CA1102778A - Hydroconversion catalyst and process - Google Patents
Hydroconversion catalyst and processInfo
- Publication number
- CA1102778A CA1102778A CA283,492A CA283492A CA1102778A CA 1102778 A CA1102778 A CA 1102778A CA 283492 A CA283492 A CA 283492A CA 1102778 A CA1102778 A CA 1102778A
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- catalyst
- catalyst according
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A B S T R A C T
An improved spherical hydroconversion catalyst is disclosed having a diameter greater than 6 mm, a surface area above 200 m2/gm, and a crush strength above 31.7 kg. Mineral oils are hydroconverted with the alumina supported catalyst composited with a Group VI-B
and a Group V?II metal.
An improved spherical hydroconversion catalyst is disclosed having a diameter greater than 6 mm, a surface area above 200 m2/gm, and a crush strength above 31.7 kg. Mineral oils are hydroconverted with the alumina supported catalyst composited with a Group VI-B
and a Group V?II metal.
Description
~7~
- This invention relates to an improved hydroconversion catalyst wherein the improvement is attributed to particular physical charac-teristics of the alumina-based catalyst, and to hydroconversion processes employing it,such as hydrogenation, hydrodemetallization, hydrodesulphurization and hydrodenitrogenation.
It is well known to purify mineral oils, such as crude oil, petroleum fract~ns, shale oils, coal tar distillates,petroleum residues and the like with hydrogen in the presence of a catalyst.
Typically the catalyst i~ deployed in the hydroconversion zone in one or more fixed beds. Often these beds are supported or retained at their inlet or outlet, or both by materials which are inert to the reaction, in order to facilitate even distribution o~ the feedstock, that is, to prevent or reduce channelling through the catalyst bed; and to trap undesirable materials in the feedstock Yuch as corroæion products and other particulate matter as may be present in the feedstock, in order to prevent such undesirable material from pluggine or otherwise deactivating the catalyst bed.
The inert materials, which conventionally are in the form of pellets or spheres, typically must be resistant to crushing under the weight of catalyst beds which in an uprieht reactor may have depths of 15 m or more.
; In many large hydroconversion reactors such as employed in petroleum refining, the inerts will occupy a substantial portion of the reaction zone, e.g., up to 15 to 20% or more of the reaction zone volume. Further, many hydroconversion processes often employ high pressures up to several hundreds kg/cm requiring e~pensive pressure reactors. Accordingly, the use of inerts adds to the capitaI
expense of a hydroconversion process both for the reactors which must be oversized to accommodate the inerts and for the costs of the inerts which do not contribute in any significant manner to desired hydroconversion of the feedstock. In addition, it would be highly desirable to increase the efficacy of existing hydroconversion processes by replncing the volume of inerts in the renction zone .
,.
~ . . . - - ~ . :
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with an active catalyst capable not only of performing the functions of the inert material, but of enhancing the desired conversion process as well. Thus, the development of a catalyst which would make it possible to carry out hydrotreatment at greater efficiency and lower cost was desired.
According to the invention there is provided an improved hydro-conversion spherical catalyst consisting essentially of alumina, optionally containing up to 6% by weight of silica, as support, and from 2 to 20% by weight of a Group VI-B metal and from 0.5 to 10%
by weight of Group VIII metal each in the form of metals or their oxides or sulphides and having a diameter greater than 6 mm, a surf&ce area above 200 m /gm and a crush strength above 31.7 kg.
The invention further provides a process for use of the catalyst which comprises passing mineral oil feedstock and a hydrogen containing gas through a reaction zone at elevated temperature and pressure and recovering the hydroconverted oil from the reaction zone.
The spherical alumina-based supports for the catalyst according to the invention are preferably gamma- or eta-~1umina. They may be prepared according to known processes in sizes from about 6 to about 30 mm. Generally, the use of spherical particles less than 6 mm tends to plug more readily and be less ef~'ective in distributing feed across the initial contact layer of catalyst, whereas the use of spherical particles having diameters above about 25-30 mm results in catalysts having significantly lower activity. Preferred are particles having diameters above 9 mm and particularly above 13 mm.
Preferably, the catalysts of the invention employed as mixtures of particles having a size ratio in the range of from about 1.5 : 1 to about 3 : 1. Thus, for example, the support materials may comprise mixtures of particles having diameters from about 6 to 9 ~m to about 8 to 25 mm. A particularly preferred cat~lyst comprises mixtures of particles having diameters in the range of from about 6 to about 13 mm. The term "spherical" herein refers to particles having both a true rounded shape and those generally spheroidal particles which _4_ ~77~ ~
do not pass perfectly rounded configurations. Procedures for preparing these particles are known in the art and are not part of the present invention.
The support is further characterized by a surface area greater than 200 square metres per gra~ and preferably above 250 square metres per gram and which may extend up to 600 square metres per gram or more. Catalysts prepared from a~umina having a surface area of less than 200 square metres per gram generally ha~e poorer activity when employed in the present hydroconversion process in comparison to catalysts in which the alumina-based support initially is characterized by a surface area in substantial excess of 200 square metres per gram. The term "surface area" as used herein designates the surface area as determined by the adsorption of nitrogen according to the method of Brunnauer et al., Journal of the American Chemical Society 60, 309 et. seq. (1938).
The alumina-based support is preferably all alumina but may contain minor amounts, i.e., up to 6% by weight of silica. The silica may be incorporated into the alumina prior to shaping, but preferably is applied as a surface coating to the preformed alumina, e.g., with sodium silicate, according to procedures well known in in the art. Preferred as catalyst supports are spherical aluminas having crush strenethsabove 36.3 kg and particularly preferred are supports having crush strengths above 40.8 ke.
The crush strength herein refers to the average value obtained on at least 20 spherical particles by the following procedure:
A catalyst particle is placed between two parallel horizontal plates, one stationary and one movable. A gradually increasing force is applied to the movable plate perpendicular to the surface of the plate until the catalyst particle breaks. That force in kilograms which was applied at the instant the particle breaks, is considered as the crush strength.
The catalyst according to this invention comprises a metal of Group VI-B and a metal of Group VIII compounded with the alumina-based .~
_5_ ~ 77~
support. Accordingly, the catalyst may comprise at least one of the metals chromium, molybdenum and tungsten in combination with at least one of e.g. the metals iron, nickel, cobalt, platinum, palladium and iridium. Of the Group VI-B metals, molybdenum is most preferred. The final catalyst most suitably will contain from 2 to 20 per cent by weight of Group VI-B metal. Of the Group VIII metals, nickel and cobalt are preferred. ~he amount of Group VIII metal in the final catalyst suitably will be in the range of from 0.5 to 10 per cent by weight. Particularly effective catalysts are obtained utilizing as Group VIII metal nickel or cobalt. The weight ratio of Group VIII metal to Group VI-B met~l is preferably from 0.20 : 1 to 0.55 : 1, with a ratio of from 0.25 : 1 to 0.5 : 1 being preferred in particular.
The metal components can be composited with the alumina-based spherical particles in any suitable manner. For example, the particles can be impregnated by dipping or soaking utilizi~g individual solutions of a suitable compound of a Group VI-B metal and a suitable Group VIII metal compound, in any convenient sequence. Alternatively, the metals may be composited with the spherical alumina particles in a common solution containing suit-able compounds of both a Group VI-B metal and a Group VIII metal.
Suitable compounds of Group VI-B metals include molybdic acid, ammonium molybdate, ammonium para-molybdate, chromium acetate, chromous chloride, = onium meta-tungstate and tungstic acid.
Compounds of Group VIII which are suitable include cobalt chloride, cobalt carbonate, cobalt sulphate, cobalt nitrate, cobalt fluoride, nickel nitrate, nic~el sulphate, nickel bromide, nickel acetate, nickel formate, nickel carbonate, ferric nitrate, ferric formate, ferric acetate, platinum chloride, chloroplatinic acid and pPl-ladium chloride. The compositing may be facilitated by the use of compositing aids, such as a~monium hydro~ide. After all the catalytic components are present in the final catalyst composite, the particles suitably are dried for a period of 1 to 20 hours at .~
-.
-6- ~ 7 ~ 8 temperatures from about 90 to about 150C and calcined in an oxidizing atmosphere such as air at temperatures from about 400 to 700 C for a period from about 1 to about 10 hours or more.
The finished catalyst is usually activated in the presence of hydrogen preferably containing about 1-30 mol. per cent of hydroeen sulphide at a temperature between 150 and 400C prior to its use.
The finished catalyst is useful for effecting various mineral oil conversion reactions, such as demetallization, desulphur-ization, denitrogenation, hydrogenation and the like. Accordingly, the process of the invention comprises passing mineral oil feed-stock and a hydrogen-containing gas through a reæction zone con-taining the catalyst of the invention at an elevated temperature of 100 to 500 C and a total pressure of 0.35 - 700 kg/cm2 and recover-ing the hydroconverted oil from the reaction zone. The catalyst is suitably employed at liquid hourly space velocities (L~SV) from about 0.2 to about 12 1. feedstock/l. catalyst per hour and from about 53 to 1780 1. of added hydrogen per 1. of feed. Particularly preferred conditions are temperatures in the range of from about 250 to 475 C, total pressures from about 7 to about 350 kg/cm ~
uid hourly space velocities from about 0.4 to about 9 1. feed-stock/l. catalyst per hour and 89 to 4~5 1. of added hydrogen per 1. of feed.
Owing to the unique combination of physical properties the ; 25 particularly preferred embodiment of the process of the invention utilizes an upright reaction zone wherein ~e feedstock contacts initially and/or finally catalyst according to the invention.
That is,the catalyst of the invention will substantially or entirely replace the inert pellets, balls or spheres conventionally employed, resulting in higher catalytic activity and conversion efficiency. ~or many existing hydroconvexsion processes the catalyst according to the invention will suitably replace only .
rT
the inert material while retaining the catalyst heretofore employed for hydrodesulphurization, hydrodenitrogenation, hydrocracking and the like. That is, the catalyst according to the invention will be disposed in layers having a depth from a few to a few fundred centimetres above and/or below the conventionally employed catalyst. This is particularly useful for processes emp~ing highly packed small sized extrudates since the generally larger spherical catalyst of the invention, owing to configuration, will have a ereater void fraction for particulate retention. However, the duration of satisfactory operation will generally be much longer when employing the catalyst of the invention, than if the inerts were replaced solely with, e.g., small-sized extrudates.
Unexpectedly, it has been found that for hydrogenation of highly unsaturated feedstocks such as pyrollizates, e.g., distillates from steam cracking of hydrocarbons, such as naphthas and gas oils, the use of the instant catalysts in place of conventional inertæ of like size results in significant reduction of polymeric deposits within the reaction zone.
Accordingly, the enhanced activity of the reaction zone employing the catalyst of the invention can be used to reduce the operatine temperatures conventionally employed, thereby conserving expensive fuel, or where equipment permits to increase throughput for a given conversion level.
In order to illustrate the method of the present invention the following examples are given.
EXAMPLE I
A mixture of alumina spheres obtained commercially and having a ; particle size in the ranee of from about 6 to 13 mm was impregnated with a solution containing nickel nitrate hexahydrate and ammonium dimolybdate in a mixture of aqua ammonia and water. The spheres were separated from the solutDn, and dried at about 95C for one hour.
The dried composite spheres, which were calcined in air for about one hour at about 500 C, were found to contain 1.8% by weight of nickel and 5.4% by weight of molybdenum. The catalyst had a -8- 1~77~
surface area of about 300 m /gm and a crush strength of about 37.3 kg.
About 10 cubic centimetres (8.3 grams) of the catalyst were placed in a fixed bed upright tubular reactor. The catalyst was sulphided by circulating hydrogen gas containing 5% by weight H2S
for 2 hours at about 204 C,for one hour at about 260C and finPlly for 2 hours at about 371C. A mid-continent catalytically cracked heavy gas oil was charged downflow through the bed in a once-through operation at a liquid hourly space velocity of about 1O5 l. feedstock/l. catPlyst per hour and in admixture with recycle hydrogen. The hydrogen was recycled to the reactor at the rate of about 4.0 hydrogen to oil molar ratio. The feedstock had a 50%w boiling point of about 350 C, an API gravity of 17.1 at 60 F,-a carbon content of 88.o3% by weight, a hydrogen content of 10.51% by weight, a sulphur concentration of 1.37% by weight and a nitrogen concentration of 87 parts ~r million. The feedstock was preheated entering the catalyst bed at a temperature of about 343 C and a total pressure of 60 kg/cm . The catQlyst was found to be effective for hydrogenation resulting in hydrogen con-sumption of 55.4 l of hydrogen per l., the hydrotreated product analyzed 0.59% by weight sulphur and 643 ppm nitrogen.
For purposes of comparison the above procedure was repeated except that a portion of the unimpregnated alumina support was used in place of the catalyst. No hydrogen consumption, de-sulphurization or denitrogenation activity was found.
For further purposes of comparison, the above procedure was again repeated except that the catalyst was replaced using com-B mercially available inert spherical material available from Norton~
and having a particle size of about 6-8 mm and a crush strength above 45.3 kg. This material too was found not to have any significant hydroconversion effect. The results of the above tests are summarized in the following Table:
~ ~/7Q~/e fr?~
.
- This invention relates to an improved hydroconversion catalyst wherein the improvement is attributed to particular physical charac-teristics of the alumina-based catalyst, and to hydroconversion processes employing it,such as hydrogenation, hydrodemetallization, hydrodesulphurization and hydrodenitrogenation.
It is well known to purify mineral oils, such as crude oil, petroleum fract~ns, shale oils, coal tar distillates,petroleum residues and the like with hydrogen in the presence of a catalyst.
Typically the catalyst i~ deployed in the hydroconversion zone in one or more fixed beds. Often these beds are supported or retained at their inlet or outlet, or both by materials which are inert to the reaction, in order to facilitate even distribution o~ the feedstock, that is, to prevent or reduce channelling through the catalyst bed; and to trap undesirable materials in the feedstock Yuch as corroæion products and other particulate matter as may be present in the feedstock, in order to prevent such undesirable material from pluggine or otherwise deactivating the catalyst bed.
The inert materials, which conventionally are in the form of pellets or spheres, typically must be resistant to crushing under the weight of catalyst beds which in an uprieht reactor may have depths of 15 m or more.
; In many large hydroconversion reactors such as employed in petroleum refining, the inerts will occupy a substantial portion of the reaction zone, e.g., up to 15 to 20% or more of the reaction zone volume. Further, many hydroconversion processes often employ high pressures up to several hundreds kg/cm requiring e~pensive pressure reactors. Accordingly, the use of inerts adds to the capitaI
expense of a hydroconversion process both for the reactors which must be oversized to accommodate the inerts and for the costs of the inerts which do not contribute in any significant manner to desired hydroconversion of the feedstock. In addition, it would be highly desirable to increase the efficacy of existing hydroconversion processes by replncing the volume of inerts in the renction zone .
,.
~ . . . - - ~ . :
~Z77~
with an active catalyst capable not only of performing the functions of the inert material, but of enhancing the desired conversion process as well. Thus, the development of a catalyst which would make it possible to carry out hydrotreatment at greater efficiency and lower cost was desired.
According to the invention there is provided an improved hydro-conversion spherical catalyst consisting essentially of alumina, optionally containing up to 6% by weight of silica, as support, and from 2 to 20% by weight of a Group VI-B metal and from 0.5 to 10%
by weight of Group VIII metal each in the form of metals or their oxides or sulphides and having a diameter greater than 6 mm, a surf&ce area above 200 m /gm and a crush strength above 31.7 kg.
The invention further provides a process for use of the catalyst which comprises passing mineral oil feedstock and a hydrogen containing gas through a reaction zone at elevated temperature and pressure and recovering the hydroconverted oil from the reaction zone.
The spherical alumina-based supports for the catalyst according to the invention are preferably gamma- or eta-~1umina. They may be prepared according to known processes in sizes from about 6 to about 30 mm. Generally, the use of spherical particles less than 6 mm tends to plug more readily and be less ef~'ective in distributing feed across the initial contact layer of catalyst, whereas the use of spherical particles having diameters above about 25-30 mm results in catalysts having significantly lower activity. Preferred are particles having diameters above 9 mm and particularly above 13 mm.
Preferably, the catalysts of the invention employed as mixtures of particles having a size ratio in the range of from about 1.5 : 1 to about 3 : 1. Thus, for example, the support materials may comprise mixtures of particles having diameters from about 6 to 9 ~m to about 8 to 25 mm. A particularly preferred cat~lyst comprises mixtures of particles having diameters in the range of from about 6 to about 13 mm. The term "spherical" herein refers to particles having both a true rounded shape and those generally spheroidal particles which _4_ ~77~ ~
do not pass perfectly rounded configurations. Procedures for preparing these particles are known in the art and are not part of the present invention.
The support is further characterized by a surface area greater than 200 square metres per gra~ and preferably above 250 square metres per gram and which may extend up to 600 square metres per gram or more. Catalysts prepared from a~umina having a surface area of less than 200 square metres per gram generally ha~e poorer activity when employed in the present hydroconversion process in comparison to catalysts in which the alumina-based support initially is characterized by a surface area in substantial excess of 200 square metres per gram. The term "surface area" as used herein designates the surface area as determined by the adsorption of nitrogen according to the method of Brunnauer et al., Journal of the American Chemical Society 60, 309 et. seq. (1938).
The alumina-based support is preferably all alumina but may contain minor amounts, i.e., up to 6% by weight of silica. The silica may be incorporated into the alumina prior to shaping, but preferably is applied as a surface coating to the preformed alumina, e.g., with sodium silicate, according to procedures well known in in the art. Preferred as catalyst supports are spherical aluminas having crush strenethsabove 36.3 kg and particularly preferred are supports having crush strengths above 40.8 ke.
The crush strength herein refers to the average value obtained on at least 20 spherical particles by the following procedure:
A catalyst particle is placed between two parallel horizontal plates, one stationary and one movable. A gradually increasing force is applied to the movable plate perpendicular to the surface of the plate until the catalyst particle breaks. That force in kilograms which was applied at the instant the particle breaks, is considered as the crush strength.
The catalyst according to this invention comprises a metal of Group VI-B and a metal of Group VIII compounded with the alumina-based .~
_5_ ~ 77~
support. Accordingly, the catalyst may comprise at least one of the metals chromium, molybdenum and tungsten in combination with at least one of e.g. the metals iron, nickel, cobalt, platinum, palladium and iridium. Of the Group VI-B metals, molybdenum is most preferred. The final catalyst most suitably will contain from 2 to 20 per cent by weight of Group VI-B metal. Of the Group VIII metals, nickel and cobalt are preferred. ~he amount of Group VIII metal in the final catalyst suitably will be in the range of from 0.5 to 10 per cent by weight. Particularly effective catalysts are obtained utilizing as Group VIII metal nickel or cobalt. The weight ratio of Group VIII metal to Group VI-B met~l is preferably from 0.20 : 1 to 0.55 : 1, with a ratio of from 0.25 : 1 to 0.5 : 1 being preferred in particular.
The metal components can be composited with the alumina-based spherical particles in any suitable manner. For example, the particles can be impregnated by dipping or soaking utilizi~g individual solutions of a suitable compound of a Group VI-B metal and a suitable Group VIII metal compound, in any convenient sequence. Alternatively, the metals may be composited with the spherical alumina particles in a common solution containing suit-able compounds of both a Group VI-B metal and a Group VIII metal.
Suitable compounds of Group VI-B metals include molybdic acid, ammonium molybdate, ammonium para-molybdate, chromium acetate, chromous chloride, = onium meta-tungstate and tungstic acid.
Compounds of Group VIII which are suitable include cobalt chloride, cobalt carbonate, cobalt sulphate, cobalt nitrate, cobalt fluoride, nickel nitrate, nic~el sulphate, nickel bromide, nickel acetate, nickel formate, nickel carbonate, ferric nitrate, ferric formate, ferric acetate, platinum chloride, chloroplatinic acid and pPl-ladium chloride. The compositing may be facilitated by the use of compositing aids, such as a~monium hydro~ide. After all the catalytic components are present in the final catalyst composite, the particles suitably are dried for a period of 1 to 20 hours at .~
-.
-6- ~ 7 ~ 8 temperatures from about 90 to about 150C and calcined in an oxidizing atmosphere such as air at temperatures from about 400 to 700 C for a period from about 1 to about 10 hours or more.
The finished catalyst is usually activated in the presence of hydrogen preferably containing about 1-30 mol. per cent of hydroeen sulphide at a temperature between 150 and 400C prior to its use.
The finished catalyst is useful for effecting various mineral oil conversion reactions, such as demetallization, desulphur-ization, denitrogenation, hydrogenation and the like. Accordingly, the process of the invention comprises passing mineral oil feed-stock and a hydrogen-containing gas through a reæction zone con-taining the catalyst of the invention at an elevated temperature of 100 to 500 C and a total pressure of 0.35 - 700 kg/cm2 and recover-ing the hydroconverted oil from the reaction zone. The catalyst is suitably employed at liquid hourly space velocities (L~SV) from about 0.2 to about 12 1. feedstock/l. catalyst per hour and from about 53 to 1780 1. of added hydrogen per 1. of feed. Particularly preferred conditions are temperatures in the range of from about 250 to 475 C, total pressures from about 7 to about 350 kg/cm ~
uid hourly space velocities from about 0.4 to about 9 1. feed-stock/l. catalyst per hour and 89 to 4~5 1. of added hydrogen per 1. of feed.
Owing to the unique combination of physical properties the ; 25 particularly preferred embodiment of the process of the invention utilizes an upright reaction zone wherein ~e feedstock contacts initially and/or finally catalyst according to the invention.
That is,the catalyst of the invention will substantially or entirely replace the inert pellets, balls or spheres conventionally employed, resulting in higher catalytic activity and conversion efficiency. ~or many existing hydroconvexsion processes the catalyst according to the invention will suitably replace only .
rT
the inert material while retaining the catalyst heretofore employed for hydrodesulphurization, hydrodenitrogenation, hydrocracking and the like. That is, the catalyst according to the invention will be disposed in layers having a depth from a few to a few fundred centimetres above and/or below the conventionally employed catalyst. This is particularly useful for processes emp~ing highly packed small sized extrudates since the generally larger spherical catalyst of the invention, owing to configuration, will have a ereater void fraction for particulate retention. However, the duration of satisfactory operation will generally be much longer when employing the catalyst of the invention, than if the inerts were replaced solely with, e.g., small-sized extrudates.
Unexpectedly, it has been found that for hydrogenation of highly unsaturated feedstocks such as pyrollizates, e.g., distillates from steam cracking of hydrocarbons, such as naphthas and gas oils, the use of the instant catalysts in place of conventional inertæ of like size results in significant reduction of polymeric deposits within the reaction zone.
Accordingly, the enhanced activity of the reaction zone employing the catalyst of the invention can be used to reduce the operatine temperatures conventionally employed, thereby conserving expensive fuel, or where equipment permits to increase throughput for a given conversion level.
In order to illustrate the method of the present invention the following examples are given.
EXAMPLE I
A mixture of alumina spheres obtained commercially and having a ; particle size in the ranee of from about 6 to 13 mm was impregnated with a solution containing nickel nitrate hexahydrate and ammonium dimolybdate in a mixture of aqua ammonia and water. The spheres were separated from the solutDn, and dried at about 95C for one hour.
The dried composite spheres, which were calcined in air for about one hour at about 500 C, were found to contain 1.8% by weight of nickel and 5.4% by weight of molybdenum. The catalyst had a -8- 1~77~
surface area of about 300 m /gm and a crush strength of about 37.3 kg.
About 10 cubic centimetres (8.3 grams) of the catalyst were placed in a fixed bed upright tubular reactor. The catalyst was sulphided by circulating hydrogen gas containing 5% by weight H2S
for 2 hours at about 204 C,for one hour at about 260C and finPlly for 2 hours at about 371C. A mid-continent catalytically cracked heavy gas oil was charged downflow through the bed in a once-through operation at a liquid hourly space velocity of about 1O5 l. feedstock/l. catPlyst per hour and in admixture with recycle hydrogen. The hydrogen was recycled to the reactor at the rate of about 4.0 hydrogen to oil molar ratio. The feedstock had a 50%w boiling point of about 350 C, an API gravity of 17.1 at 60 F,-a carbon content of 88.o3% by weight, a hydrogen content of 10.51% by weight, a sulphur concentration of 1.37% by weight and a nitrogen concentration of 87 parts ~r million. The feedstock was preheated entering the catalyst bed at a temperature of about 343 C and a total pressure of 60 kg/cm . The catQlyst was found to be effective for hydrogenation resulting in hydrogen con-sumption of 55.4 l of hydrogen per l., the hydrotreated product analyzed 0.59% by weight sulphur and 643 ppm nitrogen.
For purposes of comparison the above procedure was repeated except that a portion of the unimpregnated alumina support was used in place of the catalyst. No hydrogen consumption, de-sulphurization or denitrogenation activity was found.
For further purposes of comparison, the above procedure was again repeated except that the catalyst was replaced using com-B mercially available inert spherical material available from Norton~
and having a particle size of about 6-8 mm and a crush strength above 45.3 kg. This material too was found not to have any significant hydroconversion effect. The results of the above tests are summarized in the following Table:
~ ~/7Q~/e fr?~
.
2~
g Hydroconversion Product Properties Catalyst of the Support Inert invention Hydrogen consumed l.H2/l. oil 55-4 Nitrogen, ppm 643 871 871 Sulphur, %w 0. 59 1.37 1.37 EXAMPLE II
The catalyst preparation procedure of Example I was repeated except that in place of the nickel nitrate, cobalt nitrate hexa-hydrate was used in the solution. The final catalyst spheres were found to contain 1.8~w of cobalt, 5.4%w of molybdenum, had a surface area of above about 300 m /gm and a crush strength of about 41.2 kg-The general procedure of Example I was repeated except the feedstock was a straight-run gas oil h~ving an API gravity of 22.8 at 60 F, a carbon content of 85.24, a hydrogen content of 12.05, a sulphur content of 2.57%w and a nitrogen content of 1300 ppm. The reaction conditions included a temperature of about 371 c, a total pressure of 56 kg/~m2, a hydrogen rate of 356 l. /l. and a liquid hourly space velocity of 2.0 l. feedstock/l. catalyst per hour.
~he product ~8 found to coctsin 1.1% sulphur and 970 ppr nitrogen.
g Hydroconversion Product Properties Catalyst of the Support Inert invention Hydrogen consumed l.H2/l. oil 55-4 Nitrogen, ppm 643 871 871 Sulphur, %w 0. 59 1.37 1.37 EXAMPLE II
The catalyst preparation procedure of Example I was repeated except that in place of the nickel nitrate, cobalt nitrate hexa-hydrate was used in the solution. The final catalyst spheres were found to contain 1.8~w of cobalt, 5.4%w of molybdenum, had a surface area of above about 300 m /gm and a crush strength of about 41.2 kg-The general procedure of Example I was repeated except the feedstock was a straight-run gas oil h~ving an API gravity of 22.8 at 60 F, a carbon content of 85.24, a hydrogen content of 12.05, a sulphur content of 2.57%w and a nitrogen content of 1300 ppm. The reaction conditions included a temperature of about 371 c, a total pressure of 56 kg/~m2, a hydrogen rate of 356 l. /l. and a liquid hourly space velocity of 2.0 l. feedstock/l. catalyst per hour.
~he product ~8 found to coctsin 1.1% sulphur and 970 ppr nitrogen.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A spherical hydroconversion catalyst consisting essentially of alumina containing up to 6% by weight of silica as a support and from 2 to 20% by weight of Group VI-B metal and 0.5 to 10% by weight of Group VIII
metal each in the form of metals, their oxides or sulphides, and having a diameter greater than 6 mm, a surface area above 200 m2/gm and a crush strength above 31.7 kg.
metal each in the form of metals, their oxides or sulphides, and having a diameter greater than 6 mm, a surface area above 200 m2/gm and a crush strength above 31.7 kg.
2. A catalyst according to claim 1, in which the catalyst support is gamma- or eta-alumina and the crush strength is above 36.3 kg.
3. A catalyst according to claim 1 or 2, in which the crush strength is above 40.8 kg.
4. A catalyst according to claim 1, in which the Group VI-B metal is molybdenum.
5. A catalyst according to claim 1, in which the Group VIII metal is nickel or cobalt.
6. A catalyst according to claim 1, in which the weight ratio of Group VIII metal to Group VI-B metal is from 0.2 to 0.55.
7. A catalyst according to claim 6, in which the said ratio is from 0.25 to 0.5.
8. A process for the hydroconversion of mineral oils which comprises passing mineral oil feedstock and a hydrogen-containing gas through a reaction zone containing a catalyst according to claim 1 at an elevated temperature of 100-500°C, a total pressure of 0.35-700 kg/cm2, and recovering the hydro-converted oil from the reaction zone.
9. A process according to claim 8, in which the catalyst is employed as a mixture of particles with diameters of 6 to 13 mm.
10. A process according to claim 8 or 9, in which the reaction zone is upright and the feedstock contacts initially and/or finally a catalyst according to claim l.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72053676A | 1976-09-07 | 1976-09-07 | |
| US720,536 | 1976-09-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1102778A true CA1102778A (en) | 1981-06-09 |
Family
ID=24894346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA283,492A Expired CA1102778A (en) | 1976-09-07 | 1977-07-26 | Hydroconversion catalyst and process |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5331588A (en) |
| CA (1) | CA1102778A (en) |
| DE (1) | DE2739869A1 (en) |
| FR (1) | FR2363371A1 (en) |
| GB (1) | GB1550285A (en) |
| IT (1) | IT1084208B (en) |
| NL (1) | NL7709735A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2486094B1 (en) * | 1980-07-02 | 1985-03-22 | Catalyse Soc Prod Francais | |
| US5589057A (en) * | 1989-07-19 | 1996-12-31 | Chevron U.S.A. Inc. | Method for extending the life of hydroprocessing catalyst |
| US5492617A (en) * | 1989-07-19 | 1996-02-20 | Trimble; Harold J. | Apparatus and method for quenching in hydroprocessing of a hydrocarbon feed stream |
| US5472928A (en) * | 1989-07-19 | 1995-12-05 | Scheuerman; Georgieanna L. | Catalyst, method and apparatus for an on-stream particle replacement system for countercurrent contact of a gas and liquid feed stream with a packed bed |
| US5916529A (en) * | 1989-07-19 | 1999-06-29 | Chevron U.S.A. Inc | Multistage moving-bed hydroprocessing reactor with separate catalyst addition and withdrawal systems for each stage, and method for hydroprocessing a hydrocarbon feed stream |
| US5498327A (en) * | 1989-07-19 | 1996-03-12 | Stangeland; Bruce E. | Catalyst, method and apparatus for an on-stream particle replacement system for countercurrent contact of a gas and liquid feed stream with a packed bed |
| US5885534A (en) | 1996-03-18 | 1999-03-23 | Chevron U.S.A. Inc. | Gas pocket distributor for hydroprocessing a hydrocarbon feed stream |
| US5879642A (en) * | 1996-04-24 | 1999-03-09 | Chevron U.S.A. Inc. | Fixed bed reactor assembly having a guard catalyst bed |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3686095A (en) * | 1970-02-16 | 1972-08-22 | Texaco Inc | Desulfurization of residue-containing hydrocarbon oils |
-
1977
- 1977-07-26 CA CA283,492A patent/CA1102778A/en not_active Expired
- 1977-09-05 IT IT2726077A patent/IT1084208B/en active
- 1977-09-05 FR FR7726833A patent/FR2363371A1/en active Granted
- 1977-09-05 NL NL7709735A patent/NL7709735A/en not_active Application Discontinuation
- 1977-09-05 DE DE19772739869 patent/DE2739869A1/en active Granted
- 1977-09-05 JP JP10595677A patent/JPS5331588A/en active Pending
- 1977-09-05 GB GB3695377A patent/GB1550285A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1550285A (en) | 1979-08-08 |
| DE2739869C2 (en) | 1988-09-15 |
| FR2363371B1 (en) | 1982-02-05 |
| NL7709735A (en) | 1978-03-09 |
| JPS5331588A (en) | 1978-03-24 |
| DE2739869A1 (en) | 1978-03-09 |
| FR2363371A1 (en) | 1978-03-31 |
| IT1084208B (en) | 1985-05-25 |
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| Date | Code | Title | Description |
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