WO2000009630A1 - A process for deep hydrodesulfurization using combined hydrotreating-oxidation - Google Patents
A process for deep hydrodesulfurization using combined hydrotreating-oxidation Download PDFInfo
- Publication number
- WO2000009630A1 WO2000009630A1 PCT/US1999/016359 US9916359W WO0009630A1 WO 2000009630 A1 WO2000009630 A1 WO 2000009630A1 US 9916359 W US9916359 W US 9916359W WO 0009630 A1 WO0009630 A1 WO 0009630A1
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- WO
- WIPO (PCT)
- Prior art keywords
- process according
- peroxometal
- group
- mixtures
- sulfurs
- Prior art date
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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
- 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
Definitions
- Easy sulfurs include non-thiophenic sulfur, thiophenes, benzothiophenes, and dibenzothiophenes in which the substituents are away from the sulfur heteroatom.
- Multiring aromatics in the conventional HDS process are mostly reduced to mononuclear aromatics (e.g., tetralins).
- the present invention addresses this pressing need.
- the instant invention is directed to a process for removing hard sulfurs from hydrocarbon streams comprising: selectively oxidizing hard sulfurs in a hydrotreated stream, under oxidizing conditions in the presence of an effective amount of an oxidizing agent, wherein said oxidizing agent is a peroxometal complex and wherein said hard sulfurs are oxidized into the corresponding sulfoxides and sulfones.
- the invention is further directed to a process according to the above wherein the process further comprises adsorbing said oxidation products and recovering a product stream having a reduced concentration of hard sulfurs and oxidation products.
- Hydrotreated stream as used herein means a stream that has had the amount of easy sulfurs contained therein reduced or removed in a conventional HDS process.
- Figure 1 is a GC/MS total ion chromatogram of products from the oxidation of 4-MDBT/xylene with (HMPT)MoO(0 2 ) 2 .
- Figure 2 is the 70-eV electron ionization mass spectrum of 4- MDBT sulfoxide.
- Figure 3 is the 70-eV electron ionization mass spectrum of 4- MDBT sulfone.
- Figure 4 is a Mass chromatograms (top four traces) and GC/MS total ion chromatogram (bottom trace) for products from the oxidation of a middle distillate with (HMPT)MoO(0 2 ) 2 .
- Figure 5 is the 70-eV electron ionization mass spectrum of 4,6- DMDBT sulfoxide.
- Figure 6 is the 70-eV electron ionization mass spectrum of 4,6- DMDBT sulfone.
- Figure 7 is the 70-eV electron ionization mass spectrum of hindered C 3 -DBT sulfoxide.
- Figure 8 is the 70-eV electron ionization mass spectrum of hindered C 3 -DBT sulfone.
- the oxidant utilized in the instant invention is a peroxometal complex represented by one of the following formulas LMO(0 2 ) 2 , (LL')MO(0 2 ) 2 , and LMO(0 2 ) 2 -H 2 0 wherein M is selected from the group consisting of Mo, W, Cr and mixtures thereof and wherein L and L' are neutral ligands.
- M is selected from the group consisting of Mo, W, Cr and mixtures thereof and wherein L and L' are neutral ligands.
- Illustrative but non-limiting examples of ligands useful in this invention include hexamethylphosphoric triamide (HMPT), dimethylformamide (DMF), pyridine, etc.
- HMPT hexamethylphosphoric triamide
- DMF dimethylformamide
- pyridine pyridine
- Mo will be the metal and HMPT the preferred ligand.
- the diperoxo complex is of the formula (HMPT) 2 MoO(0 2 ) 2 .
- This complex can be prepared from the reaction of molybdenum oxide with H 2 0 2 or hydroperoxide in the presence of said ligand.
- the complex (HMPT)MoO(0 2 ) 2 -H 2 0 can also be prepared.
- the weakly bound water molecule can easily be removed and the resulting molybdenum peroxide becomes (HMPT)MoO(0 2 ) 2 , or [(CH 3 ) 2 N] 3 POMoO(0-0) 2 .
- the preparation of the peroxometal complexes is easily carried out by the skilled artisan and will be further understood by reference to the Examples, infra.
- the oxidation reaction involves oxygen transfer from the transition metal peroxide to the hard sulfur.
- To replenish the lost oxygen atom in the metal peroxide one may add an appropriate amount of hydrogen peroxide or hydroperoxide (ROOH) to the reaction system.
- the hydrogen peroxide or hydroperoxide will replenish the lost oxygen of the peroxometal complex.
- Appropriate amount as used herein is the stoichiometric amount necessary to replenish the peroxometal complex and is readily determined by the skilled artisan.
- the peroxometal complex oxidizes the hard sulfurs into their corresponding sulfoxides and sulfones with negligible if any co-oxidation of mononuclear aromatics.
- oxidation products due to their high polarity, can be readily removed by conventional separation techniques such as adsorption and extraction.
- the high selectivity of the oxidants coupled with the small amount of hard sulfurs in hydrotreated streams, makes the instant invention a particularly effective deep desulfurization means with minimum yield loss.
- the yield loss corresponds to the amount of hard sulfurs oxidized. Since the amount of hard sulfurs present in a hydrotreated crude is rather small, the yield loss is correspondingly small.
- the adsorption step can employ solid adsorbents capable of removing sulfoxides and sulfones.
- solid adsorbents capable of removing sulfoxides and sulfones.
- Non-limiting examples of such adsorbents include activated carbons, activated bauxite, activated clay, activated coke, alumina, and silica gel.
- Preferred solid adsorbents should have pores large enough to adsorb the multiring oxidation products and the hard sulfurs.
- a commercially available activated carbon useful in the instant invention is FILTRASORB 400.
- the oxidation will be conducted under conditions known to the skilled artisan.
- the oxidation reactions are rather mild and can even be carried out at temperatures as low as room temperature. Such conditions will be capable of converting the hard sulfurs into their corresponding sulfoxides and sulfones at reasonable rates and are known to the skilled artisan.
- the amount of peroxometal complex necessary for the instant invention is the stoichiometric amount necessary to oxidize the hard sulfurs contained in the hydrotreated stream being treated in accordance herewith. Preferably an amount which will oxidize all of the hard sulfurs will be used.
- (HMPT)MoO(0 ) 2 can be obtained as follows. Five grams molybdenum oxide (VI) and 25 cc hydrogen peroxide (30%) were placed in a flask and heated to 40°C and stirred for 15 minutes at 40°C. The resulting light yellow suspension was cooled to 10°C using ice water with stirring. To this suspension was added 6.23 grams HMPT dropwise and a yellow solid immediately formed. To facilitate stirring, 15 cc of ether was added at 10°C for 30 minutes. The solid product was filtered under vacuum with multiple ether washes. The product was then dried in a vacuum oven for 1 hour at 30-35°C. 9.1 grams of product were obtained and recrystallized from methanol at 40°C. The resulting mixture was filtered and methanol was removed via evaporation. A yellow solid product was obtained.
- a severely hydrotreated stream generally contains a large amount of mononuclear aromatics and a small amount of hard sulfurs. Accordingly, a model feed mixture of 5 wt% 4-methyldibenzothiophene (4-MDBT), 70 wt% p- xylene, and 25 wt% hexadecane was used.
- the purpose of this example was to show that (HMPT)MoO(0 2 ) is such a selective oxidant that it oxidizes 4-MDBT without cooxidation of p-xylene.
- Batch oxidation experiments were conducted as follows. Five grams of the feed mixture were dissolved in 125 cc methylene chloride (CH 2 C1 2 ) at 40°C.
- Figure 1 shows the GC/MS total ion chromatogram of the oxidation products obtained from the above experiment. Approximately half of the feed 4MDBT was oxidized to sulfoxide and sulfone. Moreover, xylene was not oxidized.
- Figures 2 and 3 are the 70-eV electron ionization (El) mass spectra of 4MDBT sulfoxide and sulfone, respectively. The molecular ions at mass-to-charge ratio of 214 and 230 are the most predominant ionic species present due to the stability of molecular ions with full aromaticity.
- the feed was a hydrotreated virgin middle distillate containing 390 ppm total sulfur. Inspection of this distillate with a sulfur-specific GC indicated that there are at least five hard sulfur species that survived hydrotreating. The largest one is 4,6-DMDBT. The rest are sterically hindered ethyl methyl and trimethyl DBTs.
- the oxidation reaction at room temperature proceeded as follows: five grams of oil were dissolved in 125 cc CH 2 C1 2 and 3.55 grams of (HMPT)MoO(0 2 ) 2 were dissolved in 100 cc CH 2 C1 2 . The solutions were combined at room temperature with stirring and stirred for 12 minutes. 300 cc IN HC1 was added and stirred for 15 minutes. The organic phase (the bottom portion) was then separated out and washed with IN HC1 followed by distilled water. The product was filtered and solvent evaporated.
- Figure 4 is the GC/MS selective ion chromatogram showing that hard sulfurs were removed.
- the six ion current traces shown in Figure 4 monitor the molecular ions of the sulfur compounds of interest and show the distributions of alkyldibenzothiophenes and their corresponding sulfones and sulfoxides.
- 4,6-DMDBT with molecular weight 212 is shown in the mass 212 chromatogram.
- the sulfone and sulfoxide derived from 4,6- DMDBT are found in the mass 228 and 244 chromatograms, respectively.
- FIGS. 5 and 6 are the 70-eV El mass spectra of 4,6-DMDBT sulfoxide and sulfone, respectively.
- the molecular ions of mass-to-charge ratio of 228 and 244 are the most intensive peak in these spectra.
- approximately half of the sterically hindered C 3 DBT isomers, shown in the mass 226 chromatogram, are oxidized into the corresponding sulfoxide and sulfone (mass 242 and 258 chromatograms).
- Figures 7 and 8 show typical 70-eV El mass spectra of the C 3 DBT sulfoxide and sulfone, with the molecular ions of 242 and 258 predominant in the spectra.
- Experiment 5A was the base case of direct removal of 4MDBT via adsorption using the activated carbon FILTRASORB 400 as the adsorbent.
- Experiment 5B removed 4MDBT via the oxidation followed by adsorption.
- the feed used contained 13.62 wt% 4MDBT, 0.84 wr% DBT, and 85.54 wt% hexadecane.
- the products obtained from both experiments were analyzed by GC and mass spec.
- the batch adsorption was done with an oil-to-adsorbent weight ratio of 6.5 at ambient conditions for 64 hours.
- the product after adsorption was analyzed by GC/MS. Table 1 summarizes the results. As can be seen, 44.5 % of 4MDBT was removed from the feed.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Industrial Gases (AREA)
- Treating Waste Gases (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69902047T DE69902047T2 (en) | 1998-08-14 | 1999-07-20 | METHOD FOR DEEP DESULFURATION USING A COMBINED HYDRATION OXIDATION |
CA002338625A CA2338625A1 (en) | 1998-08-14 | 1999-07-20 | A process for deep hydrodesulfurization using combined hydrotreating-oxidation |
AU51140/99A AU5114099A (en) | 1998-08-14 | 1999-07-20 | A process for deep hydrodesulfurization using combined hydrotreating-oxidation |
DK99935720T DK1109878T3 (en) | 1998-08-14 | 1999-07-20 | Process for Deep Hydrodesulfurization Using Combined Hydro Treatment Oxidation |
JP2000565067A JP2002522624A (en) | 1998-08-14 | 1999-07-20 | Deep hydrodesulfurization using a combination of hydrotreating and oxidation |
EP99935720A EP1109878B1 (en) | 1998-08-14 | 1999-07-20 | A process for deep hydrodesulfurization using combined hydrotreating-oxidation |
AT99935720T ATE220095T1 (en) | 1998-08-14 | 1999-07-20 | PROCESS FOR DEEP DESULFURIZATION USING COMBINED HYDROGENATION-OXIDATION |
NO20010648A NO20010648D0 (en) | 1998-08-14 | 2001-02-07 | A process for deep desulfurization with hydrogen using a combined hydrogen treatment oxidation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/134,300 US5958224A (en) | 1998-08-14 | 1998-08-14 | Process for deep desulfurization using combined hydrotreating-oxidation |
US09/134,300 | 1998-08-14 |
Publications (1)
Publication Number | Publication Date |
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WO2000009630A1 true WO2000009630A1 (en) | 2000-02-24 |
Family
ID=22462729
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/016359 WO2000009630A1 (en) | 1998-08-14 | 1999-07-20 | A process for deep hydrodesulfurization using combined hydrotreating-oxidation |
Country Status (11)
Country | Link |
---|---|
US (1) | US5958224A (en) |
EP (1) | EP1109878B1 (en) |
JP (1) | JP2002522624A (en) |
AT (1) | ATE220095T1 (en) |
AU (1) | AU5114099A (en) |
CA (1) | CA2338625A1 (en) |
DE (1) | DE69902047T2 (en) |
DK (1) | DK1109878T3 (en) |
ES (1) | ES2177305T3 (en) |
NO (1) | NO20010648D0 (en) |
WO (1) | WO2000009630A1 (en) |
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- 1999-07-20 AU AU51140/99A patent/AU5114099A/en not_active Abandoned
- 1999-07-20 ES ES99935720T patent/ES2177305T3/en not_active Expired - Lifetime
- 1999-07-20 DK DK99935720T patent/DK1109878T3/en active
- 1999-07-20 CA CA002338625A patent/CA2338625A1/en not_active Abandoned
- 1999-07-20 JP JP2000565067A patent/JP2002522624A/en active Pending
- 1999-07-20 EP EP99935720A patent/EP1109878B1/en not_active Expired - Lifetime
- 1999-07-20 WO PCT/US1999/016359 patent/WO2000009630A1/en active IP Right Grant
- 1999-07-20 DE DE69902047T patent/DE69902047T2/en not_active Expired - Fee Related
-
2001
- 2001-02-07 NO NO20010648A patent/NO20010648D0/en not_active Application Discontinuation
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002031086A1 (en) * | 2000-10-11 | 2002-04-18 | Consejo Superior De Investigaciones Cientificas | Process and catalysts for eliminating sulfur compounds from the gasoline fraction |
ES2179753A1 (en) * | 2000-10-11 | 2003-01-16 | Univ Valencia Politecnica | Process and catalysts for eliminating sulfur compounds from the gasoline fraction |
Also Published As
Publication number | Publication date |
---|---|
EP1109878B1 (en) | 2002-07-03 |
NO20010648L (en) | 2001-02-07 |
ATE220095T1 (en) | 2002-07-15 |
DE69902047T2 (en) | 2002-11-14 |
DK1109878T3 (en) | 2002-07-22 |
ES2177305T3 (en) | 2002-12-01 |
CA2338625A1 (en) | 2000-02-24 |
JP2002522624A (en) | 2002-07-23 |
NO20010648D0 (en) | 2001-02-07 |
AU5114099A (en) | 2000-03-06 |
DE69902047D1 (en) | 2002-08-08 |
US5958224A (en) | 1999-09-28 |
EP1109878A1 (en) | 2001-06-27 |
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