US20040159583A1 - Process for the catalytic selective oxidation of sulfur compounds - Google Patents

Process for the catalytic selective oxidation of sulfur compounds Download PDF

Info

Publication number
US20040159583A1
US20040159583A1 US10738332 US73833203A US2004159583A1 US 20040159583 A1 US20040159583 A1 US 20040159583A1 US 10738332 US10738332 US 10738332 US 73833203 A US73833203 A US 73833203A US 2004159583 A1 US2004159583 A1 US 2004159583A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
process
catalyst
hydrocarbonaceous feedstock
feed mixture
oxygen
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
Application number
US10738332
Inventor
Carolus Mesters
Ronald Schoonebeek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Oil Co
Original Assignee
Shell Oil Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10Working-up natural gas or synthetic natural gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46Ruthenium, rhodium, osmium or iridium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
    • B01J23/58Platinum group metals with alkali- or alkaline earth metals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G27/00Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen

Abstract

A process for the catalytic selective oxidation of sulfur compounds in a hydrocarbonaceous feedstock to sulfur dioxide is provided. A gaseous feed mixture of the hydrocarbonaceous feedstock and a molecular-oxygen containing gas is contacted with a catalyst at a temperature of at most 500 ° C., wherein the oxygen-to-carbon ratio of the feed mixture is below 0.15. The catalyst contains a group VIII noble metal on a catalyst carrier. The formed sulfur dioxide can be removed from the hydrocarbonaceous feedstock.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a process for the catalytic selective oxidation of sulfur compounds in a hydrocarbonaceous feedstock to sulfur dioxide. [0001]
  • BACKGROUND OF THE INVENTION
  • Hydrocarbonaceous feedstock are usually desulfurised in a hydrodesulfurisation process. In this process, the sulfur containing feedstock is contacted with a hydrodesulfurisation catalyst, typically a Co—Mo or Ni—Mo catalyst, in the presence of hydrogen, at elevated temperature and pressure. Hydrodesulfurised hydrocarbonaceous streams still contain sulfur compounds, in particular sulfur compounds that are difficult to remove such as heterocyclic sulfur compounds like thiophenes, benzothiophenes, substituted and condensed ring dibenzothiophenes. [0002]
  • Catalysts containing nickel, zinc oxide and alumina may be used for deep desulfurisation of hydrocarbon streams in the presence of hydrogen. These catalysts are able to remove “difficult” sulfur compounds and to achieve sulfur concentrations as low as 0.1 ppm. In WO 01/15804, for example, a catalyst is disclosed having 5-25 wt % Ni, 30-70 wt % ZnO and the remainder alumina. The catalyst of WO 01/15804 has a double function: nickel catalyses the reaction of sulfur with hydrogen to form hydrogen sulphide and zinc oxide absorbs the hydrogen sulphide formed. [0003]
  • Hydrocarbonaceous streams may also be desulfurized by oxidising the sulfur of the sulfur compounds to sulfur dioxide in a vapour phase process. U.S. Pat. No. 2,640,010, for example, describes the oxidation of sulfur compounds like hydrogen sulphide, mercaptans and disulphides in petroleum hydrocarbons to sulfur dioxide, by passing the vapour of the hydrocarbon over an oxidation catalyst comprising cuprous sulphide. U.S. Pat. No. 2,361,651 describes a process for sweetening and desulfurising sour hydrocarbon distillates by contacting vapours of said distillates in the presence of oxygen with a catalyst comprising copper oxide. The reaction involved in the process is an oxidation of mercaptans, sulfides and disulfides to sulfur dioxide by the action of the copper catalyst in the presence of oxygen. [0004]
  • A disadvantage of the processes disclosed in U.S. Pat. No. 2,640,010 and U.S. Pat. No. 2,361,651 is that “difficult” sulfur compounds like thiophenes are not removed. [0005]
  • SUMMARY OF THE INVENTION
  • A process for the catalytic selective oxidation of sulfur compounds in a hydrocarbonaceous feedstock to sulfur dioxide is provided, comprising the steps of: [0006]
  • contacting a gaseous feed mixture of the hydrocarbonaceous feedstock and a molecular-oxygen containing gas with a catalyst at a temperature of at most 500° C., said catalyst comprising a group VIII noble metal on a catalyst carrier, said feed mixture having oxygen-to-carbon ratio of below 0.15. [0007]
  • Further, a process for the desulfurization of a hydrocarbonacous feedstock is provided, comprising the steps of: [0008]
  • contacting a gaseous feed mixture of the hydrocarbonaceous feedstock and a molecular-oxygen containing gas with a catalyst at a temperature of at most 500° C., said catalyst comprising a group VIII noble metal on a catalyst carrier, said feed mixture having oxygen-to-carbon ratio of below 0.15, thereby selectively oxidizing sulfur compounds in the hydrocarbonaceous feedstock to sulfur dioxide; and removing the thus-formed sulfur dioxide from the hydrocarbonaceous feedstock.[0009]
  • DETAILED DESCRIPTION OF THE INVENTION
  • It has now been found that the sulfur from “difficult” sulfur compounds like thiophenes in hydrocarbonaceous streams can be converted into sulfur dioxide by catalytic selective oxidation by using a catalyst comprising a Group VIII noble metal. The thus-formed sulfur dioxide can be removed by processes known in the art. Reference herein to selective oxidation of sulfur compounds is to the oxidation of sulfur compounds with no or minimal oxidation of the non-sulfur containing hydrocarbonaceous compounds. [0010]
  • An advantage of selective oxidation followed by removal of sulfur dioxide is that no hydrogen is needed for the desulfurisation. Another advantage of the vapour phase selective oxidation process is that the process can be performed at ambient pressure. Moreover, with the process according to the invention it is possible to achieve deep desulfurisation without using nickel-containing catalysts. [0011]
  • Accordingly, the present invention relates to a process for the catalytic selective oxidation of sulfur compounds in a hydrocarbonaceous feedstock to sulfur dioxide, wherein a gaseous feed mixture of the hydrocarbonaceous feedstock and a molecular-oxygen containing gas is contacted with a catalyst at a temperature of at most 500° C., the catalyst comprising a group VIII noble metal on a catalyst carrier, wherein the oxygen-to-carbon ratio of the feed mixture is below 0.15. [0012]
  • Sulfur compounds that can be selectively oxidised by the process according to the invention are for example hydrogen sulphide, mercaptans, disulphides, or heterocyclic sulfur compounds such as thiophenes, benzothiophenes, or substituted and condensed ring dibenzothiophenes. [0013]
  • The hydrocarbonaceous feedstock is a hydrocarbonaceous feedstock that is gaseous under the conditions prevailing at the catalyst surface. Preferred feedstocks are feedstocks that are gaseous at standard temperature and pressure (STP; 0° C., 1 atm.) conditions such as methane, natural gas, LPG and other gaseous hydrocarbon streams. Further, feedstocks that are liquid under STP conditions but gaseous at the conditions prevailing at the catalyst surface such as naphtha, diesel or gasoline are suitable feedstocks. [0014]
  • The catalyst of the process according to the invention comprises as catalyst carrier an oxidising solid surface, typically in the form of solid particles. Reference herein to an oxidising surface is to a surface that is able to activate molecular oxygen. Preferably, the catalyst carrier comprises a refractory oxide. Refractory oxides such as stabilised and partially stabilised zirconia, ceria, yttria, silica, alumina, titania and combinations thereof are particularly suitable. A catalyst carrier comprising stabilised or partially stabilised zirconia is most preferred. [0015]
  • Alternatively, the catalyst carrier may comprise a non-refractory oxide bulk material having an oxidising surface. Examples of such materials are a Fe, Cr and Al containing alloy (commercialised as FECRALLOY) with an alumina or zirconia surface layer (FECRALLOY is a trademark). [0016]
  • The catalyst comprises one or more catalytically active metals supported on the solid surface or carrier. These catalytically active metals are Group VIII noble metals, more preferably platinum, rhodium, iridium or a combination of two or more thereof. [0017]
  • Typically, the catalyst comprises the catalytically active metal(s) in a concentration in the range of from 0.02 to 10% by weight, based on the total weight of the catalyst, preferably in the range of from 0.1 to 5% by weight. The catalyst may further comprise a performance-enhancing inorganic metal cation selected from Al, Mg, Zr, Ti, La, Hf, Si, Ba, and Ce which is present in intimate association supported on or with the catalytically active metal, preferably a zirconium and/or cerium cation. [0018]
  • Catalysts comprising a noble metal on a carrier are also suitable for the catalytic partial oxidation of hydrocarbons, typical at temperatures above 700° C. It has been found that at much lower temperatures, typically between 200 and 500° C., the oxidation of sulfur compounds takes preferentially place as compared to the oxidation of hydrocarbons. [0019]
  • In order to prevent degradation of hydrocarbon compounds, the process temperature is maintained at at most 500° C. Preferably, the process temperature is in the range of from 200 to 500° C., more preferably of from 200 to 300° C. [0020]
  • The pressure at which the feed mixture is contacted with the catalyst is preferably in the range of from 1 to 10 bar (absolute), more preferably of from 1 to 5 bar (absolute). Most preferably, the feed mixture is contacted with the catalystat ambient pressure. [0021]
  • The molecular-oxygen containing gas may be oxygen, air or oxygen-enriched air. Preferably, air is used as molecular-oxygen containing gas. [0022]
  • It will be appreciated that the exact process conditions, such as the temperature at which the catalyst is maintained, pressure, gas or liquid velocity and the oxygen-to-carbon ratio in the feed mixture, will inter alia depend on the catalyst used, the required sulfur conversion and selectivity, and the boiling characteristics of the hydrocarbonaceous feedstock. [0023]
  • The oxygen-to-carbon ratio of the feed mixture is at most 0.15, preferably at most 0.10. Reference herein to the oxygen-to carbon ratio is to the ratio of oxygen in the form of molecules (O[0024] 2) to carbon atoms present in the hydrocarbonaceous feedstock.
  • The process according to the invention is very suitable for deep desulfurisation of hydrocarbonaceous streams. It is particularly suitable for the removal of hydrogen sulphide from gaseous hydrocarbonaceous steams comprising up to 10% v/v hydrogen sulphide or the removal of “difficult” sulfur compounds from liquid hydrocarbonaceous steams comprising up to 1000 ppmw sulfur. [0025]
  • The sulfur dioxide formed may be removed by techniques known in the art. In liquid feedstocks, sulfur dioxide may for example be removed by distillation or stripping. Suitable techniques known in the art for the removal of sulfur dioxide from gaseous feedstocks are for example solvent extraction using an aqueous amine solution or an alkaline solution, absorption on copper, barium or cerium oxide, or reaction with lime to produce gypsum. [0026]
  • In order to remove larger amounts of hydrogen sulphide from gaseous hydrocarbonaceous feedstocks, the selective oxidation process according to the invention can suitably be applied in combination with a process for the conversion of H[0027] 2S/SO2 mixtures into elemental sulfur according to the well-known Claus reaction:
  • 2H2S+SO2→3S+2H2O
  • Part of the hydrogen sulphide, preferably about one third of the total volumetric amount of hydrogen sulphide, is then converted into sulfur dioxide by the catalytic selective oxidation process according to the invention. [0028]
  • The process according to the invention will be further illustrated by the following non-limiting examples. [0029]
  • EXAMPLE 1 Catalyst Preparation
  • Catalyst 1 [0030]
  • Particles (1 mm average diameter) of zirconia partially stabilised with yttria (Y-PSZ) were coated with a zirconia paint (zirconium oxide partially-stabilised with 4% wt CaO; type ZO; ex. ZYP Coatings Inc., Oak Ridge, USA) and provided with 0.9 wt % Rh, 0.9 wt % Ir, 0.6 wt % Zr, 1.9 wt % Ce by impregnating the painted particles with a solution containing rhodium tri chloride, iridium tetra chloride, zirconyl nitrate and cerium nitrate. The impregnated particles were dried at 140° C. during 2 hours and calcined at 700° C. during 2 hours. [0031]
  • Catalyst 2 (comparative) [0032]
  • Particles (1 mm average diameter) of zirconia partially stabilised with yttria (Y-PSZ) were coated with a zirconia paint (see above under catalyst 1) and provided with 0.5 wt % Zr, 1.6 wt % Ce by impregnating the painted particles with a solution containing zirconyl nitrate and cerium nitrate. The impregnated particles were dried at 140° C. during 2 hours and calcined at 700° C. during 2 hours. [0033]
  • Catalyst 3 [0034]
  • Particles (30-80 mesh) of Y-PSZ were coated with a zirconia paint (see above under catalyst 1) and provided with 1.6 wt % Rh, 1.0 wt % Zr, 1.6 wt % Ce by impregnating the painted particles with a solution containing rhodium tri chloride, zirconyl nitrate and cerium nitrate. The impregnated particles were dried at 140° C. during 2 hours and calcined at 700° C. during 2 hours. [0035]
  • Catalyst 4 [0036]
  • Particles (30-80 mesh) of zirconia-toughened alumina partially stabilised with ceria (Ce-ZTA) were impregnated with a solution containing H[0037] 2PtCl6 and zirconyl nitrate. The impregnated particles were dried at 140° C. during 2 hours and calcined at 700° C. during 2 hours. The resulting catalyst particles contained 5 wt % Pt and 7 wt % Zr.
  • Catalyst 5 [0038]
  • Calcined (2 hours at 1000° C.) particles (30-80 mesh) of alumina stabilised with magnesium oxide were provided with 0.6 wt % Ir by impregnating the particles with a iridium tetra chloride containing solution. The impregnated particles were dried (2 hours at 120° C.) and calcined (2 hours at 700° C.). [0039]
  • Catalyst 6 [0040]
  • Particles (1 mm average diameter) Y-PSZ were coated with a zirconia paint and provided with 0.8 wt % Rh, 0.8 wt % Ir, 0.6 wt % Zr, 1.7 wt % Ce by impregnating the painted particles with a solution containing rhodium tri chloride, iridium tetra chloride, zirconyl nitrate and cerium nitrate. The impregnated particles were dried at 140° C. during 2 hours and calcined at 700° C. during 2 hours. [0041]
  • Catalytic Selective Oxidation [0042]
  • Approximately 1 g of catalyst particles were loaded in a 6 mm inner diameter reactor tube. A gas mixture of air and H[0043] 2S-containing methane was passed over the catalyst particles at elevated temperature and at ambient pressure.
  • In Table 1, the H[0044] 2S concentration of the H2S-containing methane, the oxygen-to-carbon ratio of the air/methane mixture, the gas space velocity (N1 feed mixture per kg catalyst per hour), the temperature at which the catalyst is maintained, the H2S conversion and the selectivity are given for each catalyst. The selectivity is calculated as the quotient of the molar SO2/CO2 ratio in the effluent and the S/C ratio in the feed.
  • It can be seen from the results in Table 1 that very high H[0045] 2S conversions are obtained when the methane feed is oxidised over a catalyst comprising Pt, Rh and/or Ir (catalysts 1, 3-6). When a catalyst without catalytically active metal is used (catalyst 2), the temperature has to be increased above 500° C. in order to achieve such a high conversion.
    TABLE 1
    Selective oxidation of H2S in methane: feed composition, process conditions and results.
    Catalyst No.
    1 2 (comparison) 3 4 5 6
    H2S (% v/v) 2.8 2.0 2.5 2.5 2.0 1.7 1.5 1.6
    O2:C 0.06 0.04 0.05 0.05 0.05 0.07 0.05 0.06
    GSV (Nl/kg/h) 7,000 7,000 7,000 7,000 7,000 7,000 13,000 7,000
    T (° C.) 360 459 413 553 470 458 467 433
    H2S conversion (%) 99.9 99.7 73.7 99.9 97.1 94.7 95.2 96.7
    selectivity 222 373 5070 8400 53 57 57 57
  • EXAMPLE 2
  • 0.95 g of particles of catalyst 1 were loaded in a 6 mm inner diameter reactor tube. A gas mixture of air and thiophene-containing methane was passed over the catalyst particles at elevated temperature and ambient pressure. Two different experiments with different feed composition and different process conditions were carried out. [0046]
  • In Table 2, the sulfur concentration of the methane, the oxygen-to-carbon ratio of the air/methane mixture, the gas space velocity (N[0047] 1 feed mixture per kg catalyst per hour), the temperature at which the catalyst is maintained, the thiophene conversion and the selectivity are given for the two experiments. The selectivity is calculated as the quotient of the molar SO2/CO2 ratio in the effluent and the S/C ratio in the feed.
    TABLE 2
    Selective oxidation of thiophene in
    methane: feed composition, process conditions and results.
    experiment
    a b
    ppmw S 11,400 300
    O2:C 0.05 0.02
    GSV (Nl/kg/h) 8,000 7,000
    T (° C.) 391 304
    thiophenes conversion (%) 99.8 79.9
    selectivity 28 1816
  • EXAMPLE 3
  • 0.94 g of particles of catalyst 1 were loaded in a 6 mm inner diameter reactor tube. A mixture of air and thiophene-containing naphtha was passed over the catalyst particles at a temperature of 320° C. and ambient pressure. The naphtha had a boiling range of 40-180° C., a H/C ratio of 1.8, a density of 0.74 g/ml. [0048]
  • In Table 3, the sulfur concentration of the naphtha, the oxygen-to-carbon ratio of the air/naphtha mixture, the liquid space velocity (kg naphtha per kg catalyst per hour), the temperature at which the catalyst is maintained, the thiophene conversion and the selectivity are given. The selectivity is calculated as the quotient of the molar SO[0049] 2/CO2 ratio in the effluent and the S/C ratio in the feed.
    TABLE 3
    Selective oxidation of thiophene in naphtha:
    feed composition, process conditions and results.
    ppmw S 590
    O2:C 0.003
    LSV (kg/kg/h) 23.4
    T (° C.) 320
    thiophenes conversion (%) 62.7
    Selectivity 428
  • EXAMPLE 4 Catalyst Preparation
  • Catalyst 7 [0050]
  • Particles (30-80 mesh average diameter) of zirconia partially stabilised with yttria (Y-PSZ) were coated with a zirconia paint (zirconium oxide partially-stabilised with 4% wt CaO; type ZO; ex. ZYP Coatings Inc., Oak Ridge, USA) and provided with 2.26 wt % Ir, 0.98 wt % Zr, 1.56 wt % Ce by impregnating the painted particles with a solution containing iridium tetra chloride, zirconyl nitrate and cerium nitrate. The impregnated particles were dried at 140° C. during 2 hours and calcined at 700° C. during 2 hours. [0051]
  • Catalytic Selective Oxidation [0052]
  • 2.04 g of particles of catalyst 7 were diluted with 2.13 g SiC (0.05 mm) to improve heat transfer and flow properties and loaded in a 15 mm inner diameter reactor tube. A gas mixture of air and thiophene-containing methane was passed over the catalyst particles at elevated temperature and ambient pressure. Three different experiments with the same feed composition and different temperatures were carried out. The sulfur content of the feed was 210 ppmv thiophene. The O[0053] 2/C ratio was 0.005 and the GHSV 2500 Nl/kg/hr.
  • In Table 4, the thiophene conversion and selectivity are given for the three experiments. The selectivity is calculated as the quotient of the molar SO[0054] 2/CO2 ratio in the effluent and the S/C ratio in the feed.
    TABLE 4
    Selective oxidation of thiophene in methane
    experiment
    a b c
    temperature (° C.) 220 250 300
    thiophenes 99.8 99.8 99.8
    conversion (%)
    selectivity 2380 1590 676
  • EXAMPLE 5
  • 2.03 g of particles of catalyst 7 were diluted with 2.2 g SiC (0.05 mm) to improve heat transfer and flow properties and loaded in a 15 mm inner diameter reactor tube. A gas mixture of air and LPG (5.9% v/v butane, balance propane) containing 50 ppmv each of H[0055] 2S, COS, ethyl mercaptan, tetrahydrothiophene and diethyl disulfide was passed over the catalyst particles at elevated temperature and ambient pressure. The O2/C ratio was 0.002 and the GHSV 3600 Nl/kg/hr.
  • In Table 5, the conversion of each of the sulfur species is given for a reactor temperature of 275° C. [0056]
    TABLE 5
    Conversion of different sulfur species in LPG
    sulfur species conversion (%)
    H2S 99.97
    COS 99.9
    ethyl mercaptan 99.97
    tetrahydrothiophene 97
    diethyl disulfide 99.9
  • EXAMPLE 6 Catalyst Preparation
  • Catalyst 8 [0057]
  • Particles (20-30 mesh average diameter) of zirconia partially stabilised with yttria (Y-PSZ) were coated with a zirconia paint (zirconium oxide partially-stabilised with 4% wt CaO; type ZO; ex. ZYP Coatings Inc., Oak Ridge, USA) and provided with 0.81 wt % Rh, 0.78 wt % Ir, 0.98 wt % Zr, 1.57 wt % Ce by impregnating the painted particles with a solution containing rhodium tri chloride, iridium tetra chloride, zirconyl nitrate and cerium nitrate. The impregnated particles were dried at 140° C. during 2 hours and calcined at 700° C. during 2 hours. [0058]
  • Catalytic Selective Oxidation [0059]
  • 1.93 g of particles of catalyst 8 were mixed with 1.81 gram SiC (0.05 mm) and loaded in a 15 mm inner diameter reactor tube. A mixture of air and a hydrocracked naphtha (ex Pernis refinery, initial boiling point 91° C., final boiling point 195° C., containing a total of 32 ppmw S, predominantly as (substituted) thiophenes, sulphides and disulfides) was passed over the catalyst particles at two different temperatures, 250 and 270° C., an O[0060] 2/C ratio of 0.003 and a liquid space velocity of 3.5 kg/kg/hr.
  • In Table 6, the sulfur conversion of the naphtha, and the selectivity are given. The conversion is based on the S analysis of the liquid product. The selectivity is calculated as the quotient of the molar SO[0061] 2/CO2 ratio in the effluent and the S/C ratio in the feed.
    TABLE 6
    Selective oxidation of sulfur species in naphtha
    experiment
    a b
    temperature (° C.) 250 270
    S conversion (%) 88 92
    selectivity 334 17

Claims (44)

    We claim:
  1. 1. A process for the catalytic selective oxidation of sulfur compounds in a hydrocarbonaceous feedstock to sulfur dioxide, comprising the steps of: contacting a gaseous feed mixture of the hydrocarbonaceous feedstock and a molecular-oxygen containing gas with a catalyst at a temperature of at most 500° C., said catalyst comprising a group VIII noble metal on a catalyst carrier, said feed mixture having oxygen-to-carbon ratio of below 0.15.
  2. 2. The process of claim 1 wherein the oxygen-to-carbon ratio of the feed mixture is below 0.10.
  3. 3. The process of claim 1 wherein the catalyst carrier is a refractory oxide.
  4. 4. The process of claim 3 wherein the refractory oxide comprises partially stabilised or stabilised zirconia.
  5. 5. The process of claim 1 wherein the group VIII noble metal is Pt, Rh or Ir or a combination of two or more thereof.
  6. 6. The process of claim 5 wherein the oxygen-to-carbon ratio of the feed mixture is below 0.10.
  7. 7. The process of claim 5 wherein the catalyst carrier is a refractory oxide.
  8. 8. The process of claim 7 wherein the refractory oxide comprises partially stabilised or stabilised zirconia.
  9. 9. The process of claim 1 wherein the temperature is maintained in the range of from 200 to 500° C.
  10. 10. The process of claim 1 wherein the temperature is maintained in the range of from 200 to 300° C.
  11. 11. The process of claim 1 wherein the feed mixture is contacted with the catalyst at a pressure in the range of from 1 to 10 bar (absolute).
  12. 12. The process of claim 11 wherein the feed mixture is contacted with the catalyst at a pressure in the range of from of from 1 to 5 bar (absolute).
  13. 13. The process of claim 1 wherein the feed mixture is contacted with the catalyst at ambient pressure.
  14. 14. The process of claim 1 wherein the hydrocarbonaceous feedstock is a gaseous hydrocarbonaceous feedstock.
  15. 15. The process of claim 14 wherein the hydrocarbonaceous feedstock is methane or natural gas.
  16. 16. The process of claim 14 wherein the hydrocarbonaceous feedstock comprises hydrogen sulfide in a concentration of at most 10% v/v.
  17. 17. The process of claim 16 wherein the hydrocarbonaceous feedstock comprises hydrogen sulfide in a concentration of at most 5% v/v.
  18. 18. The process of claim 15 wherein the hydrocarbonaceous feedstock comprises hydrogen sulfide in a concentration of at most 10% v/v.
  19. 19. The process of claim 18 wherein the hydrocarbonaceous feedstock comprises hydrogen sulfide in a concentration of at most 5% v/v.
  20. 20. The process of claim 1 wherein the feedstock is a liquid hydrocarbonaceous feedstock containing at most 1000 ppmw sulfur.
  21. 21. A process for the catalytic selective oxidation of sulfur compounds in a methane or natural gas feedstock to sulfur dioxide, comprising the steps of: contacting a gaseous feed mixture of the methane or natural gas feedstock and a molecular-oxygen containing gas with a catalyst at a temperature of at most 500° C., said catalyst comprising a group VIII noble metal on a refractory oxide, said feed mixture having oxygen-to-carbon ratio of below 0.15.
  22. 22. The process of claim 21 wherein the group VIII noble metal is Pt, Rh or Ir or a combination of two or more thereof.
  23. 23. The process of claim 21 wherein the hydrocarbonaceous feedstock comprises hydrogen sulfide in a concentration of at most 10% v/v.
  24. 24. The process of claim 23 wherein the hydrocarbonaceous feedstock comprises hydrogen sulfide in a concentration of at most 5% v/v.
  25. 25. A process for the desulfurization of a hydrocarbonacous feedstock comprising the steps of: contacting a gaseous feed mixture of the hydrocarbonaceous feedstock and a molecular-oxygen containing gas with a catalyst at a temperature of at most 500° C., said catalyst comprising a group VIII noble metal on a catalyst carrier, said feed mixture having oxygen-to-carbon ratio of below 0.15, thereby selectively oxidizing sulfur compounds in the hydrocarbonaceous feedstock to sulfur dioxide; and removing the thus-formed sulfur dioxide from the hydrocarbonaceous feedstock.
  26. 26. The process of claim 25 wherein the oxygen-to-carbon ratio of the feed mixture is below 0.10.
  27. 27. The process of claim 25 wherein the catalyst carrier is a refractory oxide.
  28. 28. The process of claim 27 wherein the refractory oxide comprises partially stabilised or stabilised zirconia.
  29. 29. The process of claim 25 wherein the group VIII noble metal is Pt, Rh or Ir or a combination of two or more thereof.
  30. 30. The process of claim 29 wherein the oxygen-to-carbon ratio of the feed mixture is below 0.10.
  31. 31. The process of claim 29 wherein the catalyst carrier is a refractory oxide.
  32. 32. The process of claim 31 wherein the refractory oxide comprises partially stabilised or stabilised zirconia.
  33. 33. The process of claim 25 wherein the temperature is maintained in the range of from 200 to 500° C.
  34. 34. The process of claim 25 wherein the temperature is maintained in the range of from 200 to 300° C.
  35. 35. The process of claim 25 wherein the feed mixture is contacted with the catalyst at a pressure in the range of from 1 to 10 bar (absolute).
  36. 36. The process of claim 35 wherein the feed mixture is contacted with the catalyst at a pressure in the range of from of from 1 to 5 bar (absolute).
  37. 37. The process of claim 25 wherein the feed mixture is contacted with the catalyst at ambient pressure.
  38. 38. The process of claim 25 wherein the hydrocarbonaceous feedstock is a gaseous hydrocarbonaceous feedstock.
  39. 39. The process of claim 38 wherein the hydrocarbonaceous feedstock is methane or natural gas.
  40. 40. The process of claim 38 wherein the hydrocarbonaceous feedstock comprises hydrogen sulfide in a concentration of at most 10% v/v.
  41. 41. The process of claim 40 wherein the hydrocarbonaceous feedstock comprises hydrogen sulfide in a concentration of at most 5% v/v.
  42. 42. The process of claim 39 wherein the hydrocarbonaceous feedstock comprises hydrogen sulfide in a concentration of at most 10% v/v.
  43. 43. The process of claim 42 wherein the hydrocarbonaceous feedstock comprises hydrogen sulfide in a concentration of at most 5% v/v.
  44. 44. The process of claim 25 wherein the feedstock is a liquid hydrocarbonaceous feedstock containing at most 1000 ppmw sulfur.
US10738332 2002-12-17 2003-12-17 Process for the catalytic selective oxidation of sulfur compounds Abandoned US20040159583A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP02258672 2002-12-17
EP02258672.1 2002-12-17

Publications (1)

Publication Number Publication Date
US20040159583A1 true true US20040159583A1 (en) 2004-08-19

Family

ID=32338176

Family Applications (1)

Application Number Title Priority Date Filing Date
US10738332 Abandoned US20040159583A1 (en) 2002-12-17 2003-12-17 Process for the catalytic selective oxidation of sulfur compounds

Country Status (7)

Country Link
US (1) US20040159583A1 (en)
EP (1) EP1581601B1 (en)
JP (1) JP2006509880A (en)
CN (1) CN100532504C (en)
CA (1) CA2510182A1 (en)
DE (1) DE60322957D1 (en)
WO (1) WO2004055135A1 (en)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006071793A1 (en) * 2004-12-29 2006-07-06 Bp Corporation North America Inc. Oxidative desulfurization process
US20060254769A1 (en) * 2005-04-21 2006-11-16 Wang Dean C Systems and methods for producing oil and/or gas
US20070000385A1 (en) * 2005-07-01 2007-01-04 Stouffer Mark R Adsorbents for removing H2S, other odor causing compounds, and acid gases from gas streams and methods for producing and using these adsorbents
US20070051667A1 (en) * 2005-09-08 2007-03-08 Martinie Gary M Diesel oil desulfurization by oxidation and extraction
WO2007096345A1 (en) * 2006-02-22 2007-08-30 Shell Internationale Research Maatschappij B.V. Method for disposal of di-sulphide compounds
US20070251686A1 (en) * 2006-04-27 2007-11-01 Ayca Sivrikoz Systems and methods for producing oil and/or gas
US20080023198A1 (en) * 2006-05-22 2008-01-31 Chia-Fu Hsu Systems and methods for producing oil and/or gas
US20080087425A1 (en) * 2006-08-10 2008-04-17 Chia-Fu Hsu Methods for producing oil and/or gas
US20090056941A1 (en) * 2006-05-22 2009-03-05 Raul Valdez Methods for producing oil and/or gas
US20090155159A1 (en) * 2006-05-16 2009-06-18 Carolus Matthias Anna Maria Mesters Process for the manufacture of carbon disulphide
US20090188669A1 (en) * 2007-10-31 2009-07-30 Steffen Berg Systems and methods for producing oil and/or gas
US20090226358A1 (en) * 2006-05-16 2009-09-10 Shell Oil Company Process for the manufacture of carbon disulphide
US20100140139A1 (en) * 2007-02-16 2010-06-10 Zaida Diaz Systems and methods for absorbing gases into a liquid
US20100300938A1 (en) * 2005-09-08 2010-12-02 Martinie Gary D Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures
US20100307759A1 (en) * 2007-11-19 2010-12-09 Steffen Berg Systems and methods for producing oil and/or gas
US20110094750A1 (en) * 2008-04-16 2011-04-28 Claudia Van Den Berg Systems and methods for producing oil and/or gas
US20110108269A1 (en) * 2007-11-19 2011-05-12 Claudia Van Den Berg Systems and methods for producing oil and/or gas
US20110132602A1 (en) * 2008-04-14 2011-06-09 Claudia Van Den Berg Systems and methods for producing oil and/or gas
US20110132617A1 (en) * 2008-07-14 2011-06-09 Shell Oil Company Systems and methods for producing oil and/or gas
US20110139463A1 (en) * 2008-02-27 2011-06-16 Claudia Van Den Berg Systems and methods for producing oil and/or gas
US8097230B2 (en) 2006-07-07 2012-01-17 Shell Oil Company Process for the manufacture of carbon disulphide and use of a liquid stream comprising carbon disulphide for enhanced oil recovery
US20130028822A1 (en) * 2011-07-27 2013-01-31 Saudi Arabian Oil Company Catalytic compositions useful in removal of sulfur compounds from gaseous hydrocarbons, processes for making these and uses thereof
US9034527B2 (en) 2010-07-15 2015-05-19 Lg Fuel Cell Systems Inc. Fuel cell system and desulfurization system
US9057257B2 (en) 2007-11-19 2015-06-16 Shell Oil Company Producing oil and/or gas with emulsion comprising miscible solvent
US9062259B2 (en) 2011-07-29 2015-06-23 Saudi Arabian Oil Company Oxidative desulfurization in fluid catalytic cracking process

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100429295C (en) 2005-06-21 2008-10-29 大连理工大学 Fixed bed oxidation desulfur reaction method
DE102013005464A1 (en) * 2013-01-17 2014-07-17 Vaillant Gmbh A process for the reactive desulfurization of natural gas to fuel cell heating
CN104549123B (en) * 2013-10-28 2017-02-15 中国石油化工股份有限公司 Desulfurization and arsenic
CN104946296A (en) * 2015-05-18 2015-09-30 江苏新世纪江南环保股份有限公司 Gasoline-oxidation ammonia-process desulfurization method
CN104927894A (en) * 2015-05-18 2015-09-23 江苏新世纪江南环保股份有限公司 Diesel oxidation ammonia desulfurization method

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2361651A (en) * 1942-02-28 1944-10-31 Standard Oil Co Desulphurizing hydrocarbon distillates
US2640010A (en) * 1951-11-08 1953-05-26 Air Reduction Method of removing sulfur from petroleum hydrocarbons
US3565793A (en) * 1968-12-27 1971-02-23 Texaco Inc Desulfurization with a catalytic oxidation step
US3945914A (en) * 1974-08-23 1976-03-23 Atlantic Richfield Company Process for "sulfur reduction of an oxidized hydrocarbon by forming a metal-sulfur-containing compound"
US3978137A (en) * 1975-03-14 1976-08-31 Universal Oil Products Company Oxidation of sulfur-containing compounds
US4233276A (en) * 1979-03-30 1980-11-11 Standard Oil Company (Indiana) Process for the desulfurization of waste gases
US4382912A (en) * 1981-09-10 1983-05-10 Gulf Research & Development Company Selective combusting of hydrogen sulfide in carbon dioxide injection gas
US4399112A (en) * 1980-04-23 1983-08-16 Societe Nationale Elf Aquitaine Process for the catalytic incineration of residual gases containing a low content of at least one sulfur compound selected from COS, CS2 and the mercaptans and possibility at least one member of the group
US4419337A (en) * 1980-10-21 1983-12-06 Hudson's Bay Oil And Gas Company Limited Process and apparatus for reacting sulphur-containing material with oxidizing gas
US4440874A (en) * 1982-04-14 1984-04-03 Engelhard Corporation Catalyst composition and method for its manufacture
US4937058A (en) * 1980-04-23 1990-06-26 Rhone-Poulenc Industries Catalytic oxidation of sulfur compounds
US4946578A (en) * 1986-11-17 1990-08-07 Ensci, Inc. Process for treating hydrocarbons
US5137862A (en) * 1990-08-22 1992-08-11 Imperial Chemical Industries Plc Oxidation catalysts
US5476877A (en) * 1993-05-11 1995-12-19 Exxon Research And Engineering Company Particulate solids for catalyst supports and heat transfer materials
US5720901A (en) * 1993-12-27 1998-02-24 Shell Oil Company Process for the catalytic partial oxidation of hydrocarbons
US6946111B2 (en) * 1999-07-30 2005-09-20 Conocophilips Company Short contact time catalytic partial oxidation process for recovering sulfur from an H2S containing gas stream
US7060233B1 (en) * 2002-03-25 2006-06-13 Tda Research, Inc. Process for the simultaneous removal of sulfur and mercury
US7074375B2 (en) * 2002-12-03 2006-07-11 Engelhard Corporation Method of desulfurizing a hydrocarbon gas by selective partial oxidation and adsorption
US7374666B2 (en) * 2001-12-13 2008-05-20 Lehigh University Oxidative desulfurization of sulfur-containing hydrocarbons

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9023257D0 (en) * 1990-10-25 1990-12-05 British Petroleum Co Plc Desulphurisation of oil
WO1992020621A1 (en) * 1991-05-13 1992-11-26 Budra Research Ltd. Catalyst and process for removal of sulphur compounds and nitrogen oxides from fluid streams
FR2702674B1 (en) 1993-03-16 1995-04-28 Elf Aquitaine A method for removing sulfur compounds contained in a residual gas from the waste gas such as Claus plant sulfur, with recovery of said compounds in the form of sulfur.

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2361651A (en) * 1942-02-28 1944-10-31 Standard Oil Co Desulphurizing hydrocarbon distillates
US2640010A (en) * 1951-11-08 1953-05-26 Air Reduction Method of removing sulfur from petroleum hydrocarbons
US3565793A (en) * 1968-12-27 1971-02-23 Texaco Inc Desulfurization with a catalytic oxidation step
US3945914A (en) * 1974-08-23 1976-03-23 Atlantic Richfield Company Process for "sulfur reduction of an oxidized hydrocarbon by forming a metal-sulfur-containing compound"
US3978137A (en) * 1975-03-14 1976-08-31 Universal Oil Products Company Oxidation of sulfur-containing compounds
US4233276A (en) * 1979-03-30 1980-11-11 Standard Oil Company (Indiana) Process for the desulfurization of waste gases
US4937058A (en) * 1980-04-23 1990-06-26 Rhone-Poulenc Industries Catalytic oxidation of sulfur compounds
US4399112A (en) * 1980-04-23 1983-08-16 Societe Nationale Elf Aquitaine Process for the catalytic incineration of residual gases containing a low content of at least one sulfur compound selected from COS, CS2 and the mercaptans and possibility at least one member of the group
US4419337A (en) * 1980-10-21 1983-12-06 Hudson's Bay Oil And Gas Company Limited Process and apparatus for reacting sulphur-containing material with oxidizing gas
US4382912A (en) * 1981-09-10 1983-05-10 Gulf Research & Development Company Selective combusting of hydrogen sulfide in carbon dioxide injection gas
US4440874A (en) * 1982-04-14 1984-04-03 Engelhard Corporation Catalyst composition and method for its manufacture
US4946578A (en) * 1986-11-17 1990-08-07 Ensci, Inc. Process for treating hydrocarbons
US5137862A (en) * 1990-08-22 1992-08-11 Imperial Chemical Industries Plc Oxidation catalysts
US5476877A (en) * 1993-05-11 1995-12-19 Exxon Research And Engineering Company Particulate solids for catalyst supports and heat transfer materials
US5720901A (en) * 1993-12-27 1998-02-24 Shell Oil Company Process for the catalytic partial oxidation of hydrocarbons
US6946111B2 (en) * 1999-07-30 2005-09-20 Conocophilips Company Short contact time catalytic partial oxidation process for recovering sulfur from an H2S containing gas stream
US7374666B2 (en) * 2001-12-13 2008-05-20 Lehigh University Oxidative desulfurization of sulfur-containing hydrocarbons
US7060233B1 (en) * 2002-03-25 2006-06-13 Tda Research, Inc. Process for the simultaneous removal of sulfur and mercury
US7074375B2 (en) * 2002-12-03 2006-07-11 Engelhard Corporation Method of desulfurizing a hydrocarbon gas by selective partial oxidation and adsorption

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006071793A1 (en) * 2004-12-29 2006-07-06 Bp Corporation North America Inc. Oxidative desulfurization process
US20080308463A1 (en) * 2004-12-29 2008-12-18 Bp Corporation North America Inc. Oxidative Desulfurization Process
US20060254769A1 (en) * 2005-04-21 2006-11-16 Wang Dean C Systems and methods for producing oil and/or gas
US7601320B2 (en) 2005-04-21 2009-10-13 Shell Oil Company System and methods for producing oil and/or gas
US20080302532A1 (en) * 2005-04-21 2008-12-11 Wang Dean Chien Systems and methods for producing oil and/or gas
US7426959B2 (en) 2005-04-21 2008-09-23 Shell Oil Company Systems and methods for producing oil and/or gas
US7654322B2 (en) 2005-04-21 2010-02-02 Shell Oil Company Systems and methods for producing oil and/or gas
US20070000385A1 (en) * 2005-07-01 2007-01-04 Stouffer Mark R Adsorbents for removing H2S, other odor causing compounds, and acid gases from gas streams and methods for producing and using these adsorbents
US9499751B2 (en) 2005-09-08 2016-11-22 Saudi Arabian Oil Company Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures
US20070051667A1 (en) * 2005-09-08 2007-03-08 Martinie Gary M Diesel oil desulfurization by oxidation and extraction
US8715489B2 (en) 2005-09-08 2014-05-06 Saudi Arabian Oil Company Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures
US7744749B2 (en) 2005-09-08 2010-06-29 Saudi Arabian Oil Company Diesel oil desulfurization by oxidation and extraction
US20100300938A1 (en) * 2005-09-08 2010-12-02 Martinie Gary D Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures
US7803339B2 (en) 2006-02-22 2010-09-28 Shell Oil Company Method for disposal of di-sulphide compounds
WO2007096345A1 (en) * 2006-02-22 2007-08-30 Shell Internationale Research Maatschappij B.V. Method for disposal of di-sulphide compounds
US20090028769A1 (en) * 2006-02-22 2009-01-29 Anders Carlsson Method for disposal of di-sulphide compounds
US8459368B2 (en) 2006-04-27 2013-06-11 Shell Oil Company Systems and methods for producing oil and/or gas
US20070251686A1 (en) * 2006-04-27 2007-11-01 Ayca Sivrikoz Systems and methods for producing oil and/or gas
US20090200018A1 (en) * 2006-04-27 2009-08-13 Ayca Sivrikoz Systems and methods for producing oil and/or gas
US8722006B2 (en) 2006-05-16 2014-05-13 Shell Oil Company Process for the manufacture of carbon disulphide
US20090226358A1 (en) * 2006-05-16 2009-09-10 Shell Oil Company Process for the manufacture of carbon disulphide
US20090155159A1 (en) * 2006-05-16 2009-06-18 Carolus Matthias Anna Maria Mesters Process for the manufacture of carbon disulphide
US8511384B2 (en) 2006-05-22 2013-08-20 Shell Oil Company Methods for producing oil and/or gas
US20090056941A1 (en) * 2006-05-22 2009-03-05 Raul Valdez Methods for producing oil and/or gas
US8136590B2 (en) 2006-05-22 2012-03-20 Shell Oil Company Systems and methods for producing oil and/or gas
US20080023198A1 (en) * 2006-05-22 2008-01-31 Chia-Fu Hsu Systems and methods for producing oil and/or gas
US8097230B2 (en) 2006-07-07 2012-01-17 Shell Oil Company Process for the manufacture of carbon disulphide and use of a liquid stream comprising carbon disulphide for enhanced oil recovery
US8596371B2 (en) 2006-08-10 2013-12-03 Shell Oil Company Methods for producing oil and/or gas
US8136592B2 (en) 2006-08-10 2012-03-20 Shell Oil Company Methods for producing oil and/or gas
US20080087425A1 (en) * 2006-08-10 2008-04-17 Chia-Fu Hsu Methods for producing oil and/or gas
US8394180B2 (en) 2007-02-16 2013-03-12 Shell Oil Company Systems and methods for absorbing gases into a liquid
US20100140139A1 (en) * 2007-02-16 2010-06-10 Zaida Diaz Systems and methods for absorbing gases into a liquid
US20090188669A1 (en) * 2007-10-31 2009-07-30 Steffen Berg Systems and methods for producing oil and/or gas
US7926561B2 (en) 2007-10-31 2011-04-19 Shell Oil Company Systems and methods for producing oil and/or gas
US20110108269A1 (en) * 2007-11-19 2011-05-12 Claudia Van Den Berg Systems and methods for producing oil and/or gas
US20100307759A1 (en) * 2007-11-19 2010-12-09 Steffen Berg Systems and methods for producing oil and/or gas
US8869891B2 (en) 2007-11-19 2014-10-28 Shell Oil Company Systems and methods for producing oil and/or gas
US9057257B2 (en) 2007-11-19 2015-06-16 Shell Oil Company Producing oil and/or gas with emulsion comprising miscible solvent
US20110139463A1 (en) * 2008-02-27 2011-06-16 Claudia Van Den Berg Systems and methods for producing oil and/or gas
US8528645B2 (en) 2008-02-27 2013-09-10 Shell Oil Company Systems and methods for producing oil and/or gas
US8656997B2 (en) 2008-04-14 2014-02-25 Shell Oil Company Systems and methods for producing oil and/or gas
US20110132602A1 (en) * 2008-04-14 2011-06-09 Claudia Van Den Berg Systems and methods for producing oil and/or gas
US20110094750A1 (en) * 2008-04-16 2011-04-28 Claudia Van Den Berg Systems and methods for producing oil and/or gas
US20110132617A1 (en) * 2008-07-14 2011-06-09 Shell Oil Company Systems and methods for producing oil and/or gas
US9034527B2 (en) 2010-07-15 2015-05-19 Lg Fuel Cell Systems Inc. Fuel cell system and desulfurization system
US9515338B2 (en) 2010-07-15 2016-12-06 Lg Fuel Cell Systems Inc. Fuel cell system and desulfurization system
US9640822B2 (en) 2010-07-15 2017-05-02 Lg Fuel Cell Systems Inc. Fuel cell system and desulfurization system
US10109875B2 (en) 2010-07-15 2018-10-23 Lg Fuel Cell Systems Inc. Fuel cell system and desulfurization system
US20130028822A1 (en) * 2011-07-27 2013-01-31 Saudi Arabian Oil Company Catalytic compositions useful in removal of sulfur compounds from gaseous hydrocarbons, processes for making these and uses thereof
US9663725B2 (en) * 2011-07-27 2017-05-30 Saudi Arabian Oil Company Catalytic compositions useful in removal of sulfur compounds from gaseous hydrocarbons, processes for making these and uses thereof
US9062259B2 (en) 2011-07-29 2015-06-23 Saudi Arabian Oil Company Oxidative desulfurization in fluid catalytic cracking process

Also Published As

Publication number Publication date Type
EP1581601A1 (en) 2005-10-05 application
CN100532504C (en) 2009-08-26 grant
EP1581601B1 (en) 2008-08-13 grant
CN1729274A (en) 2006-02-01 application
DE60322957D1 (en) 2008-09-25 grant
WO2004055135A1 (en) 2004-07-01 application
CA2510182A1 (en) 2004-07-01 application
JP2006509880A (en) 2006-03-23 application

Similar Documents

Publication Publication Date Title
US6103773A (en) Gas conversion using hydrogen produced from syngas for removing sulfur from gas well hydrocarbon liquids
US5968465A (en) Process for removal of HCN from synthesis gas
US6099819A (en) Catalysts for the selective oxidation of hydrogen sulfide to sulfur
Zannikos et al. Desulfurization of petroleum fractions by oxidation and solvent extraction
US6334948B1 (en) Process for producing gasoline with a low sulphur content
US5130115A (en) Process for hydrogen production from kerosene
US6881325B2 (en) Preparation of components for transportation fuels
Suzuki et al. Steam reforming of kerosene on Ru/Al2O3 catalyst to yield hydrogen
US5284717A (en) Method for producing raw materials for a reformer by cracking and desulfurizing petroleum fuels
US6946111B2 (en) Short contact time catalytic partial oxidation process for recovering sulfur from an H2S containing gas stream
US4132632A (en) Selective hydrodesulfurization of cracked naphtha
US4115251A (en) Process for removing pollutants from catalyst regenerator flue gas
US5389240A (en) Naphthenic acid removal as an adjunct to liquid hydrocarbon sweetening
Rhodes et al. The low-temperature hydrolysis of carbonyl sulfide and carbon disulfide: a review
US5110444A (en) Multi-stage hydrodesulfurization and hydrogenation process for distillate hydrocarbons
US3284342A (en) Desulphurisation of hydrocarbon materials
US4693882A (en) Steam reforming utilizing sulfur tolerant catalyst
US5085844A (en) Sorption of trialkyl arsines
US4207211A (en) Catalyst for steam reforming of hydrocarbons and process of preparing the catalyst
US4206036A (en) Hydrodesulfurization of hydrocarbon oil with a catalyst including titanium oxide
US3449078A (en) Process for the preparation of hydrogen
US7374666B2 (en) Oxidative desulfurization of sulfur-containing hydrocarbons
US4356161A (en) Process for reducing the total sulfur content of a high CO2 -content feed gas
US4389304A (en) Catalytic hydrodesulfurization or hydrodenitrogenation of organic compounds employing alumina promoted with zinc, titanium, cobalt and molybdenum as the catalytic agent
US5026536A (en) Hydrogen production from hydrocarbon

Legal Events

Date Code Title Description
AS Assignment

Owner name: SHELL OIL COMPANY, TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MESTERS, CAROLUS MATTHIAS ANNA MARIA;SCHOONEBEEK, RONALDJAN;REEL/FRAME:015274/0692

Effective date: 20040223