CA1271441A - Process for stablizing lube base stocks derived from bright stock - Google Patents
Process for stablizing lube base stocks derived from bright stockInfo
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- CA1271441A CA1271441A CA000512865A CA512865A CA1271441A CA 1271441 A CA1271441 A CA 1271441A CA 000512865 A CA000512865 A CA 000512865A CA 512865 A CA512865 A CA 512865A CA 1271441 A CA1271441 A CA 1271441A
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
Abstract
ABSTRACT OF THE DISCLOSURE
A process for stabilizing a lubricating oil base stock derived from a nitro-aromatic-containing hydrocracked bright stock, comprising a two-step stabilizing process utilizing hydrodenitrification followed by mild hydrofinishing.
A process for stabilizing a lubricating oil base stock derived from a nitro-aromatic-containing hydrocracked bright stock, comprising a two-step stabilizing process utilizing hydrodenitrification followed by mild hydrofinishing.
Description
AN IMPROVED PROCESS FOR ST~BILI~ING
LUBE B~SE STOCKS DERIVED FROM B~IGHT STOCK
... . .. _ . .
This invention relates to a process for improving the bulk oxidation stability and storage stabili-ty of lube oil base stocks derived from hydro-cracked bright stock.
The term "oxidation stability" refers to the resistance of the oil to oxygen addition, in other words, how rapidly is oxygen picked up by and added to molecular species within the oil. Oxidation stability is indicated by the oxidator BN measured in hours. Oxidator BN is thoroughly described in U.S. Patent 3,852,207 granted December 3, 1974 to B. E. Stangeland et al at column 6, lines 15-30. Basically, the test measures the time required for 100 grams of oil to absorb one liter of oxygen. The term "storage stability" refers to the resis-tance of the oil to floc formation in the presence of oxygen.
The process comprises two steps. In the first step a hydrocracked bright stock is hydrodenitrified to reduce its heteroatom, particularly nitrogen, content using, for example, a sulfided nickel-tin catalyst having a siliceous matrix or a nickel-molybdenum hydrotreating catalyst having an alumina matrix. In the second step, the hydrocracked bright stock, having a reduced nitrogen content, is hydrofinished using, for example, an unsul-Eided nickel-tin or palladium hydrotreating catalyst having a siliceous matrix.
Both steps are carried out at an unusually low liquid hourly space velocity (LHSV), about 0.25 Hr~1. In the first step, a low LHSV permits the desired hydrodeni-trification reaction to proceed at relative low tempera-tures, about 700F. Under these conditions hydrocracking is minimized. In the second step a low LHSV permi-ts thorough saturation of aromatics which are floc-forming species. Thus, in general, the first step removes '., ~- . ' ~' Ol -2-nitrogen and sulfur, known catalyst poisons, and improves oxidation stability; and the second step saturates aro-matic Eloc precursors, and improves storage stability.
Accordingly, it has been found that the stability of the resultant lube oil hase stock is significantly improved.
Lubricant refining is based upon the fact that crude oils, as shown by experience or by assay, contain a quantity of lubricant base stocks having a predetermined set of properties such as, for example, appropriate vis-cosity, oxidation stability, and maintenance of Eluidity at low temperatures. The process of refining to isolate a lubricant base stock consists of a set of unit operations to remove or convert the unwanted components. The most common of these unit operations include, for instance, distillation, hydrocracking, dewaxing, and hydrogenation.
The lubricant base stock, isolated by these refining operations, may be used as such as a lubricant, or it may be blended with another lubricant base stock having somewhat different properties. Or, the base stock, prior to use as a lubricant, may be compounded with one or more additives which function, for example, as antioxi-dants, extreme pressure additives, and viscosity index improvers. As used herein, the term "stoclc", regardless whether or not the term is further qualified, refers to a hydrocarbon oil without additives. The term "dewaxed stock" will refer to an oil which has been treated by any method to remove or otherwise convert the wax contained therein and thereby reduce its pour point. The term "base stock" will reEer to an oil refined to a point suitable for some particular end use, such as for preparing automo-tive oils.
In general, refineries do not manufacture a si`ngle lube base stock but rather process at least one distillate fraction and one residuum fraction to produce several lube base stocks. Typically, three distillate fractions differing in boiling range and the residuum of a vacuum distillation operation are refined. These four fractions have acquired various names in the refining art, 01 -3_ the most volatile distillate ~raction often being referred to as the "light neutral" oil. The other distillates are O5 called "medium neutral" and "heavy neutral" oils. The residuum Eraction, is commonly reEerred to as "bright stock". Thus, the manufacture oE lubricant base stocks involves a process Eor producing a sla~e o~ base stocks, which slate may include a bright stock.
Processes have been proposed to produce lubri-cating oil base stocks by refining bright stocks. Most such reEining processes require hydrocracking tne bright stock to produce a hydrocrackate which is in turn dewaxed to produce a dewaxed bright stock. The problem is that lubricating oil base stocks derived from hydrocracked stocks are unstable in the presence oE oxygen and light.
Various stabilizing steps have been proposed.
U.S. Patents 3,189,540, 3,256,175 granted June 15, 1965 and June 14, 1966, respectively, to Kozlowski et al,
LUBE B~SE STOCKS DERIVED FROM B~IGHT STOCK
... . .. _ . .
This invention relates to a process for improving the bulk oxidation stability and storage stabili-ty of lube oil base stocks derived from hydro-cracked bright stock.
The term "oxidation stability" refers to the resistance of the oil to oxygen addition, in other words, how rapidly is oxygen picked up by and added to molecular species within the oil. Oxidation stability is indicated by the oxidator BN measured in hours. Oxidator BN is thoroughly described in U.S. Patent 3,852,207 granted December 3, 1974 to B. E. Stangeland et al at column 6, lines 15-30. Basically, the test measures the time required for 100 grams of oil to absorb one liter of oxygen. The term "storage stability" refers to the resis-tance of the oil to floc formation in the presence of oxygen.
The process comprises two steps. In the first step a hydrocracked bright stock is hydrodenitrified to reduce its heteroatom, particularly nitrogen, content using, for example, a sulfided nickel-tin catalyst having a siliceous matrix or a nickel-molybdenum hydrotreating catalyst having an alumina matrix. In the second step, the hydrocracked bright stock, having a reduced nitrogen content, is hydrofinished using, for example, an unsul-Eided nickel-tin or palladium hydrotreating catalyst having a siliceous matrix.
Both steps are carried out at an unusually low liquid hourly space velocity (LHSV), about 0.25 Hr~1. In the first step, a low LHSV permits the desired hydrodeni-trification reaction to proceed at relative low tempera-tures, about 700F. Under these conditions hydrocracking is minimized. In the second step a low LHSV permi-ts thorough saturation of aromatics which are floc-forming species. Thus, in general, the first step removes '., ~- . ' ~' Ol -2-nitrogen and sulfur, known catalyst poisons, and improves oxidation stability; and the second step saturates aro-matic Eloc precursors, and improves storage stability.
Accordingly, it has been found that the stability of the resultant lube oil hase stock is significantly improved.
Lubricant refining is based upon the fact that crude oils, as shown by experience or by assay, contain a quantity of lubricant base stocks having a predetermined set of properties such as, for example, appropriate vis-cosity, oxidation stability, and maintenance of Eluidity at low temperatures. The process of refining to isolate a lubricant base stock consists of a set of unit operations to remove or convert the unwanted components. The most common of these unit operations include, for instance, distillation, hydrocracking, dewaxing, and hydrogenation.
The lubricant base stock, isolated by these refining operations, may be used as such as a lubricant, or it may be blended with another lubricant base stock having somewhat different properties. Or, the base stock, prior to use as a lubricant, may be compounded with one or more additives which function, for example, as antioxi-dants, extreme pressure additives, and viscosity index improvers. As used herein, the term "stoclc", regardless whether or not the term is further qualified, refers to a hydrocarbon oil without additives. The term "dewaxed stock" will refer to an oil which has been treated by any method to remove or otherwise convert the wax contained therein and thereby reduce its pour point. The term "base stock" will reEer to an oil refined to a point suitable for some particular end use, such as for preparing automo-tive oils.
In general, refineries do not manufacture a si`ngle lube base stock but rather process at least one distillate fraction and one residuum fraction to produce several lube base stocks. Typically, three distillate fractions differing in boiling range and the residuum of a vacuum distillation operation are refined. These four fractions have acquired various names in the refining art, 01 -3_ the most volatile distillate ~raction often being referred to as the "light neutral" oil. The other distillates are O5 called "medium neutral" and "heavy neutral" oils. The residuum Eraction, is commonly reEerred to as "bright stock". Thus, the manufacture oE lubricant base stocks involves a process Eor producing a sla~e o~ base stocks, which slate may include a bright stock.
Processes have been proposed to produce lubri-cating oil base stocks by refining bright stocks. Most such reEining processes require hydrocracking tne bright stock to produce a hydrocrackate which is in turn dewaxed to produce a dewaxed bright stock. The problem is that lubricating oil base stocks derived from hydrocracked stocks are unstable in the presence oE oxygen and light.
Various stabilizing steps have been proposed.
U.S. Patents 3,189,540, 3,256,175 granted June 15, 1965 and June 14, 1966, respectively, to Kozlowski et al,
2~ describe a typical stabilization. The proposed stabiliza-tion uses a series of process steps employing a severe catalytic hydrogenation step to convert the remaining aromatic constituents into desirable lubricating oil con-stituents.
The goal oE hydrogenation is to hydrogenate the unstable species, which are thought to be partially satu-rated polycyclic compounds. ~nEortunately, severe hydro-genation oE hydrocracked bright stocks not only hydrogenates the undesirable polycyclic constituents, but also further hydrocracks desirable constituents resulting in the loss of valuable lubricant base stock. Thus, recent processing schemes have suggested several alternatives to severe hydrogenation.
ReEiners often now use mild hydrogenation (some-times referred to as hydrofinishing) to produce more stable lubricating oils. Obviously, mild hydrogenation requires a compromise between the desired stabilization and the undesired hydrocracking. Consequently, thorough stabilization is o~ten not accomplished. As an alterna-tive to hydrofinishing, stabilizing agents, such as ~7~4~L
olefins, alcohols, esters, or alkylhalides can be adcled toth~ hydrocrackec~ base stock in the presence of acidic 05 catalysts having controlled alkylation activity. The resulting alkylation stabilizes the aromatic floc formers.
While these and other processing schemes have achieved some success, in the case of highly aromatic stocks, such as bright stock, none of the previously known schemes is entirely satisfactory.
Thus, in general, at the time of the present invention, the ]iterature ~elating to lube oil stabiliza-tion taught the use of severe hydrogenation or, alter-natively, mild hydrofinishing and/or alkylation to stabilize a hydrocracked bright stock. However, in spite of the large amount of research into developing lubricant base stocks and stabilizing them, there continues to be intensive research into developing a more efficient and more convenient method for achieving those goals, especially for lubricant base stocks derived from hydro-cracked bright stocks. The object of the present invention is to provide such a process.
It has now been discovered that a two-step hydrogenation process comprising a first step to reduce the nitrogen and sulfur content and a second step to thoroughly hydrogenate unstable polycyclics will produce a more stable lubricating oil base stock from hydrocraclced bright stock. Thus, rather than e~ploying a single severe hydrogenation step, the present invention employs a rela-tively milder two-step hydrofinishing stabilization for hydrocracked bright stoclss.
SUMMARY OF THE INVENTION
The discovery of the present invention is embo-died in an improved process Eor stabilizing a lube base stock derived from hydrocracked bright stock, comprising:
(a) contacting said hydrocracked bright stock with hydrogen in the presence of a catalyst having hydrodeni-trification activity under conditions, including a low LHSV, effective to reduce the nitrogen content of said bright stock to less than about 50 ppm by weight, Ol -5-pre~erably less than 10 ppm by weight, and most preferably less than 3 ppm; and O5 (b) contacting the denitriEied product of step (a) with hydrogen in the presence of a catalyst having hydro-genation activity under conditions, including a low LHSV, effective to reduce the level of unsaturated polycyclic compounds to produce a lubricant base stock.
DETAILED DESCRIPTION
The hydrocarbonaceous feeds from which the hydrocracked bright stocks used in the process of this invention are obtained usually contain aromatic compounds as well as normal and branched paraffins of very long chain lengths. These feeds usually boil in the gas oil range. Preferred feedstocks are vacuum gas oils with normal boiling ranges above about 350C and below about 600C, and deasphalted residual oils having normal boiling ranges above about 480C and below about 650C. Reduced topped crude oils, shale oils, liquefied coal, coke dis-tillates, flask or thermally cracked oils, atmospheric residua, and other heavy oils can also be used as the feed source.
Typically, the hydrocarbonaceous feed is dis-tilled at atmospheric pressure to produce a reduced crude (residuum) which is then vacuum distilled to produce a distillate fraction and a vacuum residuum fraction.
According to the present process the residuum fraction is then hydrocracked using standard reaction conditions and catalysts in one or more reaction zones. The resulting hydrocracked bright stock can be further reEined, for instance dewaxed, or used as such as the feed stock to the two-step process of this invention.
In the first step of the present process, the hydrocracked bright stock is hydrodenitri~ied to reduce its nitrogen level. Conventional hydrodenitrification catalysts and conditions can be used when carrying out this step. However, in order for the second step, detailed below, to achieve complete, or nearly complete aromatic saturation, of the hydrocracked bright stock 01 ~6-which is essential to the present process; in the firststep a combination of catalysts and hydrogenation condi-05 tions which will reduce the nitrogen level of the hydro-cracked bright stock to below about 50 ppm by weight without substantially increasing the quantity of aromatic unsaturates by hydrocracking side reactions are essential.
In addition, it will be desirable to select catalysts and conditions which inherently result in cleavage of carbon-sulfur bonds with Eormation of hydrogen sulfide to achieve some level of hydrodesulfurization. Organic sulfur, like nitrogen, is deleterious to the activity of the hydrogena-tion catalysts used in the second step. It is desirable to reduce the sulfur level to less than about 50 ppm, preferably less than about 10 ppm, and most preferably less than about 3 ppm. Typical first step hydrodenitri-fication catalysts comprise a Group VIIIA metal, such as nickel or cobalt, and a Group VIA metal, such as molyb-denum or tungsten (unless otherwise noted references to the Periodic Table of Elements are based upon the IUPAC
notation) with an alumina or siliceous matri~. These and other hydrodenitrification catalysts, such as nickel-tin catalysts, are well known in the art~ U.S. Patent
The goal oE hydrogenation is to hydrogenate the unstable species, which are thought to be partially satu-rated polycyclic compounds. ~nEortunately, severe hydro-genation oE hydrocracked bright stocks not only hydrogenates the undesirable polycyclic constituents, but also further hydrocracks desirable constituents resulting in the loss of valuable lubricant base stock. Thus, recent processing schemes have suggested several alternatives to severe hydrogenation.
ReEiners often now use mild hydrogenation (some-times referred to as hydrofinishing) to produce more stable lubricating oils. Obviously, mild hydrogenation requires a compromise between the desired stabilization and the undesired hydrocracking. Consequently, thorough stabilization is o~ten not accomplished. As an alterna-tive to hydrofinishing, stabilizing agents, such as ~7~4~L
olefins, alcohols, esters, or alkylhalides can be adcled toth~ hydrocrackec~ base stock in the presence of acidic 05 catalysts having controlled alkylation activity. The resulting alkylation stabilizes the aromatic floc formers.
While these and other processing schemes have achieved some success, in the case of highly aromatic stocks, such as bright stock, none of the previously known schemes is entirely satisfactory.
Thus, in general, at the time of the present invention, the ]iterature ~elating to lube oil stabiliza-tion taught the use of severe hydrogenation or, alter-natively, mild hydrofinishing and/or alkylation to stabilize a hydrocracked bright stock. However, in spite of the large amount of research into developing lubricant base stocks and stabilizing them, there continues to be intensive research into developing a more efficient and more convenient method for achieving those goals, especially for lubricant base stocks derived from hydro-cracked bright stocks. The object of the present invention is to provide such a process.
It has now been discovered that a two-step hydrogenation process comprising a first step to reduce the nitrogen and sulfur content and a second step to thoroughly hydrogenate unstable polycyclics will produce a more stable lubricating oil base stock from hydrocraclced bright stock. Thus, rather than e~ploying a single severe hydrogenation step, the present invention employs a rela-tively milder two-step hydrofinishing stabilization for hydrocracked bright stoclss.
SUMMARY OF THE INVENTION
The discovery of the present invention is embo-died in an improved process Eor stabilizing a lube base stock derived from hydrocracked bright stock, comprising:
(a) contacting said hydrocracked bright stock with hydrogen in the presence of a catalyst having hydrodeni-trification activity under conditions, including a low LHSV, effective to reduce the nitrogen content of said bright stock to less than about 50 ppm by weight, Ol -5-pre~erably less than 10 ppm by weight, and most preferably less than 3 ppm; and O5 (b) contacting the denitriEied product of step (a) with hydrogen in the presence of a catalyst having hydro-genation activity under conditions, including a low LHSV, effective to reduce the level of unsaturated polycyclic compounds to produce a lubricant base stock.
DETAILED DESCRIPTION
The hydrocarbonaceous feeds from which the hydrocracked bright stocks used in the process of this invention are obtained usually contain aromatic compounds as well as normal and branched paraffins of very long chain lengths. These feeds usually boil in the gas oil range. Preferred feedstocks are vacuum gas oils with normal boiling ranges above about 350C and below about 600C, and deasphalted residual oils having normal boiling ranges above about 480C and below about 650C. Reduced topped crude oils, shale oils, liquefied coal, coke dis-tillates, flask or thermally cracked oils, atmospheric residua, and other heavy oils can also be used as the feed source.
Typically, the hydrocarbonaceous feed is dis-tilled at atmospheric pressure to produce a reduced crude (residuum) which is then vacuum distilled to produce a distillate fraction and a vacuum residuum fraction.
According to the present process the residuum fraction is then hydrocracked using standard reaction conditions and catalysts in one or more reaction zones. The resulting hydrocracked bright stock can be further reEined, for instance dewaxed, or used as such as the feed stock to the two-step process of this invention.
In the first step of the present process, the hydrocracked bright stock is hydrodenitri~ied to reduce its nitrogen level. Conventional hydrodenitrification catalysts and conditions can be used when carrying out this step. However, in order for the second step, detailed below, to achieve complete, or nearly complete aromatic saturation, of the hydrocracked bright stock 01 ~6-which is essential to the present process; in the firststep a combination of catalysts and hydrogenation condi-05 tions which will reduce the nitrogen level of the hydro-cracked bright stock to below about 50 ppm by weight without substantially increasing the quantity of aromatic unsaturates by hydrocracking side reactions are essential.
In addition, it will be desirable to select catalysts and conditions which inherently result in cleavage of carbon-sulfur bonds with Eormation of hydrogen sulfide to achieve some level of hydrodesulfurization. Organic sulfur, like nitrogen, is deleterious to the activity of the hydrogena-tion catalysts used in the second step. It is desirable to reduce the sulfur level to less than about 50 ppm, preferably less than about 10 ppm, and most preferably less than about 3 ppm. Typical first step hydrodenitri-fication catalysts comprise a Group VIIIA metal, such as nickel or cobalt, and a Group VIA metal, such as molyb-denum or tungsten (unless otherwise noted references to the Periodic Table of Elements are based upon the IUPAC
notation) with an alumina or siliceous matri~. These and other hydrodenitrification catalysts, such as nickel-tin catalysts, are well known in the art~ U.S. Patent
3,227,661 granted January 4, 1966 to Jacobson et al, describes a method which may be used to prepare a suitable hydrodenitrification catalyst.
Typical hydrodenitrification conditions which are useeul in the Eirst step of the present process vary over a fairly wide range, but in general temperatures range from about 600F to about 850F, preferably from about 650F to 800F, pressures range from about 500 psig to about 4000 psig, preferably from about 1500 psig to about 3000 psig, contact times expressed as LHSV range from about 0.1 per hour to about 3 per hour, preferably from about 0.1 per hour to about 0.8 per hour, and hydro-gen rates range from about 5000 cu. ft. per barrel to about 15,000 cu. ft. per barrel. U.S. Patent 3,227,661 describes those conditions required for various processing schemes using the denitrification catalysts taught in that ~27~4~
patent. A general discussion of hydrodenitri~ication is avail-able in U.S. Patent 3,073,221 granted on E'ebruary L9, 1963 to Beuther et al. As previously discussed, the overlying consi.-deration, when selecting suitable denitrification conditions from the general conditions taught in these patents and the art generally, is -the use of a relatively low LHSV and tempera-ture in order to achieve nearly complete denitrification with mini-mal hydrocracking.
In the second step of the present process the denitrified, "clean" stock is hydrofinished using a mild hydro-genation catalyst and conditions. Suitable catalysts can be selected from conventional hydrofinishing ca-talysts having hydrogenation activity. Since this step can also be carried out under relatively mild conditions when a low LHSV is employed, it is preferable to use a hydro~enation catalyst such as, for example, a noble metal from Group VIIIA, such as palla-dium, on a refractory oxide support, or unsulfided Group VIIIA
and Group VI, such as nickel-molybdenum, or nickel-tin cata-lysts. U.S. Patent 3,852,207 granted on December 3, 1974 to Stangeland et al, describes suitable noble metal catalysts and mild conditions.
As mentioned already, suitable hydrofinishing condi-tions should be selected to achieve as complete hydrogenation of unsaturated aromatic as possible. Since the first step has removed the common hydrogenation catalyst poisons, the second step run length can be relatively long affording the opportuni-~
ty to use a relatively low LHSV and mild conditions. Suitable conditions include a temperature ranging from about 300F to about 600F, preferably from about 350F to about 550F, a 30 pressure ranging ~rom about 500 psig to about 4000 psig, preferably from about 1500 psig to about 3000 psig, and an LHSV
ranging from about 0.1 to about 2.0 per hour, preferably from about 0.1 per hour to about 0.5 per hour. Thus, in genera~
terms the clear hydrodenitrified effluen-t of the first step is contacted with hydrogen in the presence of a hydrogenation catalyst under mild hydrogenation Ol ~~~ 61936-171~
conditions. Otller suitable catalysts are detailed, for instance in U.S. Patenk No. 4,157,294 granted June 5, 1979 05 to Iwao et al and No. 3,904,513, granted Septe~nber 9, 1975 to Fischer et alb ~
The product oE the process of the present i~nven-tion is suitable for use as a lubricant base stock.
Typically, it is dewaxed, if that has not already been done, prior to final blending.
The present invention is exemplified below. The examples are intended to illustrate representative embodi-ments of the invention and results which have been obtained in laboratory analysis. Those familiar with the lS art will appreciate that other embodiments of the inven-tion will provide equivalent results without departing from the essential eatures of the invention.
EXAMPLES
Example 1 ~U In a single step stabilization carried out for comparison with the two-step process of the present inven-tion, a solvent dewaxed hydrocracked bright stock (Table I) was hydrofinished over a sulfidcd nickel-tin on silica-alumina hydrogenation catalyst at 705-716F, 0.25 LHSV, 2200 p~ig, and 8 M SCF/bbl H2. At 1080 hours onstream and 716F, conversion below 900F was 22 wt. ~.
Product sulfur was 33 ppm and nitrogen 6.7 ppm. The prod-uct was tested for storage stability by placing 40 cc. o oil in an unstoppered cylindrical glass bottle of 1-3/8 inches diameter and putting the bottle in a forced convec-tion oven controlled at 250F. The sarnple was examined once per day for floc. The test was ended when a ~loderate to heavy floc could be observed. The product form~d heavy floc within one day. The oxidator BN was 4.6 hours.
In order to illustrate the two-step process of the present invention and obtain a comparison with the single step process described above, the denitrified prod-uct from Exa~lple l was subjected to a second hydrofinish-ing over a catalyst composed of 2 wt. ~ palladiwn on silica-alurnina. Hydrofinishing conditions were 0.25 LHSV, P~ ' '' ' ' ' ' . . ' .
~27~
400F, 2200 psig, and 8 M SCF/bbl 1~2~ The 250F storage stability of the product from 0-500 hours onstream was 15 05 days, and the oxidator BN was 20.0 hours demonstrating the significant benefit oE the two-stage process.
Example_2 In a seconA comparison with the single step process of Example 1, the denitrified product from Example 1 was subjected to a second hydrofinishing over the palla-dium catalyst of Example 1, and at the same conditions except for an LHSV of 1Ø After 48 hours onstream, the product had a 250F storage stability of 4 days, demonstrating the importance of low LHSV to successfully stabilize the bright stock.
Example 3 In another comparative test, the dewaxed hydro-cracked bright stock feed (Table I) was hydrofinished over a sulfided Ni-Mo on alumina hydrogenation catalyst at 0.5 LHSV, 760-767F, 2200 psig, and 8M SCF/bbl H2 for 584 hours. At 584 hours onstream and a catalyst tempera-ture of 767F, conversion below 900F was 26 wt. ~. Prod-uct sulfur was 4.6 ppm and nitrogen 73 ppm. The product samples were combined and tested for 250F storage stability, which was found to be less than one day.
The first stage run with Ni-Mo on alumina described above was continued for another 600 hours, but at an LHSV of 0.25 and a catalyst temperature of 742F.
Conversion below 900F was 27 wt. ~. Product sulfur was 1.8 ppm and nitrogen 17 ppm, well below that achievable at 0.5 LHSV and the same conversion. The 250F storage stability was less than one day. This product was then hydrofinished in a second stage over a fresh charge of the Pd/SiO2-A12O3 catalyst of Example 1 at 0.25 LHSV, 350F, 2200 psig, and 8 M SCF/bbl H2. ~fter 182 hours, the 250F
storage stability was 15~ days.
~L27~
T~BLE I
_ Dewaxe ~ ocracked Bri~ht Stock_Ins~ections Gravity, API 21.8 Sulfur, ppm 970 Nitrogen, ppm 980 l0 Pour Point, F +10 Viscosity, cSt, 40C 1148.0 Distillation, LV~, F
. . .
Oxidator BNr hr.2.5 ;~ () .
Typical hydrodenitrification conditions which are useeul in the Eirst step of the present process vary over a fairly wide range, but in general temperatures range from about 600F to about 850F, preferably from about 650F to 800F, pressures range from about 500 psig to about 4000 psig, preferably from about 1500 psig to about 3000 psig, contact times expressed as LHSV range from about 0.1 per hour to about 3 per hour, preferably from about 0.1 per hour to about 0.8 per hour, and hydro-gen rates range from about 5000 cu. ft. per barrel to about 15,000 cu. ft. per barrel. U.S. Patent 3,227,661 describes those conditions required for various processing schemes using the denitrification catalysts taught in that ~27~4~
patent. A general discussion of hydrodenitri~ication is avail-able in U.S. Patent 3,073,221 granted on E'ebruary L9, 1963 to Beuther et al. As previously discussed, the overlying consi.-deration, when selecting suitable denitrification conditions from the general conditions taught in these patents and the art generally, is -the use of a relatively low LHSV and tempera-ture in order to achieve nearly complete denitrification with mini-mal hydrocracking.
In the second step of the present process the denitrified, "clean" stock is hydrofinished using a mild hydro-genation catalyst and conditions. Suitable catalysts can be selected from conventional hydrofinishing ca-talysts having hydrogenation activity. Since this step can also be carried out under relatively mild conditions when a low LHSV is employed, it is preferable to use a hydro~enation catalyst such as, for example, a noble metal from Group VIIIA, such as palla-dium, on a refractory oxide support, or unsulfided Group VIIIA
and Group VI, such as nickel-molybdenum, or nickel-tin cata-lysts. U.S. Patent 3,852,207 granted on December 3, 1974 to Stangeland et al, describes suitable noble metal catalysts and mild conditions.
As mentioned already, suitable hydrofinishing condi-tions should be selected to achieve as complete hydrogenation of unsaturated aromatic as possible. Since the first step has removed the common hydrogenation catalyst poisons, the second step run length can be relatively long affording the opportuni-~
ty to use a relatively low LHSV and mild conditions. Suitable conditions include a temperature ranging from about 300F to about 600F, preferably from about 350F to about 550F, a 30 pressure ranging ~rom about 500 psig to about 4000 psig, preferably from about 1500 psig to about 3000 psig, and an LHSV
ranging from about 0.1 to about 2.0 per hour, preferably from about 0.1 per hour to about 0.5 per hour. Thus, in genera~
terms the clear hydrodenitrified effluen-t of the first step is contacted with hydrogen in the presence of a hydrogenation catalyst under mild hydrogenation Ol ~~~ 61936-171~
conditions. Otller suitable catalysts are detailed, for instance in U.S. Patenk No. 4,157,294 granted June 5, 1979 05 to Iwao et al and No. 3,904,513, granted Septe~nber 9, 1975 to Fischer et alb ~
The product oE the process of the present i~nven-tion is suitable for use as a lubricant base stock.
Typically, it is dewaxed, if that has not already been done, prior to final blending.
The present invention is exemplified below. The examples are intended to illustrate representative embodi-ments of the invention and results which have been obtained in laboratory analysis. Those familiar with the lS art will appreciate that other embodiments of the inven-tion will provide equivalent results without departing from the essential eatures of the invention.
EXAMPLES
Example 1 ~U In a single step stabilization carried out for comparison with the two-step process of the present inven-tion, a solvent dewaxed hydrocracked bright stock (Table I) was hydrofinished over a sulfidcd nickel-tin on silica-alumina hydrogenation catalyst at 705-716F, 0.25 LHSV, 2200 p~ig, and 8 M SCF/bbl H2. At 1080 hours onstream and 716F, conversion below 900F was 22 wt. ~.
Product sulfur was 33 ppm and nitrogen 6.7 ppm. The prod-uct was tested for storage stability by placing 40 cc. o oil in an unstoppered cylindrical glass bottle of 1-3/8 inches diameter and putting the bottle in a forced convec-tion oven controlled at 250F. The sarnple was examined once per day for floc. The test was ended when a ~loderate to heavy floc could be observed. The product form~d heavy floc within one day. The oxidator BN was 4.6 hours.
In order to illustrate the two-step process of the present invention and obtain a comparison with the single step process described above, the denitrified prod-uct from Exa~lple l was subjected to a second hydrofinish-ing over a catalyst composed of 2 wt. ~ palladiwn on silica-alurnina. Hydrofinishing conditions were 0.25 LHSV, P~ ' '' ' ' ' ' . . ' .
~27~
400F, 2200 psig, and 8 M SCF/bbl 1~2~ The 250F storage stability of the product from 0-500 hours onstream was 15 05 days, and the oxidator BN was 20.0 hours demonstrating the significant benefit oE the two-stage process.
Example_2 In a seconA comparison with the single step process of Example 1, the denitrified product from Example 1 was subjected to a second hydrofinishing over the palla-dium catalyst of Example 1, and at the same conditions except for an LHSV of 1Ø After 48 hours onstream, the product had a 250F storage stability of 4 days, demonstrating the importance of low LHSV to successfully stabilize the bright stock.
Example 3 In another comparative test, the dewaxed hydro-cracked bright stock feed (Table I) was hydrofinished over a sulfided Ni-Mo on alumina hydrogenation catalyst at 0.5 LHSV, 760-767F, 2200 psig, and 8M SCF/bbl H2 for 584 hours. At 584 hours onstream and a catalyst tempera-ture of 767F, conversion below 900F was 26 wt. ~. Prod-uct sulfur was 4.6 ppm and nitrogen 73 ppm. The product samples were combined and tested for 250F storage stability, which was found to be less than one day.
The first stage run with Ni-Mo on alumina described above was continued for another 600 hours, but at an LHSV of 0.25 and a catalyst temperature of 742F.
Conversion below 900F was 27 wt. ~. Product sulfur was 1.8 ppm and nitrogen 17 ppm, well below that achievable at 0.5 LHSV and the same conversion. The 250F storage stability was less than one day. This product was then hydrofinished in a second stage over a fresh charge of the Pd/SiO2-A12O3 catalyst of Example 1 at 0.25 LHSV, 350F, 2200 psig, and 8 M SCF/bbl H2. ~fter 182 hours, the 250F
storage stability was 15~ days.
~L27~
T~BLE I
_ Dewaxe ~ ocracked Bri~ht Stock_Ins~ections Gravity, API 21.8 Sulfur, ppm 970 Nitrogen, ppm 980 l0 Pour Point, F +10 Viscosity, cSt, 40C 1148.0 Distillation, LV~, F
. . .
Oxidator BNr hr.2.5 ;~ () .
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An improved process for stabilizing a lubricat-ing oil base stock derived from a hydrocracked bright stock, comprising:
(a) contacting said hydrocracked bright stock with hydrogen in the presence of a catalyst having hydrodeni-trification activity under conditions effective to reduce the nitrogen content of said stock to produce a substan-tially nitrogen-free product; and (b) contacting said substantially nitrogen-free product with hydrogen in the presence of a catalyst having hydrogenation activity under mild conditions to produce a stabilized lubricating oil base stock.
(a) contacting said hydrocracked bright stock with hydrogen in the presence of a catalyst having hydrodeni-trification activity under conditions effective to reduce the nitrogen content of said stock to produce a substan-tially nitrogen-free product; and (b) contacting said substantially nitrogen-free product with hydrogen in the presence of a catalyst having hydrogenation activity under mild conditions to produce a stabilized lubricating oil base stock.
2. A process according to Claim 1 wherein the cata-lyst having hydrodenitrification activity comprises at least metal from Group VIIIA and at least one metal from Group VIA or tin supported on an alumina or siliceous matrix.
3. A process according to Claim 2 wherein said Group VIIIA metal is nickel or cobalt and said Group VIA
metal is molybdenum or tungsten.
metal is molybdenum or tungsten.
4. A process according to Claim 3 wherein said catalyst is sulfided.
5. A process according to Claim 1 wherein said hydrodenitrification is carried out at a temperature ranging from about 600°F to about 850°F, a pressure ranging from about 500 psig to about 4000 psig, an LHSV
ranging from about 0.1 hr.-1 to about 3 hr.-1, and a sub-stantial hydrogen partial pressure.
ranging from about 0.1 hr.-1 to about 3 hr.-1, and a sub-stantial hydrogen partial pressure.
6. A process according to Claim 5 wherein said LHSV
is from about 0.1 hr.-1 to about 0.8 hr-1.
is from about 0.1 hr.-1 to about 0.8 hr-1.
7. A process according to Claim 6 wherein said LHSV is about 0.25 hr.-1.
8. A process according to Claim 1 wherein said catalyst having hydrogenation activity comprises at least one Group VIIIA noble metal supported on a refractory oxide.
9. A process according to Claim 8 wherein said noble metal is palladium.
10. A process according to Claim 1 wherein said hydro-genation of the substantially nitrogen free product is carried out at a temperature ranging from about 300°F to about 600°F
and is below the temperature at which the hydrodenitrification is carried out, a pressure ranging from about 500 psig to about 4000 psig, and an LHSV ranging from about 0.1 hr.-1 to about 2 hr.-1 and a substantial hydrogen partial pressure.
and is below the temperature at which the hydrodenitrification is carried out, a pressure ranging from about 500 psig to about 4000 psig, and an LHSV ranging from about 0.1 hr.-1 to about 2 hr.-1 and a substantial hydrogen partial pressure.
11. A process according to Claim 10 wherein said LHSV
ranges from about 0.1 hr.-1 to about 0.5 hr.-1.
ranges from about 0.1 hr.-1 to about 0.5 hr.-1.
12. A process according to Claim 11 wherein said LHSV is about 0.25 hr.-1.
13. A process according to Claim 1 wherein, the hydro-denitrification is a sulfided catalyst comprising nickel and molybdenum on an alumina support and said hydrodenitrification is carried out at a temperature of about 725°F, a pressure of about 2000 psig and an LHSV of about 0.25 hr.-1, and said cata-lyst having hydrogenation activity comprises palladium on a siliceous support and said hydrogenation is carried out at a temperature of about 400°F and an LHSV of about 0.25 hr.-1.
14. A process according to Claim 13 wherein said nitro-aromatic-containing stock is a dewaxed hydrocracked bright stock derived from a vacuum residuum fraction of a topped crude oil.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US790,704 | 1985-10-24 | ||
| US06/790,704 US4627908A (en) | 1985-10-24 | 1985-10-24 | Process for stabilizing lube base stocks derived from bright stock |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1271441A true CA1271441A (en) | 1990-07-10 |
Family
ID=25151516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000512865A Expired - Fee Related CA1271441A (en) | 1985-10-24 | 1986-07-02 | Process for stablizing lube base stocks derived from bright stock |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4627908A (en) |
| JP (1) | JPS62101689A (en) |
| CA (1) | CA1271441A (en) |
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-
1985
- 1985-10-24 US US06/790,704 patent/US4627908A/en not_active Expired - Lifetime
-
1986
- 1986-07-02 CA CA000512865A patent/CA1271441A/en not_active Expired - Fee Related
- 1986-08-25 JP JP61197456A patent/JPS62101689A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62101689A (en) | 1987-05-12 |
| US4627908A (en) | 1986-12-09 |
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