CA2535349A1 - A process for the desulfurization of hydrocarbonaceous oil - Google Patents
A process for the desulfurization of hydrocarbonaceous oil Download PDFInfo
- Publication number
- CA2535349A1 CA2535349A1 CA002535349A CA2535349A CA2535349A1 CA 2535349 A1 CA2535349 A1 CA 2535349A1 CA 002535349 A CA002535349 A CA 002535349A CA 2535349 A CA2535349 A CA 2535349A CA 2535349 A1 CA2535349 A1 CA 2535349A1
- Authority
- CA
- Canada
- Prior art keywords
- sulfur
- hydrocarbonaceous oil
- hydrocarbonaceous
- adsorbent
- stream
- 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.)
- Abandoned
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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
-
- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including oxidation as the refining step in the absence of hydrogen
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
Landscapes
- 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)
Abstract
A process for the desulfurization of hydrocarbonaceous oil wherein the hydrocarbonaceous oil is contacted with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone (3) to reduce the sulfur level to a relatively low level then contacting the resulting hydrocarbonaceous stream from the hydrodesulfurization zone with an oxidizing agent (8) to convert the residual, low level of sulfur compounds into sulfur-oxidated compounds. The resulting hydrocarbonaceous oil stream containing the sulfur-oxidated compounds is separated after decomposing any residual oxidizing agent by contacting the stream with an adsorbent material (18, 30) to adsorb the sulfur-oxidated compounds to produce a hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds. The spent adsorbent (18, 30) is regenerated and subsequently returned to adsorbent service.
Description
A PROCESS FOR THE DESULFURIZATION OF HYDROCARBONACEOUS OIL
BACKGROUND OF THE INVENTION
[0001] There is an increasing demand to reduce the sulfur content of hydrocarbonaceous oil to produce products which have very low concentrations of sulfur and are thereby marketable in the ever more demanding marketplace. With the increased environmental emphasis on the requirement for more environmentally friendly transportation fuels, those skilled in the art have sought to find feasible and economical techniques to reduce the sulfur content of hydrocarbonaceous oil to low concentrations.
BACKGROUND OF THE INVENTION
[0001] There is an increasing demand to reduce the sulfur content of hydrocarbonaceous oil to produce products which have very low concentrations of sulfur and are thereby marketable in the ever more demanding marketplace. With the increased environmental emphasis on the requirement for more environmentally friendly transportation fuels, those skilled in the art have sought to find feasible and economical techniques to reduce the sulfur content of hydrocarbonaceous oil to low concentrations.
[0002] Traditionally, hydrocarbons containing sulfur have been subjected to a catalytic hydrogenation zone to remove sulfur and produce hydrocarbons having lower concentrations of sulfur. Hydrogenation to remove sulfur is very successful for the removal of the sulfur from hydrocarbons that have sulfur components that are easily accessible to contact with the hydrogenation catalyst. However, the removal of sulfur components that are sterically hindered becomes exceedingly difficult and therefore the removal of sulfur components to a sulfur level below 100 ppm is very costly by known current hydrotreating techniques. It is also known that a hydrocarbonaceous oil containing sulfur may be subjected to oxygenation to convert the hydrocarbonaceous sulfur compounds to compounds containing sulfur and oxygen, such as sulfoxide or sulfone for example, which have different chemical and physical characteristics which make it possible to isolate or separate the sulfur bearing compounds from the balance of 2o the original hydrocarbonaceous oil. The disadvantage to this approach is that the isolated sulfur bearing hydrocarbon compounds are still not useful as a sulfur-free material and therefore the yield of a sulfur-free material from the original hydrocarbonaceous oil is less than desirable and therefore uneconomic.
INFORMATION DISCLOSURE
INFORMATION DISCLOSURE
[0003] US 2,769,760 discloses a hydrodesulfurization process which reduces the organic sulfur concentration in a hydrocarbon feedstock. The resulting hydrocarbon product from the first stage hydrodesulfurization zone contains sulfur and is subsequently introduced into a second stage partial desulfurization and/or chemical reaction wherein the second stage treatment is conducted at a temperature of approximately 232°C
(450°F) and at atmospheric pressure in the absence of hydrogen. The contact material for the reaction in the second stage is of the same type as used for the hydrodesulfurization reaction. Preferred contact materials contain cobalt and molybdenum.
(450°F) and at atmospheric pressure in the absence of hydrogen. The contact material for the reaction in the second stage is of the same type as used for the hydrodesulfurization reaction. Preferred contact materials contain cobalt and molybdenum.
[0004] Published European Patent Application No. 565324 discloses a method of recovering an organic sulfur compound from a liquid oil wherein the method comprises treating the liquid oil containing an organic sulfur compound with an oxygen agent and separating the oxidized organic sulfur compound by separation means such as distillation, solvent extraction and/or adsorption means.
[0005] US 3,551,328 discloses a process for reducing the sulfur content of heavy hydrocarbon petroleum fractions by oxidizing the sulfur compounds present in such heavy hydrocarbon fractions and contacting the heavy hydrocarbon fractions containing such oxidized sulfur compounds with a lower paraffinic hydrocarbon solvent in a concentration sufficient to separate the oxidized sulfur compounds from the heavy hydrocarbon fractions and recovering a heavy hydrocarbon fraction of reduced sulfur content.
[0006] US 6,277,271 Bl discloses a process for the desulfurization of hydrocarbonaceous oil wherein the hydrocarbonaceous oil and a recycle stream containing sulfur-oxidated compounds is contacted with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone to reduce the sulfur level to a relatively low level and then contacting the resulting hydrocarbonaceous stream from the hydrodesulfurization zone with an oxidizing agent to convert the residual, low level of sulfur compounds into sulfur-oxidated compounds. The residual oxidizing agent is decomposed and the resulting hydrocarbonaceous oil stream containing the sulfur-oxidated compounds is separated to produce a stream containing the sulfur-oxidated compounds and a hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds. At least a portion of the sulfur-oxidated compounds is recycled to the hydrodesulfurization reaction zone.
[0007] US 6,171,47 B 1 discloses a process for the desulfurization of hydrocarbonaceous oil wherein the hydrocarbonaceous oil is contacted with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone to reduce the sulfur level to a relatively low level and then contacting the resulting hydrocarbonaceous stream from the hydrodesulfurization zone with an oxidizing agent to convert the residual, low level of sulfur compounds into sulfur-oxidated compounds. The resulting hydrocarbonaceous oil stream containing the sulfur-oxidated compounds is separated by solvent extraction after decomposing any residual oxidizing agent to produce a stream containing the sulfur-oxidated compounds and a hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds.
SUMMARY OF THE INVENTION
SUMMARY OF THE INVENTION
[0008] The present invention provides a process for the desulfurization of hydrocarbonaceous oil wherein the hydrocarbonaceous oil is contacted with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone to reduce the sulfur level to a relatively low level and then contacting the resulting hydrocarbonaceous stream from the hydrodesulfurization zone with an oxidizing agent to convert the residual, low level of sulfur compounds into sulfur-oxidated compounds. The residual oxidizing agent is decomposed and the resulting hydrocarbonaceous oil stream containing the sulfur-oxidated compounds is separated to produce a stream comprising the sulfur-oxidated compounds and a hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds.
(0009] In a preferred embodiment of the present invention, the hydrocarbonaceous effluent stream from the hydrodesulfurization zone is contacted with an aqueous oxidizing solution to convert the residual, low level of sulfur compounds into sulfur-oxidated compounds. The resulting hydrocarbonaceous oil stream containing the sulfur-oxidated compounds is treated to decompose any residual oxidizing agent and is contacted with a selective adsorbent having a greater selectivity for the sulfur-oxidated compounds than for the sulfur-free hydrocarbonaceous oil to produce an adsorbent containing at least a portion of the sulfur-oxidated compounds and a hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds.
(001Oj The present invention discloses a novel integrated process that is capable of easily and economically reducing the sulfur content of hydrocarbonaceous oil while achieving high recovery of the original feedstock. Important elements of the present invention are the minimization of the cost of hydrotreating in the integrated two-stage desulfurization process and the ability to economically desulfurize hydrocarbonaceous oil to a very low level while maximizing the yield of the desulfurized hydrocarbonaceous oil.
BRIEF DESCRIPTION OF THE DRAWING
[0011] The drawing is a simplified process flow diagram of a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The present invention provides an improved integrated process for the deep desulfurization of hydrocarbonaceous oil in a two-stage desulfurization process. In accordance with the present invention, a preferred hydrocarbonaceous oil feedstock contains distillable hydrocarbons boiling in the range from 93°C (200°F) to 565°C (1050°F) and more preferably from 149°C (300°F) to 538°C (1000°F). The hydrocarbonaceous oil feedstock is contemplated to contain from 0.1 to 5 weight percent sulfur and the process is most advantageously utilized when the feedstock contains high levels of sulfur and the desired desulfurized product contains a very low concentration of sulfur. Preferred product sulfur levels are less than 100 wppm, more preferably less than 50 wppm, and even more preferably less than 30 wppm.
[0013] The hydrocarbonaceous oil containing sulfur compounds is introduced into a catalytic hydrodesulfurization zone containing hydrodesulfurization catalyst and maintained at hydrodesulfurization conditions. The catalytic hydrodesulfurization zone may contain a fixed, ebullated or fluidized catalyst bed. This reaction zone is preferably maintained under an imposed pressure from 101 kPa (14.7 psig) to 13.9 MPa (2000 psig) and more preferably under a pressure from 800 kPa (100 psig) to 12.5 MPa (1800 psig). Suitably, the hydrodesulfurization reaction is conducted with a maximum catalyst bed temperature in the range from 204°C (400°F) to 400°C (750°F) selected to perform the desired hydrodesulfurization conversion to reduce the concentration of the sulfur compounds to the desired level. In accordance with the present invention, it is contemplated that the desired hydrodesulfurization conversion includes, for example, desulfurization, denitrification and olefin saturation. Further preferred operating conditions include liquid hourly space velocities in the range from 0.05 hr.'1 to 20 hr.'i and hydrogen to feed ratios from 200 standard cubic feet per barrel (SCFB) (33.7 nm3/m3) to 50,000 SCFB (8425 nm3/m3), preferably from (33.7 nm3/m3) to 10,000 SCFB (1685 nm3/m3). The hydrodesulfurization zone operating conditions are preferably selected to produce a desulfurized hydrocarborlaceous oil containing from 100 to 1000 wppm sulfur.
[0014] The preferred catalytic composite disposed within the hereinabove-described hydrodesulfurization zone can be characterized as containing a metallic component having hydrodesulfurization activity, which component is combined with a suitable refractory inorganic oxide carrier material of either synthetic or natural origin. The precise composition and method of manufacturing the carrier material is not considered essential to the present invention. Preferred carrier materials are alumina, silica, and mixtures thereof. Suitable metallic components having hydrodesulfurization activity are those selected from the group comprising the metals of Groups V1B and VIII of the Periodic Table, as set forth in the Periodic Table of the Elements, E.H. Sargent and Company, 1964. Thus, the catalytic composites may comprise one or more metallic components from the group of molybdenum, tungsten, chromium, iron, cobalt, nickel, platinum, palladium, iridium, osmium, rhodium, ruthenium, and mixtures thereof. The concentration of the catalytically active metallic component, or components, is primarily dependent upon a particular metal as well as the physical and/or chemical characteristics of the particular hydrocarbon feedstock. For example,.
the metallic components of Group VIB are generally present in an amount within the range of from 1 to 20 weight percent, the iron-group metals in an amount within the range of 0.2 to 10 weight percent, whereas the noble metals of Group VIII are preferably present in an amount within the range of from 0.1 to 5 weight percent, all of which are calculated as if these components existed within the catalytic composite in the elemental state. In addition, any catalyst employed commercially for hydrodesulfurizing middle distillate hydrocarbonaceous compounds to remove nitrogen and sulfur may function effectively in the hydrodesulfurization zone of the present invention. It is further contemplated that hydrodesulfurization catalytic composites may comprise one or more of the following components: cesium, francium, lithium, potassium, rubidium, sodium, copper, gold, silver, cadmium, mercury and zinc.
[0015] The hydrocarbonaceous effluent from the hydrodesulfurization reaction zone is separated to produce a gaseous stream containing hydrogen, hydrogen sulfide and normally gaseous hydrocarbons, and a liquid hydrocarbonaceous stream having a reduced concentration of sulfur compounds. This resulting liquid hydrocarbonaceous stream in one prefewed embodiment of the present invention is contacted with an aqueous oxidizing solution in an oxidation zone to convert sulfur-containing compounds into sulfur-oxidated compounds. Any suitable known aqueous oxidizing solution may be used to perform the sulfur oxidation. In a preferred embodiment, the aqueous oxidizing solution contains acetic acid and hydrogen peroxide. Preferably the molar feed ratio of hydrogen peroxide to sulfur ranges from 1 to 10 or more and the molar ratio of acetic acid to hydrogen peroxide ranges from 0.1 to 10 or more.
The oxidation conditions including contact time are selected to give the desired results as described herein and the pressure is preferably great enough to maintain the aqueous solution in a liquid phase during the contacting of the hydrocarbonaceous oil. Preferred oxidation conditions include a pressure from atmospheric to 800 kPa (100 psig), and a temperature from 38°C (100°F) to 149°C (300°F). Since the aqueous oxidizing solution and the hydrocarbonaceous oil are immiscible, the oxidation zone must have the ability to intimately mix and contact the two phases to ensure the completion of the chemical oxidation. Any suitable means may be used for the contacting and preferred methods include the use of a packed mixing column with countercurrent flows of the two phases or in-line mixing apparatus.
(0016] In the event that there is residual hydrogen peroxide after the completion of the oxidation, it is preferred that the stream containing the residual hydrogen peroxide is contacted with a suitable catalyst to decompose the hydrogen peroxide. A preferred hydrogen peroxide decomposition catalyst is a supported transition metal, a transition metal complex or a transition metal oxide. The decomposition of the hydrogen peroxide is conducted to simplify the recovery and separation of the reaction products including sulfur-oxidated compounds recovered from the oxidation zone. Preferred decomposition operating conditions include a pressure from atmospheric to 800 kPa (100 psig) and a temperature from 38°C (100°F) to 149°C (300°F).
[0017] The resulting effluent from the oxidation zone after decomposition of the oxidizing agent contains desulfurized hydrocarbonaceous oil, sulfur-oxidated compounds such as sulfoxides and sulfones, for example, water and acetic acid. This resulting effluent from the oxidation zone is contacted with a selective adsorbent having a greater selectivity for the sulfur-oxidated compounds than for the sulfur-free hydrocarbonaceous oil to produce a selective adsorbent containing at least a portion of the sulfur-oxidated compounds and a hydrocarbonaceous oil having a reduced concentration of sulfur. Any suitable known selective adsorbent may be used to selectively extract the sulfur-oxidated compounds. In a preferred embodiment of the present invention, the selective adsorbent is selected from the group consisting of aluminosilicates such as X and Y type zeolites, zeolite beta, and L-zeolite, highly silaceous zeolites such as ZSM-5 and silicalite, and silica aluminophosphates such as SAPO-34. The preferred selective adsorbents are contacted with the effluent from the oxidation zone in an adsorption zone. In a preferred mode, the sulfur-oxidated compounds are adsorbed with thermally stable aluminosilicates such as Y-type zeolite, dealuminated Y type zeolite, zeolite beta, and zeolite L. The raffinate hydrocarbonaceous oil recovered from the adsorption zone preferably contains less than 100 weight ppm, more preferably less than 50 weight ppm sulfur and even more preferably less than 30 wppm.
[0018] The resulting adsorbent is regenerated to recover the adsorbed sulfur-oxidated compounds and the regenerated adsorbent is preferably recycled to the adsorption zone. The regeneration of the adsorbent may be accomplished by desorbing the adsorbed sulfur-oxidated compounds by heating and/or by contacting with a liquid or vapor desorbent.
(0019] In one embodiment, operation of the invention is achieved as a fixed bed adsorber by introducing reacted mixture from the sulfur oxidation zone to an adsorption zone until a selected portion of the adsorptive capacity of the selective adsorbent is exhausted. By suitable valuing means the flow of reacted mixture from the sulfur oxidation zone is then halted and the exhausted adsorption zone is regenerated in a desorption zone by desorbing the sulfur-oxidated compounds from the adsorbent with desorbent material. In this manner, a single fixed bed may be so employed in the desulfurization process of the instant invention.
(0020] In another embodiment, operation of the invention is achieved as a fixed bed adsorber by introducing reacted mixture from the sulfur oxidation zone to a first adsorption zone until a selected portion of the adsorptive capacity of the selective adsorbent is exhausted.
By suitable valuing means the flow of reacted mixture from the sulfur oxidation zone is then redirected to a second adsorption zone containing selective adsorbent which has been previously regenerated and the exhausted adsorption zone is regenerated in a desorption zone by desorbed the sulfur-oxidated compounds from the adsorbent with desorbent material. In this manner, any desired number of fixed beds may be so arranged in the desulfitrization of the instant invention.
_7_ [0021] In another embodiment, operation of the invention is achieved as a fluidized or ebullated bed adsorber by introducing reacted mixture from the sulfur oxidation zone to an fluidized adsorption zone until a selected portion of the adsorptive capacity of the selective adsorbent is exhausted. By suitable means at least a portion of the exhausted adsorbent from the adsorption zone is then redirected to a desorption zone and the exhausted adsorbent is regenerated desorbing the sulfur-oxidated compounds from the adsorbent with desorbent material.
[0022] In yet another embodiment, operation of the invention is achieved as simulated countercurrent adsorber by introducing reacted mixture from the sulfur oxidation zone to a moving bed adsorption zone until a selected portion of the adsorptive capacity of the selective adsorbent is exhausted. By suitable means at least a portion of the exhausted adsorbent from the adsorption zone is then redirected to a desorption zone and the exhausted adsorbent is regenerated desorbing the sulfur-oxidated compounds from the adsorbent with desorbent material.
[0023] With reference now to the drawing that illustrates a two-bed fixed adsorber operation, with one bed in the adsorption mode and one bed in the desorption mode, a hydrocarbonaceous oil containing sulfur is introduced into the process via line 1 and enters hydrodesulfurization zone 3. A fresh hydrogen stream is introduced via line 2 and is admixed with a hydrogen-rich gaseous recycle stream provided via line 7 and the resulting admixture is introduced into hydrodesulfurization zone 3 via line 2. A gaseous stream containing hydrogen, hydrogen sulfide and normally gaseous hydrocarbons is removed from hydrodesulfurization zone 3 via line 5 and at least a portion is recycled via line 7 as described hereinabove and at least another portion is removed from the process via line 6. A
hydrocarbonaceous stream having a reduced concentration of sulfur is removed from hydrodesulfurization zone 3 via line 4 and introduced into sulfur oxidation zone 8 via line 12 along with a carboxylic acid stream provided via lines 9, 11 and 12, and an aqueous hydrogen peroxide stream which is introduced into the process via lines 10, 11 and 12. The aqueous stream and the hydrocarbonaceous stream are intimately admixed in sulfur oxidation zone 8 in order to oxidize the sulfur compounds. A resulting reacted mixture is removed from sulfur oxidation zone 8 via line 13 after decomposing any residual hydrogen peroxide and is transported via line 14, valve 15, lines 16 and 17 and is introduced into adsorption zone 18 and is contacted with previously _g_ regenerated selective adsorbent. A resulting hydrocarbonaceous stream containing a reduced concentration of sulfur is removed from adsorption zone 18 via line 19, line 20, valve 21, line 22 and line 23 and recovered. Desorbent stream 25, optionally comprising fresh desorbent stream 24 and/or recycled desorbent carried via line 37 is introduced via line 25, line 26, valve 27, line 28, and line 29 into a previously exhausted adsorption zone comprising desorption zone 30. A desorption stream rich in oxidized sulfur compounds is removed from desorption zone 30 via line 31, line 32, valve 33, line 34, and line 49 and is introduced into distillation zone 35. A desorbent stream having a reduced concentration of sulfur-oxidated compounds is removed from distillation zone 35 via line 37 and is optionally recycled to desorption zone 30 as hereinabove described. Oxidized sulfur compounds are removed from distillation zone 35 via line 36 and recovered. When adsorption zone 18 becomes spent, the stream carried via line 13 is transported via line 38, valve 39, line 40, and line 31 and is introduced into previously regenerated desorption zone 30. The now adsorption zone 30 produces an effluent stream having a reduced concentration of sulfur compounds which stream is transported via line 29, line 41, valve 42, line 43, and line 23 and recovered. The spent adsorption zone 18 is regenerated by the introduction of a desorption stream carried via line 25, line 44, valve 45, line 46, and line 19 into spent adsorption zone 18. A resulting effluent is recovered via line 17, line 16, valve 47, line 48, and line 49 and introduced into distillation zone 35.
(0024] Selective adsorbents useful in the present invention are identified by the following illustrative calculations. These calculations are, however, not presented to unduly limit the selective adsorbents useful in this invention, but to illustrate the molecular properties of the sulfur-containing and sulfur-oxidated compounds that play a role in the adsorption and removal from hydrocarbonaceous oil in the hereinabove described embodiment. The following results were not obtained by the actual measurement of the properties of the compounds but are considered prospective and reasonably illustrative of the expected performance of the invention based upon sound quantum chemistry calculations.
ILLUSTRATIVE CALCULATIONS
[0025] The chemical structures and selected molecular properties of methyl thiophene, methyl thiophene sulfone, methyl thiophene sulfoxide, benzothiophene, benzothiophene sulfone, and benzothiophene sulfoxide were calculated by the use of semi-empirical molecular -g_ orbital theory using the PM3 Hamiltonian as described by J.J.P. Stewart, "Optimization of Parameters for Semi-Empirical Methods 1 -Method", Journal of Computational Chemistry, Volume 10, 1989, pages 209-220, and are presented in Table 1.
Table 1 Sulfur Atom Limiting Compound Dipole Moment,Partial ChargeDimension, (debye) (electrostatic(angstroms) units) 2-methyl thiophene 0.950 0.303 4.588 2-methyl thiophene 4.718 1.063 4.636 sulfone 2-methyl thiophene 5.669 2.285 4.654 sulfoxide Benzothiophene 1.089 0.261 5.010 Benzothiophene sulfone4.546 1.063 5.006 Benzothiophene sulfoxide5.573 2.285 5.002 (0026] A first property affecting selective adsorption of the sulfur-oxidated molecules compared to the molecules comprising is dipole moment. Dipole moment increases upon oxidation of the sulfur-containing molecules and reflects an increase in polarity of the sulfur-oxidated molecules compared to hydrocarbonaceous oil molecules and un-oxidized sulfur-containing molecules. Such an increase in dipole moment increases the adsorption selectivity for the sulfur-oxidated molecules compared to un-oxidized sulfur-containing molecules and molecules comprising hydrocarbonaceous oil, when using such adsorbents as silica, alumina, silicates, aluminosilicates and aluminophosphates in the instant invention.
(0027 A second property affecting selective adsorption of the sulfur-oxidated molecules compared to the molecules comprising is the atomic partial charge on the sulfur atom. Positive partial charge on sulfur increases upon oxidation of the sulfur-containing molecules and reflects an increase in electrostatic attraction for the sulfur-oxidated molecules to adsorbent atoms bearing negative partial charge compared to hydrocarbonaceous oil molecules and un-oxidized sulfur-containing molecules. Such an increase in electrostatic attraction increases the adsorption selectivity for the sulfur-oxidated molecules compared to un-oxidized sulfur-containing molecules and molecules comprising hydrocarbonaceous oil, when using such adsorbents such as silica, alumina, silicates, aluminosilicates and aluminophosphates in the instant invention.
[0028] A third property that affects selective adsorption of the sulfur-oxidated molecules in preference of the un-oxidized sulfur-containing molecules is molecular size.
The crystalline structure of certain selective adsorbents such as crystalline silicates, aluminosilicates, and aluminophosphates may manifest channels and pores that are of molecular dimensions. In the present invention, if the sulfur-oxidated molecules are small enough to gain access to such channels and pores, they may be selectively adsorbed compared to larger molecules in the hydrocarbonaceous oil. The calculated limiting dimensions for the sulfur-oxidated molecules indicate that such molecules can gain access to the pore structures and be selectively adsorbed by such adsorbents as X and Y-type zeolites, dealuminated Y zeolite, L-zeolite, beta zeolite, SAPO-34, and the like. In addition, because many such microporous adsorbents display a selectivity for more polar molecules compared to less polar molecules, enhancement of dipole moment and sulfur positive partial charge via sulfur oxidation while not increasing the limiting molecular dimension makes these adsorbents particularly advantageous for use in the instant invention.
ILLUSTRATIVE EMBODIMENT
[0029] A stream of straight run vacuum gas oil boiling in the range of 315°C (600°F) to 482°C (900°F) and containing 2 weight percent sulfur is introduced into a hydrodesulfurization zone containing a hydrodesulfurization catalyst which contains alumina, nickel, molybdenum and phosphorus. The hydrodesulfurization zone is operated at a pressure of 11.8 MPa (1700 psig), a hydrogen to feed ratio of 843 nm3/m3 (5000 SCFB) and a maximum catalyst temperature of 393°C (740°F) to reduce the residual sulfur in the resulting desulfurized vacuum gas oil to 500 weight ppm (0.05 weight percent). The desulfurized vacuum gas oil is then introduced into an oxidation reaction zone and contacted with acetic acid and hydrogen peroxide in water. The molar feed ratio of hydrogen peroxide to sulfur is 5 and the molar ratio of acetic acid to hydrogen peroxide is 5, and the contacting is conducted at a temperature of 65°C (150°F) and a pressure of 207 kPa (30 psig). The effluent from the oxidation reaction zone is passed over a catalyst containing a mixed oxide of iron and molybdenum to decompose the unreacted hydrogen peroxide and then introduced into an adsorber wherein the sulfur-oxide compounds are extracted with Y zeolite as a selective adsorbent to produce a finished product containing less than 30 weight ppm sulfur. A spent selective adsorbent is regenerated to remove sulfur-oxide compounds and the subsequently regenerated adsorbent is returned to adsorbent service.
(0030 The foregoing description, drawing and illustrative embodiment clearly illustrate the advantages encompassed by the process of the present invention and the benefits to be afforded with the use thereof.
(001Oj The present invention discloses a novel integrated process that is capable of easily and economically reducing the sulfur content of hydrocarbonaceous oil while achieving high recovery of the original feedstock. Important elements of the present invention are the minimization of the cost of hydrotreating in the integrated two-stage desulfurization process and the ability to economically desulfurize hydrocarbonaceous oil to a very low level while maximizing the yield of the desulfurized hydrocarbonaceous oil.
BRIEF DESCRIPTION OF THE DRAWING
[0011] The drawing is a simplified process flow diagram of a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The present invention provides an improved integrated process for the deep desulfurization of hydrocarbonaceous oil in a two-stage desulfurization process. In accordance with the present invention, a preferred hydrocarbonaceous oil feedstock contains distillable hydrocarbons boiling in the range from 93°C (200°F) to 565°C (1050°F) and more preferably from 149°C (300°F) to 538°C (1000°F). The hydrocarbonaceous oil feedstock is contemplated to contain from 0.1 to 5 weight percent sulfur and the process is most advantageously utilized when the feedstock contains high levels of sulfur and the desired desulfurized product contains a very low concentration of sulfur. Preferred product sulfur levels are less than 100 wppm, more preferably less than 50 wppm, and even more preferably less than 30 wppm.
[0013] The hydrocarbonaceous oil containing sulfur compounds is introduced into a catalytic hydrodesulfurization zone containing hydrodesulfurization catalyst and maintained at hydrodesulfurization conditions. The catalytic hydrodesulfurization zone may contain a fixed, ebullated or fluidized catalyst bed. This reaction zone is preferably maintained under an imposed pressure from 101 kPa (14.7 psig) to 13.9 MPa (2000 psig) and more preferably under a pressure from 800 kPa (100 psig) to 12.5 MPa (1800 psig). Suitably, the hydrodesulfurization reaction is conducted with a maximum catalyst bed temperature in the range from 204°C (400°F) to 400°C (750°F) selected to perform the desired hydrodesulfurization conversion to reduce the concentration of the sulfur compounds to the desired level. In accordance with the present invention, it is contemplated that the desired hydrodesulfurization conversion includes, for example, desulfurization, denitrification and olefin saturation. Further preferred operating conditions include liquid hourly space velocities in the range from 0.05 hr.'1 to 20 hr.'i and hydrogen to feed ratios from 200 standard cubic feet per barrel (SCFB) (33.7 nm3/m3) to 50,000 SCFB (8425 nm3/m3), preferably from (33.7 nm3/m3) to 10,000 SCFB (1685 nm3/m3). The hydrodesulfurization zone operating conditions are preferably selected to produce a desulfurized hydrocarborlaceous oil containing from 100 to 1000 wppm sulfur.
[0014] The preferred catalytic composite disposed within the hereinabove-described hydrodesulfurization zone can be characterized as containing a metallic component having hydrodesulfurization activity, which component is combined with a suitable refractory inorganic oxide carrier material of either synthetic or natural origin. The precise composition and method of manufacturing the carrier material is not considered essential to the present invention. Preferred carrier materials are alumina, silica, and mixtures thereof. Suitable metallic components having hydrodesulfurization activity are those selected from the group comprising the metals of Groups V1B and VIII of the Periodic Table, as set forth in the Periodic Table of the Elements, E.H. Sargent and Company, 1964. Thus, the catalytic composites may comprise one or more metallic components from the group of molybdenum, tungsten, chromium, iron, cobalt, nickel, platinum, palladium, iridium, osmium, rhodium, ruthenium, and mixtures thereof. The concentration of the catalytically active metallic component, or components, is primarily dependent upon a particular metal as well as the physical and/or chemical characteristics of the particular hydrocarbon feedstock. For example,.
the metallic components of Group VIB are generally present in an amount within the range of from 1 to 20 weight percent, the iron-group metals in an amount within the range of 0.2 to 10 weight percent, whereas the noble metals of Group VIII are preferably present in an amount within the range of from 0.1 to 5 weight percent, all of which are calculated as if these components existed within the catalytic composite in the elemental state. In addition, any catalyst employed commercially for hydrodesulfurizing middle distillate hydrocarbonaceous compounds to remove nitrogen and sulfur may function effectively in the hydrodesulfurization zone of the present invention. It is further contemplated that hydrodesulfurization catalytic composites may comprise one or more of the following components: cesium, francium, lithium, potassium, rubidium, sodium, copper, gold, silver, cadmium, mercury and zinc.
[0015] The hydrocarbonaceous effluent from the hydrodesulfurization reaction zone is separated to produce a gaseous stream containing hydrogen, hydrogen sulfide and normally gaseous hydrocarbons, and a liquid hydrocarbonaceous stream having a reduced concentration of sulfur compounds. This resulting liquid hydrocarbonaceous stream in one prefewed embodiment of the present invention is contacted with an aqueous oxidizing solution in an oxidation zone to convert sulfur-containing compounds into sulfur-oxidated compounds. Any suitable known aqueous oxidizing solution may be used to perform the sulfur oxidation. In a preferred embodiment, the aqueous oxidizing solution contains acetic acid and hydrogen peroxide. Preferably the molar feed ratio of hydrogen peroxide to sulfur ranges from 1 to 10 or more and the molar ratio of acetic acid to hydrogen peroxide ranges from 0.1 to 10 or more.
The oxidation conditions including contact time are selected to give the desired results as described herein and the pressure is preferably great enough to maintain the aqueous solution in a liquid phase during the contacting of the hydrocarbonaceous oil. Preferred oxidation conditions include a pressure from atmospheric to 800 kPa (100 psig), and a temperature from 38°C (100°F) to 149°C (300°F). Since the aqueous oxidizing solution and the hydrocarbonaceous oil are immiscible, the oxidation zone must have the ability to intimately mix and contact the two phases to ensure the completion of the chemical oxidation. Any suitable means may be used for the contacting and preferred methods include the use of a packed mixing column with countercurrent flows of the two phases or in-line mixing apparatus.
(0016] In the event that there is residual hydrogen peroxide after the completion of the oxidation, it is preferred that the stream containing the residual hydrogen peroxide is contacted with a suitable catalyst to decompose the hydrogen peroxide. A preferred hydrogen peroxide decomposition catalyst is a supported transition metal, a transition metal complex or a transition metal oxide. The decomposition of the hydrogen peroxide is conducted to simplify the recovery and separation of the reaction products including sulfur-oxidated compounds recovered from the oxidation zone. Preferred decomposition operating conditions include a pressure from atmospheric to 800 kPa (100 psig) and a temperature from 38°C (100°F) to 149°C (300°F).
[0017] The resulting effluent from the oxidation zone after decomposition of the oxidizing agent contains desulfurized hydrocarbonaceous oil, sulfur-oxidated compounds such as sulfoxides and sulfones, for example, water and acetic acid. This resulting effluent from the oxidation zone is contacted with a selective adsorbent having a greater selectivity for the sulfur-oxidated compounds than for the sulfur-free hydrocarbonaceous oil to produce a selective adsorbent containing at least a portion of the sulfur-oxidated compounds and a hydrocarbonaceous oil having a reduced concentration of sulfur. Any suitable known selective adsorbent may be used to selectively extract the sulfur-oxidated compounds. In a preferred embodiment of the present invention, the selective adsorbent is selected from the group consisting of aluminosilicates such as X and Y type zeolites, zeolite beta, and L-zeolite, highly silaceous zeolites such as ZSM-5 and silicalite, and silica aluminophosphates such as SAPO-34. The preferred selective adsorbents are contacted with the effluent from the oxidation zone in an adsorption zone. In a preferred mode, the sulfur-oxidated compounds are adsorbed with thermally stable aluminosilicates such as Y-type zeolite, dealuminated Y type zeolite, zeolite beta, and zeolite L. The raffinate hydrocarbonaceous oil recovered from the adsorption zone preferably contains less than 100 weight ppm, more preferably less than 50 weight ppm sulfur and even more preferably less than 30 wppm.
[0018] The resulting adsorbent is regenerated to recover the adsorbed sulfur-oxidated compounds and the regenerated adsorbent is preferably recycled to the adsorption zone. The regeneration of the adsorbent may be accomplished by desorbing the adsorbed sulfur-oxidated compounds by heating and/or by contacting with a liquid or vapor desorbent.
(0019] In one embodiment, operation of the invention is achieved as a fixed bed adsorber by introducing reacted mixture from the sulfur oxidation zone to an adsorption zone until a selected portion of the adsorptive capacity of the selective adsorbent is exhausted. By suitable valuing means the flow of reacted mixture from the sulfur oxidation zone is then halted and the exhausted adsorption zone is regenerated in a desorption zone by desorbing the sulfur-oxidated compounds from the adsorbent with desorbent material. In this manner, a single fixed bed may be so employed in the desulfurization process of the instant invention.
(0020] In another embodiment, operation of the invention is achieved as a fixed bed adsorber by introducing reacted mixture from the sulfur oxidation zone to a first adsorption zone until a selected portion of the adsorptive capacity of the selective adsorbent is exhausted.
By suitable valuing means the flow of reacted mixture from the sulfur oxidation zone is then redirected to a second adsorption zone containing selective adsorbent which has been previously regenerated and the exhausted adsorption zone is regenerated in a desorption zone by desorbed the sulfur-oxidated compounds from the adsorbent with desorbent material. In this manner, any desired number of fixed beds may be so arranged in the desulfitrization of the instant invention.
_7_ [0021] In another embodiment, operation of the invention is achieved as a fluidized or ebullated bed adsorber by introducing reacted mixture from the sulfur oxidation zone to an fluidized adsorption zone until a selected portion of the adsorptive capacity of the selective adsorbent is exhausted. By suitable means at least a portion of the exhausted adsorbent from the adsorption zone is then redirected to a desorption zone and the exhausted adsorbent is regenerated desorbing the sulfur-oxidated compounds from the adsorbent with desorbent material.
[0022] In yet another embodiment, operation of the invention is achieved as simulated countercurrent adsorber by introducing reacted mixture from the sulfur oxidation zone to a moving bed adsorption zone until a selected portion of the adsorptive capacity of the selective adsorbent is exhausted. By suitable means at least a portion of the exhausted adsorbent from the adsorption zone is then redirected to a desorption zone and the exhausted adsorbent is regenerated desorbing the sulfur-oxidated compounds from the adsorbent with desorbent material.
[0023] With reference now to the drawing that illustrates a two-bed fixed adsorber operation, with one bed in the adsorption mode and one bed in the desorption mode, a hydrocarbonaceous oil containing sulfur is introduced into the process via line 1 and enters hydrodesulfurization zone 3. A fresh hydrogen stream is introduced via line 2 and is admixed with a hydrogen-rich gaseous recycle stream provided via line 7 and the resulting admixture is introduced into hydrodesulfurization zone 3 via line 2. A gaseous stream containing hydrogen, hydrogen sulfide and normally gaseous hydrocarbons is removed from hydrodesulfurization zone 3 via line 5 and at least a portion is recycled via line 7 as described hereinabove and at least another portion is removed from the process via line 6. A
hydrocarbonaceous stream having a reduced concentration of sulfur is removed from hydrodesulfurization zone 3 via line 4 and introduced into sulfur oxidation zone 8 via line 12 along with a carboxylic acid stream provided via lines 9, 11 and 12, and an aqueous hydrogen peroxide stream which is introduced into the process via lines 10, 11 and 12. The aqueous stream and the hydrocarbonaceous stream are intimately admixed in sulfur oxidation zone 8 in order to oxidize the sulfur compounds. A resulting reacted mixture is removed from sulfur oxidation zone 8 via line 13 after decomposing any residual hydrogen peroxide and is transported via line 14, valve 15, lines 16 and 17 and is introduced into adsorption zone 18 and is contacted with previously _g_ regenerated selective adsorbent. A resulting hydrocarbonaceous stream containing a reduced concentration of sulfur is removed from adsorption zone 18 via line 19, line 20, valve 21, line 22 and line 23 and recovered. Desorbent stream 25, optionally comprising fresh desorbent stream 24 and/or recycled desorbent carried via line 37 is introduced via line 25, line 26, valve 27, line 28, and line 29 into a previously exhausted adsorption zone comprising desorption zone 30. A desorption stream rich in oxidized sulfur compounds is removed from desorption zone 30 via line 31, line 32, valve 33, line 34, and line 49 and is introduced into distillation zone 35. A desorbent stream having a reduced concentration of sulfur-oxidated compounds is removed from distillation zone 35 via line 37 and is optionally recycled to desorption zone 30 as hereinabove described. Oxidized sulfur compounds are removed from distillation zone 35 via line 36 and recovered. When adsorption zone 18 becomes spent, the stream carried via line 13 is transported via line 38, valve 39, line 40, and line 31 and is introduced into previously regenerated desorption zone 30. The now adsorption zone 30 produces an effluent stream having a reduced concentration of sulfur compounds which stream is transported via line 29, line 41, valve 42, line 43, and line 23 and recovered. The spent adsorption zone 18 is regenerated by the introduction of a desorption stream carried via line 25, line 44, valve 45, line 46, and line 19 into spent adsorption zone 18. A resulting effluent is recovered via line 17, line 16, valve 47, line 48, and line 49 and introduced into distillation zone 35.
(0024] Selective adsorbents useful in the present invention are identified by the following illustrative calculations. These calculations are, however, not presented to unduly limit the selective adsorbents useful in this invention, but to illustrate the molecular properties of the sulfur-containing and sulfur-oxidated compounds that play a role in the adsorption and removal from hydrocarbonaceous oil in the hereinabove described embodiment. The following results were not obtained by the actual measurement of the properties of the compounds but are considered prospective and reasonably illustrative of the expected performance of the invention based upon sound quantum chemistry calculations.
ILLUSTRATIVE CALCULATIONS
[0025] The chemical structures and selected molecular properties of methyl thiophene, methyl thiophene sulfone, methyl thiophene sulfoxide, benzothiophene, benzothiophene sulfone, and benzothiophene sulfoxide were calculated by the use of semi-empirical molecular -g_ orbital theory using the PM3 Hamiltonian as described by J.J.P. Stewart, "Optimization of Parameters for Semi-Empirical Methods 1 -Method", Journal of Computational Chemistry, Volume 10, 1989, pages 209-220, and are presented in Table 1.
Table 1 Sulfur Atom Limiting Compound Dipole Moment,Partial ChargeDimension, (debye) (electrostatic(angstroms) units) 2-methyl thiophene 0.950 0.303 4.588 2-methyl thiophene 4.718 1.063 4.636 sulfone 2-methyl thiophene 5.669 2.285 4.654 sulfoxide Benzothiophene 1.089 0.261 5.010 Benzothiophene sulfone4.546 1.063 5.006 Benzothiophene sulfoxide5.573 2.285 5.002 (0026] A first property affecting selective adsorption of the sulfur-oxidated molecules compared to the molecules comprising is dipole moment. Dipole moment increases upon oxidation of the sulfur-containing molecules and reflects an increase in polarity of the sulfur-oxidated molecules compared to hydrocarbonaceous oil molecules and un-oxidized sulfur-containing molecules. Such an increase in dipole moment increases the adsorption selectivity for the sulfur-oxidated molecules compared to un-oxidized sulfur-containing molecules and molecules comprising hydrocarbonaceous oil, when using such adsorbents as silica, alumina, silicates, aluminosilicates and aluminophosphates in the instant invention.
(0027 A second property affecting selective adsorption of the sulfur-oxidated molecules compared to the molecules comprising is the atomic partial charge on the sulfur atom. Positive partial charge on sulfur increases upon oxidation of the sulfur-containing molecules and reflects an increase in electrostatic attraction for the sulfur-oxidated molecules to adsorbent atoms bearing negative partial charge compared to hydrocarbonaceous oil molecules and un-oxidized sulfur-containing molecules. Such an increase in electrostatic attraction increases the adsorption selectivity for the sulfur-oxidated molecules compared to un-oxidized sulfur-containing molecules and molecules comprising hydrocarbonaceous oil, when using such adsorbents such as silica, alumina, silicates, aluminosilicates and aluminophosphates in the instant invention.
[0028] A third property that affects selective adsorption of the sulfur-oxidated molecules in preference of the un-oxidized sulfur-containing molecules is molecular size.
The crystalline structure of certain selective adsorbents such as crystalline silicates, aluminosilicates, and aluminophosphates may manifest channels and pores that are of molecular dimensions. In the present invention, if the sulfur-oxidated molecules are small enough to gain access to such channels and pores, they may be selectively adsorbed compared to larger molecules in the hydrocarbonaceous oil. The calculated limiting dimensions for the sulfur-oxidated molecules indicate that such molecules can gain access to the pore structures and be selectively adsorbed by such adsorbents as X and Y-type zeolites, dealuminated Y zeolite, L-zeolite, beta zeolite, SAPO-34, and the like. In addition, because many such microporous adsorbents display a selectivity for more polar molecules compared to less polar molecules, enhancement of dipole moment and sulfur positive partial charge via sulfur oxidation while not increasing the limiting molecular dimension makes these adsorbents particularly advantageous for use in the instant invention.
ILLUSTRATIVE EMBODIMENT
[0029] A stream of straight run vacuum gas oil boiling in the range of 315°C (600°F) to 482°C (900°F) and containing 2 weight percent sulfur is introduced into a hydrodesulfurization zone containing a hydrodesulfurization catalyst which contains alumina, nickel, molybdenum and phosphorus. The hydrodesulfurization zone is operated at a pressure of 11.8 MPa (1700 psig), a hydrogen to feed ratio of 843 nm3/m3 (5000 SCFB) and a maximum catalyst temperature of 393°C (740°F) to reduce the residual sulfur in the resulting desulfurized vacuum gas oil to 500 weight ppm (0.05 weight percent). The desulfurized vacuum gas oil is then introduced into an oxidation reaction zone and contacted with acetic acid and hydrogen peroxide in water. The molar feed ratio of hydrogen peroxide to sulfur is 5 and the molar ratio of acetic acid to hydrogen peroxide is 5, and the contacting is conducted at a temperature of 65°C (150°F) and a pressure of 207 kPa (30 psig). The effluent from the oxidation reaction zone is passed over a catalyst containing a mixed oxide of iron and molybdenum to decompose the unreacted hydrogen peroxide and then introduced into an adsorber wherein the sulfur-oxide compounds are extracted with Y zeolite as a selective adsorbent to produce a finished product containing less than 30 weight ppm sulfur. A spent selective adsorbent is regenerated to remove sulfur-oxide compounds and the subsequently regenerated adsorbent is returned to adsorbent service.
(0030 The foregoing description, drawing and illustrative embodiment clearly illustrate the advantages encompassed by the process of the present invention and the benefits to be afforded with the use thereof.
Claims (12)
1. A process for the desulfurization of a hydrocarbonaceous oil which process comprises:
(a) contacting the hydrocarbonaceous oil (1) with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone (3) at hydrodesulfurization conditions to produce hydrogen sulfide and a resulting first hydrocarbonaceous oil stream having a reduced concentration of sulfur (4);
(b) contacting the first hydrocarbonaceous oil stream having a reduced concentration of sulfur with an aqueous oxidizing solution (10) in an oxidation zone (8) to produce a second hydrocarbonaceous oil stream comprising sulfur-oxidated compounds (13);
(c) contacting the second hydrocarbonaceous stream comprising sulfur-oxidated compounds from step (b) with a selective adsorbent (18, 30) having a greater selectivity for the sulfur-oxidated compounds than for sulfur-free hydrocarbonaceous oil to produce an adsorbent (18, 30) containing at least a portion of the sulfur-oxidated compounds and a third hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds (23);
(d) separating the adsorbent (18, 30) containing at least a portion of the sulfur-oxidated compounds produced in step (c) to provide an adsorbent (18, 30) rich in sulfur-oxidated compounds; and (e) recovering the third hydrocarbonaceous oil stream (23).
(a) contacting the hydrocarbonaceous oil (1) with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone (3) at hydrodesulfurization conditions to produce hydrogen sulfide and a resulting first hydrocarbonaceous oil stream having a reduced concentration of sulfur (4);
(b) contacting the first hydrocarbonaceous oil stream having a reduced concentration of sulfur with an aqueous oxidizing solution (10) in an oxidation zone (8) to produce a second hydrocarbonaceous oil stream comprising sulfur-oxidated compounds (13);
(c) contacting the second hydrocarbonaceous stream comprising sulfur-oxidated compounds from step (b) with a selective adsorbent (18, 30) having a greater selectivity for the sulfur-oxidated compounds than for sulfur-free hydrocarbonaceous oil to produce an adsorbent (18, 30) containing at least a portion of the sulfur-oxidated compounds and a third hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds (23);
(d) separating the adsorbent (18, 30) containing at least a portion of the sulfur-oxidated compounds produced in step (c) to provide an adsorbent (18, 30) rich in sulfur-oxidated compounds; and (e) recovering the third hydrocarbonaceous oil stream (23).
2. The process of claim 1 wherein the hydrocarbonaceous oil (1) boils in the range from 149°C (300°F) to 538°C (1000°F).
3. The process of claim 1 wherein the hydrodesulfurization reaction zone (3) is operated at conditions which include a pressure from 800 kPa (100 psig) to 12.5 MPa (1800 psig), a maximum catalyst temperature from 204°C (400°F) to 400°C
(750°F) and a hydrogen to feed ratio from 33.7 nm3/m3 (200 SCFB) to 1685 nm3/m3 (10,000 SCFB).
(750°F) and a hydrogen to feed ratio from 33.7 nm3/m3 (200 SCFB) to 1685 nm3/m3 (10,000 SCFB).
4. The process of claim 1 wherein the hydrodesulfurization catalyst (3) comprises a Group VIB metal component, a Group VIII metal component and alumina.
5. The process of claim 1 wherein the hydrocarbonaceous oil stream having a reduced concentration of sulfur (4) and produced in step (a) has a sulfur level from 100 ppm to 1000 ppm.
6. The process of claim 1 wherein the oxidation zone (8) contains an oxidation catalyst.
7. The process of claim 1 wherein at least a portion of any residual oxidizing solution from the step (b) is decomposed.
8. The process of claim 1 wherein the aqueous oxidizing solution (10) comprises hydrogen peroxide and a carboxylic acid.
9. The process of claim 12 wherein the oxidation zone (8) is operated at conditions including a molar feed ratio of hydrogen peroxide to sulfur ranging from 1 to
10 and a molar ratio of carboxylic acid to hydrogen peroxide from 0.1 to 10.
10. The process of claim 1 wherein the oxidation zone (8) is operated at conditions including a pressure from atmospheric to 800 kPa (100 psig) and a temperature from 38°C
(100°F) to 149°C (300°F).
10. The process of claim 1 wherein the oxidation zone (8) is operated at conditions including a pressure from atmospheric to 800 kPa (100 psig) and a temperature from 38°C
(100°F) to 149°C (300°F).
11. The process of claim 1 wherein the selective adsorbent (18, 30) is selected from the group consisting of silica, alumina, silicalite, ZSM-5, zeolite L, X and Y-type zeolites, dealuminated Y-type zeolite, zeolite beta, zeolite omega, and SAPO-34.
12. The process of claim 1 wherein the contacting in step (c) is selected from the group of consisting of fixed bed, ebullated bed, fluidized bed, or counter current solid-liquid contacting.
1. A process for the desulfurization of a hydracarbonaceous oil which process comprises:
a) contacting the hydrocarbonaceous oil (1) boiling in the range from about 149°C to about 538°C with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone (3) at hydrodesulfurization conditions which include a pressure from about 800 kPa to about 12.5 MPa, a maximum temperature from about 204°C to about 400°C and a hydrogen to feed ratio from about 33.7 nm3/m3 to about 1685 nm3/m3 to produce hydrogen sulfide and a resulting first hydrocarbonaceous oil stream having a reduced concentration of sulfur;
b) contacting the first hydrocarbonaceous oil stream having a reduced concentration of sulfur with an aqueous oxidizing solution (10) comprising acetic acid and hydrogen peroxide in an oxidation zone (8) to produce a second hydrocarbonaceous oil stream comprising sulfur-oxidated compounds;
c) decomposing at least a portion of any residual oxidizing solution from the sulfur oxidation effluent;
d) contacting an effluent stream from step (c) comprising sulfur-oxidated compounds with a selective adsorbent (18,30) selected from the group consisting of silica, alumina, silicalite, ZSM-5, zeolite L, X and Y-type zeolites, dealuminated Y-type zeolite, zeolite beta, zeolite omega and SAPO-34, and having a greater selectivity for the sulfur oxidated compounds than for sulfur-free hydrocarbonaceous oil to produce an adsorbent (18,30) containing at least a portion of the sulfur-oxidated compounds and a third hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds (23);
e) separating the adsorbent (18,30) containing at least a portion of the sulfur-oxidated compounds produced in step (d) to provide an adsorbent (18,30) rich in sulfur-oxidated compounds;
f) regenerating at least a portion o~the adsorbent (18,30) from step (e) and recycling to step (d) to provide at least a portion of the selective adsorbent, and;
g) recovering the third hydrocarbonaceous ail stream (23).
1. A process for the desulfurization of a hydracarbonaceous oil which process comprises:
a) contacting the hydrocarbonaceous oil (1) boiling in the range from about 149°C to about 538°C with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone (3) at hydrodesulfurization conditions which include a pressure from about 800 kPa to about 12.5 MPa, a maximum temperature from about 204°C to about 400°C and a hydrogen to feed ratio from about 33.7 nm3/m3 to about 1685 nm3/m3 to produce hydrogen sulfide and a resulting first hydrocarbonaceous oil stream having a reduced concentration of sulfur;
b) contacting the first hydrocarbonaceous oil stream having a reduced concentration of sulfur with an aqueous oxidizing solution (10) comprising acetic acid and hydrogen peroxide in an oxidation zone (8) to produce a second hydrocarbonaceous oil stream comprising sulfur-oxidated compounds;
c) decomposing at least a portion of any residual oxidizing solution from the sulfur oxidation effluent;
d) contacting an effluent stream from step (c) comprising sulfur-oxidated compounds with a selective adsorbent (18,30) selected from the group consisting of silica, alumina, silicalite, ZSM-5, zeolite L, X and Y-type zeolites, dealuminated Y-type zeolite, zeolite beta, zeolite omega and SAPO-34, and having a greater selectivity for the sulfur oxidated compounds than for sulfur-free hydrocarbonaceous oil to produce an adsorbent (18,30) containing at least a portion of the sulfur-oxidated compounds and a third hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds (23);
e) separating the adsorbent (18,30) containing at least a portion of the sulfur-oxidated compounds produced in step (d) to provide an adsorbent (18,30) rich in sulfur-oxidated compounds;
f) regenerating at least a portion o~the adsorbent (18,30) from step (e) and recycling to step (d) to provide at least a portion of the selective adsorbent, and;
g) recovering the third hydrocarbonaceous ail stream (23).
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/644,121 | 2003-08-20 | ||
US10/644,121 US20050040078A1 (en) | 2003-08-20 | 2003-08-20 | Process for the desulfurization of hydrocarbonacecus oil |
PCT/US2004/027045 WO2005019386A1 (en) | 2003-08-20 | 2004-08-18 | A process for the desulfurization of hydrocarbonaceous oil |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2535349A1 true CA2535349A1 (en) | 2005-03-03 |
Family
ID=34194009
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002535349A Abandoned CA2535349A1 (en) | 2003-08-20 | 2004-08-18 | A process for the desulfurization of hydrocarbonaceous oil |
Country Status (5)
Country | Link |
---|---|
US (1) | US20050040078A1 (en) |
CN (1) | CN100432190C (en) |
CA (1) | CA2535349A1 (en) |
RU (1) | RU2335528C2 (en) |
WO (1) | WO2005019386A1 (en) |
Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004031969A1 (en) * | 2004-07-01 | 2006-02-16 | Wacker Polymer Systems Gmbh & Co. Kg | Soft-modified polyvinyl acetal resins |
CA2531262A1 (en) * | 2005-12-21 | 2007-06-21 | Imperial Oil Resources Limited | Very low sulfur heavy crude oil and process for the production thereof |
US9315733B2 (en) * | 2006-10-20 | 2016-04-19 | Saudi Arabian Oil Company | Asphalt production from solvent deasphalting bottoms |
US7842181B2 (en) * | 2006-12-06 | 2010-11-30 | Saudi Arabian Oil Company | Composition and process for the removal of sulfur from middle distillate fuels |
US20090145808A1 (en) * | 2007-11-30 | 2009-06-11 | Saudi Arabian Oil Company | Catalyst to attain low sulfur diesel |
US8142646B2 (en) | 2007-11-30 | 2012-03-27 | Saudi Arabian Oil Company | Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds |
WO2009099395A1 (en) * | 2008-02-06 | 2009-08-13 | Agency For Science, Technology And Research | Regeneration of solid adsorbent |
EP2250129A2 (en) | 2008-02-21 | 2010-11-17 | Saudi Arabian Oil Company | Catalyst to attain low sulfur gasoline |
US9132421B2 (en) | 2009-11-09 | 2015-09-15 | Shell Oil Company | Composition useful in the hydroprocessing of a hydrocarbon feedstock |
US9296960B2 (en) | 2010-03-15 | 2016-03-29 | Saudi Arabian Oil Company | Targeted desulfurization process and apparatus integrating oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
US20110220550A1 (en) * | 2010-03-15 | 2011-09-15 | Abdennour Bourane | Mild hydrodesulfurization integrating targeted oxidative desulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
US8658027B2 (en) * | 2010-03-29 | 2014-02-25 | Saudi Arabian Oil Company | Integrated hydrotreating and oxidative desulfurization process |
CN102294222A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Hydrocarbon oil desulfurization adsorbent and preparation method and application thereof |
CN102294224A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Hydrocarbon oil desulfurization adsorbent and preparation method and application thereof |
CN102294225A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbent and preparation method and application thereof |
CN102294223A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbent and preparation method and application thereof |
US9005432B2 (en) | 2010-06-29 | 2015-04-14 | Saudi Arabian Oil Company | Removal of sulfur compounds from petroleum stream |
CN102343250A (en) * | 2010-07-29 | 2012-02-08 | 中国石油化工股份有限公司 | Monolene desulphurization adsorbent, preparation method thereof, and application thereof |
WO2012078836A1 (en) * | 2010-12-10 | 2012-06-14 | Shell Oil Company | Hydrocracking of a heavy hydrocarbon feedstock using a copper molybdenum sulfided catalyst |
WO2012082851A1 (en) * | 2010-12-15 | 2012-06-21 | Saudi Arabian Oil Company | Desulfurization of hydrocarbon feed using gaseous oxidant |
US20120160742A1 (en) * | 2010-12-22 | 2012-06-28 | Uop Llc | High Purity Heavy Normal Paraffins Utilizing Integrated Systems |
US8535518B2 (en) | 2011-01-19 | 2013-09-17 | Saudi Arabian Oil Company | Petroleum upgrading and desulfurizing process |
KR101946791B1 (en) * | 2011-03-23 | 2019-02-13 | 아디트야 비를라 사이언스 앤 테크놀로지 컴퍼니 리미티드 | A process for desulphurization of petroleum oil |
WO2013013508A1 (en) | 2011-07-28 | 2013-01-31 | 中国石油化工股份有限公司 | Adsorbent for desulfurization of hydrocarbon oils, preparation method therefor and use thereof |
US8573300B2 (en) * | 2011-09-07 | 2013-11-05 | E I Du Pont De Nemours And Company | Reducing sulfide in oil reservoir production fluids |
US20130056214A1 (en) * | 2011-09-07 | 2013-03-07 | E. I. Du Pont De Nemours And Company | Reducing sulfide in production fluids during oil recovery |
RU2578692C2 (en) | 2011-10-24 | 2016-03-27 | Адитиа Бирла Нуво Лимитед | Improved method for carbon ash production |
US8906227B2 (en) | 2012-02-02 | 2014-12-09 | Suadi Arabian Oil Company | Mild hydrodesulfurization integrating gas phase catalytic oxidation to produce fuels having an ultra-low level of organosulfur compounds |
MX350307B (en) | 2012-03-30 | 2017-09-04 | Aditya Birla Science And Tech Company Ltd | A process for obtaining carbon black powder with reduced sulfur content. |
US8920635B2 (en) | 2013-01-14 | 2014-12-30 | Saudi Arabian Oil Company | Targeted desulfurization process and apparatus integrating gas phase oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
US10384197B2 (en) * | 2016-07-26 | 2019-08-20 | Saudi Arabian Oil Company | Additives for gas phase oxidative desulfurization catalysts |
CN108236965A (en) * | 2016-12-27 | 2018-07-03 | 中国石油天然气股份有限公司 | A kind of Hydrobon catalyst of modification and preparation method thereof |
EP3583190A1 (en) * | 2017-02-20 | 2019-12-25 | Saudi Arabian Oil Company | Desulfurization and sulfone removal using a coker |
US10752847B2 (en) | 2017-03-08 | 2020-08-25 | Saudi Arabian Oil Company | Integrated hydrothermal process to upgrade heavy oil |
US10703999B2 (en) | 2017-03-14 | 2020-07-07 | Saudi Arabian Oil Company | Integrated supercritical water and steam cracking process |
US10526552B1 (en) | 2018-10-12 | 2020-01-07 | Saudi Arabian Oil Company | Upgrading of heavy oil for steam cracking process |
JP2021038932A (en) * | 2019-08-30 | 2021-03-11 | Eneos株式会社 | Method for discriminating lubricating oil and lubricant oil composition |
RU2743291C1 (en) * | 2020-07-24 | 2021-02-16 | Федеральное государственное бюджетное учреждение высшего образования «Тамбовский государственный технический университет» (ФГБОУ ВО «ТГТУ») | Method of adsorptive desulfurization of oil and petroleum products: gasoline, diesel fuel using a composite adsorbent based on minerals of natural origin |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2769760A (en) * | 1953-09-11 | 1956-11-06 | Pure Oil Co | Production of sweet naphthas from hydrocarbon mixtures by hydrofining the hydrocarbon mixture followed by contacting the hydrocarbon product with a composition containing cobalt and molybdenum |
NL135711C (en) * | 1968-05-24 | |||
US4719007A (en) * | 1986-10-30 | 1988-01-12 | Uop Inc. | Process for hydrotreating a hydrocarbonaceous charge stock |
US5064525A (en) * | 1991-02-19 | 1991-11-12 | Uop | Combined hydrogenolysis plus oxidation process for sweetening a sour hydrocarbon fraction |
US5454933A (en) * | 1991-12-16 | 1995-10-03 | Exxon Research And Engineering Company | Deep desulfurization of distillate fuels |
FR2776297B1 (en) * | 1998-03-23 | 2000-05-05 | Inst Francais Du Petrole | PROCESS FOR THE CONVERSION OF OIL HEAVY FRACTIONS COMPRISING A STEP OF HYDROTREATMENT IN A FIXED BED, A STEP OF CONVERSION INTO A BOILING BED AND A STEP OF CATALYTIC CRACKING |
US6171478B1 (en) * | 1998-07-15 | 2001-01-09 | Uop Llc | Process for the desulfurization of a hydrocarbonaceous oil |
US6277271B1 (en) * | 1998-07-15 | 2001-08-21 | Uop Llc | Process for the desulfurization of a hydrocarbonaceoous oil |
GB9925971D0 (en) * | 1999-11-03 | 1999-12-29 | Exxon Chemical Patents Inc | Reduced particulate froming distillate fuels |
US6827845B2 (en) * | 2001-02-08 | 2004-12-07 | Bp Corporation North America Inc. | Preparation of components for refinery blending of transportation fuels |
FR2821350B1 (en) * | 2001-02-26 | 2004-12-10 | Solvay | PROCESS FOR DESULFURIZING A HYDROCARBON MIXTURE |
-
2003
- 2003-08-20 US US10/644,121 patent/US20050040078A1/en not_active Abandoned
-
2004
- 2004-08-18 RU RU2006108543/04A patent/RU2335528C2/en not_active IP Right Cessation
- 2004-08-18 WO PCT/US2004/027045 patent/WO2005019386A1/en active Application Filing
- 2004-08-18 CA CA002535349A patent/CA2535349A1/en not_active Abandoned
- 2004-08-18 CN CNB2004800270611A patent/CN100432190C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
WO2005019386A1 (en) | 2005-03-03 |
CN100432190C (en) | 2008-11-12 |
CN1852966A (en) | 2006-10-25 |
RU2335528C2 (en) | 2008-10-10 |
US20050040078A1 (en) | 2005-02-24 |
RU2006108543A (en) | 2006-08-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2535349A1 (en) | A process for the desulfurization of hydrocarbonaceous oil | |
US6277271B1 (en) | Process for the desulfurization of a hydrocarbonaceoous oil | |
US6171478B1 (en) | Process for the desulfurization of a hydrocarbonaceous oil | |
Babich et al. | Science and technology of novel processes for deep desulfurization of oil refinery streams: a review☆ | |
Hernández‐Maldonado et al. | New sorbents for desulfurization of diesel fuels via π‐complexation | |
US7875185B2 (en) | Removal of residual sulfur compounds from a caustic stream | |
Richardeau et al. | Adsorption and reaction over HFAU zeolites of thiophene in liquid hydrocarbon solutions | |
AU652600B2 (en) | Desulphurisation of hydrocarbon feedstreams with N-halogeno compounds | |
US20060226049A1 (en) | Oxidative desulfurization of hydrocarbon fuels | |
EP0590883B1 (en) | Benzene removal from hydrocarbon streams | |
US20060131217A1 (en) | Process for desulphurizing a hydrocarbon cut in a simulated moving bed | |
CA2374660C (en) | Adsorption process for producing ultra low sulfur hydrocarbon streams | |
US7186328B1 (en) | Process for the regeneration of an adsorbent bed containing sulfur oxidated compounds | |
US20040118751A1 (en) | Multicomponent sorption bed for the desulfurization of hydrocarbons | |
EP1958691A1 (en) | A process for the regeneration of an absorbent bed containing sulfur oxidated compounds | |
US20020043482A1 (en) | Process for desulfurization of petroleum distillates | |
US7452459B2 (en) | Process for the removal of sulfur-oxidated compounds from a hydrocarbonaceous stream | |
US10443001B2 (en) | Removal of sulfur from naphtha | |
US20040192986A1 (en) | Removal of sulfur compounds | |
GB2242910A (en) | Process for the isomerization of a hydrocarbon feed |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Dead |