CA1094489A - Desulfurization and demetalation of heavy charge stocks - Google Patents
Desulfurization and demetalation of heavy charge stocksInfo
- Publication number
- CA1094489A CA1094489A CA272,087A CA272087A CA1094489A CA 1094489 A CA1094489 A CA 1094489A CA 272087 A CA272087 A CA 272087A CA 1094489 A CA1094489 A CA 1094489A
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- Prior art keywords
- hydrogen
- water
- reaction zone
- sulfur
- nickel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G49/007—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 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
DESULFURIZATION AND DEMETALATION OF HEAVY
CHARGE STOCKS
ABSTRACT OF THE INVENTION
A process for the desulfurization and demetalation of a nickel and sulfur containing heavy hydrocarbon charge stock comprises: admixing the feed with hydrogen; reacting the admixture in a reaction zone containing desulfurization catalyst at desulfurization conditions; injecting water into the reaction zone at H2O/H2 molar ratios of about 0.05 to 0.5; separating and recycling both hydrogen and water from the reactor effluent; and recovering the substantially sulfur and nickel free product.
CHARGE STOCKS
ABSTRACT OF THE INVENTION
A process for the desulfurization and demetalation of a nickel and sulfur containing heavy hydrocarbon charge stock comprises: admixing the feed with hydrogen; reacting the admixture in a reaction zone containing desulfurization catalyst at desulfurization conditions; injecting water into the reaction zone at H2O/H2 molar ratios of about 0.05 to 0.5; separating and recycling both hydrogen and water from the reactor effluent; and recovering the substantially sulfur and nickel free product.
Description
~ 10~ 89 ~ACKGROUND OF THE INVENTION
Field of the Invention The invention relates to a process for the - desulfurization and demetalation of nickel and sulfur containing heavy hydrocarbon charge stocks.
Description of the Prior Art Heavy hydrocarbon charge stocks,such as residual.
petroleum oil fractions,that is,those heavy fractions produced by atmospheric and vacuum crude distillation columns, are typically characterized as being un~esirable as feed stocks for most re~ining processes due primarily to their h~gh metaland sulfur content. The presence of high concentrations of metals and sulfur and compounds thereof pre-cludes the effective use of such residua as chargestocks for cracking, hydrocracking and coking operations as well as limiting the extent to which such residua may be used as fuel oil. Perhaps the single most undesirable characteristic of such feedstocks is the high metals content. Principal metal contaminants are nickel and vanadium, with iron and small amounts of copper also sometimes present. Additionally, trace amounts of zinc and sodium are found in some feedstocks.
As the great majority of these metals,when present in crude oil,are associated with very large hydrocarbon molecules, the heavier fractions produced by crude distillation contain sub-stantially all the metal present in the crude, such metals being particularly concentrated in the asphaltene residual fraction. The metal contaminants are typically large organo-metallic complexes such as metal prophyrins and asphaltenes.
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Processes for desulfurization of such charge stocks are known, but many of these processes are not suited to effect metal removal. In U.S. 3,720,602, a process for the hydro-desulfurization of substantially non-metal containîng hydro-carbon feeds is described. This process involves the use of specific ~anadium-containing catalyst and injection of water into the desulfurization reactor to effect cooling and to enhance catalyst activity. Water thus injected is separated from the reactor effluent for recycle. Water injection between the catalyst beds of a multi-bed des~lfurization reactor is disclosed in U.S. 3,753,894. In thi reference, it was reported that processing petroleum residuum feeds with hydro-gen plus 10 volume percent water effects a supression of the normal catalyst deactivation rate particularly during the initial period of the product run.
Other disclosures have been made concerning the use of water in desulfurization. Asphaltene-containing black oil is desulfurized by admixing the oil with between
Field of the Invention The invention relates to a process for the - desulfurization and demetalation of nickel and sulfur containing heavy hydrocarbon charge stocks.
Description of the Prior Art Heavy hydrocarbon charge stocks,such as residual.
petroleum oil fractions,that is,those heavy fractions produced by atmospheric and vacuum crude distillation columns, are typically characterized as being un~esirable as feed stocks for most re~ining processes due primarily to their h~gh metaland sulfur content. The presence of high concentrations of metals and sulfur and compounds thereof pre-cludes the effective use of such residua as chargestocks for cracking, hydrocracking and coking operations as well as limiting the extent to which such residua may be used as fuel oil. Perhaps the single most undesirable characteristic of such feedstocks is the high metals content. Principal metal contaminants are nickel and vanadium, with iron and small amounts of copper also sometimes present. Additionally, trace amounts of zinc and sodium are found in some feedstocks.
As the great majority of these metals,when present in crude oil,are associated with very large hydrocarbon molecules, the heavier fractions produced by crude distillation contain sub-stantially all the metal present in the crude, such metals being particularly concentrated in the asphaltene residual fraction. The metal contaminants are typically large organo-metallic complexes such as metal prophyrins and asphaltenes.
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Processes for desulfurization of such charge stocks are known, but many of these processes are not suited to effect metal removal. In U.S. 3,720,602, a process for the hydro-desulfurization of substantially non-metal containîng hydro-carbon feeds is described. This process involves the use of specific ~anadium-containing catalyst and injection of water into the desulfurization reactor to effect cooling and to enhance catalyst activity. Water thus injected is separated from the reactor effluent for recycle. Water injection between the catalyst beds of a multi-bed des~lfurization reactor is disclosed in U.S. 3,753,894. In thi reference, it was reported that processing petroleum residuum feeds with hydro-gen plus 10 volume percent water effects a supression of the normal catalyst deactivation rate particularly during the initial period of the product run.
Other disclosures have been made concerning the use of water in desulfurization. Asphaltene-containing black oil is desulfurized by admixing the oil with between
2.0% to about 30.0%, by weight, of water, then reacting - 20 with hydrogen at desulfurization conditions over a desulfur-ization catalyst in U.S. 3~501,396. In U.S. 3,453,206, it is disclosed that in plural stage hydrorefining of petroleum crude oils and the heavier hydrocarbon fractions obtained therefrom, water may be used in the second or catalytic stage, when it is desired to maximize gasoline boiling ran~e hydro-carbons in the product as distinguished from maximizing middle distillate hydrocarbons. Both U.S. 3,471,398 and U.S. 3,475,324 are related to improved hydrocarbon quench methods in the desulfurization of high boiling hydrocarbons. These patents 3o disclose that it has been found appropriate to add water to .
10!~448~
the reaction zone in admlxture with the charge stock in some instances, however~ the use of water is not normally necessary or desirable.
None of the above references disclose the novel desul-furization and demetalation process of this invention.
SUMMARY OF THE INVENTION
A process for the improved desulfurization and demet-alation of a nickel and sulfur containing heavy hydrocarbon charge stock has now been found. This process includes the steps:
a) admixing said charge stock with a hydrogen-rich stream;
b) reacting the admixture of step (a) in a reaction zone containing a desulfurization catalyst at desulfuriza-tion conditions comprising a pressure from about 500 to 3000 psig; a temperature from about 250 to 500C;
a space velocity from about .2 to 5 LHSV and a hydrogen ratio from about 1000 to 20,000 SCF/bbl;
c) injecting water into said reaction zone at a water to hydrogen molar ratio from about 0.05 to about 0.5;
d) separating a light gas stream which contains H2, H20, H2S and light hydrocarbons from the effluent of said reaction zone;
e) separating the H20 from said light gas stream leaving a substantially dry light gas stream;
f) recycling the separated H20 for injection as in step c);
g) separating the H2S from the dry light gas stream leaving a hydrogen-rich stream;
10!~448~
the reaction zone in admlxture with the charge stock in some instances, however~ the use of water is not normally necessary or desirable.
None of the above references disclose the novel desul-furization and demetalation process of this invention.
SUMMARY OF THE INVENTION
A process for the improved desulfurization and demet-alation of a nickel and sulfur containing heavy hydrocarbon charge stock has now been found. This process includes the steps:
a) admixing said charge stock with a hydrogen-rich stream;
b) reacting the admixture of step (a) in a reaction zone containing a desulfurization catalyst at desulfuriza-tion conditions comprising a pressure from about 500 to 3000 psig; a temperature from about 250 to 500C;
a space velocity from about .2 to 5 LHSV and a hydrogen ratio from about 1000 to 20,000 SCF/bbl;
c) injecting water into said reaction zone at a water to hydrogen molar ratio from about 0.05 to about 0.5;
d) separating a light gas stream which contains H2, H20, H2S and light hydrocarbons from the effluent of said reaction zone;
e) separating the H20 from said light gas stream leaving a substantially dry light gas stream;
f) recycling the separated H20 for injection as in step c);
g) separating the H2S from the dry light gas stream leaving a hydrogen-rich stream;
3~ h) recycling said hydrogen-rich stream for admixing with said charge stock; and `` ~0~89 i) recovering a substantially nickel and sulfur-free product from the effluent of said reaction zone.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a diagrammatic representation of the process of the present invention, Figures 2, 3, 4 and 5 respectively depict percent sulfur, nitrogen, nickel and vanadium removal at various H20/H2 and N2/H2 mole ratios.
DESCRIPTION OF SPECIFIC EMBODIMENTS
me process of the present inven~on is directed to improved desulfurization and demetalation of heavy hydrocarbon charge stocks which can be any metal and sulfur containing stock, preferably one containing residual fractions. Examples include stocks such as atmospheric and vacuum resids, vacuum gas oils, tar sands, bituming cycle stocks, shale oils and the like. From what has been said, it will be clear that the feedstock can be a whole crude. However, since the high metal and sulfur com-ponents of a crude oil tend to be concentrated in the hi~ler boiling fractions, the present process more commonly will be ; 20 applied to a bottoms fraction of a petroleum oil, i.e. one which is obtained by distillation of a crude petroleum oil to remove lower boiling materials. Accordingly, the heavy hydro-carbon charge stocks used herein generally boil above about 400F., preferably a~ove about 650F, and have gravities from ~74 about 0 API to about 30 API. A general range o~ the propertles of heavy hydrocarbon charge stocks which are suitable for use in the process of this invention as well as the properties of a particular charge stock are listed in Table 1.
10~ 9 Arab Light Atmospheric General Ran~e Resid Sulfur, Wt. % 1 - 10 3-85 Nitrogen, Wt. % 0.1 - 3 0.22 Oxygen, Wt. % 0 - 10 0.13 Total Metals, ppm 10 - 3 65 Vanadium, ppm 10 - 2000 49 Nickel, ppm 1 - 3 13 Catalyst which can be used to promote desul~ur-ization reactions contain at least one metallic component selected from the Groups VIB and VIII of the Periodic Table deposited on a refractory inorganic oxide support or binder.
The preferred metallic component may be an oxide or sulfide of nlckel or cobalt, particularly the latter and an oxide or sulfide of molybdenumn or tungsten. The Group VIII metal is generally present in amounts from 1-15 percent by weight, while the Group VIB component is present in amounts from 5-25 percent by weight. The refractory inorganic oxide support may comprise alumina, silica, zirconia, magnesia, titania, boria, strontia, hafnia and mixtures thereof. Par-ticularly preferred are alumina or silica-stabilized alumina5 with the alumina being of the greater proportion. A typical catalyst consists of 3 percent CoO, 10 percent MoO3, 5 percent ; Si02 on alumina. Catalyst are generally presulfided prior to use.
Table 2 lists suitable reaction conditions for the catalytic desulfurization of heavy hydrocarbon charge stocl~s.
109A~89 TABL~ 2 DESULFURIZATIO~ COI~ITIONS
General Range Pre~erred Pressure, psig 500 - 3000 1000 - 2000 ~emperature, C 250 - 500 350 - 45 Space Velocity, LHSV 0.2 - 5 0.5 - 2 Hydrogen Rate, SCF/bbl 1000 - 20,000 4000 - 12,000 The efficaciousness of the novel desulfurization and demetalation process of this invention is in part based upon the effects of water injection on the hydro-processing of heavy charge stocks. This discovery will be described in more detail hereinafter, however, briefly, it was found that invection o~
water into the reaction zone at certain H2O/H2 molar ratios enhances both desulfurizatlon and nickel removal. Also, water in~ection in the particular specified amount was found to have no deleterious effect on nitrogen removal, catalyst aging or catalyst physical properties such as surface area. Thus, the novel process disclosed herein provides for increased sulfur and nickel removal without relying on undesirable changes of process variables such as increasing pressure or temperature.
In fact, the partial pressure of costly hydrogen in greatly reduced by the use of th~s invention.
A process incorporating the above discovery is now described. Referring to Figure 1, a heavy hydrocarbon charge stock stream 20 containing sulfur, nitrogen and oxy~en hetero-atoms plus metals such as nickel and vanadium is mixed with a hydrogen-rich gas stream 21 and the resulting admixture is heated in furnace 22 be~ore being charged to reaction zone 23.
, 109~1489 Reaction zone 23 conta.ins desulfuriza.tion ca.talyst and may include a. plurality of beds. Water from line 24~ which includes both recycled water from line 36 and make up wa.ter from line 35, as needed, is injected into rea.ction zone 23 in amounts from a.bout .05 to .5 H20/~2 (molar ratios), pre-ferably .05 to .2. If desired, a portion of the water may be injected into the reaction zone by admixture with the hydrogen rich stream, ~d ~ater being introduced via line 39.
U~ed in these amounts, the water effects increased desulfuri-zation and demetalation of the charge stock, as will be des-cribed hereinafter, as well as cooling or quenching. Water may be injected between beds if a. plurality of beds are incorporated in reaction zone 23.
The reaction zone effluent in line 37 is passed through heat exchanger 38 before it enters separator 25.
Heat exchanger 38 is used to ad~ust the temperature of the effluent, which contains H2, H20, H2S, light hydrocarbons and desulfurized a.nd demetalized products, to the conditions of separator 25, which desira.bly is a high pressure flash separator. The gaseous effluents from separator 25, which include H2, H20, H2S.and light hydrocarbons, go overhead in line 27. The desulfurized and demetalizedproduct is withdrawn in line 26. The light gas stream of line 27 is passed into condenser 28 where water is condensed from the light gas 2~ strea~, leaving a substantially dry light gas stream 29.
Water, thus sepa.rated enters recycle water line 36 for : injection as described hereinabove. The dry light gas stream 29 is passed to hydrogen sulfide recovery system 30 wherein hydrogen sulfide is removed by contact with a caustic scrubbing 3 agent such as methylamine. Scrubber effluent 33, a hydrogen-~0~4489 rich stream consisting of hydro~en and li~ht hydrocarbons is mixed with ~ake up hydrogen stream 34 to form the hydrogen- !
rich ga.s stream 21 described previously.
The substa.ntially sulfur and nickel-free products of the present invention are suited for direct use as a fuel, for example, or may be processed further. One desirable further processing use is catalytic cracking, especially fluid catalytic cra.cking (FCC). The products of the present invention are particularly desirable as cracking feed due to their low nickel and sulfur levels since it is known that nickel, contributes greatly to catalytic cracking catalyst poisoning.
EXAMPLE
Arab Light a.tmospheric resid was mixed with hydrogen.
Water, which was preheated to 100C, was added to the resid-. hydrogen mixture at certain times throughout a run sequence.
The final mixture wa.s passed over a presulfided desulfurization . catalyst containing 3% CoO, 10% MoO3 and 5~ SiO2 on aluminain a trickle bed rea.ctor at a pressure of 700 psig and tempera-tures of 750F and 8000F. The weight hourly spa.ce velocity was 2. A standard run sequence was used so that the reactor was lined out at the lower temperature for four da.ys with no water, followed by a seven day series of tests with water addition, further followed by a return to the original water-free condition to monitor aging. The sequence was continued at the higher temperature. Table 3 illustrates the standard ; run sequence.
_ g _ J 0~3L/~ 9 Standard Run Sequence Gas Circulation*
Day Temp. H20/H2 SCF/bbl 1-4 750F 0 8soo-gooo '~ 0~4 12000 6,7 ~ o . l gooo-loooo 8 tl 0.7 8soo-gooo ~ 9 " 0.4 12000 o ~ o .5 13000 1.2 8500-9500 12, 13 8500 g o o o 14,15 800 0 8soo-gooo 16 " 0.4 12000 17,18 " 0.1 8000-gooo 19 " 0.7 80oo-gooo " 0.4 12000 ~ 21,22 0 8soo-gooo * -- Includes ~ 0 .
Reaction products were separated from the water and dried over a 4A rnolecular sieve before analysis. It was determined that the water layer did not contain organic sulfur compounds, therefore, the reported effects were not artifacts of some extraction process.
In order to compare activity as a function of H20/H2 mole ratio, a second order rate expression was assumed and conversion data were mathematically ad~usted to eliminate catalyst aging. Thus, the activity for sulfur, nitrogen, nickel and vanadium removal at different H20/~ ratios is shown in Figures 2-5. Examination of the Figures shows the desulfuriza-tion activity to be markedly improved at H20/H2 molar ratios of about 0.05 to 0.5, especially 0.05-0.2. Similarly, nickel removal is increased at H20/H2 ratios greater than about 0.1.
Nitrogen removal remains unchanged while vanadium removal falls slightly with increasing H20/H2 ratios.
In a separate series of tests, equimolar ratios of N2 were substituted for the water used in the above described series of tests to isolate the effects of water from those of diffusion and of the laboratory trickle bed reactor. The results, also plotted in Figures 2-4, indicate that the beneficial nickel and sulfur removing effects are due to water injection rather than reactor or diffusional effects.
Surface area data were obtained on recovered catalyst to test the possibility of increased catalyst .~
` 10944~9 degradation in the presence of steam. me calcined, recovered catalyst showed a surface area of 295 m2/g as compared with a value of 280 for the fresh material. Thus, no such de~rada-tion was observed in these tests.
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BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a diagrammatic representation of the process of the present invention, Figures 2, 3, 4 and 5 respectively depict percent sulfur, nitrogen, nickel and vanadium removal at various H20/H2 and N2/H2 mole ratios.
DESCRIPTION OF SPECIFIC EMBODIMENTS
me process of the present inven~on is directed to improved desulfurization and demetalation of heavy hydrocarbon charge stocks which can be any metal and sulfur containing stock, preferably one containing residual fractions. Examples include stocks such as atmospheric and vacuum resids, vacuum gas oils, tar sands, bituming cycle stocks, shale oils and the like. From what has been said, it will be clear that the feedstock can be a whole crude. However, since the high metal and sulfur com-ponents of a crude oil tend to be concentrated in the hi~ler boiling fractions, the present process more commonly will be ; 20 applied to a bottoms fraction of a petroleum oil, i.e. one which is obtained by distillation of a crude petroleum oil to remove lower boiling materials. Accordingly, the heavy hydro-carbon charge stocks used herein generally boil above about 400F., preferably a~ove about 650F, and have gravities from ~74 about 0 API to about 30 API. A general range o~ the propertles of heavy hydrocarbon charge stocks which are suitable for use in the process of this invention as well as the properties of a particular charge stock are listed in Table 1.
10~ 9 Arab Light Atmospheric General Ran~e Resid Sulfur, Wt. % 1 - 10 3-85 Nitrogen, Wt. % 0.1 - 3 0.22 Oxygen, Wt. % 0 - 10 0.13 Total Metals, ppm 10 - 3 65 Vanadium, ppm 10 - 2000 49 Nickel, ppm 1 - 3 13 Catalyst which can be used to promote desul~ur-ization reactions contain at least one metallic component selected from the Groups VIB and VIII of the Periodic Table deposited on a refractory inorganic oxide support or binder.
The preferred metallic component may be an oxide or sulfide of nlckel or cobalt, particularly the latter and an oxide or sulfide of molybdenumn or tungsten. The Group VIII metal is generally present in amounts from 1-15 percent by weight, while the Group VIB component is present in amounts from 5-25 percent by weight. The refractory inorganic oxide support may comprise alumina, silica, zirconia, magnesia, titania, boria, strontia, hafnia and mixtures thereof. Par-ticularly preferred are alumina or silica-stabilized alumina5 with the alumina being of the greater proportion. A typical catalyst consists of 3 percent CoO, 10 percent MoO3, 5 percent ; Si02 on alumina. Catalyst are generally presulfided prior to use.
Table 2 lists suitable reaction conditions for the catalytic desulfurization of heavy hydrocarbon charge stocl~s.
109A~89 TABL~ 2 DESULFURIZATIO~ COI~ITIONS
General Range Pre~erred Pressure, psig 500 - 3000 1000 - 2000 ~emperature, C 250 - 500 350 - 45 Space Velocity, LHSV 0.2 - 5 0.5 - 2 Hydrogen Rate, SCF/bbl 1000 - 20,000 4000 - 12,000 The efficaciousness of the novel desulfurization and demetalation process of this invention is in part based upon the effects of water injection on the hydro-processing of heavy charge stocks. This discovery will be described in more detail hereinafter, however, briefly, it was found that invection o~
water into the reaction zone at certain H2O/H2 molar ratios enhances both desulfurizatlon and nickel removal. Also, water in~ection in the particular specified amount was found to have no deleterious effect on nitrogen removal, catalyst aging or catalyst physical properties such as surface area. Thus, the novel process disclosed herein provides for increased sulfur and nickel removal without relying on undesirable changes of process variables such as increasing pressure or temperature.
In fact, the partial pressure of costly hydrogen in greatly reduced by the use of th~s invention.
A process incorporating the above discovery is now described. Referring to Figure 1, a heavy hydrocarbon charge stock stream 20 containing sulfur, nitrogen and oxy~en hetero-atoms plus metals such as nickel and vanadium is mixed with a hydrogen-rich gas stream 21 and the resulting admixture is heated in furnace 22 be~ore being charged to reaction zone 23.
, 109~1489 Reaction zone 23 conta.ins desulfuriza.tion ca.talyst and may include a. plurality of beds. Water from line 24~ which includes both recycled water from line 36 and make up wa.ter from line 35, as needed, is injected into rea.ction zone 23 in amounts from a.bout .05 to .5 H20/~2 (molar ratios), pre-ferably .05 to .2. If desired, a portion of the water may be injected into the reaction zone by admixture with the hydrogen rich stream, ~d ~ater being introduced via line 39.
U~ed in these amounts, the water effects increased desulfuri-zation and demetalation of the charge stock, as will be des-cribed hereinafter, as well as cooling or quenching. Water may be injected between beds if a. plurality of beds are incorporated in reaction zone 23.
The reaction zone effluent in line 37 is passed through heat exchanger 38 before it enters separator 25.
Heat exchanger 38 is used to ad~ust the temperature of the effluent, which contains H2, H20, H2S, light hydrocarbons and desulfurized a.nd demetalized products, to the conditions of separator 25, which desira.bly is a high pressure flash separator. The gaseous effluents from separator 25, which include H2, H20, H2S.and light hydrocarbons, go overhead in line 27. The desulfurized and demetalizedproduct is withdrawn in line 26. The light gas stream of line 27 is passed into condenser 28 where water is condensed from the light gas 2~ strea~, leaving a substantially dry light gas stream 29.
Water, thus sepa.rated enters recycle water line 36 for : injection as described hereinabove. The dry light gas stream 29 is passed to hydrogen sulfide recovery system 30 wherein hydrogen sulfide is removed by contact with a caustic scrubbing 3 agent such as methylamine. Scrubber effluent 33, a hydrogen-~0~4489 rich stream consisting of hydro~en and li~ht hydrocarbons is mixed with ~ake up hydrogen stream 34 to form the hydrogen- !
rich ga.s stream 21 described previously.
The substa.ntially sulfur and nickel-free products of the present invention are suited for direct use as a fuel, for example, or may be processed further. One desirable further processing use is catalytic cracking, especially fluid catalytic cra.cking (FCC). The products of the present invention are particularly desirable as cracking feed due to their low nickel and sulfur levels since it is known that nickel, contributes greatly to catalytic cracking catalyst poisoning.
EXAMPLE
Arab Light a.tmospheric resid was mixed with hydrogen.
Water, which was preheated to 100C, was added to the resid-. hydrogen mixture at certain times throughout a run sequence.
The final mixture wa.s passed over a presulfided desulfurization . catalyst containing 3% CoO, 10% MoO3 and 5~ SiO2 on aluminain a trickle bed rea.ctor at a pressure of 700 psig and tempera-tures of 750F and 8000F. The weight hourly spa.ce velocity was 2. A standard run sequence was used so that the reactor was lined out at the lower temperature for four da.ys with no water, followed by a seven day series of tests with water addition, further followed by a return to the original water-free condition to monitor aging. The sequence was continued at the higher temperature. Table 3 illustrates the standard ; run sequence.
_ g _ J 0~3L/~ 9 Standard Run Sequence Gas Circulation*
Day Temp. H20/H2 SCF/bbl 1-4 750F 0 8soo-gooo '~ 0~4 12000 6,7 ~ o . l gooo-loooo 8 tl 0.7 8soo-gooo ~ 9 " 0.4 12000 o ~ o .5 13000 1.2 8500-9500 12, 13 8500 g o o o 14,15 800 0 8soo-gooo 16 " 0.4 12000 17,18 " 0.1 8000-gooo 19 " 0.7 80oo-gooo " 0.4 12000 ~ 21,22 0 8soo-gooo * -- Includes ~ 0 .
Reaction products were separated from the water and dried over a 4A rnolecular sieve before analysis. It was determined that the water layer did not contain organic sulfur compounds, therefore, the reported effects were not artifacts of some extraction process.
In order to compare activity as a function of H20/H2 mole ratio, a second order rate expression was assumed and conversion data were mathematically ad~usted to eliminate catalyst aging. Thus, the activity for sulfur, nitrogen, nickel and vanadium removal at different H20/~ ratios is shown in Figures 2-5. Examination of the Figures shows the desulfuriza-tion activity to be markedly improved at H20/H2 molar ratios of about 0.05 to 0.5, especially 0.05-0.2. Similarly, nickel removal is increased at H20/H2 ratios greater than about 0.1.
Nitrogen removal remains unchanged while vanadium removal falls slightly with increasing H20/H2 ratios.
In a separate series of tests, equimolar ratios of N2 were substituted for the water used in the above described series of tests to isolate the effects of water from those of diffusion and of the laboratory trickle bed reactor. The results, also plotted in Figures 2-4, indicate that the beneficial nickel and sulfur removing effects are due to water injection rather than reactor or diffusional effects.
Surface area data were obtained on recovered catalyst to test the possibility of increased catalyst .~
` 10944~9 degradation in the presence of steam. me calcined, recovered catalyst showed a surface area of 295 m2/g as compared with a value of 280 for the fresh material. Thus, no such de~rada-tion was observed in these tests.
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~ -12-
Claims (9)
1. A process for removing sulfur and nickel from a nickel and sulfur containing heavy hydrocarbon charge stock com-prising:
a) admixing said charge stock with a hydrogen-rich stream;
b) reacting the admixture of step (a) in a reaction zone containing a desulfurization catalyst at desulfuriz-ation conditions comprising a pressure from about 500 to 3000 psig; a temperature from about 250 to 500°C;
a space velocity from about .2 to 5 LHSV and a hydrogen ratio from about 1000 to 20,000 SCF/bbl;
c) injecting water into said reaction zone at a water to hydrogen molar ratio from about 0.05 to about 0.5;
d) separating a light gas stream which contains H2, H2O, H2S and light hydrocarbons from the effluent of said reaction zone;
e) separating the H2O from said light gas stream leaving a substantially dry light gas stream;
f) recycling the separated H2O for injection as in step c);
g) separating the H2S from the dry light gas stream leaving a hydrogen-rich stream;
h) recycling said hydrogen-rich stream for admixing with said charge stock; and i) recovering a substantially nickel and sulfur free product from the effluent of said reaction zone.
a) admixing said charge stock with a hydrogen-rich stream;
b) reacting the admixture of step (a) in a reaction zone containing a desulfurization catalyst at desulfuriz-ation conditions comprising a pressure from about 500 to 3000 psig; a temperature from about 250 to 500°C;
a space velocity from about .2 to 5 LHSV and a hydrogen ratio from about 1000 to 20,000 SCF/bbl;
c) injecting water into said reaction zone at a water to hydrogen molar ratio from about 0.05 to about 0.5;
d) separating a light gas stream which contains H2, H2O, H2S and light hydrocarbons from the effluent of said reaction zone;
e) separating the H2O from said light gas stream leaving a substantially dry light gas stream;
f) recycling the separated H2O for injection as in step c);
g) separating the H2S from the dry light gas stream leaving a hydrogen-rich stream;
h) recycling said hydrogen-rich stream for admixing with said charge stock; and i) recovering a substantially nickel and sulfur free product from the effluent of said reaction zone.
2. The process of Claim 1 further characterized in that the catalyst of step b) comprises at least one metallic component selected from the Groups VIB and VIII of the Periodic Table deposited on a refractory inorganic oxide support.
3. The process of Claim 2 wherein said catalyst comprises cobalt and molybdenum in either the oxide or sulfide form deposited on alumina.
4. The process of Claim 1 further characterized in that the charge stock contains from about 10 to about 3000 ppm total metals and from about 1 to about 10 weight percent sulfur.
5. The process of Claim 1 wherein water is injected into said reaction zone at a water to hydrogen molar ratio from about 0.05 to about 0.2.
6. The process of Claim 1 further characterized in that the separation of step d) is effected by a high temperature flash.
7. The process of Claim 1 further characterized in that the separation of step e) is effected by condensation.
8. The process of Claim 1 wherein said sulfur and nickel-free product is conducted to a catalyst cracking zone and catalytically cracked products are withdrawn from said zone.
9. The process of Claim 1 wherein a portion of said water is injected into the reaction zone by admixture with the hydrogen-rich stream.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67190676A | 1976-03-29 | 1976-03-29 | |
| US671,906 | 1976-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1094489A true CA1094489A (en) | 1981-01-27 |
Family
ID=24696365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA272,087A Expired CA1094489A (en) | 1976-03-29 | 1977-02-18 | Desulfurization and demetalation of heavy charge stocks |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS52117905A (en) |
| AU (1) | AU510360B2 (en) |
| CA (1) | CA1094489A (en) |
| DE (1) | DE2713343A1 (en) |
| FR (1) | FR2346436A1 (en) |
| GB (1) | GB1535477A (en) |
| IT (1) | IT1075588B (en) |
| ZA (1) | ZA771371B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020056664A1 (en) * | 2000-09-07 | 2002-05-16 | Julie Chabot | Extension of catalyst cycle length in residuum desulfurization processes |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1528414A (en) * | 1966-06-24 | 1968-06-07 | Universal Oil Prod Co | Crude Petroleum Oil Desulfurization Process |
| US3501396A (en) * | 1969-04-14 | 1970-03-17 | Universal Oil Prod Co | Hydrodesulfurization of asphaltene-containing black oil |
| US3753894A (en) * | 1971-02-26 | 1973-08-21 | Exxon Research Engineering Co | Water injection between catalyst beds in hydrodesulfurization of residuum feed |
| US3720602A (en) * | 1971-02-26 | 1973-03-13 | Exxon Research Engineering Co | Water injection in a hydrodesulfurization process |
| DE2207611A1 (en) * | 1972-02-18 | 1973-08-30 | Exxon Research Engineering Co | Hydrocarbon hydrodesulphurisation - with water injection over catalyst comprising vanadium, niobium or tantalum |
| DE2332834A1 (en) * | 1973-06-28 | 1975-01-23 | Exxon Research Engineering Co | Hydrodesulphurisation of residua - with water quench between catalyst beds |
| NL188659C (en) * | 1975-02-21 | 1992-08-17 | Shell Int Research | PROCESS FOR DESULFULIFYING HYDROCARBON OILS |
-
1977
- 1977-02-18 CA CA272,087A patent/CA1094489A/en not_active Expired
- 1977-03-08 ZA ZA00771371A patent/ZA771371B/en unknown
- 1977-03-09 GB GB9901/77A patent/GB1535477A/en not_active Expired
- 1977-03-14 JP JP2713877A patent/JPS52117905A/en active Pending
- 1977-03-25 FR FR7708957A patent/FR2346436A1/en active Granted
- 1977-03-25 DE DE19772713343 patent/DE2713343A1/en not_active Withdrawn
- 1977-03-28 AU AU23694/77A patent/AU510360B2/en not_active Expired
- 1977-03-28 IT IT21755/77A patent/IT1075588B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52117905A (en) | 1977-10-03 |
| FR2346436A1 (en) | 1977-10-28 |
| AU2369477A (en) | 1978-10-05 |
| FR2346436B1 (en) | 1982-06-04 |
| ZA771371B (en) | 1978-10-25 |
| IT1075588B (en) | 1985-04-22 |
| AU510360B2 (en) | 1980-06-19 |
| GB1535477A (en) | 1978-12-13 |
| DE2713343A1 (en) | 1977-10-06 |
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