WO2014011967A1 - Improved process for reducing ultra low sulfur diesel color - Google Patents
Improved process for reducing ultra low sulfur diesel color Download PDFInfo
- Publication number
- WO2014011967A1 WO2014011967A1 PCT/US2013/050227 US2013050227W WO2014011967A1 WO 2014011967 A1 WO2014011967 A1 WO 2014011967A1 US 2013050227 W US2013050227 W US 2013050227W WO 2014011967 A1 WO2014011967 A1 WO 2014011967A1
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- WIPO (PCT)
- Prior art keywords
- fraction
- hydrodesulfurization catalyst
- bottoms fraction
- ultra low
- hydrodesulfurization
- Prior art date
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011593 sulfur Substances 0.000 title claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000003208 petroleum Substances 0.000 claims abstract description 11
- 239000010779 crude oil Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000003350 kerosene Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical group [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 238000007701 flash-distillation Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000003209 petroleum derivative Substances 0.000 description 4
- 238000007655 standard test method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/22—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen dissolved or suspended in the oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Definitions
- This invention relates to processing Ultra Low Sulfur Diesel (ULSD).
- ULSD Ultra Low Sulfur Diesel
- the invention relates to hydrodesulfurizing ULSD and reducing the color of the ULSD.
- Ultra Low Sulfur Diesel must satisfy regulatory and industry standards. Some of those standards relate to impurities such as sulfur. Others relate to physical properties such as flash point. Yet, other standards relate to manufacturing controls.
- hydrocarbon fractions such as diesel fuel produced in the petroleum industry are typically contaminated with various sulfur-based impurities.
- the presence of sulfur compounds is undesirable since they result in a serious pollution problem.
- Combustion of hydrocarbons containing these impurities results in the release of sulfur oxides which are noxious and corrosive.
- ASTM International formerly known as the American Society for Testing and Materials (ASTM) has established test methods for measuring impurties such as sulfur and physical properties such as flash point.
- ASTM International sets forth a Standard Specification for Diesel Fuel Oils in ASTM D975-08. Notably, the Specification covers seven grades of diesel fuel oils for various types of diesel engines.
- ASTM D975 sets forth alternate test methods (i) ASTM D2622 "Standard Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-ray Fluorescense Spectrometry" for measuring sulfur in the range of 0.0003 to 5.3 mass %, (ii) ASTM D3120 "Standard Test Method for Trace Quantities of Sulfur in Light Liquid Petroleum Hydrocarbons by Oxidate Microcoulometry" for measuring sulfur in the range of 3.0 to 100 mg/kg (wt ppm), and (iii) ASTM D5453 "Test Method for Determination of Total Sulfur in Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by Ultraviolet Fluorescence" for measuring sulfur in the range of 0.000
- the present invention is a process for preparing ultra low sulfur diesel.
- the steps include reacting a feedstock of petroleum crude oil with hydrogen in the presence of a hydrodesulfurization catalyst under hydrodesulfurization conditions, fractionating the reaction products, flash distilling the bottoms fraction, condensing the volatile distillate fraction as ultra low sulfur diesel, and recycling the distillation bottoms fraction for further reacting with hydrogen.
- the present invention provides an improved process for preparing ultra low sulfur diesel, wherein the hydrodesulfurization catalyst is more fully utilized while retaining suitable color.
- FIG. 1 is a block flow diagram of a process according to the present invention.
- the present invention is a process for preparing ultra low sulfur diesel which is diesel having a sulfur content of less than 15 parts per million.
- the process steps include (a) reacting a feedstock of petroleum crude oil with hydrogen in the presence of a hydrodesulfurization catalyst under hydro desulfurization conditions, (b) fractionating the reaction products into a naphtha fraction, a kerosene fraction, and a first bottoms fraction, (c) flash distilling the first bottoms fraction in a distillation column having at least one stage and a total stage efficiency of less than about 99%, thereby yielding a volatile distillate fraction and a second bottoms fraction, (d) condensing the volatile distillate fraction as ultra low sulfur diesel, and (e) recycling the second bottoms fraction into the feedstock of petroleum crude oil for further reacting of the second bottoms fraction with hydrogen in the presence of the hydrodesulfurization catalyst.
- the volatile distillate fraction should have an ASTM Color of less than or equal to 2.5 and a sulfur content less than 15 ppm. More
- the hydrodesulfurization catalyst can include, but is not limited to, at least a first metal component selected from Groups 8-10 (IUPAC) metals such as iron, cobalt, and/or nickel, and at least a second metal component selected from Group 6 (IUPAC) metals such as molybdenum and/or tungsten, on a high surface area support material such as alumina.
- IUPAC Group 8-10
- IUPAC Group 6
- Other suitable desulfurization catalysts include zeolitic catalyts as well as nobel metal catalyts where the noble metal is palladium or platinum. More than one type of hydrodesulfurization catalyst can be used in the same reaction vessel or zone to remove sulfur.
- the hydrodesulfurization catalyst is a nickel molybdenum catalyst.
- the hydrodesulfurization conditions are the following operation conditions:
- the flow of a process according to the present invention includes providing a feedstock of petroleum crude oil via a line 10 into a main reactor 20 wherein hydrogen and a hydrodesulfurization catalyst are provided.
- the main reactor 20 may be a hydrotreater or other reactor as known in the art. Under hydrodesulfurization conditions, the sulfur-containing components of the feedstock and the hydrogen react.
- the reaction products flow through line 25 into the product fractionator 30, wherein products are fractionated into a naptha fraction 40 , a kerosene fraction 50, and a first bottoms fraction 60.
- the naptha fraction 40 is collected via line 45.
- the kerosene fraction is collected via line 55.
- line 45 and line 55 may be a single line.
- the first bottoms fraction 60 flows through line 65 into a flash distillation column or flash tank 70 to separate the volatile distillate fraction 80 from a second bottoms fraction 90 containing heavy diesel, sulfur, colorants, and other impurities.
- the volatile distillate fraction 80 may contain at least about 80% of the first bottoms stream's diesel having an ASTM Color of less than or equal to 2.5 and a sulfur content of less than 15 ppm.
- the corresponding second bottoms fraction 90 may contain up to about 20% of the first bottoms stream's heavy diesel.
- the distillation column for the flash distilling step will have a stage efficiency in the range of about 80% to about 99%. More preferably, the distillation column for the flash distilling step will have a stage efficiency of about 95%.
- the post- treatment methods were either (a) flash distilling the sample with a single- stage flash distillation column to 99% efficiency (i.e., 99% volatile distillate fraction and 1 % bottoms fraction) or (b) reacting the sample with hydrogen in the presence of a hydrodesulfurization catalyst under hydro desulfurization conditions in a pilot plant hydrotreater.
- the flash distillation method demonstrated that the volatile distillate fraction satisfies the ASTM Color requirement, and the additional hydrotreatment method showed conversion of the sample into ULSD that satisfies the ASTM Color specification.
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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)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention is a process for preparing ultra low sulfur diesel. The steps include reacting a feedstock of petroleum crude oil with hydrogen in the presence of a hydrodesulfurization catalyst under hydrodesulfurization conditions, fractionating the reaction products, flash distilling the bottoms fraction, condensing the volatile distillate fraction as ultra low sulfur diesel, and recycling the distillation bottoms fraction for further reacting with hydrogen.
Description
IMPROVED PROCESS FOR
REDUCING ULTRA LOW SULFUR DIESEL COLOR
CROSS-REFERNCE TO RELATED APPLICATIONS
[0001 ] This application claims benefit and priority of United States Provisional Patent Application No. 61/671,484 filed on July 13, 2012, which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to processing Ultra Low Sulfur Diesel (ULSD). In particular, the invention relates to hydrodesulfurizing ULSD and reducing the color of the ULSD.
DESCRIPTION OF RELATED ART
[0003] Ultra Low Sulfur Diesel must satisfy regulatory and industry standards. Some of those standards relate to impurities such as sulfur. Others relate to physical properties such as flash point. Yet, other standards relate to manufacturing controls.
[0004] With regard to sulfur impurities, hydrocarbon fractions such as diesel fuel produced in the petroleum industry are typically contaminated with various sulfur-based impurities. The presence of sulfur compounds is undesirable since they result in a serious pollution problem. Combustion of hydrocarbons containing these impurities results in the release of sulfur oxides which are noxious and corrosive.
[0005] Federal legislation, specifically the Clean Air Act of 1970 and its 1990 Amendments (42 U.S.C. § 7401 et seq. (2008)), has imposed increasingly more stringent requirements to reduce the amount of sulfur released to the atmosphere. Under its rule-making authority, the United States Environmental Protection Agency has lowered the sulfur standard for diesel fuel to 15 parts per million by weight (ppm or μ^).
[0006] ASTM International, formerly known as the American Society for Testing and Materials (ASTM), has established test methods for measuring impurties such as sulfur and physical properties such as flash point. ASTM International sets forth a Standard Specification
for Diesel Fuel Oils in ASTM D975-08. Notably, the Specification covers seven grades of diesel fuel oils for various types of diesel engines.
[0007] With regard to Grade No. 1 -D S15 and Grade No. 2-D S15 (both special-purpose, light middle distillate fuel for use in diesel engine applications requiring a fuel with 15 ppm sulfur (maximum)), ASTM D975 sets forth alternate test methods (i) ASTM D2622 "Standard Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-ray Fluorescense Spectrometry" for measuring sulfur in the range of 0.0003 to 5.3 mass %, (ii) ASTM D3120 "Standard Test Method for Trace Quantities of Sulfur in Light Liquid Petroleum Hydrocarbons by Oxidate Microcoulometry" for measuring sulfur in the range of 3.0 to 100 mg/kg (wt ppm), and (iii) ASTM D5453 "Test Method for Determination of Total Sulfur in Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by Ultraviolet Fluorescence" for measuring sulfur in the range of 0.0001 to 0.8 mass % or 1.0 to 8000 mg/kg (wt ppm).
[0008] Other properties specified under ASTM D975 include flash point, water and sediment, distillation temperature, kinematic viscosity, and others.
[0009] While the Clean Air Act, its related rules, or the ASTM International Standard Specifications do not set forth a color requirement for ULSD, determination of the color of petroleum products has been used for manufacturing control purposes. Furthermore, it is an important quality characteristic because color is readily observed by the user of the product. ASTM D1500 "Standard Test Method for ASTM Color of Petroleum Products (ASTM Color Scale) and ASTM D6045 "Standard Test Method for Color of Petroleum Products by the Automatic Tristimulus Method" are appropriate methods for measuring color of ULSD. A commonly- applied manufacturing control limit is 2.5 ASTM.
[0010] The manufacturing of ULSD presents challenges in satisfying regulatory and industry standards. Notably, the Clean Air Act and its related rules ensure that there is a continual need for more effective desulfurization methods. Moreover, the deterioration in ASTM Color does not correlate perfectly to the most common desulfurization method.
[0011 ] The most common method of desulfurization of fuels is hydrodesulfurization, in which the fuel is catalytically reacted with hydrogen gas at elevated temperature and high pressure in the presence of a costly catalyst. For example, United States Patent No. 5,985, 136 describes a hydrodesulfurization process to reduce sulfur level in naptha feedstreams. Organic sulfur is reduced by this reaction to gaseous ¾S, which is then oxidized to elemental sulfur by the Claus process.
[0012] With this method, it is believed that the catalyst has several months of remaining life for reducing the sulfur level even though the ASTM Color begins to exceed 2.5. It is desirable to replace the catalyst only after it is fully exhausted in the process, not as prematurely required under the current process. There is a need to improve the process so that the ASTM Color does not exceed 2.5 until the catalyst is fully exhausted with regard to hydrodesulfurization.
[0013] To cause the decay in catalytic reduction of the sulfur level to correlate more closely to the deterioration in achieving the desired ASTM Color, the inventor in copending United States Patent Application Serial No. 13/156,487 teaches installation of a high- efficiency, flash tank at the end of the hydrotreating process. The flash tank's efficiency yields an overhead stream that 99+% ULSD and a small bottom stream containing the color bodies.
[0014] It remains desirable to provide a process that does not require a flash tank with a total stage efficiency of greater than 99%.
SUMMARY OF THE INVENTION
[0015] The present invention is a process for preparing ultra low sulfur diesel. The steps include reacting a feedstock of petroleum crude oil with hydrogen in the presence of a hydrodesulfurization catalyst under hydrodesulfurization conditions, fractionating the reaction products, flash distilling the bottoms fraction, condensing the volatile distillate fraction as ultra low sulfur diesel, and recycling the distillation bottoms fraction for further reacting with hydrogen.
[0016] The present invention provides an improved process for preparing ultra low sulfur diesel, wherein the hydrodesulfurization catalyst is more fully utilized while retaining suitable color.
DESCRIPTION OF THE DRAWINGS
[0017] Further details will be apparent from the following detailed description, with reference to the enclosed drawing, in which:
[0018] FIG. 1 is a block flow diagram of a process according to the present invention.
DETAILED DESCRIPTION
[0019] In an embodiment, the present invention is a process for preparing ultra low sulfur diesel which is diesel having a sulfur content of less than 15 parts per million. The process steps
include (a) reacting a feedstock of petroleum crude oil with hydrogen in the presence of a hydrodesulfurization catalyst under hydro desulfurization conditions, (b) fractionating the reaction products into a naphtha fraction, a kerosene fraction, and a first bottoms fraction, (c) flash distilling the first bottoms fraction in a distillation column having at least one stage and a total stage efficiency of less than about 99%, thereby yielding a volatile distillate fraction and a second bottoms fraction, (d) condensing the volatile distillate fraction as ultra low sulfur diesel, and (e) recycling the second bottoms fraction into the feedstock of petroleum crude oil for further reacting of the second bottoms fraction with hydrogen in the presence of the hydrodesulfurization catalyst. The volatile distillate fraction should have an ASTM Color of less than or equal to 2.5 and a sulfur content less than 15 ppm. More preferably, the volatile distillate fraction will have an ASTM Color of less than or equal to 1.5.
[0020] The hydrodesulfurization catalyst can include, but is not limited to, at least a first metal component selected from Groups 8-10 (IUPAC) metals such as iron, cobalt, and/or nickel, and at least a second metal component selected from Group 6 (IUPAC) metals such as molybdenum and/or tungsten, on a high surface area support material such as alumina. Other suitable desulfurization catalysts include zeolitic catalyts as well as nobel metal catalyts where the noble metal is palladium or platinum. More than one type of hydrodesulfurization catalyst can be used in the same reaction vessel or zone to remove sulfur. In a preferred embodiment, the hydrodesulfurization catalyst is a nickel molybdenum catalyst.
[0021 ] In a preferred embodiment, the hydrodesulfurization conditions are the following operation conditions:
Temperature: 200-485 degrees Celsius
Pressure: 8-200 bar
Liquid Hourly Space Velocity: 0.1 - 10 hr"1
[0022] With consideration of FIG. 1, the flow of a process according to the present invention includes providing a feedstock of petroleum crude oil via a line 10 into a main reactor 20 wherein hydrogen and a hydrodesulfurization catalyst are provided. The main reactor 20 may be a hydrotreater or other reactor as known in the art. Under hydrodesulfurization conditions, the sulfur-containing components of the feedstock and the hydrogen react.
[0023] The reaction products flow through line 25 into the product fractionator 30, wherein products are fractionated into a naptha fraction 40 , a kerosene fraction 50, and a first bottoms
fraction 60. The naptha fraction 40 is collected via line 45. The kerosene fraction is collected via line 55. For convenience, line 45 and line 55 may be a single line.
[0024] The first bottoms fraction 60 flows through line 65 into a flash distillation column or flash tank 70 to separate the volatile distillate fraction 80 from a second bottoms fraction 90 containing heavy diesel, sulfur, colorants, and other impurities. Depending upon the stage efficiency of flash distillation column 70, the volatile distillate fraction 80 may contain at least about 80% of the first bottoms stream's diesel having an ASTM Color of less than or equal to 2.5 and a sulfur content of less than 15 ppm. The corresponding second bottoms fraction 90 may contain up to about 20% of the first bottoms stream's heavy diesel.
[0025] Preferably, the the distillation column for the flash distilling step will have a stage efficiency in the range of about 80% to about 99%. More preferably, the distillation column for the flash distilling step will have a stage efficiency of about 95%.
Examples
[0026] The following non-limiting examples illustrate the invention.
[0027] Samples of a first bottoms fraction were collected from a hydrodesulfurizing manufacturing plant. Each sample was evaluated for initial ASTM Color and post-treatment ASTM Color according to ASTM D6045, the contents of which are incorporated herein by reference in its entirety.
[0028] The post- treatment methods were either (a) flash distilling the sample with a single- stage flash distillation column to 99% efficiency (i.e., 99% volatile distillate fraction and 1 % bottoms fraction) or (b) reacting the sample with hydrogen in the presence of a hydrodesulfurization catalyst under hydro desulfurization conditions in a pilot plant hydrotreater. The flash distillation method demonstrated that the volatile distillate fraction satisfies the ASTM Color requirement, and the additional hydrotreatment method showed conversion of the sample into ULSD that satisfies the ASTM Color specification.
Flash Distillation
(Comparative Examples 1 and 2)
(Examples 3 and 4)
[0029] Although the invention has been described in considerable detail by the preceding specification, this detail is for the purpose of illustration and is not to be construed as a limitation upon the following appended claims. All cited ASTM standards, reports, references, U.S. patents, allowed U.S. patent applications, and U.S. Patent Applications Publications are incorporated herein by reference.
Claims
1. A process for preparing ultra low sulfur diesel comprising the steps of:
(a) reacting a feedstock of petroleum crude oil with hydrogen in the presence of a hydrodesulfurization catalyst under hydrodesulfurization conditions;
(b) fractionating the reaction products into a naphtha fraction, a kerosene fraction, and a first bottoms fraction;
(c) flash distilling the first bottoms fraction in a distillation column having at least one stage and a total stage efficiency of less than about 99%, thereby yielding
(i) a volatile distillate fraction having an ASTM Color of less than or equal to 2.5 and a sulfur content less than 15 ppm and
(ii) a second bottoms fraction;
(d) condensing the volatile distillate fraction as ultra low sulfur diesel; and
(e) recycling the second bottoms fraction into the feedstock of petroleum crude oil for further reacting of the second bottoms fraction with hydrogen in the presence of the hydrodesulfurization catalyst.
2. The process of claim 1 wherein the reacting step occurs in a hydrotreater.
3. The process of claim 1 wherein the distillation column for the flash distilling step has a stage efficiency of at least about 80%.
4. The process of claim 3 wherein the distillation column for the flash distilling step has a stage efficiency in the range of about 80% to about 99%.
5. The process of claim 4 wherein the distillation column for the flash distilling step has a stage efficiency of about 95%.
6. The process of claim 1 wherein the hydrodesulfurization catalyst is a zeolite catalyst.
7. The process of claim 1 wherein the hydrodesulfurization catalyst is a nickel molybdenum catalyst.
8 The process of claim 1 wherein the hydrodesulfurization catalyst consists of more than one hydrodesulfurization catalyst.
9. The process of claim 1 wherein the hydrodesulfurization catalyst comprises palladium.
10. The process of claim 1 wherein the hydrodesulfurization catalyst comprises platinum.
1 1. The process of claim 1 wherein the hydrodesulfurization catalyst comprises at least a first metal component selected from Group 8, 9, and 10 (IUPAC) metals and at least a second metal component selected from Group 6 (IUPAC) metals, on a high surface area support material.
12. The process of claim 1 1 wherein the first metal component is selected from the group consisting of iron, cobalt, and nickel.
13. The process of claim 1 1 wherein the second metal component is selected from the group consisting of molybdenum and tungsten.
14. The process of claim 1 1 wherein the high surface area support material is alumina.
15. The process of claim 1 1 wherein the reacting step occurs at a temperature of 200-485 degrees Celsius.
16. The process of claim 1 1 wherein the reacting step occurs at a pressure of 8-200 bar.
17. The process of claim 1 1 wherein the reaction has a liquid hourly space velocity of 0.1-10
18. A process for preparing ultra low sulfur diesel comprising the steps of:
(a) reacting a feedstock of petroleum crude oil with hydrogen in a hydrotreater in the presence of a nickel molybdenum hydrodesulfurization catalyst under hydrodesulfurization conditions of
(i) a temperature of 200-485 degrees Celsius,
(ii) a pressure of 8-200 bar, and
(iii) a liquid hourly space velocity of 0.1 - 10 hr"1 ;
fractionating the reaction products into a naphtha fraction, a kerosene fraction, and a first bottoms fraction;
flash distilling the first bottoms fraction in a distillation column having at least one stage and a total stage efficiency of less than about 99%, thereby yielding
(i) a volatile distillate fraction having an ASTM Color of less than or equal to 2.5 and a sulfur content less than 15 ppm and
(ii) a second bottoms fraction;
condensing the volatile distillate fraction as ultra low sulfur diesel; and recycling the second bottoms fraction into the feedstock of petroleum crude oil for further reacting of the second bottoms fraction with hydrogen in the presence of the nickel molybdenum hydrodesulfurization catalyst.
Applications Claiming Priority (2)
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US201261671484P | 2012-07-13 | 2012-07-13 | |
US61/671,484 | 2012-07-13 |
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WO2014011967A1 true WO2014011967A1 (en) | 2014-01-16 |
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PCT/US2013/050227 WO2014011967A1 (en) | 2012-07-13 | 2013-07-12 | Improved process for reducing ultra low sulfur diesel color |
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US (1) | US20140014556A1 (en) |
AR (1) | AR092026A1 (en) |
WO (1) | WO2014011967A1 (en) |
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JP6302814B2 (en) * | 2014-10-06 | 2018-03-28 | Jxtgエネルギー株式会社 | Method for evaluating hydrocarbon oil subjected to desulfurization reaction, method for desulfurizing hydrocarbon oil, and method for producing desulfurized oil |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6447673B1 (en) * | 2001-03-12 | 2002-09-10 | Fina Technology, Inc. | Hydrofining process |
US7005057B1 (en) * | 2002-09-05 | 2006-02-28 | Uop Llc | Hydrocracking process for the production of ultra low sulfur diesel |
WO2008010799A1 (en) * | 2006-07-19 | 2008-01-24 | Uop Llc | A hydrocarbon desulfurization process |
US20090145808A1 (en) * | 2007-11-30 | 2009-06-11 | Saudi Arabian Oil Company | Catalyst to attain low sulfur diesel |
US20110163010A1 (en) * | 2008-08-14 | 2011-07-07 | Sk Innovation Co., Ltd. | Method and apparatus for recovering hydrogen in a petroleum-based hydrocarbon desulfurization process |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US6379532B1 (en) * | 2000-02-17 | 2002-04-30 | Uop Llc | Hydrocracking process |
US7087153B1 (en) * | 2003-02-04 | 2006-08-08 | Uop Llc | Combination hydrocracking process for the production of ultra low sulfur diesel |
US7622034B1 (en) * | 2006-12-29 | 2009-11-24 | Uop Llc | Hydrocarbon conversion process |
-
2013
- 2013-07-10 AR ARP130102441A patent/AR092026A1/en unknown
- 2013-07-12 WO PCT/US2013/050227 patent/WO2014011967A1/en active Application Filing
- 2013-07-12 US US13/940,729 patent/US20140014556A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6447673B1 (en) * | 2001-03-12 | 2002-09-10 | Fina Technology, Inc. | Hydrofining process |
US7005057B1 (en) * | 2002-09-05 | 2006-02-28 | Uop Llc | Hydrocracking process for the production of ultra low sulfur diesel |
WO2008010799A1 (en) * | 2006-07-19 | 2008-01-24 | Uop Llc | A hydrocarbon desulfurization process |
US20090145808A1 (en) * | 2007-11-30 | 2009-06-11 | Saudi Arabian Oil Company | Catalyst to attain low sulfur diesel |
US20110163010A1 (en) * | 2008-08-14 | 2011-07-07 | Sk Innovation Co., Ltd. | Method and apparatus for recovering hydrogen in a petroleum-based hydrocarbon desulfurization process |
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