 3000 psig), preferably 2859 to 13891 kPa (400 to 2000 psig), a space velocity of from 0.1 to 10 liquid hourly
space velocity (LHSV), preferably 0.1 to 5 LHSV, and a hydrogen to feed ratio
of from 89 to 1780 m<sup>3</sup>/ m<sup>3</sup> (500 to 10000 scf/B), preferably 178 to 890 m<sup>3</sup>/ m<sup>3</sup>.
[0024] Hydrotreating reduces the amount of nitrogen- and sulfur-containing
contaminants to levels that will not unacceptably affect the dewaxing catalyst
in the subsequent dewaxing step. Also, there may be certain polynuclear
aromatic species that will pass through the present mild hydrotreating step.
These contaminants, if present, will be removed in a subsequent hydrofinishing
step.
[0025] Effective hydrotreating conditions are considered those conditions
which when selected, result in less than 5 wt.% of the feedstock, preferably less
than 3 wt.%, more preferably less than 2 wt.%, being converted to 650°F
(343°C) minus products. Effective hydrotreating conditions are also those that
when selected produce a hydrotreated feedstock whose VI increase is less than
4, preferably less than 3, more preferably less than 2 greater than the VI of the
feedstock. The high wax contents of the present feeds results in minimal VI
increase during the hydrotreating step. [0026] The hydrotreated feedstock may be passed directly to the dewaxing
step or preferably, stripped to remove gaseous contaminants such as hydrogen
sulfide and ammonia prior to dewaxing. Stripping can be by conventional
means such as flash drums or fractionators.
Dewaxing Catalyst
[0027] The dewaxing catalyst may be either crystalline or amorphous.
Crystalline materials are molecular sieves that contain at least one 10 or 12 ring
channel and may be based on aluminosilicates (zeolites) or on
aluminophosphates such as silicoaluminophosphates (SAPO's) and MAPO's.
Zeolites used for oxygenate treatment may contain at least one 10 or 12
channel. Examples of such zeolites include ZSM-22, ZSM-23, ZSM-35, ZSM-
48, ZSM-57, ferrierite, ITQ-13, MCM-68 and MCM-71. Examples of
aluminophosphates containing at least one 10 ring channel include ECR-42.
Examples of molecular sieves containing 12 ring channels include zeolite beta,
and MCM-68. The molecular sieves are described in US Patent Numbers
5,246,566, 5,282,958, 4,975,177, 4,397,827, 4,585,747, 5,075,269 and
4,440,871. MCM-68 is described in US Patent No. 6,310,265. MCM-71 and
ITQ-13 are described in PCT published applications WO 0242207 and WO
0078677. ECR-42 is disclosed in US 6,303,534. Suitable SAPO's for use herein include SAPO-11, SAPO-31, SAPO-41, and suitable MAPO's include
MAPO-11. SSZ-31 is also a catalyst that can be effectively used herein.
Preferred catalysts include ZSM-48, ZSM-22 and ZSM-23. Especially
preferred is ZSM-48. The molecular sieves are preferably in the hydrogen
form. Reduction can ccur in situ during the dewaxing step itself or can occur
ex situ in another vessel.
[0028] Amorphous dewaxing catalysts include alumina, fluorided alumina,
silica-alumina, fluorided silica-alumina and silica-alumina doped with Group
IIIB metals. Such catalysts are described for example in US Patent Nos.
4,900,707 and 6,383,366. The dewaxing catalysts used herein are bifunctional,
i.e., they are loaded with at least one metal hydrogenation component, which is
selected from Group VI metals, Group VIII metals, or mixtures thereof.
Preferred metals are selected from Group VIII metals. Especially preferred are
Group VIII noble metals such as Pt, Pd or mixtures thereof. These metals are
loaded at the rate of 0.1 to 30 wt.%, based on catalyst. Catalyst preparation and
metal loading methods are described for example in US Patent No. 6,294,077,
and include for example ion exchange and impregnation using decomposable
metal salts. Metal dispersion techniques and catalyst particle size control techniques are described in US Patent No. 5,282,958. Catalysts with small
particle size and well-dispersed metal are preferred.
[0029] The molecular sieves are typically composited with binder materials
which are resistant to high temperatures which may be employed under
dewaxing conditions to form a finished dewaxing catalyst or may be binderless
(self bound). The binder materials are usually inorganic oxides such as silica,
alumina, silica-aluminas, binary combinations of silicas with other metal
oxides such as titania, magnesia, thoria, zirconia and the like and tertiary
combinations of these oxides such as silica-alumina -thoria and silica-alumina
magnesia. The amount of molecular sieve in the finished dewaxing catalyst is
from 10 to 100, preferably 35 to 100 wt.%, based on catalyst. Such catalysts
are formed by methods such spray drying, extrusion and the like. The
dewaxing catalyst may be used in the sulfided or unsulfided form, and is
preferably in the sulfided form.
[0030] Effective dewaxing conditions as used herein includes temperatures
of from 250 - 400°C, preferably 275 to 350°C, pressures of from 791 to 20786
kPa (100 to 3000 psig), preferably 1480 to 17339 kPa (200 to 2500 psig),
liquid hourly space velocities of from 0.1 to 10 hr<sup>'1</sup>, preferably 0.1 to 5 hr<sup>*1</sup> and hydrogen treat gas rates from 45 to 1780 m<sup>3</sup>/ m<sup>3</sup> (250 to 10000 scf/B),
preferably 89 to 890 m<sup>3</sup>/m<sup>3</sup> (500 to 5000 scf B).
Hydrofinishing
[0031] In a preferred embodiment, at least a portion of the product from
dewaxing is passed directly to a hydrofinishing step without disengagement. It
is preferred to hydrofinish the product resulting from dewaxing in order to
adjust product qualities to desired specifications. Hydrofinishing is a form of
mild hydrotreating directed to saturating any lube range olefins and residual
aromatics as well as to removing any remaining heteroatoms and color bodies.
The post dewaxing hydrofinishing is usually carried out in cascade with the
dewaxing step. Generally the hydrofinishing will be carried out at temperatures
from about 150°C to 350°C, preferably 180°C to 250°C. Total pressures are
typically from 2859 to 20786 kPa (about 400 to 3000 psig). Liquid hourly
space velocity is typically from 0. 1 to 5 LHSV (hr<sup>'1</sup>), preferably 0. 5 to 3 hr<sup>"1</sup>
and hydrogen treat gas rates of from 44.5 to 1780 m<sup>3</sup>/m<sup>3</sup> (250 to 10,000 scf/B).
[0032] Hydrofinishing catalysts are those containing at least one metal
selected from Group VI metals, Group VIII metals, and mixtures thereof.
Preferred metals include at least one noble metal having a strong hydrogenation function, especially platinum, palladium and mixtures thereof. The mixture of
metals may also be present as bulk metal catalysts wherein the amount of metal
is 30 wt.%) or greater based on catalyst. Suitable metal oxide supports include
low acidic oxides such as silica, alumina, silica-aluminas or titania, preferably
alumina. The preferred hydrofinishing catalysts for aromatics saturation will
comprise at least one metal having relatively strong hydrogenation function on
a porous support. Typical support materials include amorphous or crystalline
oxide materials such as alumina, silica, and silica-alumina. The metal content
of the catalyst is often as high as about 20 weight percent for non-noble metals.
Noble metals are usually present in amounts no greater than about 1 wt.%.
[0033] The hydrofinishing catalyst is preferably a mesoporous material
belonging to the M41S class or family of catalysts. The M41S family of
catalysts are mesoporous materials having high silica contents whose
preparation is further described in J. Amer. Chem. Soc, 1992, 114, 10834.
Examples included MCM-41, MCM-48 and MCM-50. Mesoporous refers to
catalysts having pore sizes from 15 to 100 A. A preferred member of this class
is MCM-41 whose preparation is described in US Patent No. 5,098,684.
MCM-41 is an inorganic, porous, non-layered phase having a hexagonal
arrangement of uniformly-sized pores. The physical structure of MCM-41 is like a bundle of straws wherein the opening of the straws (the cell diameter of
the pores) ranges from 15 to 100 Angstroms. MCM-48 has a cubic symmetry
and is described for example is US Patent No. 5,198,203 whereas MCM-50 has
a lamellar structure. MCM-41 can be made with different size pore openings in
the mesoporous range. The mesoporous materials may bear a metal
hydrogenation component which is at least one Group VIII metal. Preferred
are Group VIII noble metals, most preferably Pt, Pd or mixtures thereof.
[0034] As stated above, typical hydrofinishing conditions include
temperatures from about 150°C to 350°C, preferably 180°C to 250°C. Total
pressures are typically from 2859 to 20786 kPa (about 400 to 3000 psig).
Liquid hourly space velocity is typically from 0. 1 to 5 LHSV (hr<sup>'1</sup>), preferably
0. 5 to 3 hr<sup>'1</sup> and hydrogen treat gas rates of from 44.5 to 1780 m<sup>3</sup>/m<sup>3</sup> (250 to
10,000 scf/B). Effective hydrofinishing conditions, as used herein, are
conditions within the above-defined ranges that when used in conjunction with
the selected hydrofinishing catalyst results in a lubricating oil product meeting
the desired specifications, i.e. color, etc.
[0035] The lubricating oil basestocks resulting from the presently disclosed
process will have viscosity indexes ("VI") of about 110 to about 130, preferably about 115 to about 125. These basestocks will also have excellent
volatility and low temperature properties.
[0036] The above description is directed to preferred embodiments of the
present invention. Those skilled in the art will recognize that other
embodiments that are equally effective could be devised for carrying out the
spirit of this invention.
[0037] The following examples will illustrate the improved effectiveness of
the present invention, but is not meant to limit the present invention in any
fashion.
EXAMPLES
EXAMPLE 1
[0038] A raffinate having a Viscosity Index ("VI") of 90, (following solvent
dewaxing) and having a wax content of 15 wt.% was used to produce a
basestock having a dewaxed oil VI of 115. The raffinate was hydrotreated at
370°C, hydrogen pressure of 1800 psi, and liquid hourly space velocities
("LHSV") of 0.35 hr<sup>"1</sup>. The raffinate was hydrotreated with a commercial
catalyst obtained from Akzo Nobel and marketed under the name KF-840. The
results of this Example are contained in Table 1 below. EXAMPLES 2 AND 3
[0039] It should be noted that the Examples that follow, namely Examples 2
and 3, are based on information derived from models and estimates from
related experiments. These examples illustrate approaches to upgrading a
raffinate to 115 VI but instead using a combination of hydrotreating and
hydrodewaxing. (A hydrofinishing step would normally be used in a
commercial process but was not considered germane to demonstrating the
invention) The catalyst used for hydrodewaxing comprises a noble metal on a
bound zeolite (ZSM-48).
[0040] The key properties of the solvent dewaxed basestock are the
relationship between the kinematic viscosity and volatility and formulated oil
low temperature properties. A volatility of less than 15% Noack is excellent for
a viscosity of 4.5 cSt @ lOOC. The Mini-Rotary Viscosity (MRV) in a 5W30
formulation was measured at 35,000 cP. EXAMPLE 2
[0041] The raffinate used in this Example was the same as described in
Example 1 above. The hydrotreating conditions included temperatures of 360-
380°C, pressures up to 2500 psig and liquid hourly space velocities ("LHSV")
of 0.2 to 2 hr<sup>"1</sup>, along with utilizing the same KF-840 catalyst of Example 1.
The hydrodewaxing conditions conditions needed to achieve the target pour
point of -18°C are in the range 330 to 340°C for a process operating at 1800 psi
H<sub>2</sub> and at a LHSV of 1.0 v/v/hr.
[0042] Thus, in this Example, the raffinate was hydrotreated to produce a
hydrotreated raffinate having a VI of 108. The hydrotreated raffinate was then
dewaxed under the conditions described above to produce a basestock having a
VI of 115. The results of this Example are contained in Table 1, below.
EXAMPLE 3
[0043] As mentioned above, Example 3 also used a two step process
involving hydrotreating under conditions similar to those outlined in Example 1
above followed by hydrodewaxing. However, the raffinate used in this
Example was an underextracted raffinate having a wax content of 15wt.% and a VI of 83 (dewaxed oil basis). The hydrodewaxing conditions were similar to
those described above in Example 2.
[0044] In this Example, the underextracted raffinate was hydroteated to
produce a hydrotreated underextracted raffinate having a VI of 108. The
hydrotreated underextracted raffinate was then hydrodewaxed to produce a
basestock having a VI of 115. The results of this Example are contained in
Table lj below.
TABLE 1
<img file="WO2004033596A2_D0001.tif" /> [0045] The yield of Example 1 was used as a standard yield for comparison
of the yields of Examples 2 and 3.
[0046] The data contained in Table 1 also illustrates that the process of
Example 2 using a raffinate that is not underextracted produces a basestock
having excellent Noack volatility at the given viscosity and excellent low
temperature properties as defined by Formulated Oil Mini Rotary Viscosity
(MRV) of 20,000cP. Table 1 also illustrates that the low temperature
properties of the formulated oil of Example 2 are substantially improved versus
Example 1 , however the viscosity/ volatility relationship is poorer. Example 2
also demonstrated an increased yield over that obtained by hydrotreating only
(Example 1).
[0047] The data contained in Table 1 also illustrates that the process of
Example 3 using an under-extracted raffinate produces a basestock having
excellent Noack volatility at viscosity and excellent low temperature properties
as defined by Formulated Oil Mini Rotary Viscosity (MRV) of 20,OOOcP.
Thus, Table 1 shows that the product of Example 3 has both excellent low
temperature properties and an excellent viscosity/volatility relationship. This
also results in an increased yield over that obtained by hydrotreating and hydrodewaxing the standard raffinate illustrated in Example 2. Example 3
shows the benefit of utilizing an under-extracted raffinate in a combined
hydrotreating-hydrodewaxing process.
[0048] Thus, these Examples demonstrate that by using an underextracted
raffinate, a refiner can produce superior yields of basestocks having excellent
Noack volatility and low temperature properties than by using a raffinate that is
not undterextracted.
Contents9
Every citation, both waysCites: the store holds 1 of 2
| Document | Relation | Office | Cited during |
|---|---|---|---|
| US5837639A | Cites | United States of America | Examiner |
| See references of WO 2004033596A2 | Non-patent | – | Search report |
49 members in 10 offices
Priority claims11
| Document | Office | Kind | Date |
|---|---|---|---|
| 416865P | United States of America | – | |
| 41686502 | United States of America | P | |
| 416870P | United States of America | – | |
| 41687002 | United States of America | P | |
| 0331740 | United States of America | W | |
| 416865P | – | – | – |
| 416870P | – | – | – |
| US20020416865P | – | – | – |
| US20020416870P | – | – | – |
| US2003031740 | – | – | – |
| WO2003US31740 | – | – | – |
Members49
| Document | Office | Kind | |
|---|---|---|---|
| CA2499327A1 | Canada | A1 | |
| CA2499350A1 | Canada | A1 | |
| CA2501044A1 | Canada | A1 | |
| CA2501225A1 | Canada | A1 | |
| WO2004033590A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2004033596A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2004033597A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2004033606A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2003279223A1 | Australia | A1 | |
| AU2003279860A1 | Australia | A1 | |
| AU2003282738A1 | Australia | A1 | |
| AU2003286536A1 | Australia | A1 | |
| WO2004033597A3 | World Intellectual Property Organization (WIPO) | A3 | |
| US2004108248A1 | United States of America | A1 | |
| US2004108249A1 | United States of America | A1 | |
| WO2004033596A3 | World Intellectual Property Organization (WIPO) | A3 | |
| WO2004033590A3 | World Intellectual Property Organization (WIPO) | A3 | |
| US2004129603A1 | United States of America | A1 | |
| US2005040073A1 | United States of America | A1 | |
| NO20052250L | Norway | L | |
| MXPA05003425A | Mexico | A | |
| EP1551941A2This record | European Patent Office (EPO) | A2 | |
| EP1551942A2 | European Patent Office (EPO) | A2 | |
| EP1558705A2 | European Patent Office (EPO) | A2 | |
| EP1558712A1 | European Patent Office (EPO) | A1 | |
| BR0315014A | Brazil | A | |
| US6951605B2 | United States of America | B2 | |
| CN1703495A | China | A | |
| CN1703496A | China | A | |
| CN1703497A | China | A | |
| CN1703498A | China | A | |
| JP2006502289A | Japan | A | |
| JP2006502294A | Japan | A | |
| JP2006502297A | Japan | A | |
| JP2006502303A | Japan | A | |
| US7077947B2 | United States of America | B2 | |
| US2007068850A1 | United States of America | A1 | |
| CN1320082C | China | C | |
| US7282137B2 | United States of America | B2 | |
| CN100378202C | China | C | |
| US7429318B2 | United States of America | B2 | |
| AU2003279223B2 | Australia | B2 | |
| CN100532516C | China | C | |
| CN100564491C | China | C | |
| JP4459057B2 | Japan | B2 | |
| CA2499327C | Canada | C | |
| CA2501044C | Canada | C | |
| EP1551941B1 | European Patent Office (EPO) | B1 | |
| EP1551942B1 | European Patent Office (EPO) | B1 |
100 legal events, as 9 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed because of non-payment of the annual feeLapsedMM | MM | BE | |
| Gb: european patent ceased through non-payment of renewal feeCeasedGBPC | GBPC | EP | |
| Lapsed because of non-payment of the annual feeLapsedMM | MM | NL | |
| Application deemed withdrawn, or ip right lapsed, due to non-payment of renewal feeWithdrawnR119 | R119 | DE | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Patent lapsedLapsedMM4A | MM4A | IE | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| No opposition filedOpposition26N | 26N | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Patent ceasedCeasedPL | PL | CH | |
| No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE | PLBE | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA | STAA | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| No opposition filed against granted patent, or epo opposition proceedings concluded without decisionGrantedR097 | R097 | DE | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Deletion acc. to par. 5 (withdrawal of the translation of the ep patent)MK05 | MK05 | AT | |
| Translation for ep filed (entry of ep into country)FP | FP | NL | |
| Fee paymentPLFP | PLFP | FR | |
| Reference to at number (ep patent validated in austria)REF | REF | AT | |
| Dpma publication of mentioned ep patent grantGrantedR096 | R096 | DE | |
| European patents granted designating irelandGrantedFG4D | FG4D | IE | |
| European patent takes effect as a national patent in ch/liEP | EP | CH | |
| Designated contracting statesAK | AK | EP | |
| European patent grantedGrantedFG4D | FG4D | GB | |
| Intention to grant announcedINTG | INTG | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Intention to grant announced (deleted)INTC | INTC | EP | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: THE PATENT HAS BEEN GRANTEDSTAA | STAA | EP | |
| Information related to intention to grant a patent recordedORIGINAL CODE: EPIDOSNIGR71GRAR | GRAR | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: GRANT OF PATENT IS INTENDEDSTAA | STAA | EP | |
| Amendment of ipc main classPREVIOUS MAIN CLASS: C10G0065040000R079 | R079 | DE | |
| Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deletedORIGINAL CODE: EPIDOSDIGR1GRAJ | GRAJ | EP | |
| Information related to payment of fee for publishing/printing deletedORIGINAL CODE: EPIDOSDIGR3GRAL | GRAL | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: EXAMINATION IS IN PROGRESSSTAA | STAA | EP | |
| Grant fee paidORIGINAL CODE: EPIDOSNIGR3GRAS | GRAS | EP | |
| Intention to grant announcedINTG | INTG | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOSNIGR1GRAP | GRAP | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: GRANT OF PATENT IS INTENDEDSTAA | STAA | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| Information provided on ipc code assigned before grantRIC1 | RIC1 | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Information on inventor provided before grant (corrected)RIN1 | RIN1 | EP | |
| Information on inventor provided before grant (corrected)RIN1 | RIN1 | EP | |
| Request for extension of the european patent (deleted)DAX | DAX | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Request for extension of the european patentAX | AX | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 1551941
- Publication, DOCDB
- 1551941
- Publication, EPODOC
- EP1551941
- Application
- 3774622
- Application, DOCDB
- 03774622
- Application, EPODOC
- EP20030774622
Titles3
- German
- METHODE ZUR HERSTELLUNG VON GRUNDÖLEN
- English
- A METHOD FOR MAKING LUBE BASESTOCKS
- French
- FABRICATION D'HUILES DE BASE DE GRAISSAGE
Classification
- CPC, 30
- B01J29/068
- B01J29/041
- B01J29/74
- B01J29/7461
- B01J2229/12
- B01J2229/34
- C10G45/02
- C10G45/08
- C10G45/12
- C10G45/58
- C10G45/60
- C10G45/62
- C10G45/64
- C10G65/043
- C10G69/00
- C10G2400/10
- C10M171/02
- C10M2203/1006
- C10M2205/173
- C10G2300/4018
- C10G2300/1062
- C10G2300/301
- C10G2300/4093
- C10N2020/02
- C10N2020/085
- C10N2030/02
- C10N2030/54
- C10N2030/74
- C10N2040/25
- C10N2060/02
- IPC, 12
- B01J29 04
- B01J29 74
- C10G45 02
- C10G45 08
- C10G45 12
- C10G45 58
- C10G45 60
- C10G45 62
- C10G45 64
- C10G65 04
- C10G69 00
- C10M171 02
Designated states2
- Contracting states, 1
- Türkiye
- Extension states, 1
- North Macedonia