CA2114547C - A method of presulfurizing a catalyst - Google Patents
A method of presulfurizing a catalystInfo
- Publication number
- CA2114547C CA2114547C CA002114547A CA2114547A CA2114547C CA 2114547 C CA2114547 C CA 2114547C CA 002114547 A CA002114547 A CA 002114547A CA 2114547 A CA2114547 A CA 2114547A CA 2114547 C CA2114547 C CA 2114547C
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- sulfur
- temperature
- hydrocarbon
- hydrotreating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/06—Sulfides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
Abstract
The invention relates to an improved method of presulfurizing a sulfidable metal or metal oxide-containing catalyst which sulfur stripping upon start-up of a reactor and improves catalyst activity. The method comprises contacting porous particles of the sulfidable catalyst with elemental sulfur at a temperature such that said elemental sulfur is incorporated in the pores of said catalyst by sublimation and/or melting and at the same time or subsequently heating the catalyst particles in the presence of a liquid olefinic hydrocarbon at a temperature greater than 150 °C.
Description
W093/02793 - 1 2114 ~ l 7 PCI'JUS92/06263 A METHOD OF PRESULFURI Z ING A CATALYST
This invention relates to a method of presulfurizing a metal oxide catalyst for use in hydrotreating and~or hydrocracking hydrocarbon feed stocks or in treating sulfur-containing effluent gas streams.
A hydrotreating catalyst is used to catalyze the hydrogenation of hydrocarbon feedstocks, and most particularly to hydrogenate particular components of the feed stock, such as sulfur-, nitrogen- and metals-containing organo-compounds and ùnsaturates. A
hydrocracking catalyst is used to crack massive and complex petroleum derived molecules to provide smaller molecules with the concomitant addition of hydrogen to the molecules.
A tail gas catalyst is used to catalyze the conversion of hazardous effluent gas streams to less harmful products, and most particularly to convert oxides of sulfur to hydrogen sulfide which can be recovered and readily converted to elemental sulfur.
Catalyst compositions for hydrotreating and/or hydrocracking or tail gas treating are well known and several are c~mmercially available~ Metal oxide catalysts which come within this definition include cobalt- -molybdenum, nickel-tungsten, and nickel-molybdenum, supported usually on alumina, silica and silica-alumina, including zeolite, carriers. Also, transition element catalysts may be employed for these purposes. Catalysts comprising at least one element selected from V, Cr, Mn, WO g3/02793 PCr/USg2/06263 211~S47 2-Re, Co, Ni, Cu, Zn, Mo, W, Rh, Pd, P~, Ag, Au, Cd, Sn, Sb, Bi and Te have been disclosed as suitable for these purposes.
For maximum effectiveness the metal oxide catalysts are converted at least in part to metal sulfides. The metal oxide catalysts can be sulfided in a reactor by contact at elevated temperatures with hydrogen sulfide or a sulfur-containing oil or feed stock. However, it is advantageous to the user to be supplied with presulfurized catalysts, that is metal oxide catalysts having sulfur incorporated therein. These presulfurized catalysts can be loaded into a reactor and brought up to reaction conditions in the presence of hydrogen causing the sulfur to react -~
with hydrogen and the metal oxides thereby converting them into sulfides without any additional process steps being needed. These presulfurized catalysts provide an economic advantage to the plant operator and avoid many of the hazards such as flammability and toxicity, which are encountered when using hydrogen sulfide, liquid sulfides, polysulfides and/or mercaptans to sulfide the catalysts.
The use of high boiling oils, such as vacuum gas oilc, and hydrocarbon solvents to aid the incorporation of sulfur into a catalyst is described in US-A-4,943,547.
Hydrotreating catalysts have been presulfurized by incorporating sulfur compounds into the porous catalyst prior to hydrotreating a hydrocarbon feedstock. Por example, US-A-4,530,917 discloses a method of W093/02793 2 1 1 4 5 4 7PcT/Us92/~263 _ 3 --presulfurizing a hydrotreating catalyst with organic polysulfides.
US-A-4,117,136 discloses a method of catalyst presulfurizing wherein a catalyst is treated with elemental 5 8ul fur. Hydrogen is then-used as a reducing agent to convert the elemental sulfur to hydrogen sulfide in situ.
US-A-4,089,930 discloses the pretreatment of a catalyst with elemental sulfur in the presence of hydrogen.
Prior art ex-situ methods of presulfurizing a~orted metal oxide catalysts have suffered from excessive stripping of sulfur upon start-up of a hydrotreating reactor in the presence of a hydrocarbon feedstock. As a result of sulfur stripping, a decrease in catalyst activity or stability is observed.
The present invention provides a method of presulfurizing porous particles of a sulfidable catalyst containing at least one metal or metal oxide, which method comprises (a) contacting said porous catalyst particles with elemental sulfur at a temperature such that said elemental sulfur is incorporated in the pores of said catalyst by sublimation and~or melting and at the same time or subsequently (b) heating said catalyst particles in the presence of a liquid olefinic hydrocarbon at a temperature greater than 150~C.
The method of the invention minimizes sulfur W093~0~793 P~T/U~92J~263 211 ~ 4~ 4 _ stripping upon start-up of a reactor and improves catalyst activity. The method provides a safe, stable, presulfurized hydrotreating and/or hydrocracking or tail gas treating atalyst, either fresh or regenerated, that -can be started up rapidly.
In the method of the invention porous catalyst particles are contacted with elemental sulfur under conditions which cause the sulfur to be incorporated into the pores ~f the catalyst by sublimation~ by melting or by a combination of both sublimation and melting. The sulfur-incorporated catalyst particles are contacted with a liquid olefin at elevated temperatures for times sufficient to cause the sulfur-incorporated catalyst particles to have enhanced resistance to sulfur stripping during startup in a hydrotreating and/or hydrocracking reactor in the presence of a hydrocarbon feedstock. When such olefinically treated presulfurized catalysts are used to tail gas treating, they can be started up more rapidly than conYentional catalysts.
The mechanism by which the sulfur-incorporated -catalyst becomes more resistant to sulfur stripping upon heating at elevated temperatures in the presence of the olefin is not known and will be referenced herein as "reaction" or "reacts" for lack of better terminology. In any event, the result of this mechanism can readily be - 25 determined without undue experimentation by measuring the resistance to sulfur stripping of catalysts subjected to differing temperature/time treatments with the olefin and ~093/02793 ~ 1 I 4 ~ ~ 7 PcT/us92/o6263 withour the olefin and measuring the resistance to sulfur stripping of the resulting catalysts. Catalysts produced in accordance with the invention have enhanced resistance to eulfur stripping. A suitable method for determining sulfur ~tripping resistance is described in Example 1, Part C below wherein acetone is used as a stripping agent.
The catalysts referred to herein as "sulfidable metal oxide(s) catalysts" are in ~act catalyst precursors, that is they are used as actual catalysts while in the sulfided form and not in the oxide form. While reference is made to metal oxide(s) catalysts, it should be understood that while the normal catalyst preparative techniques will produce metal oxide(s), it is possible to utilize special preparative technigues to produce the catalytic metals in a reduced form, such as the zero valent state. Since metals in the zero valent stat~ will be sulfided as well as the oxides when subjected to sulfiding conditions, catalysts containing such sulfidable metals even in reduced or zero valent states will be considered for the purposes of this invention as sulfidable metal oxide(s) catalysts. Further, since the preparative technique of the invention can be -~
applied to regenerated catalyst.s which may have the metal sulfide not completely converted to the oxides, "sulfidable metal oxide(s) catalysts" also refers to these catalysts which bave part of their metals in the sulfided state.
The catalyst is typically presulfurized by one of two methods. The first method comprises contacting the W093/02793 2 1 1 ~ ~ 4 7 - 6 PCT/US92/~6263 sulfidable catalyst with elemental sulfur at a temperature such that said elemental sulfur is incorporate~ in the pores of said catalyst by sublimation and/or melting and subsequently heating the sulfur-incorporated catalyst in the presence of a liquid olefinic hydrocarbon ~t a temperature greater than 150 C. The second method comprises contacting a sulfidable metal oxide(s)-containinq catalyst with a mixture of powdered elemental sulfur and a liquid olefinic hydrocarbon and heating the resultant mixture to a temperature above 150-C. In this second method the heating rate is sufficiently slow for the sulfur to be incorporated into the pores of said catalyst by sublimation and/or melting before reaching the tempera*ure at which the olefin reacts to make the sulfur more ~:
resistant to stripping.
In the preferred embodiment the porous catalyst particles are first contacted with elemental fiulfur at a temperature such that the sulfur is incorporated into the catalyst by sublimation and/or melting. While the catalyst particles can be contacted with sulfur in the molten state, it is preferred to first mix the catalyst paEticles with powdered elemental sulfur and then heat the mixture to above the temperature at which sublimation of the sulfur occurs.
Generally the catalyst particles are heated in the presence of the powdered elemental sulfur at a temperature greater than 80-C. Preferably this first sulfur ' wo g3/02793 2 1 1 4 ~ 4 7 PCT/US92/~263 - 7 ~
impregnation step will be carried out at a temperature of from 90-C to 130-C or higher, say up to the boiling point of sulfur of about 445 c. The lower temperature limit is fixed by the sublimation/melting characteristics of sulfur under the specific conditions of impregnation, whereas the upper temperature limit is fixed primarily by economics, -hiqher temperatures being more coctly to produce as well as more difficult to work with.
In a preferred embodiment the catalyst and sulfur are heated together at a temperature of from 105 C to 125-C. ' Typically the catalyst and powdered sulfur are placed in a vibratory or rotary mixer and heated to the desired temperature for sufficient time to allow the sulfur to be incorporated into the pores of the catalyst. Times typically will range from 0.1 to 10 hours or longer.
The amounts of sulfur used will depend upon the amounts of catalytic metal present in the catalyst that -~
needs to be converted to the sulfide. Typically the amount of sulfur used is determined on the basis of the stoichiometric amount of sulfur required to convert all of the metal in the catalyst to the sulfide form. For example a catalyst containing molybdenum would require two moles of sulfur to convert each mole of molybdenum to molybdenum disulfide, with similar determinations beinq made for other metals. On regenerated catalysts, existing sulfur levels may be factored into the calculations for the amounts of elemental sulfur required.
W093/02793 211 4 5 4 ~ PCT/US92/06263 It has been found that the addition of presulfurizing sulfur in amounts down to 50 percent of the stoichiometric requirement results in catalysts having enhanced hydrodenitrification activity, which is an important property of hydrotreating and first stage hydrocracking catalysts. Thus, the amount of presulfurizing sulfur used for incorporation into the catalyst will typically ranqe from 0.5 to l.S times the stoichiometric amount~ and ~-preferably from 0.7 to 1.2 times the stoichiometric amount.
For hydrotreating/hydrocracking and tail gas treating catalysts containing Group VIB and/or Group VIII metals the amount of sulfur employed is typically 2 to 15%, preferably 6~ to 12%, by weight of the catalyst charged. It is preferred not to add so much sulfur to the catalyst that -~
the pores are completely filled up. By leaving residual pore volume, the olefin can penetrate the pores and react therein.
The key step to the invention is to contact the sulfur impregnated metal catalyst with a liquid olefin at an elevated temperature and for sufficient time at a temperature such that the olefin reacts and provides a sulfurized catalyst that is more resistant to sulfur leaching than one not contacted with an olefin. Typically the contact temperature is greater than 150-C and typically is from 150-C to 350-C, preferably from 200-C to 325 C.
Contact times will depend on temperature and the vapor pressure of the olefin, higher temperatures and higher W093~02793 2 1 1 4 5 4 7 PCT/US92/~263 g .-vapor pressures requiring shorter times. In general times will range from o.1 to lo hours.
The key property of the olefin is that it must be a liquid at the elevated temperature of contact. It is preferred that the olefin-be a higher olefin, iSe. one ..
having a carbon number greater than six, preferably greater than eight. The upper carbon number of useful olefins is determined by the melting point of the olefin in question.
While waxy olefinic materials having carbon numbers around 60 can be used, they are inconvenient since they must be heated to a higher temperature in order to be converted into a liquid, although they can be used with a solvent to put them in liquid form. Olefins with carbon numbers ranging from 6 to 30, preferably from 8 to 25, are found most useful.
The term "olefin" as used herein refers to hydrocarbon molecules containing at least one carbon-carbon double bond and will include hydrocarbons containing at least one carbon-carbon double bond in addition to other 2~ functional moieties, such as, for example, carboxylate or halo, provided such additional moieties do not ad~ersely react with the catalytic metals on the catalyst. The olefins may be monoolefins or polyolefins, cyclic or acyclic, linear or branched. Non-limiting examples of monoolefins include decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, noadecene and eicosene, whether branched, WOg3/02793 ' PCT/US92/06263 211 ~S ~7 - lo linear or cyclic, alpha or internal olefin. Similar materials in the form of di-, tri- and polyolefins may be used. Polycyclic olefins and polyolefins may also be used. The readily available compound dicyclopentadiene can be used.
The olefins may also be mixed with non-olefinic hydrocarbons, such as alkanes or aromatic solvents. In general, the olefin content of any olefin-containing hydrocarbon used în the process of the invention should be above 5%wt., preferably above 10%wt., and most preferably above 30%wt. Generally, higher olefin contents are used, say, about 50%wt, and most conveniently the olefin is used in the undiluted form. The term "olefinic hydrocarbon" as used herein refers to a hydrocarbon that contains olefinic molecules with or without the presence of non-olefinic molecules. It is understood that the olefins may be provided as olefin precursors which are converted to olefins before or upon reaching the reaction temperature.
The minimum amount of olefin used should be such that upon reaction at elevated temperature, a catalyst is obtained that has reduced sulfur leaching properties. The maximum amount of olefin used is determined primarily by economics. In a preferred embodiment the amount of olefinic hydrocarbon is used that will just fill the pore volume of the sulfur impregnated catalyst or just slightly less, down to 60 percent, preferably down to 80 percent of the pore volume. A preferred target range is from 80 to 95 wo 93/027g3 2 1 1 ~ Pcr/us92/o6263 percent of the pore volume. In this manner, the treated ~-catalyst will be "dry" and is more convenient to handle.
In another embodiment a~cording to the present invention, the catalyst particles are contacted with both the elemental sulfur, preferably powdered, and the olefinic hydrocarbon simultaneously. According to this method, a mixture of powdered elemental sulfur and olefinic bydrocarbon solvent is first produced. A weight ratio of olefin to sulfur of from 1:1 to 4:1 is suitable, with about 2:1 being a preferred ratio. The mixture may be heated to promote hom~geneous mixing of the components, particularly if the olefinic hydrocarbon is not liquid at ambient conditions. Toluene or other light weight hydrocarbon solvents may be added to decrease the viscosity of the mixture~ Also, increased heat will achieve the same effect. The mixture is then added to a preweighed catalyst sample and mixed. The mixture is then heated to the olefin reaction temperature of above 150-C. Preferably the temperature is 150-C to 350-C and more preferably from 200 C to 325-C. The times are the same as in the preferred two-step embodiment described above, that is from 0.1 to 10 hours. During the heating process the sulfur first impregnates the pores of the catalyst and then the olefin reacts to form the sulfur leaching resistant catalyst.
The presulfurized catalyst of the instant invention may be converted to a sulfided catalyst by contact with hydrogen at temperatures greater than 200-C, preferably W093/02793 2 1 1 4 5 4 7 PCT/US92/~263 from 200-C to 425-C. Times can run from 0.5 hours to up to -~
This invention relates to a method of presulfurizing a metal oxide catalyst for use in hydrotreating and~or hydrocracking hydrocarbon feed stocks or in treating sulfur-containing effluent gas streams.
A hydrotreating catalyst is used to catalyze the hydrogenation of hydrocarbon feedstocks, and most particularly to hydrogenate particular components of the feed stock, such as sulfur-, nitrogen- and metals-containing organo-compounds and ùnsaturates. A
hydrocracking catalyst is used to crack massive and complex petroleum derived molecules to provide smaller molecules with the concomitant addition of hydrogen to the molecules.
A tail gas catalyst is used to catalyze the conversion of hazardous effluent gas streams to less harmful products, and most particularly to convert oxides of sulfur to hydrogen sulfide which can be recovered and readily converted to elemental sulfur.
Catalyst compositions for hydrotreating and/or hydrocracking or tail gas treating are well known and several are c~mmercially available~ Metal oxide catalysts which come within this definition include cobalt- -molybdenum, nickel-tungsten, and nickel-molybdenum, supported usually on alumina, silica and silica-alumina, including zeolite, carriers. Also, transition element catalysts may be employed for these purposes. Catalysts comprising at least one element selected from V, Cr, Mn, WO g3/02793 PCr/USg2/06263 211~S47 2-Re, Co, Ni, Cu, Zn, Mo, W, Rh, Pd, P~, Ag, Au, Cd, Sn, Sb, Bi and Te have been disclosed as suitable for these purposes.
For maximum effectiveness the metal oxide catalysts are converted at least in part to metal sulfides. The metal oxide catalysts can be sulfided in a reactor by contact at elevated temperatures with hydrogen sulfide or a sulfur-containing oil or feed stock. However, it is advantageous to the user to be supplied with presulfurized catalysts, that is metal oxide catalysts having sulfur incorporated therein. These presulfurized catalysts can be loaded into a reactor and brought up to reaction conditions in the presence of hydrogen causing the sulfur to react -~
with hydrogen and the metal oxides thereby converting them into sulfides without any additional process steps being needed. These presulfurized catalysts provide an economic advantage to the plant operator and avoid many of the hazards such as flammability and toxicity, which are encountered when using hydrogen sulfide, liquid sulfides, polysulfides and/or mercaptans to sulfide the catalysts.
The use of high boiling oils, such as vacuum gas oilc, and hydrocarbon solvents to aid the incorporation of sulfur into a catalyst is described in US-A-4,943,547.
Hydrotreating catalysts have been presulfurized by incorporating sulfur compounds into the porous catalyst prior to hydrotreating a hydrocarbon feedstock. Por example, US-A-4,530,917 discloses a method of W093/02793 2 1 1 4 5 4 7PcT/Us92/~263 _ 3 --presulfurizing a hydrotreating catalyst with organic polysulfides.
US-A-4,117,136 discloses a method of catalyst presulfurizing wherein a catalyst is treated with elemental 5 8ul fur. Hydrogen is then-used as a reducing agent to convert the elemental sulfur to hydrogen sulfide in situ.
US-A-4,089,930 discloses the pretreatment of a catalyst with elemental sulfur in the presence of hydrogen.
Prior art ex-situ methods of presulfurizing a~orted metal oxide catalysts have suffered from excessive stripping of sulfur upon start-up of a hydrotreating reactor in the presence of a hydrocarbon feedstock. As a result of sulfur stripping, a decrease in catalyst activity or stability is observed.
The present invention provides a method of presulfurizing porous particles of a sulfidable catalyst containing at least one metal or metal oxide, which method comprises (a) contacting said porous catalyst particles with elemental sulfur at a temperature such that said elemental sulfur is incorporated in the pores of said catalyst by sublimation and~or melting and at the same time or subsequently (b) heating said catalyst particles in the presence of a liquid olefinic hydrocarbon at a temperature greater than 150~C.
The method of the invention minimizes sulfur W093~0~793 P~T/U~92J~263 211 ~ 4~ 4 _ stripping upon start-up of a reactor and improves catalyst activity. The method provides a safe, stable, presulfurized hydrotreating and/or hydrocracking or tail gas treating atalyst, either fresh or regenerated, that -can be started up rapidly.
In the method of the invention porous catalyst particles are contacted with elemental sulfur under conditions which cause the sulfur to be incorporated into the pores ~f the catalyst by sublimation~ by melting or by a combination of both sublimation and melting. The sulfur-incorporated catalyst particles are contacted with a liquid olefin at elevated temperatures for times sufficient to cause the sulfur-incorporated catalyst particles to have enhanced resistance to sulfur stripping during startup in a hydrotreating and/or hydrocracking reactor in the presence of a hydrocarbon feedstock. When such olefinically treated presulfurized catalysts are used to tail gas treating, they can be started up more rapidly than conYentional catalysts.
The mechanism by which the sulfur-incorporated -catalyst becomes more resistant to sulfur stripping upon heating at elevated temperatures in the presence of the olefin is not known and will be referenced herein as "reaction" or "reacts" for lack of better terminology. In any event, the result of this mechanism can readily be - 25 determined without undue experimentation by measuring the resistance to sulfur stripping of catalysts subjected to differing temperature/time treatments with the olefin and ~093/02793 ~ 1 I 4 ~ ~ 7 PcT/us92/o6263 withour the olefin and measuring the resistance to sulfur stripping of the resulting catalysts. Catalysts produced in accordance with the invention have enhanced resistance to eulfur stripping. A suitable method for determining sulfur ~tripping resistance is described in Example 1, Part C below wherein acetone is used as a stripping agent.
The catalysts referred to herein as "sulfidable metal oxide(s) catalysts" are in ~act catalyst precursors, that is they are used as actual catalysts while in the sulfided form and not in the oxide form. While reference is made to metal oxide(s) catalysts, it should be understood that while the normal catalyst preparative techniques will produce metal oxide(s), it is possible to utilize special preparative technigues to produce the catalytic metals in a reduced form, such as the zero valent state. Since metals in the zero valent stat~ will be sulfided as well as the oxides when subjected to sulfiding conditions, catalysts containing such sulfidable metals even in reduced or zero valent states will be considered for the purposes of this invention as sulfidable metal oxide(s) catalysts. Further, since the preparative technique of the invention can be -~
applied to regenerated catalyst.s which may have the metal sulfide not completely converted to the oxides, "sulfidable metal oxide(s) catalysts" also refers to these catalysts which bave part of their metals in the sulfided state.
The catalyst is typically presulfurized by one of two methods. The first method comprises contacting the W093/02793 2 1 1 ~ ~ 4 7 - 6 PCT/US92/~6263 sulfidable catalyst with elemental sulfur at a temperature such that said elemental sulfur is incorporate~ in the pores of said catalyst by sublimation and/or melting and subsequently heating the sulfur-incorporated catalyst in the presence of a liquid olefinic hydrocarbon ~t a temperature greater than 150 C. The second method comprises contacting a sulfidable metal oxide(s)-containinq catalyst with a mixture of powdered elemental sulfur and a liquid olefinic hydrocarbon and heating the resultant mixture to a temperature above 150-C. In this second method the heating rate is sufficiently slow for the sulfur to be incorporated into the pores of said catalyst by sublimation and/or melting before reaching the tempera*ure at which the olefin reacts to make the sulfur more ~:
resistant to stripping.
In the preferred embodiment the porous catalyst particles are first contacted with elemental fiulfur at a temperature such that the sulfur is incorporated into the catalyst by sublimation and/or melting. While the catalyst particles can be contacted with sulfur in the molten state, it is preferred to first mix the catalyst paEticles with powdered elemental sulfur and then heat the mixture to above the temperature at which sublimation of the sulfur occurs.
Generally the catalyst particles are heated in the presence of the powdered elemental sulfur at a temperature greater than 80-C. Preferably this first sulfur ' wo g3/02793 2 1 1 4 ~ 4 7 PCT/US92/~263 - 7 ~
impregnation step will be carried out at a temperature of from 90-C to 130-C or higher, say up to the boiling point of sulfur of about 445 c. The lower temperature limit is fixed by the sublimation/melting characteristics of sulfur under the specific conditions of impregnation, whereas the upper temperature limit is fixed primarily by economics, -hiqher temperatures being more coctly to produce as well as more difficult to work with.
In a preferred embodiment the catalyst and sulfur are heated together at a temperature of from 105 C to 125-C. ' Typically the catalyst and powdered sulfur are placed in a vibratory or rotary mixer and heated to the desired temperature for sufficient time to allow the sulfur to be incorporated into the pores of the catalyst. Times typically will range from 0.1 to 10 hours or longer.
The amounts of sulfur used will depend upon the amounts of catalytic metal present in the catalyst that -~
needs to be converted to the sulfide. Typically the amount of sulfur used is determined on the basis of the stoichiometric amount of sulfur required to convert all of the metal in the catalyst to the sulfide form. For example a catalyst containing molybdenum would require two moles of sulfur to convert each mole of molybdenum to molybdenum disulfide, with similar determinations beinq made for other metals. On regenerated catalysts, existing sulfur levels may be factored into the calculations for the amounts of elemental sulfur required.
W093/02793 211 4 5 4 ~ PCT/US92/06263 It has been found that the addition of presulfurizing sulfur in amounts down to 50 percent of the stoichiometric requirement results in catalysts having enhanced hydrodenitrification activity, which is an important property of hydrotreating and first stage hydrocracking catalysts. Thus, the amount of presulfurizing sulfur used for incorporation into the catalyst will typically ranqe from 0.5 to l.S times the stoichiometric amount~ and ~-preferably from 0.7 to 1.2 times the stoichiometric amount.
For hydrotreating/hydrocracking and tail gas treating catalysts containing Group VIB and/or Group VIII metals the amount of sulfur employed is typically 2 to 15%, preferably 6~ to 12%, by weight of the catalyst charged. It is preferred not to add so much sulfur to the catalyst that -~
the pores are completely filled up. By leaving residual pore volume, the olefin can penetrate the pores and react therein.
The key step to the invention is to contact the sulfur impregnated metal catalyst with a liquid olefin at an elevated temperature and for sufficient time at a temperature such that the olefin reacts and provides a sulfurized catalyst that is more resistant to sulfur leaching than one not contacted with an olefin. Typically the contact temperature is greater than 150-C and typically is from 150-C to 350-C, preferably from 200-C to 325 C.
Contact times will depend on temperature and the vapor pressure of the olefin, higher temperatures and higher W093~02793 2 1 1 4 5 4 7 PCT/US92/~263 g .-vapor pressures requiring shorter times. In general times will range from o.1 to lo hours.
The key property of the olefin is that it must be a liquid at the elevated temperature of contact. It is preferred that the olefin-be a higher olefin, iSe. one ..
having a carbon number greater than six, preferably greater than eight. The upper carbon number of useful olefins is determined by the melting point of the olefin in question.
While waxy olefinic materials having carbon numbers around 60 can be used, they are inconvenient since they must be heated to a higher temperature in order to be converted into a liquid, although they can be used with a solvent to put them in liquid form. Olefins with carbon numbers ranging from 6 to 30, preferably from 8 to 25, are found most useful.
The term "olefin" as used herein refers to hydrocarbon molecules containing at least one carbon-carbon double bond and will include hydrocarbons containing at least one carbon-carbon double bond in addition to other 2~ functional moieties, such as, for example, carboxylate or halo, provided such additional moieties do not ad~ersely react with the catalytic metals on the catalyst. The olefins may be monoolefins or polyolefins, cyclic or acyclic, linear or branched. Non-limiting examples of monoolefins include decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, noadecene and eicosene, whether branched, WOg3/02793 ' PCT/US92/06263 211 ~S ~7 - lo linear or cyclic, alpha or internal olefin. Similar materials in the form of di-, tri- and polyolefins may be used. Polycyclic olefins and polyolefins may also be used. The readily available compound dicyclopentadiene can be used.
The olefins may also be mixed with non-olefinic hydrocarbons, such as alkanes or aromatic solvents. In general, the olefin content of any olefin-containing hydrocarbon used în the process of the invention should be above 5%wt., preferably above 10%wt., and most preferably above 30%wt. Generally, higher olefin contents are used, say, about 50%wt, and most conveniently the olefin is used in the undiluted form. The term "olefinic hydrocarbon" as used herein refers to a hydrocarbon that contains olefinic molecules with or without the presence of non-olefinic molecules. It is understood that the olefins may be provided as olefin precursors which are converted to olefins before or upon reaching the reaction temperature.
The minimum amount of olefin used should be such that upon reaction at elevated temperature, a catalyst is obtained that has reduced sulfur leaching properties. The maximum amount of olefin used is determined primarily by economics. In a preferred embodiment the amount of olefinic hydrocarbon is used that will just fill the pore volume of the sulfur impregnated catalyst or just slightly less, down to 60 percent, preferably down to 80 percent of the pore volume. A preferred target range is from 80 to 95 wo 93/027g3 2 1 1 ~ Pcr/us92/o6263 percent of the pore volume. In this manner, the treated ~-catalyst will be "dry" and is more convenient to handle.
In another embodiment a~cording to the present invention, the catalyst particles are contacted with both the elemental sulfur, preferably powdered, and the olefinic hydrocarbon simultaneously. According to this method, a mixture of powdered elemental sulfur and olefinic bydrocarbon solvent is first produced. A weight ratio of olefin to sulfur of from 1:1 to 4:1 is suitable, with about 2:1 being a preferred ratio. The mixture may be heated to promote hom~geneous mixing of the components, particularly if the olefinic hydrocarbon is not liquid at ambient conditions. Toluene or other light weight hydrocarbon solvents may be added to decrease the viscosity of the mixture~ Also, increased heat will achieve the same effect. The mixture is then added to a preweighed catalyst sample and mixed. The mixture is then heated to the olefin reaction temperature of above 150-C. Preferably the temperature is 150-C to 350-C and more preferably from 200 C to 325-C. The times are the same as in the preferred two-step embodiment described above, that is from 0.1 to 10 hours. During the heating process the sulfur first impregnates the pores of the catalyst and then the olefin reacts to form the sulfur leaching resistant catalyst.
The presulfurized catalyst of the instant invention may be converted to a sulfided catalyst by contact with hydrogen at temperatures greater than 200-C, preferably W093/02793 2 1 1 4 5 4 7 PCT/US92/~263 from 200-C to 425-C. Times can run from 0.5 hours to up to -~
3 days.
In preferred operation the presulfurized catalyst of the instant invention is loaded into a hydrotreating and/or hydrocracking reactor or tail gas reactor and hydrogen flow is started to the reactor and the reactor is heated up t~
operating (hydrotreating and/or hydrocr~cking or tail gas treating~ conditions. In the pre~ence of hydrogen, activation of the catalyst takes place. That is, the metal oxides and hydrogen react with substantially all of the sulfur incorporated into the catalyst pores, thus producinq hydrogen sulfide, water and metal sulfides. In the hydrotreating and/or hydrocracking process, a hydrocarbon feedstock flow may be started simultaneously with the lS hydrogen or later.
The process of the present invention is further applicable to the sulfurizing of spent catalysts which have been oxy-regenerated. After a conventional oxy-regeneration process, an oxy-regenerated catalyst may be ,20 presulfurized as would fresh catalyst in the manner set forth above and specifically in a manner ~et forth by way of the following examples.
The invention is also intended to encompass a method for stabilizing (enhancing the resistance to sulfur leachinq) a supported metal catalyst containing elemental sulfur, particularly a Group YIB and/or Group VIII metal catalyst, by contacting said catalyst with an olefinic ' W093/02793 ~ 11 4 ~ 4 7 P~T/USg2/~263 ': , t, '.' ~ C~
hydrocarbon at a temperature greater than 150-C.
The presulfurizin~ process is particularly suitable for application to hydrotreating and/or hydrocracking or tail gas treating ca~alysts. These catalysts typically comprise Group VIB and/or Group VIII metals supported on porous supports such as alumina, silica or silica-alumina, including zeolite. The materials are well Befined in the art and can be prepared by techniques described therein, such as in US-A-4,530,911 and US-A-4,520,128. Preferred hydrotreating and/or hydrocracking or tail gas treating catalysts will contain a group VIB metal selected from molybdenum and/or tungsten and a Group VIII metal selected from nickel and/or cobalt supported on alumina. Versatile hydrotreating and/or hydrocracking catalysts which show good activity under various reactor conditions are alumina-supported nickel-molybdenum an~ cobalt-mol~bdenum catalysts. Phosphorous is sometimes added as a promoter.
A versatile tail gas treating catalyst which shows good activity under various reactor conditions is an alumina-supported cobalt-molybdenum catalyst.
Hydrotreating catalysts which are specifically designed for hydrodenitrification operations, such as alumina-supported nickel-molybdenum catalysts, --presulfurized by the methods described herein have ~igher 25 initial activities, particularly hydrodenitrification ~-activities, than catalysts sulfided by prior art methods.
This higher initial activity, coupled with ability to avoid W093/02793 i ' PCT/US92/~263 211 4~ 4r1 sulfiding in the presence of hydrogen sulfide, provides the ~:
instant presulfurized catalysts with a significant commercial advantage. It allows the hydrotreating and/or hydrocracking reactor to get intc full operation quicker, and, once at operating conditions, have a higher activity, allowing the reactor ~o be operated at either lower temperature or higher conversion. Tail gas treating reactors can also be started up more quickly.
Thus, the invention also relates to an improved process for starting up a hydrotreating and~or hydrocracking reactor, which comprises loadinq the catalyst presulfurized according to the methods described herein into the reactor and heating the reactor to operating conditions in the presence of hydrogen and optionally a hydrocarbon feedstock. The invention also relates to an improved hydrotreating and/or hydrocrackinq process which comprises contacting at hydrotreating and/or hydrocracking conditions a hydrocarbon feedstock and hydrogen with a catalyst which has been presulfurized according to the methods described herein and which has been heated to hydrotreating and/or hydrocracking temperature in the presence of hydrogen and optionally a hydrocarbon feedstock.
Hydrotreating conditions comprise temperatures of from lOO-C to 425-C, pressures above 40 atmospheres. The : total pressure will typically range from 2.8 to 17.2 MPa gauge (400 to 2500 psig). The hydrogen partial pressure W093/02793 ~11 4 ~ ~ 7 PCT/USg2/06263 ' f., ~ .', ;
-will typically range from 104 to 15.2 MPa gauge) (200 to - 2200 psig). The hydrogen feed rate will typically range from 1.6 to ~0 Nl/hr (33.77 to 168~5 Nl (H2)/l (oil)~.
- The feedstock rate will typically have a liquid hourly space velocity ("LHSV") of from 0.1 to 15.
Hydrotreating conditions comprise temperatures of from 300~C to 500~C, pressures above about 40 atmospheres. The total pressure will typically range from 2.8 to 20.7 MPa gauge (400 to about 3000 psig). The hydrogen partial pressure will typically range from 2~1 to 17.9 MPa gauge (300 to 2600 psig). The hydrogen feed rate will typically range from 8 to 80 Nl/hr (168.85 to 1688.5 Nl (H2)/l (Oil)). The feedstock rate will typically have a liquid hourly space velocity ("LHSV") of from 0.1 to 15. First stage hydrocrackers, which carry out considerable hydrotreating of the feedstock, may operate at high temperatures than hydrotreaters and at lower temperatures than second stage hydrocrackers.
Tail gas treatment reactors typically operate at temperatures ranging from 200~C to 400~C and at atmospheric pressure. About 0.5-5% vol. of the tail gas fed to the reactor will comprise hydrogen. Standard gaseous hourly space velocities of the tail gas through the reactor will range from 500 to 10,000 hr~~. There are several ways the catalysts can be started up in a tail gas treatment reactor. Claus unit feed or tail gas can be used to start W093/02793 ~ PCT/USg2/06263 211~47 - 16 -up the subject catalysts. Supplemental hydrogen, as reguired, may be provided by a gas burner operating at a substoichiometric ratio in order to produce hydrogen.
The invention will be described by reference to the following Examples.
ample I: Presulfurization ~ethod Part A: Sulfur i~Dregnation A commercial hydrotreating catalyst having the properties listed below was used to prepare the sulfurized catalysts.
Table 1: Catalyst Properties Nickel 2.6%wt Molybdenum 14.3%wt Phosphorous 2.9%wt Support gamma alumina Surface Area, m2/g 164 Water Pore Vol., cm3/g 0.44 Size0.13cm (1/20 inch) trilobes A 430 gram sample of the above sample was dried at 370~C for one hour and then cooled to ambient under vacuum.
The sample was then placed in a flask and enough sulfur, in powdered form, was added to produce a sulfur level of about 10% by weight. The flask was provided with a slow nitrogen purge and placed in a heating mantle at 107-C for ~ hour~
During this time period the flask was vibrated continually to provide mixing of sulfur and catalyst. The final sulfur level was about 10.5% by weight of the total catalyst. The water pore volume of the sulfur-impregnated catalyst was ~ 30 determined to be about 0.3 cm3/g.
.
W093/02793 ~ i~ 4 ~ 4 7 PCT/US92/06263 Par B: Olefin Reaction The sulfur-impregnated catalyst from Part ~ was impregnat~d with the various hydrocarbons listed in Table 2. The catalyst was impregnated with hydrocarbon sufficient to fill 90% of the pore volu~e. The eicosanet vacuum gas oil ("VG0") and the C20 olefin, being solids or semi-solids at room temperature, were heated to 40-C before being applied to the catalyst. All other hydrocaxbons were simply added to the catalyst. The catalyst was chAken with the hydrocarbon until the catalyst appeared dry. This took approximately 10 minutes per sample.
100 Grams of the hydrocarbon-containing catalyst were loaded into a quartz reactor tube and placed in a furnace. '~-The reactor outlet was tubed to a liquid trap, then to a silicone oil-filled container to prevent air back-diffusion. Nitrogen flow was established to the reactor inlet at 230 cm3 /min, and the catalyst bed was purged of air for 30 minutes. The nitrogen flo~ was reduced to 30 cm3/min for the during of the heat treatment.
The reactor was heated to 205-C over the course of one hour and held there for 3 hours. After heat treatment was complete, the reactor contents were cooled to room temperature under nitrogen purge. The samples were analyzed for sulfur content.
Part C: Sulfur Leachina Tests Acetone was used as an extractive solvent for measuring the ability of the catalysts to resist sulfur , W093/02793 ; ~ ~ PCT/US92/~263 211~S47 - 18 -leaching. Acetone is a more aggressive solvent for sulfur than the typical hydrotreating and/or hydrocracking ;~
feedstocks. Catalysts that are found to be resistant to culfur leaching by acetone are also found to be resistant to leaching by hydrocarbon feedstocks and have thus acquired the benefits of the instant invention. Thus, the acetone extraction test as described herein can be used by one s~illed in the art to determine if sulfur-leaching resistant catalysts as defined and claimed herein have been obtained.
A Soxhlet extractor was used in this test. The thimble of the extractor was filled with 20 cm3 of catalyst and the flask of the extractor was filled about 3/4 full (about 600 cm3) with ace~one. The extractor was heated to the boiling point of acetone (57-C) and allowed to reflux for 18 hours. After extraction, the flask was cooled, the catalyst removed and dried at 40-C for 16 hours. The -extracted catalysts were analyzed for sulfur content. The percent of sulfur retained after extraction is shown in Table 2 below. This percent of retained sulfur is calculated as the amount of sulfur on the catalyst after the extraction of Part C divided by the sulfur in the catalyst after the heat treatment of Part B times 100%.
Table 2: Sulfur Leaching Results "Reactant" Hydrocarbon Amount of Sulfur After ~Ytraction NEODENE~ 10 olefins') 92.2 W093/02793 2 1 1 ~ 7 PCT/US92/~263 -- 1 9 ~
n-DECANE 15.6 NEODENE~ 14/16 OLEFINSb3 88.5 n-Cl~C16 BLEND" 30.6 CHEVRON TETRAMER MJ) 94.3 CHEVRON POLYMER 560') 88.5 DIESEL FUEL 77.1 VACUUM GAS OIL 85.2 NEODENE6 20 OLEFINSf) 96.4 EICOSANE 65.3 a) An olefin product manufactured by Shell Chemical Co. -whose composition is 96%wt. minimum C~0 alpha-monoolefin.
b) An olefin product manufactured by Shell Chemical Co.
whose composition is 94%wt. minimum alpha-monoolefin lS comprising 65%wt. Cl4 alpha-monoolefin and 35%wt. Cl6 alpha-monoolefin.
c) A blend of normal Cl4 and Cl6 alkanes blended to have the same C~4/Cl6 ratio as b) above.
d) An olefin product manufactured by Chevron Chemical Co. which is a tetramer of propylene.
e) An olefin product manufactured by Chevron Chemical Co. whose composition is Cl2 - C18 branched monoolefins.
f) An olefin product manufactured by Shell Chemical Co.
whose composition is 94%wt. minimum C20 alpha-monoolefin.
Example II: Use of Presulfurized Catalyst in Hvdrotreating Process Six types of catalysts, two comparative and four of W093/02793 . ~ PCT/US92/06263 Z11~5~7 - 20 -this invention, were used to demonstrate the advantaqes of the invention as applied to a hydrotreating process. These were:
1) COMP Catalyst - This is a comparative commercial S hydrotreatin~ catalyst listed in Table 1 which has been sulfided by an industry accepted sulfiding :~
method using hydrogen and hydrogen sulfide as described below.
2) Aloo Catalyst - This is a catalyst prepared as described in Example I with 100~ stoichiometric sulfur and using the normal C14/C~6 olefin blend :-~
described in Table 2 as one treating hydrocarbon~ :~
3) A~ Catalyst - This is a catalyst prepared as described in Example I with 75~ stoichiometric sulfur and using the normal C~4/Cl6 olefin blend described in Table 2 as the treating hydrocarbon. ~
In preferred operation the presulfurized catalyst of the instant invention is loaded into a hydrotreating and/or hydrocracking reactor or tail gas reactor and hydrogen flow is started to the reactor and the reactor is heated up t~
operating (hydrotreating and/or hydrocr~cking or tail gas treating~ conditions. In the pre~ence of hydrogen, activation of the catalyst takes place. That is, the metal oxides and hydrogen react with substantially all of the sulfur incorporated into the catalyst pores, thus producinq hydrogen sulfide, water and metal sulfides. In the hydrotreating and/or hydrocracking process, a hydrocarbon feedstock flow may be started simultaneously with the lS hydrogen or later.
The process of the present invention is further applicable to the sulfurizing of spent catalysts which have been oxy-regenerated. After a conventional oxy-regeneration process, an oxy-regenerated catalyst may be ,20 presulfurized as would fresh catalyst in the manner set forth above and specifically in a manner ~et forth by way of the following examples.
The invention is also intended to encompass a method for stabilizing (enhancing the resistance to sulfur leachinq) a supported metal catalyst containing elemental sulfur, particularly a Group YIB and/or Group VIII metal catalyst, by contacting said catalyst with an olefinic ' W093/02793 ~ 11 4 ~ 4 7 P~T/USg2/~263 ': , t, '.' ~ C~
hydrocarbon at a temperature greater than 150-C.
The presulfurizin~ process is particularly suitable for application to hydrotreating and/or hydrocracking or tail gas treating ca~alysts. These catalysts typically comprise Group VIB and/or Group VIII metals supported on porous supports such as alumina, silica or silica-alumina, including zeolite. The materials are well Befined in the art and can be prepared by techniques described therein, such as in US-A-4,530,911 and US-A-4,520,128. Preferred hydrotreating and/or hydrocracking or tail gas treating catalysts will contain a group VIB metal selected from molybdenum and/or tungsten and a Group VIII metal selected from nickel and/or cobalt supported on alumina. Versatile hydrotreating and/or hydrocracking catalysts which show good activity under various reactor conditions are alumina-supported nickel-molybdenum an~ cobalt-mol~bdenum catalysts. Phosphorous is sometimes added as a promoter.
A versatile tail gas treating catalyst which shows good activity under various reactor conditions is an alumina-supported cobalt-molybdenum catalyst.
Hydrotreating catalysts which are specifically designed for hydrodenitrification operations, such as alumina-supported nickel-molybdenum catalysts, --presulfurized by the methods described herein have ~igher 25 initial activities, particularly hydrodenitrification ~-activities, than catalysts sulfided by prior art methods.
This higher initial activity, coupled with ability to avoid W093/02793 i ' PCT/US92/~263 211 4~ 4r1 sulfiding in the presence of hydrogen sulfide, provides the ~:
instant presulfurized catalysts with a significant commercial advantage. It allows the hydrotreating and/or hydrocracking reactor to get intc full operation quicker, and, once at operating conditions, have a higher activity, allowing the reactor ~o be operated at either lower temperature or higher conversion. Tail gas treating reactors can also be started up more quickly.
Thus, the invention also relates to an improved process for starting up a hydrotreating and~or hydrocracking reactor, which comprises loadinq the catalyst presulfurized according to the methods described herein into the reactor and heating the reactor to operating conditions in the presence of hydrogen and optionally a hydrocarbon feedstock. The invention also relates to an improved hydrotreating and/or hydrocrackinq process which comprises contacting at hydrotreating and/or hydrocracking conditions a hydrocarbon feedstock and hydrogen with a catalyst which has been presulfurized according to the methods described herein and which has been heated to hydrotreating and/or hydrocracking temperature in the presence of hydrogen and optionally a hydrocarbon feedstock.
Hydrotreating conditions comprise temperatures of from lOO-C to 425-C, pressures above 40 atmospheres. The : total pressure will typically range from 2.8 to 17.2 MPa gauge (400 to 2500 psig). The hydrogen partial pressure W093/02793 ~11 4 ~ ~ 7 PCT/USg2/06263 ' f., ~ .', ;
-will typically range from 104 to 15.2 MPa gauge) (200 to - 2200 psig). The hydrogen feed rate will typically range from 1.6 to ~0 Nl/hr (33.77 to 168~5 Nl (H2)/l (oil)~.
- The feedstock rate will typically have a liquid hourly space velocity ("LHSV") of from 0.1 to 15.
Hydrotreating conditions comprise temperatures of from 300~C to 500~C, pressures above about 40 atmospheres. The total pressure will typically range from 2.8 to 20.7 MPa gauge (400 to about 3000 psig). The hydrogen partial pressure will typically range from 2~1 to 17.9 MPa gauge (300 to 2600 psig). The hydrogen feed rate will typically range from 8 to 80 Nl/hr (168.85 to 1688.5 Nl (H2)/l (Oil)). The feedstock rate will typically have a liquid hourly space velocity ("LHSV") of from 0.1 to 15. First stage hydrocrackers, which carry out considerable hydrotreating of the feedstock, may operate at high temperatures than hydrotreaters and at lower temperatures than second stage hydrocrackers.
Tail gas treatment reactors typically operate at temperatures ranging from 200~C to 400~C and at atmospheric pressure. About 0.5-5% vol. of the tail gas fed to the reactor will comprise hydrogen. Standard gaseous hourly space velocities of the tail gas through the reactor will range from 500 to 10,000 hr~~. There are several ways the catalysts can be started up in a tail gas treatment reactor. Claus unit feed or tail gas can be used to start W093/02793 ~ PCT/USg2/06263 211~47 - 16 -up the subject catalysts. Supplemental hydrogen, as reguired, may be provided by a gas burner operating at a substoichiometric ratio in order to produce hydrogen.
The invention will be described by reference to the following Examples.
ample I: Presulfurization ~ethod Part A: Sulfur i~Dregnation A commercial hydrotreating catalyst having the properties listed below was used to prepare the sulfurized catalysts.
Table 1: Catalyst Properties Nickel 2.6%wt Molybdenum 14.3%wt Phosphorous 2.9%wt Support gamma alumina Surface Area, m2/g 164 Water Pore Vol., cm3/g 0.44 Size0.13cm (1/20 inch) trilobes A 430 gram sample of the above sample was dried at 370~C for one hour and then cooled to ambient under vacuum.
The sample was then placed in a flask and enough sulfur, in powdered form, was added to produce a sulfur level of about 10% by weight. The flask was provided with a slow nitrogen purge and placed in a heating mantle at 107-C for ~ hour~
During this time period the flask was vibrated continually to provide mixing of sulfur and catalyst. The final sulfur level was about 10.5% by weight of the total catalyst. The water pore volume of the sulfur-impregnated catalyst was ~ 30 determined to be about 0.3 cm3/g.
.
W093/02793 ~ i~ 4 ~ 4 7 PCT/US92/06263 Par B: Olefin Reaction The sulfur-impregnated catalyst from Part ~ was impregnat~d with the various hydrocarbons listed in Table 2. The catalyst was impregnated with hydrocarbon sufficient to fill 90% of the pore volu~e. The eicosanet vacuum gas oil ("VG0") and the C20 olefin, being solids or semi-solids at room temperature, were heated to 40-C before being applied to the catalyst. All other hydrocaxbons were simply added to the catalyst. The catalyst was chAken with the hydrocarbon until the catalyst appeared dry. This took approximately 10 minutes per sample.
100 Grams of the hydrocarbon-containing catalyst were loaded into a quartz reactor tube and placed in a furnace. '~-The reactor outlet was tubed to a liquid trap, then to a silicone oil-filled container to prevent air back-diffusion. Nitrogen flow was established to the reactor inlet at 230 cm3 /min, and the catalyst bed was purged of air for 30 minutes. The nitrogen flo~ was reduced to 30 cm3/min for the during of the heat treatment.
The reactor was heated to 205-C over the course of one hour and held there for 3 hours. After heat treatment was complete, the reactor contents were cooled to room temperature under nitrogen purge. The samples were analyzed for sulfur content.
Part C: Sulfur Leachina Tests Acetone was used as an extractive solvent for measuring the ability of the catalysts to resist sulfur , W093/02793 ; ~ ~ PCT/US92/~263 211~S47 - 18 -leaching. Acetone is a more aggressive solvent for sulfur than the typical hydrotreating and/or hydrocracking ;~
feedstocks. Catalysts that are found to be resistant to culfur leaching by acetone are also found to be resistant to leaching by hydrocarbon feedstocks and have thus acquired the benefits of the instant invention. Thus, the acetone extraction test as described herein can be used by one s~illed in the art to determine if sulfur-leaching resistant catalysts as defined and claimed herein have been obtained.
A Soxhlet extractor was used in this test. The thimble of the extractor was filled with 20 cm3 of catalyst and the flask of the extractor was filled about 3/4 full (about 600 cm3) with ace~one. The extractor was heated to the boiling point of acetone (57-C) and allowed to reflux for 18 hours. After extraction, the flask was cooled, the catalyst removed and dried at 40-C for 16 hours. The -extracted catalysts were analyzed for sulfur content. The percent of sulfur retained after extraction is shown in Table 2 below. This percent of retained sulfur is calculated as the amount of sulfur on the catalyst after the extraction of Part C divided by the sulfur in the catalyst after the heat treatment of Part B times 100%.
Table 2: Sulfur Leaching Results "Reactant" Hydrocarbon Amount of Sulfur After ~Ytraction NEODENE~ 10 olefins') 92.2 W093/02793 2 1 1 ~ 7 PCT/US92/~263 -- 1 9 ~
n-DECANE 15.6 NEODENE~ 14/16 OLEFINSb3 88.5 n-Cl~C16 BLEND" 30.6 CHEVRON TETRAMER MJ) 94.3 CHEVRON POLYMER 560') 88.5 DIESEL FUEL 77.1 VACUUM GAS OIL 85.2 NEODENE6 20 OLEFINSf) 96.4 EICOSANE 65.3 a) An olefin product manufactured by Shell Chemical Co. -whose composition is 96%wt. minimum C~0 alpha-monoolefin.
b) An olefin product manufactured by Shell Chemical Co.
whose composition is 94%wt. minimum alpha-monoolefin lS comprising 65%wt. Cl4 alpha-monoolefin and 35%wt. Cl6 alpha-monoolefin.
c) A blend of normal Cl4 and Cl6 alkanes blended to have the same C~4/Cl6 ratio as b) above.
d) An olefin product manufactured by Chevron Chemical Co. which is a tetramer of propylene.
e) An olefin product manufactured by Chevron Chemical Co. whose composition is Cl2 - C18 branched monoolefins.
f) An olefin product manufactured by Shell Chemical Co.
whose composition is 94%wt. minimum C20 alpha-monoolefin.
Example II: Use of Presulfurized Catalyst in Hvdrotreating Process Six types of catalysts, two comparative and four of W093/02793 . ~ PCT/US92/06263 Z11~5~7 - 20 -this invention, were used to demonstrate the advantaqes of the invention as applied to a hydrotreating process. These were:
1) COMP Catalyst - This is a comparative commercial S hydrotreatin~ catalyst listed in Table 1 which has been sulfided by an industry accepted sulfiding :~
method using hydrogen and hydrogen sulfide as described below.
2) Aloo Catalyst - This is a catalyst prepared as described in Example I with 100~ stoichiometric sulfur and using the normal C14/C~6 olefin blend :-~
described in Table 2 as one treating hydrocarbon~ :~
3) A~ Catalyst - This is a catalyst prepared as described in Example I with 75~ stoichiometric sulfur and using the normal C~4/Cl6 olefin blend described in Table 2 as the treating hydrocarbon. ~
4) A~o Catalyst - This is a catalyst prepared as -described in ~mrle I with 50% stoichiometric sulfur and using the normal C~4/C16 olefin blend described in Table 2 as the treating hydrocarbon.
5) COMPCl4/l~ Catalyst - This is a comparative catalyst prepared as described in Example I with 100%
stoichiometric sulfur and using the normal C14/C16 alkane blend described in Table 2 as the treating hydrocarbon.
stoichiometric sulfur and using the normal C14/C16 alkane blend described in Table 2 as the treating hydrocarbon.
6) A~1~/16 Catalyst - This is a catalyst prepared as described in Example I with 100% stoichiometric W093/02793 ~ 7 PCT/US92/06263 - 21 - .
sulfur and using the normal-Cl~/C16 olefin blend described in Table 2 as the treating hydrocarbon.
This catalyst is subs~antially similar to the Aloo catalyst except the Aloo catalyst was a large scale ~:
preparation and this was a laboratory scale preparation.
Microreactors were utilized to test the hydrotreating activity of the catalysts. The catalysts were loaded into -~
the reactor as follows: 30 cm3 of catalyst (~asis -~
compacted bulk density) was divided into 3 aliquots. The first aliquot contained 2.5 cm3 of catalyst and was diluted 10:1 tSiC to catalyst) with 60/~0 mesh SiC. The remaining two aliquots contained 13.75 cm3 of catalyst each and were diluted 1:1 with 60/80 mesh SiC. These aliquots were 15 loaded into the reactor tube with the dilute one on top ~-tthe inlet end).
Part A: Short Term ActivitY Tests A blend of vacuum gas oil and light cycle oil (VGO/LCO) was u~ed as feedstock and had the following properties:
~wt Sulfur 1.7 ppm Nitrogen 1120 Refractive Index 1.51R3 (25-C) Density 0.9242 (60-F or 15-C) -1) COMP CatalYst Activation The COMP Catalyst was dried at 400-C for one hour in air, cooled in a desiccator and loaded into the reactor.
W093/02793 ~ P~T/USg2/~263 2114~ 47 It was sulfided in a flow of 45 Nl/hr of 95%vol hydrogen/5~vol hydrogen sulfide according to the following schedule:
a~ ambient to 121~C at 5.6~C/min b. 121~C to 204~C at 0.56~C/min c. hold at 204~C for 90 min ' d. heat from 204~C to 371~C at 1.1~C/min e. hold at 371~C for 60 min f. cool reactor and hold at 149~C
2) Diesel Activation This method was used to activate catalysts of this invention using a diesel refined for cars and trucks and was as follows:
a. Unit was pressurized to 4.8 MPa gauge (700 psig) and hydrogen circulation was established at 168.85 Nl (H2)/l (oil) [8 Nl of hydrogen/hr].
b. Diesel feed was started to the cataiyst bed at 1.5 LHSV and ambient temperature.
c. The reactor temperature was raised to 121~C in one hour, then increased to 343~C at 27.8~C/hour.
Temperatures were held at 343~C for 30 minutes.
d. Since the temperature ramp occurred overnight, the reactor was also cooled overnight at 149~C for feed switch in the morning.
3) Gas Activation This method was used to activate catalysts of this invention using first hydrogen, followed by diesel, and .1 W0~3~02793 2 11 4 ~ ~ I PCTJUSg2/~6263 ~
simulates the startup of certain commercial --hydrotreaters. This method is as follows:
a. Unit was pressurized to s.l MPa gauge (300 -~
psig) and hydrogen circulation was established at 168.85 Nl (H2)/l (oil) [Nl of hydrogen/hr].
b. Temperature was ramped from ambient to 121~C at -27.8~C/hr. -~
c. Temperature was ramped from 121~C to 204~C in one hour. Off gas was sampled for H2S during period.
d. When 204~C was reached, unit was pressured to 4.8 MPa gauge (700 psig) and held for one hour.
e. Diesel feed (same as in 2) above) was introduced at 204~C.
f. The temperature was ramped to 260OC at 27.8~C/hr and the unit cooled to 149~C with diesel feed continuing overnight.
4) Activity Testing For activity testing the unit was pressured up to 4.8 MPa gauge (700 psig) and heated to 246~C with a -hydrogen gas rate of 168.85 Nl (H2)/l (oil) [8 Nl of hyrogen/hr]. The VG0/LC0 feed was started to the unit at 1.5 LHSV (41.6 gm/hr). After the feed had wetted the entire bed (and product was noted in the separator), the temperature was raised to 329~C at 22.2~C/hr.
After the reactor was at 329~C, a 12 hour break-in period was begun. The product from this period was not analyzed. The run was continued with additional weight 211~547 - 24 - ;
periods of 12 hours and the products of each weight period were analyzed for nitrogen and sulfur. From these values rate constants were calculated for the hydro-denitrification ("HDN") reaction and the hydrode-sulfurization ("HDS") reaction. Rate constants provide an indication of how active the catalyst is, the higher the rate constant, the faster the reaction process, and the higher the conversion of sulfur and nitrogen at a given space velocity (feed rate). For HDN the reaction order is l.O and the k value is calculated by the equation:
k = (space velocity) *ln¦ conc. of N in feed ~ conc. of N in product For HDS the reaction is not first order and many values are used, but 1.7 is the value most used and is used herein to calculate as follows:
R - ~ space velocityl 1.7-1 J ¦ ~conc. of S in product)0-7 - ~conc. of S in feed)~-7 The relative rate constants are provided in Table 3.
They have been normalized against the values of the third weight period for the COMP Catalyst.
W093/02793 2 1 1 4 5 4 7 PCT/USg2/06263 Table 3: Short Term Activity Tests ;~
Weight Period HDS Rel. HD~ Rel.
Catalvst A~tivation (12 hrs each) K ~alue K Value CQMP 1) StAn~Ard 3rd 1.00 1.00 A~oo 3) Gas 4rtdh 1 ~01 1 15 ;~
5th 0.98 1~09 6th 1.00 1.12 Aloo 2) Diesel 3rd 0.98 1.17 :~:
4th 0.98 1.17 ~-5th 0.97 1.11 6th 1.00 1.13 -:~
7th 0.99 1.11 A~ 2) Diesel 3rd 1.04 1.23 4th 1.04 1.22 5th 1.05 1.22 6th 1.05 1.22 A~o 2) Diesel 3rd 0~92 1.13 4th 0.90 1.10 ::
5th o.s0 1.08 COMPcl4~l6 2) Diesel 34rtdh 0.76 5th 0.74 1.03 6th 0.72 0.87 ~;
Ac14/16 2) Diesel 34rtd 0.91 1.16 5th 0.91 1.14 6th 0.92 1.16 As can be seen from the above table the catalysts of this invention show a clear advantage over a traditional hydrotreatinq catalyst with regard to hydrodenitrification activity.
Part B: T~"g Term Activity Tests COMP Catalyst and Aloo Catalyst were used in long term tests to measure HDN activity.
The feed used was an Alaskan north slope diesel with WOg3/027g3 PCT/US92/~63 2114~4~
the following properties:
0.556 %wt Sulfur 269 ppm Nitrogen ~-31.1 API Gravity 13.29 ~wt Aromatics One hundred cc of catalyst was used in the microreactor with 1:1 dilution with 60/80 mesh SiC.
The operating conditions were as follows:
4.1 MPa gauge (600 psig) 168.85 Nl (H2)/l (oil) [35.6 Nl of hydrogen/hr]
2.0 space velocity 90% desulfurization The Al~ Catalyst was activated by pressuring the reactor to 600 psig with hydrogen. Hydrogen flow was started at 168.85 nl (H2)/l (oil) and diesel feed brought in at 1.5 LHSV and ambient temperature. The reactor temp-erature was raised to 121~C at 1.7~C/min, then increased to 343~C at 0.56~C/min. The reactor was then cooled to the estimated start-of-run temperature of 302OC.
The COMP Catalyst was activated using the following: ;~
a. 120 Nl/hr sf a 95% H2/5% H~S mixture b. Ramp temperature from ambient to 204~C at 0~56~C/min - c. Hold at 204~C for two hours d. Ramp to 316~C at 0.55~C/min and hold for one -hour e. Ramp to 371~C at 0.55~C/min and hold for two ~ W093/027g3 1 4 5 ~ 7 PCT/US92/~263 - ~7 -hours f. Cool to 302 C for feed introduction The operating procedure was as follows: At 302-C the feed rate was increased to 2.0 LHSV and a reactor temperature profile was taken and weight periods were started when the profile was flat and at target. The reactor lined out after about 190 hours with the reactor temperature being adjusted for 100 ppm sulfur in the product. This temperature was held for the remainder of ~;
the run. Sulfur and nitrogen were analyzed by a combustion technique. Sulfur detector was W fluorescence and nitrogen detector was chemiluminescence.
The results of these runs are shown in Tables 4 and 5 and are reported as %HDN and %HDS which is the difference in N and S in the product and feed over the N and S in the feed, expressed as a percentage.
TABLE 4: Aloo Catalyst Run ~rs. Deq. C ~HDN %HDS
191 331 55.0 90.5 216 329 53.2 90.3 271 329 89.9 287 330 52.0 90.3 311 330 52.4 90.1 335 330 52.4 89.7 359 330 52.4 89.7 ~:
WOg3/02793 PCT/US92/06263 211~547 - 28 -TABLE 5: COMP CATALYST
Run ~ De~. C %HDN ~HQS
190 329 50.2 90.5 214 329 49.8 90.5 - 268 329 49.8 90.5 286 330 49~4 90.5 310 330 49.1 90.3 324 329 49.1 90.3 348 330 48.3 90.6 As can be seen from the above, the catalyst produced in accordance with the invention retains an i~proved HDN
activity even over a long test term.
sulfur and using the normal-Cl~/C16 olefin blend described in Table 2 as the treating hydrocarbon.
This catalyst is subs~antially similar to the Aloo catalyst except the Aloo catalyst was a large scale ~:
preparation and this was a laboratory scale preparation.
Microreactors were utilized to test the hydrotreating activity of the catalysts. The catalysts were loaded into -~
the reactor as follows: 30 cm3 of catalyst (~asis -~
compacted bulk density) was divided into 3 aliquots. The first aliquot contained 2.5 cm3 of catalyst and was diluted 10:1 tSiC to catalyst) with 60/~0 mesh SiC. The remaining two aliquots contained 13.75 cm3 of catalyst each and were diluted 1:1 with 60/80 mesh SiC. These aliquots were 15 loaded into the reactor tube with the dilute one on top ~-tthe inlet end).
Part A: Short Term ActivitY Tests A blend of vacuum gas oil and light cycle oil (VGO/LCO) was u~ed as feedstock and had the following properties:
~wt Sulfur 1.7 ppm Nitrogen 1120 Refractive Index 1.51R3 (25-C) Density 0.9242 (60-F or 15-C) -1) COMP CatalYst Activation The COMP Catalyst was dried at 400-C for one hour in air, cooled in a desiccator and loaded into the reactor.
W093/02793 ~ P~T/USg2/~263 2114~ 47 It was sulfided in a flow of 45 Nl/hr of 95%vol hydrogen/5~vol hydrogen sulfide according to the following schedule:
a~ ambient to 121~C at 5.6~C/min b. 121~C to 204~C at 0.56~C/min c. hold at 204~C for 90 min ' d. heat from 204~C to 371~C at 1.1~C/min e. hold at 371~C for 60 min f. cool reactor and hold at 149~C
2) Diesel Activation This method was used to activate catalysts of this invention using a diesel refined for cars and trucks and was as follows:
a. Unit was pressurized to 4.8 MPa gauge (700 psig) and hydrogen circulation was established at 168.85 Nl (H2)/l (oil) [8 Nl of hydrogen/hr].
b. Diesel feed was started to the cataiyst bed at 1.5 LHSV and ambient temperature.
c. The reactor temperature was raised to 121~C in one hour, then increased to 343~C at 27.8~C/hour.
Temperatures were held at 343~C for 30 minutes.
d. Since the temperature ramp occurred overnight, the reactor was also cooled overnight at 149~C for feed switch in the morning.
3) Gas Activation This method was used to activate catalysts of this invention using first hydrogen, followed by diesel, and .1 W0~3~02793 2 11 4 ~ ~ I PCTJUSg2/~6263 ~
simulates the startup of certain commercial --hydrotreaters. This method is as follows:
a. Unit was pressurized to s.l MPa gauge (300 -~
psig) and hydrogen circulation was established at 168.85 Nl (H2)/l (oil) [Nl of hydrogen/hr].
b. Temperature was ramped from ambient to 121~C at -27.8~C/hr. -~
c. Temperature was ramped from 121~C to 204~C in one hour. Off gas was sampled for H2S during period.
d. When 204~C was reached, unit was pressured to 4.8 MPa gauge (700 psig) and held for one hour.
e. Diesel feed (same as in 2) above) was introduced at 204~C.
f. The temperature was ramped to 260OC at 27.8~C/hr and the unit cooled to 149~C with diesel feed continuing overnight.
4) Activity Testing For activity testing the unit was pressured up to 4.8 MPa gauge (700 psig) and heated to 246~C with a -hydrogen gas rate of 168.85 Nl (H2)/l (oil) [8 Nl of hyrogen/hr]. The VG0/LC0 feed was started to the unit at 1.5 LHSV (41.6 gm/hr). After the feed had wetted the entire bed (and product was noted in the separator), the temperature was raised to 329~C at 22.2~C/hr.
After the reactor was at 329~C, a 12 hour break-in period was begun. The product from this period was not analyzed. The run was continued with additional weight 211~547 - 24 - ;
periods of 12 hours and the products of each weight period were analyzed for nitrogen and sulfur. From these values rate constants were calculated for the hydro-denitrification ("HDN") reaction and the hydrode-sulfurization ("HDS") reaction. Rate constants provide an indication of how active the catalyst is, the higher the rate constant, the faster the reaction process, and the higher the conversion of sulfur and nitrogen at a given space velocity (feed rate). For HDN the reaction order is l.O and the k value is calculated by the equation:
k = (space velocity) *ln¦ conc. of N in feed ~ conc. of N in product For HDS the reaction is not first order and many values are used, but 1.7 is the value most used and is used herein to calculate as follows:
R - ~ space velocityl 1.7-1 J ¦ ~conc. of S in product)0-7 - ~conc. of S in feed)~-7 The relative rate constants are provided in Table 3.
They have been normalized against the values of the third weight period for the COMP Catalyst.
W093/02793 2 1 1 4 5 4 7 PCT/USg2/06263 Table 3: Short Term Activity Tests ;~
Weight Period HDS Rel. HD~ Rel.
Catalvst A~tivation (12 hrs each) K ~alue K Value CQMP 1) StAn~Ard 3rd 1.00 1.00 A~oo 3) Gas 4rtdh 1 ~01 1 15 ;~
5th 0.98 1~09 6th 1.00 1.12 Aloo 2) Diesel 3rd 0.98 1.17 :~:
4th 0.98 1.17 ~-5th 0.97 1.11 6th 1.00 1.13 -:~
7th 0.99 1.11 A~ 2) Diesel 3rd 1.04 1.23 4th 1.04 1.22 5th 1.05 1.22 6th 1.05 1.22 A~o 2) Diesel 3rd 0~92 1.13 4th 0.90 1.10 ::
5th o.s0 1.08 COMPcl4~l6 2) Diesel 34rtdh 0.76 5th 0.74 1.03 6th 0.72 0.87 ~;
Ac14/16 2) Diesel 34rtd 0.91 1.16 5th 0.91 1.14 6th 0.92 1.16 As can be seen from the above table the catalysts of this invention show a clear advantage over a traditional hydrotreatinq catalyst with regard to hydrodenitrification activity.
Part B: T~"g Term Activity Tests COMP Catalyst and Aloo Catalyst were used in long term tests to measure HDN activity.
The feed used was an Alaskan north slope diesel with WOg3/027g3 PCT/US92/~63 2114~4~
the following properties:
0.556 %wt Sulfur 269 ppm Nitrogen ~-31.1 API Gravity 13.29 ~wt Aromatics One hundred cc of catalyst was used in the microreactor with 1:1 dilution with 60/80 mesh SiC.
The operating conditions were as follows:
4.1 MPa gauge (600 psig) 168.85 Nl (H2)/l (oil) [35.6 Nl of hydrogen/hr]
2.0 space velocity 90% desulfurization The Al~ Catalyst was activated by pressuring the reactor to 600 psig with hydrogen. Hydrogen flow was started at 168.85 nl (H2)/l (oil) and diesel feed brought in at 1.5 LHSV and ambient temperature. The reactor temp-erature was raised to 121~C at 1.7~C/min, then increased to 343~C at 0.56~C/min. The reactor was then cooled to the estimated start-of-run temperature of 302OC.
The COMP Catalyst was activated using the following: ;~
a. 120 Nl/hr sf a 95% H2/5% H~S mixture b. Ramp temperature from ambient to 204~C at 0~56~C/min - c. Hold at 204~C for two hours d. Ramp to 316~C at 0.55~C/min and hold for one -hour e. Ramp to 371~C at 0.55~C/min and hold for two ~ W093/027g3 1 4 5 ~ 7 PCT/US92/~263 - ~7 -hours f. Cool to 302 C for feed introduction The operating procedure was as follows: At 302-C the feed rate was increased to 2.0 LHSV and a reactor temperature profile was taken and weight periods were started when the profile was flat and at target. The reactor lined out after about 190 hours with the reactor temperature being adjusted for 100 ppm sulfur in the product. This temperature was held for the remainder of ~;
the run. Sulfur and nitrogen were analyzed by a combustion technique. Sulfur detector was W fluorescence and nitrogen detector was chemiluminescence.
The results of these runs are shown in Tables 4 and 5 and are reported as %HDN and %HDS which is the difference in N and S in the product and feed over the N and S in the feed, expressed as a percentage.
TABLE 4: Aloo Catalyst Run ~rs. Deq. C ~HDN %HDS
191 331 55.0 90.5 216 329 53.2 90.3 271 329 89.9 287 330 52.0 90.3 311 330 52.4 90.1 335 330 52.4 89.7 359 330 52.4 89.7 ~:
WOg3/02793 PCT/US92/06263 211~547 - 28 -TABLE 5: COMP CATALYST
Run ~ De~. C %HDN ~HQS
190 329 50.2 90.5 214 329 49.8 90.5 - 268 329 49.8 90.5 286 330 49~4 90.5 310 330 49.1 90.3 324 329 49.1 90.3 348 330 48.3 90.6 As can be seen from the above, the catalyst produced in accordance with the invention retains an i~proved HDN
activity even over a long test term.
Claims (13)
1. A method of presulfurizing porous particles of a sulfidable catalyst containing at least one metal or metal oxide, which method comprises (a) contacting said porous catalyst particles with elemental sulfur at a temperature such that said elemental sulfur is incorporated in the pores of said catalyst by sublimation and/or melting and at the same time or subsequently (b) heating said catalyst particles at a temperature greater than 150°C in the presence of a hydrocarbon which is liquid at said temperature and which contains at least 10% by weight of at least one olefinic hydrocarbon of 6 to 30 carbon atoms and containing at least one carbon-carbon double bond.
2. A method according to claim 1 wherein the catalyst contains at least one oxide of a metal from Group VIB and Group VIII of the Periodic Table.
3. A method according to claim 1 wherein powdered sulfur is used in step (a).
4. A method according to claim 1, 2 or 3 wherein step (a) is carried out before step (b) at a temperature of from 90°C to 130°C.
5. A method according to claim 1, 2 or 3 wherein the amount of sulfur used in step (a) is from 0.7 to 1.2 times the stoichiometric amount required to convert the metal or metal oxides to sulfides.
6. A method according to claim 1, 2 or 3 wherein step (b) is carried out subsequent to step (a) at a temperature of from 200°C to 325°C.
7. A method according to claim 1, 2 or 3 wherein the duration of step (a) and/or step (b) is from 0.1 to 10 hours.
8. A method according to claim 1, 2 or 3 wherein said at least one olefinic hydrocarbon has from 8 to 25 carbon atoms.
9. A method according to claim 1 which comprises the further step of heating the catalyst to a temperature of from 200°C to 425°C in the presence of hydrogen to cause the sulfur to react with the metal oxides to produce metal sulfides and thereby provide a catalyst suitable for hydrotreating and/or hydrocracking a hydrocarbon stream or tail gas treating a sulfur-containing gas stream.
10. A method according to claim 9 wherein heating in the presence of hydrogen is carried out at least in part in the presence of a hydrocarbon to provide a catalyst for hydrotreating and/or hydrocracking a hydrocarbon stream.
11. A method according to claim 10 which comprises the further step of hydrotreating and/or hydrocracking hydrocarbon streams or tail gas treating sulfur-containing gas streams by contacting the streams in the presence of hydrogen with the hydrotreating and/or hydrocracking or tail gas treating catalyst.
12. A method according to claim 1 or 9 which comprises the further step of loading the catalyst into a hydrotreating and/or hydrocracking or tail gas treating reactor and heating the reactor up to a hydrotreating and/or hydrocracking or tail gas treating temperature of from 100° to 425°C in the presence of hydrogen.
13. A method according to any one of the preceding claims wherein the liquid hydrocarbon contains at least 30% by weight of the at least one olefinic hydrocarbon.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US07/737,630 US5215954A (en) | 1991-07-30 | 1991-07-30 | Method of presulfurizing a hydrotreating, hydrocracking or tail gas treating catalyst |
US737,630 | 1991-07-30 |
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CA2114547A1 CA2114547A1 (en) | 1993-02-18 |
CA2114547C true CA2114547C (en) | 1998-09-22 |
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CA002114547A Expired - Lifetime CA2114547C (en) | 1991-07-30 | 1992-07-28 | A method of presulfurizing a catalyst |
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US (4) | US5215954A (en) |
EP (1) | EP0598004B1 (en) |
JP (1) | JP3412764B2 (en) |
CA (1) | CA2114547C (en) |
DE (1) | DE69215877T2 (en) |
SA (1) | SA92130034B1 (en) |
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CA759938A (en) * | 1967-05-30 | D. Holmes Peter | Catalysts and reactors containing said catalysts | |
US2038599A (en) * | 1931-01-30 | 1936-04-28 | Standard Ig Co | Carrying out catalytic reactions |
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BE794334A (en) * | 1972-01-20 | 1973-07-19 | Unilever Nv | METAL SULPHIDE CATALYST DEPOSITED ON A SUPPORT |
US4089930A (en) * | 1976-02-12 | 1978-05-16 | New England Power Service Company | Process for the catalytic reduction of nitric oxide |
US4177136B1 (en) * | 1978-01-03 | 1994-05-03 | Standard Oil Co Ohio | Hydrotreating process utilizing elemental sulfur for presulfiding the catalyst |
FR2503733B1 (en) * | 1981-04-09 | 1985-09-06 | Inst Francais Du Petrole | PROCESS FOR HYDROTREATING A HYDROCARBON CHARGE IN THE PRESENCE OF A CATALYST SUBJECT TO PRESULFURATION |
US4368141A (en) * | 1981-06-24 | 1983-01-11 | Phillips Petroleum Company | Olefin disproportionation and catalyst therefor |
US4431747A (en) * | 1982-07-20 | 1984-02-14 | Exxon Research And Engineering Co. | Supported carbon-containing molybdenum and tungsten sulfide catalysts, their preparation and use |
FR2548205B1 (en) * | 1983-06-30 | 1985-11-29 | Eurecat Europ Retrait Catalys | PROCESS FOR PRESULFURIZING A HYDROCARBON PROCESSING CATALYST |
US4548920A (en) * | 1984-03-26 | 1985-10-22 | Shell Oil Company | Hydrodenitrification catalyst |
US4672049A (en) * | 1984-10-25 | 1987-06-09 | Mobil Oil Corporation | Hydroprocessing catalyst |
US4934547A (en) * | 1987-02-10 | 1990-06-19 | Helena Laboratories Corporation | Specimen collection container and non-removable cover |
US5051389A (en) * | 1987-09-16 | 1991-09-24 | Exxon Research And Engineering Company | Catalyst composition prepared by vapor depositing onto a carbon support |
US4943547A (en) * | 1988-09-13 | 1990-07-24 | Seamans James D | Method of presulfiding a hydrotreating catalyst |
US5041404A (en) * | 1988-09-13 | 1991-08-20 | Cri Ventures, Inc. | Method of presulfiding a hydrotreating, hydrocracking or tail gas treating catalyst |
US5053376A (en) * | 1990-06-04 | 1991-10-01 | Exxon Research & Engineering Company | Method of preparing a sulfided molybdenum catalyst concentrate |
US5215954A (en) * | 1991-07-30 | 1993-06-01 | Cri International, Inc. | Method of presulfurizing a hydrotreating, hydrocracking or tail gas treating catalyst |
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1991
- 1991-07-30 US US07/737,630 patent/US5215954A/en not_active Expired - Lifetime
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1992
- 1992-07-28 JP JP50368993A patent/JP3412764B2/en not_active Expired - Lifetime
- 1992-07-28 CA CA002114547A patent/CA2114547C/en not_active Expired - Lifetime
- 1992-07-28 WO PCT/US1992/006263 patent/WO1993002793A1/en active IP Right Grant
- 1992-07-28 SA SA92130034A patent/SA92130034B1/en unknown
- 1992-07-28 EP EP92917231A patent/EP0598004B1/en not_active Expired - Lifetime
- 1992-07-28 DE DE69215877T patent/DE69215877T2/en not_active Expired - Lifetime
- 1992-07-28 SG SG1996001485A patent/SG52259A1/en unknown
- 1992-10-30 US US07/969,660 patent/US5292702A/en not_active Expired - Lifetime
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1993
- 1993-12-13 US US08/166,133 patent/US5468372A/en not_active Expired - Lifetime
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1995
- 1995-10-26 US US08/548,570 patent/US5688736A/en not_active Expired - Lifetime
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JPH06509278A (en) | 1994-10-20 |
DE69215877D1 (en) | 1997-01-23 |
JP3412764B2 (en) | 2003-06-03 |
US5292702A (en) | 1994-03-08 |
EP0598004B1 (en) | 1996-12-11 |
US5468372A (en) | 1995-11-21 |
SA92130034B1 (en) | 2005-11-15 |
EP0598004A1 (en) | 1994-05-25 |
US5688736A (en) | 1997-11-18 |
SG52259A1 (en) | 1998-09-28 |
DE69215877T2 (en) | 1997-07-10 |
US5215954A (en) | 1993-06-01 |
CA2114547A1 (en) | 1993-02-18 |
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